Luan An

VIN HN LM KHOA HC V CNG NGH VIT NAM
HC VIN KHOA HC V CNG NGH
L TH MAI HOA
NGHIN CU TNG HP V C TRNG VT LIU MI,

CU TRC NANO NG DNG TRONG QUANG HA
XC TC PHN HY THUC NHUM
LUN N TIN S HA HC
Chuyn ngnh: Ha l thuyt v Ha l
M s: 62.44.01.19
Ngi hng dn khoa hc: PGS.TS V Anh Tun
H ni, nm 2016
LI CM N
Trc ht, em xin trn trng cm n n PGS.TS V Anh Tun v

cc thy, c gio tn tnh hng dn v truyn t kin thc, kinh
nghim, h tr v gip em trong sut qu trnh em thc hin lun n.
Ti xin chn thnh cm n tp th cn b phng Ha l B mt-

Vin Ha hc- Vin Hn lm Khoa hc v Cng ngh Vit Nam nhit
tnh gip ti trong thi gian thc hin cc ni dung ca lun n.
Ti xin chn thnh cm n su sc ti gia nh, bn b, ng

nghip ti V Gio dc v o to, Dy ngh, Ban Tuyn gio Trung
ng quan tm, ng vin v to iu kin thun li gip ti trong
sut thi hc tp v nghin cu.
Tc gi lun n
L Th Mai Hoa
i
LI CAM OAN
Ti xin cam oan, y l cng trnh nghin cu do ti thc hin

di s hng dn ca ngi hng dn khoa hc. Mt s nhim v
nghin cu l thnh qu tp th c cc ng s cho php s dng.
Cc s liu v kt qu trnh by trong lun n l trung thc v cha tng
cng b trong bt k cng trnh lun n no khc.
Tc gi lun n
L Th Mai Hoa
ii
DANH MC CC T VIT TT
GO Graphen oxit
GOVS Graphen oxit bc lp bng vi sng
GOSA Graphen oxit bc lp bng siu m
rGO Graphen oxit kh v graphen
AOPs Phng php oxy ha nng cao (Advanced Oxidation Processes)
H2O2 Hydrogen peroxide
*OH Hydroxyl
TS Tng lng cht rn (Total Solids)
SS Cht rn huyn ph (Suspended Solid)
DO Hm lng oxy ha tan (Disolved oxigen)
BOD Nhu cu oxi ha sinh hc (Biochemical oxigen Demand)
COD Nhu cu oxi ha hc (Chemical oxigen Demand)
TOC Tng cacbon hu c (Total Organic Carbon)
TOD Nhu cu oxy tng cng (Total Oxygen Demand)
Fe3O4-GO Fe3O4 bc Graphen oxit (GO)
CoFe2O4-GO Coban (Co), Fe2O4 bc Graphen oxit (GO)
ZnFe2O4-GO Km (Zn), Fe2O4 bc Graphen oxit (GO)
Fe0-Fe3O4-GO Fe, Fe3O4 bc Graphen oxit (GO)
Fe(III)-GO Fe(III) oxo cluster Graphen oxit (GO)

CVD Phng php lng ng pha hi ha hc
CNTs ng nano cacbon
XRD Ph nhiu x Rnghen (X-ray Diffraction)
FTIR Quang ph hng ngoi
(Fourier Transform Infrared Spectroscopy)
XPS Ph in t quang tia X
(X-ray Photoelectron Spectroscopy)
TEM Knh hin vi in t truyn qua
(Transmission electron microscopy)
HR-TEM Knh hin vi in t truyn qua phn gii cao
(High resolution Transmission electron microscopy)
BT ng nhit hp ph kh nitrogen (Braunauer Emmett Teller)
UV-Vis Ph hp th t ngoi kh kin
VMS Phng php xc nh t tnh ca vt liu bng t k mu rung
(Vibrating Sample Magnetometer)
iii
DANH MC CC HNH V
Hnh 1.1 Graphen - vt liu c cu trc c bn (2D) cho cc vt liu 4

cacbon khc (0D, 1D, v 3D) ...........................................
Hnh 1.2 Cc lin kt ca mi nguyn t cacbon trong mng 6
graphen.................................................................................
Hnh 1.3 Phng php tch lp graphit bng bng dnh...................... 9
Hnh 1.4 C ch to mng graphen bng phng php nung nhit 10
SiC......................................................................................
Hnh 1.5 Qu trnh oxi ha t graphit thnh GO (a) v qu trnh kh GO 12
bng hydrazine (b) c xut..................................
Hnh 1.6 C ch ngh ca qu trnh tng hp GO v graphen...... 13
Hnh 1.7 Nc thi dt nhum............................................................ 14
Hnh 1.8 Cng thc cu to ca RR195.............................................. 15
Hnh 1.9 Cc phng php loi b mu thuc nhum........................ 19
Hnh 1.10 Phn ng Fenton ng th v Fenton d th......................... 31
Hnh 1.11 C ch phn ng ca TiO2/graphen vi Methylene blue...... 41
Hnh 1.12 C ch phn ng ca ZnO vi cc cht hu c.................... 42
Hnh 1.13 C ch phn ng ca Fe3O4/graphen vi cc cht hu c 44
Hnh 2.1 S tng hp graphen oxit vi sng (GOVS) v graphen oxit 46
siu m (GOSA) t graphen oxit................................................
Hnh 2.2 S tng hp Fe3O4-GO.. 47
Hnh 2.3 S tng hp CoFe2O4-GO.. 48
Hnh 2.4 S tng hp ZnFe2O4-GO.. 50
Hnh 2.5 S tng hp Fe0-Fe3O4-GO.. 51
Hnh 2.6 ng chun v ph UV-Vis ca thuc nhum RR195.. 52
Hnh 2.7 th lgC theo t i vi phn ng bc 1 55
Hnh 2.8 S chm tia ti v chm tia nhiu x trn tinh th. 57
Hnh 2.9 t ca pic phn x gy ra do kch thc ht.................. 57
Hnh 2.10 Qu trnh pht quang in t................................................ 59
Hnh 2.11 Nguyn tc pht x tia X dng trong ph............................ 61
Hnh 2.12 S nguyn l s to nh phn gii cao trong HR- 63
TEM.......................................................................................
Hnh 2.13 Cc dng ng ng nhit hp ph-kh hp ph theo phn 64
loi IUPAC.............................................................................
Hnh 2.14 Bc chuyn ca cc electron trong phn t.. 65
iv
Hnh 3.1 Gin XRD ca graphen oxit v graphen. 67
Hnh 3.2 nh HR-TEM ca GOSA (graphen siu m) (a), GOVS 68
(graphen vi sng) (b) v rGO (c)............................................
Hnh 3.3 Ph FT-IR ca GOSA, GOVS v rGO sau khi tng hp........ 69
Hnh 3.4a Ph XPS ca GOSA (a,b), GOVS (c,d) v rGO (e,f).............. 71
Hnh 3.4b Ph XPS ca rGOSA kh nhit t GOSA............................. 72
Hnh 3.5 Gin XRD ca graphen oxit (GO). 73
Hnh 3.6 Gin XRD ca Fe3O4-GO.................................................. 74
Hnh 3.7 Gin XRD ca CoFe2O4-GO............................................. 75
Hnh 3.8 Gin XRD ca ZnFe2O4 GO............................................ 76
Hnh 3.9 Gin XRD ca Fe0-Fe3O4-GO 76
Hnh 3.10 Gin XRD ca GO v Fe(III)-GO. 77
Hnh 3.11 nh HR- TEM ca Fe3O4-GO vi phng i khc nhau....... 78
Hnh 3.12 nh HR- TEM ca CoFe2O4-GO............................................. 78
Hnh 3.13 nh HR- TEM ca ZnFe2O4 -GO ............................................. 79
Hnh 3.14 nh HR- TEM ca Fe0-Fe3O4-GO .................................... 79
Hnh 3.15 nh HR- TEM ca Fe(III)-GO vi cc phng i khc 80
nhau..........................................................................................
Hnh 3.16 Ph FTIR ca Fe3O4-GO.......................................................... 81
Hnh 3.17 Ph FTIR ca CoFe2O4-GO..................................................... 81
Hnh 3.18 Ph FTIR ca ZnFe2O4-GO...................................................... 82
Hnh 3.19 Ph FTIR ca Fe0-Fe3O4-GO..................................................... 83
Hnh 3.20 Ph FTIR ca Fe(III)-GO v GO.. 83
Hnh 3.21 Ph XPS ca Fe3O4-GO: (a)- Ph XPS tng ca Fe3O4-GO;
(b)- Ph XPS Fe2p tch ca Fe3O4-GO; (c)- Ph XPS O1s tch 84
ca Fe3O4-GO; (d) Ph XPS C1s tch ca Fe3O4-GO.............
Hnh 3.22 Ph XPS ca Fe0-Fe3O4-GO: (a)- Ph XPS tng ca Fe0-
Fe3O4-GO; (b)- Ph XPS Fe2p tch ca Fe0- Fe3O4-GO; (c)-
Ph XPS O1s tch ca Fe0-Fe3O4-GO; (d) Ph XPS C1s tch 85
ca Fe0-Fe3O4-GO...................................................................
Hnh 3.23 Ph XPS ca vt liu Fe(III)- GO: (a)- Ph XPS tng ca
Fe(III)-GO; (b)- Ph XPS O1s tch ca Fe(III)-GO; (c)- Ph
XPS Fe2p tch ca Fe(III)-GO; (d) Ph XPS C1s tch ca 87
Fe(III)-GO...............................................................................
Hnh 3.24 Phn b mao qun ca Fe0-Fe3O4-GO v Fe3O4-GO............... 88
Hnh 3.25 ng ng nhit hp ph - kh hp ph N2 ca Fe0-Fe3O4- 88
v
GO v Fe3O4-GO ...................................................................
Hnh 3.26 ng ng nhit hp ph - kh hp ph N2 ca ZnFe2O4-GO 89
Hnh 3.27 Phn b mao qun ca ZnFe2O4-GO 90
Hnh 3.28 ng cong t tr ca Fe0-Fe3O4-GO v Fe3O4-GO 91
Hnh 3.29 ng cong t tr ca ZnFe3O4-GO 92
Hnh 3.30 Hot tnh quang xc tc Fe3O4-GO.......................................... 94
Hnh 3.31 S ph thuc chuyn ha theo thi gian phn ng cc 95
iu kin khc nhau ca CoFe2O4 GO.....................................
Hnh 3.32 bn xc tc qua cc ln chy phn ng trong qu trnh phn 97
hy RR195 trn CoFe2O4-GO....................................................
Hnh 3.33 Ph UV_Vis qu trnh phn hy RR195 di iu kin chiu x 97
(A) v khng chiu x (B) trn CoFe2O4-GO..
iu kin khc nhau ca ZnFe2O4-GO.
Hnh 3.35 bn xc tc qua cc ln chy phn ng khc nhau trong qu 99
trnh phn hy RR195 trn ZnFe2O4-GO
trn ZnFe2O4-GO.
Hnh 3.37 Ph UV_Vis qu trnh phn hy RR195 di iu kin khng 100
chiu x trn ZnFe2O4-GO.
iu kin khc nhau trn Fe0 -Fe3O4-GO
Hnh 3.39 Hot tnh xc tc ca Fe0-Fe3O4-GO v Fe304-GO 103
trn Fe0-Fe3O4-GO ....................................................................
Hnh 3.41 Ph UV_Vis qu trnh phn hy RR195 di iu kin khng 104
chiu x trn Fe0-Fe3O4-GO.......................................................
Hnh 3.42 bn xc tc qua cc ln chy phn ng qu trnh phn hy 104
RR195 trn Fe0-Fe3O4-GO.

iu kin khc nhau trn Fe(III)-GO
Hnh 3.44 S ph thuc t l nng C/C0 ca thuc nhum hot tnh
RR195 theo thi gian phn ng cc iu kin khc nhau trn 108
CoFe2O4-GO
Hnh 3.45 S ph thuc t l nng C/C0 ca thuc nhum hot tnh 109
vi
RR195 theo thi gian tip xc trn CoFe2O4-GO ln 1 v ln 2
Hnh 3.46 Qu trnh phn hy RR195 trn cc loi xc tc khc nhau 111
Fe(III)-GO; Fe0-Fe3O4-GO; CoFe3O4-GO; ZnFe2O4-GO;
Fe3O4-GO..
Hnh 3.47 Kh nng t phn hy ca RR195 trong mi trng pH khc 112
nhau vi s c mt H2O2
Hnh 3.48 nh hng pH n kh nng phn hy RR195 trn Fe0-Fe3O4- 113
GO.
Hnh 3.49 nh hng ca nng H2O2 n qu trnh phn hy RR195 114
trn Fe0-Fe3O4-GO
Hnh 3.50 nh hng ca nng RR195 ban u n qu trnh phn 115
hy RR195 trn Fe0-Fe3O4-GO.
Hnh 3.51 ng hc qu trnh xc tc quang ha trong phn ng phn 117
hy RR195 trn Fe(III)-GO bc 0
hy RR195 trn Fe0-Fe3O4-GO bc 0
hy RR195 trn Fe0-Fe3O4-GO bc 1.
hy RR195 trn Fe0-Fe3O4-GO bc 2.
vii
DANH MC CC BNG
Bng 1.1 Tnh cht ca Graphen n lp.................................... 5

Bng 1.2 u v nhc im ca mt s phng php x l cc 19
hp cht hu c c mu..............................................
Bng 1.3 Th oxi ho ca mt s tc nhn oxi ho thng gp 27
Bng 1.4 Mt s phng php AOPs ph bin hin nay ang s 29
dng trong x l nc thi..........................................
Bng 1.5 Bng thng k mt vi nghin cu v TiO2/graphen..... 39
Bng 1.6 Bng thng k mt vi nghin cu v oxit kim 42
loi/graphen....................................................................
Bng 1.7 Bng thng k mt vi nghin cu v hn hp 45
oxit/graphen
Bng 2. 1 Tm tt phn ng bc 0, 1, 2 v n................................. 54
Bng 3.1 Thnh phn % cc nguyn t trong ph XPS ca GO v 73
rGO...............................................................................
Bng 3.2 Cc thng s c trng ca Fe3O4-GO.......................... 89
Bng 3.3 Cc thng s c trng ca Fe0-Fe3O4-GO.................... 89
Bng 3.4 Cc thng s c trng ca ZnFe2O4-GO...................... 90
Bng 3.5 Nng RR195 trc v sau qu trnh quang phn s 116-117
dng xc tc Fe(III)-GO ti cc nng khc nhau.
Bng 3.6 Nng RR195 trc v sau qu trnh quang phn s 119
dng xc tc Fe0-Fe3O4-GO ti cc nng khc nhau
viii
MC LC
LI CM N .. i
LI CAM OAN . ii
DANH MC CC T VIT TT iii
DANH MC CC HNH V .. iv
DANH MC CC BNG viii
T VN 1
CHNG 1. TNG QUAN TI LIU 4
1.1 Vt liu graphen v ng dng trong x l cht mu 4
1.1.1 Vt liu trn c s graphen 5
1.1.2. Tm hot ng ca graphen v graphen oxit .. 6
1.1.3 Cc phng php tng hp graphen 8
1.1.3.1. Phng php tch c hc . 8
1.1.3.2. Phng php epitaxy .. 9
C ch phn hy nhit
C ch to mng graphen
1.1.3.3. Phng php ha hc 11
1.2. Cht mu hu c v phng php x l . 13
1.2.1 Gii thiu v nhim cht mu hu c .. 13
1.2.1.1 Thuc nhum . 14
1.2.1.2 Cc thng s nh gi nc thi dt nhum . 15
1.2.2 Cc phng php x l thuc nhum hot tnh trong nc thi
dt nhum 17
1.2.2.1 Cc phng php ha l 21
Phng php keo t
Phng php hp ph
1.2.2.3 Phng php in ha 24
1.2.2.4 Phng php ha hc 25
1.3 Phng php oxi ha nng cao (AOPs) .. 26
1.3.1. Gii thiu cc qu trnh oxi ha nng cao 26
1.3.2. C s l thuyt ca qu trnh Fenton 30
1.3.2.1 Qu trnh Fenton ng th 30
1.3.2.2. Qu trnh Fenton d th. 32
1.3.2.3. Qu trnh Photo Fenton 33
1.3.2.4. Qu trnh ozon ha 34
1.3.3. Nhng yu t nh hng n qu trnh Fenton v Photo Fenton 35
1.3.3.1. nh hng ca pH .. 35
2
1.3.3.2. nh hng ca nng H2O2 v t l Fe +/H2O2 35
1.3.3.3. nh hng ca cc anion v c .. 36
1.3.4. nh hng ca bc sng bc x (i vi qu trnh Photo
Fenton) 36
1.3.4. Tnh hnh nghin cu v p dng cc qu trnh oxi ha nng cao
hin nay 36
1.3.5. Cc h xc tc trong x l cht mu hu c . 38
1.3.5.1 Xc tc quang ha TiO2/ graphen 38
1.3.5.2. Xc tc quang ha composite oxit kim loi/graphen . 40
1.3.5.3 Xc tc quang ha composit ion kim loi/graphen c t tnh 43
CHNG 2. THC NGHIM V PHNG PHAP NGHIN CU 45
2.1. Mc tiu nghin cu .. 45
2.2. Thc nghim 45
2.2.1. Tng hp vt liu graphen oxit (GO). 45
2.2.2. Tng hp vt liu graphen oxit vi sng (GOVS) v graphen oxit 46
siu m (GOSA) t graphen oxit (GO)..
2.2.3. Tng hp h vt liu nano composit oxit kim loi Fe3O4-GO trn
c s Fe3O4 ... 46
2.2.4 Tng hp h vt liu nano composit oxit kim loi CoFe2O4-GO
trn c s Fe3O4 bin tnh 47
2.2.5. Tng hp h vt liu nano composit oxit kim loi ZnFe2O4-GO
trn c s Fe3O4 bin tnh .. 49
2.2.6 Tng hp h vt liu nano composit oxit kim loi Fe0-Fe3O4-GO
trn c s Fe3O4 bin tnh 50
2.2.7 Tng hp h vt liu nano composit oxit kim loi Fe(III)-GO trn 51
c s Fe3O4 bin tnh
2.3. Phn ng Photo-Fenton .. 51
2.4. ng hc ca phn ng 53
2.5. Phng php nghin cu 56
2.5.1 Phng php nhiu x Rnghen (X-ray diffraction, XRD) . 56
2.5.2. Phng php ph hng ngoi FT-IR 57
2.5.3. Phng php ph in t quang tia X (XPS) . 59
2.5.4. Phng php ph tn sc nng lng tia X . 60
2.5.5. Phng php hin vi in t truyn qua (TEM) v knh hin vi 61
in t truyn qua phn gii cao HR-TEM ..
2.5.6. Phng php ng nhit hp ph- kh hp ph nitrogen (BET) 63
2.5.7. Phng php ph hp th t ngoi v kh kin . 64
2.5.8. Phng php xc nh t tnh ca vt liu bng t k mu rung
(Vibrating Sample Magnetometer - VSM) . 66
CHNG 3. KT QU V THO LUN .. 67
3.1. c trng ca vt liu graphen oxit v graphen tng hp c 67
3.1.1. Gin XRD ca graphen oxit v graphen .. 67
3.1.2. nh knh hin vi in t truyn qua phn gii cao (HR-TEM)
ca vt liu graphen oxit v graphen .. 68
3.1.3 Ph hng ngoi (FTIR) ca vt liu graphen oxit v graphen .. 69
3.1.4. Ph in t quang tia X (XPS) ca vt liu graphen oxit v
graphen . 71
3.2. c trng vt liu xc tc nano composit oxit kim loi
graphen/graphen oxit .. 73
3.2.1. Gin XRD ca cc h xc tc nano composit oxit kim loi
trn graphen oxit v graphen 73
3.2.1.1 Gin XRD ca h vt liu xc tc Fe3O4-GO . 73
3.2.1.2 Gin XRD ca h vt liu xc tc CoFe2O4-GO trn c s 75
Fe3O4 bin tnh ..
3.2.1.3.Gin XRD ca h vt liu xc tc ZnFe2O4-GO trn c s
Fe3O4 bin tnh .. 76
3.2.1.4 Gin XRD ca h vt liu xc tc Fe0-Fe3O4-GO trn c s
Fe3O4 bin tnh .. 76
3.2.1.5. Gin XRD ca h vt liu lai Fe(III)-GO . 77
3.2.2. nh HR-TEM ca cc h xc tc nano composit oxit kim
loi trn graphen v graphen oxit 78
3.2.2.1 nh HR-TEM ca h vt liu xc tc Fe3O4-GO 78
3.2.2.2. nh HR-TEM ca h vt liu xc tc CoFe2O4-GO trn c s
Fe3O4 bin tnh 78
3.2.2.3 nh HR-TEM ca h vt liu xc tc ZnFe2O4-GO trn c s
Fe3O4 bin tnh .. 79
3.2.2.4 nh HR-TEM ca h vt liu xc tc Fe0-Fe3O4-GO trn c s
Fe3O4 bin tnh .. 79
3.2.2.5 nh HR-TEM ca h vt liu xc tc nano composit oxit kim
loi trn c s Fe(III)-GO . 80
3.2.3 Ph hng ngoi (FTIR) ca cc h xc tc nano composit oxit
kim loi trn graphen oxit 81
3.2.3.1 Ph hng ngoi (FTIR) ca h vt liu xc tc Fe3O4 GO ... 81
3.2.3.2. Ph hng ngoi (FTIR) ca h vt liu xc tc CoFe2O4 - GO
3.2.3.2. Ph hng ngoi (FTIR) ca h vt liu xc tc ZnFe2O4-GO
3.2.3.4 Ph hng ngoi (FTIR) ca h vt liu xc tc Fe0-Fe3O4-GO
3.2.3.5 Ph FTIR ca h vt liu xc tc nano composit oxit kim loi
Fe(III)-GO . 83
3.2.4 Ph in t quang tia X (XPS) ca cc h xc tc nano
composit oxit kim loi graphen oxit 84
3.2.4.1 Ph XPS ca h vt liu xc tc Fe3O4-GO 84
3.2.4.2 Ph XPS ca h vt liu Fe0-Fe3O4-GO trn c s Fe3O4 bin
tnh .. 85
3.2.4.3 Ph XPS ca h vt liu xc tc nano composit oxit kim loi
Fe(III)-GO .. 86
3.2.5. Hp ph v kh hp ph Nit (BET) .. 88
3.2.5.1 Hp ph v kh hp ph Nit (BET) ca h vt liu xc tc
Fe0-Fe3O4-GO v Fe3O4-GO .. 88
3.2.5.2 Hp ph v kh hp ph Nit (BET) ca h vt liu xc tc
ZnFe2O4-GO . 89
3.2.6. c trng t tnh ca h xc tc nano composit oxit kim loi 91
graphen oxit
3.2.6.1. ng cong t tr ca h vt liu Fe0-Fe3O4-GO v Fe3O4-GO 91
3.2.6.2. ng cong t tr ca h vt liu ZnFe2O4-GO 92
3.3 nh gi hot tnh xc tc, bn ca cc h vt liu nano
composit oxi kim loi trn graphen oxit 93
3.3.1. nh gi hot tnh ca h vt liu xc tc nano composit Fe3O4
GO .. 94
3.3.2. nh gi hot tnh ca h vt liu xc tc CoFe2O4-GO trn c
s Fe3O4 bin tnh . 95
3.3.3.nh gi hot tnh ca h vt liu xc tc ZnFe2O4-GO trn c s
Fe3O4 bin tnh .. 97
3.3.4. nh gi hot tnh ca h vt liu xc tc Fe0-Fe3O4-GO trn c
s Fe3O4 bin tnh ... 100
3.3.5. nh gi hot tnh ca h vt liu xc tc nano composit oxit
kim loi Fe(III)-GO .. 105
3.3.6. Vai tr ca cc tc nhn trong phn ng Photo Fenton 107
3.3.6 nh gi hiu qu qu trnh phn hy thuc nhum hot tnh 111
RR195 ca cc loi xc tc Fe(III)-GO; Fe0-Fe3O4-GO; CoFe3O4-GO;
ZnFe2O4-GO; Fe3O4-GO
3.4. Nghin cu cc iu kin nh hng n kh nng phn hy
thuc nhum hot tnh RR195 trn vt liu xc tc c hot tnh
cao nht Fe0-Fe3O4-GO . 112
3.4.1 nh hng pH n kh nng phn hy thuc nhum hot tnh
RR195 trn Fe0-Fe3O4-GO . 112
3.4.2. nh hng ca nng H2O2 n qu trnh phn hy thuc
nhum hot tnh RR195 trn Fe0-Fe3O4-GO . 113
3.4.3. nh hng ca nng thuc nhum hot tnh RR195 ban u
n qu trnh phn hy trn Fe0-Fe3O4-GO 115
3.5. ng hc ca qu trnh xc tc quang ha trong phn ng 116
phn hy thuc nhum hot tnh RR195 trn mt s h xc tc .
KT LUN CHUNG 123
NHNG NG GP MI CA LUN AN .. 125
DANH MC CAC BI BAO LIN QUAN N LUN AN .. 126
TI LIU THAM KHO . 127
T VN
Ngy nay, vi s tin b ca khoa hc v cng ngh, cc ngnh cng

nghip nh cng nghip sn, dt, in, ho du...pht trin rt mnh m, tc
ng tch cc n s pht trin kinh t x hi. Tuy nhin, bn cnh nhng li ch
m n mang li th nhng tc hi m cc ngnh cng nghip ny gy ra vi mi
trng l rt ng lo ngi.
Vit Nam ang tn ti mt thc trng l nc thi cng nghip hu
ht cc c s sn xut mi ch c x l s b, thm ch thi trc tip ra mi
trng dn n mi trng nc (k c nc mt v nc ngm) nhiu khu
vc ang b nhim nghim trng. Thnh phn nc thi cng nghip ca cc
c s nh: dt may, cao su, giy, m phm, ch yu l cc cht mu, thuc
nhum hot tnh, cc ion kim loi nng, cc cht hu c,... Trong cc cht
mu thuc nhum do c tnh tan cao nn chng l tc nhn chnh gy nhim
cc ngun nc v nh hng n sc khe ca con ngi v cc sinh vt sng.
Nguy him hn na l thuc nhum trong nc thi rt kh phn hy v chng
c bn cao vi nh sng, nhit v cc tc nhn gy oxi ho. 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,
cc hp cht mu hu c, thuc nhum hot tnh c hi ra khi mi trng
nc c ngha ht sc to ln.
Trong nhng nm gn y c nhiu cng trnh nghin cu v s dng
cc phng php khc nhau nhm x l cc hp cht hu c c hi trong nc
thi. Tuy nhin, cc phng php x l nc thi truyn thng nh: phng
php c hc, phng php sinh hc, phng php ha l,... u khng x l
c hoc x l khng trit cc cht nhim ny.
c th gii quyt trit cc loi cht mu c trong nc thi kh
phn hy th phng php oxi ha nng cao (AOPs) vi c im da vo c
tnh ca cc cht oxi ha mnh nh hydrogen peroxide (H2O2), Ozon (O3), xc
tc cc phn ng quang ha, in ho hoc quang in ho kt hp vi hiu ng
Fenton c ghi nhn c hiu qu cao. Ngoi ra, phng php ny c nhng
u im khc nh khng cn nng lng kch thch tc nhn phn ng, d s
dng v t c hi. Mt trong nhng phng php trin vng gn y thng
c p dng x l nc thi l qu trnh oxi ha nng cao (AOPs) s dng
1
xc tc quang ha, xc tc Photo Fenton nh: TiO2, ZnO, CdS, H2O2, MFe2O4.
c im ca nhng cht ny l di tc ng ca nh sng s sinh ra cp
electron (e-) v l trng (h+) c kh nng phn hy cht hu c nhim thnh
nhng cht sch vi mi trng.
Tuy nhin, nhng hn ch nht nh ca phng php oxi ho nng cao
hin nay khin cho vic m rng quy m ng dng chnh l gi thnh nguyn
liu u vo vn hnh h thng vn cn cao. h gi thnh ca cng ngh
nhng li nng cao c hiu sut x l cc cht hu c c mu th vic tip tc
nghin cu hon thin cng ngh l cn thit. Nhiu nhm nghin cu kt
hp mt s phng php oxi ha nng cao (AOPs) nh UV/H2O2,
UV/H2O2/TiO2, UV/Fenton v Siu m/UV/TiO2 hay to ra cc vt liu
composit mi cho kt qu kh quan. Vt liu cacbon v vt liu trn c s
cacbon nh graphen vn c coi l nhng vt liu c s dng nhiu nht
lm vt liu hp ph do chng c b mt ring ln, n nh v bn ho hc, bn
nhit, dung lng hp ph chn lc cao vi cht mu, ion kim loi nng v cht
nhy quang hc. Gn y, Graphen l mt vt liu cacbon mi, c cu trc lp
(mt hoc vi lp), chiu dy mi lp bng kch thc nguyn t cacbon, cc
nguyn t cacbon vi lin kt sp2 to thnh mng tinh th dng t ong. Graphen
tr thnh i tng c nhiu nh khoa hc quan tm, nghin cu rng ri
bi c nhng tnh cht u vit nh: tnh cht in, in ha, quang hc, c hc
v kh nng hp ph c o ca n.
C nhiu phng php tng hp graphen, ph bin nht vn l phng
php ha hc da trn qu trnh oxi ha graphit to thnh graphen oxit (GO)
v qu trnh kh ha hc graphen oxit thnh graphen (rGO) s dng cc tc
nhn kh ph hp. Graphen, graphen oxit lm tng qu trnh trao i electron
ca chng v cc kim loi lm gim nng lng vng cm ca cc kim loi,
ngoi ra graphen, graphen oxit cn ngn chn s ti kt hp ca cp electron v
l trng to ra, chnh iu ny lm tng hiu sut quang ha. Do vy, mt s nh
nghin cu gn kt cc kim loi ln b mt ca graphen, graphen oxit lm
tng hot tnh quang ha ca chng. Xut pht t nhng l do trn chng ti la
chn ti lun n Nghin cu tng hp v c trng vt liu mi, cu trc
nano ng dng trong quang ha xc tc phn hy thuc nhum c
thc hin.
Mc tiu nghin cu ca lun n
2
Tng hp thnh cng mt s h vt liu nano composit trn c s oxit
kim loi c t tnh/graphen oxit; nghin cu nh gi hot tnh xc tc ca cc
h vt liu tng hp c trn thuc nhum hot tnh v ng dng lm xc tc
quang ha mi, hiu qu cao, c kh nng thu hi v ti s dng trong phn ng
phn hy cht mu, thuc nhum hot tnh x l nc thi dt nhum.
Ni dung nghin cu ca lun n
- Tng hp c mt s vt liu nano composit oxit kim loi/graphen oxit
trn c s oxit st t Fe3O4, Fe3O4 bin tnh v to phc Fe(III), nh h xc tc
Fe3O4-GO; CoFe2O4-GO; ZnFe2O4-GO; Fe0-Fe3O4-GO; Fe(III)-GO bng
phng php ng kt ta, phng php kh ha hc v phng php trao i
ion.
- c trng cc vt liu tng hp c bng cc phng php ha l hin
i nh XRD, FTIR, TEM, XPS, BET, UV-Vis...
- nh gi hot tnh i vi cc h xc tc tng hp c.
- Nghin cu cc iu kin nh hng nh pH, nng H2O2, nng
thuc nhum hot tnh RR195 ban u n hot tnh xc tc ca vt liu tng
hp.
- Nghin cu ng hc qu trnh xc tc quang ha trong phn ng phn
hy thuc nhum hot tnh RR195 trn h xc tc c hot tnh cao nht.
3
CHNG 1. TNG QUAN
1.1 Vt liu graphen v ng dng trong x l cht mu
Graphen vt liu cacbon mi c 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 (Hnh 1.1).
V c im trn m nhng l thuyt v graphen bt u c
nghin cu t nhng nm 1940. Nm 1946, P.R. Wallace l ngi u tin
vit v cu trc vng nng lng ca graphen, v nu ln nhng c tnh d
thng ca loi vt liu ny. Cn nhng nghin cu v thc nghim th cha
c pht trin bi v cc nh khoa hc cho rng cu trc tinh th 2 chiu vi
b dy ch bng 1 nguyn t khng tn ti v cc thit b k thut lc by gi
cng khng th quan st thy cc cu trc ny.
Hnh 1.1. Graphen - vt liu c cu trc c bn (2D)

cho cc vt liu cacbon khc (0D, 1D, v 3D [1]
n nm 2004, nhng khm ph t thc nghim ca 2 nh khoa hc
ngi Nga l Kostya Novoselov v Andre Geim thuc Trng i hc
Manchester Anh chng t s tn ti ca graphen, t vt liu ny thu
ht s quan tm c bit ca cc nh khoa hc trn th gii bi cc c tnh
vt tri ca n. Nhng tm graphen c cu trc phng v dy mt nguyn
4
t, l vt liu mng nht trong tt c cc vt liu hin c, vi cu trc bn
vng graphen c xem l vt liu cng nht hin nay v dng tinh khit
th graphen dn in nhanh hn bt c cht no khc (ngay c nhit bnh
thng). Hn na, cc electron i qua graphen hu nh khng gp in tr nn
sinh nhit thp hn in tr ca Ag v l in tr thp nht hin nay nhit
phng.
1.1.1 Vt liu trn c s graphen
Trc nhng nm 1980, h cacbon ch c bit n vi graphit v kim
cng, cho n khi s xut hin ca fullerene, v gn y l graphen thay i
hon ton iu . Trong cc vt liu cacbon ny, graphen c quan tm
nghin cu rt nhiu do c im cu trc c o v tnh cht vt tri. Hn
na chi ph sn xut graphen c cho l thp hn so vi vt liu nano
cacbon khc. Chnh v vy, s quan tm n graphen ngy cng tng trong
nghin cu cc kha cnh khc nhau. c bit, graphen c ch nh vt liu
hp ph cho x l nc thi v tnh cht c o ca graphen nh: c cu trc
hon ho, din tch b mt tng i cao c th tng hp t graphit bng
phng php ha hc, bc tch lp v kh ha hc. Mt vi nghin cu c
thc hin hp ph cc ion kim loi v cc cht hu c c hi s dng graphen.
Cc ng dng phong ph ca graphen khuyn khch s pht trin khng ch
ca n lp graphen m cn vt liu lin quan nh graphen oxit (GO). GO l
mt sn phm trung gian quan trng ca graphen thu c bng cch oxi ha
graphit v tch lp c hc. GO vi tnh cht c bn ging nh graphen nh din
tch b mt ring ln, c nhiu nhm chc trn b mt, kh nng phn tn tt
trong nc c nhiu nhm nghin cu lm cht hp ph loi b cc hp
cht cha cation v cyanotoxins t nc b nhim. Cc nhm chc cha oxy
s lin kt vi cc ion kim loi v hp cht c in t dng. Tnh cht vt l
ca n lp graphen nhit phng c Sumit Goenka [2] thng k bng
1.1.
Bng 1.1. Tnh cht ca Graphen n lp
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
5
cng 125 GPA
in tr 200 000 cm2 V-1 s-1
dn in 5000 W m-1 K-1
truyn quang 97,7%
Cu trc ca graphen
Hnh 1.2. Cc lin kt ca mi nguyn t cacbon trong mng graphen

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. Trong , mi nguyn t cacbon lin kt vi ba nguyn
t cacbon gn nht bng lin kt - to thnh bi s xen ph ca cc obitan
s-p, tng ng vi trng thi lai ho sp2 [3]. Khong cch gia cc nguyn t
cacbon gn nht l a = 0,142 nm. Theo nguyn l Pauli, cc mc nng lng
trong lin kt c lp y, do cc obitan lai ha sp2 s c trng cho
mc bn vng trong cu trc phng ca mng graphen. Obitan p cn li
ca cc nguyn t cacbon nm vung gc vi cu trc phng ca mng, xen ph
bn vi nhau hnh thnh nn lin kt , v mc nng lng ca lin kt ny
cha c lp y nn n cn c gi l cc obitan khng nh x, cc
obitan ny s ng vai tr quan trng trong vic hnh thnh nn cc tnh cht
in khc thng ca graphen (hnh 1.2).
1.1.2. Tm hot ng ca graphen v graphen oxit
Cc hp cht hu c c th c hp ph trn cc ht nano (NPs) hay vt
liu cu trc nano khng qua lin kt cng ha tr m l 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. Trong trng hp ca graphen, h thng
in t bt i xng ng vai tr ch o trong vic hnh thnh mnh m ca
6
lin kt tng tc - ca s chng xp vi mt s cht hu c c cha vng
thm. Lin kt cation cng ng gp vo qu trnh hp ph. 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 . GO mang nhiu nhm chc phong ph hnh thnh t
cc lin kt hydro hay s tng tc in t vi cc hp cht hu c c cha oxy
v nit.
Pei v cng s [4] nghin cu qu trnh hp ph ca cc aromatic vi cu
trc khc nhau trn graphen v GO nh: 4,6-trichlorophenol (TCP), 2-naphthol,
1,2,4-trichlorobenzen (TCB) v naphthalen (NAPH). Kh nng hp ph ca
chng tng ng nhau mc d tnh cht ha hc khc nhau. Ngoi vic tng
tc k nc, cc hp cht ny cn c hp ph vo graphen ch yu qua tng
tc - . So vi graphen, GO c mt electron thp hn v c nhiu nhm
chc cha oxy, v vy hp ph TCP v 2-naphthol trn GO cho thy l do s
hnh thnh cc lin kt hydro gia nhm hydroxyl vi TCP v 2-naphthol vi
cc nhm chc cha oxy trn graphen oxit. Do i lc hp ph ca cc
aromatic vi GO tng theo chiu NAPH <TCB <TCP < 2-naphthol.
Gao cng cc cng s [5] nghin cu s hp ph ca cht khng sinh
tetracyline trn graphen oxit. Kh nng hp ph ln ca GO c gii thch
bi s tng tc - v lin kt cation . Cc lin kt cation c th c hnh
thnh gia cc nhm amin trong tetracyline vi electron ca graphen.
Tetracyline cha 4 vng thm vi cc nhm chc khc nhau trn cc vng bao
gm phenol, ru, xeton v amin. Do , s tng tc tnh in v lin kt
hydro cng gp phn vo qu trnh hp ph. V vy vi cc tnh cht hp ph
, GO v graphen cng c s dng nh cht hp ph loi b thuc nhum
v cc cht hu c c hi gy nhim mi trng nc [6,7].
Qu trnh hp ph cc ion kim loi trn GO thng khng ph thuc n
lc ion m ph thuc nhiu vo dung dch pH [8,9]. Mt mt gi tr pH cao c
li cho vic ion ha ca cc nhm chc cha oxy trn b mt graphen oxit.
im pHpzc ca GO l ~ 3,9, do vy pH >3,9 (pH> pHpzc) in tch trn b
mt GO l m v s tng tc tnh in gia cc ion kim loi v GO tr nn
mnh hn. Mt khc, vi gi tr pH cao, cc hydroxit kim loi c th hnh thnh
kt ta hay nhm anion s chim u th. Tht l kh hp ph cc anion trn
GO do s tch in b mt ca GO l m, v vy gi tr pH cn la chn mt
cch cn thn c c hiu qu cao. Ngoi ra s hp ph cc kim loi trn
7
GO khng ch ph thuc vo pH hay tn ti ion kim loi m cn ca cc cht
hu c [10]. V d: Zhao cng cc cng s nghin cu nh hng ca axit
humic, thng thy trong mi trng v th hin kh nng to phc mnh vi
cc ion kim loi bi nhng nhm chc cha oxy rt phong ph .
1.1.3 Cc phng php tng hp graphen
C nhiu phng php khc nhau ch to mng graphen, cc nhm
phng php c tin hnh nhiu nht l: phng php tch lp vi c hc
ca graphit (micromechanical exfoliation of graphit), phng php epitaxy (epitaxial
growth) v phng php ch to graphen bng phng php ha hc.
1.1.3.1. Phng php tch c hc
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, ln lc cn
thit tch lp graphit l khong 300 nN/m2 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, Andre K. Geim v Kostya Novoselov [11] ti i hc
Manchester Anh tnh c tm ra c mt cch to ra graphen, h 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 graphen (hnh1.3.).
y l phng php n gin to ra nhng mu graphen nh, ph
hp cho nhng nghin cu c bn, ngoi ra khm ph ny cn c ngha quan
trng l n m ra bc ngot mi cho nhng nghin cu thc nghim v
graphen, l tin cho s thnh cng ca nhng phng php khc trong vic
ch to mng graphen, mt vt liu c cho l b lng qun trong 40 nm
qua.
8
Hnh 1.3. Phng php tch lp graphit bng bng dnh
u im: y l phng php tn km t, d thc hin v khng cn
nhng thit b c bit.
Khuyt im: Kt qu ca phng php khng nht nh m ch mang
tch cht cu may, mng to nn khng phng v y l phng php i hi
tnh t m khng ph hp cho vic ch to graphen vi s lng ln ng
dng cho sn xut cng nghip. Ngoi ra, khi s dng bng dnh hoc cc in
cc tch lp graphit, lng tp cht nh c th bm li trn b mt ca
graphen.
1.1.3.2. Phng php epitaxy
Epitaxy l phng php to mng n tinh th trn mt ca mt tinh
th. C hai c ch c nghin cu: th nht l c ch phn hy nhit ca mt
s cacbua kim loi, th hai l c ch to mng n tinh th ca graphen trn
kim loi hoc cacbua kim loi bi s lng ng hi ha hc (Chemical Vapor
Deposition) ca cc hydrocarbon.
C ch phn hy nhit: Thng c tin hnh vi silic cacbua (SiC)
1300oC trong mi trng chn khng cao hoc 1650oC trong mi trng kh
Argon, bi v s thng hoa ca Si xy ra 1150oC trong mi trng chn khng
v 1500oC 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 1.4) [12].
9
Hnh 1.4. C ch to mng graphen bng phng php nung nhit SiC
C ch to mng graphen:
Trn cc kim loi (Ni, Cu,) v cacbua kim loi c tm tt nh
sau: u tin cc c nung n nhit cao (~1000oC) trong mi trng
kh H2 v Ar loi b nhng oxit trn b mt, sau dng kh long ca
hydrocacbon c a vo, nhit cao cc hydrocacbon s b phn hy v
lng ng li trn b mt , cui cng nhit ca h thng c lm lnh
nhanh cc nguyn t cacbon phn tch (segregation) trn b mt v hnh
thnh mng graphen. Khi s dng kim loi Ni v hydrocacbon l kim loi
to ra c mng graphen vi linh ng ca ht ti t n 4000 cm2/Vs.
Mt s kt qu khc cng cho thy mng graphen ch to t phng php
ny t c truyn qua l 80% [13,14].
u im: u im ni tri ca phng php ny l ch to c cc mng
graphen din tch ln (~1cm2), ng u mng cao hn so vi cc phng
php khc. T cc mng graphen cht lng tt ny c th pha tp thch hp
to nn cc bn dn loi n, loi p. Mng graphen to t vic nung nng silic
cacbua c tin s Walter de Heer s dng ch to cc computer chip.
Khuyt im: Kh khn ca phng php ny l kh nng kim sot
hnh thi hc v nng lng bm dnh iu kin nhit cao. 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, cho nn 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.
Ngoi ra qu trnh chuyn ca mng cng cn nhiu kh khn.
10
1.1.3.3. Phng php ha hc
Hin nay, phng php ha hc chuyn graphit thnh graphen oxit
(GO) c bit n l mt phng php u vit to ra nhng tm graphen.
Graphen oxit c to thnh qua phn ng oxi ha ca graphit vi cc cht oxi
ha bao gm axit sulfuric (H2SO4) m c (98%), thuc tm KMnO4, hydro
peroxit H2O2 (30%) da trn phng php Hummer [15]. So vi graphit ban
u, graphen oxit mang nhiu nhm chc cha oxy nh hydroxyl, epoxy trn b
mt cacbon lai ha sp3. Ngoi ra cn c cc nhm cacbonyl v cacboxyl nm
cc cnh trn cacbon lai ha sp2. Do graphit oxit c tnh a nc v d dng
phn tn trong nc. Graphit oxit c phn tn trong nc theo t l 1mg/ml v
s dng phng php siu m tch lp thnh graphen oxit. Cc tm graphit
ban u c dy 0,34 nm, tm GO c cho l dy hn do s dch chuyn ca
nguyn t cacbon sp3 ln trn hoc di so vi mt phng graphen gc v s c
mt ca cc nguyn t oxy lin kt ha tr. Kt qu tng t khi pha phn tn l
cc dung mi nh: N,N-dimethylformamide (DMF), N-methyl-2-pyrolidone (NMP),
tetrahydrofuran (THF) v ethylen glycol [16]. Li v cc cng s [17] ch ra
rng b mt ca GO l c m in ln khi phn tn trong nc t kt qu o
th zeta. l do s ion ha ca nhm axit cacboxylic v phenolic hydroxyl. S
phn tn n nh ca GO trong nc khng ch do tnh a nc m cn do lc
y tnh in ca n.
Ngoi ra cn c th tch lp graphit oxit to thnh GO bng phng
php vi sng, hn hp c t trong l vi sng vi cng sut 700W trong 1
pht, nhit tng ln t ngt dn n tng tc phn hy cc nhm chc,
c bit l cc v tr epoxy v hydroxyl trn graphit oxit. Tc khuch tn ca
kh bay ra ln hn so vi lc van der walls lin kt gia chng khin cc lp s
c tch ra v to thnh graphen oxit [18] .
to ra graphen c th s dng n kh ha hc vi mt s tc nhn
ha hc nh hydrazine [19] v natri borohydrate [20]. Hydrazine hydrate khng
ging nh cc cht kh mnh khc, khng phn ng vi nc v c xc nh
l tc nhn kh tt nht. Trong qu trnh kh mu nu ca GO c phn tn
trong nc v chuyn sang dng mu en v cc tm c kh s co cm li do
qu trnh kh GO mt dn tnh a nc do c loi b cc nguyn t oxy.
11
Hnh 1.5. Qu trnh oxi ha t graphit thnh GO (a) v qu trnh kh
GO bng hydrazine (b) c xut [21]
Ngoi ra, qu trnh kh nhit cng l mt phng php kh graphen
oxit (GO) thnh graphen ang c cc nh khoa hc c bit quan tm nghin
cu. Vic dng nhit loi b cc nhm chc cha oxy trn b mt ca
graphen oxit (GO) tin hnh kh n gin, thit b vn hnh khng qu phc tp.
Nhm nghin cu ca Aksay tch lp trc v a vo kh nhit 1050oC
nhit m cc nhm chc s b loi b nh cacbon dioxit [22]. Vic loi b
cc nhm chc gy ra mt mt khi lng v li cc v tr khuyt tt v cu
trc c th nh hng n tnh c hc v in t ca graphen oxit (GO). Mt
khc, cc v tr khuyt tt ng vai tr nh tm hp ph trong qu trnh hp ph
ca graphen oxit (GO) v graphen.
12
Hnh 1.6. C ch ngh ca qu trnh tng hp GO v graphen
T vic phn tch cc u v khuyt im ca mt s phng php ang
c s dng hin nay ch to mng graphen cho thy: mc d phng
php epitaxy v CVD tng hp nn cc lp graphen cht lng cao nhng
khng c tin hnh ph bin v hiu sut thp, nhit ca qu trnh kh
cao (>1000oC), mi trng s dng l mi trng ca kh him, v c bit l
cn phi s dng cc thit b hin i vi gi thnh cao. Trong khi phng
php ha hc ch to graphen thng qua s to thnh cht trung gian l
graphit oxit c cho l kh thi nht khi cn i gia cc yu t c lin quan,
v ang c quan tm tin hnh rng ri trn th gii. Phng php ny c th
to ra lng graphen ln, cht lng tng i cao v c bit l gi thnh sn
xut thp d dng chp nhn c cho phn ln cc ng dng hin nay.
1.2. Cht mu hu c v phng php x l
1.2.1 Gii thiu v nhim cht mu hu c
Ngnh dt nhum l mt trong nhng ngnh quan trng v c t lu i
v n gn lin vi nhu cu c bn ca loi ngi l may mc. Sn lng dt trn
th gii ngy cng tng cng vi gia tng v cht lng sn phm, a dng v
mu m, mu sc ca sn phm. Vit Nam, ngnh cng nghip dt may ang
tr thnh mt trong nhng ngnh mi nhn trong cc ngnh cng nghip. Trong
nm 2014 kim ngch xut khu dt may l trn 24 t la M. Nng lc sn
xut vi ni a theo thng k ca VCOSA (Hip hi bng si Vit Nam) l gn
13
3.109 m2/ nm, theo l lng nc thi rt ln cn c x l trit trc
khi thi ra mi trng bn ngoi [23].
Hnh 1.7 Nc thi dt nhum

Ngun nc thi pht sinh trong cng ngh dt nhum l t cc cng
on h si, gi h, nu, ty, nhum v hon tt. Trong lng nc thi ch
yu do qu trnh git sau mi cng on. Nhu cu s dng nc trong nh my
dt nhum rt ln v thay i theo mt hng khc nhau. Nhu cu s dng nc
x l cho 1 mt vi nm trong phm vi t 12 - 65 lt v thi ra t 10 - 40 lt.
Do vy, vn nhim ch yu trong ngnh dt nhum chnh l nhim ngun
nc [24].
1.2.1.1 Thuc nhum
Thuc nhum l nhng cht hu c c mu, hp th mnh mt phn nht
nh ca quang ph nh sng nhn thy v c kh nng gn kt vo vt liu dt
trong nhng iu kin quy nh (tnh gn mu).
Thuc nhum c th c ngun gc thin nhin hoc tng hp. Hin nay
con ngi hu nh ch s dng thuc nhum tng hp. c im ni bt ca cc
loi thuc nhum l bn mu v tnh cht khng b phn hy. Mu sc ca
thuc nhum c c l do cu trc ha hc: mt cch chung nht, cu trc
thuc nhum bao gm nhm mang mu v nhm tr mu. Thuc nhum tng
hp rt a dng v thnh phn ho hc, mu sc, phm vi s dng. C hai cch
phn loi thuc nhum ph bin nht:
a. Phn loi theo cu trc ho hc gm c: thuc nhum azo, thuc
nhum antraquinon, thuc nhum triarylmetan, thuc nhum phtaloxiamin [24].
b. Phn loi theo c tnh p dng gm c: thuc nhum hon nguyn,
thuc nhum lu ho, thuc nhum trc tip, thuc nhum phn tn, thuc
nhum baz cation, thuc nhum axit, thuc nhum hot tnh [24].
14
Trong s cc thuc nhum c s dng trong cng nghip dt th thuc
nhum azo c s lng ln nht, chim khong 60-70% s lng cc thuc
nhum tng hp [25, 26]. y l cc hp cht c cha nhm azo (- N =N-)
trong phn t v cc nhm tr mu tu theo c tnh ca nhm tr mu. Nu
nhm tr mu mang tnh baz c cc nhm y electron mnh nh -NH2, -
NR2 gi l thuc nhum azo-baz. Nu nhm tr mu c tnh axit do cc
nhm th - OH, -COOH, -SO3H gi l thuc nhum azo-axit. Cc hp cht azo
thng l cc phm nhum c mu sc ti sng do s hin din ca mt hoc
mt vi nhm azo (-N =N-) to h lin hp vi cu trc nhn thm. Trong
khun kh lun n ny, chng ti tp trung cp n c im ca thuc
nhum axit azo (Reactive Red 195) thng c s dng trong phng th
nghim dt may v cc ngnh cng nghip khc, ng thi cng c dng lm
cht mu ch th nh gi hiu qu ca cc m hnh x l trong phn thc
nghim.
Hnh 1.8 Cng thc cu to ca thuc nhum hot tnh RR195

Cng thc phn t: C31H19ClN7Na5O19S6
Khi lng phn t: 1136,32 g/mol
1.2.1.2 Cc thng s nh gi nc thi dt nhum
pH
Tr s pH cho bit nc thi c tnh axit, kim hay trung tnh. Qu trnh
x l nc thi bng phng php sinh hc rt nhy cm vi s dao ng ca
gi tr pH (cc vi sinh vt s b c ch hoc b cht khi c s thay i pH). V
vy cn kim tra gi tr pH trong khong thch hp trc khi cho nc thi vo
h thng x l.
Mu sc
Mu sc ca nc l do cc cht bn trong nc gy nn. Mu sc ca
nc c th l do cc cht hu c v phn chit ca thc vt gi l mu thc.
Ngoi ra do cc cht v c l nhng ht rn c mu gy ra, gi l mu biu kin
c
15
c ca nc do cc ht l lng, cc cht hu c phn hy hoc do
gii thy sinh gy ra. c lm gim kh nng truyn nh sng trong nc,
nh hng n kh nng quang hp ca cc vi sinh vt t dng trong nc.
Nc cng bn, c cng cao. n v chun o c l s cn quang do 1
mg SiO2 ha tan trong 1 lt nc ct gy ra.
Tng lng cht rn (TS)
Tng lng cht rn l trng lng kh tnh bng mg ca phn cn li sau
khi bay hi 1 lt mu nc trn ni cch thy ri sy kh 103oC cho ti khi
trng lng khng i (n v : mg/l)
Cht rn huyn ph (SS)
L cht rn dng l lng trong nc. Hm lng cht rn huyn ph SS
l trng lng kh ca phn cht rn cn li trn giy lc si thy tinh khi lc 1
lt mu nc qua phu ri sy kh (n v: mg/l)
Cht rn ha tan
Hm lng cht rn ha tan chnh l thng s ca tng lng cht rn v
hm lng cht rn huyn ph.
Hm lng oxy ha tan (DO- Disolved oxigen)
L lng oxy khng kh c th ha tan vo nc trong iu kin nhit
thp, p sut xc nh. Ch s DO thp c ngha l nc c nhiu cht hu c,
nhu cu oxi ha tng nn tiu th nhiu oxy trong nc. Ngc li, ch s DO
cao c ngha l nc c nhiu rong to tham gia vo qu trnh quang hp gii
phng oxy. Ch s DO rt quan trng duy tr iu kin hiu kh v l c s
xc nh nhu cu oxi ha sinh hc.
Nhu cu oxi ha sinh hc (BOD- Biochemical oxigen Demand)
BOD c nh ngha l lng oxy cn thit oxi ha cc cht hu c
c trong nc thi bng vi sinh vt (ch yu l vi khun) hoi sinh, hiu kh. Ch
tiu ny xc nh nhim ca nc thi hoc nc sng, h do cha cc cht
dng tan, keo, khng tan kh lng.
Qu trnh ny c tm tt nh sau:
Cht hu c + O2 + (vi sinh vt) CO2 +H2O
Trong thc t, ngi ta khng th xc nh lng oxy cn thit phn
hy hon ton cht hu c bng phng php sinh hc, m ch xc nh lng
oxy cn thit trong 5 ngy u (BOD5) nhit 20oC trong bng ti ( trnh
hin tng quang hp trong nc).
16
Nhu cu oxy ha hc (COD- chemical oxigen Demand)
COD c nh ngha l lng oxy cn thit cho qu trnh oxi ha ton
b cc cht hu c c trong mu thnh CO2 v H2O. Ch s COD c dng
rng ri c trng cho hm lng cht hu c ca nc thi v s nhim
ca nc t nhin. xc nh COD ngi ta thng s dng mt cht oxi ha
mnh trong mi trng axit, nh kali bicromat (K2Cr2O7).
Ngoi ra cn c cc ch tiu:
- Tng cacbon hu c (TOC- Total Organic Carbon)
- Nhu cu oxy l thuyt (ThOD- Theoretical Oxigen Demand)
- Nhu cu oxy tng cng (TOD- Total Oxygen Demand)
TOC ch c dng khi hm lng cc cht hu c rt nh trong nc.
ThOD chnh l lng oxy cn thit oxi ha hon ton cc cht hu c c
trong nc thnh CO2 v H2O. ThOD ch tnh c gi tr khi bit r cng thc
ha hc ca cc cht hu c. V thnh phn ca nc thi rt phc tp nn
khng th tnh c ThOD chnh xc v vy c th tnh gn ng da vo gi tr
COD. Cc thng s ny c ln nh sau: ThOD> COD > BOD cui > BOD.
1.2.2 Cc phng php x l thuc nhum hot tnh trong nc thi dt
nhum
Trong vng vi nm tr li y con ngi nhn thc r rng hn v
nhng tc ng i vi mi trng v sc kho con ngi ca cc loi thuc
nhum mu, do vy vic pht trin cc phng php nhm x l tnh trng
nhim mi trng cng nh ch ng x l nc thi ca cc nh my c s
dng thuc nhum l nhu cu tt yu v bt buc. C rt nhiu phng php
c s dng c hiu qu trong vic loi mu thuc nhum, c chia thnh 3
nhm ln l cc phng php sinh hc, ho hc v vt l. Cc phng php vt
l v ho hc bao gm hp ph, quang xc tc, phn hu quang xc tc hp ph,
ozone ho, ng t, in ng t cc phng php in ho, phng php tch
mng, phng php siu m, oxi ho khng kh t, phng php mng nh
tng lng, ng dng thnh cng trong vic x l cc cht mu khc nhau.
Tuy cc phng php ny rt hiu qu v kinh t nhng ch ng dng c khi
nng cc cht hu c c mu cao nhng phi ho tan. Mt vi phng php
vn cn c gi thnh cao v thnh thong vn sinh ra cc cht ph c hi. Cc
phng php x l sinh hc loi mu thuc nhum da vo cc h thng k
kh v hiu kh, ln men cc loi bn hot tnh t nm si, nm men, vi
17
khun, qun x vi khun nm. Mc d cc phng php sinh hc c nh
gi l cc phng php kinh t nht khi so snh vi cc phng php ho l
khc, tuy nhin kh nng ng dng ca chng li b hn ch v k thut nh thi
gian x l di v thng khng hiu qu khi x l cc cht nhum mu c cu
trc polymer cao phn t bn vng. Hn na, thnh phn cc cht mu trong
nc thi thng gy c cho qun x hoc qun th vi sinh vt s dng trong
bn. Cc phng php loi b mu thuc nhum c th c chia thnh hai
nhm phn hu v khng phn hu (Hnh 1.9). Bng 1.2 tng kt cc u
im v nhc im ca mt s phng php hin nay ang s dng trong cng
ngh loi b thuc nhum.
Hnh 1.9 Cc phng php loi b mu thuc nhum

(Fernndez et al., 2010) [27]
Bng 1.2 u v nhc im ca mt s phng php x l cc hp cht hu c
c mu.
Phng php u im Nhc im
Cng ngh n gin, kinh t L nguyn nhn dn n cc
nhim khc t cc phn ng ph
v to ra hm lng bn qu ln
18
Ozon ho Khng thay i v th tch Gi thnh ozone cao, ch mt
x l lng ozone c th c chuyn
ho v tc truyn khi lng
rt chm, ch s bn thi gian
ngn (20 pht)
Quang ho Khng to ra lng bn ln, Hnh hnh cc sn phm ph,
tc x l nhanh v hiu gi thnh nng lng cao
qu hp ph cc cht mu
tt
Phn hu sinh Gi thnh kinh t, c th Tc x l chm, cn thit lp
hc thc hin c tt c cc iu kin mi trng ti u, i
quy m hi cc iu kin giu dinh
dng duy tr
Hp ph ln Kh nng hp ph cao v Gi thnh vn hnh cao, do vy
cacbon hot khng c s phn hu ho kh c th m rng quy trnh
tnh hc. C kh nng thc hin quy m ln; Khng hiu qu i
m hnh c dng chy ln, vi mt s loi thuc nhum c
cht lng nc sau x l phn tn cao
tt m khng tn d bn
cng nh cc cn cha.
in ho Khng cn b sung cc cht Gi thnh in cao
ho hc, d dng vn hnh
v kh nng loi b cht
ma cao, sn phm cui
cng khng c hi
Trao i ion Khng tht thot cc cht Gi thnh cao, khng hiu qu
hp ph, c hiu qu loi i vi thuc nhum c phn
mu tt tn cao. Khng hiu qu trong
cc h thng ct hoc dng chy
hp ph
Lc mng Thn thin vi mi trng, To ra nhiu bn; Cn p sut
c kh nng loi b hu ht ln nn gi thnh cao, khng
cc loi mu, cht lng ph hp khi x l quy m ln
nc thi tt
19
Oxi ho Qu trnh din ra nhanh v Tng hp mt s sn phm rt
hiu qu cao c nh hp cht organochlorine
Oxi ho nng Khng chuyn cc cht c Gi thnh vn hnh cao. Hiu
cao (AOPs) hi t pha ny sang pha qu x l cha tng xng vi
khc, ng thi cng khng thnh phn a dng ca nc
to ra mt lng ln bn thi dt nhum
thi c hi. Ch mt lng
nh ho cht b tiu hao v
c hiu qu cao i vi cc
loi mu bn vng. Nhng
cht hu c thng b oxi
ho n sn phm CO2
Hp ph Vn hnh n gin, khng i hi phi thay i thnh phn
c tnh chn lc cc cht c ho hc, qu trnh khng phn
v c th ti s dng cc vt hu. Qu trnh vn hnh v ti
liu hp ph. Quy trnh c hot ho thng lm mt hot
thc hin nhanh, r, thn tnh hp ph ca cacbon, do
thin vi mi trng v c dn n gi thnh s dng
th ti s dng cc vt liu phng php ny cha kinh t.
thi
in ng t C hiu qu cao i hi mt lng ln nc
to ra nng lng cho qu trnh
ng t. Thiu mt thit k
chung cho cc ni phn ng theo
m hoc lin tc. Quy trnh bao
gm nhiu c ch phc tp.
Sinh khi Gi thnh vn hnh thp, Tc x l chm v din ra
hiu qu tt i vi mt s ph thuc vo cc yu t bn
loi thuc mu, khng gy ngoi nh pH, nng v thnh
c hi ln cc t bo vi sinh phn mui
vt
Siu m Khng to ra lng bn thi i hi mt lng ln oxy ho
d tan, gi thnh cao.
20
Trong cc phng php x l thuc nhum hot tnh trong nc dt
nhum th phng php vi sinh l phng php kinh t v sinh thi nht.
Phng php ny c ngh n u tin trong qu trnh x l nc thi. Nhng
vi nhng c im ca nc thi dt nhum, nht l nc thi cha thuc
nhum hot tnh th mt mnh phng php vi sinh khng th gii quyt c
trit vn , nc thi sau x l khng m bo c tiu chun thi. V vy
ngi ta phi tin hnh tin x l cc cht mu (thuc nhum) kh hoc khng
phn gii sinh hc trong nc thi dt nhum bng phng php ha l, ha hc
ri mi x l hon tt bng phng php vi sinh. i vi thuc nhum hot
tnh, hin nay trn th gii v ti Vit Nam vn cha c mt phng php tin
x l tht s hiu qu v kinh t v c tnh tan, bn v a dng v chng loi
ca n. Phng php oxi ha, c bit l oxi ha pha lng c nghin cu v
t ra c tim nng trong gii quyt vn ny.
1.2.2.1 Cc phng php ha l
Cc phng php ha l n thun c c im chung l chuyn cht
nhim (cht mu) t pha ny sang pha khc m khng lm bin i bn cht, cu
trc cht mu. Do , trong x l cht mu th cc phng php ha l c nhc
im chung l khng x l trit cht mu chuyn chng thnh cc cht
khng gy nhim hoc cc cht d phn hy sinh hc hn.
Phng php keo t
Keo t l hin tng cc ht keo cng loi c kh nng ht nhau to thnh
nhng tp hp ht c kch thc v khi lng ln c th lng xung do
trng lc trong mt thi gian ngn. Phng php keo t x l cht mu dt
nhum l phng php tch loi cht mu gy nhim ra khi nc da trn
hin tng keo t. V nguyn tc, do c phn tn ln, din tch b mt ring
ln nn cc ht keo c xu hng ht nhau nh cc lc b mt. Tuy nhin, do cc
ht keo c cng loi in tch cng du c trng bng th zeta () nn cc ht
keo lun y nhau bi lc tnh in, cn tr s ht nhau to cc ht v lng
xung. Nh vy th cng ln h keo cc bn (kh kt ta), th cng nh th
cc ht keo cng d b keo t. Trong trng hp l tng khi th bng 0 th cc
ht khng tch in v d dng ht nhau bi lc b mt to thnh cc ht c
khi lng ln v lng xung.
Phng php keo t c s dng rng ri trong x l nc thi dt
nhum i vi cc thuc nhum phn tn v khng tan. y l phng php kh
21
thi v mt kinh t, tuy nhin n khng x l c tt c cc loi thuc nhum :
thuc nhum axit, thuc nhum trc tip; thuc nhum hon nguyn ko t tt
nhng khng lng kt d dng, bng cn cht lng thp, thuc nhum hot tnh
rt kh x l bng cc tc nhn ko t thng thng v cn t c nghin cu.
Bn cnh phng php keo t cng to ra mt lng bn thi ln v khng
lm gim tng cht rn ha tan nn gy kh khn cho tun hon nc.
Phng php hp ph
Nguyn l ca phng php da vo c tnh bn trong vt rn thng
cha cc nguyn t (ion hoc phn t), gia chng c cc lin kt cn bng
to ra cc mng lin kt cng (cht v nh hnh) hoc cc mng tinh th c qui
lut (cht tinh th). Trong khi , cc nguyn t (ion hoc phn t) nm b
mt ngoi khng c cn bng lin kt, do khi tip xc vi mt cht kh
(hi hoc lng), vt rn lun c khuynh hng thu ht cc cht ny ln b mt
ca n cn bng lin kt. Kt qu l nng ca cht b hp ph (kh, lng)
trn pha b mt ln hn trn pha th tch. Vy, hin tng hp ph l s tng
nng ca kh (hi hoc lng) trn b mt phn cch pha (rn-kh hoc rn-
lng) [28,29].
Ngay c khi b mt c lm nhn mt cch cn thn th n cng khng
thc s bng phng trn phng din vi cu trc. Thc ra trn b mt ca n
lun tn ti nhng vng bt thng vi nhng vt gp, khe ntkhng ng
nht hnh hc. Nhng vng ny thng tn ti nhng trng lc d. c bit,
cc nguyn t b mt ca cht rn c th hp dn cc nguyn t hay phn t
trong pha kh hay pha lng mi trng xung quanh. Tng t nh th, b mt
ca tinh th hon thin cng tn ti nhng trng lc khng ng nht do cu
trc nguyn t trong tinh th. Nhng b mt nh th tn ti nhng trung tm hay
tm hot tnh c kh nng hp ph cao.
R rng, cht hp ph c b mt cng pht trin th kh nng hp ph
cng tt. Vi cht hp ph c b mt cng phn cc th kh nng hp ph cc
cht phn cc tt hn trong trng hp cht c b mt km phn cc. c
th so snh kh nng hp ph gia cc cht ngi ta s dng khi nim b mt
ring, l din tch b mt ca cht hp ph tnh cho mt gam cht hp ph
(m2/g). V d: b mt ring ca silicagel c th t 200-700 m2/g, zeolit t 500-
800 m2/g
S hp ph trong mi trng nc
22
Trong nc, tng tc gia mt cht b hp ph v cht hp ph phc tp
hn rt nhiu v trong h c t nht ba thnh phn gy tng tc: nc, cht hp
ph, v cht b hp ph. Do s c mt ca dung mi nn trong h xy ra qu
trnh hp ph cnh tranh gia cht b hp ph v dung mi trn b mt cht hp
ph. Cp no c tng tc mnh th hp ph xy ra cho cp . Tnh chn lc
ca cp tng tc ph thuc vo cc yu t: tan ca cht b hp ph trong
nc, tnh a nc, tnh k nc ca cht hp ph, mc k nc ca cc cht
b hp ph trong mi trng nc. So vi hp ph trong pha kh, s hp ph
trong mi trng nc thng c tc chm hn nhiu. l do tng tc
gia cht b hp ph vi dung mi nc v vi b mt cht hp ph lm cho qu
trnh khuch tn ca cc phn t cht tan rt chm.
S hp ph trong mi trng nc chu nh hng nhiu bi pH ca mi
trng. S thay i pH khng ch dn n s thay i bn cht cht b hp ph
(cc cht c tnh axit yu, baz yu hay trung tnh phn ly khc nhau cc gi
tr pH khc nhau) m cn lm nh hng n cc nhm chc trn b mt ca
cht hp ph. Ngoi ra xt n cc cht hu c th trong mi trng nc, cc
cht hu c c tan khc nhau kh nng hp ph trn vt liu hp ph i vi
cc cht hu c c tan cao s yu hn vi cc cht hu c c tan thp hn.
Nh vy t tan ca cht hu c chng ta c th nh gi kh nng hp ph
ca chng trn vt liu hp ph.
Trong pha lng ngi ta thng gp cc trng hp hp ph sau:
- Hp ph cc cht tan trn b mt phn cch pha lng-kh, lng-lng.
- Hp ph cc cht tan trn b mt cht rn tip xc vi pha lng.
S hp ph xy ra trn b mt pha rn trong dung dch phc tp hn nhiu
so vi trong pha kh. Bi v, cc phn t dung mi c th hp ph cnh tranh vi
cc phn t cht tan: cht tan gm cc phn t trung ho in tch hoc cc tiu
phn mang in (cht in ly)...
Cc cht hp ph s dng trong x l nc thi dt nhum :
- Cacbon hot tnh: cht hp ph ph bin trong x l nc thi cha
thuc nhum, c bit l hp ph thuc nhum giai on x l trit sau
keo t. N khng c s dng n l do gi thnh cao v hiu sut thp trong
loi b cc phn t mu ln v i hi thi gian tip xc. Khi hp ph bo ha,
than hot tnh c ti sinh, lng tn tht c 1015%.
23
- Cc cht hp ph v c khc: t st, than bn, silic oxit, mt s
khong,.. cng c dng lm cht hp ph thuc nhum kh hiu qu vi gi
thnh r hn than hot tnh.
- Cc cht hp ph do mt s cng ty v t chc ch to c kh nng hp
ph tt cc thuc nhum tan, k c thuc nhum hot tnh. in hnh nh cht
hp ph acrasorb D, macrosorb, cucurbiturial.
- Sinh khi c s dng kh cht mu nc thi dt nhum bng c
ch hp ph v trao i ion. Tuy nhin nu khng c x l ha hc th kh
nng hp ph thuc nhum anion ca sinh khi rt thp. Chitin (polisacarit cu
to ging xenllulo) v chitosan (chitin loi axetyl) c bit n nhiu nht
v kh nng hp ph nhiu loi thuc nhum hot tnh. Ngoi ra ngi ta cn
phi dng xenlulo bin tnh v lignocellulose hp ph thuc nhum axit v
thuc nhum cation. Cc vt liu thin nhin nh li ng, mt ca, b ma,
tru,... cng c th nghim kh nng hp ph thuc nhum.
Hp ph l phng php c ngh n nhiu trong x l thuc nhum
hot tnh. Tuy nhin, nhc im ca phng php ny nm trong chnh bn
cht ca n l gi li cht b hp ph trn b mt cht hp ph m khng c kh
nng chuyn cht t pha ny thnh pha khc. Hn na i hi thi gian tip xc
di v to mt lng cht thi sau qu trnh hp ph., khng x l trit c
nhim.
1.2.2.3 Phng php in ha
Phng php ny da trn c s qu trnh oxi ha/ kh xy ra trn cc
in cc. anode, nc v cc ion clorua b oxi ha dn n s hnh thnh O2,
O3, Cl2 v cc gc l tc nhn oxi ha cc cht hu c trong dung dch. Qu
trnh kh in ha cc hp cht hu c nh thuc nhum, catot, kt hp vi
phn ng oxi ha in ha v qu trnh tuyn ni, keo t in ha dn n hiu
sut x l mu v khong ha cao. Phng php in ha vi cc nhm hoc st
l cng ngh x l hiu qu mu, COD, BOD, TOC, kim loi nng, cht rn
l lng. Nghin cu cho thy hiu sut x l cc loi nc thi t xng nhum
cha nhiu loi thuc nhum khc nhau c kh nng t ti 90%. y l
phng php c chng minh hiu qu i vi vic x l mu, COD, BOD,
TOC, kim loi nng, cht rn l lng ca nc thi dt nhum. Tuy nhin
phng php in ha c gi thnh cao do tiu tn nng lng v kim loi lm
in cc.
24
1.2.2.4 Phng php ha hc
u im ni bt ca phng php ha hc so vi cc phng php ha l
l bin i, phn hy cht nhim (cht mu) thnh cc cht d phn hy sinh
hc hoc khng nhim ch khng chuyn chng t pha ny thnh pha khc.
So vi phng php vi sinh th tc x l cht thi bng phng php ha hc
cn nhanh hn nhiu.
Kh ha hc
c ng dng nhiu trong trng hp nc thi cha cc cht d b kh.
Phng php kh ha hc hiu qu vi cc thuc nhum azo nh phn gii lin
kt azo to thnh cc amin thm khng mu c kh nng phn gii vi sinh hiu
kh tt hn thuc nhum gc.
Kh ha hc trn c s natri bohidrid, xc tc bisunfit p dng vi thuc
nhum tan trong nc nh thuc nhum trc tip, axit, hot tnh cha cc nhm
azo hoc cc nhm kh c v thuc nhum phc ng. Quy trnh ny c th
kh mu trn 90%.
Oxi ha ha hc
Oxi ha bng cc tc nhn oxi ha thng thng:
Cc cht oxi ha thng thng nh: clo, clodioxit, natri hipoclorit, kali
permanganate, ozon, dicromat, hydropeoxit,... c th c s dng oxi ha
cc cht nhim ni chung v thuc nhum ni ring. Qu trnh oxi ha tiu tn
mt lng ln tc nhn oxi ha, do qu trnh oxi ha ha hc ch c s
dng trong trng hp khi cht nhim khng th loi b bng cc phng
php khc.
Clo ha c nh gi cao v hiu qu x l mu nhng khi s dng
nng cao kh mu s li d lng ln trong nc thi. N c th kh
mu nhanh thuc nhum axit v thuc nhum hot tnh. Vi thuc nhum phn
tn v thuc nhum trc tip th ngay c nng clo cao cng khng thu c
hiu qu ng k. Nhn chung, clo khng c a dng trong x l nc thi v
sinh ra cc hp cht clo gy ung th v c hi vi mi trng.
Ozon l cht oxi ha mnh v c th oxi ha thuc nhum trong nc thi
m khng sinh ra cc hp cht hu c th cp c hi pH< 5, ozon tn ti
dng O3 v oxi ha chn lc ni i trong thuc nhum. pH > 8, ozon phn hy
to gc t do (*OH) phn ng khng chn lc vi cc cht hu c (theo c ch
ca qu trnh oxi ha nng cao). Ozon c hiu qu nht trong loi b thuc
25
nhum hot tnh. Tuy nhin, nhc im ln nht ca phng php ny nm
gi thnh cao v thi gian tn ti ca ozon ngn, chi ph cho thit b to ozon
cao.
Thuc tm (KMnO4), hydroxyl peroxit (H2O2) l nhng cht oxi ha c
th oxi ha cha cao phn hy cc thuc nhum. Hn na chi ph ha cht
nu s dng hai cht oxi ha ny l kh ln.
1.3 Phng php oxi ha nng cao (AOPS)
1.3.1. Gii thiu cc qu trnh oxi ha nng cao
nh ngha: Cc qu trnh oxi ha nng cao l nhng qu trnh phn hy
oxi ha da vo gc t do hot ng hydroxyl (*OH) c to ra ngay trong qu
trnh x l.
Qu trnh oxi ho cc hp cht ho hc l hnh thc khong ho cc hp
cht ny n sn phm cacbon dioxide, nc v cc cht v c, hoc t nht l
chuyn ho cc hp cht t dng c hi thnh khng c hi. Cc phng php
x l trc y hu nh mi ch p dng c cho cc hp cht d phn hu.
i vi cc hp cht c bn ho hc cao hoc kh phn hu thnh dng
khong ho hon ton th phi pht trin cc h thng hiu qu hn nh phng
php oxi ho nng cao. Rt nhiu nghin cu c tin hnh khng nh
vai tr ni bt ca phng php nh iu kin tin hnh phn ng gn vi nhit
v p sut mi trng xung quanh.
Oxi ho l qu trnh trong electron c chuyn t cht ny sang cht
khc. iu ny to ra mt hiu in th c tnh bng volt da trn hiu in
th in cc hydro bng 0. Mi tc nhn oxi ho u c mt th oxi ho khc
nhau v i lng ny dng so snh kh nng oxi ho mnh yu ca chng
(Bng 1.3).
Bng 1.3 Th oxi ho ca mt s tc nhn oxi ho thng gp
Tc nhn oxi ho Th oxi ho [V]
- Gc hydroxyl 2,8
- Oxy nguyn t 2,42
- Ozone (O3) 2,08
- Hydrogen peroxit 1,78
- Permanganate 1,68
- Hydrobromic axit 1,59
- Hypochlorite 1,49
- Hypoiodic axit 1,45
26
- Chlorine 1,36
- Chlorine dioxide 1,27
- Oxy phn t 1,23
- Brome 1,09
- Iodine 0,54
Mc d qu trnh oxi ha nng cao (AOPs) l tp hp ca rt nhiu

phng php nhng chng u ging nhau ch l nhng qu trnh phn hu
oxi ho da vo vic tng hp cc gc t do hot ng nh hydroxyl (*OH)
trong qu trnh x l. Cc phng php oxi ha nng cao (AOPs) c c
trng bi s phn gii cc hp cht hu c chn lc, v vy vic tm kim s
dng cc tc nhn oxi ho hiu qu trong vic x l nc thi nhim l cn
thit. Tuy nhin, phng php oxi ha nng cao (AOPs) cng c th trin khai
linh hot v thc t c nhiu gii php tng hp nn cc gc t do *OH
(hydroxyl), v y chnh l im u vit ca phng php so vi cc phng
php x l nc thi thng thng khc.
Nhng u im v nhng hn ch ca qu trnh oxi ha nng cao (AOPs)
nh sau:
- u im:
+ C kh nng phn hu c nhng hp cht hu c c hi m
khng gy chuyn ho nhim t pha ny sang pha khc;
+ L qu trnh x l rt hiu qu hu ht cc cht hu c gy nhim
v loi b mt s kim loi gy c;
+ C th x l c nc thi t nhiu ngun thi khc nhau: bnh
vin, cng nghip, nng nghip...;
+ Gi thnh lp t r;
+ C th thc hin ngay c nhng m hnh nh cc nc ang pht
trin.
+ Ngoi ra do tc dng oxi ha cc mnh nn chng c th tiu dit
c cc loi vi khun thng thng v nhng loi vi khun nh
Campylobacter, Yersina, Mycrobacteria, Legionella, Cryptosporidium. Mt
khc tc nhn (*OH) khng to ra cc sn phm ph gy ung th nh cc hp
cht cha clortrihalometan.
- Nhc im:
27
+ Mc d gi thnh lp t r nhng gi thnh vn hnh li cao do gi
thnh ca u vo (cc ho cht hoc/v nng lng);
+ S hnh thnh cc hp cht oxi ho trung gian c th gy c;
+ Trong qu trnh thit k v vn hnh lun phi c ngi thc hin v
gim st;
+ L cng ngh mi nn vn tip tc cn hon thin.
hon thin v ng dng cng ngh oxi ha nng cao (AOPs) thng
xut pht t cc mc tiu:
- To ra c cc khi nim mi, cc quy trnh v cng ngh mi trong
x l nc thi. Cc cng ngh mi c nhiu li ch tim nng, m bo cht
lng nc thi n nh, tit kim nng lng v chi ph vn hnh, bo v mi
trng;
- To ra c h thng tiu chun tin tin trong x l nc thi;
- To ra c cc phng php mi trong x l nc thi v cc iu kin
thc hin qu trnh x l;
- To ra c cc b quyt mi, gp phn tng tng s cnh tranh trong
vic sn xut nc sch ca cc nh my.
C nhiu phng php c s dng trong qu trnh oxi ha nng cao
(AOPs), c th tm chia vo hai dng: oxi ha nng cao (AOPs) sng v oxi ha
nng cao (AOPs) ti (Bng 1.4). Qu trnh AOPs thng s dng cc tc nhn
oxi ho mnh nh hydroxyl peroxit (H2O2) hoc ozone (O3), cc cht xc tc
nh ion st, cc cht in phn v oxit kim loi, chiu x (tia UV, nh sng mt
tri hoc sng siu m). Cc phng php c s dng c th tch ri c lp
hoc kt hp vi nhau di iu kin bnh thng. Tuy nhin, trong s cc
phng php oxi ha nng cao (AOPs) th cc phng php oxi ha nng cao
(AOPs) sng c s dng rng ri hn trong x l nc thi bi c th tn
dng nng lng t nh sng mt tri nhng ni c cng chiu sng
mnh, lm gim chi ph vn hnh h thng v nng cao hiu qu x l.
28
Bng 1.4 Mt s phng php oxi ha nng cao (AOPs) ph bin hin nay ang
s dng trong x l nc thi
Oxi ha nng cao (AOPs) Oxi ha nng cao (AOPs)
khng chiu sng c chiu sng
- Ozone (O3) - Quang phn (UV + H2O2)
- Fenton (Fe2+ + H2O2) - Quang xc tc (nh sng + cht xc tc)
- in phn - Quang-Fenton (nh sng mt tri + Fenton)
- Siu m
Qu trnh oxi ha nng cao (AOPs) bao gm nhiu bc, c th tm tt
trong 3 bc sau:
- Hnh thnh cht oxi ho mnh (v d cc gc t do hot ng hydroxyl).
- Phn ng gia cc cht oxi ho mnh ny vi cc hp cht hu c trong
nc to dng sn phm trung gian c th phn hu sinh hc c.
- Phn ng gia cc cht phn hu sinh hc trung gian vi cc cht oxi ho
to thnh dng khong ho (nc, cacbon dioxide v cc mui v c).
Mc d c nhiu nghin cu s dng cc phng php AOPs vo vic x
l nc thi, tuy nhin gi thnh vn hnh mt quy trnh AOPs cn cao, do
vy hin nay vic tp trung h gi thnh cng ngh cng l mt trong nhng
hng nghin cu c u tin. Cc nh cng ngh c th phi hp mt s
phng php oxi ha nng cao (AOPs) x l nc thi nh UV/H2O2,
UV/H2O2/TiO2, UV/Fenton v Siu m/UV/TiO2. Vic phi hp ny thng cho
kt qu x l cao hn so vi vic p dng mt phng php n l do mi
phng php li c th phn hu mt s cc hp cht ring bit trong hn hp
cc cht hu c. Mt khc, mi phng php oxi ha nng cao (AOPs) c th
chuyn ho cc hp cht hu c t dng kh phn hu sang dng pha khc d
dng x l bng cc bin php truyn thng nh keo t, lng, lc, hp ph..., do
vy phng php oxi ha nng cao (AOPs) c th c coi l phng php tin
x l nc thi trc khi s dng cc phng php phn hu sinh hc. Phng
php oxi ha nng cao (AOPs) c bit hiu qu i vi vic x l cc nc thi
sinh hc c hi hoc cha cc hp cht khng phn hu c nh cc hp cht
vng thm, cc cht dit c, cc hp cht du m v cc hp cht hu c bay
hi. Nc thi ca cc nh my dt nhum hin nay ang l i tng c cc
nh nghin cu, cc cng ty trin khai p dng cng ngh oxi ha nng cao
(AOPs) loi b hiu qu cc hp cht mu bn vng, kh phn hu, p ng
29
c tiu chun nc sch u ra theo TCVN QCVN 40:2011/BTNMT ca B
Ti nguyn Mi trng.
1.3.2. C s l thuyt ca qu trnh Fenton
Nm 1894 trong tp ch ca Hi ha hc M cng b nghin cu ca
tc gi J.H.Fenton, trong ng quan st thy phn ng oxi ha ca axit malic
tng mnh khi c mt cc ion st. Sau t hp H2O2 v mui st Fe2+
c s dng lm tc nhn oxi ha rt hiu qu cho nhiu i tng cc cht
hu c v c mang tn tc nhn Fenton. Qu trnh Fenton u vit ch tc
nhn H2O2 v mui st tng i r v c sn, ng thi khng c hi v d
vn chuyn, d s dng trong khi hiu qu ca oxi ha nng cao hn rt nhiu so
vi ch s dng H2O2 c lp. p dng qu trnh Fenton x l nc thi c
th dn n khong ha hon ton cc hu c thnh CO2, H2O v cc ion v c.
Hnh 1.10: Phn ng Fenton ng th v Fenton d th

1.3.2.1 Qu trnh Fenton ng th
Thng thng qu trnh oxi ha Fenton ng th gm 4 giai on:
- iu chnh pH cho ph hp;
- Phn ng oxi ha: Trong giai on phn ng oxi ha xy ra s hnh
thnh gc t do *OH hot tnh v phn ng oxi ha cht hu c. C ch hnh
thnh gc t do *OH s c xt c th sau. Gc t do *OH hnh thnh s tham
gia vo phn ng oxi ha cc hp cht hu c c trong nc cn x l, chuyn
30
cht hu c t dng cao phn t thnh cc cht hu c c khi lng phn t
thp.
- Trung ha v keo t: Sau khi xy ra qu trnh oxi ha cn nng pH dung
dch ln > 7 thc hin kt ta Fe3+ mi hnh thnh. Kt ta Fe(OH)3 mi hnh
thnh s thc hin cc c ch keo t, ng t, hp th mt phn cc cht hu c
ch yu l cc cht hu c cao phn t.
- Qu trnh lng: Cc bng keo sau khi hnh thnh s lng xung khin
lm gim COD, mu, mi trong nc thi. Sau qu trnh lng, cc cht hu c
cn li (nu c) trong nc thi ch yu l cc cht hu c c khi lng phn
t thp s c x l b sung bng phng php sinh hc hoc bng phng
php khc.
a, Phn ng gia H2O2 v cht xc tc Fe2+
Mc d tc nhn Fenton c bit n hng th k nay nhng c ch phn
ng Fenton cho n nay vn cn ang tranh ci, thm ch c kin tri ngc
nhau.
H tc nhn Fenton c in l mt hn hp cc ion st ha tr 2 v
hydroxyl peroxit H2O2, chng tc dng vi nhau sinh ra gc t do *OH, cn
Fe2+ b oxi ha thnh Fe3+ theo phn ng sau:
Fe2+ + H2O2 Fe3+ + *OH + OH- (1.1)
Phn ng Fenton tip tc c nghin cu bi nhiu tc gi sau ny,
cc nghin cu ny cho thy, ngoi phn ng (1.1) trn l phn ng chnh, trong
qu trnh Fenton cn xy ra cc phn ng khc. Tng hp li bao gm:
Fe2+ + H2O2 Fe3+ + *OH + OH- (1.1)
Fe3+ + H2O2 Fe2+ +*HO2 + H+ (1.2)
*OH +Fe2+ OH- + Fe3+ (1.3)
*OH + H2O2 H2O + *HO2 (1.4)
2+ 3+
Fe + *HO2 Fe + HO2 (1.5)
Fe3+ + *HO2 Fe2+ + O2 + H+ (1.6)
*HO2 + *HO2 H2O2 + O2 (1.7)
Theo cc tc gi trn th gc t do *OH sinh ra c kh nng phn ng vi
2+
Fe v H2O2 theo cc phn ng (1.3) v (1.4) nhng quan trng nht l kh
nng phn ng vi nhiu cht hu c (RH) to thnh cc gc hu c c kh
nng phn ng cao, t pht trin tip tc theo kiu dy chui:
*OH + RH H2O + *R oxi ha tip cc cht khc (1.8)
31
Tuy c ch hnh thnh gc hydroxyl vn cn nhiu tranh ci, nhng i a
s u s dng c ch qu trnh Fenton xy ra theo cc phn ng (1.1)- (1.7) nu
trn v tha nhn vai tr ca gc hydroxyl to ra trong qu trnh ny [30].
b, Phn ng gia H2O2 v cht xc tc Fe3+
Phn ng (1.2) xy ra xem nh phn ng phn hy H2O2 bng cht xc
tc Fe v to ra Fe2+ sau tip tc xy ra theo phn ng (1.1) hnh thnh
3+
gc hydroxyl theo phn ng Fenton. Tuy nhin tc ban u ca phn ng oxi

ha bng tc nhn H2O2/Fe3+chm hn rt nhiu so vi tc nhn Fenton
H2O2/Fe2+. Nguyn nhn v trong trng hp ny Fe3+ phi c kh thnh Fe2+
trc khi hnh thnh gc hydroxyl. Nh vy v tng th qu trnh Fenton c
xem nh khng ph thuc g vo trng thi ha tr hai hay ba ca cc ion st.
Mt khi gc t do c hnh thnh, lp tc xy ra hng lot cc phn ng
tip theo kiu dy chui vi nhng gc hot ng mi. V vy, s hnh thnh
gc hydroxyl c xem nh khi u cho hng lot phn ng xy ra trong dung
dch.
1.3.2.2. Qu trnh Fenton d th
Qu trnh Fenton ng th c nhc im rt ln l phi thc hin pH
thp, tip phi nng pH ca nc thi sau x l ln > 7 bng nc vi trong
hoc dung dch kim nhm chuyn cc ion Fe3+ va hnh thnh t chui phn
ng trn sang dng keo Fe(OH)3 kt ta. Lng kt ta ny c tch khi nc
nh qu trnh lng hoc lc, kt qu l to ra mt lng bn st kt ta kh
ln. khc phc nhc im trn, c nhiu cng trnh nghin cu thay th
xc tc st dng dung dch (mui st) bng qung st goethite (-FeOOH), ct
c cha st, hoc st trn cht mang Fe/SiO2, Fe/TiO2, Fe/than hot tnh,
Fe/zeolit [31]. Qu trnh ny xy ra cng ging nh qu trnh Fenton cp
trn nn gi l qu trnh kiu Fenton h d th.
C ch qu trnh d th kiu nh Fenton xy ra vi H2O2 trn qung st
loi goethite (-FeOOH) c th xy ra theo c ch n gin nht nh sau [32]:
Phn ng Fenton c khi u bng vic sinh ra Fe2+ nh s c mt ca
H2O2 xy ra hin tng kh - ha tan goethite:
-FeOOH (r) + 2H+ + H2O2 Fe2+ + O2 + 2H2O (1.9)
3+
Sau xy ra s ti kt ta Fe v goethite:
Fe2+ + H2O2 Fe3+ + *OH + OH- (1.1)
Fe3+ + H2O + OH- -FeOOH (s) + 2H+ (1.10)
32
Theo c ch trn, trn kha cnh no th qu trnh d th cng tng t
nh qu trnh Fenton ng th l xy ra s kh v ha tan Fe2+ vo dung dch.
Mt s u im ng ch ca qu trnh Fenton d th trn goethite:
- Cht xc tc ny c th s dng trong mt thi gian di m khng cn
phi hon nguyn hoc thay th ng thi v c th tch ra d dng khi khi
phn ng. Trong qu trnh Fenton ng th, ion st ha tan khng th tch ra
khi khi phn ng mt cch n gin bng qu trnh lng, lc, ch c cch dng
kim keo t v kt ta, sau lng v lc, sinh ra mt khi lng ln bn keo
t cha nhiu st.
- Tc hnh thnh gc hydroxyl tng theo tng pH trong khong t 5-
9, trong khi Fenton ng th tc gim mnh khi pH tng.
- Hiu qu oxi ha xc tc ca goethite khng b nh hng ng k bi
nng cacbonat v c.
1.3.2.3. Qu trnh Photo Fenton
Phn ng Fenton l phn ng phn hy H2O2 di tc dng xc tc ca
Fe2+
Fe2+ + H2O2 Fe3+ + OH- + *OH (1.1)
Gc t do *OH to ra c th tc dng vi cc cht nhim hu c trong
nc phn hy khong ha chng, hoc cng c th tc dng li vi ion Fe2+
to thnh Fe3+ :
*OH + Fe2+ Fe3+ + OH- (1.3)
Mt khc, s phn hy H2O2 cng c th xy ra di tc dng xc tc ca
3+
Fe theo phn ng:
Fe3+ + H2O2 Fe2+ + *HO2 + H+ (1.2)
Phn ng (1.2) dn n s to thnh Fe2+ nn li tip tc xy ra phn ng
(1.1). Tuy nghin v hng s tc ca phn ng (1.3) rt thp so vi tc
phn ng (1.1), nn qu trnh phn hy H2O2 ch yu do phn ng (1.1) thc
hin. V th, phn ng (1.1) xy ra vi tc chm dn sau khi ton b Fe2+
s dng ht v chuyn thnh Fe3+ .
Cc nghin cu lin quan tin hnh trong khong 2 thp k tr li y
u cho thy tc phn ng (1.1) v thm ch c phn ng (1.3), nu thc hin
vi s c mt ca nh sng thuc vng t ngoi (UV) v ln cn t ngoi vi
kh kin (UV-Vis) u c nng cao r rt v nh c th khong ha d
dng cc cht nhim hu c, thm ch c nhng cht hu c kh phn hy nh
33
cc loi thuc tr su hay cc cht dit c. Qu trnh ny c gi l qu trnh
Photo Fenton.
Bn cht ca hin tng trn l pH thp (pH< 4), ion Fe3+ phn ln s
nm di dng phc [Fe3+(OH)]2+ v chnh dng ny hp th nh sng UV trong
min bc sng 250 nm < < 400 nm rt mnh (mnh hn hn so vi ion Fe3+ ).
S hp th bc x ca [Fe(OH)]2+ trong dung dch cho php to ra mt s gc
hydroxyl (*OH) ph thm:
Fe3+ + H2O [Fe3+ (OH)]2+ + H+ (1.11)
3+ 2+ 2+
[Fe (OH)] + hv Fe + *OH (1.12)
Tip theo sau phn ng (1.12) s l phn ng Fenton thng thng
c cp trn (1.1). Nh vy, r rng l nh tc dng ca bc x UV, ion
st c chuyn ha t trng thi Fe3+ sang Fe2+ v sau ngc li t Fe2+
sang Fe3+ bng qu trnh Fenton thng thng to thnh mt chu k khng
dng. y chnh l im khc bit c bn gia qu trnh Photo Fenton vi qu
trnh Fenton thng thng l qu trnh b chm dn do Fe2+ chuyn mt chiu
thnh Fe3+ cho n khi khng cn Fe2+ trong dung dch .
1.3.2.4. Qu trnh ozon ha
Ozon ha c xem l mt trong nhng qu trnh oxi ha nng cao pH
cao do cc cht hu c b oxi ha bi gc t do *OH hot ng to ra trong qu
trnh phn hy ozon. Trong mi qu trnh ozon ha, cht hu c b oxi ha mt
phn do phn ng ca cc gc t do, mt phn l s ozon ha trc tip hu c.
Bi l ozon l cht oxi ha mnh hn oxy v v mt l thuyt ozon c th oxi
ha vi hu ht cc hp cht hu c. Nhc im ln nht ca phng php ny
l kh khn trong vic thu c ozon v yu cu pH ca qu trnh. Hin nay,
ozon ha c s dng cng on lm trng trong sn xut giy.
Cc qu trnh ozon ha gm c:
- Qu trnh UV/O3: qu trnh ozon ha c h tr bng vic chiu nh
sng t ngoi tng hiu qu to *OH hay to 2*OH vi nng cao hn
H2O + O3 = 2*OH + O2 (1.13)
- Qu trnh H2O2/O3: phn ng gia O3 v H2O2 tng s to thnh gc t
do *OH. Trong trng hp ny, ngoi gc *OH cn c gc *HO2 (to ra t
H2O2). V vy phn ng oxi ha cht hu c t hiu qu cao hn.
H2O2 + 2O3 = 2*OH + 2O2 (1.14)
34
- Qu trnh H2O2/UV/O3: l s kt hp ca cc qu trnh UV/O3, H2O2/O3,
UV/H2O2 thu c h bc 3. y l qu trnh hiu qu nht trong x l nc
thi nhim nng v cho php gim TOC, khong ha hon ton cht nhim.
C ch to gc t do c ch ra trong phn ng :
H2O2 + 2O3 = 2*OH + 3O2 (1.15)
1.3.3. Nhng yu t nh hng n qu trnh Fenton v Photo Fenton
1.3.3.1. nh hng ca pH
Trong qu trnh Fenton ng th v Photo Fenton, pH nh hng rt
ln n tc phn ng v hiu qu phn hy cc cht hu c. Nhn chung mi
trng axit rt thun li cho qu trnh to gc hydroxyl t do *OH theo phn
ng (1.1), trong khi mi trng pH cao, qu trnh kt ta Fe3+ xy ra nhanh
hn qu trnh kh ca phn ng (1.3) lm gim ngun to ra Fe2+ , tr thnh yu
t hn ch tc phn ng. Nhiu nghin cu cho thy phn ng Fenton xy
ra thun li khi pH t 3-4, v t c tc cao nht khi pH nm trong khong
trn di 3. Mt s thc nghim biu hin khi pH > 4 tc phn ng oxi ha
cht hu c chm li. Theo cc tc gi, nguyn nhn c th l khong pH > 4,
cc cht trung gian hot ng km hn c gc hydroxyl hoc cht trung gian
khng gii phng ra gc hydroxyl hot ng (cc phc hydroxo ca st III)
hnh thnh thay v gc hydroxyl.
1.3.3.2. nh hng ca nng H2O2 v t l Fe2+/H2O2
Tc phn ng Fenton tng khi nng H2O2 tng, ng thi nng
H2O2 cn thit li ph thuc vo nng cht nhim cn x l, c trng bng
ti lng COD. Thng th hiu qu x l s tng khi nng H2O2 v Fe tng,
tuy nhin khi nng cc tc nhn Fenton qu cao c th pht sinh ra cc vn
nh lng st hydroxit kt ta qu nhiu v bn thn H2O2 l yu t c ch vi
sinh vt. Theo kinh nghim, t l mol/ mol H2O2: COD dao ng kh ln, trong
khong 0,5 -3:1 i vi tng loi nc thi khc nhau .
Ngoi ra, t l Fe2+/H2O2 c nh hng n s to thnh v s tiu hao
gc hydroxyl theo cc phng trnh (1.1), (1.2), (1.4), v th tn ti mt t l
Fe2+/H2O2 ti u khi s dng. T l ti u ny nm trong khong rng, khong
0,5/10 n 0,5/14 (mol/mol) ty theo i tng cht cn x l v do cn phi
xc nh bng thc nghim khi p dng vo ty i tng c th.
35
1.3.3.3. nh hng ca cc anion v c
Mt s anion v c thng c trong nc ngm v nc thi cng c th
lm gim hiu qu ca qu trnh Fenton, c bit l nc thi dt nhum do qu
trnh nhum s dng nhiu cht h tr c ngun gc v c. Nhng anion v c
thng gp nht l cc ion cacbonat (CO32-), bicacbonat (HCO3-), ion Cl-).
Nhng ion ny gi chung l gc lm gim hydroxyl v chng tham gia phn ng
vi gc hydroxyl OH* lm gim kh nng tin hnh phn ng oxi ha hoc
cng c th to thnh nhng phc cht khng hot ng vi Fe(III) nh cc gc
sunfat (SO42-), nitrat (NO3-), photphat (H2PO4-) cng lm hiu qu ca qu trnh
Fenton gim i.
Phn ng ca mt s gc thng gp trong h Fenton:
OH* + CO2-3 =CO3* + OH- (k = 4.2x108 M-1 s-1) (1.13)
OH* + HCO-3 = HCO3* + OH- (k= 1.5x107 M-1 s-1) (1.14)
- - -1 -1
OH* + Cl = ClOH * (k= 4.3 x 109 M s ) (1.15)
Ta thy hng s tc phn ng gia OH* v ion cacbonat ln hn nhiu
so vi ion bicacbonat, v vy khi tng pH cn bng ca cacbonat-bicacbonat s
chuyn dch theo hng to thnh cacbonat, gy bt li cho phn ng oxi ha
nng cao. Trong khi , axit H2CO3 khng phi l cht lm gim hydroxyl, v
vy trong trng hp nu kim cao, bng cch chnh pH sang mi trng axit
chuyn cn bng cacbonat-bicacbonat t cacbonat sang axit H2CO3 s c th
tng tc phn ng ca cc ion cacbonat v bicacbonat. Ni chung, cc ion
clorua, cacbonat v bicacbonat thng c nh hng km hm tc phn ng.
Trong khi cc ion sunfat, photphat hay nitrat c nh hng mc thp
hn. nh hng trn c th coi l khng ng k i vi qu trnh Fenton d th.
1.3.3.4. nh hng ca bc sng bc x (i vi qu trnh Photo
Fenton)
Tc qu trnh kh quang ha ca Fe3+ to ra gc hydroxyl *OH v Fe2+
ph thuc vo chiu di ca bc sng bc x. Bc sng cng di th hiu sut
lng t to ra gc hydroxyl *OH cng gim, do hiu qu x l cng gim
theo.
1.3.4. Tnh hnh nghin cu v p dng cc qu trnh oxi ha nng cao
hin nay
Nh nhng u th ni bt trong vic loi b cht nhim hu c, c bit
l nhng cht nhim hu c kh phn hy, trong vic kh trng an ton v
36
trit . Cng ngh p dng cc qu trnh oxi ha nng cao da trn gc t do
hydroxyl (*OH) c xem nh cha kha vng gii cc bi ton thch thc
cho vic x l nc thi dt nhum hin nay. l l do v sao qu trnh oxi
ha nng cao (AOPs) c mnh danh l qu trnh x l nc ca th k 21.
Nm 1997 S.H. Lin v C.C.Lo nghin cu phn ng Fenton cho qu trnh x
l nc thi cho thy vic tng nng FeSO4 lm tng mc loi b COD.
Nhit ti u vn hnh l 30oC v vic ng t sau phn ng Fenton gip gi
li nng st trong khong gii hn [33]. Nm 2001, E.Chamarro v cc cng
s nghin cu nh hng ca nng H2O2 v st n ng hc phn ng
phn hy axit formic, phenol, 4-chlorophenol, 2,3-dichlorophenol v
nitrobenzen [34]. Cng nm 2001, F.J. Rivas cng cc cng s nghin cu
phn ng Fenton oxi ha poli-hydroxybenzoic s dng xc tc 250-2250
mg/l, nhit phng, H2O2 khong 0-1600 mg/l, pH nghin cu khong 2- 9
cho thy hiu qu loi b COD tt nht iu kin pH 3,5, hiu qu tng khi
lng Fe2+ tng ln n 500mg/l [35]. Nm 2005, E.M. Siedlecka v P.
Stepnowski bo co s nh hng ca ion clorua v sunfat n phn ng phn
hy phenol, 2-chlorophenol (2-CP) v 2-notrophenol (2-NP) [36]. Cng nm ,
A.A. Burbano v cc cng s nghin cu ng hc phn ng oxi ha v nh
hng ca iu kin pH n phn ng phn hy MTBE (metyl tert butyl ete) v
thy rng khong 90-99% MTBE b phn hy trong 1 gi phn ng s dng
Fe2+/H2O2= 1/1 (mol) v Fe2+/MTBE = 10/1 (mol), pH = 3-7 [37]. Nm 2008,
P.J.D. Ranjit cng cc cng s nghin cu ng hc phn hy 2,4-
dichlorophenol (2,4-DCP) vi nng Fe2+ = 20mg/l v H2O2 l 580mg/l iu
kin pH = 2,5 phn hy c 70% 2,4-DCP [38]. Nm 2009, M.S. Yalfano
cng cc cng s nghin cu qu trnh phn hy phenol thy rng phn hy
60% iu kin pH 3- 3,5 s dng Fe2+ = 10ppm, H2O2 = 300- 600 ppm trong 6
gi v nghin cu s dng xc tc Al/Pd thay th cho Fe2+ [39]. Cng nm ny,
G. Lofrano cng cc cng s bo co hiu qu ca phn ng oxi ha catechol
vi s kt hp ca xc tc quang ha v qu trnh Fenton, Like-Fenton, thc
nghim thc hin iu kin nhit phng, pH = 3, s dng H2SO4 v FeSO4,
t 75-700 mg/l x l trong 30 pht v thy rng loi b c 83% COD, loi b
93% aromatic trong 30 pht iu kin H2O2/FeSO4 t l 600/500 (khi lng).
Phn tch GC/MS cho thy loi b hon ton catechol t l H2O2/FeSO4 =
2000/500 (khi lng) trong 30 pht [40]. Nm 2010, C.Jiang cng cc cng s
37
bo co phn ng Fenton nng st thp c hiu qu hn so vi phn ng
Like- Fenton cng iu kin trong nghin cu phn hy phenol. V cho rng
phn ng Fenton pH hiu qu nht l khong 2,5- 6 cn Like-Fenton pH = 2,8
- 3,8 [41].
1.3.5. Cc h xc tc trong x l cht mu hu c
Qu trnh oxi ha nng cao (AOPs) c nng cao hiu qu x l bng
cch s dng cc cht xc tc khc nhau. Cc cht xc tc c th to c ra t
rt nhiu vt liu bao gm cc kim loi, oxit kim loi, sunfua kim loi v cc
oxit cch nhit. Tu thuc vo mc ch s dng, cc vt liu xc tc c th
dng khng cht nn hoc cht nn trn mt cht mang. Dng thc ca cht xc
tc c quyt nh bi thit b nh v phn ng dng xc tc.
Cc cht xc tc quang ha, xc tc cho qu trnh Photo Fenton nh:
TiO2, ZnO, CdS, H2O2, MFe2O4 (M=cation kim loi)... c im ca nhng
cht ny l di tc ng ca nh sng s sinh ra cp electron (e-) v l trng
(h+) c kh nng phn hy cht hu c nhim thnh nhng cht sch vi
mi trng.
Trong nhng phng php c s dng, phng php oxi ha nng cao
(AOPs) c ch , trong cc cht nhim b oxi ha bi cc cht phn ng
ozone, H2O2, O2 v khng kh. Cc k thut ny c th kt hp vi tia UV v
cc cht xc tc khc nhau to ra cc gc t do *OH. Ph bin nht l s
dng cc cht kh Fenton. Qu trnh oxi ha nng cao (AOPs) c bit hiu qu
trong vic loi b cc cht hu c kh phn hy trong nc thi. C ch ca qu
trnh oxi ha nng cao (AOPs) l to ra cc gc t do c hot tnh cao, cc gc
t do *OH phn ng nhanh v khng chn lc vi hu ht cc hp cht hu c
giu gc in tch.
1.3.5.1 Xc tc quang ha TiO2/ graphen
TiO2 l mt xc tc quang ha ph bin rng nht v c kho st,
nghin cu nhiu trong vic lm sch nc. Nhng li th ca TiO2 so vi cc
oxit kim loi khc l khng c hi, gi r v n nh v mt ha hc. Do c
rng vng cm khong 3.2 eV ca TiO2, nn tnh quang ca n ch c gii hn
vng t ngoi v mt s cch nh doping to ra cc khuyt tt v kt hp TiO2
vi vt liu nhn electron lm gim bt khong bin lm cho vt liu TiO2
hot ng vng nh sng nhn thy. Ngoi vic kt hp vi vt liu nhn
electron nh mt cch thng thng nht th Graphen cng c nghin cu nh
38
phn t c kh nng nhn electron to composit vi TiO2 v mt s kt qu
nghin cu composit TiO2/graphen trnh by bng 1.5.
Bng 1.5: Bng thng k mt vi nghin cu v TiO2/graphen
Graphen Kch thc Hm lng Cht c loi b Ti liu

composit ht TiO2 graphen Wt% tham kho
(nm)
TiO2/GR 8.6-9.1 3 methylene blue 42
TiO2/GR 15 - rhodamine B 43
Ag2Se
TiO2 320 length, 90 - 2,4- 44
nanotubes/ pore diameter dichlorophenoxyacetic
GR axit
Pt-GP- 30 0,5 dodecylbenzesulfonate 45
TiO2/GR (DBS)
TiO2/GR 4-5 75 methylene blue 46
TiO2 /GR 12-16 2 rhodamine B 47
TiO2/GR 20 1 rhodamine B 48
TiO2- 25 5 reactive red 195, 2,4- 49
CeO2/GR dichlorophenoxyacetic
axit
TiO2/GO 20-40 4,6 methyl orange 50
G-Au- 100-200 - methyl blue 51

TiO2/GR
Fe-TiO2/GR 8-12 - methyl orange 52
S ghp ni gia TiO2 v graphen c chng minh tng cng

hiu qu tnh quang ca composit. S kt hp ca cc ht nano oxit kim loi vi
dn xut graphen dn n vic lm gim cc khong trng ca cc oxit kim loi
thng qua di nng lng lai gia nguyn t obitan O2p v C2p hnh thnh
cc ng bin mi. Hin nay, i vi hiu qu tc ng h tr xc tc din ra,
hm lng oxit kim loi trn vt liu graphen cn c iu chnh mt cch ph
hp.
39
Hnh 1.11: C ch phn ng ca TiO2/graphen vi Methylene blue
Trong thc t, t l % hm lng graphen ng vai tr quyt nh n hot
tnh quang xc tc ca composit v s bin i v lng thnh phn graphen tc
ng n hiu sut ca xc tc quang ha. Ni chung vic gia tng hm lng
graphen ci thin tnh quang ha nhng tng hm lng graphen ngoi mc gii
hn nht nh c th dn n s gim hot tnh quang qua tng cng qu trnh
hp ph v tn x ca Fenton bi hm lng cacbon d tha c trong composit.
Wang v cc cng s nghin cu nh hng hm lng graphen n hot tnh
ca composit TiO2/graphen v ti u ha % graphen ngng (0,05%) cho thu
c hot tnh quang ha cc i. Hot tnh xc tc quang ha ca vt liu li rt
ph thuc vo b mt ca TiO2 v graphen. Mt lin kt gia TiO2 v graphen
to iu kin tch in t v lm chm ti t hp. Trong mt vi bo co, cc
php o quang c thc hin kho st, th vai tr ca graphen oxit trong qu
trnh lm chm s ti t hp. Shi v cc cng s quan st thy dng quang gp
6 ln trong trng hp TiO2/graphen so vi ch TiO2. S tng cng ny trong
quang in c gn cho vic bt gi ngay lp tc cc electron thu ht quang bi
graphen t TiO2 v sau vn chuyn nhanh chng n mch in bn ngoi.
Trong thc t, vi mu TiO2/graphen cc sung vng mt, do s chuyn
electron t vng dn n cc vng ngoi t ch ra rng vic ni TiO2 v
graphen khng ch tng cng cc phn ng quang in m nng cao cht lng
quang in.
1.3.5.2. Xc tc quang ha composit oxit kim loi/graphen
Ngoi TiO2, lng ln oxit kim loi v hn hp oxit ca chng nh ZnO,
WO3, CuO, Mn3O4, Mn2O3, SnO2, cng c th kt hp vi graphen lm
xc tc quang ha. Kch thc ht, hm lng graphen v mc tiu cc cht
40
nhim khc nhau cho cc loi composit oxit kim loi/graphen khc nhau c
tm tt bng 1.6.
Bng 1.6: Bng thng k mt vi nghin cu v oxit kim loi/graphen
Graphen Kch thc ht Hm lng Cht nhim Ti liu tham
composit oxit kim loi graphen (Wt%) loi b kho
(nm)
ZnO/GR 5 2,5 methylene blue 53
Mn2O3/GR 8-10 15 methylene blue, 54
rhodamine B
SnO2/GR 3-5 - methylene blue 55
Mn3O4/GR 29,2 - methylene blue, 56
rhodamine B,
methyl orange
SnO2/GR 3,4 15 rhodamine B 57
ZnO/GR 30 ZnO/Gr 40:1 methylene blue 58
ZnO/GR 10-20 - rhodamine B 59
SnO2/GR 3-5 methylene blue 60
Cu2O/GR 100-500 - methylene blue 61
ZnO/GR 90-120 - malachite green 62
W18O49/GR 2-3 - methyl orange 63
WO3 Di 700 v 3,5 rhodamine B 64
nanorods/GR ng knh 65
Trong mt s trng hp, vt liu composit oxit kim loi/graphen khc

TiO2 cho thy hiu qu quang ha cao hn khi so snh vi composit
TiO2/graphen. Wang v cng s [48] chng minh kt hp ca SnO2 vi
graphen ci thin hot tnh quang ca SnO2 cho vic loi b pendimethalin, l
do chuyn d dng cc electron t pendimethalin sang SnO2. Mt s khc bit
in t ln gia pendimathalin v SnO2 lm cho qu trnh chuyn in t thun
li hn cho SnO2 so vi cc bn dn khc (TiO2 v ZnO). Hng s tc qu
trnh phn hy cho composit SnO2/graphen c quan st cao hn so vi cc hp
cht bn dn khc nh: P25-graphen, TiO2-graphen, ZnO-graphen di nh sng
nhn thy.
41
Hnh 1.12: C ch phn ng ca ZnO vi cc cht hu c
Fan v cc cng s [58] thc hin nghin cu chi tit nghin cu c

ch c th lin quan n hot tnh quang ha ca ZnO/graphen v cho rng hnh
thnh cc nhm oxi ha hot ng nh O2-, *OH v l trng tc ng chnh n
quang phn hy methylene blue. Qu trnh oxi ha trc tip l trng v oxi ha
O2- l cc phn ng ch yu tham gia vo qu trnh quang xc tc. Nng cao hot
tnh quang ha ca ZnO/graphen so snh vi ZnO v graphen cho thy mc
tng tc in t gia ZnO v graphen tc ng n tnh quang xc tc ca
composit. Mt dng quang in cao gp 3,5 ln c thy trong trng hp
ZnO/graphen so vi in cc ZnO c th gim electron ti t hp l trng. Mt
thay i tch cc hn na trong dy in t, thu c t gin ca Mott-
Sckotky cho thy ZnO/graphen (-0,29V) so vi ZnO (-0,36V) v gi tr thp hn
vng tuyn tnh ca composit ZnO/graphen ph hp vi mt cao hn. Mc
khuyt tt trong cu trc tinh th thnh phn oxit kim loi ca composit cng
nh hng n hiu sut quang xc tc ca composit. Chen v cc cng s
nghin cu nh hng ca cc v tr km v oxy trong mng ZnO n tnh quang
xc tc ca ZnO/graphen composit. S c mt ca cc v tr km v oxy ci thin
tnh quang xc tc bng cch ngn vic ti t hp cc ht mang in tch. Bn
cnh cc khuyt tt ca ZnO, s c mt graphen trong composit lm vt liu
tng tc tip tc ci thin hn na tnh quang xc tc bng cch ly cc in t
t vng dn ca ZnO. in tch m ca cu trc ZnO vi in tch dng ca
graphen to iu kin cho dng electron t ZnO n graphen.
42
1.3.5.3 Xc tc quang ha composit ion kim loi/graphen c t tnh
Hnh 1.13 C ch phn ng ca Fe3O4/graphen vi cc cht hu c

Cng ngh Fenton c s dng rng ri nh qu trnh oxi ha nng cao
(AOPs) x l cc cht c hu c khc nhau trong nc c bit cc cc cht
nhim bn nhit v khng b phn hy sinh hc. Fenton l phn ng lin quan
n cc cht xc tc kim loi v hydrogen peroxit to ra gc hydroxyl c th
tc ng cc hp cht hu c dn n khong ha chng. Cc cht xc tc
Fenton ng th truyn thng c nhiu nhc im nh yu cu pH khong hp
v to lng st bn sau phn ng. khc phc nhng hn ch trn, xc tc d
th c a ra thay th cho xc tc ng th. C nhiu loi xc tc oxit st
nh: magnetic, hermatic, goethite, Fe0/Fe2O3, Fe0/Fe3O4 c th c s dng nh
cc cht xc tc d th kch hot H2O2 to thnh cc gc hydroxyl c th
phn hy c cc cht nhim hu c thnh H2O, CO2 v cc mui v c.
Tuy nhin v c bn cc xc tc ny hot ng tng i yu v tc
phn hy tng i thp. Bn cnh vic to composit vi graphen gip ngn
chn qu trnh ti t hp in t ca Fe3O4 v nng cao hot tnh xc tc do s
tng tc gia Fe3O4 v graphen.
Trong nhng nm qua, spinel cc loi ht nano ferrit (NPs) vi cng thc
chung MFe2O4 (M = Mn, Fe, Co, Ni, Cu) c s dng nhiu trong ng dng
nh lu tr t mt cao, xc tc quang ha v x l mi trng, do c tnh
ni bt ca n c kch thc nanomet, din tch b mt ln, siu thn t v
bo ha t cao. S thu hi ca vt liu t tnh MFe2O4 l kh d dng bng cch
s dng t trng cho dung dch sau phn ng, do vy cho hiu qu chi ph v
cho kh nng ng dng thc t. Gn y, CuFe2O4 v CoFe2O4 c tm thy do
43
c tnh nng trong qu trnh kch hot cho phn ng oxi ha cc cht c hu c.
Mc d MFe2O4 th hin hiu sut xc tc cao, din tch b mt ln v tnh cht
t c o ca vt liu nano ferrit dn n mt s kt hp kt qu cho xc tc
hiu qu thp. gii quyt vn ny, mt s vt liu cacbon c din in
cao v c s dng nh cht nn cho MFe2O4 phn tn ln b mt ln nng cao
hiu qu xc tc. So vi cc vt liu cacbon khc nh than hot tnh, than ch,
CNTs th graphen c s ch ln h tr kim loi v oxit kim loi do n c
dn in cao, bn c hc, din tch b mt ln. K t khi graphen c biu
hin tch cc, cc nh nghin cu c gng to composit vi MnFe2O4,
CuFe2O4, NiFe2O4 v CoFe2O4.
Bng 1.7: Bng thng k mt vi nghin cu v hn hp oxit/graphen
Graphen Kch thc Hm lng Cht nhim loi Ti liu

composit ht oxit kim graphen b tham
loi (nm) (Wt%) kho
CoFe2O4/GR 6 40 methylene blue, 65
rhodamine B
ZnFe2O4/GR 7-10 20 methylene blue 66

CuFe2O4/GR 120-150 25 methylene blue 67
CuO/TiO2/GR 30-50 - methylene blue 68
ZnFe2O4/GR 40 15 p- chlorophenol 69
ZnO/ZnFe2O4/GR 10-20 4 methylene blue 70
Fe2O3/ZnO/GR <10 - methylene blue 71
44
CHNG 2
THC NGHIM V PHNG PHAP NGHIN CU
2.1. Mc tiu nghin cu

Tng hp mt s h vt liu nano composit graphen oxit trn c s oxit
kim loi c t tnh nh: Fe3O4-GO, Fe0-Fe3O4-GO, MFe2O4-GO (M=Zn, Co);
nghin cu nh gi hot tnh xc tc ca cc h vt liu tng hp c trn
thuc nhum hot tnh RR195 v ng dng lm xc tc quang ha mi, hiu qu
cao, c kh nng thu hi v ti s dng trong phn ng phn hy cht mu,
thuc nhum hot tnh x l nc thi dt nhum.
2.2. Thc nghim
2.1.1. Tng hp vt liu graphen oxit (GO)
Quy trnh tng hp graphen oxit c tin hnh nh sau:
Bc 1: Cho 3g bt graphit vo 42 ml dung dch H2SO4 98% trong mt
cc 1000 ml c ngm sn trong chu mui lnh (0oC) thit lp ch
khuy c lin tc vi tc 350 vng/pht trong 30 pht.
Bc 2 : Thm t t 0,45g KMnO4 vo hn hp ang c khuy bc
1. Tc cho KMnO4 phi m bo sao cho hn hp khng vt qu 05oC.
Sau b chu lnh v t h vo trong thit b n nh nhit gia nhit
n nhit mong mun.
Bc 3: Thm t t Xg (x=3g, 6g, v 9g) KMnO4 vo hn hp ang c
khuy bc 2. Tc cho vo KMnO4 phi m bo sao cho hn hp khng
vt qu 353oC, khuy tip trong 30 pht.
Bc 4: B sung rt t t vo hn hp 120 ml H2O nc ct trnh hin
tng qu nhit cc b, nhit ca h c gi X0C (900C), tip tc khuy
trong 30 pht
Bc 5: Thm tip 80 ml H2O dng phn ng, nhit ~ 500C, khuy
tip 20 pht.
Bc 6: Cho t t 10,5 ml dung dch H2O2 30% vo hn hp bc 5 v
khuy khong 20 pht.
Bc 7: Sn phm c lc ra vi dung dch HCl 0,1M, sau ra
nhiu ln vi nc ct v ly tm n pH=7, sy kh nhit 60oC trong chn
khng, sn phm thu c graphen oxit.
45
Bc 8: Hn hp sy kh c nghin mn bng ci m no v
bo qun trong bnh kn.
Bc 9: Graphit oxit c bc tch lp v graphen oxit vi sng (GOVS)
s dng l vi sng Goldsun MWO-G20SA, iu kin 700 W, trong thi gian 2
pht.
2.2.2. Tng hp GOSA (grphen oxit siu m) v GOVS (grphen oxit vi
sng) t graphit oxit
Graphit oxit
Graphit oxit, Graphit oxit,

0,1g/50ml H2O 0,5g
Bransonic 2510E- Goldsun, MWO-G20SA,

DTH,Xp,100W,42KHz 700W, 2 pht
Dung dch GOSA GOVS
T= Z0C, tc gia nhit

Sy chn khng 50C/pht, N2:15ml/p, 1h
600C, 24h
GOSA Graphen
Hnh 2.1.S tng hp GOSA v GOVS

2.2.3. Tng hp h vt liu nano composit oxit kim loi graphen oxit
Fe3O4-GO trn c s Fe3O4
a. Ha cht s dng
+ Graphen oxit (GO): s dng vt liu tng hp bng phng php oxi ha
t ca nhm nghin cu phng Ha hc b mt- Vin Ha hc.
+ FeCl3.6H2O (Sn phm ca Merk)
+ FeCl2.4H2O (Sn phm ca Merk)
+ NH4OH (Sn phm ca Trung Quc)
46
+ C2H5OH (Sn phm ca Merk)
b. Quy trnh tng hp
Cc bc tin hnh:
Bc 1: Cn mt lng graphen oxit (GO) theo tnh ton phn tn vi
110 ml nc ct, sau t vo trong thit b phn ng bnh 3 c dung tch 1lit
vi thit b sc kh N2.
Bc 2: Cn lng mui Fe3+ v Fe2+ theo t l Fe3+/Fe2+ = 2:1, ri nh
vo hn hp graphen oxit (GO) c phn tn bc 1, sao cho nng
Fe3+ v Fe2+, theo t l 0,1M/0,05M, khuy u trong 15 pht v duy tr tc
khuy 500 vng/pht.
Bc 3: Nng nhit ln 800C ri thm nhanh NH4OH vo hn hp
bc 2, sao cho pH = 10 v khuy u trong 45 pht.
Bc 4: Sn phm c lc ra bng H2O v C2H5OH n pH =7 v sy
chn khng nhit 600C trong 6 gi.
Hnh 2.2.S tng hp Fe3O4-GO
47
2.2.4 Tng hp h vt liu nano composit oxit kim loi graphen oxit
CoFe2O4-GO trn c s Fe3O4 bin tnh
a. Ha cht s dng
+ Fe(NO3)3.9H2O (Sn phm ca Merk).
+ Co(NO3)2.6H2O (Sn phm ca Merk).
+ NH4OH (Sn phm ca Trung Quc).
+ C2H5OH (Sn phm ca Merk).
b, Quy trnh tng hp
Cc bc tin hnh:
vi thit b sc kh N2.
Bc 2: Cn lng mui Fe3+ v Co2+ theo t l Fe3+/Co2+ = 2:1, ri nh
vo hn hp graphen oxit (GO) c phn tn bc 1, sao cho nng
Fe3+ v Co2+, theo t l 0,1M/0,05M, khuy u trong 15 pht, duy tr tc
khuy c 500 vng/pht.
Bc 3: Nng nhit ln 800C ri thm nhanh NH4OH 25% vo hn
hp bc 2, sao cho pH = 10, khuy u trong 2 gi.
48
Hnh 2.3.S tng hp CoFe2O4-GO
2.2.5. Tng hp h vt liu nano composit oxit kim loi graphen oxit
ZnFe2O4-GO trn c s Fe3O4 bin tnh
a. Ha cht s dng
+ Fe(NO3)3.9H2O (Sn phm ca Merk).
+ Zn(NO3)2.6H2O (Sn phm ca Merk).
b. Quy trnh tng hp
Cc bc tin hnh:
vi thit b sc kh N2.
Bc 2: Cn lng mui Fe3+ v Zn2+ theo t l Fe3+/Zn2+ = 2:1 ha tan
trong dung dch H2O + C2H5OH vi t l nht nh ri nh vo hn hp GO
c phn tn bc 1, khuy u trong 30 pht v duy tr tc khuy 500
vng/pht.
49
Bc 3: Thm nhanh NH4OH 25% vo hn hp bc 2, sao cho pH =
10, khuy u trong 3 gi.
Bc 5: Kh nhit sn phm sau khi sy chn khng ti nhit T=
0
650 C trong dng N2 99 % thi gian 2 gi thu c ZnFe2O4-GO.
Hnh 2.4.S tng hp ZnFe2O4-GO

2.2.6 Tng hp h vt liu nano composit oxit kim loi graphen oxit Fe0-
Fe3O4-GO trn c s Fe3O4 bin tnh
a. Ha cht s dng
+ FeCl3.6H2O (Sn phm ca Merk).
+ NaBH4 (sn phm ca Merk).
b. Quy trnh tng hp
50
Cc bc tin hnh
Bc 1: Cn 1g Fe3O4-GO c tng hp, phn tn trong 100 ml nc
ct c thit b sc kh N2 v hn hp c khuy mnh trong 30 pht.
Bc 2: Nh git 100 ml FeCl3.6H2O (theo tnh ton 10% khi lng)
vo hn hp Fe3O4-GO chun b bc 1 v khuy trong 1gi.
Bc 3: Nh t t dung dch 100 ml NaBH4 0,15 M vo hn hp bc
2 v khuy tip trong 2 gi.
Bc 4: Lc ra sn phm v sy chn khng nhit T= 600C, trong 6
gi thu c sn phm Fe0-Fe3O4-GO.
Hnh 2.5.S tng hp Fe0-Fe3O4-GO

2.2.7 Tng hp h vt liu nano composit oxit kim loi graphen oxit
Fe(III)-GO trn c s Fe3O4 bin tnh
a. Ha cht s dng
b. Quy trnh tng hp
Cc bc tin hnh
Bc 1: Cn mt lng graphen oxit (GO) phn tn trong 110 ml dung
dch nc ct, siu m hn hp trong 30 pht to thnh hn hp ng nht.
51
Bc 2: Nh t t dung dch mui FeCl3 0,2M vo hn hp c
phn tn bc 1, kt hp khuy v nhit duy tr nhit 600C trong 10
gi.
Bc 3: Lc ra sn phm n pH = 7 v sy chn khng nhit T =
0
60 C trong 6 gi thu c Fe(III)-GO.
2.3. Phn ng Photo Fenton
Phn ng phn hy (quang ha) thuc nhum hot tnh RR195 c thc
hin trong iu kin dung dch c khuy lin tc (250 vng/pht), duy tr
nhit phn ng 300C, thi gian phn ng t 60-120 pht (ty tng vt liu)
di iu kin s dng n m phng nh sng mt tri (simulated sun-light)
cng sut 15W c 4-6% tia UV (bc sng t 340 nm n 315 nm). Trong phn
ng quang ha, 100 ml dung dch thuc nhum hot tnh RR195 c nng
kho st t 50mg/L (50 ppm) n 150 mg/L (150 ppm), nng cht xc tc c
nh 0,3g/L - 0,5g/L. Nng H2O2 (30%) c kho st ln lt t (0,2 -
3mL/100 mL RR195). pH dung dch c kho st trong khong t 1 - 8. Sau
tng khong thi gian xc nh lc tch cht rn em dung dch thu c phn
tch trn thit b o quang ph UV-Vis (LAMBDA 35 UV/Vis) da trn pic
bc sng =542 nm. Xc nh nng thuc nhum hot tnh RR195 cn li
trong dung dch bng phng php ng chun.
ng chun ca RR195 dng trong qu trnh hp ph c m t trn
hnh sau.
2,5
542 nm
ABS(cng hp ph)
2
hp ph )
1,5
Abs (a.u)
pH =5.5
Abs (Cng
1 y = 0,020x + 0,032 pH = 8.0

R = 0,997
0,5 pH =3.0
0
300 400 500 600 700
0 20 40 60 80 100
Wavelength (nm)
Nng (mg/L hoc ppm) Bc sng (nm)
Hnh 2.6. ng chun v ph UV-Vis ca thuc nhum hot tnh RR195
Hiu sut qu trnh c tnh ton thng qua cng thc

H(%)= (C/C0)x 100%.
52
Trong Co, C l nng u v nng sau khong thi gian (t) phn
ng (mg/L, hoc ppm)
nh kh nng ti sinh ca xc tc trong qu trnh hp ph x l cht
mu chng ti tin hnh thu hi xc tc sau phn ng bng t tnh v tin hnh
ra bng nc v ethanol + methanol. Xc tc sau thu hi c sy chn khng
nhit 60oC, trong 24 gi. Sau tin hnh nh gi kh nng hp ph thuc
nhum hot tnh RR195 ti nng 50mg/L, vi cc iu kin nh trn. Sn
phm sau phn ng c o bng thit b o UV- Vis LAMBDA 35UV/Vis -
Vin Ha hc.
2.4. ng hc ca phn ng
ng ha hc l khoa hc nghin cu v tc phn ng ha hc. Tc
phn ng ha hc b nh hng bi nhiu yu t. Cc yu t l nng ,
nhit , p sut, dung mi, cht xc tc, hiu ng th, hiu ng ng v, hiu
ng mui... Nh hiu r c ch phn ng, cho php chng ta la chn cc yu t
thch hp tc ng ln phn ng, tnh ton ch lm vic ti u ca l phn
ng lm cho phn ng c tc ln, hiu sut cao, to ra sn phm theo
mun.
Ngi ta phn bit ng ha hc hnh thc v ng ha hc l thuyt.
ng ha hc hnh thc ch yu thit lp cc phng trnh lin h gia nng
cht phn ng vi hng s tc v thi gian phn ng, cn ng ha hc l
thuyt da trn c s c hc lng t, vt l thng k, thuyt ng hc cht kh
tnh c gi tr tuyt i ca hng s tc phn ng.
Tc phn ng
c trng cho s nhanh chm ca phn ng, ngi ta dng khi nim
tc phn ng v c nh ngha nh sau: "Tc phn ng l bin thin
nng ca mt cht cho (cht u hoc cht cui) trong mt n v thi
gian.
Tc tc thi ca phn ng ha hc c o bng bin thin nng
ca cc cht phn ng (hay sn phm phn ng) trong mt n v thi gian.
53
Vi v l tc phn ng tc thi, C l bin thin nng trong khong
thi gian t.
Phn loi ng hc phn ng
V phng din ng ha hc, ngi ta c th chia cc phn ng ha hc
theo phn t s v bc phn ng.
Phn t s phn ng
Phn t s phn ng l s phn t tng tc ng thi vi nhau trc
tip gy ra bin ha ha hc trong mt phn ng c bn. Cn phn ng c bn
(hay phn ng s cp) l phn ng ch mt giai on duy nht, cht phn ng
tng tc vi nhau trc tip cho sn phm phn ng.
Da vo khi nim phn t s phn ng, chng ta c th phn bit ba loi
phn ng: phn ng n phn t, lng phn t v tam phn t. Khi cc phn t
tng tc vi nhau, khng phi tt c cc va chm gia chng u dn n bin
ha ha hc, m ch mt phn nh va chm trong cc va chm dn n bin ha
ha hc, va chm gi l va chm c hiu qu hay va chm hiu dng.
Khi phn ng ha hc din ra, m bo cho cc phn t va chm ng
thi dn n bin i ha hc, th phn ng cng nhiu phn t tham gia cng
kh thc hin iu kin trn. Ngi ta tnh xc sut v chm, th xc sut va
chm ba l b nht, c ngha phn ng tam phn t rt him, trong thc t ngi
ta cha tm thy phn ng c phn t s cao hn 3.
iu dn n s ra i mt khi nim khc mi thay th cho khi nim
phn t s, l bc phn ng.
Bc phn ng
i vi phn ng tng qut:
aA + bB + xX + yY + (2.2)
phng trnh ng hc c dng v k[ A]n .[ B]n ...
1 2
(2.3)
t n = n1 + n2 +
y: n l bc ton phn ca phn ng
n1 l bc ring phn i vi cht A
n2 l bc ring phn i vi cht B
T dn n nh ngha bc phn ng: "Bc phn ng i vi mt cht
cho trc l s m nng ca cht y trong phng trnh ng hc ca phn
ng".
Bng 2.1: Tm tt phn ng bc 0, 1, 2 v n
54
Bc 0 Bc 1 Bc n
Phng trnh ng d[A] d[A] d[A]
k k[A] k[A]n
hc dng vi phn dt dt dt
1 1
Phng trnh ng n 1
n 1
(n 1)kt
[A] [A]0 kt [ A] [ A] 0 e kt [ A] [ A]0
hc dng tch phn
(tr phn ng bc 1)
n v hng s tc
M.s-1 s-1 M1-n.s-1
1
theo t
th xc nh k [A] theo t Ln([A]) theo t [A] n 1
(tr phn ng bc 1)
2 n 1 1
[A]0 ln( 2) t1/ 2 n 1
Thi gian bn hy t1/ 2 t1/ 2 (n 1)k[A]0
2k k
(tr phn ng bc 1)
So snh phn t s v bc phn ng

-Bc phn ng c th l s nguyn dng, v cng c th l m, khng
hoc phn s na, cn phn t s c gi tr nguyn, dng. Tr s cao nht ca
bc phn ng v phn t s l ba.
- Khi nim phn t s ch c p dng cho phn ng c bn (1 giai
on) khng p dng cho phn ng phc tp bao gm nhiu giai on (phn ng
c bn), cn bc phn ng ch c xc nh bng thc nghim.
Cc phng php xc nh hng s tc phn ng:
Xc nh k theo tng thi im thc nghim:
Mi thi im thc nghim ng vi mt gi tr no ca t v C.
1 C0
Nu bit chnh xc C0 th c th tnh k theo cng thc: k ln vi dy
t C
im thc nghim ri ly gi tr trung bnh.
Nu khng bit C0 th dng th xc nh k theo tng cp im. Bin i
1 C0
cng thc k ln sang dng tuyn tnh lnC = lnC0 k.t .T dy nng Ci
t C
ti cc thi im ti suy ra cc gi tr lnCi. Dng th lnC = f(t). th thu c
l mt ng thng c h s gc l tg = -k v tung gc bng lnC0.
55
lnC
lnC0
Hnh 2.7. th lgC theo t i vi phn ng bc 1

Ch : ng thng phi i qua nhiu im thc nghim nht, loi b
nhng im qu sai lch.
Xc nh k theo tng cp im
Phng php ny cng khng cn bit C0. Ly tch phn gii hn phng
trnh ng hc vi phn theo cc thi gian t1 o c ta c biu thc tnh k theo
cc cp thi gian ti v nng Ci. Thay cc gi tr t v C tng ng ta c cc
gi tr ki sau ly gi tr trung bnh th c k.
Ch : xc nh k c chnh xc th khng nn xc nh nng cht
phn ng thi im t = 0 v t = (thi im kt thc phn ng).
2.5. Phng php nghin cu
2.5.1 Phng php nhiu x Rnghen (X-ray diffraction, XRD)
[79,80,81]
Bn cht vt l ca tia X l bc x sng in t va c tnh cht sng va
c tnh cht ht. Tia X c truyn i trong khng gian vi tc nh sng v
mang nng lng t 200eV n 1 MeV v c xc nh theo phng trnh:
E = h = hc/ (2.4)
Trong : l tn s ca bc x tia X, Hz
l bc sng ca bc x tia X, (t 102 n 10-2 )
c l s tc nh sng, c= 2,998 x 108 m/s
h l hng s Planck, h= 4,136 x 10-15 eV.
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
56
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 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 song song (dhkl ), gc gia
chm tia X v mt phng phn x () vi bc sng () c biu th bng h
phng trnh Vulf Bragg : 2dhklsin = n
Hnh 2.8. 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 ca ht tnh theo phng trnh Scherrer nh sau:
d=0,9./[1/2.cos] (2.5)
Trong di bc sng ca bc x Cu K, =1,5406, 1/2 l bn
rng vch nhiu x, l gc Brag
57
Hnh 2.9. t ca pic phn x gy ra do kch thc ht
Trong lun n ny cc mu c o XRD trn thit b o D8 Advance
(Bruker) dng bc x ca Cu K , =1.5406 Ao, khong qut 2 = 1-70o.
2.5.2. Phng php ph hng ngoi FT-IR
Trong FT-IR, 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 (2.6)
Trong , Io l cng nh sng ti, I l cng nh sng truyn qua
v 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:
T (%) = (I0 / I) x 100 (2.7)
T(%) khng t l vi c. i vi vic phn tch nh lng, ngi ta
thng s dng i lng hp th quang A, c nh ngha nh sau:
A = lg (Io/I) (2.8)
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).
Da vo s hp th c trng, c th chia ph hng ngoi thnh ba vng:
58
- Vng sng ngn (4000 - 1300 cm-1): gi l cc vng nhm chc, v d
cc di hp th ca cc nhm chc hu c nh hydroxyl, amin, cacboxyl,... u
xut hin vng ny.
- Vng sng trung bnh (1300 909 cm-1): gi l vng ch vn tay v c
dng so snh hnh dng cc di hp th ca cc mu xem c ng nht khng
v mt ha hc. S th hin cc di ph y kh phc tp do cc dao ng
tng tc gy ra. Phn tch cc di vng ny rt c gi tr khi so snh vi cc
di hp th hai vng kia.
- Vng sng di (909 650 cm-1): vng ny c trng cho cc dao ng
bin dng.
Trong lun n ny cc mu c o ph FT-IR k thut p vin vi KBr
FT/IR- 4100, JASCO(USA), Hn Quc v FT-IR 6700 Thermo Nicolet
ThermoElectro. Ti trng i hc Bch khoa H Ni.
2.5.3. Phng php ph in t quang tia X (XPS)
K thut ph in t quang tia X (X-ray Photoelectron Spectroscopy-
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 ra. Trong k thut ny b mt mu
c bn ph bi tia X nng lng thp t ngun nhm hoc magie trong s
dng peak Ka. 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). Qu trnh pht
x in t quang XPS v UPS khi b mt mu c bn ph bi cc photon
nng lng Ex=hv 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
E=hv-Eb-F (2.9)
Trong n l tn s ca photon, Eb l nng lng lin kt in t, F l
cng thot ca in t. Mi nguyn t s c mt tp pic c trng trong ph
in t quang ti cc ng nng c xc nh bi nng lng photon 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 quan 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
59
ca cc nguyn t c mt. ng dng chnh ca ph in t quang tia X l
nghin cu c th pht sinh vi lp ngoi cng ca b mt vt liu.
Hnh 2.10. Qu trnh pht quang in t

Trong lun n ny, cc mu c o ph XPS trn my ESCALab MKII,
s dng tia pht x Mg K. Thc nghim: Quang ph XPS c ghi trn thit b
o THERMO VG SCIENTIFIC(U,K), MultiLab2000, Hn Quc.
2.5.4. Phng php ph tn sc nng lng tia X
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 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 (xem hnh 2.10). 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
60
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 (2.10)
Trong me l khi lng ca in t; qe l in tch ca in t, h l
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.
Hnh 2.11. Nguyn tc pht x tia X dng trong ph
C nhiu thit b phn tch EDX nhng ch yu EDX c o bng cc

knh hin vi in t qut hay truyn qua.
Trong lun n ny, cc mu c o EDX trn thit b o JEOL JSM
6500F. Vin Vt liu Vin Hn Lm Khoa hc v Cng Ngh Vit Nam.
2.5.5. Phng php hin vi in t truyn qua (TEM) v knh hin vi
in t truyn qua phn gii 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.
61
V mt l thuyt, phn gii cc i, d, nhn c bi nh sng b gii hn
bi bc sng ca cc photon m c dng quan st mu.

d
2n sin (2.11)
Vo u th k 20, cc nh khoa hc c gng gii quyt gii hn
phn gii ca knh hin vi do dng nh sng kh kin vi bc sng tng i
ln (400 - 700 nm) bng cch dng chm in t (electron bean). Theo l thuyt
Broglie, cc in t va c tnh cht sng va c tnh cht ht. iu ny c
ngha l chm in t c th ng vai tr nh l chm bc x in t. Bc
sng ca in t lin h vi ng nng thng qua phng trnh Broglie.
h
0
E
2m0 E (1 )
2m0 c 2
(2.12)
Trong , h l hng s Planck, mo l khi lng tnh ca in t v E l
nng lng ca electron c tng tc.
Cc in t c to ra t s pht x ion nhit t mt dy tc lm bng
tungsten. Cc in t ny c tng tc bng mt in trng (c tnh bng
volt). 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 (thng c vit tt l
HR TEM xut pht t thut ng ting Anh (High resolution Transmission
Electron Microscopy) 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 HRTEM 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.
62
Hnh 2.12. S nguyn l s to nh phn gii cao trong HR-TEM
Trong lun n ny, nh HR-TEM c ghi trn thit b o HR-TEM JEM-
2100F, Hn Quc, v TEM - JEM1010 o ti Vin V sinh Dch t Trung ng
c cc thng s M= x50 - x600.000, d=3A0, U= 40-100kV.
2.5.6. Phng php ng nhit hp ph- kh hp ph nitrogen (BET)
[81,82]
B mt ring xc nh theo phng php 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= nmAmN (m2/g) (2.13)
Trong : S: din tch b mt (m2/g)
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) 77K 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 = 4,35Vm (2.14)
S tng nng cht kh trn b mt phn cch pha gia cht b hp ph
v cht hp ph (cht rn) c gi l s hp ph kh. Lng kh b hp ph V
c biu din thng qua th tch cht b hp ph l i lng c trng cho s
phn t b hp ph, ph thuc vo p sut cn bng P, 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
63
ng "ng nhit kh hp ph". Theo phn loi ca IUPAC (Lin minh quc t
v Ha hc thun ty v Ha hc ng dng- International Union of Pure
Applied Chemistry), c cc loi ng ng nhit hp ph - kh hp ph biu
din trn hnh 2.12.
Hnh 2.13. Cc dng ng ng nhit hp ph-kh hp ph

theo phn loi IUPAC
ng ng nhit kiu I trong hnh 2.12 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. Din tch b mt ring thng c tnh theo
phng php Brunauer-Emmett-Teller (BET) 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).
Trong lun n ny, phng php ng nhit hp ph-kh hp ph N2
c thc hin nhit 77K, trn thit b o Tristart-3000 Micromeritic ti
i hc S phm H Ni.
2.5.7. Phng php ph hp th t ngoi v kh kin
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. Nng lng lin kt c xc nh bi phng trnh
sau:
E = h. (2.15)
64
Trong : E l nng lng (J), h l hng s Planck (6,62x10-34 J.s), v v l
tn s (s-1). Bc x in t c th c xem l s kt hp trng in v t c
truyn qua khng gian di dng sng. Gia tn s (v,s-1), bc sng (, m) v
tc nh sng (c = 3x108 m.s-1) lin h bng biu thc:
c h.c
E
suy ra (2.16)
Trong : h l hng s Planck; c l vn tc nh sng
Khi phn t b kch thch, cc electron ca cc nguyn t trong phn t
thc hin cc bc nhy sau:
Hnh 2.14. 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:
I0
A lg .l.C
I (2.17)
Trong : A: hp th nh sng (hp th quang)
I0, I: cng bc x in t trc v sau khi qua cht phn tch
: h s hp th
65
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.
Trong lun n ny, xc nh nng cn li ca thuc nhum hot tnh
RR195 trn thit b o UVVis spectrophotometer (DR/4000U) ti Vin Ha
hc-Vin Hn Lm Khoa hc v cng ngh Vit Nam.
Ph UV-Vis rn ghi trn thit b o UV-2200A, Shimadzu i hc S
phm H Ni.
2.5.8. Phng php xc nh t tnh ca vt liu bng t k mu rung
(Vibrating Sample Magnetometer - VSM)
H o VSM ti phng th nghim t v siu dn thuc Vin Khoa hc Vt
liu - Vin 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 13kOe.
+ Di nhit o t 77 1000K.
+ Cng t trng 1 Tesla.
66
CHNG 3. KT QU V THO LUN
3.1. c trng ca vt liu graphen oxit v graphen tng hp c

3.1.1. Gin XRD ca graphen oxit v graphen
GOSA
Cuong do (tuy chon)
GOVS Graphen
10 20 30 40 50
Goc 2 thetha
Hnh 3. 1. Gin XRD ca graphen oxit siu m,
graphen oxit vi sng v graphen
T hnh 3.1 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 11,20 (002) c trng cho vt liu
graphen oxit (GO) [72,73]. iu ny chng t cc nhm chc c cha oxy
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 [72] v 1,2 nm cho mu
ngm nc dn ti s chuyn dch v gi tr 2 (002) nh hn (t 26,5o xung
11,2o) [73]. i vi GOVS (graphen oxit vi sng) 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 graphen oxit (GO) ra xa, lm cho
lc lin kt ca chng yu i qua lm s lng cc tm v khong cch gia
67
cc tm graphen oxit (GO) tng ln [74], 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 graphen oxit vi sng (GOVS) bng nhit
600oC 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 graphen -rGO [73, 75]. Quan st pic c trng trn
graphen- 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 graphen - rGO tng hp c c
nhng khuyt tt so vi graphit ban u [76,77].
3.1.2. nh knh hin vi in t truyn qua phn gii cao (HR-TEM)
ca vt liu graphen oxit v graphen
nh HR-TEM ca GO v rGO c minh ho hnh 3.2 (a, b v c).
0,6nm
a a
b b
68
0,4nm
c c
Hnh 3.2. nh HR-TEM ca GOSA (a) , GOVS (b) v rGO (c)

T nh HR-TEM ca GOSA (graphen oxit siu m) (hnh 3.2a) cho thy
s xut hin nhng np gy trn b mt ca vt liu graphen oxit (GO) c th do
b mt b rn nt trong qu trnh x l siu m hoc cng c th do b mt b
rn nt khi o HR-TEM ca graphen oxit (GO) do s dng nng lng cao. i
vi vt liu GOVS (graphen oxit vi sng) cho thy s chng xp cc lp gim so
vi GOSA (graphen oxit siu m), s lp cng gim t khong 10 lp (GOSA)
xung 7-8 lp (GOVS). Hnh nh HR-TEM ca graphen -rGO khi so snh vi
nh HR-TEM GOVS (graphen oxit vi sng) nhn thy graphen- rGO tng hp
c c cu trc n lp hoc vi lp nh trong ti liu cng b [73]. T
hnh 3.2c cng cho thy rGO c cu trc 5-6 lp, chiu dy mi lp khong 0,4
nm, i vi GOSA (graphen oxit siu m) chiu dy mi lp khong 0,6 nm.
Nhn thy, c s khc bit nh khi so snh chiu dy 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 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.
69
3.1.3 Ph hng ngoi (FTIR) ca vt liu graphen oxit v graphen
Hnh 3.3. Ph FT-IR ca graphen oxit siu m (GOSA), graphen oxit vi sng
(GOVS) v graphen (rGO) sau khi tng hp
Hnh 3.3(A) m t ph FTIR ca GOSA (graphen oxit siu m), GOVS
(graphen oxit vi sng) v graphen (rGO). Quan st ph FTIR ca GOSA cho
thy c s tn ti ca nhm cacbonyl C=O (trong khong 1700 -1730 cm-1)
[78]. Cc pic nm trong khong 1200-1250 cm-1 c trng cho s tn ti ca lin
kt CO [79]. 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 [78, 80], pic nm trong khong
1060 cm-1 c trng cho lin kt C-O-C [79]. Ngoi ra chng ta cn thy s c
mt ca cc nhm -OH c cc pic nm trong khong t 3400 3850 cm-1 [78,
80]. 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 [78, 80]. 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 trn b mt GOVS. Sau qu trnh kh nhit
quan st FTIR ca rGO (hnh 3.3A) cho thy cc nhm chc gn nh khng cn
trn b mt ca vt liu, nh vy qu trnh kh lm mt i mt lng ln cc
nhm chc trn b mt GO. ng FTIR ca graphen hu nh l dng ng
70
thng l do s mt i lng ln cc nhm chc ca GOVS. Mt iu c bit c
th nhn thy khi quan st FTIR ca c ba 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 [80]. Gii thch cho iu ny l do trong
khong nhit t 50-120oC, GO d dng hnh thnh lin kt vi CO2 [80, 81],
lin kt ny b ph v khi nhit > 210oC [81], qu trnh sy chn khng loi
nc trn GO din ra 60oC 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 v H2O 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 v H2O, ph FTIR ca GOSA (hnh
3.3B) 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.
3.1.4. Ph in t quang tia X (XPS) ca vt liu graphen oxit v

graphen
71
C D
F
E
Hnh 3.4a. Ph XPS ca graphen oxit siu m -GOSA (a,b), graphen oxit vi
sng -GOVS (c,d) v graphen -rGO (e,f)
Qua nh ph XPS ca graphen oxit (GO), cho thy u xut hin nhng
lin kt O1s vi pic c trng mc nng lng 500eV c trong nh ph ng
thi cng pic ca O1s vi mc nng lng
lin kt ln n xp x 4,5x105 ht/s chng t c
kh nhiu oxy trong vt liu v c nhng nhm
chc cha oxy hnh thnh trong vt liu [78]. i
vi ph XPS ca graphen (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 3.4a/E)
v 3. 105 ht/s (hnh 3.4b) cho thy lng oxy
72 Hnh 3.4b. Ph XPS ca

rGO kh nhit t GOSA
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 3.4a/C) cho thy sau khi kh graphen oxit (GO) thnh graphen (rGO) v l
thuyt graphen khng cha oxy nhng trong thc tin cng nh cc cng trnh
cng b [72, 73, 75, 80] th qu trnh kh ch c khong 80% .
Tuy vy, s liu bng 3.1 cho thy, 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 graphen oxit siu m (GOSA) v graphen (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 graphen oxit vi sng (GOVS) v lm mt i mt phn lng oxy
so vi graphen oxit siu m (GOSA), do khi kh graphen oxit vi sng
(GOVS) v graphen (rGO) qu trnh kh din ra tt hn v cao hn so vi kt
qu ca nhm tc gi Abhijit Ganguly [77] khi kh graphen oxit (GO) v
graphen (rGO) ti nhit 6000C (C/O~6,57).
Bng 3.1. Thnh phn % cc nguyn t trong ph XPS ca graphen oxit (GO)
v graphen (rGO)
Mu/ nguyn t C O C/O

rGO (graphen) 91,59 7,41 10,89
GOVS (graphen oxit vi sng) 73,92 25,08 2,98
GOSA (graphen oxit siu m) 69,88 30,12 2,32
Graphen kh nhit t GOSA 86,02 13,98 6,15
Graphen, 6000C [77] 86,80 13,20 6,57
Phn tch ph XPS C1s (hnh 3.4a/B -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 oxy), tng t vi pic tng ng mc nng lng 286,8 eV l ca lin
kt CO [78, 83], pic tng ng vi mc nng lng 289-290 eV l ca lin kt
OC= O [77, 83] v 287,9 eV l ca lin kt C = O [77]. Cng ca cc pic
ny trong graphen oxit -GO cao hn so vi cng ca cc pic trong graphen
73
(rGO) chng t lng oxy lin kt vi cacbon trn b mt graphen (rGO) mt
i mt lng ln, qu trnh kh nhit GO v rGO cn c th hin r trn pic
291,5eV c trng cho cc lin kt * ca cacbon trong vng thm [77]. Kt
hp tham kho mt s ti liu [73, 75, 82, 84].
3.2. c trng vt liu xc tc nano composit oxit kim loi graphen oxit
3.2.1. Gin XRD ca cc h xc tc nano composit oxit kim loi trn
graphen oxit
3.2.1.1 Gin XRD ca h vt liu xc tc Fe3O4-GO
Hnh 3. 5: Gin XRD ca graphen oxit (GO)

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Sample GO-Fe3O4
400
300
Cng (Cps)
d=2.508
d=2.953
d=2.095
d=1.701
d=1.621
d=1.473
Lin (Cps)
200
100
5 10 20 30 40 50 60 70
2-Theta - Scale
Gc 2 theta
File: Canh VH mau GO-Fe3O4.raw - Type: 2Th/Th locked - Start: 5.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 14 s - 2-Theta: 5.000 - Theta: 2.500 - Chi: 0
00-001-1111 (D) - Magnetite - Fe3O4 - Y: 86.78 % - d x by: 1. - WL: 1.5406 - Cubic - a 8.37400 - b 8.37400 - c 8.37400 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fd-3m (227) - 8 - 587.
Hnh 3.6: Gin XRD ca Fe3O4-GO
74
T hnh 3.5 v hnh 3.6 nhn thy, khi a Fe3O4 ln graphen oxit (GO),
trn gin XRD ca Fe3O4-GO xut hin cc pic 2 = 18,27o, 30,1o, 35,4o,
43,05o, 62,51o v 63,95o tng ng vi cc pic chun cho cu trc spinel Fe3O4.
Tuy nhin, pic c trng cho cu trc ca graphen oxit (GO) gi tr 2= 11,5o
[85, 86] khng thy xut hin. iu ny c th gii thch l do s hnh thnh cc
ht nano Fe3O4 trn b mt lp graphen oxit (GO) chn gia cc lp ca graphen
oxit (GO) gy bin dng do khng th pht hin pic 11,5o (tng ng
khong cch cc lp d= 0,71nm). Kt qu ny cng ph hp vi kt qu cng b
ca Yang v cc cng s [86].
3.2.1.2 Gin XRD ca h vt liu xc tc CoFe2O4-GO trn c s Fe3O4 bin

tnh
200
180
160
Cuong do (Cps)
140
120
100
80
60
10 20 30 40 50 60 70
Goc 2 Theta
Hnh 3.7: Gin XRD ca CoFe2O4-GO
Quan st hnh 3.7 cho thy qu trnh a CoFe2O4 ln graphen oxit (GO)
lm cho pic 2=11,5o khng cn nh nhn thy trng hp ca Fe3O4-
GO v thay vo l s xut hin ca cc pic vi gi tr 2 tng ng l:
18,471 (111), 30,4 (220), 35,76 (311), 43,48 (400), 53,8 (422), 57,5 (511)
v 63,13 (440) ph hp vi cc d liu nhiu x tia X tiu chun cho cu trc
spinel ca CoFe2O4 [87]. Kt qu ny chng minh s hnh thnh ca cc ht
nano CoFe2O4 ln cc lp ca graphen oxit (GO).
75
3.2.1.3.Gin XRD ca h vt liu xc tc ZnFe204-GO trn c s Fe3O4 bin
tnh
Cuong do tuy chon (a.u)
ZnFe2O4-rGO
20 25 30 35 40 45 50 55 60 65 70
Goc 2 Theta
Hnh 3.8: Gin XRD ca ZnFe2O4 -GO

Quan st hnh 3.8 cho thy qu trnh a ZnFe2O4 ln graphen oxit (GO)
lm bin mt pic 2 =11,5o c trng cho cu trc lp ca GO bin dng v
thay vo l s xut hin ca cc pic cng cao vi gi tr 2 tng ng l:
30,1 (220), 35,3 (311), 43,0 (400), 53,5 (422), 56,3 (511) v 62,3 (440)
ph hp vi cc d liu nhiu x tia X tiu chun cho cu trc spinel ZnFe2O4
[88, 89]. Kt qu ny chng minh s hnh thnh cc ht nano ZnFe2O4 ln cc
lp ca graphen oxit (GO).
3.1.2.4 Gin XRD ca h vt liu xc tc Fe0-Fe3O4-GO trn c s Fe3O4
bin tnh
Hnh 3. 9: Gin XRD ca Fe0-Fe3O4-GO
76
T gin XRD hnh 3.9 cho thy, qu trnh a Fe3O4 ln graphen oxit
(GO) kh ha hc 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, 422), 62,51 (511) v 63,95 (440) ph
hp vi cc d liu nhiu x tia X tiu chun cho cu trc spinel Fe3O4 [90]. Kt
qu ny chng minh s hnh thnh ca cc ht nano Fe3O4 ln graphen oxit
(GO). Sau qu trnh kh bng NaBH4 cc nh pic c trng cho Fe3O4 vn cn,
tuy nhin cng pic gim nhiu so vi trc khi kh, trn gin XRD
ca Fe0-Fe3O4-GO cho thy c s xut hin cc pic 2 tng ng l 45 v 68
c trng cho s hnh thnh ca Fe0 trn vt liu [91].
3.1.2.5. Gin XRD ca h vt liu lai Fe(III)-GO
Hnh 3.10. Gin XRD ca GO v Fe(III)-GO

T hnh 3.10 cho thy pic 2 ~ 11,5o c trng cho vt liu graphen oxit
(GO) vi khong cch gia cc lp = 0,71 nm c cho l do s c mt ca s
lng ln cc nhm chc cha oxy trong GO tng hp c [5]. Qu trnh a
ion Fe(III) ln trn graphen oxit (GO) lm cho pic 2 ~11,5o c cng gim
mnh v gn nh bin mt. Hn na, s hnh thnh pha FeO hay Fe2O3 cng
khng pht hin thy. Kt qu trn c th l gii l khi cc ion Fe3+ vi kch
thc 0,067 nm tng tc vi cc nhm chc ca GO nh hydroxyl, cacbonyl,
epoxy v c bit l nhm chc axit cacboxylic to Fe(III) oxo cluster [93] c
ch khung kim loi-hu c (MOFs) hnh thnh vt liu lai. Cc Fe(III) oxo
cluster hnh thnh trn vt liu lai Fe(III)-GO c kch thc rt nh (<5 nm)
(nh HR-TEM) nn khng th pht hin c bng XRD.
77
3.2.2. nh HR-TEM ca cc h xc tc nano composit oxit kim loi trn
graphen oxit
3.2.2.1 nh HR-TEM ca h vt liu xc tc Fe3O4-GO
Hnh 3.11. nh HR- TEM ca Fe3O4-GO vi phng i khc nhau

T nh HR-TEM ca Fe3O4-GO vi phng i khc nhau c trnh
by hnh 3.11, ta thy Fe3O4 c kch thc ht nano tng i ng u c 50-
60 nm c kt tp t nhng ht nh kch thc di 10 nm. Cc ht nano
Fe3O4 c phn tn kh ng u trn cc lp graphen oxit (GO).
3.2.2.2 nh HR- TEM ca h vt liu xc tc CoFe2O4-GO trn c s Fe3O4
bin tnh
T nh HR- TEM (hnh 3.12) nhn thy cc ht nano CoFe2O4 phn tn kh
ng u trn cc lp ca graphen oxit (GO), kch thc ht nano CoFe2O4 nm
trong khong t 20 - 30 nm. S t cc ht CoFe2O4 b kt tp li c kch thc nm
trong khong t 50 - 60nm.
Hnh 3.12. nh HR- TEM ca CoFe2O4-GO

78
3.2.2.3 nh HR- TEM ca h vt liu xc tc ZnFe2O4-GO trn c s Fe3O4 bin
tnh
Hnh 3. 13: nh HR- TEM ca ZnFe2O4 -GO

T nh HR- TEM (hnh 3.13) nhn thy graphen oxit (GO) c cu trc lp,
cc ht nano ZnFe2O4 phn tn kh ng u trn cc lp ca GO, kch thc ht
nano ZnFe2O4 nm trong khong t 20 - 40 nm. S t cc ht ZnFe2O4 b kt tp li
c kch thc nm trong khong t 60 - 80nm. Kch thc cc ht ZnFe2O4 tnh
ton c t gin XRD (34 nm) khc phn bit so vi kch thc thu c t
nh TEM ca vt liu.
3.2.2.4 nh HR- TEM ca h vt liu xc tc Fe0-Fe3O4-GO trn c s Fe3O4
bin tnh
Hnh 3.14. nh HR- TEM ca Fe0-Fe3O4-GO

79
T nh HR- TEM hnh 3.14 cho thy Fe0 v Fe3O4 phn tn kh ng u
trn cc lp ca graphen oxit (GO), kch thc ht nano Feo, Fe3O4 nm trong
khong t 10-20 nm. Cc ht nano Feo c tng hp trc tip c kch thc
nm trong khong 50-100 nm do chng b kt tp li [95]. Khi a chng ln
cc lp ca graphen oxit (GO) th kch thc ht nano Feo <10 nm do cc ht
ny phn tn u, n nh v t co cm hn [95, 96].
3.2.2.5 nh HR- TEM ca h vt liu xc tc nano composit oxit kim loi
Fe(III)-GO
Hnh 3.15 : nh HR- TEM ca Fe(III)-GO vi cc phng i khc nhau
T hnh 3.15 cho thy cc Fe(III) oxo cluster phn b kh ng u trn

b mt cc lp graphen oxit (GO). Cc ht c kch thc rt nh < 5nm. Trong
nh HR-TEM nhn thy cc ht ion Fe(III) c xu hng tp hp li thnh nhng
nhm ln hn (10-20 nm). iu ny c th l do s tng tc gia cc ion
Fe(III) v cc nhm hydroxyl, cacbonyl trong cu trc graphen oxit (GO) hnh
thnh cc cluster cha st [97, 98].
80
3.2.3 Ph hng ngoi (FTIR) ca cc h xc tc nano composit oxit kim
loi trn graphen oxit
3.2.3.1 Ph hng ngoi (FTIR) ca h vt liu xc tc Fe3O4 -GO
Hnh 3.16 Ph FTIR ca Fe3O4-GO

Quan st ph FTIR hnh 3.16 ca Fe3O4-GO cho thy s hnh thnh ca lin
kt Fe-O ln trn vt liu graphen oxit (GO) vi m ph c trng 589 cm-1 [99,
109]. Lin kt Fe-O c hnh thnh do lc ht tnh in gia cc nhm chc
(COOH, C-OH, C-O-C) trn b mt graphen oxit (GO) vi ion Fe3+ [101]. m
ph 1235 cm-1, 1576 cm-1 c trng cho lin kt C=O v C- O trong cu trc
graphen oxit (GO) [ 102].
3.2.3.2. Ph hng ngoi (FTIR) ca h vt liu xc tc CoFe2O4 - GO trn c s
Fe3O4 bin tnh
Hnh 3.17: Ph FTIR ca CoFe2O4-GO
81
Quan st ph FTIR hnh 3.17 ca CoFe2O4-GO cho thy s ging nhau gia
ph FTIR ca Fe3O4-GO v CoFe2O4-GO vi s hnh thnh ca lin kt Co-O ln
trn vt liu graphen oxit (GO) vi m ph c trng 588 cm-1 [100]. Lin kt
Fe(Co)-O c hnh thnh do lc ht tnh in gia cc nhm chc (COOH, C-
OH, C-O-C) trn b mt graphen oxit -GO vi ion Co2+ v ion Fe3+[ 102]. m
ph 1239 cm-1, 1576 cm-1 c trng cho lin kt C=O v C-O trong cu trc
graphen oxit (GO) [ 99].
3.2.3.2. Ph hng ngoi (FTIR) ca h vt liu xc tc ZnFe2O4-GO trn c s
Fe3O4 bin tnh
ZnFe2 O4 -GO
Cuong do tuy chon (%T)
1630
437
564
3420 GO
4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
So Song (cm )
Hnh 3. 18: Ph FTIR ca ZnFe2O4-GO

Hnh 3.18 cho thy ph FTIR ca ZnFe2O4-GO. Khi quan st ph FTIR
ca graphen oxit (GO) nhn thy cc nhm chc gn nh khng cn trn b mt
ph gn nh mt ng thng l do qu trnh kh i mt lng ln cc nhm
chc trn b mt graphen oxit (GO).
Kt qu ph FTIR ca ZnFe2O4-GO cng cho thy s hnh thnh ca lin
kt Fe-O ln trn vt liu graphen oxit (GO) vi m ph c trng 437 cm-1. m
ph 564 cm-1 c trng cho lin kt Zn-O [103]. m ph 1400 cm-1, 1630 cm-
1
c trng cho lin kt C=O v C=C trong cu trc graphen oxit GO [105]. T kt
qu FTIR cho thy qu trnh kh nhit lm hnh thnh nn hn hp composit
gia ZnFe2O4 v graphen oxit (GO).
82
3.2.3.4 Ph hng ngoi (FTIR) ca h vt liu xc tc Fe0-Fe3O4-GO trn c s
Fe3O4 bin tnh
Hnh 3. 19: Ph FTIR ca Fe0-Fe3O4-GO

Kt qu ph FTIR ca vt liu Fe0-Fe3O4-GO hnh 3.19 cho thy s hnh
thnh ca Fe0 ln trn vt liu Fe3O4-GO vi pic c trng 1048,5 cm-1 [105].
Pic 589,2 cm-1 c trng cho lin kt Fe-O trong Fe3O4, pic 1239,3 cm-1, 1574,7
cm-1 c trng cho lin kt C=O v C-O trong cu trc graphen oxit (GO).
3.2.3.5 Ph FTIR ca h vt liu xc tc nano composit oxit kim loi Fe(III)-GO
Cng truyn qua (T%)
-C=O
C=C C-O-
GO
O-Fe
Fe-O-C=O- C-O-Fe
O-Fe
GO-Fe
S Sng (cm-1)
Hnh 3.20: Ph FTIR ca Fe(III)-GO v GO

Quan st ph FTIR ca GO trn hnh 3.20 cho thy c s tn ti ca
nhm cacbonyl C=O (trong khong 1700 -1730 cm-1) [106]. Cc pic nm
trong khong 1200-1250 cm-1 c trng cho s tn ti ca lin kt CO [106,
83
107]. 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 [106]. Qu trnh a ion Fe (III) ln
trn graphen oxit (GO) lm cng cc pic c trng ca graphen oxit (GO)
gim i thay vo l s xut hin ca cc pic c trng cho lin kt Fe(III) vi
cc nhm chc ca GO. Pic 1550 cm-1 c trng cho lin kt Fe-O-C=O, pic
1050 cm-1 c trng cho lin kt C-O- Fe, pic 800 cm-1 c trng cho lin kt
O-Fe [107] v pic 570cm-1 c trng cho s hnh thnh Fe2O3-GO.
3.2.4 Ph in t quang tia X (XPS) ca cc h xc tc nano composit
oxit kim loi graphen oxit
3.2.4.1 Ph XPS ca h vt liu xc tc Fe3O4-GO
a Intensity (a.u)
Intensity (a.u)
Na1s
Fe2p
O1s
C1s
730 720 710 700
Binding Energy (eV)
1300 1100 900 700 500 300 100

Binding Energy (E)
C-C 284.8 eV
c Fe-O 529.9 eV
d
Intensity (a.u)
Intensity (a.u)
-C=O 288.3 eV
C-O 535 eV C=O 531.5 eV
C-O 285.5 eV
C=C 291.5 ev
296 294 292 290 288 286 284 282 280
Binding Energy (eV)
540 538 536 534 532 530 528 526
Binding Energy (eV)
Hnh 3.21. Ph XPS ca Fe3O4-GO: (a)- Ph XPS tng ca Fe3O4-GO; (b)- Ph

XPS Fe2p tch ca Fe3O4-GO; (c)- Ph XPS O1s tch ca Fe3O4-GO; (d) Ph
XPS C1s tch ca Fe3O4-GO
84
3.2.4.2 Ph XPS ca h vt liu Fe0-Fe3O4-GO trn c s Fe3O4 bin tnh
725 eV b
711 eV
a
715,5 eV
Intensity (a.u)
740 735 730 725 720 715 710 705
Binding Energy (eV)
c
d
Hnh 3.22. Ph XPS ca Fe0-Fe3O4-GO: (a)- Ph XPS tng ca Fe0- Fe3O4-GO;

(b)- Ph XPS Fe2p tch ca Fe0- Fe3O4-GO; (c)- Ph XPS O1s tch ca Fe0-
Fe3O4-GO; (d) Ph XPS C1s tch ca Fe0-Fe3O4-GO
Quan st ph XPS tng (hnh 3.21 v hnh 3.22) ca c hai vt liu Fe3O4-
GO v Fe0-Fe3O4-GO u thy xut hin cc pic vi mc nng lng 284 eV,
528 eV v 711 eV tng ng vi C1s, O1s v Fe2p tn ti trong cu trc vt
liu. Ngoi ra quan st ph XPS C1 c s xut hin ca pic c cng thp 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 graphen
oxit (GO), graphen iu ny l do NaBH4 ngoi nhim v kh Fe3+ v Fe0 th
85
NaBH4 cn l tc nhn kh graphen oxit (GO) v graphen [108] do vy trong
qu trnh tng hp Fe0-Fe3O4-GO c th mt phn nh graphen oxit (GO) b kh
v graphen, v vy tn ti pic 291,5 eV c trng cho lin kt -* [109, 110].
- Gi thuyt 2, pic 291,5eV c trng cho trng thi lin kt gia cp
electron v l trng tn ti trong cu trc graphen oxit (GO) v graphen- rGO
[109]. Ph XPS O1s (hnh 3.22) 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
[112].
T hnh 3.21 cho thy vi vt liu Fe3O4-GO 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
cc pic vi mc nng lng 710 eV, 719eV v 724 eV c trng cho cu trc
ca -Fe2O3 [112, 113].
i vi mu Fe0-Fe3O4-GO ngoi pic 711eV v 725 eV c trng cho
Fe3O4-GO cn xut hin mt pic cng nh 719eV, y c th l do c s
tng tc gia Fe v Fe3O4-GO to thnh Fe2O3, FeOOH vi pic c trng
719eV [114, 115]. Ngoi ra hnh 3.22 cng nhn thy s tn ti pic vi mc
nng lng 705,5 eV c trng cho s c mt ca cc ht nano Fe0 vi kch
thc nh <10 nm [116] 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 Fe0 trong iu kin
vng mt Fe3O4 [117].
Kt qu ny khng nh s tng tc in t gia Fe0, Fe3O4 v graphen
oxit (GO) lm thay i cu trc in t ca cu t hp phn vt liu composit.
3.2.4.3 Ph XPS ca h vt liu xc tc nano composit oxit kim loi Fe(III)-GO

S c mt ca oxy v st trn cc vt liu GO v Fe(III)-GO ln lt c
xc nh qua ph XPS trn hnh:
86
a
b
726eV 712.6eV
285
-C=0 287,8
-COO 290,2
Hnh 3.23: Ph XPS ca vt liu Fe(III)- GO: (a)- Ph XPS tng ca Fe(III)-
GO; (b)- Ph XPS O1s tch ca Fe(III)-GO; (c)- Ph XPS Fe2p tch ca Fe(III)-
GO; (d) Ph XPS C1s tch ca Fe(III)-GO
Quan st hnh 3.23 cho thy, trong vt liu graphen oxit (GO) v composit
Fe(III)-GO c s xut hin ca O1s, C1s v Fe2p tng ng vi cc mc nng
lng 285, 530, 711 v 725 eV. S hnh thnh cc phc gia ion Fe(III) trn b
mt vi cc nhm hydroxyl, cacbonnyl trn graphen oxit (GO) lm tng hm
lng oxy (30,43%) trong vt liu Fe(III)-GO, t l C/O trong vt liu Fe(III)-
GO khong 2,32. Ph C1s cho thy cc pic 287,8 eV v 290,2 eV c trng s
hnh thnh cc nhm chc C=O, -COO vi Fe trn graphen oxit (GO).
87
Hnh 3.23 cho thy cc pic 712,6eV v 726eV c trng cho s hnh
thnh ca Fe(III) trn graphen oxit (GO). Thy rng vi Fe2O3-GO hnh thnh
cc pic 710eV, 719eV v 724eV [118], vi Fe3O4-GO c trng vi cc pic
711eV, 716eV v 725eV [119] vi FeOOH-GO c trng vi pic 711,8 eV v
724,4eV [118]. S tn ti ca cc pic 712,6eV v 726eV chng t c s tng
tc gia Fe v cc nhm chc trn graphen oxit -GO hnh thnh cc Fe(III) oxo
cluster.
3.2.5. Hp ph v kh hp ph Nit (BET) ca cc h xc tc nano
composit oxit kim loi graphen oxit
3.2.5.1 Hp ph v kh hp ph Nit (BET) ca h vt liu xc tc Fe0-Fe3O4-
GO v Fe3O4-GO
Hnh 3.24 Phn b mao qun ca Fe0-Fe3O4-GO v Fe3O4-GO
Hnh 3.25 ng ng nhit hp ph - kh hp ph Nit

ca Fe0-Fe3O4-GO v Fe3O4-GO
88
T hnh 3.24 v 3.25 nhn thy, ng ng nhit hp ph - kh hp ph
Nit ca Fe3O4-GO v Fe0-Fe3O4-GO 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 s liu bng 3.2 v bng 3.3 cho thy Fe0-Fe3O4-GO c din tch b
mt ring v th tch xp ln, so vi Fe3O4-GO th Fe0-Fe3O4-GO 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 1-2%. ng knh mao qun trung
bnh 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 [120, 121, 122].
Bng 3.2. Cc thng s c trng ca vt liu Fe3O4-GO
Thng s Fe3O4-GO
2
Din tch b mt (BET-m /g) 169
Th tch vi mao qun (cm3/g) 0,0033
Tng th tch mao qun (cm3/g) 0,499
ng knh mao qun trung bnh (nm) 8,8-12,1
Bng 3.3. Cc thng s c trng ca vt liu Fe0-Fe3O4-GO

Thng s Fe0-Fe3O4-GO
Din tch b mt (BET-m2/g) 177
Th tch vi mao qun (cm3/g) 0,0043
3
Tng th tch mao qun (cm /g) 0,523
ng knh mao qun trung bnh (nm) 8,9-12,3
3.2.5.2 Hp ph v kh hp ph Nit (BET) ca h vt liu xc tc ZnFe2O4-GO
Hnh 3.26. ng ng nhit hp ph - kh hp ph Nit ca ZnFe2O4-GO

89
Hnh 3.27. Phn b mao qun ca ZnFe2O4-GO
Quan st trn hnh 3.26 v hnh 3.27 cho thy, ng ng nhit hp ph
- kh hp ph Nit ca ZnFe2O4-GO 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. 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 khong 1%. ng knh mao qun trung bnh ca c vt
liu nm trong khong 8-12 nm.
Bng 3.4. Cc thng s c trng ca vt liu ZnFe2O4-GO
Thng s ZnFe2O4-GO
Din tch b mt (BET-m2/g) 83
3
Th tch vi mao qun (cm /g) 0,003
Tng th tch mao qun (cm3/g) 0,252
ng knh mao qun trung bnh (nm) 8,3 -11,9
S liu bng 3.4 cho thy, din tch b mt ca vt liu ZnFe2O4-GO thp
hn so vi vt liu Fe0-Fe3O4-GO. Tuy nhin ng knh mao qun trung bnh
nm trong khong 8,3 -11,9 nm kh tng ng so vi vt liu Fe0-Fe3O4-GO.
90
3.2.6. c trng t tnh ca cc h xc tc nano composit oxit kim loi
graphen oxit
3.2.6.1.ng cong t tr ca h vt liu Fe0-Fe3O4-GO v Fe3O4-GO
Tin hnh kho st t tnh ca cc mu bng phng php t k mu rung
(VSM), ta c cc ng cong t tr nh hnh .
Hnh 3.28: ng cong t tr ca Fe0-Fe3O4-GO v Fe3O4-GO

Theo th trn hnh 3.28, ta thy lc khng t ca c hai vt liu Fe0-
Fe3O4-GO v Fe3O4-GO gn nh bng khng. T bo ha ca Fe3O4-GO v
Fe0-Fe3O4-GO c gi tr tng ng bng 35emu/g v 29emu/g. iu ny cho
thy cc vt liu nano composit u mang tnh siu thun t, vi lc khng t
gn nh bng khng v gi tr t bo ha cao, do vy cc vt liu ny c th
d dng tch ra khi nc x l nh s tr gip ca t trng bn ngoi [122].
Theo mt s ti liu [123, 124] cho thy kch thc ht nano Fe3O4 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 graphen oxit vi sng 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 [126]. 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 mmen tr nn
phc tp. Mmen t nguyn t b mt c ng gp khng ng k vo mmen
91
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 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 (2) trong nghin cu ca
mnh [127]:
( D / 2) d 3
MS MS0 ( ) (3.1)
D/2
D: l ng knh ca ht nano
MS0: l mmen t bo ha ca vt liu khi
d: dy ca lp v
Nu kch thc ht D >> d th mmen t s khng b nh hng, trong
khi cc ht nh hn d mc d nh nhng c th c so snh vi D th
mmen t s b nh hng. T bo ha ca ca Fe3O4-GO vi sng, theo m
hnh li - v th trong Fe3O4-GO vi sng hnh thnh lp v graphen oxit -GO
dy hn lp v trong ht Fe3O4 v vy t bo ha ca Fe3O4 ln hn nhiu
gi tr ca mu Fe3O4-GO vi sng. Tuy nhin, qu trnh pha tp thm Fe0 ln b
mt Fe3O4-GO vi sng lm bo ha t gim i, iu ny c th l do
NaBH4 l cht kh mnh lm gim i mt phn s c mt ca pha Fe3O4 ln
b mt graphen oxit vi sng v to ra mt s pha tp khng mong mun, nhng
lng pha tp ny nh v khng pht hin c trn ph nhiu x tia X (XRD).
3.2.6.2.ng cong t tr ca h vt liu ZnFe2O4-GO
Hnh 3.29: ng cong t tr ca vt liu ZnFe2O4-GO
92
T kt qu trn th trn hnh 3.29, nhn thy lc khng t ca vt liu
gn nh bng khng. T bo ha ca ZnFe2O4-GO c gi tr tng ng bng
35emu/g. iu ny cho thy vt liu nano composit u mang tnh siu thun t,
vi lc khng t gn nh bng khng v gi tr t bo ha cao.
3.3 nh gi hot tnh xc tc, bn ca cc h vt liu nano

composit oxit kim loi trn graphen oxit
X l nc thi dt nhum l mt vn ln trong x l v bo v mi
trng nc. Trong thnh phn nc thi dt nhum, ngoi cc cht mu th
thuc nhum hot tnh l rt kh phn hy do c cu trc bn, x l bng
phng php vi sinh khng hiu qu. Cng ngh x l hiu qu thuc nhum
hot tnh trong nc thi c p dng u tin l s dng xc tc cho qu trnh
Fenton ng th vi tc nhn oxi ha l H2O2. Do khng c kh nng thu hi
c xc tc Fe2+ trong dung dch, bc pht trin tip theo l d th ha Fenton
ng th, gn Fe2+ ln vt liu rn to xc tc cho qu trnh Fenton d th c
th thu hi c xc tc.
Tuy nhin, c th thu hi xc tc mt cch trit , cc nh nghin cu
hng ti xc tc cho qu trnh Fenton d th c t tnh. H xc tc c nghin
cu lm tin l h nano Fe3O4 phn tn trn cht mang. Mt s nghin cu
cng b gn y ch ra rng cc h xc tc mi da trn c s Fe (c gi l
xc tc cho qu trnh Fenton like) c hot tnh phn hy quang ha cao i vi
cc cht mu, hu c c hi. Theo xu hng mi trn, ti lun n tp trung
vo cc h xc tc mi trn c s Fe nh Fe3O4-GO, Fe3O4 bin tnh (kh):
CoFe2O4-GO, ZnFe2O4-GO v Fe0-Fe3O4-GO cng nh vt liu Fe(III)-GO.
Thuc nhum hot tnh RR195 l thuc nhum c thng mi ha v
s dng rng ri trong cng nghip dt nhum hin nay. nh gi hot tnh
xc tc ca cc h vt liu mi tng hp c, chng ti s dng thuc nhum
hot tnh RR195 lm cht phn ng m hnh. Qu trnh phn hy xc tc thuc
nhum hot tnh l mt qu trnh phc tp, lin quan n nhiu qu trnh khc
nhau nh qu trnh hp ph, qu trnh oxi ha Fenton, Photo Fenton. Ngoi ra
cc yu t nh hng n cng cn c nghin cu.
Trong lun n ny, chng ti tin hnh nghin cu nh gi hot tnh ca
cc h xc tc khc nhau tm ra c h xc tc c hot tnh cao nht. i
vi tng h xc tc chng ti nghin cu mt cch ring bit ng gp ca tng
93
qu trnh nh hp ph, xc tc cho qu trnh Fenton, xc tc cho qu trnh Photo
Fenton. i vi h xc tc c hot tnh quang ha cao nht, chng ti tin hnh
nghin cu cc yu t nh hng nh nng cht tham gia phn ng, nng
xc tc, pH v c bit l bn xc tc. Ngoi ra, chng ti cng tin hnh
nghin cu ng hc ca qu trnh quang ha phn hy thuc nhum hot tnh
RR195 trn h xc tc c hot tnh cao nht.
3.3.1. nh gi hot tnh ca h vt liu xc tc nano composit graphen
oxit Fe3O4 -GO
Hnh 3.30 Hot tnh quang xc tc ca Fe3O4-GO

Hot tnh xc tc ca Fe3O4 c thc hin trong iu kin nh sau:
50ppm (50 mg/L) nng thuc nhum hot tnh RR195 ban u, nng
H2O2 l 0,5 mL/100 mL, nng cht xc tc Fe3O4 l 0,5 g/L, pH = 3,5, s
dng n nh sng m phng mt tri vi thi gian chiu n trong 120 pht,
nhit 300C. chuyn ha (C/Co) theo thi gian phn ng c th hin
hnh 3.30.
Nh thy hnh 3.30, vt liu Fe3O4-GO c hot tnh thp, sau 120
pht phn ng chuyn ha ch t 28%. Do vy, phn bit hot tnh xc
tc vi s ng gp ca hp ph, chng ti tin hnh o hp ph thuc nhum
hot tnh RR195 trong iu kin: nng 50 mg/L trong 3 gi (t cn bng),
nng cht xc tc Fe3O4 l 0,5 g/L, pH = 3,5 nhit 300C v khng s
dng H2O2, khng chiu n (trong ti).
Kt qu hnh 3.30 cho thy Fe3O4-GO c kh nng hp ph thuc
nhum hot tnh RR195 c 20% sau 3 gi, so snh vi chuyn ha 28%, th
94
c th kt lun rng Fe3O4-GO c hot tnh xc tc quang ha thp, s gim
nng thuc nhum hot tnh RR195 ch yu l do hp ph.
3.3.2. nh gi hot tnh ca h vt liu xc tc CoFe2O4-GO trn c s
Fe3O4 bin tnh
Hot tnh quang xc tc cc iu kin khc nhau:
(A): Khng xc tc : Nng RR195 ban u l 50 mg/L; nng H2O2 =
2 mL/100 mL, pH = 5,5; nhit T = 30oC v chiu n trong 120 pht;
(B): Hp ph trong ti: Nng RR195 ban u l 50 mg/L; nng xc
tc CoFe2O4-GO =0,5g/L; pH = 5,5 ; nhit T= 30oC v khng chiu n
(bng ti);
(C): Xc tc cho qu trnh Fenton : Nng RR195 ban u l 50 mg/L;
nng H2O2 = 2 mL/100 mL; nng xc tc CoFe2O4-GO =0,5g/L; pH = 5,5;
nhit T= 30oC v khng chiu n (bng ti);
(D): Xc tc cho qu trnh Photo Fenton: Nng RR195 ban u l 50
mg/L; nng H2O2 = 2 mL/100 mL; nng xc tc CoFe2O4-GO =0,5g/L;
pH = 5,5; nhit T= 30oC v chiu n trong 60 pht.
1
Khng xc tc A
0.8
0.6
C/Co
Xc tc cho qu trnh Fenton

0.4
0.2
Xc tc cho qu trnh Photo Fenton
0
0 10 20 30 40 50 60
Thi gian phn ng (pht)
Hnh 3. 31: S ph thuc chuyn ha theo thi gian phn ng

cc iu kin khc nhau ca CoFe2O4-GO
(A): Khng xc tc (RR195, H2O2)
(B): Hp ph trong ti (RR195, xc tc CoFe2O4-GO, khng c H2O2)
95
(C): Xc tc cho qu trnh Fenton (RR195, xc tc CoFe2O4-GO, H2O2);
(D): Xc tc cho qu trnh Photo Fenton (RR195, xc tc CoFe2O4-GO,
H2O2, nh sng nhn thy).
Quan st hnh 3.31 cho thy, trong iu kin khng c cht xc tc
CoFe2O4-GO, tc nhn H2O2 khng lm thay i nng thuc nhum hot tnh
RR195 sau 25 pht chiu n. ng thi, kt qu cng cho thy, kh nng hp
ph thuc nhum hot tnh RR195 l 30% khi c mt cht xc tc CoFe2O4-GO
nhng khng chiu n. Kh nng hp ph RR195 l do cc lin kt - ca
sp2C v sp3C [128] trn b mt ca GO, cc lin kt ny c i lc ln i vi cc
nhn thm trong thuc nhum hot tnh RR195 [129]. chuyn ha thuc
nhum hot tnh RR195 t khong 60% trong s c mt ca CoFe2O4-GO v
H2O2. Trong khi , khi chiu n vi s c mt ca CoFe2O4-GO v H2O2 th
sau 45 pht hiu sut phn hy t 78%. iu ny c th l gii l do khi c mt
ca CoFe2O4-GO v H2O2 di iu kin chiu n to iu kin hnh thnh
nhiu gc t do *OH t nhng phn ng c th xy ra nh sau [130, 131]:
CoFe2O4 +hv e-cb + h+vb GO, rGO (e-) + h+
CoFe2O4 (h+vb) + OH- *OH + CoFe2O4
CoFe2O4 (e-cb) + O2 *O-2 + CoFe2O4 H O
2 *OH + CoFe2O4
GO, rGO (e-) + O2 *O-2 + GO, rGO
RR195 + *OH + *O2- CO2 + H2O + Cl- + NO3- +
nh gi bn ca xc tc, chng ti tin hnh chy phn ng 3 ln
lin tc khng hot ha li trong iu kin thc nghim c gi nguyn: Nng
thuc nhum hot tnh RR195 ban u l 50 mg/L; nng xc tc CoFe2O4-
GO = 0,5g/L, nng H2O2= 2 mL/100 mL; pH = 5,5 , nhit T= 30oC chiu
n trong 60 pht trong mt ln ti sinh. Kt qu c th hin hnh 3.32.
96
1
0.8 Chy ln 1 Chy ln 2 Chy ln 3
0.6
C/Co
0.4
0.2
0
0 30 60 90 120 150 180
Hnh 3.32: bn xc tc qua cc ln chy phn ng trong qu trnh

phn hy thuc nhum hot tinh RR195 trn CoFe2O4-GO
Hnh 3.33: Ph UV_Vis qu trnh phn hy thuc nhum hot tnh RR195
di iu kin chiu n (A) v khng chiu n (B) trn CoFe2O4--GO
Cc kt qu trn chng minh rng vt liu xc tc CoFe2O4-GO c hot
tnh phn hy thuc nhum hot tnh RR195 trong vng nh sng nhn thy.
3.3.3. nh gi hot tnh ca h vt liu xc tc ZnFe2O4-GO trn c s
Fe3O4 bin tnh
(A): Khng xc tc : Nng RR195 ban u l 50 mg/L; nng H2O2
= 1 mL/100 mL, pH = 5,5; nhit T = 30oC v chiu n trong 120 pht.
97
(B): Hp ph trong ti : Nng RR195 ban u l 50 mg/L; nng xc
tc ZnFe2O4-GO =0,5g/L; pH = 5,5 ; nhit T= 30oC v khng chiu n
(bng ti).
nng H2O2 = 1 mL/100 mL; nng xc tc ZnFe2O4-GO =0,5g/L; pH = 5,5
; nhit T= 30oC v khng chiu n (bng ti).
(D): Xc tc cho qu trnh Photo Fenton : Nng RR195 ban u l 50
mg/L; nng H2O2 = 1 mL/100 mL; nng xc tc ZnFe2O4-GO =0,5g/L;
pH = 5,5 ; nhit T= 30oC v chiu n trong 120 pht.
1
Khng xc tc A
0.8
Hp ph
B
0.6
C/Co
Xc tc cho qu trnh Fenton

C
0.4

0.2
D
0
0 20 40 60 80 100 120
Hnh 3.34: S ph thuc chuyn ha theo thi gian phn ng

cc iu kin khc nhau ca ZnFe2O4-GO
(B): Hp ph trong ti (RR195, xc tc ZnFe2O4-GO, khng c H2O2)
(C): Xc tc cho qu trnh Fenton (RR195, xc tc ZnFe2O4-GO, H2O2)
(D): Xc tc cho qu trnh Photo Fenton (RR195, xc tc ZnFe2O4-GO,
H2O2, nh sng nhn thy)
Quan st hnh 3.34 cho thy, trong iu kin khng c cht xc tc
ZnFe2O4-GO, tc nhn H2O2 khng lm thay i nng thuc nhum hot tnh
ph RR195 l 35% khi c mt cht xc tc ZnFe2O4-GO nhng khng chiu
98
n. Kh nng hp ph thuc nhum hot tnh RR195 l do cc lin kt - ca
sp2C v sp3C trn b mt ca graphen oxit (GO), cc lin kt ny c i lc ln
i vi cc nhn thm trong thuc nhum hot tnh RR195. chuyn ha
thuc nhum hot tnh RR195 t khong 42% trong s c mt ca ZnFe2O4-
GO v H2O2. Trong khi , khi chiu n vi s c mt ca ZnFe2O4-GO v
H2O2 th sau 120 pht hiu sut phn hy t 92%. iu ny l do khi c mt
ca ZnFe2O4-GO v H2O2 di iu kin chiu n s xy ra phn ng.
ZnFe2O4 +hv ZnFe2O4 (h+ + e-) (1)
- -
ZnFe2O4(e ) +graphen ZnFe2O4 +graphen (e ) (2)
Graphen (e-) +H2O2 *OH +OH- + graphen (3)
Fe3+ + e- Fe2+ (4)
Fe2+ + H2O2 Fe3+ + *OH + OH- (5)
Fe3+ + hv + OH- Fe2+ + *OH (6)
1
0.8 Chy ln 1 Chy ln 2 Chy ln 3
0.6
C/Co
0.4
0.2
0
0 30 60 90 120 150 180 210 240 270 300 330 360
Hnh 3.35: bn xc tc qua cc ln chy phn ng khc nhau trong

qu trnh phn hy thuc nhum hot tnh RR195 trn ZnFe2O4-GO
iu kin thc nghim c gi nguyn sau ba ln nh gi bn xc

tc: Nng RR195 ban u l 50 mg/L; nng xc tc ZnFe2O4-GO =
0,5g/L, nng H2O2= 1 mL/100 mL; pH = 5,5 ; nhit T= 30oC chiu n
trong 120 pht.
nh gi bn xc tc chng ti tin hnh thu hi xc tc sau phn
ng bng t tnh v tin hnh ra bng nc v ethanol, sn phm sau c
sy chn khng 600C, tip xc tc c nh gi hot tnh cho cc ln th
99
nghim tip theo, nhn thy rng hao ht khi lng ca xc tc gn nh
khng ng k. Kt qu c th hin trn hnh 3.35.
T hnh 3.35 cho thy bn ca xc tc tng i tt, iu ny c
chng minh qua ba ln kim tra bn hot tnh quang xc hiu sut phn hy
ln lt l 92%, 86% v 82%. Nh vy, s gim hiu sut phn hy c th l do
sau cc ln th nghim th s che ph cc tm xc tc bi thuc nhum hot tnh
RR195 cng nh cc sn phm ph cng tng ln, ngoi ra qu trnh suy gim
nng ZnFe2O4 trong xc tc xy ra do qu trnh leaching cng l nguyn
nhn gy gim hot tnh xc tc.
Hnh 3.36: Ph UV_Vis qu trnh phn Hnh 3.37: Ph UV_Vis qu trnh phn
hy RR195 di iu kin hy RR195 di iu kin
chiu n trn ZnFe2O4-GO khng chiu n trn ZnFe2O4-GO
Cc kt qu trn chng minh rng vt liu xc tc ZnFe2O4-GO c hot

tnh phn hy thuc nhum hot tnh RR195 trong vng nh sng nhn thy.
3.3.4 . nh gi hot tnh ca h vt liu xc tc Fe0-Fe3O4-GO trn c
s Fe3O4 bin tnh
(A): Khng xc tc: Nng RR195 ban u l 50 mg/L; nng H2O2 =
0,5 mL/100 mL, pH = 5,5; nhit T = 30oC v chiu n trong 90 pht.
tc Fe0-Fe3O4-GO =0,3g/L; pH = 3,5 ; nhit T= 30oC v khng chiu n
(bng ti).
100
nng H2O2 = 0,5 mL/100 mL; nng xc tc Fe0-Fe3O4-GO =0,3g/L; pH =
3,5 ; nhit T= 30oC v khng chiu n (bng ti).
mg/L; nng H2O2 = 0,5 mL/100 mL; nng xc tc Fe0-Fe3O4-GO =0,3g/L;
pH = 3,5 ; nhit T= 30oC v chiu n trong 90 pht.

cc iu kin khc nhau trn Fe0 -Fe3O4-GO
(B): Hp ph trong ti (RR195, xc tc Fe0 -Fe3O4-GO, khng c H2O2)
(C): Xc tc cho qu trnh Fenton (RR195, xc tc Fe0 -Fe3O4-GO, H2O2)
(D): Xc tc cho qu trnh Photo Fenton (RR195, xc tc Fe0 -Fe3O4-GO,
H2O2, nh sng nhn thy)
Quan st hnh 3.38 cho thy, trong iu kin khng c cht xc tc Fe0-
Fe3O4-GO, tc nhn H2O2 khng lm thay i nng thuc nhum hot tnh
ph ca thuc nhum hot tnh RR195 l 20% khi c mt cht xc tc Fe0-
Fe3O4-GO nhng khng chiu n. Kh nng hp ph RR195 l do cc lin kt
- ca sp2C v sp3C [128] trn b mt ca graphen oxit GO, cc lin kt ny c
i lc ln i vi cc nhn thm trong thuc nhum hot tnh RR195 [129].
chuyn ha RR195 t khong 60% trong s c mt ca Fe0-Fe3O4-GO v H2O2.
101
Trong khi , khi chiu n vi s c mt ca Fe0-Fe3O4-GO v H2O2 th sau 90
pht hiu sut phn hy t 95%.
Kt qu cng cho thy, hiu sut phn hy thuc nhum hot tnh RR195
trn vt liu Fe0-Fe3O4-GO cao hn nhiu so vi vt liu xc tc Fe3O4-GO l do
vt liu xc tc Fe0-Fe3O4-GO c s chuyn dch cc electron t Fe0 sang Fe3O4
to ra nhiu Fe2+ trn b mt [130, 131], trong khong pH 3-5 cc ion Fe2+ cng
vi tc nhn oxi ha H2O2 s sn sinh ra nhiu gc *OH., OOH., cc gc ny s
l tc nhn tham gia phn ng phn hy thuc nhum hot tnh RR195. C ch
ca qu trnh nh sau [132, 133]:
Feo + 2Fe3+ 2Fe2+
Fe2+ + H2O2 Fe3+ +OH- + *OH (1)
*OH + H2O2 *HO2 + H2O (2)
Fe3+ + *HO2 Fe2+ + H+ + O2 (3)
Fe2+ + *HO2 Fe3+ + HO2 (4)
Fe2+ + *OH Fe3+ + OH- (5)
HO. + RR195 sn phm
So snh nh gi hot tnh xc tc ca Fe0-Fe3O4-GO v Fe304-GO
chng ti tin hnh trong iu kin (p dng qu trnh xc tc Photo Fenton)
nh sau: i vi Fe0-Fe3O4-GO: Nng thuc nhum hot tnh RR195 ban u
l 50 mg/L; nng xc tc =0,5g/L; nng H2O2 = 0,5 mL/100 m; pH = 3,5 ;
nhit T= 30oC v chiu n trong 90 pht. Cn i vi h xc tc Fe3O4-GO:
Nng thuc nhum hot tnh RR195 ban u l 50 mg/L, nng xc tc
=0,5g/L; nng H2O2 = 0,5 mL/100 mL; pH = 3,5 ; nhit T= 30oC v chiu
n trong 360 pht. Kt qu c th hin trn hnh 3.39.
102
Hnh 3.39: Hot tnh xc tc ca vt liu Fe0-Fe3O4-GO v Fe304-GO
di iu kin chiu n trn Fe0-Fe3O4-GO
103
di iu kin khng chiu n trn Fe0-Fe3O4-GO
Cc kt qu trn chng minh rng Fe0-Fe3O4-GO c hot tnh phn hy
thuc nhum hot tnh RR195 trong vng nh sng nhn thy.
nh gi bn xc tc ca vt liu Fe0-Fe3O4-GO, chng ti tin
hnh thu hi xc tc sau phn ng bng t tnh v tin hnh ra bng nc v
ethanol. Sn phm sau c sy chn khng 600C, tip xc tc c nh
gi hot tnh cho cc ln th nghim tip theo, nhn thy hao ht khi lng
ca xc tc gn nh khng ng k.
iu kin thc nghim c gi nguyn sau ba ln nh gi bn xc
tc i vi Fe0-Fe3O4-GO nh sau: nng thuc nhum hot tnh RR195 ban
u l 50 mg/L; nng xc tc Fe0-Fe3O4-GO = 0,3g/L, nng H2O2= 0,5
mL/100 mL; pH = 3,5 ; nhit T= 30oC chiu n trong 90 pht trong mt ln
ti sinh. Kt qu c th hin trn hnh 3.42
1
Chy ln 1 Chy ln 2 Chy ln 3
0.8
0.6
C/Co
0.4
0.2
0
0 25 50 75 100 125 150 175 200 225 250
Hnh 3.42. bn xc tc qua cc ln chy phn ng trong

qu trnh phn hy thuc nhum hot tnh RR195 trn Fe0-Fe3O4-GO
104
T hnh 3.42 c th thy rng bn ca xc tc ca Fe0-Fe3O4-GO tng
i tt, iu ny c chng minh qua ba ln kim tra bn hot tnh quang
xc hiu sut phn hy ln lt l 95%, 90% v 88%. S gim hiu sut phn
hy c th l do sau cc ln th nghim th s che ph cc tm xc tc bi thuc
nhum hot tnh RR195 cng nh cc sn phm ph cng tng ln, ngoi ra qu
trnh suy gim nng Fe trong xc tc Fe0-Fe3O4-GO xy ra do qu trnh lc
cng l nguyn nhn gy gim hot tnh xc tc [134].
3.3.5. nh gi hot tnh ca h vt liu xc tc nano composit oxit kim
loi Fe(III)-GO
(A): Khng xc tc : Nng RR195 ban u l 50 mg/L; nng H2O2 =
0,5 mL/100 mL, pH = 5,5; nhit T = 30oC v chiu n trong 120 pht.
tc Fe(III)-GO =0,5g/L; pH = 3,5 ; nhit T= 30oC v khng chiu n (bng
ti) trong 120 pht.
nng H2O2 = 0,5 mL/100 mL; nng xc tc Fe(III)-GO =0,5g/L; pH = 3,5
; nhit T= 30oC v khng chiu n (bng ti) trong 120 pht.
mg/L; nng H2O2 = 0,5 mL/100 mL; nng xc tc Fe(III)-GO =0,5g/L; pH
= 3,5 ; nhit T= 30oC v chiu n trong 120 pht.
T hnh 3.43 cho thy qu trnh quang ha phn hy thuc nhum hot
tnh RR195 s dng tc nhn H2O2 v khng c xc tc t hiu qu rt thp,
hiu sut qu trnh t khong hn 95% sau 120 pht.
Nh vy, c th thy thuc nhum hot tnh RR195 c bn mu cao.
Qu trnh hp ph thuc nhum hot tnh RR195 trn Fe(III)-GO t 45% iu
ny c th l do Fe(III) chim gi cc tm hp ph trn b mt ca GO [135].
Trong iu kin khng chiu n v c s hin din ca cht xc tc kt hp vi
H2O2 th qu trnh phn hy t 60% sau 120 pht.
105
1
Khng xc tc A
0.8
Hp ph
0.6 B
C/Co
0.4
Xc tc cho qu trnh Fenton C
0.2
D
0
0 20 40 60 80 100 120

cc iu kin khc nhau trn Fe(III)-GO
(A): Khng xc tc (RR195, H2O2);
(B): Hp ph trong ti (RR195, xc tc Fe(III)-GO, khng c H2O2);
(C): Xc tc cho qu trnh Fenton (RR195, xc tc Fe(III)-GO, H2O2)
(D): Xc tc cho qu trnh Photo Fenton (RR195, xc tc Fe(III)-GO,
H2O2, nh sng nhn thy).
Tuy nhin, t hnh 3.43 cng cho thy khi chiu n th qu trnh phn
hy thuc nhum hot tnh RR195 tng mnh v t 95% sau 120 pht. Gii
thch iu ny l do Fe(III) tng tc vi cc nhm chc b mt ca graphen
oxit GO to thnh cc tm xc tc c hot tnh cao: Fe2O3, Fe(III)OH, FeOOH
nh phn tch trong phn c trng XPS ca vt liu lai Fe(III)-GO. Cc oxit
st (III) c nng lng vng cm nh (2,2-2,5eV) nhng s ti t hp gia
electron v l trng din ra nhanh v vy khc phc iu ny, cc oxit st (III)
c mang ln GO hnh thnh nn cc ht nano phn tn u c kch thc nh
< 5 nm. Cc ht oxit st (III) c kch thc nh l cc tm hot ng mnh trong
phn ng Photo Fenton [136].
Hn na, cht nn graphen oxit GO cng ng gp vai tr ln trong qu
trnh phn ng Photo-Fenton, vi kh nng chuyn in t khc phc qu
106
trnh ti t hp nhanh chng gia electron v l trng [137] trn cc tm xc tc
Fe2O3, FeOOH trong vt liu Fe(III)-GO.
C ch lin quan n qu trnh Photo Fenton c th hin nh sau:
Fe3+ + H2O2 + hv Fe2+ + *OH + H+
Fe3+ + GO Fe3+ + GO(e-)
Fe2+ + GO Fe3+ + *OH + OH-
Fe2+ + *OH Fe3+ + OH-
*OH + RR195 Sn phm
Ngoi ra, s hnh thnh cc cluster Fe(III)-OH do tng tc ca Fe3+ vi
nhm chc ca graphen oxit GO di tc dng chiu n cng to ra cc gc t
do *OH theo s sau:
hv
Fe(III)-OH Fe(II)+ *OH
[O]
Fe(III) c ti sinh do qu trnh ti oxi ha ca Fe(II) vi oxy ha tan
[O].
3.3.6. Vai tr ca cc tc nhn trong phn ng Photo Fenton

nh gi vai tr ca xc tc, H2O2 v nh sng trong phn ng Photo
Fenton, xc tc CoFe2O4-GO c s dng nghin cu. Cc thc nghim
c tin hnh vi iu kin nng thuc nhum hot tnh RR195 ban u l
50 mg/L, pH = 5,5, nhit 30oC v cc iu kin khc c th nh sau:
(a) Khng c xc tc, c H2O2 vi nng 2 mL/100 mL dung dch
RR195, trong bng ti.
(b) Khng c xc tc, c H2O2 vi nng 2 mL/100 mL dung dch
RR195, c chiu sng.
(c) C xc tc CoFe2O4-GO, khng c H2O2, trong bng ti.
(d) C xc tc CoFe2O4-GO, khng c H2O2, c chiu n.
(e) C xc tc CoFe2O4-GO, c H2O2 vi nng 2 mL/100 mL dung
dch RR195, trong bng ti.
(f) C xc tc CoFe2O4-GO, c H2O2 vi nng 2 mL/100 mL dung
dch RR195, c chiu n.
107
1.2
(a) H2O2 (bng ti)
(a) (b) H2O2 (nh sng)

1.0 (c) Hp phu (bng ti)
(b)
(d) Hp phu (nh sng)
(e) Fenton
0.8
(f) Photo-Fenton
C/Co (c)
0.6
(d)
0.4
(e)
0.2 (f)
0.0
0 10 20 30 40 50 60 70
t (min)
Hnh 3.44: S ph thuc t l nng C/Co ca thuc nhum hot tnh RR195
theo thi gian phn ng cc iu kin khc nhau trn CoF2O4-GO
Hnh 3.44 gii thiu s bin thin t l C/Co ca nng thuc nhum
hot tnh RR195 theo thi gian trong cc th nghim tng ng trn. T y
nhn thy, theo thi gian, khi c mt H2O2, trong bng ti, t l C/Co = 1. iu
ny chng t H2O2 khng c kh nng oxi ha thuc nhum hot tnh RR195.
Khi c nh sng (chiu n), t l C/Co nh hn 1. Tuy nhin, theo thi
gian t l ny gim khng ng k, cn 96% so vi ban u sau 60 pht. S
gim nng ny c gii thch nh sau: di tc dng ca nh sng (chiu
n), H2O2 c kh nng phn hy rt chm thnh gc t do *OH [10], cc gc
ny tip tc oxi ha thuc nhum hot tnh RR195. Tuy nhin do s phn hy
ny xy ra rt chm nn nng thuc nhum hot tnh RR195 khng gim
nhiu trong khong thi gian kho st.
Ngoi ra, quan st ng (c), (d) trn hnh 3.44 cng cho thy hai ng
ny gn nh trng nhau. Sau 30 pht, nng thuc nhum hot tnh RR195
cn li 70% so vi ban u v khng i trong thi gian cn li ca phn ng.
Do c th khng nh c CoFe2O4-GO ng vai tr l cht hp ph trong
qu trnh loi b thuc nhum hot tnh RR195.
lm sng t hn kt lun ny, chng ti tip tc tin hnh thc nghim
vi iu kin nng thuc nhum hot tnh RR195, nhit v pH khng i,
trong xc tc CoFe2O4-GO sau ln s dng u tin c lc, kh t
108
nhin v tip tc c cho vo dung dch thuc nhum hot tnh RR195 ln 2.
Kt qu c trnh by trn hnh 3.45.
1.1
(a) Hp phu ln 2
(c) Hp phu ln 1
1.0 (a)
0.9
C/Co
0.8
0.7
0.6 (b)
0.5
0 10 20 30 40 50 60 70
t (min)
Hnh 3.45: S ph thuc t l nng C/Co ca thuc nhum hot tnh

RR195 theo thi gian tip xc trn CoF2O4-GO ln 1 v ln 2.
D nhn thy rng, nng thuc nhum hot tnh RR195 khng thay i
trong ln th 2 s dng xc tc. iu ny c gii thch nh sau: qu trnh hp
ph thuc nhum hot tnh RR195 trn CoFe2O4-GO t n trng thi bo
ha, vt liu khng c kh nng hp ph thm RR195 nn khng lm thay i
nng cht ln s dng th 2. Ngoi ra c th nhn thy, qu trnh hp ph
thuc nhum hot tnh RR195 t cn bng nhanh trong ln s dng u tin,
sau 30 pht, nng RR195 khng thay i. Nh cp trn, cc tc
gi [9,10] cho rng trn b mt GO c cc lin kt - ca sp2C v sp3C, cc lin
kt ny c i lc ln i vi cc nhn thm trong thuc nhum hot tnh RR195.
Vi mc ch nghin cu loi b RR195 bng phn ng Photo Fenton nn qu
trnh hp ph RR195 trn vt liu khng c nghin cu chi tit y.
Qu trnh loi b thuc nhum hot tnh RR195 t hiu qu khi trong
hn hp phn ng va c mt xc tc CoFe2O4 v H2O2. Kt qu c chng
minh qua ng (e) v (f) trn th hnh 3.31. Sau 60 pht phn ng, khi
khng c v c chiu sng, nng cht mu gim ln lt 68,20% v 71,25%.
109
iu ny c th c hiu nh sau: khi trong hn hp phn ng c mt ng
thi CoFe2O4-GO v H2O2, phn ng Fenton xy ra theo c ch [138]:
Fe2+ + H2O2 Fe3+ + *OH + OH- (1)
Fe3+ + H2O2 Fe2+ + HOO + H+ (2)
Cc tm hot ng Fe2+ phn hy H2O2 b hp ph trn b mt xc tc
thnh cc gc *OH v HOO. theo phng trnh (1) v (2). Cc gc ny tip tc
oxi ha thuc nhum hot tnh RR195 to thnh cc cht v c khng c
hi.
Ngoi ra, kt qu cng cho thy khi c chiu sng thuc nhum hot tnh
RR195 b loi b nhiu hn so vi khi khng c chiu sng. Hay ni cch
khc, phn ng Photo Fenton cho hiu qu x l tt hn so vi phn ng Fenton
thng thng. Gii thch v iu ny, Sakthivel Thangavel v cng s [138]
cho rng: di tc dng ca nh sng ngoi phn ng Fenton cn xy ra cc qu
trnh khc nh c cp n di y:
GO + GO (h+ + e-) (3)
GO(e-) + Fe3+ Fe2+ + GO (4)
GO(h+) + Fe3+ Fe4+ + GO (5)
Fe4+ + OH- Fe3+ + *OH (6)
Hn na, graphen va ng vai tr l cht mang xc tc, hp ph thuc
nhum, va ng vai tr nh mt cht bn dn. Khi c chiu sng, cc in t
s chuyn sang vng dn v thc hin mt lot cc qu trnh khc. Graphen c
tc dng ngn cn s ti t hp ca l trng v vng bn dn [138]. Nu nh
trong phn ng Fenton, cc tm xc tc Fe2+ c phc hi theo phng trnh
(2) th trong phn ng Photo Fenton chng cn c phc hi theo phng
trnh (6). ng thi gc t do *OH cng c tng cng thng qua phn ng
(6). Do , phn ng Photo Fenton cho hiu sut loi b thuc nhum hot tnh
RR195 cao hn hn so vi phn ng Fenton thng thng.
110
3.3.7. nh gi hiu qu qu trnh phn hy thuc nhum hot tnh RR195
ca cc loi xc tc khc nhau (Fe(III)-GO; Fe0-Fe3O4-GO; CoFe2O4-GO;
ZnFe2O4-GO; Fe3O4-GO)
nh gi hot tnh xc tc ca cc h xc tc c tng hp gm: Fe(III)-
GO; Fe0-Fe3O4-GO; CoFe2O4-GO; ZnFe2O4-GO v Fe3O4-GO trong qu trnh
phn hy thuc nhum hot tnh RR195 c thc hin iu kin: Nng
RR195 ban u l 50 mg/L; nng cc xc tc ni trn l =0,5g/L; nng
H2O2= 0,5 mL/100 mL; pH = 3,5 ; nhit T= 30oC v chiu n trong 120
pht. Kt qu c th hin trn hnh 3.44.
Hnh 3.46: Qu trnh phn hy RR195 trn cc loi xc tc khc nhau:

Fe(III)-GO; Fe0-Fe3O4-GO; CoFe2O4-GO; ZnFe2O4-GO; Fe3O4-GO
T hnh 3.46 trn cho thy qu trnh quang ha phn hy thuc nhum
hot tnh RR195 s dng tc nhn H2O2 ca cc loi xc tc vi qu trnh chiu
n. Nhn thy, xc tc Fe(III)-GO v Fe0-Fe3O4-GO cho chuyn ha sau 90
pht l cao nht vi gi tr t 95%. Cc h xc tc cn li: CoFe2O4-GO;
ZnFe2O4-GO cho chuyn ha thp hn sau 120 pht chiu n.
111
Hn na c th thy rng bn ca cc h xc tc tng hp c l
tng i tt, iu ny c chng minh qua ba ln chy phn ng lin tc
khng hot ha, bn xc tc n nh, hot tnh gim khng ng k.
T cc kt qu thu c c th nh gi hot tnh xc tc ca cc h vt
liu tng hp c theo trnh t sau:
Fe(III)-GO; Fe0-Fe3O4-GO > ZnFe2O4-GO; CoFe2O4-GO > Fe3O4-GO
3.4. Nghin cu cc iu kin nh hng n kh nng phn hy thuc
nhum hot tnh RR195 trn h xc tc c hot tnh cao nht Fe0-Fe3O4-GO
3.4.1 nh hng pH n kh nng phn hy thuc nhum hot tnh
RR195 trn Fe0-Fe3O4-GO
Mt s thuc nhum c kh nng t phn hy trong mi trng pH thp
vi s c mt ca H2O2 [139] do vy trong nghin cu ny chng ti nh gi
kh nng t phn hy ca thuc nhum hot tnh RR195 vi s c mt H2O2 ti
cc pH khc nhau trong iu kin chiu n, kt qu c a ra trong hnh
3.45.
Hnh 3.47: Kh nng t phn hy ca thuc nhum hot tnh RR195

trong mi trng pH khc nhau vi s c mt H2O2
Quan st hnh 3.47 cho thy rng thuc nhum hot tnh RR195 khng b
phn hy trong iu kin pH thp vi s c mt ca H2O2. Cc nh pic cc i
cng khng thay i trong qu trnh kho st vi pH t 3-8.
Kho st nh hng ca pH qu trnh phn hy thuc nhum hot tnh
RR195 trn h xc tc Fe0-Fe3O4-GO c thc hin trong iu kin: Nng
RR195 ban u l 50 mg/L; nng xc tc Fe0-Fe3O4-GO =0,3g/L; nng
112
H2O2= 0,5 mL/100 mL; pH thay i ln lt t 3,5 ; 5,5 v 8 ; nhit T= 30oC
v chiu n trong 90 pht (trong pH = 5,5 l pH t sinh ca dung dch
RR195).
Kt qu c m t trn hnh 3.48
1
0.8
pH= 5.5
pH=4.5
0.6
pH=8
C/Co
0.4
0.2
0
0 10 20 30 40 50 60 70 80 90
Hnh 3.48: nh hng pH n kh nng phn hy thuc nhum hot tnh

RR195 trn Fe0-Fe3O4-GO
T hnh 3.46 cho thy khi pH cng thp th tc cng nh hiu sut
phn hy thuc nhum hot tnh RR195 cng tng. Khi pH = 3,5 hiu sut phn
hy t 95% ch trong 90 pht, khi tng pH ln 5,5 sau 90 pht hiu sut cng
ch t 65% v khi pH=8 th hiu sut hp ph gim mnh (15% sau 90 pht).
Gii thch cho iu ny l do trong mi trng pH t 3- 5 th tc sinh
ra cc gc t do *OH tng, do tc v hiu sut phn hy tng [140]. Trong
mi trng OH- th lm gim qu trnh sinh ra gc t do *OH do vy tc v
hiu sut phn hy u gim [141]. V vy pH = 4,5 c la chn cho cc qu
trnh nghin cu tip theo.
3.4.2. nh hng ca nng H2O2 n qu trnh phn hy thuc
nhum hot tnh RR195 trn Fe0-Fe3O4-GO
Kho st nh hng ca nng H2O2 n qu trnh phn hy thuc
nhum hot tnh RR195 trn h xc tc Fe0-Fe3O4-GO c thc hin trong iu
kin: Nng RR195 ban u l 50 mg/L; nng xc tc Fe0-Fe3O4-GO
113
=0,3g/L; nng H2O2 thay i t 0,2mL n 1 mL/100 mL; pH = 3,5; nhit
T= 30oC v chiu n trong 90 pht.
Kt qu c m t trn hnh 3.49:
1
1ml H2O2
0.8mL H2O2
0.8
0.3mL H2O2
0.5ml H202
0.6
C/Co
0.4
A
0.2 B
C
D
0
0 10 20 30 40 50 60 70 80 90
Hnh 3.49: nh hng ca nng H2O2 n qu trnh

phn hy thuc nhum hot tnh RR195 trn Fe0-Fe3O4-GO
Quan st hnh 3.49 cho thy khi nng H2O2 (0,5ml) kt hp vi xc tc

trong iu kin chiu n gi mt tri cho kh nng phn hy thuc nhum hot
tnh RR195 t 95% trong khong thi gian 90 pht. Khi tng nng H2O2
(0,8-1ml) th qu trnh phn hy RR195 sau 90 pht khng xy ra nhanh hn m
c chiu hng gim i (78% v 68%). Nu gim lng H2O2 (0,3ml) th tc
cng nh hiu sut phn hy thuc nhum hot tnh RR195 cng gim (82%).
iu ny l do cc gc t do *OH t H2O2 c to ra nhiu lm thc y
qu trnh phn ng dn n tc cng nh hiu sut phn hy tng. Tuy nhin,
khi nng H2O2 trong dung dch qu cao hoc qu thp s lm gim gc t do
*
OH xy ra theo phng trnh [142, 143, 144]:
H2O2 + *OH *HO2 + H2O
*
HO2 + *OH O2 + H2O
114
Ngoi ra nng H2O2 cao cng lm cc tm hot ng ca xc tc b no
ha (bo ha) do lm gim tc phn ng. Do vy chng ti chn nng
H2O2 (0,4ml) p dng cho qu trnh ny.
3.4.3. nh hng ca nng thuc nhum hot tnh RR195 ban u
n qu trnh phn hy trn Fe0-Fe3O4-GO
Kho st nh hng ca nng thuc nhum hot tnh RR195 ban u
n qu trnh phn hy trn h xc tc Fe0-Fe3O4-GO c thc hin trong iu
kin: Nng RR195 ban u thay i t 50 mg/L-100 mg/L (50ppm-100ppm);
nng xc tc Fe0-Fe3O4-GO =0,3g/L; nng H2O2 =0,5 mL/100 mL; pH =
3,5; nhit T= 30oC v chiu n trong 90 pht.
Kt qu c m t trn hnh 3.50
1
50ppm
0.8
75 ppm
0.6 100 ppm

C/Co
0.4
0.2
0
0 20 40 60 80
Hnh 3.50: nh hng ca nng thuc nhum hot tnh RR195

ban u n qu trnh phn hy RR195 trn Fe0-Fe3O4-GO
Hnh 3.50 cho thy, i vi nng thuc nhum hot tnh RR195 ban
u l 50 mg/L (50ppm) sau 90 pht phn ng th hiu sut kh RR195 t
95%. Khi tng nng RR195 ban u ln 75 mg/L (75ppm) v 100 mg/L
(100ppm) th hiu sut kh ch t tng ng l 85% v 70%. Ngoi ra tc
qu trnh phn hy cng gim khi nng RR195 ban u tng.
Nh vy, c th kt lun chuyn ha v tc phn hy gim khi nng
RR195 ban u tng. iu ny c th gii thch nh sau: nng thuc
nhum hot tnh RR195 ban u cao, lng tm xc tc cn chuyn ha ln,
tc khuch tn ca cc anion RR195 n b mt tm hot ng gim. Trong
iu kin thc hin phn ng y nng xc tc s dng tng i thp
115
(0,3g/L) nn khng lng tm chuyn ha ht thuc nhum hot tnh
RR195. Tht vy, khi tng nng xc tc t 0,3g/L ln 0,5g/L, chuyn ha
t 98% sau 90 pht phn ng.
3.5. ng hc ca qu trnh xc tc quang ha trong phn ng phn hy
thuc nhum hot tnh RR195 trn mt s h xc tc c hot tnh cao
Qu trnh phn hy thuc nhum hot tnh RR195 trn cc h xc tc
Fe(III)-GO v Fe0-Fe3O4-GO l mt qu trnh xc tc d th, v th c th tun
theo phng trnh Langmuir- Hinshelwood. Trong tc phn ng t l vi
phn din tch b mt b che ph bi cht phn ng. Nh vy i vi cc
dung dch long, tc phn ng quang xc tc ph thuc bc nht vo nng
. Tuy nhin, cng theo mt s nghin cu qu trnh quang xc tc trn cc vt
liu khng phi lc no cng tun theo phng trnh ng hc bc 1. Tc gi
Sumaeth Chavadej [145] cho thy qu trnh quang xc tc phn hy 2-propanol
trn xc tc Pt/TiO2 tun theo ng hc bc 0. Tc gi Antonino Sclafani [146]
cho thy qu trnh phn hy 4-nitrophenol trn TiO2 tun theo ng hc bc 0.
Mt khc nhm tc gi Sang Bum Kim [147] li cho thy qu trnh phn hy
volatile organic trn TiO2 li tun theo ng hc bc 1. Tc gi N. Guetta [148]
cho thy qu trnh quang xc tc phn hy methyl orange trn TiO2 tun theo
bc 1. Gn y, tc gi Nor Aida Zubir [149] cho thy qu trnh quang xc tc
phn hy thuc nhum axit orange 7 (AO7) trn Fe3O4-GO tun theo ng hc
bc 1.
Do vy trong phn ny, cc phng trnh ng hc bc 0, 1 v 2 c a
ra v p dng cho qu trnh phn hy thuc nhum hot tnh RR195 trn hai h
xc tc Fe(III)-GO v Fe0-Fe3O4-GO.
ng hc qu trnh phn hy thuc nhum hot tnh RR195 trn h xc
tc Fe(III)-GO v Fe0-Fe3O4-GO c m phng thng qua cc phng trnh
ng hc bc 0, bc 1 v bc 2.
Phng trnh ng hc bc 0 dng tch phn : [A] [A]0 kt
Phng trnh ng hc bc 1 dng tch phn: [A] [A]0 e kt
Phng trnh ng hc bc 2 dng tch phn (n=2):
Bng 3.5 : Nng thuc nhum hot tnh RR195 trc v sau qu trnh quang
phn s dng xc tc Fe(III)-GO ti cc nng khc nhau
116
50mg Fe(III)-GO, pH = 3,5, T= 30oC, [H2O2] = 0,5 mL/100 mL
Nng thuc nhum hot tnh RR195 (mg/L)
Thi gian
RR195 RR195 sau RR195 RR195 RR195 RR195
(pht)
ban u phn ng ban u sau phn ban u sau phn
ng ng
0 50 50 75 75 100 100
20 50 20,102 75 53.656 100 79.115
40 50 11,517 75 42.296 100 68.140
60 50 6,497 75 35.227 100 55.772
90 50 2.103 75 22.584 100 42.823
120 50 1.049 75 12.0853 100 34.132
T s liu bng 3.5 v p dng cc phng trnh ng hc bc 0, bc 1 v

bc 2. Qu trnh quang xc tc ca thuc nhum hot tnh RR195 trn h xc tc
Fe(III)-GO c th hin thng qua cc hnh 3.51, 3.52 v 3.53.
60
50
40
50 y = 0,346x + 15,70
Co-C
R = 0,706 50 Bac O
30
75 Bac O
75 y = 0,491x + 7,854
20 R = 0,951 100 Bac O
100y = 0,499x + 8,378
10 R = 0,927
0
0 20 40 60 80 100 120
Hnh 3.51. ng hc qu trnh xc tc quang ha trong phn ng

phn hy thuc nhum hot tnh RR195 trn Fe(III)-GO bc 0
117
4 50mg/L, K =0,032
R = 0,992
3
75 mg/L K= 0,014x
Ln (Co/C)
2
R = 0,985
1
100 mg/L K=0,008
R = 0,990
0
0 20 40 60 80 100 120
-1

0.6 50 y = 0,007x - 0,145
50 Bac 2 R = 0,855
75 Bac 2
0.4 100 Bac 2
1/C-1/Co
75 y = 0,001x - 0,007
0.2 R = 0,871
0
0 20 40 60 80 100 120
y = 0,001x - 0,002
R = 0,971
-0.2

Nhn thy rng gi tr R2 ca phng trnh ng hc bc 1 xp x 1, cn

h s tng quan (R2) ca phng trnh bc 0 v bc 2 thp. Nh vy qu trnh
hp ph thuc nhum hot tnh RR195 trn Fe(III)-GO tun theo phng trnh
bc 1.
Qu trnh phn hy thuc nhum hot tnh RR195 trn vt liu xc tc
Fe(III)-GO tun theo phng trnh ng hc bc 1 v tc phn hy gim khi
nng RR195 ban u tng. T hnh 3.52 cho thy tc phn hy gim dn
118
t 0,032 pht-1, 0,014 pht-1 v 0,008 pht-1 tng ng vi nng u RR195
l 50 mg/L, 75 mg/L v 100 mg/L.
iu ny c th gii thch nh sau: nng thuc nhum hot tnh
RR195 ban u thp, tc khuch tn thuc nhum hot tnh RR195 n b
mt xc tc nh, che ph ca RR195 thp trong khi lng tm hot ng
ca xc tc p ng chuyn ha ht thuc nhum hot tnh RR195. Khi
tng nng ban u RR195 cao hn, tc khuch tn RR195 n b mt xc
tc tng (theo nh lut khuch tn Fick). Mt RR195, che ph bi RR195
trn b mt xc tc tng trong khi lng tm hot ng trn b mt xc tc
khng thay i dn n chuyn ha RR195 khng ht, h qu l tc phn hy
gim. Do nh hng ca tc nhn H2O2 nn trong qu trnh phn ng lm cho
hng s tc c thay i khng nn c gi l hng s tc biu kin.
ng hc qu trnh phn hy thuc nhum hot tnh RR195 trn h xc
tc Fe0-Fe3O4-GO c m phng thng qua cc phng trnh ng hc bc 0,
bc 1 v bc 2 v c th hin trong bng 3.6.
Bng 3.6: Nng thuc nhum hot tnh RR195 trc v sau qu trnh
quang phn s dng xc tc Fe0-Fe3O4-GO ti cc nng khc nhau
30 mg Fe0-Fe3O4-GO, pH = 3,5, T= 30oC, [H2O2] = 0,5 mL/100 mL

Thi Nng thuc nhum hot tnh RR195 (mg/L)
gian RR195 RR195 sau RR195 RR195 RR195 RR195
(pht) ban u phn ng ban u sau phn ban u sau phn
ng ng
0 50 50 75 75 100 100
10 50 25.765 75 56.180 100 79.081
20 50 20.301 75 41.323 100 66.324
40 50 10.355 75 25.351 100 52.771
60 50 6.202 75 19.635 100 41.543
90 50 2.053 75 10.180 100 24.014
T s liu bng 3.6 v p dng cc phng trnh ng hc bc 0, bc 1 v

bc 2. Qu trnh quang xc tc ca thuc nhum hot tnh RR195 trn vt lic
xc tc Fe0-Fe3O4-GO c th hin thng qua cc hnh 3.54; 3.55 v 3.56.
119
80 75y = 0,691x + 11,78
100y = 0,745x + 10,26
R = 0,867
70 R = 0,918
60
50
75 Bac O
Co-C 40
100 Bac O
30 50 Bac 0
20 50y = 0,448x + 14,45
R = 0,751
10
0
0 20 40 phn ng60(pht)
Thi gian 80 100

phn hy thuc nhum hot tnh RR195 trn Fe0-Fe3O4-GO bc 0
3.5
75 y = 0.0334x + 0.1783
3 100 R2 = 0.9891
2.5 50
y = 0.0216x + 0.093
Ln Co/C
2
R2 = 0.9873
1.5
1 y = 0.0149x + 0.0508
R2 = 0.9897
0.5
0
0 20 40 60 80 100

120
0.5
75 Bac 2
0.4 50 y = 0,004x - 0,053
100 Bac 2 R = 0,845
0.3 50 Bac 2
1/C-1/Co
75 y = 0,001x - 0,005
0.2
R = 0,947
0.1
0
0 20 40 60 80 100
-0.1 100y = 0,0003x - 0,0017
Thi gian phn ng (pht) R = 0,939

Qu trnh phn hy thuc nhum hot tnh RR195 trn vt liu Fe0-Fe3O4-
GO l mt qu trnh xc tc d th v th c th tun theo nh lut Langmuir-
Hinshelwood. Trong tc phn ng t l vi phn din tch b mt b che
ph bi cht phn ng. Nh vy i vi cc dung dch long, tc phn
ng quang xc tc ph thuc bc nht vo nng . Hn na so snh cc gi tr
R2, nhn thy rng gi tr R2 ca phng trnh ng hc bc 1 xp x 1, cn h
s tng quan (R2) ca phng trnh bc 0 v bc 2 thp. Nh vy c th kt
lun rng quy lut phn hu tun theo quy lut bc 1.
Qu trnh phn hy thuc nhum hot tnh RR195 trn vt liu Fe0-Fe3O4-
GO tun theo phng trnh ng hc bc 1 v tc phn hy gim khi nng
RR195 ban u tng. T hnh 3.56 cho thy tc phn hy gim dn t
0,033 pht-1, 0,021 pht-1 v 0,015 pht-1 tng ng vi nng u ca thuc
nhum hot tnh RR195 l 50 mg/L, 75 mg/L v 100 mg/L.
So snh tc phn hy thuc nhum hot tnh RR195 trn hai h xc tc
Fe(III)-GO v Fe0 Fe3O4-GO ta c th nhn thy l tc phn hy thuc
nhum hot tnh RR195 l nh nhau (0,032- 0,033 pht-1) nng ban u
RR195 thp (50mg/L). Tuy nhin, nng ban u RR195 cao (100mg/L),
tc phn hy thuc nhum hot tnh RR195 trn Fe0 -Fe3O4-GO cao gn gp
i (0,15 pht-1) so vi xc tc Fe(III)-GO (0,008 pht-1). Kt qu ny chng t
121
h xc tc Fe0 Fe3O4-GO c lng tm hot ng Fe cao hn so vi h xc tc
Fe(III)-GO. iu ny rt ph hp vi kt qu c trng bng XPS v EDX cho
thy hm lng Fe trong xc tc Fe0 Fe3O4-GO cao hn nhiu so vi hm
lng Fe c trong xc tc Fe(III)-GO.
Tht vy, nh trnh by phn phn tng hp v c trng, ch c
mt lng nh Fe3+ trao i v lin kt vi cc nhm chc ca graphen oxit GO
trong vt liu Fe(III)-GO, trong khi i vi vt liu Fe0 Fe3O4-GO composit,
mt lng ln Fe c a ln b mt cc lp ca graphen oxit GO.
122
KT LUN CHUNG
Trn c s cc kt qu t c, c th rt ra mt s kt lun chnh

nh sau:
1. ch to thnh cng cc h vt liu xc tc mi nano composit
t tnh trn c s oxit st v graphen oxit (GO): Fe3O4 GO; CoFe2O4-
GO; ZnFe2O4- GO;
2. ch to thnh cng cc h vt liu xc tc mi nano composit
Fe0-Fe3O4-GO bng phng php kh ha hc v vt liu lai Fe(III)-GO
bng phng php trao i ion Fe3+ vi cc nhm chc ca graphen oxit
(GO).
3. T kt qu c trng chng minh vt liu nano composit Fe3O4
GO; CoFe2O4- GO v ZnFe2O4- GO c cu trc spinel, c t tnh v kch
thc ht t 30-60 nm. i vi vt liu Fe0-Fe3O4-GO v vt liu lai
Fe(III)-GO, c kch thc ht nh hn nhiu, trong khong 5-10 nm. Bng
phng php FTIR v XPS chng minh c s hnh thnh vt liu lai
Fe(III)-GO thng qua tng tc gia ion Fe3+ vi cc nhm chc ca
graphen oxit (GO).
4. Hot tnh quang xc tc ca cc vt liu c kho st trong phn
ng phn hy thuc nhum hot tnh RR195 trong nc v tun theo trt
t sau:
Fe(III)-GO; Fe0-Fe3O4-GO > ZnFe2O4-GO; CoFe2O4-GO> Fe3O4-GO
5. nh hng ca cc thng s nh nng ban u thuc nhum
hot tnh RR195, nng xc tc, nng H2O2, pH, c kho st
trong phn ng phn hy quang ha thuc nhum hot tnh RR195 trong
nc trn cc h xc tc Fe0-Fe3O4-GO v Fe(III)-GO. Kt qu thu c
cho thy cc thng s trn u c nh hng n hot tnh xc tc, trong
nh hng ca pH l mnh nht, hot tnh t gi tr cao nht pH thp
123
t 3,5-4. nh hng ca nng H2O2 n hot tnh xc tc rt khc nhau:
hot tnh tng tuyn tnh khi nng H2O2 t 0-0,5ml, nhng hot tnh li
gim khi tip tc tng nng H2O2 t 0,5 -1ml.
6. tin hnh nghin cu ng hc qu trnh xc tc quang ha
trong phn ng phn hy thuc nhum hot tnh RR195 trn h xc tc
Fe(III)-GO v Fe0-Fe3O4-GO, kt qu cho thy qu trnh phn hy thuc
nhum hot tnh RR195 u tun theo phng trnh ng hc biu kin
bc 1. Kt qu ny ph hp vi cc nghin cu c cng b mi y.
Cc kt qu thu c m ra trin vng p dng phng php oxi ha
nng cao (AOPs) bng phn ng quang ha Fenton trong phn hy thuc
nhum hot tnh ng dng trong x l nc thi dt nhum.
124
NHNG NG GP MI CA LUN N
1. tng hp thnh cng cc h vt liu xc tc nano composit mi

trn c s oxit st t (Fe3O4), oxit st t bin tnh CoFe2O4, ZnFe2O4 v
graphen oxit (GO) c hot tnh trong phn ng quang ha phn hy thuc
nhum hot tnh RR195 trong nc v c kh nng thu hi xc tc cao khi
p dng t trng.
2. ch to thnh cng vt liu mi nano composit Fe0-Fe3O4-GO
bng phng php kh ha hc v vt liu lai mi Fe(III)-GO bng
phng php trao i ion Fe3+ vi cc nhm chc ca graphen oxit (GO).
C hai loi vt liu mi trn u cho hot tnh quang xc tc v bn cao
nht trong phn ng phn hy thuc nhum hot tnh RR195 trong nc
di nh sng nhn thy (m phng nh sng mt tri).
3. tin hnh nghin cu ng hc ca qu trnh phn hy quang
xc tc trn hai h vt liu nano composit mi: Fe0-Fe3O4-GO v Fe(III)-
GO. Kt qu cho thy qu trnh phn hy quang ha thuc nhum hot tnh
RR195 trong nc di bc x nh sng nhn thy (m phng nh sng
mt tri) tun theo phng trnh ng hc biu kin bc 1.
125
DANH MC CAC BI BAO LIN QUAN N LUN N
1. L Th Mai Hoa, H Quang nh, L H Giang, Nguyn K Quang, o c

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4. L Th Mai Hoa, H Quang nh, L H Giang, Nguyn K Quang, Ng Tin
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ch Xc tc v hp ph, ISSN 0866-7411, T4, N02, 2015, 39-44
5. L Th Mai Hoa, L H Giang, Nguyn K Quang, H Quang nh, o c
Cnh, Nguyn Trung Kin, Trn Th Kim Hoa, ng Tuyt Phng v V Anh
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6. L Th Mai Hoa, L H Giang, H Quang nh, Nguyn K Quang, o c
Cnh, Trn Th Kim Hoa, ng Tuyt Phng and V Anh Tun, Tng hp vt
liu composit GO-Fe(III) c hot tnh cao trong qu trnh phn hy thuc
nhum, Tp ch Khoa hc v Cng ngh, i hc Cng nghip H Ni,
T12.N031, 2015, 88-92
7. 7. L Th Mai Hoa, H Quang nh, L H Giang, Nguyn K Quang, Ng
Tin Quyt, o c Cnh, Nguyn Trung Kin, ng Tuyt phng, Trn Th
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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,

Ngi hng dn khoa hc: PGS.TS V Anh Tun

Trc ht, em xin trn trng cm n n PGS.TS V Anh Tun v

Ti xin chn thnh cm n tp th cn b phng Ha l B mt-

Ti xin chn thnh cm n su sc ti gia nh, bn b, ng

Ti xin cam oan, y l cng trnh nghin cu do ti thc hin

ZnFe2O4-GO Km (Zn), Fe2O4 bc Graphen oxit (GO)

Fe0-Fe3O4-GO Fe, Fe3O4 bc Graphen oxit (GO)

Fe(III)-GO Fe(III) oxo cluster Graphen oxit (GO)

Hnh 1.1 Graphen - vt liu c cu trc c bn (2D) cho cc vt liu 4

Hnh 3.43 S ph thuc chuyn ha theo thi gian phn ng cc 106

Bng 1.1 Tnh cht ca Graphen n lp.................................... 5

Ngy nay, vi s tin b ca khoa hc v cng ngh, cc ngnh cng

Hnh 1.1. Graphen - vt liu c cu trc c bn (2D)

Hnh 1.2. Cc lin kt ca mi nguyn t cacbon trong mng graphen

Hnh 1.7 Nc thi dt nhum

Hnh 1.8 Cng thc cu to ca thuc nhum hot tnh RR195

Hnh 1.9 Cc phng php loi b mu thuc nhum

Mc d qu trnh oxi ha nng cao (AOPs) l tp hp ca rt nhiu

Hnh 1.10: Phn ng Fenton ng th v Fenton d th

gc hydroxyl theo phn ng Fenton. Tuy nhin tc ban u ca phn ng oxi

Graphen Kch thc Hm lng Cht c loi b Ti liu

G-Au- 100-200 - methyl blue 51

S ghp ni gia TiO2 v graphen c chng minh tng cng

Trong mt s trng hp, vt liu composit oxit kim loi/graphen khc

Fan v cc cng s [58] thc hin nghin cu chi tit nghin cu c

Hnh 1.13 C ch phn ng ca Fe3O4/graphen vi cc cht hu c

Graphen Kch thc Hm lng Cht nhim loi Ti liu

ZnFe2O4/GR 7-10 20 methylene blue 66

2.1. Mc tiu nghin cu

Graphit oxit, Graphit oxit,

Bransonic 2510E- Goldsun, MWO-G20SA,

Dung dch GOSA GOVS

T= Z0C, tc gia nhit

Hnh 2.1.S tng hp GOSA v GOVS

Hnh 2.2.S tng hp Fe3O4-GO

Hnh 2.4.S tng hp ZnFe2O4-GO

Hnh 2.5.S tng hp Fe0-Fe3O4-GO

1 y = 0,020x + 0,032 pH = 8.0

Hnh 2.6. ng chun v ph UV-Vis ca thuc nhum hot tnh RR195

Hiu sut qu trnh c tnh ton thng qua cng thc

So snh phn t s v bc phn ng

Hnh 2.7. th lgC theo t i vi phn ng bc 1

Hnh 2.8. 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

Hnh 2.10. Qu trnh pht quang in t

Hnh 2.11. Nguyn tc pht x tia X dng trong ph

C nhiu thit b phn tch EDX nhng ch yu EDX c o bng cc

Hnh 2.13. Cc dng ng ng nhit hp ph-kh hp ph

Hnh 2.14. Bc chuyn ca cc electron trong phn t

3.1. c trng ca vt liu graphen oxit v graphen tng hp c

Hnh 3.2. nh HR-TEM ca GOSA (a) , GOVS (b) v rGO (c)

3.1.4. Ph in t quang tia X (XPS) ca vt liu graphen oxit v

72 Hnh 3.4b. Ph XPS ca

Mu/ nguyn t C O C/O

Hnh 3. 5: Gin XRD ca graphen oxit (GO)

Hnh 3.6: Gin XRD ca Fe3O4-GO

3.2.1.2 Gin XRD ca h vt liu xc tc CoFe2O4-GO trn c s Fe3O4 bin

Hnh 3.7: Gin XRD ca CoFe2O4-GO

Cuong do tuy chon (a.u)

Hnh 3.8: Gin XRD ca ZnFe2O4 -GO

Hnh 3. 9: Gin XRD ca Fe0-Fe3O4-GO