Lun N H Quang NH NP HC Vin

VIN HN LM KHOA HC V CNG NGH VIT NAM
HC VIN KHOA HC V CNG NGH
H QUANG NH
NGHIN CU TNG HP V C TRNG VT LIU MI

CU TRC NANO TRN C S GRAPHEN NG DNG
TRONG X L MI TRNG
LUN N TIN S HA HC
H Ni, 2016
VIN HN LM KHOA HC V CNG NGH VIT NAM
HC VIN KHOA HC V CNG NGH
H QUANG NH
NGHIN CU TNG HP V C TRNG VT LIU MI

CU TRC NANO TRN C S GRAPHEN NG DNG
TRONG X L MI TRNG
Chuyn ngnh: Ha l thuyt v Ha l

M s: 62.44.01.19
LUN N TIN S HA HC
NGI HNG DN KHOA HC:

1. PGS.TS. V Anh Tun
2. TS. V nh Ng
H Ni, 2016
LI CAM OAN
Ti xin cam oan y l kt qu nghin cu ca ring ti v khng trng lp

vi bt k cng trnh khoa hc no khc. Cc s liu kt qu l trung thc, mt s
kt qu trong lun n l kt qu chung ca nhm nghin cu di s hng dn ca
PGS.TS. V Anh Tun Vin Ha hc Vin Hn lm Khoa hc v Cng ngh
Vit Nam.
H Ni, ngy 01 thng 4 nm 2016
Tc gi lun n
H Quang nh
LI CM N
Ti xin by t lng bit n su sc, s cm phc v knh trng ti PGS. TS.

V Anh Tun v TS. V nh Ng nhng ngi Thy tn tm hng dn khoa
hc, nh hng nghin cu lun n c hon thnh, ng vin khch l v
to mi iu kin thun li cho ti trong sut qu trnh thc hin lun n.
Ti xin trn trng cm n Ban lnh o Vin Ha hc, Hc vin Khoa hc
v Cng ngh Vin Hn lm Khoa hc v Cng ngh Vit Nam cng cc cn b
trong Vin, Hc vin quan tm gip v to iu kin thun li cho ti trong
qu trnh hc tp v nghin cu thc hin lun n.
Ti xin chn thnh cm n tp th cn b, nhn vin phng Ha hc B mt -
Vin Ha hc lun gip , ng h v to mi iu kin tt nht cng nh
nhng ng gp v chuyn mn cho ti trong sut qu trnh thc hin v bo v
lun n.
Ti xin chn thnh cm n ng y, Ban Gim hiu Trng i hc Cng
nghip Vit Tr, lnh o Khoa Cng ngh Ha hc v cc ng nghip trong Khoa
Cng ngh Ha hc to mi iu kin tt nht cho ti trong sut qu trnh hc
tp v nghin cu.
Cui cng ti xin by t li cm n su sc nht n gia nh, ngi thn v
bn b lun quan tm, khch l, ng vin v to mi iu kin thun li cho ti
trong sut thi gian thc hin lun n ny.
Tc gi lun n
H Quang nh
MC LC
LI CAM OAN
LI CM N
DANH MC CC CH VIT TT, K HIU
DANH MC HNH V
DANH MC BNG
M U ................................................................................................................1
CHNG 1: TNG QUAN ................................................................................4
1.1. Gii thiu chung v vt liu trn c s cacbon .............................................4
1.1.1. Kim cng v graphit...............................................................................................................4
1.1.2. Vt liu cacbon cu trc nano ................................................................................................5
1.2. Vt liu graphen v graphen oxit.................................................................10
1.2.1. Cu trc ca graphen [18] ................................................................................................... 10
1.2.2. Cu trc graphen oxit (GO) ................................................................................................. 10
1.2.3. Tm hot ng ca graphen v graphen oxit ................................................................. 12
1.2.4. Cc phng php tng hp GO ......................................................................................... 13
1.2.5. Cc phng php tng hp graphen ................................................................................. 15
1.2.6. Cc vt liu nano composit c t tnh trn c s GO, rGO ....................................... 26
1.3. ng dng v trin vng ca cc vt liu nghin cu trong hp ph cht mu
hu c v cc ion kim loi nng .........................................................................33
1.3.1. ng dng ca cc vt liu GO, rGO trong hp ph cht mu v cc ion kim loi nng . 33
1.3.2. ng dng ca vt liu composit trn c s GO, rGO trong hp ph .................... 36
CHNG 2: PHNG PHAP NGHIN CU V THC NGHIM ........39
2.1. Thc nghim ................................................................................................39
2.1.1. Ha cht ..................................................................................................................................... 39
2.1.2. Tng hp vt liu graphit oxit ............................................................................................. 39
2.1.3. Tng hp vt liu GOSA, GOVS v rGO...................................................................... 40
2.1.4. Tng hp vt liu nano composit Fe3O4-GOVS........................................................... 42
2.1.5. Xc nh im ng in ca Fe3O4-GOVS v Fe-Fe3O4-GOVS [70]................. 45
2.1.6. nh gi kh nng hp ph thuc nhum hot tnh RR195...................................... 45
2.1.7. nh gi kh nng hp ph As (V) ................................................................................... 46
2.1.8. nh gi kh nng hp ph Cu(II), Cd(II) ...................................................................... 47
2.1.9. nh gi kh nng ti sinh ca vt liu t tnh Fe-Fe3O4-GOVS ............................ 47
2.2. Tnh ton qu trnh hp ph.........................................................................47
2.2.1. Tnh ton hiu sut qu trnh hp ph............................................................................... 47
2.2.2. Mt s m hnh ng nhit hp ph [71, 72] ................................................................. 48
2.2.3. ng hc qu trnh hp ph [71, 72] ................................................................................ 49
2.3. Phng php nghin cu c trng vt liu ................................................50
2.3.1. Phng php nhiu x Rnghen (X-ray diffraction, XRD) [72, 73] ...................... 50
2.3.2. Phng php ph hng ngoi bin i Fourier-FTIR [75]........................................ 52
2.3.3. Phng php ph in t quang tia X (XPS)................................................................. 52
2.3.4. Phng php ph tn sc nng lng tia X (EDX) ..................................................... 53
2.3.5. Phng php hin vi in t truyn qua (TEM) v knh hin vi in t truyn
qua phn gii cao (HR-TEM) ......................................................................................................... 55
2.3.6. Phng php hin vi in t qut phn gii cao (FE-SEM)...................................... 56
2.3.7. Phng php ng nhit hp ph- kh hp ph N2 (BET) [72]............................... 56
2.3.8. Phng php ph hp th t ngoi v kh kin UV - Vis [73] ................................ 58
2.3.9. Phng php quang ph hp th nguyn t (AAS) [76]............................................ 59
2.3.10. Phng php xc nh t tnh vt liu bng thit b t k mu rung .................... 60
CHNG 3: KT QU V THO LUN ....................................................61
3.1. Kho st cc yu t nh hng n qu trnh tng hp GO v rGO...........61
3.1.1. Gin XRD ca graphit ban u v sau qu trnh oxy ha .................................... 61
3.1.2. Mt s yu t nh hng n qu trnh bc lp graphit oxit s dng k thut vi
sng v k thut siu m................................................................................................................... 62
3.1.3. nh hng ca nhit n qu trnh kh GOVS v rGO ...................................... 69
3.2. c trng vt liu GO v rGO tng hp c ............................................70
3.2.1. Phng php nhiu x tia (XRD) ...................................................................................... 70
3.2.2. Ph hng ngoi chuyn dch Fourier (FTIR) ................................................................. 71
3.2.3. Knh hin vi in t truyn qua phn gii cao (HR TEM) ................................ 72
3.2.4. Hp ph v kh hp ph Nit (BET) ............................................................................... 74
3.2.5. Ph in t quang tia X (XPS) ........................................................................................... 75
3.3. Kho st mt s yu t nh hng n qu trnh tng hp Fe3O4-GOVS .78
3.3.1. Kho st nh hng ca nhit phn ng ng kt ta........................................... 79
3.3.2. nh hng nng u ....................................................................................................... 83
3.3.3. nh hng pH ......................................................................................................................... 87
3.3.4. nh hng ca tc khuy .............................................................................................. 88
3.4. Tng hp vt liu Fe3O4-GOVS v Fe-Fe3O4-GOVS ................................90
3.5. c trng vt liu Fe3O4-GOVS v Fe-Fe3O4-GOVS.................................91
3.5.1. Nghin cu nhiu x tia X (XRD)..................................................................................... 91
3.5.2. Knh hin vi in t truyn qua TEM v knh hin vi in t truyn qua phn
gii cao HR-TEM ............................................................................................................................... 92
3.5.3. Ph hng ngoi chuyn dch Fourier (FTIR) ................................................................. 93
3.5.4. Ph tn sc nng lng tia X (EDX) ca Fe-Fe3O4-GOVS v Fe3O4-GOVS .... 94
3.5.5. Hp ph v kh hp ph Nit (BET) ca Fe-Fe3O4-GOVS v Fe3O4-GOVS ... 95
3.5.6. Ph quang in t tia X (XPS) ca Fe-Fe3O4-GOVS v Fe3O4-GOVS ............... 96
3.5.7. T tnh ca vt liu Fe-Fe3O4-GOVS v Fe3O4-GOVS ............................................. 98
3.6. nh gi kh nng hp ph ca GOSA, GOVS v rGO .............................99
3.6.2. ng hc qu trnh hp ph RR195 trn GOVS v rGO ........................................ 106
3.7. nh gi kh nng hp ph ca Fe3O4-GOVS v Fe-Fe3O4-GOVS .........110
3.7.1. nh gi kh nng hp ph RR195 ca Fe3O4-GOVS v Fe-Fe3O4-GOVS .... 110
3.7.2. Hp ph ion kim loi nng Cu(II) v Cd(II) ................................................................. 111
3.7.3. Hp ph As(V) trn vt liu GOVS, Fe3O4-GOVS v Fe-Fe3O4-GOVS........... 121
3.8. nh gi kh nng ti s dng ca vt liu ...............................................128
KT LUN ........................................................................................................132
DANH MC CC CNG TRNH CNG B.. 134
NHNG IM MI CA LUN N ...........................................................135
TI LIU THAM KHO ................................................................................136
PH LC...........................................................................................................150
DANH MC CC CH VIT TT, K HIU
AAS Atomic Absorption Spectroscopy (Ph hp th nguyn t)

At Atomic (Nguyn t)
BET Brunauer-Emmett-Teller
CNTs Carbon nanotubes (ng nano cacbon)
CVD Chemical Vapor Deposition (Lng ng pha hi ha hc)
EDX Energy-dispersive X-ray spectroscopy (Ph tn x nng lng tia X)
FE-SEM Field emission - Scanning electron microscopy (Knh hin vi
in t qut pht x trng)
Fe3O4-GOVS Fe3O4 trn GOVS
Fe-Fe3O4-GOVS Fe, Fe3O4 trn GOVS
FTIR Fourier transform infrared spectroscopy (Ph hng ngoi
bin i Fourie)
GO Graphene oxit (Graphen oxit)
GOVS Graphen oxit bc lp bng vi sng
GOSA Graphen oxit bc lp bng siu m
HR-TEM High Resolution -Transmission Electron Microscopy (Knh
hin vi in t truyn qua phn gii cao)
M-rGO Vt liu composit c t tnh trn rGO
M-GO Vt liu composit c t tnh trn GO
rGO Reduced graphene oxide (Graphen oxit kh)
RR195 Reactive Red 195 (Thuc nhum hot tnh RR195)
SEM Scanning Electron Microscopy (Knh hin vi in t qut)
UV-vis Ultraviolet - Visible (Ph t ngoi kh kin)
TEM Transmission Electron Microscopy (Hin vi in t truyn qua)
VSM Vibrating sample magnetometry (T k mu rung)
v/p Vng/pht
XRD X-Ray Diffraction (Nhiu x tia X)
XPS X-ray Photoelectron Spectroscopy (Quang in t tia X)
DANH MC HNH V
Hnh 1.1 Cu trc tinh th ca kim cng v graphit (3D) 4

Hnh 1.2 Graphen cu trc c bn (2D) v cc vt liu cacbon khc (0D, 5
1D v 3D)
Hnh 1.3 Graphen hin hu vi mt li lm ca khng gian 3 chiu 8
Hnh 1.4 S lng cc cng trnh cng b v graphen trong 10 nm gn 9
y (tng hp t cc cng trnh ng trn cc tp ch lin quan
n khoa hc)
Hnh 1.5 S phn b ca cc cng trnh cng b lin quan n ba vt liu 9
fullerene, CNTs v graphen trn th gii
Hnh 1.6 Cc lin kt ca nguyn t cacbon trong mng graphen 10
Hnh 1.7 Cu trc xut ca GO bi cc nh nghin cu khc nhau 11
Hnh 1.8 Lin kt hydro gia cc lp graphit oxit 11
Hnh 1.9 Cc phng php tng hp GO 13
Hnh 1.10 C ch hnh thnh GO t graphit 15
Hnh 1.11 S chuyn ha t graphit thnh rGO 16
Hnh 1.12 C ch kh nhm epoxy ca hydrazine 16
Hnh 1.13 S m t c ch kh nhit cho GO ch ra s phn hy ca 18
cc dng xy qua s khi mo phn gc
Hnh 1.14 S biu din phng php LPE 19
Hnh 1.15 Tng hp graphen t graphit bng phng php LPE s dng 20
cc dung mi khc nhau
Hnh 1.16 S v hnh nh ca s gin n ca in cc graphit s dng 21
qu trnh hai giai on
Hnh 1.17 Gin minh ha bc lp in ha graphit 22
Hnh 1.18 Phng php tch lp graphit bng bng dnh 23
Hnh 1.19 C ch to mng graphen bng phng php nung nhit SiC 24
Hnh 1.20 Cu trc ca GO, rGO v GP 25
Hnh 1.21 nh dung dch fucsin (20 mg/L, bn phi) v dung dch sau khi 27
c hp ph bi Fe3O4-rGO trong 1 h v c tch bi mt
nam chm (tri)
Hnh 1.22 C ch hnh thnh v pht trin ht nano trong dung dch 28
Hnh 1.23 Qu trnh hnh thnh Fe3O4-GO bng phng php ng kt ta 30
Hnh 1.24 S tng hp Fe3O4-rGO bng phng php tng hp thy 31
nhit dung mi
Hnh 1.25 Qu trnh tng hp Fe3O4-GO v Fe-Fe3O4-GO bng phng 32
php kt tinh ti ch
Hnh 2.1 S tng hp graphit oxit t graphit 40
Hnh 2.2 S tng hp GOSA, GOVS v rGO 41
Hnh 2.3 Thit b phn ng nhit tng hp rGO t GO 42
Hnh 2.4 S tng hp Fe3O4-GOVS 43
Hnh 2.5 S tng hp Fe-Fe3O4-GOVS 44
Hnh 2.6 ng chun, cu trc ha hc v ph UV-Vis ca thuc 46
nhum RR195
Hnh 2.7 S chm tia ti v chm tia nhiu x trn tinh th 51
Hnh 2.8 t ca pic phn x gy ra do kch thc ht 51
Hnh 2.9 Qu trnh pht quang in t 53
Hnh 2.10 S nguyn l s to nh phn gii cao trong HR-TEM 55
Hnh 2.11 Cc dng ng ng nhit hp ph-kh hp ph theo phn loi 57
IUPAC
Hnh 2.12 Bc chuyn ca cc electron trong phn t 58
Hnh 2.13 Mi quan h gia cng vch ph A v nng cht Cx 59
Hnh 3.1 Gin XRD ca graphit trc v sau qu trnh oxy ha 61
Hnh 3.2 Sn phm GOVS bc lp bng k thut vi sng ti cc thi 62
im khc nhau
Hnh 3.3 Gin XRD ca cc mu GOVS c thi gian vi sng khc 63
nhau GVS1, GVS2 v GVS3
Hnh 3.4 Gin XRD (a) v ph FTIR (b) ca cc mu GOVS cc 65
cng sut vi sng khc nhau GVS1, GVS4, GVS5 v GVS6
Hnh 3.5 Sn phm GOSA bc lp bng k thut siu m vi cc thi 67
gian khc nhau
Hnh 3.6 Gin XRD (d) v nh HR-TEM ca cc mu GOSA vi thi 68
gian siu m khc nhau: graphit oxit (a), GSA2 (b), GSA3 (c)
Hnh 3.7 Gin XRD (A) v FTIR (B) ca rGO cc iu kin nhit 69
khc nhau G1, G2, G3 v G4
Hnh 3.8 Gin XRD ca GOSA, GOVS v rGO sau tng hp 70
Hnh 3.9 Ph FTIR ca GOSA, GOVS v rGO sau tng hp 71
Hnh 3.10 nh HR-TEM ca GOSA (a), GOVS (b) v rGO (c) 73
Hnh 3.11 ng ng nhit hp ph - kh hp ph N2 77 K (a) v ng 74
phn b kch thc mao qun rGO (b), GOSA (c) v GOVS (d)
Hnh 3.12 Ph XPS ca GOSA (a, b), GOVS (c, d) v rGO (e, f) 76
Hnh 3.13 Ph XPS ca rGO kh nhit t GOSA 77
Hnh 3.14 S qu trnh kh nhit t GOVS v rGO 77
Hnh 3.15 Gin XRD ca cc mu Fe3O4-GOVS tng hp trong iu 79
kin nhit khc nhau GF1, GF2 v GF3
Hnh 3.16 Ph XPS (a,b) ca cc mu GF1, GF2 v GF3 tng hp trong 80
iu kin nhit khc nhau
Hnh 3.17 nh TEM vi phn gii khc nhau ca cc mu Fe3O4-GOVS 82
tng hp iu kin nhit khc nhau: GF1 (a), GF2 (b) v
GF3 (c)
Hnh 3.18 Gin XRD ca Fe3O4-GOVS tng hp iu kin nng 84
khc nhau
Hnh 3.19 nh TEM ca Fe3O4-GOVS tng hp iu kin nng khc 85
nhau: N (a), GF3 (b), N1 (c) v N2 (d)
Hnh 3.20 ng cong t ha ca Fe3O4-GOVS tng hp iu kin nng 86
khc nhau
Hnh 3.21 nh FE-SEM ca Fe3O4-GOVS tng hp trong cc iu kin 87
pH khc nhau GF3 (a), GF4 (b) v GF5 (c)
Hnh 3.22 Gin XRD ca Fe3O4-GOVS tng hp iu kin tc 88
khuy khc nhau
Hnh 3.23 nh TEM ca Fe3O4-GOVS tng hp iu kin tc khuy 89
khc nhau V1 (a), V2 (b), GF3 (c) v V4 (d)
Hnh 3.24 S tng hp Fe3O4 - GOVS iu kin thch hp 90
Hnh 3.25 Gin XRD ca Fe3O4-GOVS v Fe-Fe3O4-GOVS 92
Hnh 3.26 nh TEM ca Fe3O4-GOVS(a) v Fe-Fe3O4-GOVS(b,c) 93
Hnh 3.27 Ph FTIR ca Fe-Fe3O4-GOVS v Fe3O4-GOVS 94
Hnh 3.28 Ph EDX ca Fe3O4-GOVS v Fe-Fe3O4-GOVS 95
Hnh 3.29 ng ng nhit hp ph - kh hp ph N2 (a) v phn b mao 95
qun (b) ca Fe-Fe3O4-GOVS v Fe3O4-GOVS
Hnh 3.30 Ph XPS ca Fe-Fe3O4-GOVS (a-d) v Fe3O4-GOVS (a) 97
Hnh 3.31 ng cong t ha ca Fe-Fe3O4-GOVS v Fe3O4-GOVS 98
Hnh 3.32 nh hng pH n qu trnh hp ph RR195 trn GO v rGO 100
Hnh 3.33 S ph thuc dung lng hp ph RR195 (200 mg/L) theo thi 101
gian (a) v ng ng nhit hp ph Langmuir ca RR195 trn
GO v rGO (b)
Hnh 3.34 ng hp ph ng nhit Langmuir ca RR195 trn GO v rGO 103
Hnh 3.35 Gi tr RL ph thuc vo nng RR195 ban u 104
Hnh 3.36 ng hp ph ng nhit Freundlich ca RR195 trn GO v rGO 105
Hnh 3.37 C ch hp ph RR195 ln trn vt liu hp ph rGO 106
Hnh 3.38 Mi quan h Ln(Qe-Qt) theo thi gian (ng hc biu kin bc1) 107
ca qu trnh hp ph RR195 trn GOVS v rGO
Hnh 3.39 Mi quan h t/Qt theo thi gian (ng hc biu kin bc 2) ca 108
qu trnh hp ph RR195 trn GOVS v rGO
Hnh 3.40 Hiu sut hp ph RR195 trn cc vt liu hp ph khc nhau 110
Hnh 3.41 im ng in (pHpzc) ca Fe3O4-GOVS (a) v Fe-Fe3O4- 111
GOVS (b)
Hnh 3.42 ng ng nhit hp ph Cu(II), Cd(II) (a), ng nhit 112
Langmuir ca Fe3O4-GOVS v GOVS (b, c)
Hnh 3.43 ng hp ph ng nhit Freundlich ca Cd(II) v Cu(II) trn 113
GOVS v Fe3O4-GOVS
Hnh 3.44 ng ng nhit hp ph Cu(II), Cd(II) (a), ng nhit 115
Langmuir ca Fe-Fe3O4-GOVS (b)
Hnh 3.45 ng hp ph ng nhit Freundlich ca Cd(II) v Cu(II) trn 116
Fe-Fe3O4-GOVS
Hnh 3.46 S ph thuc dung lng hp ph Cd(II) trn Fe-Fe3O4-GOVS 119
theo thi gian ti nng 50 mg/L v 100 mg/L
Hnh 3.47 Mi quan h Ln(Qe-Qt) theo thi gian (ng hc biu kin bc 1) 119
Hnh 3.48 Mi quan h t/Qt theo thi gian (ng hc biu kin bc 2) 120
Hnh 3.49 nh hng pH n qu trnh loi b As(V) trn vt liu GOVS, 121
Fe3O4-GOVS v Fe-Fe3O4-GOVS, (nng As(V) 7 mg/L,
m/V= 0,4 g/L, T=30 oC)
Hnh 3.50 S ph thuc dung lng hp ph As(V) theo thi gian nng 122
10 mg/L (a) v ng ng nhit hp ph (b) trn vt liu Fe-
Fe3O4-GOVS v Fe3O4-GOVS, m/V= 0,4 g/L, T=30 oC
Hnh 3.51 Cc loi tng tc khc nhau tham gia vo s hp th cc cht 125
nhim trn Fe3O4-GOVS v Fe-Fe3O4-GOVS [38]
Hnh 3.52 Mi quan h Ln(Qe-Qt) theo thi gian (ng hc biu kin bc1) 126
ca qu trnh hp ph As(V) trn ca Fe-Fe3O4-GOVS v
Fe3O4-GOVS
Hnh 3.53 Mi quan h t/Qt theo thi gian (ng hc biu kin bc 2) ca qu 127
trnh hp ph ca As(V) trn Fe-Fe3O4-GOVS v Fe3O4-GOVS
Hnh 3.54 Kh nng hp ph RR195 (a) v ph UV-Vis sau hp ph 129
RR195 trn Fe-Fe3O4-GOVS qua ba ln ti sinh (b) (pH = 5,5,
m/V = 1 g/L)
Hnh 3.55 Hiu sut hp ph Cd(II) trn vt liu Fe-Fe3O4-GOVS sau ba 129
ln ti sinh (pH = 6, m/V = 0,1 g/L)
DANH MC BNG
Bng 1.1 Tnh cht ca SWCNTs v MWCNTs 6

Bng 1.2 Tnh cht vt l ca n lp graphen nhit phng 8
Bng 1.3 Mt s tnh cht c bn ca cc vt liu GP, GO v rGO 26
Bng 2.1 Danh mc ha cht chnh dng trong lun n 39
Bng 2.2 K hiu cc mu GOSA tng hp cc thi gian siu m khc nhau 41
Bng 2.3 K hiu cc mu GOVS tng hp cc thi gian v cng sut 41
khc nhau
Bng 2.4 K hiu cc mu rGO c tng hp t kh GOVS cc nhit 42
khc nhau
Bng 2.5 K hiu tn cc mu Fe3O4-GOVS tng hp cc iu kin 43
nhit v pH khc nhau
nng mui st ban u khc nhau
tc khuy khc nhau
Bng 3.1 Kho st nh hng ca thi gian vi sng n hiu sut thu hi 64
Bng 3.2 Kho st nh hng ca cng sut vi sng n hiu sut thu hi 65
Bng 3.3 Cc thng s c trng ca GOSA, GOVS v rGO theo 74
phng php BET
Bng 3.4 Thnh phn cc nguyn t trong ph XPS ca GOVS, GOSA 77
v rGO (%At)
Bng 3.5 Thnh phn cc nguyn t trong ph XPS ca Fe3O4-GOVS (%At) 81
Bng 3.6 Kch thc ht mu Fe3O4-GO tng hp iu kin nhit 81
khc nhau
Bng 3.7 Kch thc ht mu Fe3O4-GOVS tng hp iu kin nng 85
khc nhau
Bng 3.8 Thnh phn cc nguyn t trong Fe3O4-GOVS v Fe-Fe3O4- 94
GOVS (%At)
Bng 3.9 Cc thng s c trng ca Fe3O4-GOVS v Fe-Fe3O4-GOVS 96
Bng 3.10 S ph thuc dung lng hp ph RR195 trn vt liu rGO v 100
GO vo pH (nng 100 mg/L, thi gian hp ph 10h)
Bng 3.11 S ph thuc dung lng hp ph vo nng i vi RR195 102
Bng 3.12 Cc thng s ng nhit hp ph Langmuir v Freundlich ca 103
GO v rGO ca RR195
Bng 3.13 Phn loi s ph hp ca m hnh ng nhit bng tham s RL 104
Bng 3.14 Gi tr tham s cn bng RL ca qu trnh hp ph RR195 bng 104
rGO v GO
Bng 3.15 S ph thuc LnQe vo LnCe i vi m hnh Freundlich ca 105
RR195
Bng 3.16 Gi tr Ln(Qe-Qt) theo thi gian i vi RR195 105
Bng 3.17 Gi tr t/Qt theo thi gian i vi RR195 108
Bng 3.18 Mt s tham s ca phng trnh ng hc biu kin bc nht 108
(RR195)
Bng 3.19 Mt s tham s ca phng trnh ng hc biu kin bc hai 108
(RR195)
Bng 3.20 Tng kt cc thng s c trng ca GO v rGO 109
Bng 3.21 Tng kt ng nhit Langmuir v Fredulich ca qu trnh hp 109
ph RR195 trn GO v rGO
Bng 3.22 Cc tham s ca phng trnh ng hc biu kin bc hai qu 109
trnh hp ph RR195 trn GOVS, GOSA v rGO
Bng 3.23 Kh nng hp ph ca cc mu kho st nng khc nhau 112
Bng 3.24 S ph thuc LnQe vo LnCe i vi m hnh Freundlich 113
GOVS v Fe3O4-GOVS
Bng 3.26 Dung lng hp ph Cd(II) v Cu(II) bng Fe- Fe3O4-GOVS 115
cc nng ban u khc nhau
Bng 3.27 S ph thuc LnQe vo LnCe i vi m hnh Freundlich 116
Cu(II) v Cd(II) trn Fe-Fe3O4-GOVS
Bng 3.29 Dung lng hp ph ca mt Cu(II) v Cd(II) ca mt s vt liu 118
Bng 3.30 Mt s tham s ca phng trnh ng hc biu kin bc 1 v bc 2 120
Bng 3.31 Nng hp ph ca cc mu kho st 122
As(V) trn Fe3O4-GOVS v Fe-Fe3O4-GOVS
Bng 3.33 Dung lng hp ph As(V) ca mt s vt liu cha st 124
Bng 3.34 Gi tr Ln(Qe-Qt) theo thi gian ca qu trnh hp ph As(V) 126
Bng 3.35 Gi tr t/Qt theo thi gian ca qu trnh hp ph As(V) 127
Bng 3.36 Mt s tham s ca phng trnh ng hc biu kin bc nht As(V) 128
Bng 3.37 Mt s tham s ca phng trnh ng hc biu kin bc hai As(V) 128
Bng 3.38 Tng kt cc thng s c trng ca Fe3O4-GOVS v Fe- 130
Fe3O4-GOVS
Bng 3.39 Tng kt dung lng hp ph cc i RR195, Cu(II), Cd(II) v 130
As(V) trn GOVS, Fe3O4-GOVS v Fe-Fe3O4-GOVS
Bng 3.40 Cc tham s ca phng trnh ng hc biu kin bc hai qu trnh 131
hp ph Cd(II), As(V) trn Fe3O4-GOVS v Fe-Fe3O4-GOVS
M U
Hin nay, cng vi s pht trin mnh m ca cc hot ng cng nghip,

nng nghip c tc ng tch cc n s pht trin kinh t x hi, tuy nhin bn
cnh n cng dn n tng vng lun chuyn ca cc cht nhim c hi trong
cc ngun nc. Nc ngt c th b nhim bi v s cc cht gy nhim khc
nhau nh: thuc nhum, cc hp cht phenon, thuc tr su, thuc dit c, dc
phm, cc ion kim loi nng. Nhng cht gy nhim c th c tch t sinh
hc, tc ng bt li n s tn ti ca sinh vt di nc, h ng thc vt cng
nh nh hng to ln ti sc khe con ngi. V vy, bn cnh vic nng cao
thc bo v mi trng ca con ngi, sit cht cng tc qun l mi trng th vic
tm ra phng php nhm loi b cc ion kim loi nng, thuc nhum hot tnh c
hi,... ra khi mi trng nc c ngha ht sc to ln.
Hp ph l mt trong nhng bin php hiu qu nht trong x l nc. So

snh vi cc phng php x l nc khc n cung cp mt li th nh d thc
hin, khng pht sinh cht c hi trong sut qu trnh x l v hn tt c l n loi
b gn nh tt c cc cht nhim trong nc [1]. Trong nhng nm qua, vt liu
cacbon v vt liu trn c s cacbon vn l nhng vt liu c s dng nhiu nht
lm vt liu hp ph [1, 2], do chng c b mt ring ln, n nh v bn ha
hc, bn nhit. Vt liu d bin tnh nhm thay i tnh cht ha hc v vt l
hp ph chn lc ng thi c hp cht hu c c hi nh cc cht mu v c ion
kim loi nng, ngoi ra vic bin tnh cn lm tng dung lng hp ph, tng hiu
qu x l cc cht thi c hi.
Trong thp k qua, vt liu cu trc nano cacbon, chng hn nh ng nano

cacbon (CNTs) c ph bin ng k. Mc d c nhiu tin b c thc
hin trong nhng nm gn y v kh nng ng dng hp ph ca CNTs, nhng do
chi ph ch to cao hn ch cc ng dng thc t ca chng [3]. V vy, vic
thm d cc cht hp ph mi y ha hn vn l mong mun ln.
Gn y, graphen v vt liu trn c s graphen l loi vt liu nhn c s

quan tm c bit. K t khi ln u tin graphen c gii thiu v cc tnh cht
1
in t nm 2004 v gii thng Nobel Vt l v vt liu ny nm 2010, ngy nay
graphen tr thnh i tng c nhiu nh khoa hc quan tm, nghin cu rng
ri t tnh cht in, in ha, quang hc, c hc v kh nng hp ph c o ca
n [3, 4, 5, 6]. Graphen l mt vt liu cacbon mi, n c nh ngha l mt lp
hoc vi lp mng cc nguyn t cacbon vi lin kt sp2 to thnh dn tinh th hnh
t ong [3]. C nhiu phng php tng hp graphen c xut nhng ph bin
nht vn l phng php CVD v phng php ha hc (da trn qu trnh oxi ha
graphit, bc tch lp to thnh graphen oxit (GO) v qu trnh kh ha hc GO
thnh graphen (rGO) [7, 8]. Tuy nhin, phng php CVD i hi thc hin trong
iu kin khc nghit, s dng thit b chuyn dng, nng lng ln, gi thnh cao
v ch iu ch c lng nh [7, 9]. Vi din tch b mt ln (gi tr l thuyt
2630 m2/g) v tnh cht vt l, ha hc c bit, graphen v GO thc s thu ht
nhiu s quan tm trong nhiu lnh vc bao gm c trong nh gi hp ph [5, 10].
Mc d vy, cc nghin cu trc y tp trung nhiu vo nghin cu tng

hp v nh gi kh nng ng dng ca vt liu graphen, vt liu trn c s graphen
ch yu trong lnh vc in ha, s lng cc cng b khoa hc v ng dng trong
lnh vc hp ph cn cha nhiu v ri rc. Hn na qu trnh tng hp GO v rGO
t graphit ch yu s dng k thut bc tch lp trong pha lng [8], qu trnh bc
tch lp graphit oxit thnh GO s dng k thut vi sng v qu trnh kh GO v
rGO bng tc nhn nhit cn t c cp.
Vit Nam, vic nghin cu vt liu graphen v vt liu trn c s graphen

cn rt mi m, ch c mt s c s nghin cu khoa hc nh: Trng i hc
Khoa hc T nhin, i hc Quc gia Thnh Ph H Ch Minh [11], Vin Ha hc,
Vin Khoa hc Vt liu thuc Vin Hn lm Khoa hc v Cng ngh Vit Nam
[12], Trng i hc Khoa hc T nhin - i hc Quc Gia H Ni [13]. Vin
Ha hc cng nghip [14, 15], Trng i hc Quy Nhn [16, 17]. Do vy
nghin cu mt cch c h thng qu trnh tng hp v kh nng hp ph c bit
ca vt liu graphen v vt liu trn c s graphen, ti la chn ti nghin cu
sinh ca mnh l: Nghin cu tng hp v c trng vt liu mi cu trc nano trn
c s graphen ng dng trong x l mi trng
2
Mc tiu ca lun n:
Tng hp c GO (GOVS, GOSA), rGO, Fe3O4-GO v Fe-Fe3O4-GO. c

trng cc vt liu tng hp c v nh gi kh nng hp ph thuc nhum hot
tnh, asen v cc ion kim loi nng ca vt liu tng hp c.
Lun an c trnh bay theo cac mc chinh sau:
Phn m u
Chng 1. Tng quan
Chng 2. Phng phap nghin cu v thc nghim
Chng 3. Kt qua v thao lun cac vn sau:
- Nghin cu cc yu t nh hng n qu trnh tng hp vt liu GO v rGO:
Nghin cu mt s iu kin nh hng n qu trnh bc tch lp graphit
oxit thnh GO v qu trnh kh GO v rGO.
c trng vt liu graphit oxit, GO v rGO tng hp c.
- Nghin cu mt s yu t nh hng n qu trnh tng hp vt liu Fe3O4-
GOVS nh: pH, nng mui Fe3+/Fe2+, nhit v tc khuy.
- Tng hp vt liu Fe-Fe3O4-GOVS.
- S dng cc phng php phn tch ha l hin i nh: XRD, XPS, FTIR,
HR-TEM... c trng sn phm liu Fe3O4-GOVS v Fe-Fe3O4-GOVS
tng hp c.
- Nghin cu ng nhit hp ph, ng hc hp ph thuc nhum hot tnh v
cc ion kim loi nng trn cc vt liu: GOVS, rGO, Fe3O4-GOVS v Fe-
Fe3O4-GOVS tng hp c.
Kt lun
Danh mc cac bi bao lin quan n lun an
Nhng im mi ca lun n
Ti liu tham khao
Ph lc
3
CHNG 1: TNG QUAN
1.1. Gii thiu chung v vt liu trn c s cacbon
Cacbon l nguyn t ng vai tr quan trng cho s sng v l nguyn t c

bn ca hng triu hp cht ha hc hu c. Trong mt nguyn t cacbon, cc
electron lp ngoi cng c th hnh thnh nn nhiu kiu lai ha khc nhau. Do
khi cc nguyn t ny lin kt li vi nhau chng cng c kh nng to nn nhiu
dng cu trc tinh th nh: Cu trc tinh th ba chiu (3D), hai chiu (2D), mt
chiu (1D) v khng chiu (0D). iu ny c th hin thng qua s phong ph v
cc dng th hnh ca vt liu cacbon l: Kim cng, graphit, graphen, ng nano
cacbon v fullerens [4].
1.1.1. Kim cng v graphit

Kim cng v graphit l hai dng th hnh c cu trc tinh th 3 chiu ca
cacbon c bit n nhiu. Mi nguyn t cacbon trong kim cng lin kt cng
ha tr vi 4 nguyn t cacbon khc bng 4 lin kt trng thi lai ha sp3 trong
mt mng t din vi di lin kt C-C khong 0,1544 nm. Cu trc tinh th kim
cng dng ny l cu trc lp phng tm mt (FCC) (Hnh 1.1). vi hng s mng
a= 3.567. Ngoi ra cn c kim cng c cu trc tinh th lc gic hay c gi vi
tn khc l kim cng su phng (lonsdaleite), ch c tm thy mt s thin
thch cha cacbon ri xung tri t, di lin kt C-C khong 0,152 nm[18].
Hnh 1.1. Cu trc tinh th ca kim cng v graphit (3D)

Vi cu trc bn vng, kim cng c nhng tnh cht vt l hon ho, n c
cng rt cao ( cng Mohs l 10), bn nhit (nhit nng chy cao khong
4500 K trong chn khng) v tn sc cc tt, v th chng c rt nhiu ng dng
trong c cng nghip v ngnh kim hon.
4
Khc vi kim cng, graphit c kh nng dn in t tt v trong cu trc
graphit, mi nguyn t cacbon lin kt cng ha tr vi 3 nguyn t cacbon khc
hnh thnh nn mng phng vi cc hnh lc gic, do mi nguyn t cacbon
trong mng cn d 1 electron. Cc electron cn li ny c th chuyn ng t do
bn trn v bn di mt mng, gp phn vo tnh dn in ca graphit. Cc nguyn
t cacbon trong graphit lin kt vi nhau bng hai lin kt n () v mt lin kt
i (). Khong cch gn nht ca hai nguyn t cacbon l 0,142 nm. Cc n lp
graphit lin kt vi nhau bng lc Van der Waals hnh thnh nn cu trc tinh th 3
chiu (Hnh 1.1). Khong cch gia cc lp graphit vo khong 0,334 nm. Do c
im cu trc c s lin kt lng lo gia cc tm (lp) trong graphit nn cc lp
graphit d trt ln nhau, ngc li do lin kt gia cc nguyn t cacbon trong
cng mt n lp rt mnh nn mt graphit rt bn vng v mt c hc. Do vy n
thng c dng trong cng nghip vi vai tr l cht bi trn dng rn, chi
than,... Cng v c im ny nn graphit thng d v, d tch lp [18].
1.1.2. Vt liu cacbon cu trc nano
1.1.2.1. Fullerene
Fullerene (C60) l mt dng th hnh ca cacbon vi cu trc tinh th 0 chiu

(0D), thng c dng hnh
cu, (cn c gi l
buckyball) v c ch to
u tin vo nm 1985 bi
Kroto v cng s [3], sau
nhm nghin cu ny
t gii Nobel ha hc nm
1996. Cu trc ca
fullerene c xem nh to
thnh t vic qun li ca
mt lp n trong cu trc Hnh 1.2. Graphen cu trc c bn (2D) v
ca graphit (Hnh 1.2) cc vt liu cacbon khc (0D, 1D v 3D)[19]
(c gi l graphen trong cc phn trnh by sau), v khi qun li nh vy th mt
5
s lin kt sp2 trong graphit s bin i thnh lin kt sp3 trong kim cng, iu ny
lm cho cc nguyn t trong fullerene tr nn n nh hn [20]. Trong vi thp nin
qua, fullerene c ng dng trong nhiu lnh vc nh: dng lm lp bc bn
ngoi ca o gip, thuc khng sinh khng khun v c bit l ph hy mt s
t bo ung th nh U melanin, ngoi ra n cng c dng ch to cc cht
khng vi sinh vt nhy sng [1].
1.1.2.2. ng nano cacbon (Cacbon Nanotube CNTs)
CNTs l mt dng th hnh ca cacbon vi cu trc tinh th 1 chiu (1D) (hnh

1.1), c ch to u tin vo nm 1991 bi Lijima v cc cng s [3]. Cu trc
ca n xem nh mt tm graphen c cun trn li thnh hnh tr vi ng knh
c nanomet. CNTs c nhng c im u vit v tnh cht vt l, ha hc v in t
nn chng c nghin cu ng dng trong nhiu lnh vc khoa hc k thut khc
nhau nh x l nc thi, kh thi, cng ngh sinh hc, nng lng ti to, siu t
in v nano composit thn thin vi mi trng. Cc ng nano cacbon c chia
lm 2 loi chnh: n vch (SWCNTs) v a vch (MWCNTs). Tnh cht ca chng
c thng k bi Xie cng cc cng s nm 2005 [21] nh Bng 1.1.
Bang 1.1. Tnh cht ca SWCNTs v MWCNTs
Tnh cht SWCNTs MWCNTs
3
Khi lng ring (g/cm ) 0,8 1,8
M un n hi (TPa) ~1 ~ 0,3 - 1
bn (GPa) 50 500 10 60
in tr sut (cm) 5 50 5 50
dn in (W m-1 K-1) 3000 3000
Tnh n nh nhit, C >700 >700
(trong khng kh)
Din tch b mt (m2/g) ~ 400-900 ~ 200 - 400
Tm hot ng ca CNTs
CNTs vi s lng tm hot ng ln trn b mt v c th iu chnh kch
thc mao qun nn c kh nng hp ph c bit cao, hiu qu hn so vi than
hot tnh thng thng. CNTs hot ng ha hc mnh hn so vi graphen. Tuy
nhin, thc t cho thy CNTs vn tng i tr v mt ha hc, do tng hot
6
tnh ha hc ca CNTs ta phi to ra cc khuyt tt (defect) trn b mt ca ng,
gn kt vi cc phn t hot ng khc. Cc nghin cu c Li v Gao cng cng
s tng hp v a ra trong bi tng quan [3] ch ra rng, CNTs c ng knh cng
nh th hot ng ha hc cng mnh, song hin tng t m xy ra nhiu. l
do nh hng ca hiu ng kch thc v hiu ng b mt xy ra vi cc vt liu
nano. S t m ny lm gim kh nng hot ng ha hc ca cc ng CNTs. V
vy, vn quan trng l tch b CNTs thnh cc ng ring r bng cc phng
php l, ha ph hp. Nhiu nghin cu rng ri pht hin kh nng hp ph ca
CNTs ph thuc vo nhng nhm chc trn b mt v bn cht ca cht b hp ph.
i vi CNTs c b mt axit (cha cc nhm chc cacboxylic, lactonic v
phenolic) c li cho s hp ph cc hp cht c tnh phn cc [22]. Mt khc vi
CNTs c b mt khng cha nhm chc c chng minh c kh nng hp ph tt
hn vi cc cht a vng thm khng phn cc nh hydrocacbon [22]. Kh nng
hp ph ca CNTs ch yu lin quan n tng tc ha hc ca cc hp cht phn
cc v tng tc vt l ca cc hp cht khng phn cc. S hp ph ca c 2 cht
khng phn cc v phn cc gn vi ng nhit hp ph Langmuir v Freundlich
[22]. Mc d CNTs c gi thnh cao hn so vi than hot tnh nhng s hp ph v
gii hp ca chng tt hn than hot tnh thng thng [1].
Cac phng phap tng hp CNTs
Hin nay, bn phng php chnh v ang c nghin cu s dng tng
hp CNTs bao gm: Phng php h quang (Arc Electrique), phng php ct gt
Laser (Ablation Laser), phng php nghin bi v nhit, phng php lng ng
pha hi ha hc (CVD), trong phng php CVD c nhiu u im hn c [3].
Mt th thch rt ln i vi vic sn xut CNTs l cc nh khoa hc vn
cha th cun trn ng nano theo cch h mun. Ngoi ra chi ph cho vic sn xut
CNTs cn rt cao [3].
1.1.2.3. Vt liu Graphen
Graphen l mt mt phng n lp ca nhng nguyn t cacbon c sp xp

cht ch trong mng tinh th hnh t ong 2 chiu (2D). Graphen c cun li s to
nn dng th hnh fullerene 0D, c qun li s to nn dng th hnh cacbon
nanotube 1D, hoc c xp chng ln nhau s to nn dng th hnh graphit 3D
7
(Hnh 1.2) [19]. Nt in hnh ca cu trc l sp xp cc nguyn t cacbon trn
nh cc lc gic u, nm cch nhau nhng
khong nht nh l 1,42 v lin kt vi
nhau bi nhng lin kt sp2.
Graphen c hai nh khoa hc ngi Anh
gc Nga l Andre Geim v Konstantin
Novoselov (i hc Manchester, Anh) khm
ph ra vo nm 2004, nm 2010 gii Nobel Vt
l c trao cho hai nh khoa hc ny. Di Hnh 1.3. Graphen hin hu vi mt
knh hin vi h quan st c nhng mng li lm ca khng gian 3 chiu
graphen l lng trong trng thi t do khng phng m li lm nh mt sng vi m

trong khng gian 3 chiu (Hnh 1.3). Tnh cht vt l ca n lp graphen nhit
phng c Rajasekhar Balasubramanian [23] thng k li Bng 1.2 nh sau:
Bang 1.2. Tnh cht vt l ca n lp graphen nhit phng [23]
Tnh cht Gi tr
Chiu di lin kt C-C 0,142 nm
Mt 0,77 mg.m-2
Din tch b mt l thuyt 2630 m2 g-1
M un n hi 1100 GPA
cng 125 GPA
linh ng ca ht ti in 200 000 cm2 V-1 s-1
dn nhit 5000 W m-1 K-1
truyn quang 97,7%
Chnh nh nhng c im u vit trn m graphen ang l mi quan tm

hng u ca nhng nh nghin cu trong mi lnh vc. Hnh 1.4 ch ra s lng
bi bo nghin cu v graphen trong mi nm qua. T Hnh 1.4 cho thy cc vt
liu cu trc nano trn c s cacbon nh fullerene, CNTs v graphen ang rt c
quan tm, nm 2005 s lng cng trnh cng b lin quan n ba vt liu trn ch
t khong 5000 cng trnh, n nm 2014 tng ln 30000 cng trnh gp 6 ln
so vi nm 2005. Trong xu hng nghin cu v graphen tng mnh t khi
gii Nobel v graphen c cng b nm 2010.
8
Hnh 1.4. S lng cc cng trnh cng b v graphen trong 10 nm gn y
(tng hp t cc cng trnh ng trn cc tp ch lin quan n khoa hc) [3]
S lng cc cng trnh cng b v graphen tng gp 8 ln trong vng 5 nm
qua, nm 2010 ch vi 2000 cng trnh cng b trong khi nm 2014 ln n
16000 cng b cho thy graphen ang l mi quan tm hng u trong cc vt liu
cacbon. Cc nc tp trung nghin cu v fullerene v CNTs nhiu nht l Trung
Quc, M v Nht, trong khi Hn Quc, M v Trung Quc li tp trung nhiu
v nghin cu graphen. Hnh 1.5 m t s phn b ca cc cng trnh cng b lin
quan n ba vt liu: Fullerene, CNTs v graphen.
Hnh 1.5. S phn b ca cc cng trnh cng b lin quan n ba vt liu

fullerene, CNTs v graphen trn th gii [3]
Trn th gii, trong s cc cng trnh cng b lin quan n cc lnh vc ng
dng vt liu trn graphen, trong nm 2014 c 16000 cng trnh cng b v
khong 4000 sng ch lin quan n vt liu graphen [24]. Cc sng ch v graphen
c phn b nhiu quc gia v tp trung ch yu t cc nh khoa hc ca Sam
Sung (700), Vin Hn lm Khoa hc Trung Quc (400), IBM M (300) [24].
9
Mc d vy, cc sng ch ny tp trung ch yu vo lnh vc in t v cng ngh
vt liu mi, i vi lnh vc hp ph cn rt hn ch. Do tim nng nghin cu
ng dng vt liu graphen v vt liu trn c s graphen ng dng trong lnh vc
hp ph cn mi v tnh ng dng cao.
1.2. Vt liu graphen va graphen oxit
1.2.1. Cu trc ca graphen [18]

V mt cu trc, mng graphen c to thnh t cc nguyn t cacbon sp
xp theo cu trc lc gic trn cng mt mt phng, hay cn c gi l cu trc t
ong. Do ch c 6 in t to thnh lp
v ca nguyn t cacbon nn ch c
bn in t phn b trng thi 2s v
2p ng vai tr quan trng trong vic
lin kt ha hc gia cc nguyn t
vi nhau. Cc trng thi 2s v 2p ca
nguyn t cacbon lai ha vi nhau to Hnh 1.6. Cc lin kt ca nguyn t
cacbon trong mng graphen
thnh 3 trng thi sp, cc trng thi
ny nh hng theo ba phng to vi nhau mt gc 120o. Mi trng thi sp ca
nguyn t cacbon ny xen ph vi mt trng thi sp ca nguyn t cacbon khc
hnh thnh nn lin kt cng ha tr sigma () bn vng. Chnh cc lin kt ny
quy nh cu trc mng tinh th graphen hnh dng t ong v l gii ti sao
graphen rt bn vng v mt c hc v tr v mt ha hc trong mt phng mng.
Ngoi cc lin kt sigma, gia hai nguyn t cacbon ln cn cn tn ti mt lin kt
pi () khc km bn vng hn hnh thnh do s xen ph ca cc orbitan pz khng b
lai ha vi cc orbitan s. Do lin kt ny yu v c nh hng khng gian vung
gc vi cc orbitan sp nn cc in t tham gia lin kt ny rt linh ng v quy
nh tnh cht in v quang ca graphen. Hnh 1.6 m hnh ha cc lin kt ca
mt nguyn t cacbon trong mng graphen.
1.2.2. Cu trc graphen oxit (GO)

Mc d GO c nghin cu trong hn mt th k, cc cu trc ha hc
chnh xc ca GO vn cn cha r rng. Bn cht ca cc nhm chc oxy v cch
10
gn kt trn mng li cacbon l rt quan trng c c mt cu trc GO chnh
xc [25]. Cu trc ca GO ph thuc nhiu vo phng php tng hp v c a
ra bi nhiu nh nghin cu khc nhau th hin trong Hnh 1.7.
Hnh 1.7. Cu trc xut ca GO bi cc nh nghin cu khc nhau [26]
Nhng trong m hnh ca Lerf Klinowski ph bin hn c [26]. Theo ,

graphit sau khi oxi ha, trn mt phng nm ngang ca cc lp c cc nhm
hydroxyl, epoxy v trn cc gc ca mt
phng nm ngang c th hnh thnh cc
nhm chc carbonyl hoc carboxylic.
Gn y (2013) nhm tc gi Ayrat

M v cng s [27] xut mt m
hnh GO mi, tn gi l DSM (Dynamic
Structural Model). Ngc li vi tt c
cc m hnh xut trc y, nhm tc
gi khng xem xt cc GO nh mt cu Hnh 1.8. Lin kt hydro gia cc
lp graphit oxit [26]
trc tnh vi mt tp hp cc nhm chc.
Thay vo , h cho rng cc nhm chc mi lin tc pht trin v bin i. Vai tr
quan trng trong tt c nhng bin i thuc v nc kt hp vo GO chuyn i
c cu ca n, v sau ri khi cu trc thng qua cc phn ng khc nhau. ng
lc ca s bin i l tch t ca in tch m trn lp GO, c n nh bng s
cng hng v hnh thnh ca mt lp in tch kp.
11
Cc vng thm, cc ni i, cc nhm epoxy c cho l nm trn mng li
cacbon gn nh phng, trong khi cacbon ni vi nhm OH hi lch so vi cu trc
t din dn n cu trc lp hi cong. Cc nhm chc c cho l nm c trn ln
di cc lp GO. V mi lp u cha cc nhm chc c oxi mang in tnh m, do
c lc y xut hin gia cc lp, ng thi lm cho GO th hin tnh a nc
v trng c trong nc. Hn na, vic to lin kt hydro gia cc lp graphit
oxit thng qua cc nhm hydroxyl, epoxi v nc khin cc khong cch gia cc
tm GO c ni rng ng k hn so vi graphit (0,65 - 0,75 nm so vi 0,34 nm,
c xc nh thng qua gin XRD) [25].
dy ca n lp tm GO c bo co xp x 1- 2 nm [26], xp x 4 ln
dy ca mt lp graphen 0,34 nm [3]. im ng in pHpzc = 3,9, in tch b
mt GO trong nc mang in tch m v GO l cht a nc k du [5].
1.2.3. Tm hot ng ca graphen v graphen oxit

Cc hp cht hu c c th c hp ph trn cc ht nano hay vt liu cu
trc nano thng qua nhng tng tc sau: tng tc in t, lin kt hydro, s xp
chng lin kt - , lc phn tn, lin kt cho - nhn v hiu ng k nc [10].
Trong trng hp ca graphen, h thng in t bt i xng ng vai tr ch o
trong vic hnh thnh mnh m ca lin kt tng tc - ca s chng xp vi mt
s cht hu c c cha vng thm. Tng tc cation - cng ng gp vo qu
trnh hp ph [10]. Tng tc ny b chi phi bi s phn cc cation, lc tnh in
gia cc cation v cu trc in t aromatic giu electron [28].
GO mang nhiu nhm chc phong ph do vy hnh thnh t cc lin kt hydro

hay s tng tc in t vi cc hp cht hu c c cha oxi v nit. Cc nhm
chc cha oxy phn cc ca GO lm cho vt liu ny c xu hng a nc. GO
phn tn tt trong nc v c th b tch lp trong nhiu loi dung mi [26]. S
hin din ca cc nhm chc hot ng nh cacbonyl, epoxy, hydroxyl trn b mt
ca GO cho php n tng tc vi rt nhiu cc phn t tri di trn b mt bin
tnh. Hn na, nhng nhm hot ng ny ca GO cng c th lin kt vi cc ion
kim loi nng c mt trong dung dch thng qua phc b mt, hoc tng tc tnh
in gia b mt m GO v cc cation kim loi, cht mu do n cng c th s
dng tch cc ion t dung dch [10].
12
Qu trnh hp ph cc ion kim loi v hp cht hu c trn graphen v GO
thng ph thuc nhiu vo pH v bn cht ca cc cht hu c (s vng thm
trong cu trc) [27, 29]. Khi gi tr pH thp c li cho vic ion ha ca cc nhm
chc cha oxi trn b mt GO. Do in t trn b mt GO l m nn s tng tc
tnh in gia cc ion kim loi v GO tr nn mnh hn. Khi gi tr pH cao, cc
hydroxit kim loi c th hnh thnh kt ta hay nhm anion s chim u th v vy
xy ra hiu ng y gia anion v b mt GO. Do , cn tm ra gi tr pH ti u
nng cao hiu qu ca qu trnh hp ph.
1.2.4. Cac phng phap tng hp GO
Graphit oxit l sn phm ca qu trnh trnh oxy ha graphit. Nghin cu u tin

v graphit oxit c thc hin cch y hn 150 nm [30], cho thy c th sn xut vt
liu ny trn c s graphit vi gi thnh tng i thp. Vo nm 2004, khi xut hin
graphen th vt liu ny bt u c gi l GO. Theo quan im ha hc th dng
nh khng c nhiu s phn bit gia hai khi nim ny, tuy nhin, hiu chnh xc hn
th GO chnh l mt n lp ca graphit oxit (cng tng t nh graphen l n lp
ca graphit). GO vi tnh cht c bn ging nh graphen nn c nhiu nhm
nghin cu lm cht hp ph loi b cc cht nhim trong nc.
GO c tng hp bng ba phng php chnh l Brodie (1859) [30],

Staudenmaier (1899) [31] v Hummers
v Offeman (1958) [32]. Trong
phng php Brodie v Staudenmaier
s dng kt hp c KClO3 v HNO3
oxy ha graphit. Trong khi , phng
php Hummers s dng cch x l
graphit vi KMnO4 v H2SO4 (Hnh
1.9). Vi phng php Brodie bng
cch s dng phng php phn tch
nguyn t, phn t ca sn phm cui
Hnh 1.9. Cc phng php tng hp GO
c cng thc C11H4O5. Sn phm ny c
tnh axit nh v c kh nng phn tn trong mi trng kim, song li c cu trc
13
khng hon ho. Vi phng php Staudenmaier c s thay i so vi phng
php Brodie khi s dng tc nhn oxy ha KClO3 tng mc oxy ha ca GO.
Tuy nhin phng php ny rt nguy him v KClO3 l cht d gy kch n v sn
phm kh ClO2 c to thnh c nguy c chy n cao.
Phng php Hummers s dng hn hp H2SO4, NaNO3 v KMnO4 gip cho

sn phm GO c mc oxy ha cao hn cc sn phm c tng hp bng cc
phng php trc [32]. Mc d KMnO4 l mt cht oxy ha c s dng,
nhng thc t th tc nhn Mn2O7 mi l tc nhn chnh tham gia qu trnh oxy ha
graphit thnh GO theo phn ng sau [26]:
KMnO4 + 3H2SO4 K+ + MnO3+ + H3O+ + 3HSO4-
MnO3+ + MnO4- Mn2O7
Mn2O7 l cht oxy ha hot ng, tuy nhin Mn2O7 b kch n khi un nng
n nhit trn 55 oC hoc khi tip xc vi hp cht hu c. Do , vic kim sot
nhit trong phn ng l rt quan trng, c bit l quy m cng nghip [26].
Trong ba phng php trn th phng php Hummers l phng php ph

bin hn c. Trong nhng nm qua phng php Hummers c ci tin nhiu
nhm loi b vic s dng NaNO3 do ngn nga to ra kh c hi trong qu
trnh tng hp [26], cc phng php ny c gi l phng php Hummers bin
tnh (Modified Hummers).
C ch hnh thnh GO c xc nh bi ba bc ring bit c lp a

ra Hnh 1.10. Bc 1: Graphit tip xc vi axit H2SO4 th axit ny an xen vo
cc lp ca graphit hnh thnh nn hp cht trung gian th nht (gi l GIC). Bc
2: GIC tc dng vi cht oxi ha KMnO4 to thnh hp cht trung gian th 2 (gi l
PGO). Bc 3: PGO tc dng vi H2O to thnh GO [8]. Hnh 1.10 cho thy s
hnh thnh ca hai sn phm trung gian (GIC v PGO) cng vi sn phm GO. Cc
ng mu en lin i din cho lp graphen; ng mu en chm i din cho
lp duy nht ca GO; ng mu xanh rng i din cho H2SO4/HSO4- xen k;
ng mu tm rng i din cho lp hn hp H2SO4/HSO4- xen k vi dng thu
gn ca tc nhn oxi ha.
14
Cc sn phm oxy ha vi t l C:O trong khong t 2,1 n 2,9. GO cha cc
nhm chc c cha oxi, trong c 4 nhm chc ch yu l: Hydroxyl (OH),
epoxy (-O-) nh trn b mt, v cacboxyl (-COOH), cacbonyl (-CO-) nh mp
ca cc n lp, nhng GO vn gi nguyn dng cu trc lp ban u ca graphit
[32]. Ph thuc vo phng php tin hnh oxi ha m t l cng nh s lng
nhm chc c khc nhau, v d Graphit oxit c tng hp bng phng php
Hummers c nhiu nhm epoxy hn nhm hydroxyl [25].
Hnh 1.10. C ch hnh thnh GO t graphit [8]
Tch lp graphit oxit bi k thut vi sng [33] hoc k thut siu m trong cc
dung mi thch hp [8, 26] th thu c GO.
1.2.5. Cac phng phap tng hp graphen
1.2.5.1. Graphen (rGO) tng hp t graphit oxit
S chuyn ha graphit thnh rGO c th hin Hnh 1.11.
Qu trnh kh cc nhm chc cha oxy trn b mt GO s chuyn cc C-sp3

C-sp2, sn phm ca phn ng kh ny c a ra bng mt lot cc tn, v nh:
Graphen oxit b kh, graphen oxit b kh v mt ha hc hay rGO.
15
Vi sng
Hnh 1.11. S chuyn ha t graphit thnh rGO [34]
Cc phng php kh GO v rGO c nghin cu rng ri trong thp k

qua [6, 8]. Qu trnh kh ha hc GO c thc hin vi cc tc nhn kh nh:
hydrazin monohydrat (N2H4.H2O), natri Bohidrua (NaBH4), dimethyl hydrazin, axit
hydriodic (HI), kh hidro nhit cao, ancol, [8]. Mi tc nhn kh c hot tnh
vi mt nhm chc nht nh v hiu qu kh ca cc tc nhn l khc nhau, v d
vi Na-NH3 kh trong 30 pht thu c rGO c t l C:O ~ 16,61:1 [35], trong khi
vi hydrazin c hot tnh kh mnh vi nhm epoxy v cacboxylic trong iu
kin kh 80 100 oC, t l C: O ~ 10,3 : 1 [8], c ch kh ca hydrazin c minh
ha bi Hnh 1.12.
Hnh 1.12. C ch kh nhm epoxy ca hydrazin [26]
Theo Hnh 1.12 cho thy hydrazin d dng phn ng vi cc nhm chc
epoxy trn b mt mng ca GO hnh thnh nn hydrazin alcohol, cc nhm ny
khng bn s chuyn ha nhanh thnh aminoaziridine, sau cc nhm
aminoaziridine ny c loi b nhit khong 80 - 100 oC hnh thnh nn
lin kt i, khi phc li mng li ca rGO ti v tr .
Tc nhn kh NaBH4 cho thy hiu qu hn so vi hydrazin, n hiu qu cao

vi nhm C=O, hiu qu thp vi nhm epoxy v cacboxylic, nhit kh khong
80 oC, t l C:O ~ 13,4 : 1 cao hn so vi hydrazin C:O ~ 6,2 : 1 [26]. Axit HI c
s dng nh mt cht kh mnh trong mi trng axit [8], ion I- c hot tnh mnh
vi nhm epoxy v hydroxyl trn GO, y l hai nhm chc chim t l ln trong
16
GO, s dng khong 55% axit HI kh GO v rGO cho hiu qu cao, phn tch ph
XPS cho t l C:O ~ 12,0 : 1. Trong nc, nhm tc gi H Thc Huy i hc
Quc gia Thnh ph H Ch Minh kh GO bng tc nhn kh NaBH4, N2H4 v
HI + CH3COOH kt qu thu c chng minh hiu sut kh tt nht vi tc
nhn kh l HI + CH3COOH ri n NaBH4 v cui cng l N2H4 (thng qua nh
gi dn in) [11].
Tuy nhin, cc phng php kh ha hc trn cho thy mt s nhc im nh:

to ra cht thi c hi v c hi cho mi trng (hi hydrazin l cht rt c). Do ,
vic tm ra cc cht kh hiu qu cao v thn thin mi trng l cn thit thay th
cc phng php kh GO truyn thng. Gn y tc nhn kh thn thin mi trng,
chng hn nh vitamin C, bt nhm, kh ng, axit amin, Na2CO3, c
nghin cu s dng kh GO v rGO [36]. trong nc, nhm tc gi V Th Thu
H - Vin Ha hc cng nghip tng hp GO bng phng php Hummers ri kh
GO v rGO bng tc nhn kh xanh caffeine, rGO thu c khong 6 lp [14].
Ngoi phng php s dng cc cht ha hc kh cc nhm chc cha oxi

trn GO cn c phng php kh nhit.
* S kh nhit
Kh ha hc l phng php ph bin nht kh GO, thay v s dng mt

cht kh ha hc loi cc nhm chc cha oxi t b mt y s dng nhit
kh grapht oxit hoc GO trong l nung (mi trng chn khng cao hoc trong mi
trng kh Ar, H2, N2,). Bn cnh qu trnh kh cn c qu trnh bc lp, qu trnh
bc lp xy ra l v cc kh CO, CO2, hi H2O v cc phn t hydro nh c to ra
bng cch nung nng graphit oxit, GO ln nhit cao, to ra p lc rt ln trong cc
lp xp chng ln nhau (40 MPa ti nhit 300 oC, 130 MPa khi nhit t 1000
o
C) khi p sut ln s tch cc lp GO ra xa [26]. nh gi ca hng s Hamaker
d on rng p sut ch 2,5 MPa l cn thit tch hai tm GO xp chng ln nhau
[26]. Ngoi ra, CO cng ng vai tr l cc tc nhn kh i cc nhm chc trn b
mt GO [37].
Mt vi lp rGO thu c bng vic kh nhit GO trong mi trng nit

trong khong nhit t 200-1000 oC [38]. rGO c tng hp 800 oC (6 lp) c
17
mt cht lng cao hn so vi nhit khc, rGO ny c din tch b mt ring
ln (560,6 m2/g) v cu trc nano-xp. Loi b oxy trong qu trnh kh GO cng
ph thuc vo mi trng kh s dng (chn khng, Ar, N2 hoc H2), tc gia
nhit v ng hc nh trnh by trong ti liu [38]. C ch ca qu trnh kh
nhit c ch ra Hnh 1.13.
Hnh 1.13. S m t c ch kh nhit cho GO ch ra s phn hy ca cc dng

xy qua s khi mo phn gc vi: (I) s hnh thnh cc gc thng qua cc phn
ng t chy (hnh thnh cc gc hydroxyl, hydro, v hydroperoxy (HO2), (II) S
lan truyn thng qua phn ng kh carboxyl hoc tn cng vo cc nhm hydroxyl
cng nh m cc vng epoxy, (III) chm dt vo cc gc benzyl/phenyl vi sn
phm CO/CO2 [38]
18
1.2.5.2. Graphen tng hp bng phng php ha hc t
*Bc tch lp trong pha lng (Liquid-phase exfoliation - LPE)
Bc tch lp trong pha lng (LPE) thng lin quan n s phn tn ca

graphit trong mt dung mi. Qui trnh ny da trn qu trnh sonvat ha, ngha l
to ra s n nh enthalpy ca nhng mng graphen phn tn bi s hp ph dung
mi [8]. S biu din phng php LPE cho Hnh 1.14.
Hnh 1.14. S biu din phng php LPE [8]

Phng php ny c th hin qua ba giai on: phn tn graphit trong dung
mi, bc lp graphit thnh graphen v cui cng l lm sch sn phm graphen [8].
Vic bc cc lp graphit thnh cng i hi phi thng c lc lin kt Van der
Waals gia cc lp lin k. Mt trong nhng phng php hiu qu nht v n
gin lm gim lc lin kt Van der Waals l cho graphit vo mt mi trng
lng, trong mi trng lng din tch b mt ca cc phn t s gim i dn n s
suy gim ca lc phn tn London v dn n s yu i ca lc lin kt Van der
Waals. Nng lng b mt ca graphen c c tnh l 46,7 mJ/m2 [8]. V vy,
cc dung mi vi mt sc cng b mt nm trong khong ~40 mJ/m2, chng hn
nh N-methylpyrrolidone (40 mJ/m2), N, N'-dimetylformamide (DMF) (37,1
mJ/m2) v -butyrolactone (35,4 mJ/m2) l cc dung mi tt nht cho bc lp
graphit [8]. Trong cng b ca nhm tc gi Paolo Samor [39] bng vic s dng
19
mt lot cc dung mi t dn xut benzene, toluene, nitrobenzene v pyridine vi
nng khc nhau 0,05 - 0,1 mg/mL bc tch thnh cng graphen t graphit
(Hnh 1.15). Kt qu thu c rt kh quan, tuy nhin hiu sut li rt thp (1-2%),
hiu sut cao nht (2%) khi tc gi s dng dung mi pentafluorobenzonitrile vi
nng 0,1 mg/mL.
Hnh 1.15. Tng hp graphen t graphit bng phng php LPE s dng cc
dung mi khc nhau [39]
Cch ny c u im l c tin hnh n gin, graphen LPE c cht lng
cao v c kh nng m rng sn xut [8, 35]. Tuy nhin vn cn mt s hn ch
nh: Nng sut thp, tm c kch thc nh (< 5 m), phn tn hn ch, tnh c
hi ca cc dung mi s dng nh hng nhiu n mi trng, gi thnh ca dung
mi cao v vic loi b nhng lng dung mi d tha trong sn phm l khng
hon ton.
* Bc lp in ha graphit
Ni chung, phng php in ha s dng mt cht in phn lng dn in
v dng in mt chiu lm dn n cu trc graphit. C hai loi bc lp in ha
l:
in phn s dng dung mi khng cha nc
Trong cng trnh Wang v cng s [40] vi lp graphen c phn lp
thnh cng qua an xen in ha ion liti (Li) trong mt cht in phn propylene
carbonate (PC) bng cch p dng mt in th m cao (-15 V) kt hp siu m ko
di trong dung mi DMF. Kt qu, hn 70% cc tm graphen thu c c dy t
hn nm lp. Tuy nhin, hn 80% graphen li c kch thc nh hn 2 m do thi
20
gian siu m di. ci tin cht lng graphen tc gi Zhong s dng mt qu
trnh tng hp hai giai on, giai on 1 gin n cc lp graphit ban u bng dung
mi propylen carbonat cha LiClO4, giai on th 2 l bc lp graphit trong cht
in phn tetra-n-butylammonium (TBA) vi in th l -5 V c p dng cho
c hai giai on (Hnh 1.16). Cui cng l siu m nh (khong 15 pht) c thc
hin thu c cc lp graphen.
Hnh 1.16. S v hnh nh ca s gin n ca in cc graphit s dng qu

trnh hai giai on. Trong giai on u, cc in cc than ch gin n do s an
xen ca cc ion liti. Giai on th 2 l gin n bi cc ion tetra-n-butylammonium
tip tc xen vo graphit [8]
in phn s dng dung mi cha nc:
Trong phng php ny, cc in cc than ch thng hot ng nh mt cc

dng; nc cung cp khng ch nh l mt dung mi m cn c th to thnh lin
kt C-O pha ra ngoi graphit giai on ban u. Sau , cc anion m c
xen vo v bt u vic gin n v bc lp. Mt in p dng tng i cao (10
V) c s dng cho cc in cc graphit trong axit sulfuric long, s bc lp
ca graphit c thc hin bng s gii phng mnh m cc kh thng qua vic kh
in ha ca cc ion sunfat (SO42-) [8]. Trong mt th nghim in hnh, mt dy
bch kim c s dng nh mt in cc i, graphit c s dng nh mt in
cc lm vic, v dung dch H2SO4 c s dng nh mt dung dch in phn
(Hnh 1.17). Cc c ch cho qu trnh bc lp in ha graphit c th hin nh
sau: (i) qu trnh in phn nc ti in cc to ra hydroxyl v gc oxi t do; (ii)
cc gc t do xy ha cnh v/hoc trong cc ranh gii ht ca than ch; (iii) qu
trnh oxy ha mp v ranh gii ht dn n s kh phn cc v s m rng ca
21
cc lp graphit, to iu kin cho cc anion SO42- theo cng vi nc an xen vo
bn trong cc lp graphit; v (iv) s kh cc anion SO42- xen vo gia v s t oxy
ha nc to ra cc loi kh nh SO2 v O2, chng tc dng mt lc ln trn lp
graphit do lm yu lin kt gia cc lp graphit vi nhau (Hnh 1.17e). Bng cch
thay i nng ca H2SO4 v/hoc in th, nhm tc gi Khaled Parvez [8] t
c hiu sut bc lp graphit (vi dy ca tm bc l nh hn 2 nm) ~60% khi
lng vi nng ln ti 1 mg/ml trong dung mi DMF (Hnh 1.17d). Vi nng
H2SO4 0,1 M thu c 80% graphen vi s lp t 1-3 lp, t l C/O l 12,3.
Hnh 1.17. (a) Gin minh ha bc lp in ha graphit, (b) hnh nh ca

mnh graphit trc v sau khi bc lp, (c) graphen bc lp ni trn dung dch in
phn, (d) c phn tn nhng tm graphen (nng 1 mg/ml) trong DMF v (e)
s minh ha c ch ca vic bc lp in ha graphit thnh rGO [8].
Bc lp in ha c u im: Hiu sut cao, sn xut nhanh, hiu qu chi ph,

tnh gia cng cao v mi trng lnh tnh. Nhc im: S oxy ha thp, dy
tm khng ng nht.
22
1.2.5.3. Graphen tng hp t phng php vt l
Graphen c tng hp bng phng php vt l trong cu trc s khng c

nhm chc oxy, loi graphen ny c gi l graphen nguyn bn (pristine
graphen), k hiu: GP.
a, Bc lp c hc
Bc lp c hc, l k thut u tin c s dng tng hp graphen

Phng php ny s dng cc lc c hc tc ng t bn ngoi tch vt liu
graphit dng khi ban u thnh cc lp graphen. Vi nng lng tng tc Van
der Waals gia cc lp khong 2 eV/nm2, lc cn thit tch lp graphit l khong
300 nN/m2 [41] y l lc kh yu v d dng t c bng cch c xt mt mu
graphit trn b mt ca SiO2 hoc Si, hoc dng bng keo dnh.
Nm 2004, Geim v Novoselov tm ra cch ch to graphen thng qua dn

nhng mnh vn graphit trn mt ming bng keo, gp dnh n li, ri ko git ra,
tch ming graphit lm i. H c lm nh vy nhiu ln cho n khi ming graphit
tr nn tht mng, sau dn ming bng keo ln silicon xp v ma st n, khi
c vi mnh graphit dnh trn ming silicon xp, v nhng mnh c th c b
dy l 1 nguyn t, chnh l GP (Hnh 1.18).
Hnh 1.18. Phng php tch lp graphit bng bng dnh

u im: D thc hin v khng cn nhng thit b c bit, chi ph thp.
Khuyt im: Phng php i hi tnh t m, kt qu ca phng php khng
nht nh m ch mang tch cht cu may, khng ph hp cho vic ch to GP vi
s lng ln ng dng cho sn xut cng nghip.
b, Phng php epitaxy v CVD [7]
23
* Phng phap epitaxy thng c tin hnh vi silic cacbua (SiC)
1300 oC trong mi trng chn khng cao hoc 1650 oC trong mi trng kh
Argon, do s thng hoa ca Si xy ra 1150 oC trong mi trng chn khng v
1500 oC trong mi trng kh Argon. Khi c nng nhit n nhit cao cc
nguyn t Si s thng hoa, cc nguyn t cacbon cn li trn b mt s c sp
xp v lin kt li trong qu trnh graphit ha nhit cao, nu vic kim sot qu
trnh thng hoa ca Si ph hp th s hnh thnh nn mng graphen rt mng ph
ton b b mt ca SiC (Hnh 1.19). Phng php ny to nn cc mng
graphen n lp vi linh ng ca ht ti ln n 2000 cm2/Vs 27 K, mt
ht ti tng ng l ~1013 cm-2 [41].
Hnh 1.19. C ch to mng graphen bng phng php nung nhit SiC
*Phng phap CVD: Phng php CVD dng l nhit cao ging nh
phng php tng hp ng than nano. Niken (Ni), platin (Pt), coban (Co), ng
(Cu) l cc cht nn (substrate) ph bin, cc cht nn c un nng nhit
khong 1000 C v ngun cacbon (thng dng nht l kh mtan (CH4)) c thi
qua cht nn, graphen s c hnh thnh trn b mt cht nn [7]. Sau c
kh i l ra mng graphen t do. Trong phng php CVD th cht nn c s
dng nhiu nht l Cu [7, 9]. Trong nc c nhm tc gi Nguyn Vn Chc - Vin
Khoa hc Vt liu - Vin Hn lm Khoa hc v Cng ngh Vit Nam tng hp
graphen bng phng php CVD, cc mng graphen vi chiu dy 4 nm c
tng hp trn l Cu [12]. dy ca mng graphen v chiu rng ca di graphen
c kim sot chnh xc bng cch iu chnh nhit , thi gian tip xc ca
cc cht kh v la chn cc cht nn lng ng.
24
u im: u im ni bt ca nhng phng php ny l ch to c cc
mng graphen din tch ln (~1 cm2) v c ng u cao hn so vi cc phng
php khc. T cc mng graphen cht lng tt ny c th pha tp hoc chc ha
b mt.
Khuyt im: Kh nng kim sot hnh thi hc v nng lng bm dnh
iu kin nhit cao vn l th thch ca phng php ny. Tn s plasma
(plasma-enhanced CVD), s nhit phn ca kh v s ng u ca mng l cc yu
t rt kh kim sot. Bn cnh , phng php ny cn c nhng thit b v
cht lng cao, do sn phm to thnh s c gi thnh cao v ch c th p ng
cho mt s ng dng tiu biu, khng thch hp cho vic sn xut vi s lng ln
phc v cho nhng ng dng cng nghip.
1.2.5.4. So snh GO, graphen tng hp t cc phng php khc nhau
Trong phng php tng hp graphen (rGO) i t GO, mc d qu trnh kh

GO v rGO c th kh phn ln nhm chc cha oxy trn b mt, tuy nhin lm
tng t l C/O = 2:1 ln n C/O = 246:1 (Bng 1.3) ang l mt thch thc khng
nh [42]. Quan trng hn l qu trnh kh GO s dng tc nhn ha hc, tc
nhn nhit to thnh rGO c th lm thay i cu trc ca cacbon [42] v lm rGO
tng hp c c nhng khuyt tt trong n. S thay i v mt cu trc cho thy
s khc nhau gia rGO kh bng tc nhn ha hc cng khc so vi graphen
nguyn bn. Cu trc ca graphen nguyn bn (GP), GO v rGO c th hin trn
Hnh 1.20.
Hnh 1.20. Cu trc ca GO, rGO v GP [42]
25
T Hnh 1.20 cho thy so vi GP th rGO c cu trc gn ging nhau, tuy nhin
trn b mt vn tn ti s t cc nhm cha oxy v c bit l n c nhng khuyt tt
so vi GP. Mt s tnh cht ca GP, GO v rGO c th hin trn Bng 1.3.
Bang 1.3. Mt s tnh cht c bn ca cc vt liu GP, GO v rGO [42]
Tng hp GP bng cc Tng hp GO Tng hp rGO
Tnh cht vt liu phng php: CVD, bng phng bng phng
sau tng hp Epitaxy trn SiC v php: Oxy ha bc php: Kh GO
tch lp graphit tch lp graphit v rGO
C:O Khng c oxy 2-4 8 - 246
dn in (S/m) 10000 - 50000 Cch in 0,05 - 200
Cht lng Cao Thp Thp
M un bin dng 1 0,2 0,25
Mc d rGO tng hp t GO c cha khuyt tt v vn cn tn ti nhiu nhm

oxy. Tuy nhin, c th nhn thy u im ca phng php tng hp rGO i t GO
l: hiu sut cao, phn tn cao, c th gia cng cao, phng php c th m
rng a vo sn xut. Trong cu trc ca rGO tng hp theo phng php ha hc
thng c nhiu khuyt tt tuy vy nhng khuyt tt ny lm cho rGO d dng lin
kt vi cc ion kim loi hoc kim loi thng qua lin kt tnh in [42]. S kt hp
gia oxit kim loi, kim loi trn vt liu nn GO v rGO lm ci thin r tnh
cht trong cc ng dng nh: quang xc tc, y sinh, in t v trong lnh vc xc
tc - hp ph [6].
T nhng phn tch trn, trong lun n ny graphen (rGO) c tng hp bng
phng php ha hc oxy ha graphit thnh GO, sau s dng tc nhn nhit kh
GO v rGO.
1.2.6. Cac vt liu nano composit c t tnh trn c s GO, rGO

Ngoi cc vt liu nano composit trn c s rGO vi kim loi v oxit kim loi
nh: Ag, Au, Pt, TiO2, ZnO, SnO2, Cu2O, MnO2, NiO[6, 42, 43] th mt trong
nhng vt liu nano composit kim loi, a kim loi c t tnh trn nn rGO (M-
rGO), v GO (M-GO) cng ang c quan tm nghin cu do cc vt liu ny d
dng thu hi v ti sinh li sau phn ng nh s tr gip ca t trng bn ngoi do
t tnh ca loi vt liu ny [44]. Trong bi tng quan ca mnh Virender K. Sharma
26
[45] cho thy rt nhiu vt liu M-rGO v M-GO nh: Fe2O3/rGO, Fe3O4/rGO,
MnO2/Fe3O4/GO, Fe/GO c tng hp bng nhiu phng php khc nhau
nh ng kt ta, thy nhit, s chiu x vi sng Cc vt liu ny u cho thy
dung lng hp ph cao i vi cht mu v cc ion kim loi nng, v d nh
Fe3O4/GO c b mt 94 m2/g cho dung lng hp ph cc i Qmax = 73,3 mg/g i
vi cht mu MB [45], hoc Fe3O4/rGO vi din tch b mt 165 m2/g cho dung
lng hp ph cc i Cr(IV) t 160 mg/g, MnO2/Fe3O4/GO vi b mt ring 165
m2/g cho dung lng hp ph cc i Cr(IV) t 174,5 mg/g [45].
Trong cc vt liu nano composit c t tnh trn c s rGO th vt liu lai ca
rGO, GO vi vt liu nano t tnh Fe3O4, Fe-Fe3O4 ang c nghin cu nhiu v
ng dng rng ri cho vic loi b cc cht gy nhim trong nc [46]. Lin kt
ca ca M vi rGO v GO l do lin kt cng ha tr [46]. S kt hp gia hai vt
liu ny khc phc c mt s nhc im ca Fe3O4 v GO, rGO khi s dng
chng lm cht hp ph ring bit: Fe3O4, Fe kh s dng trong cc dng chy lin
tc do chng c kch thc ht nh, d b oxy ha v khng n nh d co cm [47].
GO, rGO c kh nng hp ph cao cho thuc nhum cation khc nhau. Tuy nhin
do s phn tn trong nc cao, phn tch n sau hp ph cn k thut ly tm tc
cao do vy hn ch ng dng thc t ca n [8].
S kt hp ca cc ht nano oxit kim
loi trn rGO v GO hn ch vic sp xp
v t hp ca chng, qua tng cng
din tch b mt ca composit [46]. S
tng trng ti ch ca cc ht nano oxit
kim loi trn tm rGO dn n gim s kt
t gia cc ht, lm tm nn cho cc ht
nano tng trng v gi chng li dng
phn tn. Ngoi ra, s hnh thnh composit
khng ch gip tng cng tui th ca ht
nano Fe3O4 m cn cho php thu hi d Hnh 1.21. nh dung dch fucsin (20
mg/L, bn phi) v dung dch sau khi
dng sau khi hon thnh hp ph. Sau khi c hp ph bi Fe O -rGO trong 1 h v
3 4
hp ph, cc composit Fe3O4- rGO c th c tch bi mt nam chm (tri) [46]
27
d dng tch ra khi dung dch qua s dng ca mt nam chm (Hnh 1.21) [46].
1.2.6.1. Cc phng php tng hp Fe3O4 -GO

a, Phng phap ng kt ta
Phng php ng kt ta l phng php ch to Fe3O4-GO n gin, hiu
qu v c s dng rng ri [46]. C hai cch thc ng kt ta to Fe3O4-GO:
Cch th nht s dng Fe3O4 c ch to sn ri a ln GO [16, 17, 48]. Cch
th hai s dng cc mui st (Fe3+, Fe2+) v GO l cht ban u [49-51]. Bn cht
ca phng php l kt ta ng thi tt c cc ion c trong thnh phn ca oxit
phc hp t dung dch m thng di dng hydroxit, cacbonat, oxalate, citrate
bng cch trn cc mui Fe3+ v Fe2+ c ho tan theo mt t l xc nh vi
mt dung mi. Sau , hn hp c lng, lc tch thu c ht c kch c nh.
Trong phng php kt ta t dung dch, khi nng ca cht t n mt
trng thi bo ha ti hn, trong dung dch s xut hin t ngt nhng mm kt t.
Cc mm kt t s pht trin thng qua qu trnh khuch tn ca vt cht t dung
dch ln b mt ca cc mm cho n khi mm tr thnh ht nano (Hnh 1.22) [52].
Hnh 1.22. C ch hnh thnh v pht trin ht nano trong dung dch [52]
Kch thc ca cc ht nano Fe3O4 trn GO ph thuc vo thi gian pht trin
mm. Nu thi gian pht trin mm nhanh (xy ra ngay sau giai on dung dch t
trng thi bo ha) th kch thc ht nano nh, phn b u. Ngc li, nu thi
gian pht trin mm ko di th cc ht nano Fe3O4 thu c c s phn b kch
thc rng. Khng ch tt cc iu kin tng hp nh: pH v nng ion trong
dung dch c th thu c ht c kch thc nh mong mun ng thi lm thay i
28
din tch b mt ca cc ht c hnh thnh [52]. u im ca phng php
ng kt ta l c th tng hp c mt lng mu ln, tuy nhin ht c ch to
theo phng php ny thng c phn b kch thc rng bi s pht trin ht ph
thuc vo ng nng khuch tn ca cc ion.
* C ch ca phng phap ng kt ta
Phng php ng kt ta ch to ht Fe3O4 da trn phn ng ho hc:
Fe2+ + 2Fe3+ + 8OH- = Fe3O4 + 4H2O (1)
Phn ng ny t kt ta hon ton pH 8 -14 vi t l Fe2+ v Fe3+ = 1/2
khng i. Tuy nhin do Fe2+ d dng b oxi ho v vy m sn phm to ra c th
lm thay i t l mong mun gia Fe2+ v Fe3+. Do , khi lm th nghim nn lm
trong mi trng kh tr (thng l N2) trnh sn phm ph nh hng ti
tinh khit ca sn phm.
Mt s nhng phn ng ph v sn phm ca chng:
4Fe(OH)2 + O2 + 2H2O = 4Fe(OH)3 (2)
Fe3O4 + 0,5O2 = 3Fe2O4 (3)
Trong dung dch mui Fe2+ v Fe3+ b thu phn v cung cp nhng phn t st
c cu trc n men. Mui Fe2+ v Fe3+ b phn li v to ra ion hexa-aq nh sau:
FeCl3 + 6H2O = Fe(H2O)63+ + 3Cl- (4)
FeCl2 + 6H2O = Fe(H2O)62+ + 2Cl- (5)
Trong iu kin thun li: pH cao v nhit ph hp, ion hexa-aq thu phn
v to thnh chui mm tinh th lin kt vi nhau. Phn ng thu phn n gin
c m t theo phng trnh (6), vi z l ho tr ca ion kim loi, n l s bc ca
phn ng thu phn [52].
Fe(H2O)6Z+ + H2O = Fe(H2O)6-n(OH)n(z-n) + 3H3O+ (6)
Khi baz c thm vo dung dch phc a nhn mu m c to ra c

cng thc: [Fe(II)Fe(III)2Ox(OH)2(3-x)]m2m+ v c m t bng phn ng (7):
mFe2+ + 2mFe3+ + 6mOH- = [Fe(II)Fe(III)2Ox(OH)2(3-x)]m2m+ + mxH2O (7)
Phc ny c t l Fe(III)/Fe(II) ging vi t l ca Fe3O4. Sau phc c mu

m s bt u kt ta to ra nhng ht mu en Fe3O4. kt ta hon ton th
pH ca dung dch t c t nht l 9 - 10 [50, 51]. Khi Fe3O4 c hnh thnh,
29
trn b mt GO c cha cc nhm chc cha oxy do s hnh thnh lin kt Fe-O-
C gia Fe3O4 vi GO to thnh vt liu composit [50]. Qu trnh hnh thnh Fe3O4-
GO c m t thng qua Hnh 1.23.
Hnh 1.23. Qu trnh hnh thnh Fe3O4-GO bng phng php ng kt ta
y l phng php ph bin nht hin nay iu ch M-rGO v M-GO.

Vi cch th nht c th kim sot c kch thc ht Fe3O4 trc khi to thnh
vt liu composit, cch ny thng c s dng nghin cu s lin kt gia
nhm chc ca GO v Fe3O4 ng dng trong x l cc cht mu v ion kim loi
nng [17, 46]. Vi cch th hai kch thc ht Fe3O4 kh c kim sot, cch ny
thng c dng nghin cu cc tnh cht ca Fe3O4 - GO v kh nng x l
As(III), As(V), Cr(VI), x l mu [51].
b, Phng phap thy nhit
Phng php thy nhit l phng php s dng nhit cao v p sut cao
tng hp vt liu. Hn hp dung dch c chun b ging nh phng php ng
kt ta. Hn hp sau c thy nhit trong bnh thy nhit (bnh Teflon) [53].
Trong qu trnh ch to Fe3O4 bng phng php thy nhit tc nhn kt ta s dng
l NaOH. Phng php thy nhit khc vi phng php ng kt ta c ch kt
ta to thnh Fe3O4. C hai phng php lc u u to ra phc a nhn mu
m c cng thc [Fe(II)Fe(III)2Ox(OH)2(3-x)]m2m+ v c m t bng phn ng (7).
Phng php thy nhit dng iu kin nhit cao b gy cc phc a

nhn mu to thnh Fe3O4. Trong khi , phng php ng kt ta s dng yu
t pH. u im ca phng php thy nhit ch to ht Fe3O4 c kch thc nh,
chng oxi ha. Tuy nhin thi gian tng hp mu di v b gii hn v khi lng
do ph thuc vo thit b tng hp.
30
Thy nhit tng hp Fe3O4-GO c chia thnh hai loi ph thuc vo thnh
phn dung dch: loi th nht l Hydrothermal, loi th hai l Solvothermal. S
khc nhau ca hai loi ny l thnh phn dung mi phn tn cc cht tham gia
phn ng. Hydrothermal s dng dung mi l nc, Solvothermal s dng dung
mi hu c nh ethylene glycol (EG), diethylenen glycol (DEG). Chengzhong Yu
v cng s [54] s dng phng php ny tng hp Fe3O4-GO vi kch thc
< 20 nm, s tng hp c th hin trong Hnh 1.24.
Hnh 1.24. S tng hp Fe3O4-rGO bng phng php thy nhit dung mi [54]
Hin nay, phng php thy nhit cn c kt hp vi cc phng php

khc nh, thy nhit vi vi sng (microwave hydrothermal processing), vi in
ha (hydrothermal electrochemical synthesis), vi siu m (hydrothermal
sonochemical synthesis), Vi cc phng php ny ta c th to ra vt liu c
kch thc v hnh dng nh mong mun [53].
c, Mt s phng phap khac
Ngoi hai phng php chnh l: ng kt ta v thy nhit c trnh by trn,

tng hp Fe3O4-GO cn c thc hin bi mt s phng php khc nh: phng
php lng ng in ha, x l nhit, sol - gel [55].
c bit gn y mt s nh nghin cu kt hp a ng thi kim loi, oxit

kim loi ln nn vt liu graphen lm tng tnh cht ca chng. Xinhua Xu [56]
s dng ng thi phng php ng kt ta tng hp Fe3O4/GO sau tin hnh
a kim loi Feo ln trn vt liu Fe3O4-GO bng tc nhn kh NaBH4 to thnh vt
liu Fe-Fe3O4-GO cho dung lng hp ph Cr(IV) cao Qmax = 100 mg/g v cao hn so
vi nano Fe3O4 Qmax = 19,2 mg/g. Ngoi ra nhm tc gi Bo Yang [57] cng s dng
31
phng php nh nhm tc gi Xinhua Xu tng hp Fe-Fe3O4-GO cho hot tnh quang
ha cao phn hy 98% thuc nhum xanh methylen nng 50 mg/L sau thi gian 60
pht chiu n vi nng xc tc ch cn 0,1 g/L. S m phng qu trnh tng hp
Fe/Fe3O4/GO c chng ti m phng li theo Xinhua Xu [56] v Bo Yang [57].
Hnh 1.25. Qu trnh tng hp Fe3O4-GO v Fe-Fe3O4-GO bng phng php

kt tinh ti ch
1.2.6.2. Tm hot ng ca vt liu nano composit c t tnh trn c s GO, rGO
Tm hot ng ca vt liu composit M-rGO v M-GO ng vai tr quyt

nh n tnh cht hp ph ca vt liu. S hp ph cc cht hp ph trn M-GO,
M-rGO ch yu l do to phc b mt, trao i ion, ht tnh in v tng tc -
i vi nhn thm trong cu trc ca cht b hp ph [45, 46].
Zhi Wang v cng s [58] bo co v s hp ph nhanh chng thuc nhum

hu c, fucsin (C20H19N3) trn nano composit Fe3O4-rGO, trong , gn 96% thuc
nhum b hp ph trong vng 10 pht. S hp ph nhanh chng fuchsin l do hai
loi tng tc khc nhau gia graphen v phn t thuc nhum, bao gm: (i) Tng
tc gia cc nhm chc b mt vi cc phn t thuc nhum v cc nguyn t
cacbon trong cu trc lc gic, (ii) tng tc - ca s chng xp vi mt s vng
thm ca cht hu c.
Qu trnh hp ph ph thuc nhiu vo pH dung dch. Chandra v cng s

[59] s dng composit M-rGO (Fe3O4-rGO) cho vic loi b cc ion Asen v cng
nghin cu nh hng ca pH n hiu qu hp ph ca vt liu lai ny. Thy rng
32
hiu qu hp ph ph thuc nhiu vo cc gi tr pH. C ch hp ph l lc ht tnh
in gia cc in tch dng M-rGO v in tch m asen/axit asen (H3AsO4). Khi
pH ca dung dch nh hn im ng in (pHpzc), M-rGO tch in dng do
kh nng hp ph cc anion As(V) cao. Khi pH ca dung dch c tng cao hn
pHpzc in tch dng trn b mt M-rGO gim, nhng s phn ly anion As(III)
cng tng ln ko theo s gia tng hp ph. Do tc gi a ra nhn nh, s
hp ph As(V) khc vi s hp ph As(III). Qu trnh hp ph As(III) trn M-rGO
l do phc b mt thay v tng tc tnh in.
1.3. ng dng va trin vng ca cac vt liu nghin cu trong hp ph cht

mau hu c va cc ion kim loi nng
1.3.1. ng dng ca cac vt liu GO, rGO trong hp ph cht mu v cc ion kim
loi nng
1.3.1.1. Hp ph cht mu, cht hu c
Cc vt liu GO v rGO cng c s dng lm cht hp ph hiu qu cho

qu trnh loi b cc cht nhim hu c: thuc nhum, thuc khng sinh, thuc
tr su, nc nhim du, v cc cht hu c t nhin [10, 42]. C ch hp ph ca
vt liu hp ph v cc cht hu c ph thuc vo tnh cht v cu trc ca chng
(cu to phn t, momen lng cc, s hin din ca cc nhm chc trn b mt).
Do vy kh nng v hiu sut hp ph ca cc vt liu s khc nhau cho d chng
u c cu to t GO, rGO hoc graphen nguyn bn. Tng t nh vy, s c
mt hay vng mt ca cc nhm chc nh: NH2, OH, COOH trong cht hp ph
cng s xc nh c ch v hiu qu ca qu trnh hp ph [42]. Cc c ch hp ph
trn vt liu c s graphen nguyn bn, rGO, GO ch yu l: lc ht tnh in,
hiu ng k nc, tng tc -, lin kt hydro, lin kt cng ha tr [10, 22].
Liu v cng s [60] bo co vic s dng rGO l mt vt liu hp ph loi

b methylene xanh t dung dch nc. Dung lng hp ph thuc nhum tng t
153,85 mg/g - 204,08 mg/g ng vi tng nhit t 293 K n 333 K, trong khi
vic loi b thuc nhum ti a (~ 99,68%) c quan st thy pH 10,0. ng
hc hp ph tun theo m hnh ng hc biu kin bc hai. ng nhit hp ph tun
theo m hnh ng ng nhit Langmuir hn so vi m hnh Freundlich. Tnh ton
33
cc thng s nhit ng lc hc ch ra rng hp ph xanh methylene trn rGO l
mt qu trnh t din bin v thu nhit.
Zhang v cng s [61] bo co kh nng hp ph xanh methylene ca GO

t ti a l 1939 mg/g pH = 7. Ngoi ra Sampath v cng s [62] cho thy rGO
c kh nng hp ph thuc nhum hot tnh O range vi Qmax = 5,96 mg/g, c ch
hp ph thng qua tng tc xp chng -.
Trong bi tng quan v ng dng ca GO v rGO ca Rajasekhar
Balasubramanian [22] cp n kh chi tit trong cng trnh ca mnh, c th
th n nh: Nghin cu bi Li v cng s v qu trnh hp ph cation X-GRL
trn graphen, dung lng hp ph cc i l 238,10 mg/g ti 333 K, s hp ph l
qu trnh t din bin v thu nhit, ng hc hp ph tun theo m hnh ng hc
biu kin bc 2. Nghin cu ca Wu v cng s trong vic s dng graphen loi
b xanh metylen, lng thuc nhum hp th c xc nh l ph thuc mnh m
vo nng ban u ca xanh methylen, qu trnh hp ph t c trng thi cn
bng sau 1 h. Phn tch nhit ng lc hc cho thy qu trnh hp ph l t din
bin v thu nhit. Graphen cho thy mt kh nng hp ph thuc nhum rt cao vi
dung lng hp ph cc i l 1,52 g/g, nguyn nhn ch yu l do tng tc xp
chng - c suy ra thng qua cc nghin cu quang ph hunh quang. Cc nh
nghin cu cng iu tra kh nng ti sinh v ti s dng graphen v thy rng
khng c thay i ng k hiu qu hp ph ca graphen t nht l trong nm chu
k u tin ca qu trnh hp ph-gii hp.
1.3.1.2. Hp ph cc ion kim loi nng
i vi rGO trong cu trc vn cn tn ti s t cc nhm carboxyl (- COOH)

v cacbonyl (- C=O) nm cc cnh tm, cc nhm epoxy (C - O - C) v nhm
hydroxyl (- OH) nm trn mt phng [22]. Trong khi , GO c tnh axit rt cao do
n c th d dng hp ph cc phn t baz v cc cation [10]. S hin din ca
cc nhm chc hot ng nh cacbonyl, epoxy, hydroxyl trn b mt ca GO v
rGO cho php n tng tc vi rt nhiu cc phn t tri di trn b mt bin tnh.
Hn na, nhng nhm hot ng ny ca GO cng c th lin kt vi cc ion kim
loi nng c mt trong dung dch thng qua phc b mt, do n cng c th s
34
dng tch cc ion t dung dch [5]. Kh nng hp ph cc ion kim loi nng nh:
As, Fe, Cu, Co, Cd... cng c Rajasekhar Balasubramanian [22] cp n
nhiu. Trong cc cng trnh tiu biu ca cc nh nghin cu c a ra.
Kh nng hp ph Fe(II) v Co(II) trong dung dch nc bi rGO c Chang v
cng s cp. rGO c tng hp bng phng php in ha, dung lng hp
ph cc i 299,3 mg/g v 370 mg/g tng ng cho Fe(II) v Co(II).
Wu v cng s [63] th nghim kh nng hp ph ca GO loi b Cu(II)

t dung dch nc. Cc iu kin ti u cho loi b Cu(II) bi GO: pH 5,3, nng
Cu(II) 1 mg/mL v thi gian tip xc cn bng l 150 pht. Qu trnh hp ph
Cu(II) ph hp hn vi m hnh ng nhit Freundlich, dung lng hp ph cc i
Cu(II) l 117,5 mg/g. S hp ph Cu(II) trn GO l do to phc b mt, lc ht tnh
in theo phng trnh thc nghim sau y:
GO COOH + Cu2+ GO COO- - Cu2+ + H+
(GO COOH)2 + Cu2+ (GO COOH)2 Cu2+ + 2H+
GO OH + Cu2+ GO O- Cu2+ + 2H+
(GO OH)2 + Cu2+ (GO O )2 Cu2+ + 2H+
C ch hp ph c xut c h tr bi thc t l pH dung dch cn

bng thp hn pH dung dch ban u, iu ny ch yu l do s gii phng cc
proton t cc nhm -COOH v -OH ca GO. Th nghim s dng HCl l cht gii
hp chng minh rng hn 74% Cu(II) hp ph c th c gii hp pH < 1.
Sitko v cng s [64] nghin cu s hp ph cc ion Cu (II), Zn(II), Cd(II)

v Pb(II) trn GO. i lc hp ph c pht hin theo th t Pb(II) > Cd(II) >
Zn(II) > Cu(II) trong h n kim loi, nhng theo th t Pb(II) > Cu(II) > Cd(II) >
Zn(II) trong cc h hai kim loi. Nghin cu s hp ph ng nhit v ng hc cho
thy s hp ph ion kim loi trn GO l n lp v kim sot bi s hp ph ha
hc lin quan mnh m ti s to phc b mt ca cc ion kim loi vi cc nhm
cha oxy trn b mt ca GO.
Qua cc v d trn cho thy GO v rGO vi nhng tnh cht t bit vt tri
vi din tch b mt ring cao, tnh n nh ha hc tt, cng vi tng tc - mnh
ca vng thm ha hn cho hiu qu hp ph tt i vi cc cht nhum mu, cc
35
ion kim loi nng. Tuy nhin, kh nng thu hi GO v rGO sau khi s dng thp, mt
khc nhm ci thin hn na kh nng hp ph ca chng hin nay tng hp v ng
dng vt liu nano composit trn c s GO v rGO trong hp ph x l mi trng
ang l mt trong nhng hng i c cc nh nghin cu quan tm.
1.3.2. ng dng ca vt liu composit trn c s GO, rGO trong hp ph

1.3.2.1. Hp ph cht mu
Gn y, nhiu nghin cu s dng vt liu nano oxit kim loi trn rGO, GO
loi b cc cht nhim trong nc c bo co.
Susanta Sinha Roy [46] trong bi tng quan ca mnh nu ra rt nhiu cng
trnh ca cc tc gi khc nhau trong vic ng dng vt liu composit M-rGO v M-
GO x l cht mu hu c c hi. Trong c th k n cc tc gi nh:
Chunjiao Zhou s dng phng php ng kt ta tng hp Fe3O4-GO ti pH = 10
vi tc nhn iu chnh pH l NaOH. Kch thc ht nano Fe3O4 ~ 20 nm. Hiu
sut hp ph xanh methylen t 75 %, tc hp ph nhanh. Qu trnh hp ph trn
vt liu tun theo m hnh ng nhit Langmuir. Li v cng s thnh cng tng
hp composit CoFe2O4 rGO, kh nng hp ph metyl da cam t 71,54 mg/g.
Mingce Long [49] tng hp Fe3O4- GO t ngun FeCl2 v FeCl3 bng
phng php ng kt ta s dng tc nhn kt ta l NH4OH. Kch thc ht nano
Fe3O4 vo khong 10- 20 nm, din tch b mt BET 296,2 m2/g, s dng cho hp
ph Rhodamin B, kt qu thu c m hnh hp ph ph hp vi Langmuir, dung
lng hp ph cc i t 432,91 mg/g, so vi than hot tnh th cao hn 3,7 ln.
Vi cc ht nano Fe3O4 l cht xc tc ti ch (in situ), hiu sut hp ph ca vt
liu tng hp c th c phc hi bng cch thc hin mt phn ng kiu Fenton
(Fenton-like reaction), y c th l mt cch ti to y ha hn cho cc cht hp
ph trong vic loi b cht nhim hu c trong nc thi.
Jintu Fan v cng s [65] chun b composit Fe3O4- GO c lin kt cng
ha tr rng buc gia Fe3O4 v GO. B mt ca Fe3O4 c bin tnh vi tetraethyl
orthosilicate v (3-aminopropyl) triethoxysilane, nh km cc nhm amino hot
ng vo b mt ca Fe3O4. Hn na, cc nhm amino hot ng trn b mt ca
Fe3O4 khi tip xc vi nhm carboxylic trn b mt ca GO dn n s hnh thnh
36
lin kt cng ha tr. Fe3O4-GO c dung lng hp ph ln gn 190,14 v 140,79
mg/g tng ng cho xanh methylene v mu trung tnh.
1.3.2.2. Hp ph cc ion kim loi nng
Kh nng hp ph cc ion kim loi nng ca cc vt liu trn c s GO v
rGO cng c nhiu tc gi cp:
Liu v cc ng nghip [66] nghin cu nh hng ca pH n s hp ph
Co(II) trn Fe3O4- rGO. Mt s gia tng n nh trong hp ph c quan st vi
mc tng pH 3-6, nhng tc hp ph tng t ngt trong phm vi pH 6-8,5.
Nhng nh hng ca s c mt cation v anion ngoi n kh nng hp ph ca ion
Co(II) trn Fe3O4- rGO c nghin cu. Tc gi ch ra, i vi cation kh
nng hp ph gim dn theo chiu K+ > Na+ > Mg2+, i vi anion ClO4- > NO3- > Cl-.
Mt nghin cu ca Zhu v cng s [67] cho thy rng vic loi b cc ion
crom bi composit Fe3O4 - rGO ph thuc nhiu vo pH, pH = 1-3 th loi b hon
ton Cr(VI). Ti pH c tnh axit, nng cc ion HCrO4- cao hn v th hp ph trn
composit chim u th hn CrO42-. S hp ph Cr(VI) gim khi pH c nng t axit
ti baz, nguyn nhn l do s tp trung cao ca cc ion OH- trn b mt ca
composit, cnh tranh vi cc ion crm cho cc v tr hp ph c sn trn b mt
composit. Tng t nh vy, dung dch c tnh axit cao cng c th cn tr kh nng
hp ph ca composit v pH c tnh axit cao, nng ca cc ion H+ ln c th
cnh tranh vi cc ion kim loi v c th hn ch s hp ph cc ion kim loi [46].
Xinhua Xu v cng s [56] tng hp nano st ha tr khng (nZVI) trn vt
liu t Fe3O4/Graphen (nZVI@MG) v s dng n loi b Cr(VI) trong dung
dch nc. Hiu qu loi b 83,8%, cao hn nhiu so vi cc cht ring bit (18,0%
cho nZVI, 21,6% cho Fe3O4 v 23,7% i vi graphen). Qu trnh hp ph tun
theo m hnh ng hc biu kin bc hai. Dung lng hp ph cc i Cr(VI) t
66,2-101,0 mg/g tng ng vi s gim pH 8,0 - 3,0 30 oC. Nhm tc gi cng
ch ra rng khi a cc ht Fe/Fe3O4 ln b mt GO th qu trnh hp ph xy ra
theo m hnh Langmuir do b mt c tnh ng nht hn.
Bhunia v cng s [68] tng hp thnh cng Fe-Fe3O4-rGO v s dng n
nh l cht hp ph loi b As(III) trong mi trng nc. Qu trnh hp ph
tun theo m hnh Langmuir v ng hc biu kin bc hai. Dung lng hp ph
37
cc i As(III) t 44,4 mg/g. H cng so snh kh nng hp ph As(III) ca Fe-
Fe3O4-rGO vi Fe-rGO v Fe3O4-rGO thy rng Fe-Fe3O4-rGO hp ph As(III)
hiu qu nht. Do kh nng hp ph tuyt vi ca n m vic loi b mt s ion kim
loi khc bi Fe-Fe3O4-rGO cng c nghin cu. Dung lng hp ph ti a ca
Fe-Fe3O4-rGO loi b Cr(VI), Hg(II), Pb(II) v Cd(II) c tm thy tng
ng l 31,1, 22,0, 19,7 v 1,91 mg/g.
Ngoi Fe3O4, nhiu oxit kim loi khc nh SiO2, ZnO, MnO2, CoFe2O4, Cu2O,
NiO v ZrO2 cng c a ln b mt rGO, GO lm cc cht xc tc v hp
ph [43, 46]. c mt vi bo co v tnh chn lc cao ca nanocomposit rGO
cho cc ion kim loi nht nh cng c Susanta Sinha Roy [46] nu ra. Lee v
Yang [69] nghin cu nh hng ca thi gian x l thy nhit ti hiu qu hp
ph ca composit TiO2-GO cho vic loi b cc ion Zn2+, Cd2+ v Pb2+. Thi gian
x l thy nhit t 6 gi n 12 gi, din tch b mt ca cc vt liu tng hp c
cng tng tng ng t 88,97 - 132,74 m2/g v hiu qu hp ph t 44,8 3,4 mg/g
n 88,9 3,3 mg/g cho Zn2+, 65,1 4,4 mg/g n 72,8 1 mg/g cho Cd2+, v 45,0
3,8 mg/g n 65,6 2,7 mg/g cho Pb2+.
38
CHNG 2: PHNG PHAP NGHIN CU V THC NGHIM
2.1. Thc nghim
2.1.1. Ha cht
Cc ha cht s dng trong lun n c lit k Bng 2.1.

Bang 2.1. Danh mc ha cht chnh dng trong lun n
STT Ha cht Ngun gc
1 Graphit loi tinh khit > 99%, c ht < 45 m, Sigma- Aldrich

loi bt (powder).
2 H2SO4 (98%) Merck
3 KMnO4 (loi tinh th, 99%) Merck
4 C2H5OH (99,5%) Merck
5 H2O2 (30%) Sigma- Aldrich
6 FeCl3.6H2O (99%) Merck
7 FeCl2.4H2O (99%) Merck
8 NaBH4 (98%) Trung Quc
9 NH4OH (25%) Trung Quc
10 NaH2AsO4.7H2O (99%) Merck
11 HCl (36%) Trung Quc
12 Dung dch NaOH (0,1M) Trung Quc
13 Dung dch NaCl (0,1 M) Trung Quc
Thuc nhum hot tnh RR195
14 Trung Quc
(C31H19ClN7Na5O19S6)
15 Dung dch Cu(NO) tiu chun 1000 ppm Merck
16 Dung dch Cd(NO) tiu chun 1000 ppm Merck
17 Kh N2 loi tinh khit 99,99% Vit Nam
2.1.2. Tng hp vt liu graphit oxit
Qu trnh tng hp graphit oxit c tin hnh theo Hnh 2.1.
B1: Cho 3 g bt graphit vo 42 ml dung dch H2SO4 98% trong mt cc 1000

ml c ngm sn trong chu mui lnh (0 oC), khuy c lin tc trong 30 pht
vi tc khuy 350 vng/pht.
39
Hnh 2.1. S tng hp graphit oxit t graphit
B2: Thm t t 0,45 g KMnO4 vo hn hp ang c khuy trn. Tc cho

KMnO4 phi m bo sao cho nhit hn hp khng vt qu 05 oC.
B3: Thm 9 g KMnO4 vo hn hp ang c khuy trn, tc cho KMnO4 phi

m bo sao cho nhit hn hp khng vt qu 353 oC. Khuy tip trong 30 pht.
B4: 120 mL nc ct c thm vo hn hp rt t t trnh hin tng qu

nhit cc b, nhit ca h c gi 90 oC, tip tc khuy trong 30 pht.
B5: Thm tip 80 mL H2O dng phn ng, nhit ~ 50 oC, khuy tip 20 pht.
B6: 10,5 mL dung dch H2O2 30% c cho vo hn hp, khuy khong 20 pht.
B7: Sn phm c lc ra vi dung dch HCl 0,1 M, sau ra nhiu ln vi

nc ct v ly tm n pH = 7, sy kh nhit 60 oC trong chn khng, sn
phm thu c graphit oxit.
B8: Hn hp sy kh c nghin mn bng ci m no v bo qun trong

bnh kn.
2.1.3. Tng hp vt liu GOSA, GOVS v rGO
a/ Tng hp vt liu GOSA, GOVS

Qu trnh tng hp GOSA, GOVS c tin hnh theo Hnh 2.2:
40
Hnh 2.2. S tng hp GOSA, GOVS v Graphene (rGO)
i vi graphit oxit c bc lp bng k thut siu m, nh hng ca thi
gian siu m n qu trnh tng hp GOSA c kho st. K hiu cc mu c
trnh by trong Bng 2.2.
Bang 2.2. Ky hiu cc mu GOSA tng hp cc thi gian siu m khc nhau
K hiu mu Thi gian siu m (pht) T l graphit oxit/H2O (g/L)
GSA0 0 2
GSA1 30 2
GSA2 60 2
GSA3 120 2
i vi graphit oxit c bc lp bng k thut vi sng, nh hng ca thi

gian vi sng v cng sut vi sng n qu trnh tng hp GOVS c kho st. K
hiu cc mu c trnh by trong Bng 2.3.
Bang 2.3. Ky hiu cc mu GOVS tng hp cc thi gian v cng sut khc nhau
K hiu Thi gian vi Cng sut vi Lng graphit oxit
mu sng (pht) sng (W) s dng (g)
GVS1 1 700 1
GVS2 2 700 1
GVS3 3 700 1
GVS4 4 700 1
GVS5 2 216 1
GVS6 2 1000 1
GVS7 2 1200 1
41
b/ Tng hp rGO t GO
Cho 0,5 g GO vo v c nh v tr gia ng phn ng sau a vo thit b
phn ng. Thit b phn ng c gia nhit vi tc 20 oC/pht v nhit nng
ln n nhit kho st, lu lng dng kh Nit l 10-15 mL/pht, thi gian phn
ng l 1 gi tnh t lc thit b phn ng t nhit yu cu. Sau khi ht thi gian
phn ng ngng gia nhit v ngui t nhin xung nhit phng ri ly sn
phm ra khi thit b phn ng thu c rGO. K hiu cc mu tng hp rGO cc
nhit kh khc nhau c trnh by Bng 2.4.
Bang 2.4. Ky hiu cc mu rGO c tng hp t kh GOVS cc
nhit khc nhau
Nhit Tc gia nhit Lu lng kh N2
K hiu mu
(oC) (/pht) (ml/pht)
G1 400 20 15-20
G2 600 20 15-20
G3 800 20 15-20
G4 1000 20 15-20
Hnh 2.3. H thit b phn ng nhit tng hp rGO t GO
2.1.4. Tng hp vt liu nano composit Fe3O4-GOVS

Qu trnh tng hp Fe3O4-GOVS vi t l 1:1 v khi lng c tin hnh
theo Hnh 2.4.
B1: Cn mt lng GOVS theo tnh ton phn tn vi 110 mL nc ct sau
cho vo trong thit b phn ng bnh 3 c dung tch 1L vi thit b sc kh N2.
B2: Nh dung dch hn hp hai mui Fe3+ v Fe2+ (t l mol Fe3+/Fe2+ = 2:1) vo h
phn ng cha GOVS sao cho nng Fe3+/Fe2+ theo t l aM/bM khc nhau
42
(0,01M/0,005M; 0,1M/0,05M; 1M/0,5M v 2M/1M), tc khuy c duy tr cc
gi tr X vng/pht (X = 200 v/p; 350 v/p; 500 v/p v 1000 v/p) v khuy 15 pht.
Hnh 2.4. S tng hp Fe3O4-GOVS

B3: Nng nhit ln Y oC (Y= 30, 50 v 80 oC) ri thm NH4OH vo h phn
ng sao cho pH = Z (vi Z= 8, 10 v 12), khuy u trong 45 pht.
B4: Sn phm c lc ra bng H2O v C2H5OH n pH = 7 v sy chn khng
60 oC trong 6 gi.
K hiu cc mu kho st cc nhit , pH, nng mui st ban u, tc
khuy c trnh by trong Bng 2.5, Bng 2.6 v Bng 2.7.
Bang 2.5. Ky hiu tn cc mu Fe3O4-GOVS tng hp cc iu kin
nhit v pH khc nhau
Tc khuy
K hiu mu Nhit (oC) Nng Fe3+/Fe2+ pH
(v/p)
GF1 30 0,1M/0,05M 10 500
GF2 50 0,1M/0,05M 10 500
GF3 80 0,1M/0,05M 10 500
GF4 80 0,1M/0,05M 8 500
GF5 80 0,1M/0,05M 12 500
43
nng mui st ban u khc nhau
Nng Fe3+/Fe2+ Nhit Tc khuy
K hiu mu pH
(aM/bM) (oC) (v/p)
N 0,01M/0,005M 10 80 500
GF3 0,1M/0,05M 10 80 500
N1 1M/0,5M 10 80 500
N2 2M/1M 10 80 500

tc khuy khc nhau
K hiu Nhit Tc khuy
Nng Fe3+/Fe2+ pH
mu (oC) (v/p)
V1 80 0,1M/0,05M 10 200
V2 80 0,1M/0,05M 10 350
GF3 80 0,1M/0,05M 10 500
V4 80 0,1M/0,05M 10 1000
Qu trnh tng hp Fe-Fe3O4-GOVS vi hm lng 10% Feo v khi lng

c tin hnh theo s Hnh 2.5.
Hnh 2.5. S tng hp Fe-Fe3O4-GOVS

B1: 1 g Fe3O4-GOVS c phn tn trong 100 mL nc ct c thit b sc kh N2
v hn hp c khuy mnh (500 v/p) trong 30 pht.
B2: FeCl3.6H2O (Fe theo tnh ton ~10% khi lng) vo h phn tn Fe3O4-
GOVS chun b trn, khuy trong 1 gi trao i ion.
B3: Nh t t 100 mL dung dch NaBH4 0,15 M vo h phn tn B2, v khuy
tip trong 2 gi.
44
B4: Lc ra sn phm v sy chn khng 60 oC trong 6 h thu c Fe-Fe3O4-
GOVS v bo qun trong bnh kn.
2.1.5. Xac nh im ng in ca Fe3O4-GOVS v Fe-Fe3O4-GOVS [70]

Phng php xc nh im ng in ca Fe3O4-GOVS v Fe-Fe3O4-GOVS
(in tch khng, pHpzc): cho vo 6 bnh tam gic dung tch 100 mL, mi bnh 25
mL dung dch NaCl 0,1M. Gi tr pH ca dung dch trc hp ph (pHi) c iu
chnh t 2 n 12 bng dung dch HCl 0,1M hay NaOH 0,1M. Sau , cho khong
0,05 g vt liu Fe3O4-GOVS v Fe-Fe3O4-GOVS vo mi bnh tam gic trn, y
kn v khuy bng my khuy vi tc 500 v/p trong 48 gi. Dung dch thu c
em ly tm ly phn dung dch ri o li cc gi tr pH gi l pH f. th biu din
s ph thuc chnh lch gia cc gi tr pH ban u v sau cng (pH = pHf
pHi) vo pHi l mt ng cong. Giao ca ng cong v trc honh cho ta gi tr
pHpzc cn xc nh.
2.1.6. anh gia kha nng hp ph thuc nhum hot tnh RR195
Tnh ton kh nng hp ph RR195 ca GOSA, GOVS v rGO
Thc nghim: Pha thuc nhum RR195 c nng 1g/L vo trong bnh nh
mc 1000 mL, dung dch thuc nhum hot tnh ny c iu chnh pH t 4-10
bng cc dung dch NaOH 0,1 M v HCl 0,1 M. Tin hnh phn tn ln lut 0,08 g
cht hp ph vo trong 100 mL dung dch thuc nhum c nng t 100 - 500
mg/L, khuy c Yellow-line-ost20 digital vi tc khuy 150 v/p v gi nhit
(30 1) oC, sau tng khong thi gian c nh ly mu em ly tm lc tch cht rn,
dung dch thu c phn tch xc nh nng trn my quang ph UV-Vis.
nh gi kh nng hp ph RR195 ca GOSA, GOVS, rGO, Fe3O4-GOVS v
Fe-Fe3O4-GOVS
Thc nghim: Dung dch thuc nhum hot tnh RR195 c iu chnh pH =
5,5 bi cc dung dch NaOH 0,1 M v HCl 0,1 M. Tin hnh phn tn ln lut 0,1 g
cht hp ph vo trong 100 mL dung dch thuc nhum RR195 nng 100 mg/L,
s dng khuy c Yellow-line-ost20 digital vi cnh khuy bng inox trnh hin
tng vt liu t bm ln cnh khuy gy nh hng n qu trnh hp ph, tc
khuy 150 v/p v gi nhit (30 1) oC, sau tng khong thi gian c nh ly
45
mu em ly tm lc tch cht rn, dung dch thu c phn tch trn my quang ph
UV-Vis.
tnh nng cn li sau cc khong thi gian nht nh ta xy dng ng
chun ca thuc nhum ri p dng cng thc 2.1.
At .Co
Ct
A0 (2.1)
Trong :
Ct: nng cn li sau khong thi gian t
Co: nng dung dch chun
Ao, At: mt quang (Abs) ca dung dch chun v ti thi im t
ng chun ca thuc nhum RR195 dng trong qu trnh hp ph v cu
trc ha hc ca thuc nhum RR195 c m t trn Hnh 2.6.
2,5
542 nm
ABS(cng hp ph)
hp ph )
1,5
Abs (a.u)
pH =5.5
Abs (Cng
1 y = 0,020x pH = 8.0
R = 0,997
0,5 pH =3.0
0
0 20 40 60 80 100 300 400 500 600 700
Nng (mg/L hoc ppm) Wavelength

Bc (nm)
sng (nm)
Hnh 2.6. ng chun, cu trc ha hc v ph UV-Vis ca thuc nhum RR195
2.1.7. anh gia kha nng hp ph As (V)

Thc nghim: Pha dung dch As(V) c nng 0,1 g/L t mui
NaH2AsO4.7H2O. Qu trnh pha As(V) c chun li trn thit b o AAS da trn
phng php ng chun, nng As(V) c chun li c gi tr = 0,1001
g/L do chng ti tin hnh s dng dung dch trn lm dung dch chun cho
nhng nghin cu tip theo. S dng dung dch chun 0,1 g/L pha trn pha
long thnh cc dung dch tng ng: 3, 5, 7, 10, 15 40 mg/L, iu chnh pH ca
dung dch bng HCl 0,01 M v NaOH 0,01 M. Qu trnh hp ph As(V) trn Fe3O4-
GOVS v Fe-Fe3O4-GOVS c tin hnh ng thi trn cc bnh nn dung tch
100 mL, T = 30 oC, tc khuy 150 v/p (s dng khuy c Yellow-line-ost20
digital vi cnh khuy bng inox trnh hin tng vt liu t bm ln cnh
46
khuy gy nh hng n qu trnh hp ph). Sau tng khong thi gian (t, pht)
ly mu lc tch cht rn bng ly tm v u lc mu (Syringe Filter) Bule 0,45 m
ri em dung dch thu c phn tch bng phng php AAS.
2.1.8. anh gia kha nng hp ph Cu(II), Cd(II)

Thc nghim: Dung dch Cu(II), Cd(II) c nng : 10, 20, 30 100 mg/L
c pha t dung dch chun 1 g/L, pH ca dung dch c iu chnh bng HCl
0,01 M v NaOH 0,01 M. Qu trnh hp ph Cu(II), Cd(II) trn Fe3O4-GOVS v
Fe-Fe3O4-GOVS c tin hnh ng thi trn cc bnh nn 100 mL, s dng
khuy c tc khuy 150 v/p, T=30 oC, m/V= 1 g/L. Sau tng khong thi gian (t,
pht) ly mu lc tch cht rn bng ly tm v u lc mu Blue 0,45 m ri em
dung dch thu c phn tch xc nh nng bng phng php AAS.
2.1.9. anh gia kha nng tai sinh ca vt liu t tnh Fe-Fe3O4-GOVS
nh gi kh nng ti sinh ca vt liu trong qu trnh hp ph chng ti
tin hnh thu hi vt liu sau qu trnh hp ph bng t tnh v tin hnh ra bng
nc v ethanol + methanol i vi hp ph x l thuc nhum hot tnh v ra
bng axit HCl 0,1M, pH = 2 i vi qu trnh hp ph kim loi nng. Tip theo tt
c cc mu vt liu u c ra bng nc ct ti pH = 7. Vt liu sau thu hi
c sy chn khng 60 oC, trong 24 gi.
Sau tin hnh nh gi kh nng hp ph RR195 ti nng 100 mg/L,
m/V = 1 g/L, pH = 5,5. nh gi kh nng hp ph Cd(II) ti nng 10 mg/L,
m/V = 0,1 g/L, pH = 6.
Sn phm sau phn ng (thuc nhum cn li) c xc nh bng my UV-
Vis LAMBDA 35UV/Vis, nng Cd(II) cn li c xc nh bng my AAS
630 Shimadzu ti Vin Ha hc.
2.2. Tinh toan qua trnh hp ph
2.2.1. Tnh toan hiu sut qua trnh hp ph

Hiu sut qu trnh hp ph (H %) c tnh theo cng thc 2.2:
Cdau Ccuoi
H (%) x100% (2.2)
Cdau
Trong : Cdau: nng ban u khi cha hp ph (mg/L)
Ccuoi: nng sau qu trnh hp ph (mg/L)
47
2.2.2. Mt s m hnh ng nhit hp ph [71, 72]
nh gi kh nng hp ph ca mt h hp ph, c bit l hp ph trong
mi trng nc, c nhiu phng trnh c a ra nh: phng trnh Toth,
Redlich-Peterson, Langmuir, Freundlich, Temkin, Polanyi-Dulinin, Trong
phng trnh Langmuir v Freundlich c s dng ph bin hn c, phng trnh
Langmuir thng c p dng cho cc vt liu c b mt ng nht, phng trnh
Freundlich thng c p dng cho hp ph cht tan trong pha lng trn cc vt c
b mt khng ng nht.
xy dng phng trnh ng nhit hp ph, trc ht cn phi xc nh
cc thng s c trng cho quan h gia hp ph v p sut (nng ) ca cht
b hp ph ti nhit khng i (T = const). Trong nghin cu hp ph ngi ta
thng quan tm n th tch (V) cht b hp ph vi p sut cn bng (P) ca kh
(hi) trn b mt cht rn (cht hp ph) ti mt nhit khng i (T = const).
Mi quan h V = f(P) T = const c gi l ng ng nhit hp ph (phng
trnh hp ph ng nhit).
Ty thuc vo bn cht lc hp ph, bn cht v c im ca cht hp ph
v b hp ph m c nhng ng ng nhit hp ph khc nhau.
ng nhit hp ph Langmuir
Phng trnh ng nhit hp ph Langmuir cho s hp ph cht tan trong
dung dch trn cht hp ph rn c dng sau:
Qmax K L C e
Qe (2.3)
1 K L Ce
Trong :
Qmax: lng cht b hp ph cc i n lp trn mt n v khi lng
cht hp ph (mg/g)
KL: hng s hp ph Langmuir (L/mg)
Ce: nng cn bng ca dung dch (mg/L)
Qe: dung lng cn bng hp ph ca cht b hp ph (mg/g)
Dng phng trnh (2.3) c th vit li nh sau:
Ce C 1
e (2.4)
Qe Qmax Qmax K L
48
Cc tham s Qmax v KL c th xc nh bng phng php hi quy tuyn
tnh cc s liu thc nghim da vo th tng quan gia C/Qe v Ce.
Dung lng hp ph ti thi im t c xc nh theo phng trnh 2.5:
(Co Ct )V
Qt (2.5)
W
Trong :
Qt: lng cht b hp ph thi im t (mg/g)
Co: nng cht b hp ph ban u (mg/L)
Ct: nng cht b hp ph thi im t (mg/L)
V: th tch dung dch cht b hp ph (L)
W: khi lng cht hp ph (g)
ng nhit hp ph Freundlich
M hnh Freundlich l mt phng trnh kinh nghim p dng cho s hp
ph trn b mt khng ng nht:
x
Qe K F Ce1 n (2.6)
m
Trong :
x: khi lng cht b hp ph (mg)
m: khi lng cht hp ph (g)
Ce: nng cn bng ca dung dch (mg/L)
Qe: dung lng cn bng hp ph ca cht b hp ph (mg/g)
KF: hng s Freundlich [(mg/g)(L/mg)1/n]
n: h s d th
ng ng nhit hp ph Freundlich c th c vit li nh sau:
1
LnQe LnKF LnCe hoc LogQe= LogKF +1/n LogCe (2.7)
n
Gi tr KF v n c th c tnh theo gin s ph thuc gia LnQe v LnCe hoc
LogQe v LogCe bng phng php hi quy tuyn tnh t cc s liu thc nghim.
2.2.3. ng hoc qu trnh hp ph [71, 72]

Cc tham s ng hc hp ph rt quan trng trong nghin cu ng dng cc
cht hp ph. Tuy nhin, cc tham s ng hc thc rt kh xc nh, v qu trnh
49
hp ph kh phc tp, b nh hng nhiu yu t: khuch tn, bn cht cu trc xp,
thnh phn ha hc ca cht hp ph, Do , hin nay ngi ta thng ng dng
cc phng trnh ng hc hnh thc xc nh cc hng s tc biu kin.
- Phng trnh ng hoc hp ph biu kin bc nht Lagergren: Theo , tc
ca qu trnh hp ph ph thuc bc nht vo dung lng cht hp ph theo
phng trnh:
dQt
k1 Qe Qt (2.8)
dt
Dng tch phn ca phng trnh trn l Ln(Qe Qt) = LnQe k1t (2.9)
- Phng trnh ng hoc hp ph biu kin bc hai: Theo , tc ca qu
trnh hp ph ph thuc bc hai vo dung lng ca cht hp ph theo phng
dQt
k2 Qe Qt
2
trnh: (2.10)
dt
t 1 1
Dng tch phn ca phng trnh trn l: 2
t (2.11)
Qt k2Qe Qe
Trong :
Qe: dung lng hp ph thi im cn bng (mg/g)
Qt: dung lng hp ph thi im t (mg/g)
k1: hng s tc hp ph bc nht biu kin (h-1)
k2: hng s tc hp ph bc hai biu kin (g/mg.h)
Da vo cc phng trnh , xc nh thc nghim Qt theo t, chng ta c th
xc nh c k1 v k2.
2.3. Phng phap nghin cu c trng vt liu
2.3.1. Phng phap nhiu x Rnghen (X-ray diffraction, XRD) [72, 73]
C s ca phng php nhiu x tia X l da vo hin tng nhiu x ca
chm tia X trn mng li tinh th. Khi bc x tia X tng tc vi vt cht s to
hiu ng tn x n hi vi cc in t ca cc nguyn t trong vt liu c cu trc
tinh th, s dn n hin tng nhiu x tia X.
Theo l thuyt cu to tinh th, mng tinh th c xy dng t cc nguyn
t hay ion phn b u n trong khng gian theo mt trt t nht nh. Khi chm
tia X ti b mt tinh th v i su vo bn trong mng li tinh th th mng li
50
ny ng vai tr nh mt cch t nhiu x c bit. Cc nguyn t hoc ion b kch
thch bi chm tia X s thnh cc tm pht ra cc tia phn x. Mt khc, cc nguyn
t hoc ion ny c phn b trn cc mt phng song song.
Mi lin h gia khong cch hai mt nhiu x (hkl), gc gia chm tia X v
mt phng phn x () vi bc sng () c biu th bng h phng trnh Vulf
Bragg: 2 dhkl sin = n (2.12)
Hnh 2.7. S chm tia ti v chm tia nhiu x trn tinh th

y l phng trnh c bn nghin cu cu trc tinh th. Cn c vo cc i
nhiu x trn gin (gi tr 2) c th suy ra d theo cng thc trn. So snh gi tr d tm
c vi gi tr d chun s xc nh c cu trc mng tinh th cht cn nghin cu.
Kch thc ht tinh th c th tnh theo phng trnh Scherrer [74] nh sau:
dnm = 0,9./[1.Cos] (2.13)
Trong di bc sng ca bc x Cu K, =1,5406 , 1 l bn rng
vch nhiu x, l gc Bragg.
Hnh 2.8. t ca pic phn x gy ra do kch thc ht

Thc nghim: Trong lun n ny, cc mu c o XRD trn my D8
Advance (Bruker- c) ti Trng i hc Khoa hc T nhin - i hc Quc gia
H Ni. Dng bc x ca Cu K, =1.5406 , khong qut 2 = 1 - 70o.
51
2.3.2. Phng phap ph hng ngoi bin i Fourier-FTIR [75]
Trong FTIR, ta c th o s hp th nh sng hng ngoi nh l mt hm ca

s sng. Phn t hp th nng lng E = h t ngun hng ngoi ti mi dch
chuyn dao ng. Cng hp th hng ngoi c xc nh t nh lut
Lambert-Beer:
I I o e cd (2.14)
Trong : I v Io ln lt l cng ca chm nh sng ti v chm nh
sng truyn qua, l h s hp th phn t, cn c v d ln lt l nng ca mu
v b rng ca cuvet.
Trong ph IR, ngi ta thng biu din truyn qua (T) theo s sng:
I
T (%) .100
Io (2.15)
T(%) khng t l vi c. i vi vic phn tch nh lng, ngi ta thng s
dng i lng cng hp th A, c nh ngha nh sau:
Ph hng ngoi l ng cong biu din s ph thuc cng hp th bc

x hng ngoi ca mt cht vo s sng hoc bc sng. Trn ph hng ngoi, trc
ngang biu din bc sng (tnh theo m) hoc s sng (tnh theo cm-1), trc thng
ng biu din cng hp th ( truyn qua T(%)).
S dao ng ca cc nguyn t trong phn t to ra ph dao ng. Trong phn

t c hai dng dao ng: dao ng ha tr (hay dao ng ko cng, stretching) v
dao ng bin dng (bending).
Thc nghim: Trong lun n ny cc mu c o ph FTIR k thut p

vin vi KBr trn my FTIR-4100, JASCO (USA) ti Hn Quc v FTIR 6700
Thermo Nicolet ThermoElectro ti Trng i hc Bch khoa H Ni.
2.3.3. Phng phap ph in t quang tia X (XPS)
K thut ph in t quang tia X (XPS) s dng cc photon ion ha cc

nguyn t b mt, ng thi thu nhn v o nng lng cc in t quang pht bt
52
ra. Trong k thut ny b mt mu c bn ph bi tia X nng lng thp t
ngun nhm hoc magi trong s dng pic K. i khi cc photon nng lng
thp hn hoc cao hn c s dng nh photon pht ra t bia silic v cc ngun
cc tm trong ph in t quang cc tm (Ultraviolet Photonelectron Spectroscopy-
UPS). Hnh 2.9 minh ha qu trnh pht x in t quang XPS v UPS khi b mt
mu c bn ph bi cc photon nng lng Ex = h v in t bt ra t lp in
t ha tr hoc t lp in t trong cng. Nng lng E ca lp ny c cho bi
biu thc 2.17.
E = h - Eb - (2.17)
Trong :
h: Hng s Planck
: tn s ca photon
Eb: nng lng lin kt in t
: cng thot ca in t
Mi nguyn t s c mt tp pic c
trng trong ph in t quang ti cc ng
Hnh 2.9. Qu trnh pht quang
nng c xc nh bi nng lng photon
in t
v cc nng lng lin kt tng ng. Bng
cch o ng nng in t quang v bit nng lng photon ti th nng lng lin
kt in t c th xc nh c. Nng lng lin kt chnh l i lng c trng
cho nguyn t m t c th nhn c mt s thng tin quang trng v mu
nghin cu nh cc nguyn t c mt trong mu; hm lng phn trm ca mi
nguyn t v trng thi ha hc ca cc nguyn t c mt.
Thc nghim: Trong lun n ny, cc mu c o ph XPS trn my

THERMO VG SCIENTIFIC(U,K), MultiLab2000 ti Hn Quc, s dng tia pht
x Mg K.
2.3.4. Phng phap ph tan sc nng lng tia X (EDX)
Ph tn x sc nng lng tia X (thng c gi l EDS, EDX hay XEDS)

(t y gi l ph EDX) l mt k thut phn tch dng phn tch nguyn t ca
53
mu rn. Nguyn tc da trn s tng tc ca ngun tia X kch thch vo mu cn
phn tch. Mi nguyn t ho hc c mt cu trc nguyn t xc nh to ra cc ph
tia X c trng ring bit cho nguyn t . kch thch bc x c trng tia X t
mu, mt dng nng lng cao ca cc ht tch in nh in t hay photon, hay
chm tia X c chiu vo mu cn phn tch. Cc nguyn t trong mu ny cc
trng thi c bn (cha b kch thch), cc in t cc mc nng lng ring bit
xoay quanh ht nhn. Khi dng tia ti kch thch cc in t lp bn trong, nh
bt n ra khi v in t to thnh l trng in t, mt in t t lp bn ngoi c
nng lng cao hn nhy vo in vo l trng . S khc nhau nng lng gia
lp v nng lng cao v lp v nng lng thp hn to ra tia X. Cng ca tia
X pht ra t mu c th c o bng ph k tn x nng lng (energy-dispersive
spectrometer). T ch nng lng tia X l c trng cho hiu s nng lng ca hai
lp v in t v c trng cho cu to ca nguyn t pht x ra tia X , nn
cng ca tia X ny c th dng c trng nh tnh cng nh nh lng cc
nguyn t c trong mu. Tn s (f) ca tia X c xc nh qua nh lut Mosley
nh sau:
me qe4 3
f 3 2 Z 1 2, 48 x 105 Hz Z 1
2 2
8h e0 4 (2.18)
Trong :
me: khi lng ca in t

qe: in tch ca in t
h: hng s Planck
Theo nh lut ny, tn s tia X pht ra l c trng i vi nguyn t ca mi

cht c mt trong cht rn. Vic ghi nhn ph tia X pht ra t vt rn s cho thng
tin v cc nguyn t ha hc c mt trong mu ng thi cho cc thng tin v t
phn cc nguyn t ny.
C nhiu thit b phn tch EDX nhng ch yu EDX c o bng knh hin
vi in t qut.
Thc nghim: Trong lun n ny, cc mu c o EDX trn my JEOL JSM

6500F Vin Khoa hc Vt liu Vin Hn lm Khoa hc v Cng ngh Vit Nam.
54
2.3.5. Phng phap hin vi in t truyn qua (TEM) v knh hin vi in t truyn
qua phn giai cao (HR-TEM)
Hin vi in t truyn qua (thng
vit tt l TEM) l mt k thut hin vi
trong dng in t i xuyn qua mt
mng mng ca mu o v tng tc vi
n. Mt hnh nh c to thnh t s
tng tc ca in t i xuyn qua mu
o, hnh nh ny c phng i v tp
trung ln mt thit b nhn nh nh l
mn hnh hunh quang (fluorescent
screen) hay lp phim.
Cc in t c to ra t s pht Hnh 2.10. S nguyn ly s to nh
x ion nhit t mt dy tc lm bng phn gii cao trong HR-TEM
tungsten. Cc in t ny c tng tc
bng mt in trng (c tnh bng volts). Cc in t khi i qua mu cha ng
nhng thng tin v mt in t, pha cu trc tinh th, dng in t ny dng
to hnh nh.
Hin vi in t truyn qua phn gii cao (HRTEM) l mt ch ghi nh
ca knh hin vi in t truyn qua cho php quan st nh vi cu trc ca vt rn vi
phn gii rt cao, quan st c s tng phn ca cc lp nguyn t trong vt
rn c cu trc tinh th. Ngy nay HR-TEM l mt trong nhng cng c quan st
vi cu trc ti cp nguyn t. Khc vi cc nh TEM thng thng c tng
phn ch yu l tng phn bin do hiu ng hp th th HR-TEM hot ng da
trn nguyn l tng phn pha, tc l nh to ra nh s giao thoa gia chm tia thng
gc v chm tia tn x. Khi chm in t chiu qua mu (c chiu dy, sch v s
nh hng thch hp) s b tn x theo nhiu hng khc nhau v sng tn x s ghi
li thng tin v cu trc, v tr cc nguyn t... Vt knh phi c quang sai nh
v c phn gii im ln hi t cc chm tn x ny, thc hin vic giao
thoa vi chm chiu thng gc to ra nh c phn gii cao.
55
Thc nghim: Trong lun n ny, nh HR-TEM c ghi trn my HR-TEM
JEM-2100F ti Hn Quc v nh TEM c ghi trn my - JEM1010 ti Vin V sinh
Dch t Trung ng.
2.3.6. Phng phap hin vi in t qut phn giai cao (FE-SEM)

Knh hin vi in t qut phn gii cao (FE-SEM) l mt loi knh hin vi in
t, n to ra hnh nh ca mu bng cch qut qua mu mt dng in t. Cc in
t tng tc vi cc nguyn t trong mu, to ra nhng tn hiu khc nhau cha
ng nhng thng tin v hnh thi cng nh thnh phn ca mu. Dng in t
thng c qut trong my raster v v tr ca dng in t kt hp vi cc tn
hiu to ra hnh nh. FE-SEM c th t n phn gii 1 nm.
Cc loi tn hiu sinh ra do dng in t qut l in t th cp (secondary
electrons (SE)), in t tn x ngc (back-scattered electrons (BSE), tia X c
trng (characteristic X ray) v.v... Detector in t th cp l ph bin cho tt c cc
loi my FE-SEM. Rt t my c detetor dng cho tt c cc tn hiu. Trong a s
cc trng hp, tn hiu t in t th cp (secondary electron image) hay FE-SEM
cho hnh nh vi phn gii cao v bc l ra nhng chi tit trn b mt c th ln
n 1 nm. Do dng in t hp, nh FE-SEM c su ca trng (depth of field)
ln to ra b mt ba chiu r rng rt hu ch cho vic nghin cu b mt vt liu.
in t tn x ngc (BSE) l dng in t phn x t mu bi tn x n hi.
BSE thng dng phn tch FE-SEM cng vi ph t tia X c trng bi v
cng tn hiu ca tn hiu BSE ph thuc vo phn t khi (Z) ca mu. nh
BSE cung cp thng tin v s phn b cc nguyn t khc nhau trong mu.
Thc nghim: Trong lun n ny, nh hin vi in t FE-SEM c ghi trn
my S-4800 (FE-SEM, Hitachi) ti Vin V sinh dch t Trung ng.
2.3.7. Phng phap ng nhit hp ph- kh hp ph N2 (BET) [72]

B mt ring xc nh theo phng php BET (t y gi l BET) l tch s ca
s phn t b hp ph vi tit din ngang ca mt phn t chim ch trn b mt vt
rn. Din tch b mt ring c tnh theo cng thc:
S= nm.Am.N (m2/g) (2.19)
Trong :
S: din tch b mt (m2/g)
56
nm: dung lng hp ph (mol/g)
Am: din tch b chim bi mt phn t (m2/phn t)
N: s Avogadro (s phn t/mol)
Trng hp hay gp nht l hp ph
vt l ca Nit (N2) 77 K c tit din
ngang ca bng 0,162 nm2. Nu Vm c
biu din qua n v cm3/g v SBET l
m2/g th ta c biu thc:
SBET = 4,35.Vm (2.20)
Vi Vm l th tch ca lp hp ph
n phn t tnh cho mt gam cht hp
ph trong iu kin tiu chun.
Lng kh b hp ph V c biu
din thng qua th tch cht b hp ph l
Hnh 2.11. Cc dng ng ng nhit
i lng c trng cho s phn t b hp hp ph-kh hp ph theo phn loi
ph, ph thuc vo p sut cn bng P, IUPAC
nhit T, bn cht ca kh v bn cht ca vt liu rn. Th tch kh b hp ph V

l mt hm ng bin vi p sut cn bng. Khi p sut tng n p sut hi bo
ha Po, ngi ta o cc gi tr th tch kh hp ph cc p sut tng i (P/Po) th
thu c ng ng nhit hp ph, cn khi o V vi P/Po gim dn th nhn
c ng ng nhit kh hp ph. Theo phn loi ca Hip hi quc t ha
hc c bn v ng dng (IUPAC), c cc loi ng ng nhit hp ph - kh hp
ph biu din trn Hnh 2.11.
ng ng nhit kiu I trong Hnh 2.11 tng ng vi vt liu vi mao qun
hoc khng c mao qun. Kiu II v III l ca vt liu c mao qun ln (d > 50
nm). ng ng nhit kiu IV v V tng ng vt liu mao qun trung bnh. Kiu
bc thang VI t gp. Da vo d kin BET xy dng ng phn b mao qun,
t tm kch thc trung bnh ca mao qun theo phng php BJH (Barrett,
Joyner v Halenda).
57
Thc nghim: Trong lun n ny, phng php ng nhit hp ph-kh hp
ph N2 c thc hin nhit 77 K, trn my TriStar-3000 ca M ti Trng
i hc S phm H Ni.
2.3.8. Phng phap ph hp th t ngoi v kha kin UV - Vis [73]

S hp th ca phn t trong vng quang ph t ngoi v kh kin (UV-Vis)
ph thuc vo cu trc electron ca phn t.
S hp th nng lng c lng t ha v do cc electron b kch thch
nhy t obitan c mc nng lng thp ln cc obitan c mc nng lng cao gy
ra. Bc chuyn nng lng ny tng ng vi s hp th cc tia sng c bc
sng khc nhau. Khi phn t b kch thch, cc electron ca cc nguyn t trong
phn t thc hin cc bc nhy nh trn Hnh 2.12.
Hnh 2.12. Bc chuyn ca cc electron trong phn t

Trong :
n: obitan phn t khng kin kt
: obitan phn t lin kt
*: obitan phn t phn lin kt
: obitan phn t lin kt
*: obitan phn t phn lin kt
Cc electron khi b kch thch bi cc bc x in t s nhy ln cc obitan c
mc nng lng cao hn, cc bc nhy c th l: *, *, n *, n
*, ty vo nng lng kch m cc electron thc hin cc bc chuyn nng lng
khc nhau. C s ca phng php ny l da vo nh lut Lambert-Beer.
Phng trnh:
58
I0
A lg .l.C
I (2.21)
Trong :
A: hp th nh sng (t l thun vi nng C)
I, I0: cng bc x in t trc v sau khi qua cht phn tch
: h s hp th
l: dy cuvet
C: nng cht phn tch
Phng php ph hp th t ngoi v kh kin UV-Vis c s dng rt thun
li v ph bin phn tch cc cht.
Thc nghim: Trong lun n ny, xc nh nng thuc nhum RR195 trn
my UVVis LAMBDA 35UV/Vis ti Vin Ha hc - Vin Hn lm Khoa hc v
Cng ngh Vit Nam.
2.3.9. Phng phap quang ph hp th nguyn t (AAS) [76]

Trong iu kin bnh thng nguyn
t khng thu v cng khng pht ra nng
lng di dng cc bc x. l trng
thi bn vng v ngho nng lng nht
ca nguyn t. Nhng khi nguyn t
trng thi hi t do, nu ta chiu mt chm
tia sng c nhng bc sng (tn s) xc
nh vo m hi nguyn t , th cc
nguyn t t do s hp th cc bc x
c bc sng nht nh ng ng vi
Hnh 2.13. Mi quan h gia cng
nhng tia bc x m n c th pht ra
vch ph A v nng cht Cx
c trong qu trnh pht x ca n. Lc
ny nguyn t nhn nng lng ca cc tia bc x chiu vo n v chuyn ln
trng thi kch thch c nng lng cao hn trng thi c bn. l tnh cht c
trng ca nguyn t trng thi hi. Qu trnh c gi l qu trnh hp th nng
lng ca nguyn t t do trng thi hi v to ra ph nguyn t ca nguyn t .
Ph sinh ra trong qu trnh ny c gi l ph hp th nguyn t.
59
Phng trnh c s ca php o nh lng cc nguyn t theo ph hp th
nguyn t:
A = a.C.b (2.22)
Trong :
a = K.Ka: hng s thc nghim, ph thuc vo tt c cc iu kin
thc nghim ha hi v nguyn t ha mu
C: nng cht phn tch
b = 1 (vng tuyn tnh AB); b < 1 (vng khng tuyn tnh BC) -
Hnh 2.13
Thc nghim: Trong lun n ny, cc mu c o trn my quang ph AAS

630 Shimadzu - Nht Bn, Vin Ha hc - Vin Hn lm Khoa hc v Cng ngh
Vit Nam.
2.3.10. Phng phap xac nh t tnh vt liu bng thit b t k mu rung

Thit b t k mu rung (VSM) l mt thit b dng xc nh tnh cht t
ca mu. Nguyn l hot ng ca thit b ny da trn c s hin tng cm ng
in t. Bng cch thay i v tr tng i ca mu c m men t M vi cun dy
thu, t thng qua tit din ngang ca cun dy s thay i theo thi gian lm xut
hin trong n mt sut in ng cm ng. Cc tn hiu o c (t l vi M) s
c chuyn sang gi tr ca i lng t cn o bng mt h s chun ca h o.
thc hin php o ny, mu ng rung vi tn s xc nh trong vng t
trng ng nht ca mt nam chm in. T trng ny s t ha mu v mu
rung s to ra hiu in th cm ng trn cun dy thu tn hiu. Tn hiu c thu
nhn, khuch i ri c x l trn my tnh v cho ta bit gi tr t ca mu.
Thc nghim: Trong lun n ny, cc mu c o trn h o VSM ti Vin
Khoa hc Vt liu - Vin Hn lm Khoa hc v Cng ngh Vit Nam. H o ny c
cc tnh nng nh sau:
+ H c kh nng o t ph thuc nhit v ph thuc t trng ngoi
vi nhy 10-4 emu.
+ T trng cc i l 13 kOe.
+ Di nhit o t 77 1000 K.
+ Cng t trng 1 T.
60
CHNG 3: KT QU V THO LUN
3.1. Kho sat cc yu t nh hng n qua trnh tng hp GO v rGO
3.1.1. Gian XRD ca graphit ban u v sau qua trnh oxy ha

Cu trc tinh th ca vt liu graphit ban u v graphit oxit sau qu trnh oxy
ha c xc nh qua gin nhiu x tia X trn Hnh 3.1.
Facul ty o f Che mistry, HUS , VNU, D8 ADVA NCE-Bruke r - Samp le Graph ene H Q
26,5o
3500
3400
Graphit
3300
3200
3100
Graphit oxit
d=3.376
3000
2900
2800
2700
2600
2500
2400
2300
2200
2100
L in ( C p s) 2000
1900
(a.u) (a.u)
1800
1700
1600
1500
1400
1300
chon
1200
1100
1000
900
800
700
600
do tuy
500
400
d=2.042
d=3.745
d=2.132
CuongCng
300
200
100
0
5 10 20 30 40 50
2 - Th e t a - S c al e
File:C anh VH mauGrapheneH Q(2).raw - Type: 2Th/Th locked - Start:5.000 - E nd: 50.000 - Step:0.030 - Step tim e: 1.s - Temp.: 25C (Room) - Time Started: 11 s - 2-Theta: 5.000 - Theta: 2.500 -
26,5o
10 20 30 40 50
Gc
Goc2 Theta ()(do)
2 Theta
Hnh 3.1. Gin XRD ca graphit trc v sau qu trnh oxy ha

Hnh 3.1 cho thy pic c cng cao ti 2 = 26,5o (002) c trng cho cu
trc graphit ca vt liu [77]. Cng t gin XRD cho thy ng nn ca nguyn
liu t nhiu v st gn trc ta chng t tinh khit ln, nu ngun nguyn
liu cng c nhiu tp cht th lng H2SO4 v KMnO4 cng cn nhiu cho qu
trnh oxy ha loi b cc tp cht trong nguyn liu u do vy lm gim qu
trnh oxy ha graphit. V vy, trong lun n ny chng ti tin hnh tng hp vt
liu graphit oxit i t graphit Sigma-Aldrich c tinh khit (99%).
Sau qu trnh oxy ha bng tc nhn KMnO4 v H2SO4 cho thy pic 26,5o ca
graphit khng cn quan st thy, thay vo l s hnh thnh mt pic vi cng
cao ti 2 = 11o. S thay i ny cng ph hp vi kt qu thc nghim trong
nghin cu ca Jeong HK v cng s [78]. S hnh thnh pic 2 = 11o cho thy c
s chn cc nhm oxy trong cc lp graphit v hnh thnh ln cu trc GO [79-81].
Nh vy c th thy rng graphit oxit tng hp c theo t l KMnO4/graphit =
61
3:1 oxy ha hon ton graphit thnh graphit oxit. iu ny c gii thch l do khi
tng hp graphit theo phng php Hummers th bc u tin H2SO4 an xen vo
gia cc lp graphit to thnh hn hp H2SO4 Graphit hnh thnh nn hp cht
trung gian c cng thc C(21-28)+.3HSO4-.2,5H2SO4. Bc th 2 s dng cht oxy
ha mnh KMnO4 l cht oxi ha c tc dng oxi ha mp ngoi v m mp cc
lp graphit ra to thnh hp cht trung gian th 2. Cui cng H2O tc dng vi hp
cht trung gian th 2 v to thnh graphit oxit [32, 81]. S an xen cc nhm chc
cha oxy trong cu trc graphit oxit lm gia tng khong cch gia cc lp do vy
pic 26,5 oC mt i v thay vo l s hnh thnh pic 11 oC tng ng vi khong
cc lp d = 0,81 nm [80, 81].
3.1.2. Mt s yu t anh hng n qua trnh bc lp graphit oxit s dng k thut

vi sng v k thut siu m
Mc tiu nghin cu trong phn ny l tng hp c GOVS v GOSA vi
cc tnh cht c trng cho GO vi pic c trng 2 = 10-12o v trn b mt tn ti
cc nhm chc cha oxy [77, 80-82].
* Nghin cu nh hng ca thi gian vi sng
iu kin kho st: Cng sut 700 W, khi lng graphit oxit 1 g, kho st
cc thi gian vi sng khc nhau: 1 pht, 2 pht, 3 pht v 4 pht. Kt qu th
nghim trn cc mu c a ra trong Hnh 3.2 v Bng 3.1.
Hnh 3.2. Sn phm GOVS bc lp bng k thut vi sng ti cc

thi im khc nhau
62
T Hnh 3.2 cho thy graphit oxit ban u s dng k thut vi sng trong thi
gian 1 pht th mt phn khi lng sn phm c bc tch lp thnh cng to
thnh GOVS, tuy nhin trong sn phm sau cng vn quan st thy graphit oxit ban
u cha bc lp ht. i vi GOVS - 2 pht v GOVS 4 pht khng quan st
thy graphit d cn li sau khi s dng k thut vi sng. iu ny c th l do vi
thi gian ngn (1 pht) vi lng mu 1 g th nng lng vi sng cha thi gian
lm bay hi ht cc phn t H2O c trong mu do ch mt phn b mt ca
graphit c bc lp thnh cng. Nh vy c th thy, lng mu quyt nh n
thi gian phn ng. Tht vy, trong lun vn ca tc gi Nguyn K Quang [83] s
dng 0,15 g graphit oxit th sau 1 pht phn ng, sn phm khng cn thy s xut
hin ca graphit d. Sau qu trnh vi sng th tch ca GOVS tng ln so vi graphit
oxit ban u chng t din ra qu trnh ko dn cc tm graphit oxit ra xa.
Cu trc ca graphit oxit, GOVS 2 pht, GOVS 3 pht v GOVS 4 pht
c chp XRD quan st r hn s thay i ca vt liu GOVS so vi graphit
ban u v c th hin trn Hnh 3.3.
Graphit oxit
chon)
(a.u)
26o
do (tuy
GOVS - 3 pht
Cng
Cuong
GOVS - 2 pht
GOVS - 1 pht
10 20 30 40 50
Goc
Gc22thetha
Theta ()
Hnh 3.3. Gin XRD ca cc mu GOVS c thi gian vi sng khc nhau
GVS2, GVS3 v GVS4
T Hnh 3.3 cho thy graphit oxit vi pic c trng 2 = 11o tng ng vi
khong cch cc lp d = 0,81 nm [84]. Sau cc khong thi gian vi sng khc nhau
cng pic 2 = 10 - 13o gim so vi cng pic ca graphit oxit ban u. i
vi mu GOVS (2 pht), pic 2 c s dch chuyn nh t 11 v 11,5o tng ng vi
63
khong cch cc lp d = 0,71 nm. Khi thi gian vi sng tng ln 3 - 4 pht quan st
Hnh 3.3 cho thy cc pic 2 c s dch chuyn mnh t 11 v 130 chn pic m rng
chng t khong cch cc lp gim hn nhiu so vi GOVS (2 pht), khi thi gian
vi sng tng ln trn gin XRD ca cc mu 3 pht v 4 pht cn c s xut hin
ca pic 2 26o c trng cho vt liu rGO [85, 86]. Tht vy, trong nghin cu ca
mnh Rodney S. Ruoff v cng s [33] cho rng vi GO s dng k thut vi sng
trong thi gian 1 pht c s dch chuyn ca pic 2 = 10o (d = 0,88 nm) v pic 2
= 25o (d = 0,36 nm) v khng cn gi c hnh dng ph c trng ca GO ban u.
Nghin cu ca Rodney S. Ruoff cng a ra khuyn co phng php s dng k
thut vi sng rt kh iu khin v i vi mi loi GO tng hp theo phng php
khc nhau th cn phi c nhng nghin cu thi gian vi sng ph hp.
Bang 3.1. Kho st nh hng ca thi gian vi sng n hiu sut thu hi
GVS2 GVS3 GVS4
Mu (thi gian)
2 pht 3 pht 4 pht
Ln 1 0,6267 0,4047 0,1250
Khi lng sau
Ln 2 0,6238 0,4034 0,1288
vi sng (g)
Ln 3 0,6227 0,4048 0,1284
Kt qu trung bnh (g) 0,6249 0,4043 0,1274
Hiu sut (%) 62,490 40,430 12,740
Quan st kt qu trong Bng 3.1 cho thy c s chnh lch nhiu v hiu sut
thu hi, khi thi gian tng ln hiu sut thu hi gim, c bit khi thi gian tng ln
4 pht hiu sut ch t 12,74%, quan st trong khi tin hnh th nghim cng cho
thy khi thi gian tng ln 3 pht ko theo khi en v s bng chy d di ca
GOVS trong l vi sng, chnh s bt chy ny ko theo s mt khi lng ln
ca GOVS tng hp c. Da vo nhng phn tch trn chng ti chn thi gian
vi sng thch hp l 2 pht.
* Nghin cu nh hng ca cng sut vi sng
iu kin kho st: khi lng graphit oxit ban u 1 g, thi gian 2 pht, cc
ch vi sng khc nhau: 216 W, 700 W, 1000 W v 1200 W. Gin XRD v
ph FTIR ca cc mu GOVS cc cng sut vi sng khc nhau c a ra trn
Hnh 3.4. i vi GVS5 vi cng sut 216 W quan st th nghim thy rng khng
c hin tng xy ra. i vi cc mu c cng sut 700 W, 1000 W v 1200 W u
64
c s thay i ca vt liu to thnh, tuy nhin t 1000 W tr ln quan st thc
nghim cho thy c khi en d di ko theo s bt chy nhanh ca vt liu v hon
ton trng vi nhng m t trong th nghim ca Rodney S. Ruoff [33].
Graphit oxit
a GOVS, 2pht -1000W
b
(% T)
chon)
truyn qua (%T)

(a.u)
26o
Transmittance
GOVS 2pht - 700W
do (tuy
Cng
GOVS 2pht -1000W GOVS,2pht-1200w

Cuong
GOVS 2pht - 1200W
GOVS, 2pht- 700W
500 1000 1500 2000 2500 3000 3500 4000

10 20 30 40 50
Goc
Gc22thetha
Theta () S Sng (cm-1
wavenumber )
(cm-1)
Hnh 3.4. Gin XRD (a) v ph FTIR (b) ca cc mu GOVS cc cng sut
vi sng khc nhau GVS2, GVS4, GVS5 v GVS6
Bang 3.2. Kho st nh hng ca cng sut vi sng n hiu sut thu hi
GVS2 GVS7
Cng sut vi sng
(700 W) (1200 W)
Ln 1 0,6267 0,1501
Khi lng sau
Ln 2 0,6238 0,1460
vi sng (g)
Ln 3 0,6227 0,1560
Kt qu trung bnh (g) 0,6249 0,1507
Hiu sut (%) 62,490 15,070
Tc gi Rodney S. Ruoff v cng s [33] cho thy vi cng sut < 280 W s
bc tch lp graphit oxit hon ton khng xy ra. Gii thch cho iu ny theo
chng ti, khi cng sut tng ln tng ng vi thi gian nh sng ca ngun pht
sng (Magnetron) [87, 88] s ko di hn do nng lng s ln hn so vi cng
sut nh. Trong cu trc ca graphit oxit trn b mt c cha nhiu nhm chc do
chng rt d hp ph cc phn t H2O [26, 32]. Phn t nc c cu to bi
mt nguyn t oxy (O) v hai nguyn t hydro (H) v chng khng mang in. Tuy
nhin oxy c tng ngoi cng cha 6 in t nn c khuynh hng thu thm 2 in
t bo ho, bn hn do c tnh m v vy nhng electron c khuynh hng
ko v nguyn t oxy kt qu nguyn t hydro b mt bt tnh m in nn c
khuynh hng mang in tch dng. Ngha l trong phn t nc c u dng
ca hydro v mt u m ca oxy. S mt thng bng to mt in trng nh
65
trong mi phn t nc. iu ny gy cho phn t nc tr nn rt nhy cm i
vi tia in t, c bit l tia sng vi-ba [87,88].
Trong qu trnh bc lp graphit oxit v GOVS, s gia nhit ca vi sng xy ra

do thit b vi sng to ra trng in t tng tc vi cc phn t phn cc hoc cc
ion ca nguyn liu phn ng. Khi cc phn t hoc ion ny tm cch sp xp cc
lng cc ca chng cho ph hp vi trng in t ang dao ng, chng s quay,
di chuyn v c xt vo nhau, do b nng ln v pht sinh nhit. y cc sng
dao ng s c pht ra mt tn s nht nh, thng l khong 2,45 GHz, nh
vy trong 1 giy phn t nc s c 2,45 t dao ng v pht sinh ra nhit, khi cng
sut tng ln c ngha thi gian nh sng s di thm v nng lng nhit sinh ra
thng c lc lin kt Van der Waals do y cc tm graphit oxit ra xa to
thnh GOVS. Tuy nhin khi cng sut tng ln nhiu, lng nhit sinh ra qu ln
ko theo s bng chy d di ca graphit oxit do dn n hiu sut gim c 5 ln
(Bng 3.2). Khi lng nhit tng cng vi s bc chy graphit oxit nhit cao
sinh ra cc tc nhn kh CO [37] lm kh i cc nhm chc trn b mt GOVS do
vy quan st trn ph XRD Hnh 3.4a cho thy xut hin pic 2 = 26o c trng cho
vt liu rGO [85] khi cng sut tng ln 1000 1200 W. Ph FTIR Hnh 3.4b cho
thy i vi GOVS 700 W cho thy cc pic 3460 3500 cm-1 c trng cho nhm
hydroxyl (-OH), pic 1633 cm-1 c trng cho nhm C=C, pic nm trong khong
1168 cm-1 c trng cho nhm C-O, pic nm trong khong 1728 cm-1 c trng
cho nhm cacbonyl C=O [79, 89]. GOVS 1000 W ch xut hin pic 1110 cm-1 v
1700 cm-1 tng ng vi nhm chc C-O v C=O [79] cn vi GOVS 1200 W trn
ph FTIR gn nh khng thy xut hin cc pic c trng chng t c s mt s
lng ln nhm chc trn b mt GOVS 1200 W.
Nh vy vi yu cu t ra l bc lp graphit oxit s dng k thut vi sng

thnh GOVS. GOVS tng hp c phi tn ti pic c trng cho GO (11 - 14o),
khng c s hnh thnh pic mi (20 - 30o) c trng cho vt liu rGO v duy tr
c s lng ln nhm chc trn b mt. Do , trong lun n ny iu kin thch
hp: cng sut vi sng 700 W v thi gian 2 pht vi lng mu c nh 1 g graphit
oxit ban u c chn.
66
*Nghin cu nh hng thi gian siu m n qu trnh iu ch GOSA t
graphit oxit
Rodney S. Ruoff [26] tng hp cc nghin cu v a ra t l siu m tch
lp vi dung mi H2O t graphit oxit thnh GO tng ng 1 mg/mL - 4 mg/mL.
Ngoi ra mt s nh nghin cu khc [82, 90, 91] cng a ra t l siu m tch lp
vi dung mi H2O l 0,1 mg/mL- 1 mg/mL. Trong lun n ny chng ti c nh t
l graphit oxit/ H2O = 2 mg/mL. Lng graphit oxit siu m mi mu 0,1 g. Cng
sut my 40 W. Thi gian siu m 0 pht (GOSA0), 30 pht (GOSA1) 60 pht
(GOSA2) v 120 pht (GOSA3).
Hnh 3.5. Sn phm GOSA bc lp bng k thut siu m vi cc thi gian

khc nhau
T Hnh 3.5 cho thy khi thi gian siu m < 60 pht lng graphit oxit trong
mu sau qu trnh tch lp vn cha phn tn u trong nc. Khi thi gian siu m
60 pht graphit oxit phn tn u trong dung mi nc. gii thch cho iu
ny, thy rng sng siu m chnh l sng m vi tn s t 15 - 10000 kHz. Sng
siu m c tn sut rt cao v bc sng ngn. Trong mi trng cht lng sng
siu m lm cho dung dch lc th b nn li lc li dn ra nhanh chng to ra nhng
bt bong bng chn khng siu nh, vi kch thc siu nh ny n c th xm
nhp vo cc lp ca graphit oxit. Nng lng nhit c to ra trong sut qu trnh
cng vi sng p v sng gim p khin cho cc bt kh v cng hng v ra dn
n s tng p sut lm y cc tm graphit oxit ra xa [92]. Do vy, nu cng sut
67
my c nh 40 W trong thi gian ngn p sut cha bc tch ht cc lp
graphit oxit. Tht vy, trong nghin cu ca tc gi [90] cho thy vi t l 1 mg/1
mL thi gian siu m l 2 gi dung dch ng nht, cn i vi tc gi [91] cng
vi t l 1 mg/mL thi gian cn thit l 3 gi, trong khi vi tc gi Won-Chun
Oh [82] s dng lng 20 mg/200 mL ch cn 30 pht cng sut 1,3x105 J, sn
phm GO phn tn ng nht trong nc. Theo chng ti c s khc nhau nh
vy l do khi lng graphit oxit s dng, thi gian v cng sut ca mi h my
siu m ca cc tc gi trn l khc nhau. Nh vy nh tnh c th thy rng mu
GOSA2 v GOSA3 l tt hn so vi GOSA1. lm r hn tnh cht ca cc mu,
graphit oxit ban u, GOSA2 v GOSA3 c chp HR- TEM v XRD.
(a) (b)
(c) (d)
do
Cng
Cuong chon)
(a.u)
(tuy
GOSA- 120pht
GOSA-120p
GOSA-60p
GOSA- 60pht
Graphit oxit
10 20 30 40 50
Goc2 2Theta
Gc thetha()
Hnh 3.6. Gin XRD (d) v nh HR-TEM ca cc mu GOSA vi thi gian

siu m khc nhau: graphit oxit (a), GSA2 (b), GSA3 (c)
T gin XRD hnh 3.6 (d) cho thy sau khi siu m, cc mu GOSA u
tn ti pic c trng 2 = 11o, 11,5o v 12o c trng cho vt liu graphen oxit [79,
93]. Tuy nhin khi thi gian siu m ko di th cn thy s xut hin ca pic 2 =
26o c trng cho vt liu rGO [85, 86] trn vt liu GOSA3. Nh vy khi tng thi
gian siu m ln th mt phn GO b kh v thnh rGO. Quan st Hnh 3.6 cng cho
68
thy i vi graphit oxit ban u khng siu m th c s phn pha gia cht rn v
lng, khi tng thi gian siu m ln th GOSA phn tn u trong dung dch nc.
nh HR-TEM (Hnh 3.6a-c) cho thy i vi GOSA2 cc lp c bc tch ra so
vi GOSA0, khi tng thi gian ln th nng lng siu m lm ph v cc lin kt
C-C lm chng phn thnh nhng mnh nh kch thc < 0,1 m (Hnh 3.6c) v
mt phn b kh v rGO [94]. Trong nghin cu ca Won-Chun Oh v cng s [82]
cho thy siu m trong thi gian ngn th GO tng hp c c cc cu trc XRD
v FTIR hon ton ging nhau, ch khc l so vi graphit oxit ban u c khong
cch lp d = 0,85 nm, sau siu m 60 pht khong cch lp ca GO c gim i vi
d = 0,798 nm. Do vy, thi gian siu m l 60 pht c chn bc tch lp
graphit oxit v GOSA.
3.1.3. nh hng ca nhit n qua trnh kh GOVS v rGO

Trong cng b ca Won-Chun Oh cng cng s [82] tc nhn nhit 1000 oC
c la chn kh GO v rGO, ngoi ra Seung Hun Huh [85] cng nghin cu
qu trnh kh GO v rGO vi cc iu kin nhit t 200 - 800 oC, kt qu ch ra
rng ti nhit 600 oC rGO to thnh vi 8 lp. Do vy, trong phn ny chng ti
ch nghin cu qu trnh kh GOVS v rGO ti cc nhit t 400 - 1000 oC, vi
tc gia nhit 20 oC/pht v lu lng kh N2 15-20 mL/pht. Kt qu XRD v
ph FTIR ca cc mu rGO kh nhit vi nhit khc nhau c th hin trong
2D Graph 1
Hnh 3.7.
a C-O C-O
C=C
C=O OH b
(%T)
(a.u)(a.u)
(%T)
400oC
quaqua
chon
truyen
tuy
1000oC 600oC
truyn
Cng
Cuong do
do
800oC
Cuong
800oC
400oC
600oC
500 1000 1500 2000 2500 3000 3500 4000

10 20 30 40 50
Gc 2 Theta
Goc ()
2-Thetha S sng ) -1)
(cm-1(cm
So song
Hnh 3.7. Gin XRD (a) v FT-IR (b) ca rGO cc iu kin nhit
khc nhau G1, G2, G3 v G4
GO nhit cao trong dng N2 to ra CO l tc nhn kh i cc nhm chc
b mt trn GO to thnh rGO [37]. Vt liu graphit dng ht (powder) ban u cho
69
nh ph c trng ca mt mng (002) 26,5o (Hnh 3.1). Sau qu trnh x l nhit
400 oC nh ph ny dch chuyn dn v 24,5o, chng t cu trc lp ca tinh th
graphit c hi phc [85]. Khi nhit t > 600 oC tr ln th hnh thnh r pic
trong khong 25,8o c trng cho vt liu rGO [85, 86]. Tuy nhin rng pic 25,8o
ti 800 oC v 1000 oC ln hn so vi pic 25,8 ti nhit 600 oC. Tnh ton theo cng
thc Bragg [95], dy mi lp gim dn theo chiu tng ng vi nhit kh 600
o
C > 800 oC >1000 oC. Quan st trn ph FTIR Hnh 3.7b cho thy r iu ny, khi
nhit 400 oC th qu trnh kh vn cha hon ton, trn ph FTIR vn cn quan st
thy cc nhm chc C=O, COOH, C-O-C [79, 89] mc d cng gim i rt
nhiu so vi GOVS ban u (Hnh 3.9), khi nhit > 600 oC qu trnh kh phn
ln cc nhm chc trn b mt (FTIR ca rGO c dng gn nh ng thng). Do
vy qu trnh kh din ra c hon ton, cng nh tit kim ngun nng lng,
chng ti chn nhit cho qu trnh kh GOVS v rGO l 600 oC. Hiu sut qu
trnh tng hp rGO t GOVS nm trong khong 50 - 60%.
Cc mu GOSA, GOVS v rGO tng hp c theo s Hnh 2.8 vi cc

thng s kho st c v sn phm c c trng bng cc phng php ha
l hin i s c phn tch phn tip theo ca lun n ny.
3.2. c trng vt liu GO va rGO tng hp c
3.2.1. Phng phap nhiu x tia (XRD)

Gin cc mu GOSA, GOVS v rGO c th hin trn Hnh 3.8.
GOSA
Cuong do (tuy chon)
Cng (a.u)
GOVS rGO
10 20 30 40 50
Goc22Theta
Gc thetha()
Hnh 3.8. Gin XRD ca GOSA, GOVS v rGO sau khi tng hp
70
Gin XRD ca graphit nguyn liu (Hnh 3.1) vi pic c trng cng
cao v sc nt vi gc 2 ti 26,5o (JCPDS card no. 8-415), tng ng vi khong
cch cc lp l 0,335 nm [80, 86]. T Hnh 3.8 cho thy, sau qu trnh oxi ha v
bc tch lp bng k thut siu m pic c trng ca graphit 2 ti 26,5o (002)
hu nh khng cn v thay vo l s xut hin ca pic 2 bng 11,2o (002) c
trng cho vt liu GO [82, 85].
iu ny chng t cc nhm chc c cha oxi c hnh thnh chn vo
khong khng gian gia cc lp graphit, lm cho khong cch gia cc lp tng ln
khong 0,78 nm [82] v 1,2 nm cho mu ngm nc [96] dn ti s chuyn dch v
gi tr 2 (002) nh hn (t 26,5o xung 11,2o) [85]. i vi GOVS qu trnh s dng
tc nhn nhit cao trong thi gian ngn lm cc gc OH- v H2O s b kh v bay hi
nhanh chng to ra lng kh ln y cc lp GO ra xa, lm cho lc lin kt ca
chng yu i qua lm s lng cc tm v khong cch gia cc tm GO tng ln
[33], do vy pic c trng 2 vn nm khong 11,5o tng ng vi khong cch lp
d = 0,71 nm tuy nhin cng pic gim cng nh rng chn pic tng hn
nhiu so vi graphit oxit trc vi sng. Sau qu trnh kh GOVS bng nhit 600 oC
loi b cc nhm chc trn b mt cho thy nh ph c trng ca GO 11,5o c
s gim dn v thay vo l s chuyn dch nh ph 2 v 25,8o c trng cho
vt liu rGO [85, 86]. Quan st pic c trng trn rGO cho thy c s gim v cao
cng nh khng c sc nt so vi vt liu graphit ban u iu ny l do rGO tng
hp c c nhng khuyt tt so vi graphit ban u [42, 97].
3.2.2. Ph hng ngoi chuyn dch Fourier (FTIR)

Ph FTIR ca cc mu GOVS, GOSA v rGO c th hin trn hnh 3.10.
a b
C=O
C-O-C
C=C GOVS
C-O GOSA
GOSA da
loiloai
COCO
do (%T)
(%T)
2 2
do (%T)
(%T)
truyn qua
-OH
Cuongqua
CO2 GOSA
C=O
Cuong
truyn
C=C
C-O-C C-O
rGO -OH GOSA
GOSAchua
chaloai
loiCO
CO22
500 1000 1500 2000 2500 3000 3500 4000 500 1000 1500 2000 2500 3000 3500 4000
Ssng
Sng (cm -1
S
Ssng
Sng(cm -1
(cm-1 ) S (cm-1))
Hnh 3.9. Ph FTIR ca GOSA, GOVS v rGO sau tng hp
71
Hnh 3.10 (a) m t ph FTIR ca GOSA, GOVS v rGO. Quan st ph FTIR
ca GOSA cho thy c s tn ti ca nhm cacbonyl C=O (trong khong 1700 -
1730 cm-1) [79]. Cc pic nm trong khong 1200-1250 cm-1 c trng cho s tn ti
ca lin kt CO [80]. Cc pic nm trong khong 1500-1600 cm-1 c trng cho s
tn ti ca lin kt C=C trong cc hp cht aromatic [79, 89], pic nm trong khong
1060 cm-1 c trng cho lin kt C-O-C [80]. Ngoi ra cc pic nm trong khong t
3400 3850 cm-1 c trng cho s c mt ca cc nhm -OH [79, 89]. Sau qu
trnh vi sng, cc pic c s dch chuyn nh 3460 3500 cm-1 vn c trng cho
nhm hydroxyl (-OH), pic 1633 cm-1 c trng cho nhm C=C, pic nm trong
khong 1168 cm-1 c trng cho nhm C-O, pic nm trong khong 1728 cm-1 c
trng cho nhm cacbonyl C=O [79, 89]. Cng cc pic ny u gim i so vi
GOSA c th l do tc nhn nhit trong khi vi sng ko theo s gim i s lng
nhm chc trn b mt GOVS. Sau qu trnh kh nhit ng FTIR ca rGO hu
nh khng cn quan st thy cc pic c trng cho cc nhm chc nh trong ph
FTIR ca GO (Hnh 3.9a) cho thy qu trnh kh lm mt i mt lng ln cc
nhm chc trn b mt GO. Mt iu c bit c th nhn thy khi quan st FTIR
ca c 03 vt liu GOVS, GOSA v rGO u nhn thy s xut hin ca mt pic rt
ln ti khong 2342 cm-1, pic ny c trng cho lin kt gia GO v CO2 [89]. Gii
thch cho iu ny l do trong khong nhit t 50-120 oC, GO d dng hnh
thnh lin kt vi CO2 [89, 98] lin kt ny b ph v khi nhit >210 oC [98] qu
trnh sy loi nc trn GO din ra chn khng 60 oC do vy CO2 vn cn hnh
thnh lin kt vi GO. Khi o FTIR nu qu trnh x l mu khng c qu trnh loi
b CO2 (degas) th lin kt ny vn hnh thnh v xut hin trn ph FTIR, iu ny
c chng minh khi tin hnh x l mu loi b CO2, ph FTIR ca GOSA
(Hnh 3.9b) trc v sau khi loi b CO2 trng nhau, ch khc l s gim mnh ca
pic nm trong khong 2342 cm-1 c trng cho lin kt CO2 v GO.
3.2.3. Knh hin vi in t truyn qua phn giai cao (HR TEM)
nh gi v hnh thi hc, cc mu GO v rGO c o HR-TEM. nh

HR-TEM ca GO v rGO c minh ho Hnh 3.10.
72
(a) (a)
0,6nm
(b) (b)
(c) (c)
0,4nm
Hnh 3.10. nh HR-TEM ca GOSA (a), GOVS (b) v rGO (c)

T nh HR-TEM ca GOSA (Hnh 3.10a) cho thy s xut hin nhng np
gy trn b mt ca vt liu GOSA c th do b mt b rn nt trong qu trnh x l
siu m. i vi vt liu GOVS cho thy s chng xp cc lp gim so vi GOSA,
s lp cng gim t khong t khong 10 lp (GOSA) xung 7 - 8 lp (GOVS).
Hnh nh HR-TEM ca rGO khi so snh vi nh HR-TEM ca GOVS nhn thy
rGO tng hp c c cu trc vi lp nh trong ti liu cng b [85]. T Hnh
3.11c cho thy rGO c cu trc khong 5-6 lp, khong cch mi lp khong 0,4
nm, i vi GOSA khong cch mi lp khong c tnh khong 0,6 nm. Nhn
thy c s khc bit nh khi so snh khong cch gia cc lp ca GO bng hai
phng php XRD (0,78 nm) v HR-TEM (0,6 nm). iu ny l do qu trnh x l
73
mu ca hai phng php l khc nhau, i vi phng php nhiu x tia X (XRD)
cc mu c o trong mi trng khng kh, trong khi i vi phng php
HR-TEM cc mu c x l trong mi trng chn khng.
3.2.4. Hp ph v kh hp ph Nit (BET)

B mt ring, kch thc l xp, th tch v s phn b l xp c xc nh
bng phng php ng nhit hp ph - kh hp ph N2 theo phng php BET.
ng ng nhit hp ph - kh hp ph N2 i vi GO v rGO c trnh by
Hnh 3.11. Cc thng s c trng ca vt liu (din tch b mt, tng th tch mao
qun, ng knh mao qun) c trnh by Bng 3.3.
Bang 3.3. Cc thng s c trng ca GOSA, GOVS v rGO theo phng php BET
Thng s GOSA GOVS rGO
Din tch b mt (m2/g) 56 331 300
Th tch vi mao qun (cm3/g) 0,0004 0,0015 0,018
Tng th tch mao qun (cm3/g) 0,283 1,719 1,596
ng knh mao qun trung bnh (nm) 9,6 - 21,4 7,8 - 21,2 8,8 - 22,5
1200
a
Lng hp ph (cm/g STP)
1000 Hp ph
rGO b
800 Kh Hp ph
GOVS
600
GOSA
400
200
0
0 0,2 0,4 0,6 0,8 1
p sut tng i (p/p)
c d
Hnh 3.11. ng ng nhit hp ph - kh hp ph N2 77 K (a) v ng

phn b kch thc mao qun rGO(b), GOSA(c) v GOVS(d)
74
T Hnh 3.11 a v b cho thy ng ng nhit hp ph - kh hp ph N2 ca
GO v rGO c dng tip IV, c trng cho vt liu c cu trc lp. S xut hin ng
tr chng t c s ngng t mao qun. T Bng 3.3 cho thy so vi GOSA th GOVS
v rGO c din tch b mt ring v tng th tch l xp ln hn c 6 ln. D dng
nhn thy i vi c 2 mu GO v rGO h mao qun ch yu l mao qun trung bnh
99% cn vi mao qun l khng ng k (khong 1%). ng knh mao qun nm
trong khong 8 - 22 nm. Din tch b mt ln cng vi ng knh mao qun rng l
iu kin thch hp cho s khuch tn nhanh cc cht b hp ph ti cc tm hp ph
trong vt liu hp ph, qua lm tng dung lng hp ph [71, 72].
3.2.5. Ph in t quang tia X (XPS)

hiu r hn thnh phn c bn, trng thi ha hc, trng thi in t ca
cc nguyn t trn b mt vt liu GO v rGO, cc mu c tin hnh o ph in
t quang tia X (XPS) v c trnh by trn Hnh 3.12.
Qua nh ph XPS ca GO, cho thy u xut hin nhng lin kt O1s vi pic
c trng mc nng lng 500 eV c trong nh ph ng thi cng pic ca
O1s vi mc nng lng lin kt ln n xp x 4,5x105 ht/s cho thy c kh nhiu
oxi trong vt liu chng t c nhng nhm chc cha oxi hnh thnh trong vt
liu [79]. i vi ph XPS ca rGO nng lng lin kt ca O1s mc xp x 500
eV nh pic gim xung cn xp x 2,5.105 ht/s (Hnh 3.12e) v 3.105 ht/s
(Hnh 3.13) cho thy lng oxi trong vt liu gim xung t chng t qu
trnh kh nhit loi b phn ln cc nhm chc cha oxy trn b mt GO. So
snh t cng ca pic O1s (Hnh 3.12c) cho thy sau khi kh GO thnh rGO v
l thuyt rGO khng cha oxi nhng trong thc tin cng nh cc cng trnh cng
b [26, 82, 85, 86] qu trnh kh ch c khong 80%.
Tuy vy quan st Bng 3.4 thy rng sau qu trnh kh nhit hm lng oxy
gim < 10%, t l C/O tng ln t 2,98 (GOVS) ln 10,89 (rGO) trong khi cng
iu kin qu trnh kh GOSA v rGO ch lm tng t l C/O ln 6,15, iu ny c
th l do qu trnh vi sng ko dn cc lp ca GOVS v lm mt i mt phn
lng oxy so vi GOSA do khi kh GOVS v rGO qu trnh kh din ra tt hn
v cao hn so vi kt qu ca nhm tc gi Abhijit Ganguly [97] khi kh GO v
rGO ti nhit 600 oC (C/O ~ 6,57).
75
a b
c d
e
f
Hnh 3.12. Ph XPS ca GOSA (a,b), GOVS (c, d) v rGO (e, f)
Phn tch ph XPS C1s (Hnh 3.12b -f) cho thy xut hin cc pic tng ng
vi mc nng lng 284,8 eV (C1s) l ca lin kt sp2 C-C (lin kt khng cha
oxi), tng t vi pic tng ng mc nng lng 286,8 eV l ca lin kt CO
76
[79, 99], pic tng ng vi mc nng
lng 289 - 290 eV l ca lin kt OC=
O [97, 99] v pic vi mc nng lng
287,9 eV c trng cho lin kt C = O
[97]. Cng ca cc pic ny trong GO
cao hn so vi cng ca cc pic trong
rGO chng t lng oxi lin kt vi
cacbon trn b mt rGO mt i mt
lng ln, qu trnh kh nhit GO v rGO
cn c th hin r trn pic 291,5 eV c
trng cho cc lin kt * ca cacbon Hnh 3.13. Ph XPS ca rGO
kh nhit t GOSA
trong vng thm [97].
Bang 3.4. Thnh phn cc nguyn t trong ph XPS ca GOVS, GOSA v rGO (%At)
Mu/nguyn t C O C/O
rGO 91,59 7,41 10,89
GOVS 73,92 25,08 2,98
GOSA 69,88 30,12 2,32
rGO kh nhit t GOSA 86,02 13,98 6,15
Graphen, 600 oC [Ti liu 97] 86,80 13,20 6,57
C ch kh GOVS v rGO s dng tc nhn nhit trong dng N2 sinh ra CO
[31] l tc nhn kh theo mt s ti liu [26, 38, 85, 97] nh sau:
Hnh 3.14. S qu trnh kh nhit t GOVS v rGO
77
3.3. Kho sat mt s yu t nh hng n qua trnh tng hp Fe3O4-GOVS
Trong phn u chng ti nghin cu v a ra quy trnh tng hp c

vt liu GOVS, GOSA v rGO. Tuy nhin, vt liu ny c p dng rng ri th
vic thu hi li cht xc tc sau qu trnh hp ph vn kh tin hnh. c nhiu
nh nghin cu [6, 42, 46] gn kt cc cht c t tnh ln b mt vt liu nhm d
dng thu hi xc tc sau phn ng bng t trng ngoi [44]. Mt trong nhng xu
hng th gii ang quan tm v trng vi hng nghin cu ca lun n (2012-
2015) l vic gn kt cc ht nano Fe3O4 ln b mt vt liu rGO v GO [46, 47
58]. n nay theo hiu bit ca chng ti, qu trnh gn cc ht nano Fe3O4 ln b
mt GOVS vn cha c nhm tc gi no cng b. Trong nc c nhm tc gi
Nguyn Th Vng Hon [16, 17] ang nghin cu v vt liu Fe3O4 trn GO. Tuy
nhin phng php tng hp ca tc gi dng l phng php gin tip (tng hp
Fe3O4 ring bit trong mi trng kim s dng NaOH v sau mi phn tn cc
ht nano ny ln b mt GO). Tc gi Ninh Th Huyn [13] trong lun vn thc s
ca mnh s dng NaOH l tc nhn iu chnh mi trng pH v ng dng
Fe3O4 trn GO hp ph xanh methylen. Nhm tc gi H Th Tuyt Trinh [100]
ch to Fe3O4/graphen s dng hp ph cht mu Rhodmin B. Ngoi ra, cht lng
v kch thc ca ht nano Fe3O4 to ra ph thuc nhiu vo cc yu t thc nghim
nh: pH, nhit , nng , tc khuy v t l cc cht tham gia phn ng [6,
43, 101]. Nu khng khng ch tt cc iu kin thc nghim ht nano thu c
thng c phn b kch thc rng, khng ng u d b co cm, ng thi ngoi pha
Fe3O4 c th tn ti cc pha khc nh -Fe2O3, -Fe2O3 hay cc hydroxit v nh hnh [45,
102]. Do , vi mi h khc nhau i hi phi c nhng nghin cu c th.
C rt nhiu yu t nh hng n qu trnh tng hp tuy nhin nh phn

tch trong ph XPS ca c hai GOSA v GOVS cho thy t l C/O= 2,32 - 2,98, s
lin kt gia Fe3O4 vi GOVS c to thnh bng cc lin kt cng ha tr Fe-O-C
[50] nh vy theo tnh ton phn trm nguyn t (%At) ca nguyn t Fe c trong
vt liu composit Fe3O4-GOVS chim ~20% tng ng t l Fe3O4 so vi GOVS
l 1:1 (50% v khi lng), ngoi ra tc nh dung dch Fe3+/Fe2+ vo dung dch
GOVS trong lun n ny u c c nh. Do , trong phn ny chng ti ch tp
78
trung nghin cu tng hp v kho st tnh cht ca Fe3O4-GOVS theo phng
php ng kt ta c kch thc ht nh, phn b u v d dng thu hi bng t
trng ngoi.
3.3.1. Khao sat anh hng ca nhit phan ng ng kt ta
kho st nh hng ca nhit phn ng ng kt ta ln s hnh thnh

pha, kch thc v hnh thi hc ca vt liu nano Fe3O4-GOVS, chng ti tin hnh
nghin cu cc mu vt liu c ch to cc nhit khc nhau. Cc mu c k
hiu GF1, GF2 v GF3, tng ng vi nhit phn ng l 30 oC, 50 oC v 80 oC.
Chi tit thc nghim ca h mu c trnh by trong chng 2. Kt qu nghin cu
c thc hin thng qua cc phng php: nhiu x tia X (XRD), quang ph XPS
v hin vi in t truyn qua TEM.
3.3.1.1. Pha cu trc v kch thc tinh th
Hnh 3.15 trnh by gin XRD ca cc vt liu composit Fe3O4 GOVS tng
hp bng phng php ng kt ta cc nhit phn ng khc nhau. Kt qu
phn tch cho thy gin XRD ca cc mu GF2 v GF3 u cha cc nh nhiu
x c trng cho vt liu c cu trc ferrit spinel: (111), (220), (311), (222), (440),
(442), (511) v (440) [50, 51].
i vi mu tng hp
T=800 C
chon (a.u)
o
nhit 30 C cc nh nhiu
x khng c r rng, tuy vy T=500 C
(a.u)
tuy
quan st gin XRD ca c

Cngdo
T=300 C
Cuong
o
03 mu u thy pic 2 = 11,5
khng cn. L gii v s bin
mt ca nh ph 2 = 11,5o c
10 20 30 40 50 60 70
hai nguyn nhn, mt l do cc Goc
Gc 22 Theta
Theta ()
ht nano Fe3O4 c phn tn Hnh 3.15. Gin XRD ca cc mu Fe3O4-GOVS

tng hp trong iu kin nhit khc nhau GF1,
trn tm GOVS nhiu hn lm GF2 v GF3
cho cng cc nh tng
ng vi cacbon gim i [103]. Nguyn nhn th hai l do tn hiu ca ht Fe3O4
mnh hn c xu hng ln t tn hiu ca cc nh cacbon [103]. Cc nh nhiu x
79
c m rng vch ph (1) ca mu ln chng t mu c kch thc nh [74]. Trn
thc t, khi xt gin XRD ca cc hp cht cha oxit st, thng kh phn bit
gia pha Fe3O4 v pha - Fe2O3, bi hai pha vt liu ny c cu trc tinh th tng
t v v tr vch nhiu x gn tng ng vi nhau. Do vy, xc nh chnh xc
Fe3O4 tn ti sch pha trn GOVS hay khng, 03 mu tng hp nhit khc
nhau c c trng bng php o ph XPS v c th hin trn Hnh 3.16. Quan
st ph XPS ca 03 vt liu tng hp cc nhit khc nhau cho thy ch tn ti
cc pic vi mc nng lng 711 eV v 725 eV tng ng vi Fe2p3/2 v Fe2p1/2
trong cu trc Fe3O4 m khng thy s xut hin ca cc pic 710,35 eV, 719 eV v
724 eV chng t khng tn ti s c mt ca -Fe2O3 [104]. Ngoi ra s xut hin
ca mt di di pic 715,5 eV (Hnh 3.16b) cho thy s hnh thnh ca oxit Fe3O4
trong vt liu nano composit Fe3O4-GOVS tng hp c [57].
Fe2p3/2 Fe2p 1/2
711 eV
725 eV
0
T=80 C
a b
715,5 eV
(a.u)
(a.u)
(a.u)
(a.u)
T=500C
Intensity
Intensity
Cng
Cng
T=300C
740 735 730 725 720 715 710 705 700 740 735 730 725 720 715 710 705
Binding
Nng lng Energy
lin (eV)
kt (eV)
Binding
Nng lngEnergy (eV)
lin kt (eV)
Hnh 3.16. Ph XPS (a,b) ca cc mu GF1, GF2 v GF3 tng hp trong

iu kin nhit khc nhau
Nh vy, cc kt qu nghin cu v cu trc (XRD) v quang ph XPS trn cc

mu chng minh c th tng hp c vt liu nano Fe3O4 trn GOVS sch pha vi
cc nhit phn ng t nhit 30 oC n 80 oC. Mc d nhit 30 oC Fe3O4 vn
tn ti sch pha trn GOVS nhng gin XRD li khng thy r cc nh nhiu x
c trng cho vt liu ny, iu ny l do hm lng st tn ti khc nhau trong cc
mu GOVS. Tht vy, quan st Bng 3.5 cho thy hm lng Fe (% nguyn t) phn
tch theo ph XPS ca 3 mu ln lt l 1,51%; 9,13% v 17,23%, vi gii hn pht
hin ca php o XRD > 5% th mu nhit 30 oC c hm lng Fe c 1,51% nn
khng th quan st cc nh ph c trng ca Fe3O4 l hp l.
80
Bang 3.5. Thnh phn cc nguyn t trong ph XPS ca Fe3O4-GOVS (%At)
Mu/ nguyn t C O Fe
GF1, T=30 oC 68,6 30,43 1,51
GF2, T=50 oC 60,13 30,74 9,13
GF3, T=80 oC 39,96 44,81 17,23
Mt s nghin cu cho rng ht nano Fe3O4 ch to thnh n pha khi nhit

trn 60 oC, v nhit phn ng thp hn, s oxi ha ca cc hydoxit din ra
khng hon ton. Sn phm kt ta ca mui Fe2+ v Fe3+ trong mi trng kim
ngoi Fe3O4, -Fe2O3 cn c FeOOH v -Fe2O3, kh to thnh ht Fe3O4 n pha
[102, 105]. Theo chng ti, trong phn ng ng kt ta, yu t nhit ch c tc
dng thc y qu trnh phn ng xy ra nhanh hn. Qu trnh oxi ha cc hydroxit
c th din ra hon ton nhit phng (30 oC) nu iu chnh pH ca dung
dch ph hp vi t l ion Fe2+/Fe3+ khng i l 1:2.
Nhn nh ny ph hp vi kt qu nghin cu ca Gnanaprakash v cng s
[106]. Nhm tc gi ny tng hp ht nano Fe3O4 v kho st s hnh thnh ca
ht nano Fe3O4 theo pH ca dung dch mui ban u 25 oC v 60 oC. Kt qu cho
thy ht nano Fe3O4 to ra sch pha nhit 25 oC v 60 oC. Tuy nhin, yu t
nhit li nh hng ti kch thc ht, mu to ra 25 oC c kch thc tinh th
l 6,47 nm v mu to ra 60 oC c kch thc tinh th l 8,2 nm. Nh vy, c th
cho rng nhit nh hng ti kch thc ht Fe3O4. nh gi chnh xc hn
nh hng ca nhit phn ng ln kch thc tinh th ca vt liu, tin hnh xc
nh kch thc tinh th ca cc mu da trn cng thc Scherrer [74]. Cng thc
Scherrer thng c p dng tnh cho nh nhiu x c cng mnh nht l
nh (311). Cc kt qu tnh ton c a ra trong Bng 3.6.
Bang 3.6. Kch thc ht mu Fe3O4-GOVS tng hp iu kin
nhit khc nhau
Mu GF1 GF2 GF3

dXRD (nm) - 11,8 13,4
Nh vy c th thy nhit phn ng tng dn n kch thc ht nano

Fe3O4 trn GOVS tng ln. Tuy nhin, kch thc ht tnh bng phng php XRD
81
c chnh xc cao khi tha mn iu kin cn thit l s phn b cc ht Fe3O4
phi rt ng u trn GOVS [107]. Do vy xc nh chnh xc hnh dng kch
thc ht ca Fe3O4 trn GOVS chng ti tin hnh o TEM ca 03 mu.
3.3.1.2. nh TEM
Hnh 3.17 trnh by nh TEM ca 03 mu vt liu Fe3O4-GOVS tng hp

trong cc iu kin nhit khc nhau.
(a) (a)
(b) (b)
(c) (c)
Hnh 3.17. nh TEM vi phn gii khc nhau ca cc mu Fe3O4-GOVS

tng hp iu kin nhit khc nhau GF1 (a), GF2 (b) v GF3 (c)
82
Khi so snh gi tr kch thc tinh th v kch thc ht thc, thy c s
chnh lch gia hai gi tr ny. Kch thc ht thc ca cc mu c xc nh t
nh TEM ln hn kch thc tinh th xc nh t nhiu x tia X. S sai khc gia
hai phng php l do vic xc nh kch thc tinh th bng XRD l phng php
gin tip v phng php TEM l trc tip. Hai phng php ny c tnh thng k
khc nhau: phng php nhiu x tia X ghi nhn kt qu trn tp hp c s lng
ht ln hn rt nhiu so vi cc phng php hin vi in t truyn qua [107, 108].
Phng php XRD v TEM xc nh kch thc ht tinh th ca mu khng

c s khc bit qu nhiu (13,4 nm v 15 nm) c th l do s phn b kch thc
ht Fe3O4 kh ng u trn GOVS [107].
Trong lun n ny vi nhit cao hn 80 oC chng ti khng nghin cu v

tc nhn kim s dng cho phng php ny l NH4OH 25%, do vy khi nhit
>100 oC s bay hi nc cng vi NH4OH tng mnh rt kh iu chnh pH v
nng mui trong dung dch, nhng tc nhn ny nh hng ln n qu trnh
khng ch kch thc ht [43, 101]. Hn na, trong bo co ca nhm tc gi
Nguyn Th Vng Hon [48] cho thy rng Fe3O4 tng hp c sch pha n 100
o
C. Nh vy t phng php phn tch XRD, XPS v TEM cho thy nhit nh
hng n kch thc ca ht Fe3O4 trn GOVS. Ti nhit tng hp 30 oC v 50
o
C cho kch thc ht nh hn so vi 80 oC tuy nhin quan st nh TEM chng ta
thy s phn b Fe3O4 li khng ng u bng mu nhit 80 oC, quan st
bng phn tch nguyn t theo XPS cng cho thy hm lng nguyn t Fe (%
nguyn t) ti mu 80 oC l cao nht (17,23%), ngoi ra tham kho mt s ti liu
[51, 59] cng cho thy rng tng hp Fe3O4 s dng tc nhn kim NH4OH iu
kin 80 oC cho kt qu hp ph tt. Do trong lun n ny, nhit thch hp cho
qu trnh tng hp Fe3O4-GOVS l 80 oC c la chn lm nhit thch hp cho
cc nghin cu tip theo.
3.3.2. nh hng nng u
Trong phn ng ng kt ta, bn cnh yu t nhit v pH ca dung dch phn

ng, nng cc cht u vo cng l nhng yu t nh hng n kch thc ht v
t tnh ca ht nano [101]. Theo kt qu nghin cu ca tc gi ZHAO Yuanbi
83
[109], khi thay i nng dung dch mui FeCl2 t 0,01 M n 0,03 M thu c
ht nano Fe3O4 c tinh th cao vi kch thc thay i t 10,4 nm n 17,7 nm.
Da trn cc nghin cu c thc hin, chng ti tin hnh nghin cu ch to
ht nano Fe3O4 cc nng dung dch mui ban u khc nhau vi iu kin
nhit thch hp T= 80 oC.
3.3.2.1. Gin XRD
xt nh hng ca nng mui ban u ln kch thc tinh th ca vt liu

nano Fe3O4, chng ti so snh gin nhiu x ca cc mu c ch to cc nng
mui Fe3+/Fe2+ khc nhau N (0,01M/0,005M), GF3 (0,1M/0,05M), N1 (1M/0,5M) v
N2 (2M/1M). Kt qu chp XRD th hin trn Hnh 3.18.
0,01M/0,005M
0,1M/0,05M
(a.u)
(a.u)
Intensity
1M/0,5M
Cng
2M/1M
10 20 30 40 50 60 70
2-Theta- Scale ()
Gc 2 Theta
Hnh 3.18. Gin XRD ca Fe3O4-GOVS tng hp iu kin nng khc nhau
T Hnh 3.18 cho thy cng XRD cc nh tng dn v m rng vch

hp dn khi tng nng mui. Trn gin nhiu x ca mu N2 v N1 xut hin
nh (311) th hin r nt vi cng cao, ngc li trn gin ca mu N v
GF3 nh (311) thp v c rng chn pic ln hn so vi cc mu N2 v N1. iu
ny cho thy kch thc tinh th ca cc mu tng dn khi tng nng mui. Kt
qu tnh ton kch thc tinh th ca cc mu theo cng thc Scherrer ti nh nhiu
x (311) (Bng 3.7) ph hp vi nhn nh trn.
84
Bang 3.7. Kch thc ht mu Fe3O4-GOVS tng hp iu kin
nng khc nhau
Mu N GF3 N1 N2
dXRD (nm) 7,3 13,4 18,2 36,1
Cc mu ln lt c kch thc tinh th tng ng l l 7,3 nm, 13,4 nm, 18,2 nm

v 36,1 nm. Theo l thuyt c in v s hnh thnh v pht trin mm ht trong dung
dch, nng ca cht u vo l mt trong nhng yu t nh hng ti tc pht
trin ca mm ht trong qu trnh khuch tn [103]. Khi nng tng qung ng
khuch tn ca cc mm ht ngn hn v tc pht trin ca ht nhanh hn, do ht
thu c c kch thc ln hn. Nghin cu ca tc gi Nguyn Th Vng Hon [48]
chng minh tnh ng n ca l thuyt trn. xc nh chnh xc hnh dng kch
thc ht ca Fe3O4 trn GOVS 04 mu c tin hnh o TEM v HR-TEM.
3.3.2.2. nh TEM, HR-TEM v t tnh ca Fe3O4-GOVS tng hp iu kin nng

khc nhau
Hnh 3.19 trnh by nh TEM v HR-TEM ca 04 mu (N, GF3, N1 v N2)
tng hp cc nng khc nhau, trong mu N c kch thc rt nh nn c
gi sang Hn Quc o HR-TEM.
(a) (b)
(c) (d)
Hnh 3.19. nh TEM ca Fe3O4-GOVS tng hp iu kin nng khc nhau:

N (a), GF3 (b), N1 (c) v N2 (d)
85
Khi so snh nh TEM ca cc mu tng hp trong cc iu kin khc nhau
cho thy r s thay i ca kch thc ht. c im cc ht Fe3O4 c dng ta cu,
phn tn kh ng u v nm xen k trn cc lp GOVS. Gi tr kch thc trung
bnh ca cc mu N, GF3, N1 v N2 ln lt l 8 nm, 15 nm, 25 nm v 40 nm. Cc
ht nano Fe3O4 phn tn kh ng u trn b mt ca GOVS. Tuy nhin mu N2
c kch thc ht phn b trong gii rng 15 - 40 nm. iu ny c th gii thch l
do khi nng mui thp chng ch tham gia vo qu trnh to mm v lc qu
trnh to mm v pht trin tinh th c tch ri nhau, cc ht Fe3O4 to thnh
tng i ng nht. Cn khi tng hp nng mui cao, sau khi qu trnh pht
trin mm ti trng thi siu bo ha th xy ra tip qu trnh pht trin tinh th
[52], lc ny qu trnh to mm v pht trin tinh th cng xy ra ng thi nn cc
ht to thnh c kch thc khng ng nht, phn b trong khong rng. Kt qu
ny hon ton ph hp vi gi thit ca LaMer v Dinegar [52], kt qu nghin cu
ca Nguyn Th Vng Hon [48] v ZHAO Yuanbi [109] cng chng minh
tnh ng n ca gi thit trn. Nh vy t XRD v TEM cho thy mu tng hp
trong iu kin 80 oC, nng mui ban u Fe3+/Fe2+ = 0,01M/0,005M cho ht c
kch thc nh nht (~ 8 nm). Tuy nhin vi mc ch ch to c vt liu Fe3O4-
GOVS ngoi kch thc ht nh th chng cn phi c thu hi d dng bng t
trng ngoi, do vy 03 vt liu, N, GF3 v N1 l nhng vt liu c kch thc ht
nm trong vng siu thun t (6-30 nm, theo tnh ton l thuyt) [110] c tin
hnh o t tnh c th hin trn Hnh 3.20.
50
1M/0,5M
0,1M/0,05M
Lc khng t (emu/g)
25
0,01M/0,005M
-10000 -5000 0 5000 10000
-25
-50
Applied magnetic field (Oc)
T trng (Oe)
Hnh 3.20. ng cong t ha ca Fe3O4-GOVS tng hp iu kin
nng khc nhau
86
T Hnh 3.20 cho thy ti 3 nng khc nhau, lc khng t ca mu Fe3O4-
GOVS gn nh bng khng. iu ny cho thy cc mu nano composit u mang
tnh siu thun t. T bo ha ca mu GN3 v N1 c gi tr tng ng bng 35
emu/g v 40 emu/g ph hp vi cc kt qu khc c cng b [49, 51, 91].
Thc nghim cho thy, i vi mu N t bo ha thp ~5 emu/g kh thu hi
bng t trng ngoi. Trong khi , vi cc mu GF3, N1 c t bo ha cao nn
d dng tch cht hp ph sau phn ng bng t trng ngoi. Ngoi ra kch thc
ht ca mu GF3 ~ 15 nm nn chng ti chn nng thch hp cho cc nghin
cu tip theo l 0,1M/0,05M.
3.3.3. nh hng pH
Ngoi cc yu t v nhit , nng mui Fe3+/Fe2+ th pH ca dung dch

cng c xem l mt yu t quan trng nh hng n kch thc ht. Mt s ti
liu [45, 51] v tc gi Jing Sun cng cng s [101] cho thy rng qu trnh tng
hp Fe3O4 thun li pH trong khong 8 -13 do vy trong lun n ny, chng ti
tin hnh nghin cu nh hng ca pH n kch thc ht vi cc gi tr pH = 8
(GF4), pH =10 (GF3), pH = 12 (GF5). Hnh dng, kch thc ht c quan st
bng nh FE-SEM. Hnh 3.21 trnh by nh FE-SEM ca 03 mu vt liu Fe3O4-
GOVS tng hp trong cc iu kin pH khc nhau.
(a) (b)
(c)
Hnh 3.21. nh FE-SEM ca Fe3O4-GOVS tng hp trong cc iu kin pH

khc nhau GF3(a), GF4(b) v GF5(c)
87
Hnh 3.21 cho thy mu tng hp pH = 8 (GF4) c kch thc c 20 nm,
pH = 10 (GF3) c kch thc c 15 nm v mu tng hp pH = 12 (GF5) c kch
thc c 18 nm. Nh vy, pH nh hng n kch thc ca Fe3O4 trn GOVS.
Qu trnh hnh thnh Fe3O4 c th xy ra theo qu trnh sau [101].
Fe3+ + 3OH- = Fe(OH)3 FeOOH + H2O
Fe2+ + 2OH- = Fe(OH)2
2FeOOH + Fe(OH)2 = Fe3O4 + 2H2O
Do , khi pH tng cao to thun li cho qu trnh thun xy ra lm tng s
kt dnh cc ht li vi nhau, do c th lm tng kch thc ht. T cc kt qu
phn tch trn kt hp vi tham kho cc ti liu [51, 58], trong lun n ny pH
=10 c la chn tng hp Fe3O4-GOVS. pH ny c p dng cho cc
nghin cu tip theo.
3.3.4. nh hng ca tc khuy
Trong phn ng ng kt ta, bn cnh yu t nhit , pH ca dung dch phn
ng v nng cc cht u vo th tc khuy cng l yu t nh hng n kch
thc ht v t tnh ca ht [101]. Nghin cu ca Jing Sun v cng s [101] cho
thy c th iu khin kch thc v hnh dng ht nano bng cch thay i tc
khuy t vi kch thc ht thay i t 5-25 nm tng ng 1200 v/p xung 600 v/p.
Do vy chng ti tip tc nghin cu nh hng ca tc khuy n kch thc
ht vi tc : 200 v/p (V1), 350 v/p (V2), 500 v/p (GF3) v 1000 v/p (V4)
3.3.4.1. Gin XRD
Gin XRD ca cc mu V1, V2, GF3 v V4 c trnh by Hnh 3.22.
1000
1000v/phut
v/p
500 v/phut
500 v/p
(a.u)
Intensity (a.u)
350
350v/phut
v/p
Cng
200 v/phut
200 v/p
10 20 30 40 50 60 70
Gc 2 2-
Theta ()
Theta- Scale
Hnh 3.22. Gin XRD ca Fe3O4-GOVS tng hp iu kin tc khuy
khc nhau
88
Hnh 3.22 cho thy cc mu (V1, V2, GF3 v V4) u c cc pic vi 2 tng
ng l: 18,27 (111), 30,1 (220), 35,4 (311), 43,05 (400), 57,2 (511) v 62,5
(440) ph hp vi cc d liu nhiu x tia X tiu chun cho cu trc spinel Fe3O4 [49,
51]. Kt qu ny chng minh s bc ph ca cc ht nano Fe3O4 ln GOVS. Quan st
Hnh 3.22 cho thy rng ph (311) cc mu V1 v V2 hp hn so vi cc mu
GF3 v V4 chng t kch thc tinh th gim dn khi tng tc khuy. Kt qu tnh
ton kch thc tinh th ca cc mu theo cng thc Scherrer [74] ti nh nhiu x
(311) ph hp vi nhn nh trn. Cc mu V1, V2, GF3 v V4 c kch thc tng
ng 24,1 nm; 14,08 nm; 13,4 nm v 12,7 nm. Gii thch iu ny, theo chng ti khi
tc khuy c tng ln th lm cho ng nng ca cc ht mm Fe3O4 tng ln dn
n thi gian pht trin mm nhanh, lm chng phn tn thnh cc ht nh trong
dung dch [52]. Nh vy, vn tc khuy ln s lm gim kch thc trung bnh ca
ht v cc ht t b co cm hn hn. xc nh chnh xc hnh dng kch thc ht
ca Fe3O4 trn GOVS 04 mu V1, V2, V4 v GF3 c tin hnh o TEM.
3.3.4.2. nh TEM
Hnh 3.23 trnh by nh TEM ca 4 mu tng hp cc iu kin tc

khuy c khc nhau.
(a) (b)
(c) (d)
Hnh 3.23. nh TEM ca Fe3O4-GOVS tng hp iu kin tc khuy khc

nhau V1 (a), V2 (b), GF3 (c) v V4 (d)
89
Khi so snh nh TEM cc mu trn cng mt thang o 100 nm cho thy kch
thc ht ca cc mu c s thay i, mu V4 c kch thc nh nht (14 nm) v
mu V1 c kch thc ln nht (30 nm). Gi tr kch thc ht trung bnh ca cc
mu V1, V2, GF3 v V4 tng ng l 30 nm, 20 nm, 15 nm v 14 nm. Kt qu
nhn c t nh TEM cho thy xu hng nh hng tc khuy vo kch thc
ht ph hp vi kt qu nghin cu nhiu x tia X. Kch thc ht thc gim khi
tng tc khuy. Tuy nhin, khi tng tc khuy t 500 v/p ln 1000 v/p th kch
thc ht gim i khng ng k, hn na khi tng tc ln 1000 v/p vi quan st t
thc nghim cho thy c nhiu bong bng v dung dch phn ng b bn ln thnh bnh rt
nhiu. Do vy tc thch hp trong nghin cu ny tng hp vt liu Fe3O4-GOVS
c la chn l 500 v/p.
3.4. Tng hp vt liu Fe3O4-GOVS v Fe-Fe3O4-GOVS
Nh vy t nhng kt qu nghin cu nh hng cc iu kin n qu trnh

tng hp Fe3O4-GOVS bng phng php ng kt ta chng ti a ra c
quy trnh thch hp tng hp Fe3O4-GOVS trong nghin cu ca lun n ny.
Quy trnh tng hp c th hin bng s Hnh 3.24.
Hnh 3.24. S tng hp Fe3O4 - GOVS iu kin thch hp
90
Da vo s Hnh 3.24 chng ti tin hnh tng hp mu Fe3O4- GOVS
iu kin thch hp. Sn phm c tin hnh c trng mu bng cc phng php
ha l hin i xc nh c trng cu trc v hnh thi hc ca vt liu.
Tuy nhin, thi gian mi y nhiu kt qu nghin cu cng ch ra rng cc
ht nano st ha tr khng (Feo) c kh nng loi b tt cc cht gy nhim mi
trng nh cc dung mi clo, thuc tr su clo hu c, thuc nhum hu c, cc
cht nhim v c v cc ion kim loi nng [56]. Mc d vy, vt liu Feo khng
th c p dng trong cc h thng dng chy lin tc do cc ht c kch thc
nh, d b oxy ha khi tip xc vi khng kh v hiu sut tng hp thp [111]. Do
, vic kt hp qu trnh gn kt cc ht Feo v Fe3O4 ln b mt GO khng nhng
lm cc ht Feo n nh hn m cn d dng tch chng ra khi nc x l nh s
tr gip ca t trng bn ngoi [44, 57]. Tha hng nhng kt qu nghin cu
trn tng hp mu Fe3O4-GOVS trong iu kin thch hp nht sau tin hnh
a cc ht nano Feo ln b mt vt liu Fe3O4-GOVS bng cch s dng tc nhn
kh NaBH4 v ngun Fe3+ trong iu kin c mt ca kh tr N2, chi tit thc
nghim c trnh by chng 2. Trong lun n ny, lng Feo c a ln
Fe3O4-GOVS khong 10% v khi lng theo tnh ton. S hnh thnh Feo v Fe3O4
cng tn ti trn GOVS c chng ti phn tch v chng minh bng cc phng
php ha l hin i c a ra phn tip theo ca lun n.
3.5. c trng vt liu Fe3O4-GOVS v Fe-Fe3O4-GOVS
3.5.1. Nghin cu nhiu x tia X (XRD)

Gin XRD ca cc mu Fe3O4-GOVS v Fe-Fe3O4-GOVS c trnh by
trn Hnh 3.25.
Nh thy trong Hnh 3.25, qu trnh a Fe3O4 ln GOVS lm cho pic
2 = 11,5o khng cn v thay vo l s xut hin ca cc pic c cng cao
vi gi tr 2 tng ng l: 18,27 (111), 30,1 (220), 35,4 (311), 43,05 (400),
52,7 (511) v 62,5 (440) ph hp vi cc d liu nhiu x tia X tiu chun cho
cu trc spinel Fe3O4 [51, 57]. Kt qu ny chng minh s bc ph thnh cng ca
cc ht nano Fe3O4 ln GOVS v kh tng ng vi nghin cu ca Hongkun He
[112]. Theo tc gi pic c trng ca GOVS khng cn quan st thy l do nh
hng ca cc ht Fe3O4 khi mang ln GO th mt che ph ca cc ht trn b
91
mt cc tm GOVS l ln lc khng xut hin cc nh pic ca cacbon trong
mu [112]. M: Fe3 O4
422
220
511
440
311
111
Sau qu trnh kh
400
*: Feo *
M M M M M M M *
bng NaBH4 cc nh pic
chon)
(tuy(a.u)
c trng cho Fe3O4 vn Fe3O4-GOVS
do
Cng
cn, tuy nhin cng pic
Cuong
gim nhiu so vi trc
Fe-Fe3O4-GOVS
khi kh. Quan st trn gin
XRD ca Fe-Fe3O4-
10 20 30 40 50 60 70
Goc
Gc 2 Thetha
2 Theta ()
GOVS cho thy c s xut
hin cc pic 2 tng ng Hnh 3.25. Gin XRD ca Fe3O4-GOVS v
Fe-Fe3O4-GOVS
l 45 v 68 c trng cho
s hnh thnh ca Feo trn vt liu [111].
3.5.2. Knh hin vi in t truyn qua TEM v knh hin vi in t truyn qua
phn giai cao HR-TEM
nh gi hnh thi v kch thc ht tht ca mu chng ti tin hnh o
TEM v HR-TEM i vi mu Fe3O4-GOVS, i vi mu Fe-Fe3O4-GOVS vi gi
thit ca chng ti l kch thc ht Fe nh hn Fe3O4 do vy php o HR-TEM
c s dng nghin cu. Kt qu c a ra trn Hnh 3.26. T nh TEM v
HR-TEM (Hnh 3.26) cho thy kch thc ht nano Fe3O4 nm trong khong t 12 -
17 nm. Mt s t cc ht nano Fe3O4 b kt tp li c kch thc nm trong khong
20 nm. Kt qu xc nh kch thc t nh TEM v phng php XRD c tng
ng chng t Fe3O4 v Fe-Fe3O4 phn tn kh ng u trn cc lp ca GOVS.
i vi mu Fe-Fe3O4 kch thc ht ca cc ht nano Feo nm trong khong 5 - 10
nm. iu ny c th gii thch l do cc ht nano Feo c tng hp trc tip s c
kch thc nm trong khong 50 - 100 nm do chng b kt tp li [113]. Khi a
chng ln GOVS th kch thc ht nano Feo <10 nm (Hnh 3.26c) do cc ht ny
phn tn u, n nh v t co cm hn [111, 114]. Theo hai tc gi Xinhu Xu [56]
v Bo Yang [57] u s dng ngun Fe2+ v tc nhn kh NaBH4 th kch thc ca
Feo trn vt liu Fe-Fe3O4-GO tng hp nm trong khong 100 nm. Trong khi
92
kch thc Feo theo phng php chng ti tng hp ch nm trong khong 5 - 10
nm. Gii thch iu ny theo chng ti l do hm lng Feo tn ti trong vt liu.
(a) (b)
(c)
Hnh 3.26. nh TEM ca Fe3O4-GOVS (a) v Fe-Fe3O4-GOVS (b,c)
Theo tc gi Tianxi Liu [111] th kch thc ht Feo < 10 nm khi lng Feo <
20%, khi tng nng Feo ln > 20% th kch thc Feo tng mnh, cn theo
Fenglin Liu [114] vi hm lng Feo chim 20% trong vt liu th kch thc Feo ~
15 nm, nu tng hm lng Feo ln 40% th kch thc Feo tng ln ~ 80 nm, v vy
vi lng Feo a vo c tnh ton c 10% khi lng do vy kch thc ht Feo
nm trong khong 5 - 10 nm l hp l.
3.5.3. Ph hng ngoi chuyn dch Fourier (FTIR)
Kt qu o ph FTIR ca Fe3O4-GOVS v Fe-Fe3O4-GOVS c th hin trn

Hnh 3.27.
Nh phn tch phn trn ph FTIR ca GOVS tn ti cc pic nm trong

khong 3460 3500 cm-1 c trng cho nhm hydroxyl (-OH), pic 1633 cm-1 c
93
trng cho nhm C=C, pic nm trong khong 1168 cm-1 c trng cho nhm C-O,
pic nm trong khong 1728 cm-1 c trng cho nhm cacbonyl C=O [79, 89].
Cng (ABs)
S Sng (cm-1)
Hnh 3.27. Ph FTIR ca Fe-Fe3O4-GOVS v Fe3O4-GOVS
Khi a cc ht nano Fe3O4 ln GOVS, xut hin pic 578,2 cm-1 c trng
cho lin kt Fe-O trong Fe3O4, Fe-Fe3O4 vi GOVS [57, 115]. Cc pic trong khong
1230 cm-1 v 1576 cm-1 c trng cho lin kt C=O v C-O [79, 116]. Pic nm
trong khong 2342 cm-1 c trng cho cc lin kt CO2 vi Fe3O4-GOVS v Fe-
Fe3O4-GOVS [116]. Ph FTIR Hnh 3.27 cn cho thy s hnh thnh ca Feo ln
trn vt liu Fe3O4-GOVS vi pic c trng 1048,5 cm-1 [114].
3.5.4. Ph tan sc nng lng tia X (EDX) ca Fe-Fe3O4-GOVS v Fe3O4-GOVS
Ph EDX ca Fe-Fe3O4-GOVS v Fe3O4-GOVS c trnh by trn Hnh 3.28

v Bng 3.8.
Bang 3.8. Thnh phn cc nguyn t trong Fe3O4-GOVS v Fe-Fe3O4-GOVS (%At)

Nguyn Fe3O4-GOVS Fe-Fe3O4-GOVS
t % Khi lng % Nguyn t % Khi lng % Nguyn t
C 35,97 74,46 29,96 57,98
O 15,44 19,98 12,36 17,97
Fe 48,59 17,96 57,68 24,05
Tng 100 100 100 100
94
Hnh 3.28. Ph EDX ca Fe3O4-GOVS v Fe-Fe3O4-GOVS
T Hnh 3.28 v Bng 3.8 cho thy hm lng st (Fe) trong Fe3O4-GOVS chim
48,59% v khi lng v ~ 18% v nguyn t kh gn vi tnh ton ban u (Fe chim
50% v khi lng v 20% v nguyn t). Sau qu trnh a thm 10% Feo v khi
lng vo trong Fe3O4-GOVS nhn thy khi lng Fe tng ln 57,68% (tng tng
ng ~9,1% v khi lng) kh st vi tnh ton. Hm lng Feo thm vo > 5% do
trn gin XRD xut hin cc pic c trng vi gi tr 2 = 45o v 68o l hp l.
3.5.5. Hp ph v kh hp ph Nit (BET) ca Fe-Fe3O4-GOVS v Fe3O4-GOVS

0,20
350 0,16
a 0,18
b
0,14
Pore Volume (cm/gnm)
Quantity Adsorbed (cm/g STP)
300 Adsorption 0,12

Desorption 0,16
Pore Volume (cm/gnm)
250 Fe3O4- GOVS 0,14

0,10
0,08
0,12 0,06
200
Fe-Fe3O4- GOVS 0,10
0,04
0,02 Fe3O4-GOVS
150 0,08 0,00
0 10 20 30 40 50
100 0,06 Pore Diameter (nm)

0,04
50
0,02 Fe-Fe3O 4-GOVS
0 0,00
0 0,2 0,4 0,6 0,8 1 0 10 20 30 40 50
Relative Pressure (p/p) Pore Diameter (nm)
Hnh 3.29. ng ng nhit hp ph - kh hp ph N2 (a) v phn b mao

qun (b) ca Fe-Fe3O4-GOVS v Fe3O4-GOVS
95
ng ng nhit hp ph - kh hp ph N2 ca Fe3O4-GOVS v Fe-Fe3O4-
GOVS Hnh 3.29 (a) c dng tip IV, c trng cho vt liu c cu trc lp. S xut
hin ng tr chng t c s ngng t mao qun. T Bng 3.9 cho thy Fe-Fe3O4-
GO c din tch b mt ring v th tch xp ln, so vi Fe3O4-GOVS th Fe-Fe3O4-
GOVS c din tch b mt ring v th tch xp ln hn. Tuy nhin, s chnh lch l
khng ng k (8 m2/g). H mao qun ca c hai vt liu ch yu l mao qun trung
bnh (99%) cn vi mao qun l khng ng k ch chim khong 1%. ng knh
mao qun ca c vt liu nm trong khong 8-13 nm. Kt qu ny cng ph hp vi
mt s cng trnh cng b gn y [49, 50, 56]. Din tch b mt tng i ln v
ng knh mao qun rng lm tng hiu qu hp ph ca cht xc tc [71, 72].
Bang 3.9. Cc thng s c trng ca Fe3O4-GOVS v Fe-Fe3O4-GOVS

Thng s Fe3O4-GOVS Fe-Fe3O4-GOVS
Din tch b mt (m2/g) 169 177
Th tch vi mao qun (cm3/g) 0,0033 0,0043
Tng th tch mao qun (cm3/g) 0,499 0,523
ng knh mao qun trung bnh (nm) 8,8 - 12,1 8,9 - 12,3
3.5.6. Ph quang in t tia X (XPS) ca Fe-Fe3O4-GOVS v Fe3O4-GOVS
Quang ph XPS ca Fe-Fe3O4-GOVS v Fe3O4-GOVS c th hin trn

Hnh 3.30.
Quan st ph XPS tng (Hnh 3.30a) ca hai vt liu Fe3O4- GOVS v Fe-
Fe3O4-GOVS u thy xut hin cc pic vi mc nng lng 285 eV, 530 eV v
711 eV tng ng vi C1s, O1s v Fe2p tn ti trong cu trc vt liu. i vi ph
XPS C1 (Hnh 3.30d) cho thy tn ti cc pic vi mc nng lng tng ng 284,8
eV; 285,5 eV; 288,3 eV c trng cho cc lin kt C-C, C-O, O-C=O [59, 91].
Ngoi ra quan st ph XPS C1 c s xut hin ca pic c cng thp vi mc
nng lng ti 291,5 eV. Theo chng ti c hai gi thuyt ca s tn ti pic ny: gi
thuyt 1 pic 291,5 eV c trng lin kt -* ca vt liu rGO, GO iu ny l do
NaBH4 ngoi nhim v kh Fe3+ v Feo th NaBH4 cn l tc nhn kh GO v rGO
[3, 8] do vy trong qu trnh tng hp Fe-Fe3O4-GOVS c th mt phn nh GOVS
b kh v rGO, v vy tn ti pic 291,5 eV c trng cho lin kt -* [7, 117].
96
(a) (b) Fe 2p1/2 725 eV Fe2p3/2 711 eV
3+
Fe 733eV
Fe3 O4 -GOVS
Fe-Fe3 O4 -GOVS Fe3+ 719 eV
(a.u)
Cng (a.u)
(a.u)
(a.u)
Na1s
Intensity
Intensyty
Fe2p
Fe3 O4 -GOVS
O1s
Cng
C1s
Fe-Fe3 O4 -GOVS Fe0 706 eV
1300 1100 900 700 500 300 100 740 735 730 725 720 715 710 705 700
Binding
Nng Energy
lng lin (E)
kt (eV) Binding
Nng lngEnergy
lin kt(eV)
(eV)
(c) Fe-O 529.9 eV

(d) C-C 284.8 eV
(a.u)(a.u)
(a.u)(a.u)
Intensity
C-O 535 eV C=O 531.5 eV
Intensity
-C=O 288.3 eV
Cng
Cng
C-O 285.5 eV
291.5 ev
540 538 536 534 532 530 528 526

296 294 292 290 288 286 284 282 280
Binding
Nng lngEnergy (eV)
lin kt (eV)
Binding Energy
Nng lng (eV)
lin kt (eV)
Hnh 3.30. Ph XPS ca Fe-Fe3O4-GOVS (a-d) v Fe3O4-GOVS (a)
Gi thuyt 2, pic 291,5 eV c trng cho trng thi lin kt gia cp electron
v l trng tn ti trong cu trc GO v rGO [118].
Ph XPS O1s (Hnh 3.31c) cng cho thy s xut hin ca cc lin kt Fe-O,
C=O, C-O vi mc nng lng tng ng l 529,9 eV, 531 eV v 534 eV [59]. T
Hnh 3.30b cho thy vi Fe3O4-GOVS ch tn ti cc pic vi mc nng lng 711
eV v 725 eV tng ng vi Fe2p3/2 v Fe2p1/2 m khng thy xut hin cc pic vi
mc nng lng 710 eV, 719 eV v 724 eV c trng cho cu trc ca -Fe2O3 [91,
104]. i vi mu Fe-Fe3O4-GOVS ngoi pic 711 eV v 725 eV c trng cho
Fe3O4-GOVS cn xut hin mt pic cng nh 719 eV v 733 eV, y c th
l do c s tng tc gia Feo v Fe3O4-GOVS to thnh pha Fe2O3, FeOOH [119,
120]. Ngoi ra, Hnh 3.30b cng nhn thy s tn ti pic vi mc nng lng 706
eV c trng cho s c mt ca cc ht nano Feo vi kch thc nh < 10 nm [111]
ln trn b mt vt liu tng hp c v khng c s kt tp li thnh di di ging
nh trong qu trnh tng hp Feo trong iu kin vng mt Fe3O4 [114]. Kt qu ny
97
khng nh s tng tc in t gia Feo, Fe3O4 v GOVS lm thay i cu trc
in t ca cu t hp phn vt liu composit.
3.5.7. T tnh ca vt liu Fe-Fe3O4-GOVS v Fe3O4-GOVS

Tin hnh kho st t tnh ca cc mu bng phng php VSM, ta c cc
ng cong t ha nh Hnh 3.31.
40
Fe3O4-GOVS
Fe-Fe3O4-GO
30
Fe3O4-GO
(emu/g)
20 Fe-Fe3O4-GOVS
Lc khng t (emu/g)
10
Magnetization
0
--10000 -5000 0 5000 10000
-10
-20
-30
-40
Applied
Tmagnetic field (Oc)
trng (Oe)
Hnh 3.31. ng cong t ha ca Fe-Fe3O4-GOVS v Fe3O4-GOVS
Theo th Hnh 3.31 cho thy lc khng t ca c hai mu gn nh bng

khng. T bo ha ca mu Fe3O4-GOVS v Fe-Fe3O4-GOVS c gi tr tng
ng bng 35 emu/g v 29 emu/g. iu ny cho thy cc mu nano composit u
mang tnh siu thun t (kch thc ht nh < 30 nm), vi lc khng t gn nh
bng khng v gi tr t bo ha cao, do vy c th d dng tch chng ra khi
nc x l nh s tr gip ca t trng bn ngoi [44]. Theo mt s ti liu [121,
122] cho thy kch thc ht nano Fe3O4 dng khi t 10 - 18 nm th t bo ha
ca mu thay i t 46,7 - 82,5 emu/g. Thy rng kch thc ht nano Fe3O4 trn
GOVS nm trong khong 15 nm tuy nhin t bo ha ch t 35 emu/g nh hn
so vi Fe3O4 dng khi. Nguyn nhn ca s gim t tnh v thay i kch thc ht
c th c l gii theo m hnh li v trong ht nano t do Kodama v Berkowitz
xut [123]. Cc spin sp xp hn lon trn b mt ht nano t, gy nn tng tc
trao i gia b mt v li lm cho phn b spin bn trong ht c kch thc n
men tr nn phc tp. Mmen t nguyn t b mt c ng gp khng ng k
vo mmen t chung ca ht. Gi lp b mt ln xn ny l lp v c b dy l d.
Do c nh hng ca lp v ny nn mmen t ca ht nano thp hn mmen t
98
ca vt liu khi. S ph thuc ca mmen t bo ha Ms vo gi tr ca lp v
c tc gi A. Millan v cng s th hin bng cng thc s 2 trong nghin cu
ca mnh [124]:
( D / 2) d 3
MS MS0( ) (3.1)
D/2
Trong :
D: ng knh ca ht nano
MS0: mmen t bo ha ca vt liu khi
d: dy ca lp v
Nu kch thc ht D ln hn rt nhiu so vi d th mmen t s khng b nh

hng. Ngc li, nu kch thc ht D nh (c nm), mc d d nh nhng c th
c so snh vi D do mmen t s b nh hng. Theo m hnh li - v trong
trng hp ca hai vt liu Fe3O4-GOVS v Fe- Fe3O4-GOVS u hnh thnh lp
v GO dy hn lp v trong ht Fe3O4 (dGOVS > dFe3O4) v vy t bo ha ca
Fe3O4 ln hn nhiu gi tr ca mu Fe3O4-GOVS. Tuy nhin qu trnh a thm
Feo ln b mt Fe3O4-GOVS lm bo ha t gim i, iu ny c th l do
NaBH4 l cht kh mnh to ra mt s lng pha tp khng mong mun, nhng
lng pha tp ny nh v khng pht hin c trn gin nhiu x tia X (XRD).
3.6. anh gia kh nng hp ph ca GOSA, GOVS v rGO
Trong phn tip theo ca lun n chng ti nh gi kh nng hp ph thuc

nhum hot tnh RR195 i vi GOSA, GOVS v rGO, cn i vi Fe3O4-GOVS
v Fe-Fe3O4-GOVS chng ti nh gi s b kh nng hp ph RR195 v tp trung
nghin cu, nh gi kh nng hp ph ca chng i vi mt s ion kim loi nng
in hnh nh Cu(II), Cd(II) v As(V).
3.6.1. Kha nng hp ph thuc nhum hot tnh RR195 ca GOVS, GOSA v rGO
3.6.1.1. nh hng ca pH
nh hng pH n dung lng hp ph RR195 ca cc vt liu c th hin

qua Bng 3.10 v Hnh 3.32. T kt qu trong Bng 3.10 v th Hnh 3.32 cho
thy pH c nh hng n kh nng hp ph RR195 ca rGO v GO. Tuy nhin nh
99
hng ca pH i vi rGO khng qu nhiu, iu ny l do b mt ca rGO b kh
lng ln cc nhm chc cha oxy do vy s hp ph RR195 ch yu xy ra do cc
lin kt mnh ca nhn thm trong cu trc RR195 vi lin kt - ca rGO [10, 62].
Bang 3.10. S ph thuc dung lng hp ph RR195 trn vt liu rGO v GO

vo pH (nng 100 mg/L, thi gian hp ph 10 h)
pH rGO GOVS GOSA
4 85,68 70,12 45,30
5,5 84,67 68,71 32,65
6,5 78,71 64,71 25,10
8 78,35 58,71 22,22
10 81,35 53,35 15,11
90
80
Hiu sut loi b(%)
70
60
50
40
rGO GOVS GOSA
30
20
10
0
4 5 6 7 8 9 10
Gia tr pH
Hnh 3.32. nh hng pH n qu trnh hp ph RR195 trn GO v rGO
C th, trong khong pH t 4 n 10 hiu sut hp ph ca rGO gim khong

7% ti nng 100 mg/L. i vi GOVS v GOSA pH nh hng ln n kh
nng hp ph RR195, pH cng cao dung lng hp ph cng gim, iu ny l do
pH cng ln th b mt GOSA v GOVS cng m [5], do vy lm tng lc y i
vi cc anion m RR195 v vy hiu sut hp ph gim mnh. Thy rng dung
lng hp ph RR195 pH = 4 l cao nht iu ny l do pHpzc ca GO c gi tr
3,9 [5], tuy vy chng ti vn tin hnh chn pH = 5,5 l v khi pH qu thp (pH <
5) th s lm gim kh nng ng dng vo thc tin v cc my mc thit b s d
dng b n mn trong iu kin pH qu thp, hn na s gim hiu sut hp ph
RR195 ca cc vt liu GOVS v rGO ti pH = 5,5 so vi pH = 4 l ch ~ 1 - 2%.
100
3.6.1.2. nh gi kh nng hp ph RR195 trn GOVS, GOSA v rGO
nghin cu ng hc qu trnh hp ph RR195 trn GO v rGO. iu kin

thc nghim c p dng nhit (30 oC) vi cc nng RR195 khc nhau:
100 mg/L n 500 mg/L, ti pH = 5,5; tc khuy 150 v/p.
160 300
140
250
120 a b
200
100
Qe (mg/g)
Qt (mg/g)
80 150 rGO GOSA GOVS

GOVS rGO GOSA
60
100
40
50
20
0 0
0 4 8 12 16 20 24 0 100 200 300 400 500
Thi gian (gi) Ce (mg/L)
Hnh 3.33. S ph thuc dung lng hp ph RR195 (200 mg/L) theo thi gian (a)
v ng ng nhit hp ph Langmuir ca RR195 trn GO v rGO (b)
Quan st Hnh 3.33a cho thy kh nng hp ph cc anion RR195 trn ba

vt liu hp ph c chiu hng gim dn t rGO > GOVS > GOSA. i vi
rGO qu trnh hp ph din ra nhanh trong khong thi gian u (t 0 2 gi),
vi GOVS qu trnh hp ph din ra chm hn rGO. i vi GOSA kh nng
hp ph thp hn nhiu so vi rGO v GOVS cng nng (200 mg/L), qu
trnh hp ph din ra chm. Gii thch cho iu ny l do i vi rGO, b mt
tn ti t nhm chc tch in m nn hiu ng y vi anion RR195 gim, ngoi
ra qu trnh kh nhit lm tng cc lin kt - ca sp2C v sp3C [85, 97] cc
lin kt ny c i lc ln i vi cc nhn thm trong thuc nhum hot tnh
RR195 [10, 28] do vy tc hp ph din ra nhanh v dung lng hp ph
cng cao nht. Vi GOVS mc d qu trnh vi sng kh nhanh mt s nhm
chc trn b mt tuy nhin b mt ca GOVS vn tch in m (th zeta phn
ph lc) do vy xy ra hiu ng y i vi cc anion m RR195, lm gim tc
khuch tn ca anion RR195 n cc tm hp ph trn b mt GOVS. Quan
st Hnh 3.33a thy rng dung lng hp ph ca GOVS thp hn khng nhiu
so vi rGO (thp hn 20 mg/g ti thi im cn bng), iu ny c th l do qu
trnh bc tch lp graphit oxit bng k thut vi sng lm gia tng cc tm GO v
101
lm tng din tch b mt do vy cc anion RR195 vn c th xm nhp d dng
vo khong cch gia cc tm cng nh lm tng s tip xc cc tm hp ph
trn GOVS vi anion RR195 hn so vi GOSA. i vi GOSA b mt m hn
so vi GOVS, din tch b mt cng thp hn nhiu (56 m2/g) so vi GOVS v
rGO (300 m2/g; 331 m2/g) do vy ngn cn s tip xc cc tm hp ph i vi
RR195 do vy dung lng hp ph ca GOSA thp hn nhiu so vi rGO v
GOVS ti cng nng 200 mg/L. Ti thi im cn bng dung lng hp ph
thp hn 110 mg/g so vi rGO v 90 mg/g so vi GOVS.
Da vo ng hp ph trn, c th kt lun khong thi gian ti u ca qu

trnh hp ph bng rGO v GOVS l t 0 - 6 gi vi GOSA l t 0 - 8 gi, thi
gian qu trnh hp ph t cn bng l khong 8 gi. Phn tch cc d liu thu
c t ng ng nhit hp ph (Hnh 3.33b) ri thay vo cc m hnh ng
ng nhit khc nhau tm ra m hnh hp ph ph hp cho vt liu rGO v GO
tng hp c.
3.6.1.3. Nghin cu ng nhit hp ph
Qu trnh hp ph tin hnh pH = 5,5 vi cc nng RR195 ban u khc

nhau, phn tch hi quy Ce/Qe v Ce i vi m hnh Langmuir v hi quy LnQe v
LnCe i vi m hnh Freundlich. Nng cht hp ph trng thi cn bng c
tnh ton da trn cc ng ng nhit hp ph cc nng khc nhau.
M hnh Langmuir
Bang 3.11. S ph thuc dung lng hp ph vo nng i vi RR195
Co Ce GOVS Ce - GOSA Ce rGO

M (g) V (L)
(mg/L) (mg/L) (mg/L) (mg/L)
100 31,29 69,35 15,32 0,80 1,0
200 88,66 159,55 71,87 0,80 1,0
300 166,89 257,34 138,31 0,80 1,0
400 253,77 350,82 215,69 0,80 1,0
500 340,98 451,68 311,30 0,80 1,0
102
8
7 rGO GOSA GOVS

6
Ce/Qe (g/L)
5 GOSA (R = 0,997)
4
3
GOVS (R = 0,999)
2
1
rGO (R = 0,994)
0
0 100 200 300 400 500
Ce (mg/L)
Hnh 3.34. ng hp ph ng nhit Langmuir ca RR195 trn GO v rGO

Qua th Hnh 3.34 cho thy m hnh hp ph ng nhit Langmuir m t
tng i chnh xc s hp ph RR195 trn vt liu hp ph GOVS, GOSA v rGO,
thng qua h s tng quan ca hai i lng Ce/Qe v Ce l R2 = 0,999; 0,997 v
0,994. T phn tch hi quy ta tnh c cc h s ca phng trnh Langmuir nh sau:
Ce
0, 0047Ce 0, 2475 (GOVS) (3.2)
Qe
Ce
0, 0150Ce 0,8492 (GOSA) (3.3)
Qe
Ce
0, 0040Ce 0,1286 (rGO) (3.4)
Qe
T cc phng trnh trn ta tnh c dung lng hp ph cc i Qmax ln
lt ca cc vt liu GOVS, GOSA v rGO, tnh ton c hng s ca m hnh
Langmuir l KL = 0,017 - 0,031 (L/mg) (Bng 3.12), ngoi ra ta thy dung lng
hp ph RR195 ca vt liu GOVS, GOSA v rGO tng i cao.
Bang 3.12. Cc thng s ng nhit hp ph Langmuir v Freundlich ca GO v
rGO ca RR195
ng nhit GOSA GOVS rGO
Langmuir
Qmax (mg/g) 66,67 212,7 250
KL (L/mg) 0,017 0,019 0,031
R2 0,994 0,999 0,997
RL 0,105 0,095 0,061
Freundlich
1/n 0,251 0,346 0,279
KF [(mg/g)(L/mg)1/n] 14,39 27,29 49,48
R2 0,856 0,976 0,989
103
xc nh qu trnh hp ph RR195 bng GO v rGO c ph hp vi dng
hp ph n lp theo m t ca m hnh Langmuir hay khng, chng ti nh gi
mc ph hp thng qua tham s cn bng RL. Tham s RL c tnh theo nng
u (Co) nh sau [125]:
1
RL (3.5)
1 K LCo
Da vo tham s RL theo Bng 3.13 nh gi mc ph hp ca m hnh

hp ph Langmuir i vi GO v rGO.
Bang 3.13. Phn loi s ph hp ca m hnh ng nhit bng tham s RL [125]

Gi tr RL Dng m hnh ng nhit
RL > 1 Khng ph hp
RL = 1 Tuyn tnh
0 < RL < 1 Ph hp
RL= 0 Khng thun nghch
Bang 3.14. Gi tr tham s cn bng RL ca qu trnh hp ph RR195

bng rGO v GO
Co (mg/L) 100 200 300 400 500

RL - GOVS 0,344 0,208 0,149 0,116 0,095
RL - GOSA 0,370 0,227 0,164 0,128 0,105
RL - rGO 0,244 0,139 0,097 0,074 0,061
0,4
0,35
0,3 GOVS
0,25 GOSA
rGO
RL
0,2
0,15
0,1
0,05
0
100 200 300 400 500
Co (mg/L)
Hnh 3.35. Gi tr RL ph thuc vo nng RR195 ban u
104
T gi tr tham s RL tnh ton c trnh by trong Bng 3.14 v th Hnh
3.35, cho thy gi tr ny trong khong t 0,074 0,344 u nh hn 1 nn c th
xc nh c m hnh hp ph ng nhit Langmuir l ph hp vi qu trnh hp
ph RR195 bng GO v rGO.
M hnh Freundlich
Bang 3.15. S ph thuc LnQe vo LnCe i vi m hnh Freundlich ca RR195
Co GOSA GOVS rGO
(mg/L)
LnQe LnCe LnQe LnCe LnQe LnCe
100 3,645 4,239 4,453 3,443 4,661 2,729
200 3,923 5,072 4,935 4,484 5,076 4,274
300 3,976 5,550 5,114 5,117 5,308 4,929
400 4,118 5,860 5,208 5,536 5,439 5,373
500 4,121 6,112 5,292 5,832 5,462 5,741
5,5 rGO (R = 0,989)
rGO GOSA GOVS

5
GOVS (R = 0,976)
Ln Qe
4,5
GOSA (R = 0,856)
4
3,5
2,5 3 3,5 4 4,5 5 5,5 6
Ln Ce
Hnh 3.36. ng hp ph ng nhit Freundlich ca RR195 trn GO v rGO

Bng 3.15 v th Hnh 3.36 m t qu trnh hp ph RR195 trn vt liu
hp ph theo m hnh ng nhit Freundlich. Cc h s ca phng trnh
Freundlich thu c t qu trnh hi quy LnQe theo LnCe nh sau:
LnQe = 0,346 LnCe + 3,307 (GOVS) (3.6)
LnQe = 0,237 LnCe + 2,667 (GOSA) (3.7)
LnQe = 0,279 LnCe + 3,902 (rGO) (3.8)
T cc phng trnh trn ta tnh c hng s hp ph Freundlich KF = 14,39
49,48 [(mg/g)(L/mg)1/n] v gi tr hng s 1/n = 0,251 - 0,346. H s tng quan
ca LnQe v LnCe l R2 ~ 0,86 - 0,98.
105
T kt qu trong Bng 3.12 cho thy h s xc nh R2 ca m hnh Langmuir
tin gn n 1 hn so vi m hnh Freundlich. Nh vy, c th xc nh qu trnh
hp ph RR195 bng vt liu hp ph rGO v GO tun theo m hnh ng nhit
Langmuir. Dung lng hp ph Qmax RR195 i vi rGO cao nht (250 mg/g) do
qu trnh kh lm mt i cc nhm chc tch in m trn b mt v vy gim hiu
ng y v tng i lc gia cc lin kt - i vi cc nhn thm trong cu trc
RR195 [10, 62]. Dung lng hp ph Qmax RR195 ca GOVS > GOSA. Gii thch
iu ny theo chng ti l do GOVS tch bc bng vi sng to sung n hiu qu
hn nhiu so vi phng php siu m, iu ny c minh chng qua kt qu o
BET ca vt liu (b mt ca GOVS l 331 m2/g ln gp 6 ln so vi GOSA l 56
m2/g). T nhng phn tch trn c ch hp ph da trn tng tc - theo mt s
tc gi [10, 45, 62, 126] c trnh by Hnh 3.37.
Hnh 3.37. C ch hp ph RR195 ln trn vt liu hp ph rGO
3.6.2. ng hoc qua trnh hp ph RR195 trn GOVS v rGO

T Bng 3.12 cho thy dung lng hp ph Qmax anion m RR195 ca GOVS
v rGO u cao gp 3,3 3,7 ln so vi GOSA. V vy, trong lun n ny ch
nghin cu ng hc ca qu trnh hp ph RR195 trn 02 loi vt liu l GOVS v
rGO nhm xc nh qu trnh hp ph ny tun theo dng phng trnh ng hc
biu kin bc 1 hay bc 2.
Phng trnh ng hc bc 1
Cc gi tr Ln(Qe-Qt) ca cc mu theo thi gian c trnh by trong Bng 3.16.
106
Bang 3.16. Gi tr Ln(Qe-Qt) theo thi gian ca qu trnh hp ph RR195
Ln(Qe-Qt)
Cht hp t (gi) (ti nng RR195= 200 mg/L)
ph 0 0,5 1 2 4 6 8
GOVS 5,29 4,48 4,24 3,99 3,55 2,79 2,71
rGO 5,29 - 3,43 2,84 2,29 1,15 0,93
5
GOVS R = 0,966
GOVS rGO
4
Ln (Qe-Qt)
rGO R = 0,962
2
0
0 2 4 6 8
Thi gian (gi)
Hnh 3.38. Mi quan h Ln(Qe-Qt) theo thi gian (ng hc biu kin bc1) ca
qu trnh hp ph RR195 trn GOVS v rGO
T gi tr cc tham s ca phng trnh ng hc bc 1 trong Bng 3.16 v
th Hnh 3.38 cho thy h s xc nh R2 trong khong 0,96. Bn cnh , gi tr
dung lng hp ph cn bng tnh ton c t cc phng trnh ng hc u
khc bit so vi gi tr thc nghim (Bng 3.18). Vy phng trnh ng hc bc 1
khng ph hp vi qu trnh hp RR195 trn GOVS v rGO.
Phng trnh ng hc bc 2
T cc gi tr thc nghim, tin hnh hi quy tuyn tnh cc gi tr t/Qt vi t
theo phng trnh (chng 2) thu c gi tr cc tham s ca phng trnh ng
hc bc 2 nh trong Bng 3.17.
th Hnh 3.39 cho thy h s xc nh R2 u t 0,99. Bn cnh , gi tr dung
lng hp ph cn bng tnh ton c t cc phng trnh ng hc u rt gn so
vi gi tr thc nghim ng thi gi tr k2 cng thay i t hn (Bng 3.19). V vy
c th kt lun phng trnh ng hc biu kin bc 2 ph hp vi qu trnh hp
ph RR195 bng rGO v GOVS.
107
Bang 3.17. Gi tr t/Qt theo thi gian ca qu trnh hp ph RR195
t/Qt x 10-3
Cht hp t (gi) (ti nng RR195 = 200 mg/L)
ph 0 1 2 4 6 8 10
GOVS 0 9,78 14,17 23,29 38,05 48,54 63,98
rGO 0 - 7,74 13,98 26,62 38,21 50,75
0,07
0,06 GOVS rGO
0,05
0,04
t/Qt
0,03
0,02 rGO R = 0,999
0,01 GOVS R = 0,994
0
0 2 4 6 8
Thi gian (gi)
Hnh 3.39. Mi quan h t/Qt theo thi gian (ng hc biu kin bc 2) ca qu
trnh hp ph RR195 trn GOVS v rGO
Mt s thng s ca phng trnh ng hc biu kin bc 1 v bc 2 c cho
Bng 3.18 v 3.19.
Bang 3.18. Mt s tham s ca phng trnh ng hc biu kin bc nht (RR195)
Dng phng trnh k1 Qe, exp Qe, cal
Vt liu R12
ng hc (h-1) (mg/g) (mg/g)
GOVS Ln(Qe-Qt) = 4,514 - 0,247.t 0,966 0,247 140,01 90,03
rGO Ln(Qe-Qt) = 3,678 - 0,368.t 0,962 0,368 160,16 39,12
Bang 3.19. Mt s tham s ca phng trnh ng hc biu kin bc hai (RR195)
Dng phng trnh ng Qe, exp Qe, cal

Vt liu R22 k2(g/mg.h)
hc (mg/g) (mg/g)
t
GOVS = 0,0077 + 0,0071.t 0,999 0,0065 140,01 140,84
Qt
t
rGO = 0,0018 + 0,0061.t 0,994 0,0206 160,16 163,93
Qt
Qe, cal: gi tr dung lng hp ph cn bng tnh ton theo phng trnh ng hc
Qe, exp: gi tr dung lng hp ph cn bng theo thc nghim
108
Quan st Bng 3.19 cho thy tc hp ph RR195 nng 200 mg/L trn
rGO (0,0206 g/mg.h) cao gp 3 ln so vi trn GOVS (0,0065 g/mg.h). iu ny
ph hp vi nhng phn tch trn, b mt rGO b kh lng ln cc nhm
chc tch in m, nn gim hn hiu ng y gia b mt m v cc anion m
RR195, cc nhn thm d dng to thnh cc i lc mnh i vi cc lin kt -
ca sp2C v sp3C do tc hp ph cao hn nhiu so vi GOVS [10, 62].
Di y l Bng 3.20, 3.21 v 3.22 tng hp cc kt qu c trng ca GO
v rGO cng nh nh gi kh nng hp ph, ng hc qu trnh hp ph bc 2 ca
thuc nhum hot tnh RR195 trn vt liu GOVS, GOSA v rGO tng hp c.
Bang 3.20. Tng kt cc thng s c trng ca GO v rGO
XPS
XRD BET Vmao qun HR-TEM FTIR
Mu (t l
2 (m2/g) (cm3/g) (s lp ) (cc nhm chc)
C/O)
C=O, C-O, C=C, -
GOSA 11,2 56 0,283 >10 lp 2,32
OH (cng cao)
C=O, C-O, C=C, -
GOVS 11,5 331 1,719 7-8 lp 2,98
OH (cng thp hn)
Hu nh khng tn ti
rGO 25,8 300 1,596 5-6 lp cc nhm chc
10,89
Bang 3.21. Tng kt ng nhit Langmuir v Freundlich ca qu trnh hp ph

RR195 trn GO v rGO
Cht hp Langmuir Freundlich
ph Qmax KL R2 KF 1/n R2
GOVS 212,7 0,019 0,999 27,29 0,346 0,976
GOSA 66,67 0,017 0,994 14,39 0,251 0,856
rGO 250 0,031 0,997 49,48 0,279 0,989
Bang 3.22. Cc tham s ca phng trnh ng hc biu kin bc hai qu trnh

hp ph RR195 trn GOVS, GOSA v rGO
Phng trnh
Thng s GOVS GOSA rGO
ng hc
Qe, cal 140,84 - 163,93
Bc 2 - RR195
(200 mg/L) k2 (mg/g. h) 0,0065 - 0,0206
R2 0,999 - 0,994
109
3.7. anh gia kh nng hp ph ca Fe3O4-GOVS v Fe-Fe3O4-GOVS
3.7.1. anh gia kha nng hp ph RR195 ca Fe3O4-GOVS v Fe-Fe3O4-GOVS

nh gi kh nng hp ph RR195 ca Fe3O4-GOVS v Fe-Fe3O4-GOVS
chng ti tin hnh so snh kh nng hp ph ca chng i vi GOVS, GOSA,
rGO trong cng iu kin pH, nhit 30 oC, m/V = 1 g/L, nng u RR195 =
100 mg/L kt qu a ra trn Hnh 3.40.
100
90
Hiu sut hp ph (%)
80
70
60
50
40
30
20
10
0
GOSA GOVS rGO Fe3O4-GOVS Fe- Fe3O4-GOVS
Hnh 3.40. Hiu sut hp ph RR195 trn cc vt liu hp ph khc nhau

T Hnh 3.40 cho thy kh nng hp ph gim dn theo chiu rGO > GOVS >
Fe-Fe3O4-GOVS > Fe3O4-GOVS > GOSA. i vi Fe-Fe3O4-GOVS, Fe3O4-GOVS
kh nng hp ph RR195 thp hn so vi rGO v GOVS iu ny c th l do kh
nng hp ph thuc nhum cao trn GO ch yu l do din tch b mt ln v tng tc
- vi nhn thm trong cu trc RR195. Khi a Fe-Fe3O4 v Fe3O4 ln GOVS, din
tch b mt gim cng vi cc ht nano ny chim gi ti cc v tr c tm hp ph
cht mu, thuc nhum hot tnh [58, 115] do lm gim kh nng hp ph RR195
ca hai vt liu ny. i vi GOSA dung lng hp ph thp nht l do din tch b
mt thp v b mt cha nhiu nhm chc mang in m xy ra hiu ng y i vi
anion RR195. Ngoi ra, Mingce Long [49] v cng s cho thy kh nng hp ph
Rodamin B (RhB) thp i vi vt liu Fe3O4/rGO dung lng hp ph t 66,67
mg/g. Tc gi H Th Tuyt Trinh [100] vi vt liu rGO/Fe3O4 dung lng hp ph
cc i RhB ch t 38,8 mg/g. Tc gi Chun Wang [58] vi vt liu Fe3O4 trn rGO
dung lng hp ph cc i xanh methylen t 84,9 mg/g. Nh vy c th nhn thy
ng dng hp ph mu ca cc vt liu Fe3O4 trn cht mang GO v rGO l cha cao.
Do vy phn tip theo ca lun n tp trung s dng vt liu Fe-Fe3O4-GOVS, Fe3O4-
GOVS ng dng hp ph cc ion kim loi nng Cu(II), Cd(II) v As(V).
110
3.7.2. Hp ph ion kim loi nng Cu(II) v Cd(II)
3.7.2.1. im ng in ca Fe3O4-GOVS v Fe-Fe3O4-GOVS
Trong phn ny lun n khng nghin cu nh hng pH ca tng qu trnh
hp ph m da vo phn tch im ng in (pHpzc) ca hai vt liu tm ra pH
thun li cho qu trnh hp ph xy ra.
5 5
4 4
pH= (pH u- pH cui)

a
pH= (pH u- pH cui)
3 3 b
2 2
1
1
0
0
2 3 4 5 6 7 8 9 10 11 12 2 3 4 5 6 7 8 9 10 11 12
-1
-1
pH ban u
-2
-2 pH ban u
Hnh 3.41. im ng in (pHpzc) ca Fe3O4-GOVS (a) v Fe-Fe3O4-GOVS (b)

Hnh 3.41a cho thy im ng in (pHpzc) Fe3O4-GOVS c gi tr ~ 5,2. Qu
trnh a thm Feo vi hm lng theo tnh ton 10% lm tng gi tr pHpzc ln ~
5,4 (Hnh 3.41b). Chng ta bit rng cc ion kim loi nng (M) nh Cu(II) v Cd(II)
tn ti trong nc di dng M2+, -M(OH)+, -M(OH)2o, M(OH)3-,... ty thuc vo
pH ca dung dch [5]. i vi Cd(II) logK1 = 3,9; logK2= 7,7; logK3= 8,7 [5], do
vy khi pH < 8 ch yu xy ra qu trnh hp ph cc ion kim loi ln b mt cht
hp ph. i vi Cu(II) th khi pH > 6,1 ngoi cc ion Cu2+, cn xut hin thm
Cu(OH)+, Cu2(OH)22+, Cu3(OH)42+ [127]. Qu trnh hp ph Cu(II) v Cd(II) b chi
phi bi lc ht tnh in v tng tc ca cation kim loi vi cc nhm chc trn
b mt Fe3O4-GOVS v Fe-Fe3O4-GOVS khi pH < pHpzc b mt ca hai vt liu
mang tch in dng do vy kh nng hp ph Cu(II) v Cd(II) gim, khi pH >
pHpzc th b mt Fe3O4-GOVS v Fe-Fe3O4-GOVS mang in tch m do vy lm
cho qu trnh hp ph tng ln. Ngoi ra nu pH qu thp (mi trng axit mnh)
hoc cao (mi trng kim cao) th cation b y ra do i lc ca n yu hn so vi
proton (H+) hay hydroxyl (OH-) [128]. i vi Cu2+, khi pH = 8 bt u xut hin
kt ta Cu(OH)2 khi pH tng ln 10 ch yu xy ra qu trnh kt ta Cu(OH)2 v
Cu(OH)3-. Mt khc, trong lun n ca tc gi Bi Minh Qu [128] cho thy rng
kh nng hp ph Cd(II) trn cc compozit (polyme dn PANi v ph thi) tt nht
trong mi trng axit yu (pH = 6). T nhng phn tch trn, pH = 6 c la chn
p dng trong thc nghim.
111
3.7.2.2. Nghin cu ng nhit hp ph Cu(II), Cd(II) trn GOVS v Fe3O4-GOVS
Qu trnh hp ph tin hnh pH = 6 vi cc nng Cu(II), Cd(II) ban u
khc nhau, phn tch hi quy Ce/Qe v Ce i vi m hnh Langmuir v hi quy
LnQe v LnCe i vi m hnh Freundlich.
M hnh hp ph Langmuir
Bang 3.23. Kh nng hp ph ca cc mu kho st nng khc nhau
Ce- Ce- Ce-Fe3O4- Ce-Fe3O4-
Co M V
GOVS/Cd GOVS/Cu GOVS /Cd GOVS/Cu
(mg/L) (g) (L)
(mg/L) (mg/L) (mg/L) (mg/L)
10 1,080 3,379 0,201 0,069 0,1 0,1
20 4,364 8,103 0,503 2,983 0,1 0,1
30 9,351 15,230 0,8091 6,207 0,1 0,1
40 15,973 22,870 2,364 12,586 0,1 0,1
50 25,046 32,014 5,509 21,724 0,1 0,1
Phn tch cc s liu trong Bng 3.23 chng ta thu c ng ng nhit

hp ph v ng ng nhit hp ph Langmuir c trnh by trn Hnh 3.42.
2
(a) Langmuir GOVS/ Cu (II) R = 0,998

0,16
(b)
1,6
0,12
Ce/Qe (mg/g)
Ce/Qe (mg/g)
Fe3O4-GOVS/ Cd (II) R = 0,998

1,2
0,08
GOVS/ Cd (II) R = 0,997
0,8
0,04
0,4
Fe3 O4 -GOVS- Cu (II) R = 0,992
0
0 0 1 2 3 4 5 6
0 5 10 15 20 25 30 35
Ce (mg/L)
Ce (mg/L)
30
(c) Fe3 O4 -GOVS/ Cu (II)
GOVS/ Cd (II)
25
20 GOVS/ Cu (II)
Qe (mg/g)
15
50
40
Qe (mg/g)
10 30
20
Fe3 O4 -GOVS/ Cd (II)
10
5 0
0 1 2 3 4 5 6
Ce (mg/L)
0
0 5 10 15 20 25 30 35
Ce (mg/L)
Hnh 3.42. ng ng nhit hp ph Cu(II), Cd(II) (a), ng nhit Langmuir

ca Fe3O4-GOVS v GOVS (b, c)
112
Qua th Hnh 3.42a,b cho thy m hnh hp ph ng nhit Langmuir m t
tng i chnh xc s hp ph Cd(II), Cu(II) trn vt liu hp ph GOVS, Fe3O4-
GOVS thng qua h s tng quan ca hai i lng Ce/Qe v Ce l R2 = 0,997;
0,998; 0,998 v 0,992. T phn tch hi quy Hnh 3.42c ta tnh c cc h s ca
phng trnh Langmuir nh sau:
Ce
0, 036Ce 0,103 (GOVS Cd(II)) (3.9)
Qe
Ce
0, 044Ce 0,342 (GOVS-Cu(II)) (3.10)
Qe
Ce
0, 019Ce 0, 015 (Fe3O4-GOVS-Cd(II)) (3.11)
Qe
Ce
0, 033Ce 0, 040 (Fe3O4-GOVS -Cu (II)) (3.12)
Qe
M hnh Freundlich
Bng 3.24 v th Hnh 3.43 m t qu trnh hp ph Cd(II) v Cu(II) trn
vt liu GOVS v Fe3O4-GOVS theo m hnh ng nhit Freundlich.
Bang 3.24. S ph thuc LnQe vo LnCe i vi m hnh Freundlich
Fe3O4- Fe3O4-
Co GOVS/Cd(II) GOVS/Cu(II)
GOVS/Cd(II) GOVS/Cu(II)
(mg/L)
LnCe LnQe LnCe LnQe LnCe LnQe LnCe LnQe
10 0,076 2,188 1,217 1,890 -1,609 2,282 -2,673 2,295
20 1,473 2,749 2,092 2,476 -0,693 2,970 1,092 2,834
30 2,235 3,027 2,723 2,692 -0,211 3,373 1,825 3,169
40 2,770 3,179 3,129 2,840 0,860 3,627 2,532 3,311
50 3,221 3,216 3,466 2,889 1,706 3,795 3,078 3,342
5
3
Ln Qe
2 R = 0,978
GOVS- Cd (II)
GOVS - Cu (II) R = 0,955
1 Fe3O4-GOVS - Cd (II) R = 0,899
Fe3O4-GOVS -Cu (II) R = 0,963
0
-2 -1 0 Ln Ce 1 2 3 4
Hnh 3.43. ng hp ph ng nhit Freundlich ca Cd(II) v Cu(II) trn

GOVS v Fe3O4-GOVS
113
Cc h s ca phng trnh Freundlich thu c t qu trnh hi quy LnQe
theo LnCe nh sau:
LnQe = 0,339 LnCe + 2,208 (GOVS/Cd(II)) (3.13)
LnQe = 0,444 LnCe + 1,434 (GOVS/Cu(II)) (3.14)
LnQe = 0,440 LnCe + 3,205 (Fe3O4-GOVS/Cd(II)) (3.15)
LnQe = 0,188 LnCe + 2,769 (Fe-Fe3O4-GOVS/Cu(II)) (3.16)
T cc phng trnh trn ta tnh ton c cc tham s trong phng trnh
Langmuir v Frenudlich, cc tham s c trnh by trong Bng 3.25.
Bang 3.25. Cc thng s ng nhit hp ph Langmuir v Freundlich ca
GOVS v Fe3O4-GOVS
Vt liu, pH=6
ng nhit
Fe3O4-GOVS GOVS Fe3O4-GOVS GOVS
Hp ph Hp ph Hp ph Hp ph
Langmuir
Cd(II) Cd(II) Cu(II) Cu(II)
Qmax (mg/g) 52,63 29,41 30,3 22,73
KL (l/mg) 1,27 0,28 0,83 0,13
R2 0,998 0,998 0,992 0,998
RL 0,15 0,067 0,24 0,13
Freundlich
1/n 0,440 0,339 0,188 0,444
KF[(mg/g)(L/mg)1/n] 21,33 9,09 15,92 4,12
R2 0,899 0,978 0,963 0,955
Cc thng s ghi trong Bng 3.25 cho thy qu trnh hp ph cc ion kim loi
Cu(II) v Cd(II) trn Fe3O4-GOVS v GOVS ph hp hn vi m hnh ng nhit
Langmuir (gi tr hng s tng quan R2 ~ 0,99 ln hn nhiu so vi hng s tng
quan Freundlich). Dung lng hp ph Cu(II) v Cd(II) ti pH = 6 ca Fe3O4-GOVS
tng ng Qmax = 30,3 mg/g v 52,63 mg/g cao hn so vi GOVS. Nh vy c th
thy vic a cc ht nano Fe3O4 ln b mt ca GOVS khng nhng lm cho kh
nng tch cc ion kim loi ra khi dung dch sau x l d dng hn m cn lm tng
dung lng hp ph ca chng. i vi ion kim loi nng Cd(II) (c hi nht trong
cc kim loi nng), dung lng hp ph cc i trn Fe3O4-GOVS cao hn so vi kt
qu ca Jin Hur v cng s [129] mi c cng b. Dung lng hp ph ca Fe3O4-
GOVS cng cao hn hn ca Fe3O4 v GOVS. Kt qu ny c th l gii l i vi
114
GOVS qu trnh hp ph Cu(II) v Cd(II) ph thuc vo tng tc tnh in gia b
mt m ca GOVS vi cation Cu(II) v Cd(II). Trong khi i vi Fe3O4-GOVS
ngoi tng tc tnh in cn c s tng tc to phc gia cc cation kim loi vi
cc nhm chc hydroxyl (C OH, Fe OH) trn b mt Fe3O4-GOVS [130, 131].
3.7.2.3. Nghin cu ng nhit hp ph Cu(II), Cd(II) trn Fe-Fe3O4-GOVS
Qu trnh hp ph tin hnh pH = 6 vi cc nng Cu(II) v Cd(II) ban

u khc nhau, phn tch hi quy Ce/Qe v Ce i vi m hnh Langmuir v hi quy
LnQe v LnCe i vi m hnh Freundlich.
Kt qu xc nh nng cn bng (Ce) ca qu trnh hp ph Cu(II) v Cd(II)
trn Fe-Fe3O4-GOVS c trnh by Bng 3.26.
Bang 3.26. Dung lng hp ph Cd(II) v Cu(II) bng Fe- Fe3O4-GOVS cc
nng ban u khc nhau
Co Ce /Cd(II) Ce /Cu(II)
M (g) V (L)
(mg/L) (mg/L) (mg/L)
20 0,521 0,800 0,1 0,1
30 0,890 1,461 0,1 0,1
40 1,550 2,960 0,1 0,1
50 2,561 4,262 0,1 0,1
100 11,021 23,053 0,1 0,1
T kt qu thu c tin hnh xy dng mi quan h gia Qe v Ce theo cc

m hnh ng nhit hp ph Langmuir v Freundlich. Cc thng s ng nhit hp
ph Langmuir, Freundlich ca Fe-Fe3O4-GOVS c trnh by trong Bng 3.26.
100
0,35
Fe-Fe3O4-GOVS/ Cd(II) R = 0,987
Fe-Fe3 O4 -GOVS / Cd(II) 0,3
Fe-Fe3O4-GOVS/ Cu(II) R = 0,986 b
80
a 0,25
Ce/Qe (g/L)
0,2
60
Qe (mg/g)
Fe-Fe3 O4 -GOVS / Cu(II) 0,15
40
0,1
0,05
20
0
0 5 10 15 20 25
0
0 5 10 15 20 25 30 Ce (mg/L)
Ce (mg/L)
Hnh 3.44. ng ng nhit hp ph Cu(II), Cd(II) (a), ng nhit Langmuir

ca Fe-Fe3O4-GOVS (b)
115
Qua th Hnh 3.44 cho thy m hnh hp ph ng nhit Langmuir m t
tng i chnh xc s hp ph Cd(II), Cu(II) trn vt liu hp ph Fe-Fe3O4-
GOVS thng qua h s tng quan R2 = 0,992 v 0,998. T phn tch hi quy ta
tnh c cc h s ca phng trnh Langmuir nh sau:
Ce
0, 009Ce 0, 024 (Fe-Fe3O4-GOVS/Cd(II)) (3.17)
Qe
Ce
0, 011Ce 0, 039 (Fe-Fe3O4-GOVS/Cu(II)) (3.18)
Qe
M hnh hp ph Freundlich
Bang 3.27. S ph thuc LnQe vo LnCe i vi m hnh Freundlich
Co Fe-Fe3O4-GOVS/Cd(II) Fe-Fe3O4-GOVS/Cu(II)
(mg/L) LnCe LnQe LnCe LnQe
20 -0,652 2,969 -0,223 2,954
30 -0,116 3,371 0,378 3,351
40 0,262 3,655 1,085 3,612
50 0,994 3,856 1,449 3,823
100 2,399 4,488 3,137 4,343
T kt qu thu c chng ti xy dng mi quan h gia LnQe v LnCe theo

Freundlich.
5
4,5
4
3,5
3
Ln Qe
2,5
R = 0,972 Fe-Fe3O4-GOVS/ Cd(II)
2
1,5
R2 =0,975 Fe-Fe3O4-GOVS/ Cu(II)
1
0,5
0
-1 0 1 2 3 4
Ln Ce
Hnh 3.45. ng hp ph ng nhit Freundlich ca Cd(II) v Cu(II) trn
Fe-Fe3O4-GOVS
Bng 3.27 v th Hnh 3.45 m t qu trnh hp ph Cd(II) v Cu(II) trn
vt liu Fe-Fe3O4-GOVS theo m hnh ng nhit Freundlich.
116
Cc h s ca phng trnh Freundlich thu c t qu trnh hi quy LnQe
theo LnCe nh sau:
LnQe = 0,473 LnCe + 3,395 (Fe-Fe3O4-GOVS/Cd(II)) (3.19)
LnQe = 0,401 LnCe + 3,148 (Fe-Fe3O4-GOVS/Cu(II)) (3.20)
T cc phng trnh trn ta tnh ton c cc tham s trong phng trnh

Langmuir v Frendulich, cc tham s c trnh by trong Bng 3.28.
Bang 3.28. Cc thng s ng nhit hp ph Langmuir v Freundlich ca

Cu(II) v Cd(II) trn Fe-Fe3O4-GOVS
Fe-Fe3O4-GOVS, pH = 6, Fe-Fe3O4-GOVS, pH = 6,
ng nhit
Cu(II) Cd(II)
Langmuir
Qmax (mg/g) 90,9 108,6
KL (L/mg) 0,282 0,375
R2 0,996 0,987
RL 0,034 0,026
Freundlich
1/n 0,401 0,473
KF [(mg/g)(L/mg)1/n] 23,068 29,507
R2 0,975 0,972
Cc thng s trong Bng 3.28 cho thy dung lng hp ph cc i Cd(II) v

Cu(II) ca Fe-Fe3O4-GOVS vi Qmax= 108,6 mg/g v 90,9 mg/g cao hn so vi
Fe3O4-GOVS (52 mg/g v 30,3 mg/g, xem Bng 3.25) ti pH = 6. iu ny l do s
hnh thnh cc tm hp ph mi, Feo, Fe2O3, FeOOH trn b mt vt liu Fe-Fe3O4-
GOVS lm tng dung lng hp ph [57, 132, 133]. Kt qu trong Bng 3.28 cng
cho thy h s tng quan ca phng trnh ng nhit hp ph theo m hnh
Freundlich (R2 = 0,972 - 0,975) thp hn so vi m hnh ng nhit Langmuir (R2=
0,987 0,998). Do , qu trnh hp ph Cd(II), Cu(II) trn Fe-Fe3O4-GOVS tun
theo m hnh ng nhit Langmuir. So snh vi mt s kt qu hp ph Cu(II) v
Cd(II) da trn cc vt liu cacbon c cng b (Bng 3.29) u cho thy vt
liu trong lun n c dung lng hp ph cao hn.
117
Bang 3.29. Dung lng hp ph Cu(II) v Cd(II) ca mt s vt liu
iu kin thc Qmax Ti liu

Cht hp ph
nghim (mg/g) tham kho
GO Cd(II), pH = 5,6 14,9 1,5 [22]
Graphen/ng nano cacbon Cu(II), pH = 6 9,8 [22]
rGO-Fe/Fe3O4 Cd(II), pH = 7 1,91 [133]
GO aerogel Cu(II), pH = 6,3 17,73 [133]
GO/Fe3O4 Cu(II), pH = 5,3 18,26 [134]
Polyanilin v lc Cd(II), pH = 6 21 [135]
Fe-Fe3O4-GOVS Cu(II), pH = 6 90,9
Cd(II), pH = 6 108,6
Cu(II), pH = 6 30,3
Fe3O4-GOVS
Cd(II), pH = 6 52,63 Lun n
Cu(II), pH = 6 22,7
GOVS
Cd(II), pH = 6 29,41
T nhng kt qu trn cho thy, c ba vt liu GOVS, Fe3O4-GOVS v Fe-

Fe3O4-GOVS u c kh nng hp ph cc kim loi Cu(II), Cd(II) ti pH = 6. Trong
Fe-Fe3O4-GOVS cho thy tim nng l vt liu c tnh hp ph u vit, khi a
thm 10% Feo vo trong Fe3O4-GOVS ta nhn thy kh nng hp ph Cu(II) v
Cd(II) cao gp 2 - 3 ln so vi Fe3O4-GOVS. Trong Cd(II) l kim loi nng c
hng u, dung lng hp ph cc i (Qmax) cao nht (108,6 mg/g). Do chng
ti i su nghin cu ng hc ca qu trnh hp Cd(II) trn Fe-Fe3O4-GOVS
lm r hn bn cht ca qu trnh hp ph Cd(II) trn h vt liu ny tun theo
phng trnh ng hc bc 1 hay bc 2.
3.7.2.4. ng hc qu trnh hp ph Cd(II) trn Fe-Fe3O4-GOVS
Hnh 3.46 th hin s ph thuc dung lng hp ph Cd(II) trn Fe-Fe3O4-

GOVS theo thi gian ti nng 50 mg/L v 100 mg/L.
118
100
80
Fe-Fe3O4-GOVS/ Cd (II)- 100 mg/L
Qt (mg/g)
60
40
20
0
0 20 40 60 80
Thi gian (pht)
Hnh 3.46. S ph thuc dung lng hp ph Cd(II) trn Fe-Fe3O4-GOVS theo

thi gian ti nng 50 mg/L v 100 mg/L
Kt qu Hnh 3.46 cho thy tc v dung lng hp ph Cd(II) trn vt
liu Fe-Fe3O4-GOVS xy ra nhanh trong khong thi gian ngn. iu ny l do c
s chuyn dch in t t Feo sang Fe3O4 lm hnh thnh nn cc oxit Fe2O3,
FeOOH trn b mt vt liu ng vai tr l cc tm hp ph [57, 120, 132] do vy
lm tng dung lng cng nh tc hp ph cc ion Cd(II). Phng trnh ng
hc bc 1 v bc 2 c a ra trong cc cng thc chng 2. Da trn s liu
thc nghim trn Hnh 3.46, biu th mi quan h Ln(Qe-Qt) theo thi gian (ng
hc biu kin bc 1) v t/Qt theo thi gian (ng hc biu kin bc 2) c th hin
Hnh 3.47 v Hnh 3.48.
Phng trnh ng hoc bc 1
4
Fe-Fe3O4-GOVS/Cd (II)- 50 mg/L R = 0,935
3
Fe-Fe3O4-GOVS/ Cd (II)- 100 mg/L R = 0,705
2
Ln (Qe-Qt)
0
5 15 25 35 45
-1 Thi gian (pht)
-2
Hnh 3.47. Mi quan h Ln(Qe-Qt) theo thi gian (ng hc biu kin bc 1)
Hnh 3.47 cho thy gi tr h s tng quan R2 ca 2 ng biu din s ph
thuc ca Ln(Qe-Qt) vo thi gian nh hn 1.
119
2

1,5 R = 0,999
t/Qt Fe-Fe3O4-GOVS/ Cd (II)- 50 mg/L
1 R = 0,999
0,5
0
0 20 40 60 80
Thi gian (pht)
Hnh 3.48. Mi quan h t/Qt theo thi gian (ng hc biu kin bc 2)
Hnh 3.48 cho thy vi phng trnh ng hc biu kin bc 2 c 2 gi tr R2
ng vi 2 ng biu din ca Fe-Fe3O4-GOVS u xp x gn bng 1. T cc s
liu ng hc hp ph biu kin bc 1 v bc 2 khng nh rng ng hc hp ph
Cd(II) trn Fe-Fe3O4-GOVS tun theo ng hc biu kin bc 2. khng nh
thm chng ti so snh thm cc thng s tnh ton l thuyt v thng s thu c
t thc nghim. Kt qu c trnh by Bng 3.30.
Bang 3.30. Mt s tham s ca phng trnh ng hc biu kin bc 1 v bc 2
Fe-Fe3O4- Dng phng trnh k1 Qe, exp Qe, cal
R1 2
GOVS ng hc biu kin bc 1 (pht-1) (mg/g) (mg/g)
50 mg/L Ln(Qe-Qt) = 2,647 - 0,094.t 0,935 0,094 47,296 11,107
100 mg/L Ln(Qe-Qt) = 2,615 - 0,057.t 0,705 0,057 88,980 13,663
Fe-Fe3O4- Dng phng trnh Qe, exp Qe, cal
R2 2 k2(g/mg.pht)
GOVS ng hc biu kin bc 2 (mg/g) (mg/g)
50 mg/L t/Qt = 0,021.t + 0,023 0,999 0,019 47,296 47,619
100 mg/L t/Qt = 0,011.t + 0,008 0,999 0,015 88,980 90,909
Cc kt qu trong Bng 3.30 cho thy dung lng hp ph tnh ton theo l
thuyt v thc nghim bc 1 c s chnh lch rt ln trong khi s chnh lch
dung lng hp ph tnh ton theo l thuyt v thc nghim bc 2 l khng ng k,
120
iu ny khng nh mt ln na qu trnh hp ph Cd(II) trn Fe-Fe3O4-GOVS
tun theo ng hc biu kin bc 2.
3.7.3. Hp ph As(V) trn vt liu GOVS, Fe3O4-GOVS v Fe-Fe3O4-GOVS
3.7.3.1. nh hng ca pH
Hnh 3.49. nh hng pH n qu trnh loi b As(V) trn vt liu GOVS,

Fe3O4-GOVS v Fe-Fe3O4-GOVS, (nng As(V) 7 ppm, m/V= 0,4 g/L, T=30 oC)
Hnh 3.49 cho thy pH nh hng n qu trnh hp ph As(V) trn vt liu

Fe3O4-GOVS v Fe-Fe3O4-GOVS. Mui NaH2AsO4 trong dung dch nc phn ly
to thnh cc anion H2AsO4- pH thp (pH = 2,2 - 6,9 [51]). Qu trnh hp ph
As(V) b chi phi bi lc ht tnh in v lc y, in tch b mt v kh nng to
phc ca asen vi b mt vt liu. Khi pH < pHpzc (pHpzc ~ 5,2) b mt ca Fe3O4-
GOVS tch in dng do vy kh nng hp ph As(V) cao do lc ht tnh in v
kh nng to phc. Khi pH > pHpzc th b mt Fe3O4-GOVS mang in tch m, qu
trnh hp ph As(V) gim mnh bi lc y tnh in [51]. i vi Fe-Fe3O4-GO
pHpzc ~ 5,4 do vy khi pH > 5,4 th b mt ca Fe-Fe3O4-GOVS mang in m nn
qu trnh hp ph As(V) cng gim mnh v tng t nh vt liu Fe3O4-GOVS. V
vy, pH = 5 c la chn cho qu trnh hp ph As(V). i vi GOVS vi pH = 5
b mt mang in m nn kh nng hp ph As(V) thp vi hiu sut t 10% ti
nng 7 mg/L (Qmax = 1,75 mg/g).
121
3.7.3.2. Nghin cu ng nhit hp ph
Qu trnh hp ph tin hnh pH = 5 vi cc nng As(V) ban u khc

nhau, phn tch hi quy Ce/Qe v Ce i vi m hnh Langmuir v hi quy LnQe v
LnCe i vi m hnh Freundlich:
Bang 3.31. Nng hp ph ca cc mu kho st
Ce- Qe-
Ce-Fe3O4- Qe-Fe3O4-
Fe-Fe3O4- Fe-Fe3O4-
Co GOVS/ GOVS/ M V
GOVS/ GOVS/
(mg/L) As(V) As(V) (g) (L)
As(V) As(V)
(mg/L) (mg/g)
(mg/L) (mg/g)
3 0,541 6,147 0,480 6,300 0,04 0,1
7 1,081 14,797 1,302 14,245 0,04 0,1
10 3,378 16,550 2,037 19,907 0,04 0,1
15 7,973 17,567 3,833 27,917 0,04 0,1
20 11,703 20,743 6,838 32,905 0,04 0,1
25 16,486 21,285 10,170 37,075 0,04 0,1
40 29,643 25,892 24,575 38,563 0,04 0,1
35 30
Fe-Fe3O4-GOVS
30 25
Fe-Fe3O4-GOVS/ As (V)- 20 mg/L
(a) (b)
25
20
Qe (mg/g)
Qt (mg/g)
20 Fe3O4-GOVS
Fe3O4-GOVS/ As (V)- 20 mg/L 15
15
10
10
5
5
0 0
0 2 4 6 8 10 0 5 10 15 20 25 30
Thi gian (gi) Ce (mg/L)
Hnh 3.50. S ph thuc dung lng hp ph As(V) theo thi gian nng
20 mg/L (a) v ng ng nhit hp ph (b) trn vt liu Fe-Fe3O4-GOVS v
Fe3O4-GOVS, m/V= 0,4 g/L, T=30 oC
Quan st Hnh 3.50a cho thy t khong thi gian t 0 2 gi kh nng hp

ph tng nhanh do qu trnh khuch tn ti b mt ln, khng c s cn tr cng
vi l trong khong thi gian u s lng tm hp ph trng cn nhiu, v hm
lng As(V) trn Fe-Fe3O4-GOVS v Fe3O4-GOVS nh hn nhiu so vi hm
lng As(V) trong dung dch. Khi thi gian tng ln, s khuch tn ca As(V) gim
122
do s tm cn trng gim trong khi qu trnh gii hp ph tng ln do hm lng
As(V) trn Fe-Fe3O4-GOVS v Fe3O4-GOVS ln hn hm lng As(V) trong dung
dch [71]. Do vy khi t n trng thi cn bng, tc hp ph As(V) gim. i
vi Fe-Fe3O4-GOVS qu trnh hp ph xy ra nhanh trong khong thi gian u so
vi Fe3O4-GOVS l do s hnh thnh thm cc tm hp ph mi FeOOH, Fe2O3...
(nh phn tch trong ph XRD v XPS) l nhng tm hp ph kim loi mnh
trn b mt Fe-Fe3O4-GOVS [136, 137]. Thi gian t trng thi cn bng ca Fe-
Fe3O4-GOVS l khong 3 gi v i vi Fe3O4-GOVS l 4 gi. Cn bng hp ph
ca As(V) trn Fe3O4-GOVS v Fe-Fe3O4-GOVS c tnh ton theo Bng 3.31 v
m phng theo hai m hnh Langmuir v Freundlich dng tuyn tnh. Phn tch
cc d liu thu c t ng ng nhit hp ph (Hnh 3.50b) ri thay vo cc m
hnh ng ng nhit khc nhau tm ra m hnh hp ph ph hp cho vt liu
Fe3O4-GOVS v Fe-Fe3O4-GOVS tng hp c. Kt qu phn tch cc hng s
ca phng trnh Langmuir v Freundlich c a ra trong Bng 3.32.
Bang 3.32. Cc thng s ng nhit hp ph Langmuir v Freundlich ca As(V)

trn Fe3O4-GOVS v Fe-Fe3O4-GOVS
Vt liu
ng nhit Fe3O4-GOVS, Fe-Fe3O4-GOVS,
pH = 5 pH = 5
Langmuir
Qmax (mg/g) 25 43,47
KL (l/mg) 0,406 0,451
R2 0,981 0,996
RL 0,058 0,053
Freundlich
1/n 0,284 0,421
KF [(mg/g)(L/mg)1/n] 2,737 6,410
R2 0,802 0,940
T Bng 3.32 cho thy qu trnh hp ph As(V) trn Fe-Fe3O4-GOVS v Fe3O4-

GOVS ph hp vi m hnh ng nhit Langmuir (gi tr hng s tng quan R2 ln
lt l 0,981v 0,996 ln hn nhiu so vi hng s tng quan Freundlich R2 = 0,94
v 0,802. Theo kt qu nghin cu ca nhm tc gi Nguyn Th Vng Hon [16,
123
48] th qu trnh hp ph As(V) xy ra trn b mt Fe3O4-GO tun theo m hnh
Freundlich, iu ny c th l do hai phng php tng hp Fe3O4-GO khc nhau
v c bn, trong lun n ny s dng phng php ng kt ta trc tip nn b mt
bng phng hn cn nhm tc gi Nguyn Th Vng Hon li tng hp bng
phng php gin tip (tng hp Fe3O4 v GO ring bit), vi phng php gin
tip khi a Fe3O4 ln GO to b mt khng bng phng do m hnh Freundlich
ph hp hn. Tht vy, theo Xinhua Xu v cng s [136] cho thy qu trnh hp
ph kim loi xy ra trn b mt nano Fe-Fe3O4 tng hp trong iu kin vng mt
GO u ph hp vi c hai m hnh hp ph Langmuir v Freundlich (R2 = 0,999
v 0,984). Tuy nhin khi a cc ht nano Fe-Fe3O4 ln b mt ca GO th qu trnh
hp ph xy ra theo m hnh Langmuir do b mt c tnh ng nht hn [50]. Dung
lng hp ph As(V) ti pH = 5 i vi Fe3O4-GOVS l Qmax = 25 mg/g v vi Fe-
Fe3O4-GOVS c gi tr Qmax = 43,47 mg/g v cao hn so vi cc kt qu cng b
trc y (Bng 3.33).
Bang 3.33. Dung lng hp ph As(V) ca mt s vt liu cha st
Qmax Ti liu
STT Vt liu hp ph iu kin thc nghim
(mg/g) tham kho
pH = 7, T = 298K,
1 Fe3O4-rGO 5,83 [59]
m/V = 0,2 g/L
2 GO/FeOOH pH = 4-9 23,78 [134]
3 FeOOH (dng ht) pH = 6,5, T = 293 K 3,1 [138]

pH = 4,7, T = 298 K,
4 St/than hot tnh (ht) 6,6 [138]
m/V = 3,0 g/L
Oxit Fe3+/Ethylendiami/ pH = 4,0, T = 298 K,
5 10,4 [138]
ng nano cacbon m/V = 0,1 g/L
Feo/tinh bt/Carboxymethyl pH = 5,0, T = 298 K,
6 14,0 [138]
cellulose m/V = 0,3 g/L
St v 1,3,5-
pH = 4, m /V = 5,0 g/L,
7 benzenetricarboxylic 12,87 [138]
T = 298 K
(FeBTC)/MOFs
pH = 6, T = 303K
8 Ct thch anh ph -Fe2O3 1,89 [139]
m/V = 1 g/L
pH = 5, m /V = 0,4 g/L,
9 Fe3O4-GOVS 25
T = 303 K
Lun n
pH = 5, m /V = 0,4 g/L,
10 Fe-Fe3O4-GOVS 43,47
T = 303 K
124
Dung lng hp ph As(V) ca Fe-Fe3O4-GOVS ln hn gn 2 ln so vi
Fe3O4-GOVS. iu ny c th l gii l do s tng tc gia cc ht nano Feo v
Fe3O4 vi GOVS to tm hp ph mi (Fe2O3, FeOOH), c i lc tng tc mnh
vi As(V). So snh vi vt liu nano Fe3O4 cng b bi nhm tc gi Bang-Jing
Zhu [140], I. Zouboulis v cng s [141], dung lng hp ph As(V) ch t Qmax=
6,356 mg/g v 3,7 mg/g. c bit so snh vi vt liu Fe3O4-GO ca nhm tc gi
Kwang S. Kim [59] trong bo co, tc gi tng hp Fe3O4-GO (t l Fe3O4 30%)
cho kh nng hp ph As(V) ch t 5,27 mg/g vi As(V) v 10,2 mg/g vi As(III),
khi tng hm lng Fe3O4 ln 70% th dung lng hp ph cc i As(V) t 5,83
mg/g v 13,10 mg/g vi As(III). Nh vy, vt liu mi nanocompozit Fe3O4-GOVS
v Fe-Fe3O4-GOVS c tng hp trong lun n ny c dung lng hp ph As(V)
vt tri (4 - 8 ln) so vi kh nng hp ph As(V) ca vt liu nano Fe3O4.
Phng thc tng tc ca cc ion kim loi nng, asen v thuc nhum hot
tnh trn cc vt liu composit Fe3O4-GOVS v Fe-Fe3O4-GOVS c m t thng
qua Hnh 3.51 [46].
Hnh 3.51. Cc tng tc khc nhau tham gia vo s hp th cc cht nhim

trn Fe3O4-GOVS v Fe-Fe3O4-GOVS [46]
Trong qu trnh to phc gia As(V) v Fe3+ trong vt liu Fe3O4-GOVS v

Fe-Fe3O4-GOVS c m t thng qua phng trnh:
125
FeOOH + 3H2AsO4 + 3H+ = Fe(H2AsO4)3 + 2H2O
3.7.3.3. Nghin cu ng hc qu trnh hp ph As(V) trn Fe3O4-GOVS v Fe-

Fe3O4-GOVS
Cc gi tr Ln(Qe-Qt) ca cc mu theo thi gian c trnh by trong Bng 3.34.
Bang 3.34. Gi tr Ln(Qe-Qt) theo thi gian ca qu trnh hp ph As(V)
Ln(Qe-Qt)
t (gi) (ti nng As(V) = 20 mg/L)
Cht hp ph
0,5 1 2 4 6 8 10
Fe-Fe3O4-GOVS 2,03 1,46 0,65 -0,21 -0,98 -1,93 -3,1
Fe3O4-GOVS 2,05 1,37 0,98 -0,02 -0,54 -0,99 -3,0
3
R = 0,953 Fe3O4-GOVS/20mg/L- Bc 1
2
R = 0,988 Fe-Fe3O4-GOVS/20mg/L- Bc 1
1
Ln (Qe-Qt)
0
0 2 4 6 8 10
-1
-2
-3
Thi gian (gi)
-4
Hnh 3.52. Mi quan h Ln(Qe-Qt) theo thi gian (ng hc biu kin bc1) ca
qu trnh hp ph As(V) trn ca Fe-Fe3O4-GOVS v Fe3O4-GOVS

th Hnh 3.52 cho thy h s xc nh R2 trong khong 0,988. Bn cnh , gi tr
dung lng hp ph cn bng tnh ton c t cc phng trnh ng hc u
khc bit so vi gi tr thc nghim (Bng 3.36). Vy phng trnh ng hc bc 1
khng ph hp vi ca qu trnh hp ph ca As(V) trn Fe-Fe3O4-GOVS v
Fe3O4-GOVS.
126
T cc gi tr thc nghim, tin hnh hi quy tuyn tnh cc gi tr t/Qt vi t

theo phng trnh ng hc bc 2 (chng 2) thu c gi tr cc tham s ca
phng trnh ng hc bc 2 nh trong Bng 3.35.
Bang 3.35. Gi tr t/Qt theo thi gian ca qu trnh hp ph As(V)
t/Qt x 10-2
t (gi) (ti nng As(V) = 20 mg/L)
Cht hp ph
0,5 1 2 4 6 8 10
Fe-Fe3O4-GOVS 1,97 3,49 6,45 12,46 18,44 24,42 30,43
Fe3O4-GOVS 3,85 5,95 11,07 20,24 29,76 39,27 48,33
0,5
Fe3O4-GOVS/20 mg/L- Bc 2
0,4 R = 0,999
Fe-Fe3O4-GOVS/20mg/L- Bc 2
0,3
R = 0,999
t/Qt
0,2
0,1
0
0 2 4 6 8 10
Thi gian (gi)
Hnh 3.53. Mi quan h t/Qt theo thi gian (ng hc biu kin bc 2) ca qu
trnh hp ph ca As(V) trn Fe-Fe3O4-GOVS v Fe3O4-GOVS

th Hnh 3.53 cho thy h s xc nh R2 u t 0,999. Bn cnh , gi tr dung
lng hp ph cn bng tnh ton c t cc phng trnh ng hc u rt gn so
vi gi tr thc nghim (Bng 3.37). V vy c th kt lun phng trnh ng hc
biu kin bc 2 ph hp vi qu trnh hp ph ca As(V) trn Fe-Fe3O4-GOVS v
Fe3O4-GOVS.
127
Bang 3.36. Mt s tham s ca phng trnh ng hc biu kin bc nht As(V)

Cht hp ph R1 2
ng hc (h-1) (mg/g) (mg/g)
Fe-Fe3O4-GOVS Ln(Qe-Qt) = 1,968 - 0,503.t 0,988 0,503 32,905 7,151
Fe3O4-GOVS Ln(Qe-Qt) = 2,304 - 0,457.t 0,953 0,457 20,743 10,011
Bang 3.37. Mt s tham s ca phng trnh ng hc bc hai biu kin As(V)

Cht hp ph R2 2
ng hc (g/mg.h) (mg/g) (mg/g)
t
Fe-Fe3O4-GOVS = 0,004 + 0,030.t 0,999 0,220 32,905 33,333
Qt
t
Fe3O4-GOVS = 0,014 + 0,047.t 0,999 0,150 20,743 21,276
Qt
Quan st Bng 3.37 nhn thy rng tc hp ph As(V) nng 20 mg/L

trn Fe-Fe3O4-GOVS (0,22 g/mg.h) cao gp 1,5 ln so vi trn Fe3O4-GOVS (0,15
g/mg.h). iu ny cho thy tc hp ph As(V) ca Fe-Fe3O4-GOVS cao hn so
vi Fe3O4-GOVS v ph hp vi nhng phn tch trn.
3.8. anh gia kh nng tai s dng ca vt liu
T cc kt qu thu c cho thy vt liu Fe-Fe3O4-GOVS c dung lng hp
ph thuc nhum, ion kim loi nng Cu(II), Cd(II) v As(V) u cao hn so vi vt
liu Fe3O4-GOVS. Do vy, vt liu Fe-Fe3O4-GOVS c chng ti s dng nh
gi kh nng ti s dng sau 3 ln s dng. nh kh nng ti s dng ca vt liu
trong qu trnh hp ph x l thuc nhum chng ti tin hnh thu hi vt liu sau
hp ph bng t tnh v tin hnh ra bng nc v ethanol + methanol [49, 57].
i vi qu trnh hp ph ion kim loi nng, vt liu hp ph thng c ti
sinh trong mi trng axit nh axit acetic [142], axit HCl ti pH ~2 [143] hoc HNO3
ti pH ~ 2 [133]. Do vy, trong lun n la chn HCl 0,1M ti pH ~ 2 loi b ion
kim loi nng hp ph. Sn phm sau c sy chn khng 60 oC, tip vt
liu c nh gi kh nng ti s dng cho cc ln th nghim tip theo, hao ht
khi lng ca vt liu gn nh khng ng k. Kt qu c th hin trn Hnh 3.54.
128
3,0
60
a 2,5
b
50
Hiu sut hp ph (%)

542 nm
Cuong do hap phu (ABs)

2,0
40 100 mg/L
1,5
30 Lan 3
Lan 2
1,0 Lan 1
20
0,5
10
0 0,0
350 400 450 500 550 600 650 700
Fe-Fe3O4-GOVs/RR195 Fe-Fe3O4-GOVs/RR195 Fe-Fe3O4-GOVs/RR195 Buoc song (nm)
/Ln 1 /Ln 2 /Ln 3
Hnh 3.54. Kh nng hp ph RR195 (a) v ph UV-Vis sau hp ph RR195 trn

Fe-Fe3O4-GOVS qua ba ln ti sinh (b) (pH = 5,5; m/V = 1 g/L)
T Hnh 3.54 c th thy rng bn ca Fe-Fe3O4-GOVS tng i tt, iu
ny c chng minh qua ba ln ti s dng, hiu sut hp ph ln lt l 50%,
48,9% v 45,5% ti nng 100 mg/L. iu ny kh tng ng vi kt qu ca
Chun Wang [58] khi s dng Fe3O4/graphen cho qu trnh hp ph thuc nhum
Fuchsine sau 5 ln ti s dng kh nng hp ph hu nh khng i. i vi Yalin
Qin [49] khi s dng methanol ti sinh vt liu sau qu trnh hp ph RhB. Sau 1
ln ti sinh gim hiu sut hp ph l khng ng k. S gim hiu sut hp ph
c th l do sau cc ln th nghim th s che ph cc tm xc tc bi RR195 [57].
i vi qu trnh hp ph Cd(II) trn Fe-Fe3O4-GOVS qua ba ln kim tra kh

nng ti s dng ca vt liu, hiu sut hp ph ln lt l 98,6%, 95,7% v 93,1%
ti nng Cd(II) = 10 mg/L (Hnh 3.55).
Hnh 3.55. Hiu sut hp ph Cd(II) trn vt liu Fe-Fe3O4-GOVS sau ba ln

ti sinh (pH = 6; m/V = 0,1 g/L)
129
Nh vy c th thy vt liu Fe-Fe3O4-GOVS c hot tnh cao v bn ca vt
liu tt. Tht vy, theo nghin cu ca Jie Li [133], HNO3 ti pH ~ 2 c dng ti
sinh vt liu GO/Fe3O4, vt liu c hot tnh tt sau 5 ln ti s dng cho qu trnh hp
ph Cu(II). Hiu sut ca qu trnh gim khng qu 5% khi so snh sau 5 ln ti sinh.
Tc gi Lulu Fan [143] s dng HCl ti pH ~ 2 ti sinh Fe3O4/chitosan/GO cho qu
trnh hp ph Pb(II). Sau 4 ln ti sinh u tin hiu sut hp ph u t khong 90%
v hiu sut hp ph ch gim xung (75%) sau 6 ln ti sinh. Ngoi ra, Lulu Fan [143]
cng cho thy vic s dng HCl vi pH = 1 ti sinh vt liu Fe3O4/chitosan/GO sau
48 gi khng thy s xut hin ca Fe3+, Fe2+ trong dung dch chng t bn cao ca
loi vt liu ny.
Di y l Bng 3.38, 3.39 v 3.40 tng hp cc kt qu c trng ca
Fe3O4-GOVS v Fe-Fe3O4-GOVS cng nh nh gi kh nng hp ph, ng hc
qu trnh hp ph bc 2 ca Cd(II), As(V) trn vt liu Fe3O4-GOVS v Fe-Fe3O4-
GOVS, GOVS tng hp c.
Bang 3.38. Tng kt cc thng s c trng ca Fe3O4-GOVS v Fe-Fe3O4-GOVS
ng FTIR
HR- EDX
XRD BET knh mao (cc VSM XPS
Mu TEM %Fe
2 (m2/g) qun nhm Hc (Oe) Fe2p
d(nm) (wt)
(nm) chc)
Pic Pic
C=O,
Fe3O4- c dFe3O4= 35 711eV,
166 8,8-12,1 48,59 C-O,
GOVS trng 15 nm emu/g 725eV
Fe-O
35,4 (Fe3O4)
C=O,
Pic Pic
Fe- dFe3O4= C-O,
c 711eV,
Fe3O4- 15 nm Fe-O, 29
trng 177 8,9-12,3 57,68 725eV
GOVS dFeo=5- Fe0- emu/g
45o, Pic 706
10 nm Fe3O4-
68o eV (Fe0)
GOVS
Bang 3.39. Tng kt dung lng hp ph cc i RR195, Cu(II), Cd(II) v As(V)

trn GOVS, Fe3O4-GOVS v Fe-Fe3O4-GOVS
Cht hp ph
GOVS Fe3O4-GOVS Fe-Fe3O4-GOVS
Qmax (mg/g) Qmax (mg/g) Qmax (mg/g)
Cht b hp ph
RR195 212,7 47- -
Cu(II) 22,73 30,3 90,9
Cd(II) 29,41 52,63 108,6
As(V) 7,0 25,0 43,47
130
Bang 3.40. Cc tham s ca phng trnh ng hc biu kin bc hai qu trnh
hp ph Cd(II), As(V) trn Fe3O4-GOVS v Fe-Fe3O4-GOVS
Dng phng trnh Qe, exp Qe, cal

R22 k22(g/mg.h)
ng hc bc 2 (mg/g) (mg/g)
Fe3O4-GOVS t
= 0,014 + 0,047.t 0,999 0,150 20,743 21,276
(As(V) 20 mg/L) Qt
Fe-Fe3O4-GOVS t
= 0,004 + 0,030.t 0,999 0,220 32,905 33,333
(As(V) 20 mg/L) Qt
Fe-Fe3O4-GOVS t
= 0,023 + 0,021.t 0,999 0,019 47,296 47,619
(Cd(II) 50 mg/L) Qt
Fe-Fe3O4-GOVS t
= 0,008 + 0,011.t 0,999 0,015 88,980 90,909
(Cd(II) 100 mg/L) Qt
131
KT LUN
- tng hp thnh cng GO, rGO t graphit bng phng php Hummers ci
tin s dng tc nhn oxy ha H2SO4 v KMnO4. Tch lp GO s dng k thut siu
m, vi sng v kh GO v rGO bng tc nhn nhit nhit 600 oC trong dng N2.
GO v rGO tng hp c c dng lp vi khong cch lp thay i t 0,4 nm 0,6
nm. T l C/O thay i t 2,32 10,89 tng ng vi GO v rGO. Trn b mt GO
v rGO tn ti cc nhm chc: -OH, C=O, C-O, COO-, cng nhm chc trn b
mt ca GO v rGO tng dn theo chiu hng rGO < GOVS < GOSA. rGO v
GOVS u c b mt ring ln, v cao hn nhiu vi GOSA (5 ln).
- tng hp thnh cng vt liu composit Fe3O4-GOVS bng phng php
ng kt ta trong mi trng baz ca dung dch NH3 v vt liu composit Fe-
Fe3O4-GOVS bng phng php kh ha hc s dng NaBH4 lm tc nhn kh.
Bng cc phng php phn tch ha l hin i chng minh s tn ti ng thi
ca Fe3O4 v Feo trn b mt GOVS. Fe3O4 v Feo lin kt vi GOVS thng qua
lin kt Fe-O. Qu trnh hnh thnh Fe3O4 ln b mt GOVS hon ton sch pha
trong iu kin nhit phng, kch thc ht ph thuc vo cc iu kin nhit ,
pH, nng mui v tc khuy. T XRD v TEM cho thy kch thc ht Fe3O4
tn ti trn GOVS khong 15 nm, Feo c kch thc < 10 nm. C hai vt liu Fe3O4-
GOVS v Fe-Fe3O4-GOVS u c t tnh v t bo ha cao (35 emu/g v 29
emu/g) d dng thu hi bng t trng ngoi.
- C 5 vt liu: GOVS, GOSA, rGO, Fe3O4-GOVS v Fe-Fe3O4-GOVS u c
kh nng hp ph thuc nhum hot tnh RR195. Dung lng hp ph ti a t t
(66,67 - 300 mg/g). Kh nng hp ph thuc nhum hot tnh trn 05 vt liu tng
dn theo th t: GOSA < Fe3O4-GOVS < Fe-Fe3O4-GOVS < GOVS < rGO.
- Ba vt liu: GOVS, Fe3O4-GOVS v Fe-Fe3O4-GOVS u c kh nng hp
ph cc ion kim loi nng: Cu(II), Cd(II) v As(V); kh nng hp ph trn ba vt liu
tng dn theo chiu hng GOVS < Fe3O4-GOVS < Fe-Fe3O4-GOVS. c bit vi
s tn ti 10% Feo v khi lng trong Fe3O4-GOVS lm tng mnh dung lng
hp ph cc ion kim loi nng Cu(II), Cd(II) v As(V) so vi Fe3O4-GOVS ban u.
Vi Fe3O4-GOVS th Qmax ca Cu(II), Cd(II) v As(V) ln lt 30,3 mg/g; 52,63 mg/g
132
v 25 mg/g, cn vi Fe-Fe3O4-GOVS gi tr Qmax ln lt 90,9 mg/g; 108,6 mg/g v
43,47 mg/g.
- Nghin cu m hnh hp ph ng nhit v ng hc hp ph cho thy: qu
trnh hp ph RR195 trn GOVS, GOSA, rGO v qu trnh hp ph Cd(II), Cu(II),
As(V) trn Fe3O4-GOVS v Fe-Fe3O4-GOVS ph hp vi m hnh hp ph ng
nhit Langmuir v theo phng trnh ng hc hp ph biu kin bc 2. Hng s
tc v dung lng hp ph Cd(II), Cu(II) v As(V) ca Fe-Fe3O4-GOVS cao hn
1,5 ln so vi Fe3O4-GOVS.
133
DANH MC CAC CNG TRNH CNG B
1. L H Giang, H Quang nh, Nguyn K Quang, Ng Tin Quyt, Ng Quang

Binh, o c Cnh, Nguyn Trung Kin, ng Tuyt Phng, Trn T. Kim
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2014, 6A-52, 143-148
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3. H Quang nh, L H Giang, Nguyn K Quang, V nh Ng v V Anh
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5. H Quang nh, L Th Mai Hoa, L H Giang, Nguyn K Quang, o c
Cnh, Nguyn Trung Kin, Trn Th Kim Hoa, ng Tuyt Phng v V Anh
Tun, Nghin cu s hp ph RodaminB trong dung dch nc trn vt liu
graphen oxit v graphen, Tp ch Xc tc hp ph, 2015, T.4, N02, 160-168
6. H Quang nh, L Th Mai Hoa, L H Giang, Nguyn K Quang, Ng Tin
Quyt, o c Cnh, Nguyn Trung Kin, ng Tuyt phng, Trn Th Kim
Hoa v V Anh Tun, Nghin cu tng hp, c trng v kh nng hp ph cht
mu ca graphen oxit v graphen t graphit t nhin, Tp ch Xc tc hp ph,
2015, T.4, N04B,
7. H Quang nh, L Th Mai Hoa, L H Giang, Nguyn K Quang,V nh
Ng v V Anh Tun, Nghin cu kh nng hp ph thuc nhum RR195 trong
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134
NHNG IM MI CA LUN AN
1. tng hp thnh cng GO v rGO vi chiu dy vi lp nguyn t cacbon (< 8

lp) bng phng php oxy ha t graphit t nhin, bc tch lp bng k thut
vi sng to GO v phng php kh nhit to rGO. Cc vt liu ny c din tch
b mt ln, c kh nng hp ph cao i vi cht mu v cc ion kim loi nng.
2. tng hp thnh cng vt liu composit mi Fe3O4-GOVS v Fe-Fe3O4-GOVS

bng phng php kt ta ti ch In situ v kh bng phng php ha hc s
dng NaBH4 lm tc nhn kh. Vt liu composit mi c kch thc ht nano 10-
20 nm phn tn u trn b mt GO v rGO.
3. Vt liu mi Fe-Fe3O4-GOVS c kh nng hp ph chn lc v dung lng hp

ph cc ion kim loi nng Cd(II), Cu(II) v As(V) cao hn nhiu so vi cc vt
liu hp ph c cng b. Kt qu ny m ra trin vng ng dng ca vt
liu mi composit Fe-FeOx/GO, rGO trong x l asen v cc ion kim loi nng
trong dung dch nc.
4. M hnh hp ph ng nhit v ng hc hp ph ca vt liu mi Fe-Fe3O4-GOVS
i vi ion kim loi nng Cd(II) v As(V) c nghin cu. Kt qu thu c ch

ra rng m hnh ng nhit tun theo m hnh Langmuir v ng hc hp ph ph
hp vi phng trnh ng hc biu kin bc 2. y l nhng kt qu mi hu nh
cha c cng b trn tp ch quc t cng nh trong nc.
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149
PH LC
Ph XRD ca mu GOVS
Ph XRD ca mu graphit oxit
150
Ph XRD ca mu GOSA
Ph XRD ca mu rGO
151
in th b mt GOSA
in th b mt ca GOVS
152
Kt qua chp BET ca mu GOVS
153
Kt qua chp BET ca mu GOSA
154
Kt qua chp BET mu rGO
155
Kt qua chp BET mu Fe -Fe3O4-GOVS
156
Kt qua chp BET mu Fe3O4-GOVS
157
Ph XPS ca mu Fe3O4- GOVS
Ph FTIR ca mu Fe-Fe3O4-GOVS
158
Ph FTIR ca mu Fe3O4-GOVS
159

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VIN HN LM KHOA HC V CNG NGH VIT NAM

HC VIN KHOA HC V CNG NGH

NGHIN CU TNG HP V C TRNG VT LIU MI

NGHIN CU TNG HP V C TRNG VT LIU MI

Chuyn ngnh: Ha l thuyt v Ha l

NGI HNG DN KHOA HC:

Ti xin cam oan y l kt qu nghin cu ca ring ti v khng trng lp

Ti xin by t lng bit n su sc, s cm phc v knh trng ti PGS. TS.

AAS Atomic Absorption Spectroscopy (Ph hp th nguyn t)

Hnh 1.1 Cu trc tinh th ca kim cng v graphit (3D) 4

Bng 1.1 Tnh cht ca SWCNTs v MWCNTs 6

Hin nay, cng vi s pht trin mnh m ca cc hot ng cng nghip,

Hp ph l mt trong nhng bin php hiu qu nht trong x l nc. So

Trong thp k qua, vt liu cu trc nano cacbon, chng hn nh ng nano

Gn y, graphen v vt liu trn c s graphen l loi vt liu nhn c s

Mc d vy, cc nghin cu trc y tp trung nhiu vo nghin cu tng

Vit Nam, vic nghin cu vt liu graphen v vt liu trn c s graphen

Tng hp c GO (GOVS, GOSA), rGO, Fe3O4-GO v Fe-Fe3O4-GO. c

1.1. Gii thiu chung v vt liu trn c s cacbon

Cacbon l nguyn t ng vai tr quan trng cho s sng v l nguyn t c

1.1.1. Kim cng v graphit

Hnh 1.1. Cu trc tinh th ca kim cng v graphit (3D)

1.1.2. Vt liu cacbon cu trc nano

Fullerene (C60) l mt dng th hnh ca cacbon vi cu trc tinh th 0 chiu

1.1.2.2. ng nano cacbon (Cacbon Nanotube CNTs)

CNTs l mt dng th hnh ca cacbon vi cu trc tinh th 1 chiu (1D) (hnh

1.1.2.3. Vt liu Graphen

Graphen l mt mt phng n lp ca nhng nguyn t cacbon c sp xp

graphen l lng trong trng thi t do khng phng m li lm nh mt sng vi m

Chnh nh nhng c im u vit trn m graphen ang l mi quan tm

Hnh 1.5. S phn b ca cc cng trnh cng b lin quan n ba vt liu

1.2. Vt liu graphen va graphen oxit

1.2.1. Cu trc ca graphen [18]

1.2.2. Cu trc graphen oxit (GO)

Hnh 1.7. Cu trc xut ca GO bi cc nh nghin cu khc nhau [26]

Nhng trong m hnh ca Lerf Klinowski ph bin hn c [26]. Theo ,

Gn y (2013) nhm tc gi Ayrat

1.2.3. Tm hot ng ca graphen v graphen oxit

GO mang nhiu nhm chc phong ph do vy hnh thnh t cc lin kt hydro

1.2.4. Cac phng phap tng hp GO

Graphit oxit l sn phm ca qu trnh trnh oxy ha graphit. Nghin cu u tin

GO c tng hp bng ba phng php chnh l Brodie (1859) [30],

Phng php Hummers s dng hn hp H2SO4, NaNO3 v KMnO4 gip cho

KMnO4 + 3H2SO4 K+ + MnO3+ + H3O+ + 3HSO4-

MnO3+ + MnO4- Mn2O7

Trong ba phng php trn th phng php Hummers l phng php ph

C ch hnh thnh GO c xc nh bi ba bc ring bit c lp a

Hnh 1.10. C ch hnh thnh GO t graphit [8]

1.2.5. Cac phng phap tng hp graphen

1.2.5.1. Graphen (rGO) tng hp t graphit oxit

S chuyn ha graphit thnh rGO c th hin Hnh 1.11.

Qu trnh kh cc nhm chc cha oxy trn b mt GO s chuyn cc C-sp3

Hnh 1.11. S chuyn ha t graphit thnh rGO [34]

Cc phng php kh GO v rGO c nghin cu rng ri trong thp k

Hnh 1.12. C ch kh nhm epoxy ca hydrazin [26]

Tc nhn kh NaBH4 cho thy hiu qu hn so vi hydrazin, n hiu qu cao

Tuy nhin, cc phng php kh ha hc trn cho thy mt s nhc im nh:

Ngoi phng php s dng cc cht ha hc kh cc nhm chc cha oxi

Kh ha hc l phng php ph bin nht kh GO, thay v s dng mt

Mt vi lp rGO thu c bng vic kh nhit GO trong mi trng nit

Hnh 1.13. S m t c ch kh nhit cho GO ch ra s phn hy ca cc dng

*Bc tch lp trong pha lng (Liquid-phase exfoliation - LPE)

Bc tch lp trong pha lng (LPE) thng lin quan n s phn tn ca