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LI CM N
Em xin chn thnh cm n thy H Thc Huy, ngi thy truyn t kin
thc v tn tnh hng dn cho em trong sut nhng nm hc qua cng nh trong
qu trnh thc hin ti tt nghip.
Em xin cm n thy inh Tn Thnh tn tm gip em trong bui u
thc hin ti tt nghip.
Em xin cm n anh Mai Thanh Tm, anh Thanh Long, anh Hunh Lp
Trung, ch Khnh Vn, ch inh Th Nho, ch Thu Hin v cc anh ch cao hc
phng Ha L Polymer chia s nhng kinh nghim qu bu v gip em rt
nhiu trong qu trnh thc hin ti.
Xin cm n cc thy c trng i hc Khoa Hc T Nhin dy d em
trong sut 4 nm hc qua.
Cm n cc bn 09Polymer, 09T Y Sinh v cc bn khoa Ha chia s v
ng vin ti vt qua nhng thi im kh khn trong qu trnh thc hin ti.
V cui cng, con xin cm n b ni, ba m v mi ngi trong gia nh
lun bn con v ng h con.

Tp. HCM thng 07/2013

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LI M U
Lch s cho thy s pht trin ca vt liu gn lin vi nn vn minh ca
nhn loi. Tri qua qu trnh lch s lu di vt liu c nhiu thay i t thi k
qua ngv hin nay l thi k ca nhiu loi vt liu tin tin. c pht
hin v c lp thnh cng nm 2004, graphene c v nh mt vt liu thn k
vi nhiu tnh cht u vit m trc nay cha vt liu no c. Song cc cng trnh
nghin cu gn mi nm qua ch tp trung vo cu trc dng tm (2D) ca
graphene m t ch n cu trc dng xp (3D). Trong nm nm tr li y, cu
trc xp (3D) bc u c nghin cu vi s k vng vo ng dng trong cc
lnh vc y sinh nh lm v ca cht mang thuc, to khung cho m.. hay trong lnh
vc hp ph v nng lng.
Trn th gii cc nghin cu v xp graphene cn kh t, trong ti ny
chng ti xin a ra phng php tng hp xp graphene v bc u kho st s
hp ph du. Hy vng ti nghin cu ny s gp mt phn nh, b sung thm
kin thc v vt liu graphene.

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MC LC
Phn 1.TNG QUAN .............................................................................................11
1.1.Gii thiu chung v graphite ..................................................................11
1.2. Vt liu Graphene .................................................................................12
1.2.1. Lch s tm ra graphene .................................................................12
1.2.2 Cu trc ca graphene ....................................................................12
1.2.3. Cc phng php tng hp graphene ............................................14
1.3. Gii thiu v graphite oxide (GO) ........................................................16
1.3.1 Tng hp Graphite oxide (GO) ......................................................17
1.3.2. Cu trc v tnh cht ca GO .........................................................17
1.3.4. Cc phng php kh GO .............................................................19
1.4. Vt liu xp trn c s graphene ..........................................................20
1.4.1 Xp graphene ..................................................................................21
1.4.2 Phng php ch to xp graphene. ...............................................22
1.4.3. Mt s nghin cu tng hp xp graphene. ................................24
1.4.3.1 Phng php kh thy nhit to xp graphene khng s dng
cht kh. ........................................................................................................24
1.4.3.2 Phng php kh thy nhit to xp graphene s dng cht
kh ................................................................................................................25
1.4.3.3 Phng php kh thy nhit to xp graphene s dng
Ammoniac .....................................................................................................27
1.5.Mt s k thut v phng php nghin cu .........................................29
1.5.1 Phng php ng c (Freeze Drying or Lyophillisation) .............29
1.5.1.1 C s khoa hc ca phng php ng c .............................30
1.5.1.2. Quy trnh ng c ....................................................................31

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1.5.2. Phn tch nhiu x tia X (X-Ray) ..................................................32

1.5.3. Ph hng ngoi (FT-IR).................................................................33
1.5.4. Phng php o ng nhit hp ph - kh hp ph nit (BET) ..33
1.5.5. Knh hin vi in t qut (SEM) ...................................................34
1.5.6. Phn tch gim cp nhit Thermo Gravimetric Analysis (TGA) 34
Phn 2. Thc nghim ..............................................................................................37
2.1. Thit b v dng c................................................................................37
2.1. Ha cht ................................................................................................37
2.3. Thc nghim .........................................................................................38
2.3.1. Quy trnh thc nghim ch to Graphite oxide (GO) ....................38
2.3.2. Qu trnh tng hp gel graphene t GO bng phng php kh
tnh. ...................................................................................................................40
2.3.2.1. Quy trnh kh tnh GO s dng cht kh l ammoniac (rGONH3) .............................................................................................................40
2.3.2.2. Quy trnh kh tnh GO s dng cht kh Vitamin C (rGOVitC) ..............................................................................................................41
2.3.2.3. Quy trnh kh tnh GO s dng cht kh HI. (rGO- HI) ........42
2.3.4. Tng hp xp graphene t gel graphene bng phng php ng
c ......................................................................................................................43
Phn 3. Kt qu v bn lun ..................................................................................44
3.1. Kt qu tng hp graphite oxide theo phng php Hummers ............44
3.1.1. Gin XRD ca mu graphite v GO .........................................44
3.1.2. Kt qu ph FT-IR ca mu GO....................................................45
3.1.3. Gin TGA ca mu GO v graphite .........................................46
3.2. Kt qu phn tch tng hp cc cht kh trong qu trnh ch to gel ...47
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3.2.1 Hnh nh cc mu gel GO c tng hp sau qu kh tnh ...........47

3.2.2. Cc kt qu phn tch cc mu rGO sau qu trnh kh .................49
3.2.2.1 Gin XRD ca mu GO v cc mu GO sau qu trnh kh
(rGO) .............................................................................................................49
3.2.2.2. Ph FT-IR ca mu GO v rGO..............................................50
3.2.2.3. Ph tn x Raman ca graphite, GO v rGO ..........................51
3.2.2.4. Gin TGA ca mu GO v cc mu rGO sau qu trnh kh
.......................................................................................................................52
3.2.2.5. Kt qu o dn in ca mu GO v rGO..........................53
3.2.2.6. Kt qu tng hp xp graphene t gel graphene sau qu trnh
ng c ..........................................................................................................55
3.3. Cc kt qu kho st xp graphene (rGO-HI) ......................................56
3.3.1 Kt qu chp SEM xp graphene rGO-HI .....................................58
3.3.2 Kt qu o din tch b mt ca xp graphene rGO-HI. ................59
Phn 4. Kt lun v kin ngh ................................................................................61
4.1. Kt lun .................................................................................................61
4.2. Kin ngh ...............................................................................................61
TI LIU THAM KHO ......................................................................................62
PH LC

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DANH MC HNH NH
Hnh 1.1 Cu trc ca graphite .................................................................................11
Hnh 1.2 Cu trc ca graphene ................................................................................12
Hnh 1.3 Cc hnh thi ca graphene ........................................................................13
Hnh 1.4 K thut ch to graphene t graphite .......................................................15
Hnh 1.5 K thut ch to graphene t CVD ............................................................16
Hnh 1.6 M hnh kh graphene oxide to graphene. ...............................................16
Hnh 1.6 Cu trc ca graphite oxide (GO) theo m hnh ca Lerf Klinowski .....18
Hnh 1.7 Lin kt hydro gia cc lp graphite oxide [2]. ...........................................18
Hnh 1.8 Cu trc graphite oxide (a) v graphene oxide (b) ....................................19
Hnh 1.9 Xp graphene. ............................................................................................21
Hnh 1.10 M t qu trnh to mng khng gian trong qu trnh tng hp xp
graphene 3D s dng cation ......................................................................................22
Hnh 1.11 Quy trnh tng hp graphene t GO ........................................................23
Hnh 1.12 M hnh kh tnh ......................................................................................23
Hnh 1.13 Gin XRD ...........................................................................................24
Hnh 1.14 Gel graphene trc v sau khi kh tnh ...................................................25
Hnh 1.15 Xp graphene (a), Hnh SEM ca xp graphene (b) ...............................26
Hnh 1.16 Cu trc v qu trnh hp ph du ca xp ..............................................28
Hnh 1.17 Kh nng hp ph dung mi ca xp graphene .......................................28
Hnh 1.18 Gin pha ca nc...............................................................................30
Hnh 1.19 Biu din qu trnh ng c. ....................................................................31
Hnh 1.20 My ng c .............................................................................................32
Hnh 1.21 Nguyn l chiu x tia X ..........................................................................32

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Hnh 1.22 Dng th ng thng BET .................................................................34

Hnh 2.1 H tng hp GO .........................................................................................38
Hnh 2.2 S oxi ha graphite ...............................................................................39
Hnh 2.3 H GO huyn ph sau khi tng hp ...........................................................39
Hnh 2.4 Gel GO.. .....................................................................................................39
Hnh 2.8 Hn hp Graphene oxide v cht kh trc khi phn ng ........................40
Hnh 2.9 H autoclave ...............................................................................................40
Hnh 2.10 S kh tnh s dng cht kh ammoniac ............................................41
Hnh 2.11 S kh thy nhit s dng cht kh Vitamin C ..................................42
Hnh 2.12 S kh tnh s dng cht kh HI ........................................................43
Hnh 3.1 Ph XRD ca mu GO v graphite ............................................................44
Hnh 3.2 Ph FT-IR ca mu GO .............................................................................45
Hnh 3.3 Gin TGA ca GO v graphite .............................................................46
Hnh 3.4 Graphene oxide trc khi kh (a); .............................................................47
gel graphene to thnh sau khi kh (b) .....................................................................47
Hnh 3.5 Gel graphene sau qu trnh kh bng NH3 ................................................47
Hnh 3.6 Gel graphene sau qu trnh kh bng Vitamin C (VitC) ...........................47
Hnh 3.7 Gel graphene sau qu trnh kh bng HI ...................................................48
Hnh 3.8 Gin XRD ca mu GO, rGO-HI, rGO-VitC, rGO-NH3 ......................49
Hnh 3.9 Ph FT-IR ca mu GO, rGO-HI, rGO-VitC, rGO-NH3 ...........................50
Hnh 3.10 Ph raman ca Graphite, GO v ca cc mu rGO .................................51
Hnh 3.11 Biu t l cng ID/IG .....................................................................52
Hnh 3.12 Gin TGA ca cc mu GO v rGO-HI, rGO-VitC, rGO-NH3. ........53
Hnh 3.13 Mu p vin i o d dn in .................................................................54

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Hnh 3.14 Cc mu rGO-NH3, rGO-HI, rGO-VitaminC (vitC) sau khi ng c. ....55

Hnh 3.15. M hnh in t trn benzen v 3 cu hnh sp xp ca vng thm
theo tng tc ...................................................................................................56
Hnh 3.16 Xp graphene rGO-HI sau ng c. ........................................................57
Hnh 3.17 Hnh chp SEM mu xp rGO-HI cc kch thc khc nhau. .............58
Hnh 3.18 M hnh in t ca vng thm theo tng tc ..............................58

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DANH MC BNG
Bng 1.1 Cc thng s ca graphite....11
Bng 1.2 So snh kh nng kh GO ca cc cht kh....27
Bng 3.1 dn in v in tr mt ca cc mu54
Bng 3.2 Kho st khi lng hp ph du diezen ca xp rGO-HI..59

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DANH MC CC T VIT TT
GO: Graphite oxide.
rGO-HI: Graphite oxide kh bng HI.
rGO-VitC: Graphite oxide kh bng Vitamin C.
rGO-NH3: Graphite oxide kh bng NH3.
XRD (X Ray Diffraction): nhiu x tia X.
FT-IR (Fourier transform Ifrared spectroscopy): Ph hng ngoi Fourier
TGA (Thermo gravimetric analysis): Phn tch nhit trng lng

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Phn 1.TNG QUAN

1.1.Gii thiu chung v graphite [1]
Graphite l mt dng th hnh ca carbon. Carbon trong cu trc graphite c
dng lai ha sp, trong 1 nguyn t carbon lin kt cng ha tr vi ba nguyn t
carbon khc to thnh mt phng gm cc vng lc gic dung hp.

Hnh 1.1 Cu trc ca graphite

Graphite c th tm thy trong t nhin hoc c tng hp. Graphite t
nhin gm ba loi chnh: dng flake (phin mng) hay thng c gi l than ch
(plumbago), dng kt tinh (crytalline) v dng v nh hnh (amrophous).
Cc tnh cht vt l ca graphite nh nhit si, nhit nng chy
c xc nh nhit cao trn 3000 K nn cc s liu mc kh nhiu sai s
v cha thng nht.
Bng 1.1 Cc thng s tnh cht ca graphite
T trng, 300 K, 1atm

2.26g/cm

Th tch nguyn t

5.315 cm/mol

Nhit thng hoa, 1 atm

4000 K

im ba (c lng)

4200 K

Nhit si (c lng)

4560 K

Nhit ha hi

716.9 kJ/mol

m in Pauling

2.5

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Tnh cht ha hc: graphite tr vi phn ln cc cht nh axit, kim, cc cht

n mn tuy nhin hot tnh phn ng ca graphite c th tng ng k khi c mt
tp cht ( ng vai tr xc tc ca graphite vi ha cht), nhng khuyt tt trong
tinh th (tng nng lng hot ha), xp ( xp cng cao, din tch b mt cng
ln lm tng hot tnh phn ng ca graphite).
1.2. Vt liu Graphene [2]
1.2.1. Lch s tm ra graphene
Nhng bi bo co v graphene ln u xut hin vo nm 1970 nhng phi
n nm 2004 th graphene mi c c lp bng cch tch bc c hc t khi
graphite bi nhm ca gio s Andre Geim- Khoa Vt l i Hc Manchester,
Anh Quc. T lc c bc tch v c lp thnh cng, graphene xut hin trong
rt nhiu cc cng trnh nghin cu trong hu khp cc lnh vc ca khoa hc nh
dn in, cc b cm ng, lm u d kh, gia cng cho cc polymervv. Rt
nhiu tnh nng ang dn c khm ph v trong vt liu hp ph, lu tr
graphene cng l vt liu y tim nng.
1.2.2 Cu trc ca graphene

Hnh 1.2 Cu trc ca graphene

Graphene c cu trc n lp nguyn t, c dng tm bao gm cc nguyn
t carbon trng thi lai ha sp trong cu trc t ong. Khong cch gia hai
nguyn t carbon k cn l 0.142 nm, khong cch gia hai lp graphene l 3- 4
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chiu dy mi tm graphene l 0.35 1,0 nm. Graphene c xem nh l vt liu

mng nht trong v tr. Graphene cng l cu trc c bn hnh thnh cc vt liu
khc nh graphite, cacbon nanotube, fullerences.

Hnh 1.3 Cc hnh thi ca graphene

Thn du k nc
Graphene c cu trc n lp nguyn t, c dng tm bao gm cc nguyn

t cacbon sp lin kt vi nhau to thnh mng li t ong 2D. iu ny quyt nh

nn tnh cht ca graphene l vt liu k nc thn du.

T trng thp
n v lc gic ca graphene gm mi cnh l 2 nguyn t s c din tch

l 0.052nm. Suy ra t trng ca graphene l 0.77mg/m. Vi t trng thp, graphene

nu c cu trc xp 3D s l mt trong nhng vt liu nh nht gip chng d dng
ni trn b mt cht lng (c t trng cao hn graphene nh nc).

Din tch b mt.

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Din tch b mt ca graphene khong 2600m/g, cao hn din tch b mt

ca than hot tnh v ca ng nano cacbon. Do kh nng hp ph ca graphene
l rt ln.

dn in
Graphene n lp c tnh cht dn in c bit, nng lng vng cm hu

nh khng c. iu ny c gii thch da trn cu trc ca graphene, trong

mi carbon trng thi sp s dng 3 AO sp (mi AO c 1 electron c thn) lin
kt vi 3 AO sp ca 3 carbon k cn, cn 1 AO p (c cha 1 electron c thn) s
xen ph vi cc AO p cn li ca cc carbon k cn to mng li lin kt - rng
khp. Do cc electron c th d dng di chuyn gia cc AO p m khng gp bt
c tr ngi no hay ni cch khc: graphene n lp l vt liu siu dn in.

dn nhit
S dn nhit ca graphene b chi phi bi cc phonon v c o xp x
. ng thi nhit phng graphene c dn nhit l 401

l 5000

. Nh th, graphene dn nhit tt hn ng gp 10 ln.

1.2.3. Cc phng php tng hp graphene
Trong cu trc ca graphite, cc lp graphene lien kt vi nhau bng lc
Vander Wall. Do khong cch gia cc lp rt nh (0,34nm) nn lc ny tng tc
ng k khin cho vic tch cc lp rt kh khn. Hai phng php ch yu ch
to graphene l:
Phng php i t trn xung (top down) [1]
y l phng php to ht kch thc nano t cc ht c kch thc ln
hn. Bng k thut nghin v bin dng bin vt liu th khi vi t chc ht th
thnh c ht kch thc nano. y l cc phng php n gin, r tin nhng rt
hiu qu, c th tin hnh cho nhiu loi vt liu vi kch thc kh ln (ng dng
lm vt liu kt cu)

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Hnh 1.4 K thut ch to graphene t graphite, phn tn graphite oxide (a),

dung dch graphene oxide (b), tm graphene oxide (c).
i t than ch Graphite:
Tch c hc: dng lc c hc tch lp Grapite.
Dng sng siu m tch cc lp graphite trong dung dch.
Phng php in ha.
S thy ha graphite.
i t dn xut graphite oxide (GO):
Phng php phn tn dung dch keo (GO colloid).
Phng php kh ha hc graphene oxide trn c s ha tan (CRG).
Phng php kh nhit.
Phng php t di ln (bottom up)
y l phng php hnh thnh ht nano t cc nguyn t. Nguyn l ca
phng php ny l hnh thnh vt liu nano t cc nguyn t hoc ion. Bao gm:
Phng php lng ng hi ha hc CVD.
Phng php phng in h quang.

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Phng php epitaxial pht trin trn SiC.

Hnh 1.5 K thut ch to graphene t CVD

Phng php i t di ln cho graphene tinh khit hn nhng hm lng
graphene thu c theo phng php ny l rt thp. Hn na gi thnh sn xut rt
cao nn phng php i t trn xung thng c s dng trong cc lnh vc
khng i hi qu cao v tinh khit ca graphene. y l phng php mang li
nhiu hiu qu quy m phng th nghim. thu c graphene, ti thc hin
theo phng php php t trn xung vi nguyn liu ban u l GO (graphite
oxide). C th qu trnh thc hin nh sau: bin tnh graphite to hp cht thn
nc l GO v sau kh li thu c n lp graphite vi nhng tnh cht u
vit nh ban u.

Hnh 1.6 M hnh kh graphene oxide to graphene.

1.3. Gii thiu v graphite oxide (GO)
Graphite oxide (GO) hay cn gi l acid graphite, c Brodie tng hp ln
u vo nm 1859, bng cch x l graphite vi hn hp kali chlorate v acid nitric
m c. V sau cc phng php tng hp GO u da trn hn hp oxi ho mnh
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m Brodie a ra hn hp cha mt hoc nhiu acid mnh v cht oxide ho

m c.
1.3.1 Tng hp Graphite oxide (GO)
oxi ha graphite, s dng cc tc cht oxi ha mnh vi iu kin, thi
gian tin hnh phn ng thch hp, graphite c th b oxi ha cc mc khc
nhau. Khi graphite b oxi ha, cc ni i C=C dn b thay th bi cc nhm chc
phn cc nh OH, -COOH, -CHO, nhm epoxy H lin hp ca graphite b ph
hy nn graphite c mu nht hn graphite ban u. Ty theo phng php v loi
graphite s dng m mu sc graphite oxide khc nhau (t l C/O ln dung dch c
mu en nu, t l C/O nh dung dch c mu vng). Sau khi oxi ha, cc tnh cht
ca graphite gim ng k nh tnh dn in, dn nhit Cc tc cht oxi ha
thng dng l H2SO4 c, HNO3, KMnO4, KNO3, C ba phng php ch
yu iu ch graphite: phng php Brodie, phng php Staudenmeier, phng
php Hummers. Trong phng php Hummers c dng kh ph bin.
Phng php Brodie (y l phng php c in ra i sm nht) [3]
u im: n gin d thc hin.
Nhc im: hao tn nhiu ha cht ra sn phm.
Phng php Staudenmeier: [3]
u im: n gin.
Nhc im: thi gian phn ng lu, h khng an ton vi ngi lm th
nghim.
Phng php Hummers: [4]
u im: thao tc an ton, to c graphite oxide vi hiu sut cao.
Nhc im: phc tp qua nhiu giai on.
1.3.2. Cu trc v tnh cht ca GO
C nhiu m hnh a ra m t cu trc ca graphite oxide nhng m hnh
ca Lerf Klinowski ph bin hn c. Theo , graphite sau khi oxi ha, trn mt
phng nm ngang ca cc lp c cc nhm hydroxyl, epoxy.. v trn cc gc ca
mt phng nm ngang c th hnh thnh cc nhm chc carbonyl hoc carboxylic[5]

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Hnh 1.6 Cu trc ca graphite oxide (GO) theo m hnh ca Lerf Klinowski
Cc vng thm, cc ni i, cc nhm epoxide c cho l nm trn mng
li Carbon gn nh phng, trong khi carbon ni vi nhm OH hi lch so vi cu
trc t din dn n cu trc lp hi cong. Cc nhm chc c cho l nm c trn
ln di cc lp GO. V mi lp u cha cc nhm chc c oxygen mang in
tnh m, do c lc y xut hin gia cc lp, ng thi lm cho GO th hin
tnh a nc v trng c trong nc. Hn na, vic to lin kt hydrogen gia
cc mt phng thng qua cc nhm hydroxyl, epoxide v nc khin cc khoang
GO c nong rng ng k hn so vi graphite (0.65-0.75nm so vi 0.34nm, c
xc nh thng qua gin XRD).

Hnh 1.7 Lin kt hydro gia cc lp graphite oxide [2].

T nhng tnh cht trn , cc nh khoa hc hy vng rng t graphite oxide c
th bc tch cc lp ra vi nhau mt cch hon ton (trng thi exfoliated), sau
kh cc lp graphene oxide ny v cc lp graphene hi phc cc tnh cht vn
c ca graphene.

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7,5 8,0

b
a
Hnh 1.8 Cu trc graphite oxide (a) v graphene oxide (b)
1.3.4. Cc phng php kh GO
Tuy khi nim graphene c t lu, nhng vic tng hp chng vi s
lng ln lun gp kh khn. Nhng nghin cu gn y u tp trung vo nguyn
liu u l GO. Sau GO c kh bng nhit (thermal), in ha hay ha hc
khi phc li tnh cht ca graphene.
Kh bng in ha: y l k thut s dng ngun in ngoi kh cc
mng graphite oxide thnh graphene. Trong phng php graphite oxide ny c
phn tn trong dung mi (thng l nc) ri sau c tch bc thnh graphene
oxide , tip theo graphene oxide c ph ln (thy tinh, vng .) cui cng
ghp mt in cc (dn in nu khng dn in) vo lp graphene oxide va
ph. Trong trng hp graphene oxide c ph trc tip ln in cc dn in th
khng cn . Sau thit lp h in ha cho qu trnh kh din ra.Vi qu trnh
kh graphene oxide, phn ng bt u xy ra ti th (-0,6 V v cao nht l -0.87 V).
Thi gian phn ng rt nhanh khong 300 giy v c th ko di n 5000 giy.
Kh bng nhit: y l phng php s dng nhit thiu hy cc nhm
chc trn b mt GO ng thi tng p sut khin cc lp GO tch ri nhau.
Quy trnh: khi gia nhit, cc nhm chc trn GO b kh thnh CO2 (vic kh
cc nhm chc thnh CO2 tng ng vi vic gim khong 30% khi lng ca sn

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phm), CO2 bay i to p sut bn trong cc lp. nhit cao vic nc bn

trong cc lp bay hi cng to nn mt p sut ln. Cc tnh ton c lng lc
lin kt van der Waals gia cc lp graphite l khong 26 Mpa, p sut to ra c
t kh CO2 v nc cn st li trong GO ln lt l 100 v 60 Mpa, c 2 p sut to
c ny u d thng c lc lin kt gia cc lp graphite. Do , cc lp
graphite oxide di tc dng ca p sut ln b tch ra to thnh cc tm n lp
graphene[7].
Kh bng phng php ha hc: y l phng php dng cc cht kh
ha hc (nh hydrazine, NaB

, Iodo, Hidro, NaHS

v.vv.) phn ng vi cht

oxi ha l graphene oxide nhm kh cc nhm chc ha hc v chuyn Csp3 thnh

Csp2. Do khi phc li tm n lp graphene vi nhng tnh cht c bit vn c.
Quy trnh: graphite oxide c phn tn hon ton trong mi trng acid,
base hay nc (ty iu kin phn ng) thnh dung dch graphene oxide. Sau ,
mt lng cht kh ha hc c thm vo dung dch to thnh h oxi ha kh.
Hin c 2 phng php kh graphene oxide l thc hin trong iu kin kh
ng (c khuy) hay kh tnh (khng khuy).
Theo cc nghin cu gn y, phng php x l bng nhit, in ha hay
phng php kh ha hc (trong iu kin kh ng) khng to c cu trc xp
graphene 3D, ch c phng php kh bng ha cht mi cho cu trc xp graphene
3D.
1.4. Vt liu xp trn c s graphene
Xut hin t nm 2004 n nay, graphene l ti c nghin cu v pht
trin rt nhiu, c mnh danh l vt liu thn k. V trong nm nm tr li y,
mt vt liu mi da trn c s graphene: xp graphene vi cu trc 3D c tng
hp thnh cng, nhanh chng thu ht s ch ca gii khoa hc vi nhiu ng
dng, gp phn m rng thm tim nng ca vt liu graphene.

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1.4.1 Xp graphene
Xp graphene 3D l vt liu da trn c s tm graphene 2D. Theo , cc
tm graphene khi xp chng mt cch mt trt t s to nn cu xp graphene 3D
v nh hnh.

Hnh 1.9 Xp graphene.

V dng cu trc xp 3D nn cc tnh cht ca graphene (dng tm 2D) b
gim bt nh din tch b mt, tnh cht dn in, dn nhit Nhng vi xp
cao, khi lng ring thp, l xp c kch thc micromet cho php cc ion c th
hp ph v gii hp nn xp graphene li l vt liu tim nng mang li mt s ng
dng trong nhiu lnh vc nh:
Y hc: to nn trong k thut nui cy t bo (substrate for cell growth) , to
khung cho m (tissue scaffolds), l v ca vt liu mang thuc (drug-delivery) [8]
Vt liu hp ph, cm bin: xp graphene s dng lm vt liu trong cc
thit b cm ng, lnh vc xc tc
[12]

[9] [10] [11]

v vt liu hp ph du y tim nng

.
in t- nng lng: xp graphene rt c k vng trong vic ch to siu

t in, lu tr v chuyn i nng lng[13] [14].

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1.4.2 Phng php ch to xp graphene.

D ch mi c nghin cu gn y nhng xp graphene c nhiu quy trnh
tng hp khc nhau nh: quy trnh tng hp xp graphene khng s dng cht kh
ha hc

[13]

hay s dng cc cht kh ha hc l HI, Vitamin C..

cht to mng khng gian nh cc cation 2+ (Mg2+, Ca2+)

[16]

[15]

hay s dng

v cc amine nh

EDA (ethylene diamine) [17]

Hnh 1.10 M t qu trnh to mng khng gian trong qu trnh tng hp xp

graphene 3D s dng cation[16].
Tuy xp graphene c nhiu quy trnh tng hp nhng u c mt im
chung l c tng hp da trn phng php kh tnh. Phng php kh tnh l
phng php kh in-situ trong qu trnh kh v qu trnh t sp xp cc tm
graphene din ra cng mt lc. Phng php kh ny thc hin trn quy trnh sau:

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Hnh 1.11 Quy trnh tng hp graphene t GO

Hnh 1.12 M hnh kh tnh

Nguyn l ca phng php ny l[13] [15]:
GO cha cc nhm chc COO-, -OH, C=O nn mang tnh a nc do
c th phn tn hon ton (di tc dng ca sng siu m) to thnh graphene
oxide (h huyn ph). Khi qu trnh kh tnh (khng c khuy) xy ra (di tc
dng ca nhit , p sut, cht kh), cc nhm chc trn b mt graphene oxide b
mt i, tnh k nc ca tm graphene oxide tng ln v c xu hng t li, xp
chng ln nhau. Cc tm ny c th xp song song vi nhau, hoc an cho m
khng tun theo mt quy lut sp xp c trt t. Kt qu l xp graphene 3D l xp
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c cu trc v nh hnh (hnh 1.13c,d,e) v c kch thc l xp khng u (kch

c micromet). Lc lin kt gia cc tm graphene trong khi xp l lc vt l nh:
tng tc , lin kt Vander Wall v lin kt hydrogen. Bn cnh , qu trnh
cc tm graphene kt t li s y nc ra khi cu trc khin cho gel graphene c
hnh dng nht nh (hnh dng ca bnh phn ng) (hnh 1.13b). Graphene c
tng hp theo hng bottom- up bng phng php ha hc kh t c trng thi
kh hon ton m vn cn mt s nhm chc phn cc trn b mt, chnh cc nhm
chc ny to lin kt hydrogen vi nc iu ny l gii cho gel graphene thu c
c cha nc bn trong cu trc v lin kt ny cng gp phn to khung nng
cho gel graphene trong qu trnh tng hp.

Hnh 1.13 Gin XRD ca GO (mu xanh), graphite (mu en), xp graphene
(mu ) v hnh cc mu graphene oxide (a), gel graphene (b), xp graphene
(c), hnh chp SEM ca xp graphene (d,e)
1.4.3. Mt s nghin cu tng hp xp graphene.
1.4.3.1 Phng php kh thy nhit to xp graphene khng s dng cht
kh[13].
Vo thng 3 nm 2011, cc nh khoa hc Yuxi Xu, Kaixuan Sheng v cc
cng s thuc i hc Thanh Hoa cng b trn tp ch ACS Nano phng php
kh thy nhit to xp graphene khng s dng cht kh. Theo bi bo ny, xp
graphene c tng hp dng nguyn liu l GO theo quy trnh sau:

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GO c phn tn vo trong nc to dung dch huyn ph. Sau , dung

dch huyn ph c cho vo bnh Teflon (h autoclave) v gia nhit ln 180 C
trong 24 gi. Kt thc qu trnh kh thy nhit thu c gel graphene. Gel graphene
c lm kh to xp graphene 3D.

Hnh 1.14 Gel graphene trc v sau khi kh tnh (a), xp graphene (b), nh SEM
xp graphene (c,d,e), bng o in tr ca xp graphene (f).
Bi bo tng hp thnh cng xp graphene vi dn in khong
5.

S/cm, modul tr (storage modulus) t 450kPa- 490kPa. Xp graphene 3D

c k vng ng dng lm siu t in vi in dung 175F/g. bn nhit ca

xp t nhit phng n 100 C.
1.4.3.2 Phng php kh thy nhit to xp graphene s dng cht kh [15]
Thng 4 nm 2011, trn trang RSC ng ti cng trnh nghin cu ca hai
nh khoa hc Wufeng Chen v Lifeng Yan v tng hp xp graphene 3D bng
phng php kh thy nhit s dng cc cht kh ha hc. Theo , xp graphene
3D c tng hp theo quy trnh nh sau:

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GO c phn tn vo trong nc to dung dch huyn ph. Sau cc tc

cht kh ha hc (Vitamin C, HI,

, hydorquinon) c thm vo

dung dch huyn ph v ton b dung dch cho vo bnh Teflon (h autoclave) v
gia nhit ln 95 C trong 3 gi. Kt thc qu trnh kh thy nhit thu c gel
graphene. Gel graphene c ra sch v lm kh bng phng php ng c.
Ring vi xp

, sau khi ng c thu c khi xp, khi xp ny tip tc

c gia nhit ti 400 C trong 5 gi trong mi trng chn khng ( kh ht cc

nhm chc vn cn trn b mt tm graphene).

Hnh 1.15 Xp graphene (a), Hnh SEM ca xp graphene (b)

Kt qu bi bo thu c nhiu xp graphene ng vi mi cht kh khc
nhau. Trong xp graphene c tng hp bng s dng cht kh HI cho dn
in cao nht.

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Bng 1.2 So snh kh nng kh GO ca cc cht kh [15]

Cht kh

Vitamin C

Na2S

HI

NaHSO3

dn in (S/m)
Khi lng ring
(mg/cm3)
T s C/O

23
21

6.8
15

110
37

17
18

NaHSO3
(chiu x)
87
15

6.8

5.8

8.5

7.0

10.1

Bi bo tng hp xp graphene c in dung khong 156 F/g 166 F/g,

modul n hi khong 28KPa - 0.13MPa. Xp graphene rt nh, xp vi khi lng
ring 18mg/ cm, kch thc l trng khong t 3m- 6m.
1.4.3.3 Phng php kh thy nhit to xp graphene s dng Ammoniac [12]
Xp graphene c cng b trn tp ch Materials View (Wileyonlinelibraly
6/2012) bi cc nh khoa hc Hengchang Bi , Xiao Xie, Rodney S. Ruoff * v cc
cng s ti Trung Quc v M. Theo nghin cu ny, xp graphene c s dng
lm vt liu hp ph cc dung mi hu c v du m.
Phng php iu ch xp graphene:
Xp graphene c iu ch t nguyn liu u l GO. GO c phn tn
trong hn hp 35ml nc ct v NH3, sau hn hp c khuy siu m trong
15pht. Hn hp c mu en sm s c a vo bnh kn v gia nhit n 180C
trong 24gi. Sau ngui v nhit thng. Gel graphene sau khi c thu li
s tip tc s dng phng php ng c trong 48 gi thu xp graphene.
Tnh cht ca xp:
Xp graphene l xp nano, c ch to trn c s kh tnh GO. Kho st
cu trc xp cho thy xp l xp microporous, khong cch gia cc tm l 570620 micromet.

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Hnh 1.16 Cu trc v qu trnh hp ph du ca xp, qu trnh hp ph du

trong thi gian 80 giy ca xp (a-f),
gc thm t (g), nh SEM(h,i), nh TEM (j).
Xp graphene c kh nng hp ph t 20 n 80 ln khi lng du so vi
khi lng ban u ca xp (hnh 1.17). Xp c th hp ph cc dung mi l du,
cht bo v c dung mi phn cc nh dimethyl sulfoxide.

Hnh 1.17 Kh nng hp ph dung mi ca xp graphene

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Tnh cht ny c c l do: xp c ngun gc hu c v c cu trc l cc

tm graphene c gin cch nhau. Gc thm t ca xp t 1142, do xp l
vt liu k nc nn d dng hp ph du v cc dung mi hu c khng phn cc
nh cht bo, dung mi hu c. Mt khc, qua qu trnh kh graphene oxide to
xp graphene, mt lng nh cc nhm chc nh hydroxyl, carbonyl ..cn trn b
mt xp lm cho xp c kh nng hp ph mt s dung mi phn cc. Tnh cht
trn ca xp graphene c ng dng nhiu trong vic hp ph cc dung mi c
hi. Theo cc gi tr o c, xp c khi lng ring thp (density = 12 mg 5/
cm) v din tch b mt ring ln t 423m/g (BET) lm tng din tch tip xc t
tng hiu sut hp ph.
Kh nng thu hi dung mi v ti s dng xp:
Thu hi dung mi v ti s dng xp l yu cu quan trng i vi vt liu
hp ph du khi vn nhim mi trng ngy cng gia tng.. Bng cch chng
ct, du sau khi hp ph c th c thu hi. Xp graphene c kh nng thu hi du
t 99,9% v gim 1% kh nng thm ht sau 10 ln ti s dng. Do xp
graphene c k vng rt ln trong lnh vc ch to vt liu hp ph.
1.5.Mt s k thut v phng php nghin cu
1.5.1 Phng php ng c (Freeze Drying or Lyophillisation)
Trong qu trnh ch to xp graphene, vic tch nc ra khi gel graphene
m khng lm thay i, ph v cu trc ca xp l mt vn kh khn. Do nc
chim cc l trng c kch thc rt nh ( c micromet) v khi lng ca nc
trong gel graphene ln ti 90% . Nhm gii quyt vn kh khn ny, cc nh
khoa hc p dng phng php ng c vo trong qu trnh ch to xp
graphene.
Phng php ng c (hay cn gi l ng kh, sy thng hoa) do k s
G.I.Lappa Stajenhexki pht minh 1921 ti Nga v c s dng rt rng ri trong
cc ngnh cng nghip thc phm v dc phm. u im ca phng php ny l

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tch loi nc ra khi cc loi thc phm (dc liu) m khng lm ph v cu trc
cng nh bin i cc tnh cht , thnh phn ca thc phm (dc liu).
1.5.1.1 C s khoa hc ca phng php ng c [19]
Trong t nhin, nc tn ti 3 trng thi l rn ,lng , kh (gin pha ca
nc).

Hnh 1.18 Gin pha ca nc

Tch nc th lng ra khi vt liu l qu trnh chuyn nc sang th kh
v nc bay hi. Hai cch tch c p dng:
Sy thng thng: l qu trnh chuyn nc t th lng sang th kh (ng
a-b-c hnh 1.18). y l qa trnh sy s dng nhit cao vi nhc im l
khng gi c cu trc, tnh cht ban u ca vt liu.
ng c: l qu trnh chuyn nc t th lng sang th rn, sau nc
thng hoa. Qu trnh ny gip cho vt liu sau khi tch nc vn gi li c cu
trc, tnh cht nh ban u.

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Hnh 1.19 Biu din qu trnh ng c.

1.5.1.2. Quy trnh ng c [19]
Quy trnh ng c gm 3 giai on: lm ng, thng hoa nc v bc hi
m.
Giai on 1: Lm ng vt liu, chuyn nc trong vt liu t th lng sang
th rn. Yu cu ca giai on ny l nc c ng bng tht nhanh to thnh cc
tinh th rt nh ( nhit -50 0C n -800C), trnh lm ph hy cu trc ca vt
liu.
Giai on 2: Thng hoa nc, nc chuyn t th rn sang th kh trong mi
trng chn khng vi p sut < 4.58mmHg (di im bar ca nc) v nhit
-500C.
Giai on 3: l giai on bc hi m cn li trong vt liu (cn goi l sy
chn khng vt liu). Mc ch ca giai on ny l lm bay hi m lin kt trong
vt liu. Khi kt thc giai on ny, m ca vt liu t t 2% ti 4% .

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Hnh 1.20 My ng c
1.5.2. Phn tch nhiu x tia X (X-Ray)
Mt phng php phn tch cu trc tinh th ca vt liu, y l phng
php chiu mt chm tia X ti mu, ti y xy ra qu trnh nhiu x, pht ra cc tia
th cp v cho mi vi iu kin theo nh lut Bragg :
nh lut Bragg

n = 2dsin

Hnh 1.21 Nguyn l chiu x tia X

Nh vy ch nhng cu trc kt tinh th mi cho mi trn gin XRD
(khong cch d theo 2). Mi kiu kt tinh khc nhau th c d khc nhau nn dn
n v tr cc mi trn gin cng khc nhau. T ta c th phn bit nh tnh

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cc kiu tinh th khc nhau, XRD cng c th phn tch nh lng thnh phn pha
da vo din tch mi trn gin .
1.5.3. Ph hng ngoi (FT-IR)
Da trn dao dng ca cc nguyn t, ch yu l s thay i v moment
lng cc. Cc nguyn t trong phn t dao ng khng ngng v tng tch ln
nhau, mi nguyn t li c s dao ng khc nhau. Nh vy, cung cp thng tin v
cu trc phn t, nh danh cc nhm chc phn cc trong vt liu, nhn din hp
cht.
1.5.4. Phng php o ng nhit hp ph - kh hp ph nit (BET)[19]
Vt liu hp ph du c xc nh din tch b mt ring bng cch p dng
phng trnh hp ph ng nhit theo Braunauner- Emmett- Teller (BET).
p dng phng trnh BET o b mt ring:
Phng trnh BET:

Trong :
P- p sut cn bng.
P p sut hi bo ha ca cht b hp ph nhit thc nghim.
V th tch ca kh b hp ph p sut P.
Vm - th tch ca lp hp ph n phn t tnh cho 1 gam cht hp ph trong
iu kin tiu chun.
C- hng s BET.

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Hnh 1.22 Dng th ng thng BET

th :

theo P/ P l mt ng thng, t c th xc nh Vm

v C. Bit Vm, ta c th tnh c din tch b mt cht hp ph:

S
Trong :
N: s Avogadro.
Wm: b mt chim bi mt phn t cht b hp ph lp n phn t.
Vo: th tch ca mt mol kh iu kin chun (22400 cm/ mol).
1.5.5. Knh hin vi in t qut (SEM)
Knh hin vi in t qut (SEM) s dng 1 chm in t hp (chm cc
electron) qut trn b mt mu, vic to nh mu dc thc hin thng qua vic ghi
nhn v phn tch cc bc x pht ra t b mt vt liu khi tng tc vi b mt
mu. Do cung cp thng tin b mt cng nh hnh thi ca vt liu.
1.5.6. Phn tch gim cp nhit Thermo Gravimetric Analysis (TGA)
TGA k thut phn tch n gin tnh khi lng mu vt liu mt i (hay
tng ln) theo nhit . Vt liu c gia nhit v b gim khi lng do s bay hi

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nc hoc t cc phn ng ha hc chuyn ha vt liu thnh kh. Tuy nhin cng

c mt vi vt liu tng khi lng sau khi gia nhit do phn ng vi kh quyn
trong cc mi trng. Khi tin hnh phn tch gim cp nhit, cu trc ca mu b
ph hy ng thi cho bit ln, gii hn nhit dn n cc phn ng xy ra v
bn nhit ca vt liu.

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Mc tiu ca ti :
Vi cu trc xp, nh, dn in cao, din tch b mt ln, xp graphene 3D
ang l vt liu xp cho nhng ng dng y tim nng trong cc lnh vc y sinh,
vt liu hp ph, in t ,nng lng Da trn c s l thuyt v vt liu
graphene, chng ti xin a ra quy trnh tng hp xp graphene. Theo , xp
graphene c ch to t graphite thng qua trung gian GO. T GO chng ti s s
dng phng php kh tnh v qu trnh ng c kho st qu trnh to xp
graphene vi cc cht kh khc nhau nh:
-

Cht kh Vitamin C: y l cht kh thn thin vi mi trng, gi thnh

r, mang li kt qu kh kh hiu qu. [15] [23]

Cht kh NH3: y va l cht kh va gip to mi trng phn tn

graphite oxide thnh graphene oxide, h tr cho qu trnh kh thy nhit
nhit v p sut cao. [12]

Cht kh HI: y l cht kh mang li kt qu kh mang li hiu qu cao

cho vt liu graphene ng dng trong dn in. [15] [24]
Vi mc tiu ni trn, ti s c tin hnh vi cc ni dung sau :
Tng hp graphit oxide bng phng php Hummers
Ch to gel graphene bng phng php kh tnh vi cc tc nhn
kh ln lt l : vitamin C, NH3, HI.
Ch to xp graphene t gel graphene thng qua quy trnh ng c.

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Phn 2. Thc nghim

2.1. Thit b v dng c
Pipet 1.00ml, 5.00mL, 25.00mL.
Phu nh git.
My khuy c IKA, model RW16B, c.
My khuy t iu nhit IKA, model RCT basic, c.
My c quay BIBBY model RE100B, M.
My li tm, phng th nghim Polymer, trng H KHTN
Bn siu m ELMA, model LC60H, HF- Frequ: 36kHz, c.
Thanh siu m model UP400S, HF- Frequ: 24kHz, c.
T sy VENTICELL, M.
Cn phn tch Sartorius, chnh xc 0.0001g.
Cn in t, model EK-610i, chnh xc 0.01g.
My chp XRD gc rng, vin Du kh, Tp. H Ch Minh.
My o TGA, Trung tm Manar, H Quc Gia Tp. H Ch Minh.
My chp SEM, Vin khoa hc v cng ngh.
My ph hng ngoi FT-FT-IR, Trung tm Manar, H Quc Gia Tp. H Ch
Minh.
My chp BET, Trung tm Manar, H Quc Gia Tp. H Ch Minh.
-My ng c, phng Hu C, H KHTN.
2.1. Ha cht
Graphite: sigma.
Acid sulfuric 98%, H2SO4, Trung Quc.
Sodium nitrat, NaNO3, tinh khit 99%, Trung Quc.
Kali permanganat tinh khit, KMnO4,Vit Nam.
Hydrogen peroxide 30%, H2O2, Trung Quc.
Etanol 99% tinh khit, Vit Nam.
Aceton tinh khit, Chemsol, Vit Nam.
Acid Iodua, HI, Trung Quc.

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Vitamin C, borid acid, Trung Quc.

Amoniac,

, hm lng 25%, Trung Quc.

Acid acetic,

, Trung Quc.

Nc ct.
2.3. Thc nghim
2.3.1. Quy trnh thc nghim ch to Graphite oxide (GO)

Hnh 2.1 H tng hp GO

Oxi ha graphite bng phng php Hummers theo quy trnh nh sau:
Khuy 10.0 g graphite v 5,0 g
bnh cu 2 mnh 0 C. Cho t t 30 g

trong 230 ml

m c trong

vo hn hp trn, tip tc khuy

mnh hn hp trong 30 pht. Nng nhit ca bnh phn ng ln 35 C v duy tr

nhit ny trong vng 1 gi 30 pht phn ng oxi ha xy ra, dung dch s dn
chuyn mu nu vng c kh mu nu thot ra v tng dn nht. Sau gim
nhit ca h xung 15 C v thm 460 ml nc ct vo bnh phn ng, c khi
trng thot ra mnh, dung dch c mu nu vng sng. Tip tc nng nhit hn
hp ln 98 C v gi trong vng 15 pht. Kt thc 15 pht thm 1000 ml nc ct
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vo hn hp. Sau khi thm nc ct, h nhit v

hn hp kh

ri thm 500 ml

vo

, khuy trn u dung dch c mu vng

sng, sau ngui v nhit phng. GO c tch ra khi hn hp bng cch

ly tm v ra li nhiu ln vi nc ct (khong 7 ln) v PH = 5- 6 loi b ht
acid v ra li ln cui vi aceton. Sn phm cui cng thu c c dng gel mu
nu.

Hnh 2.2 S oxi ha graphite

Hnh 2.3 H GO huyn ph sau khi

tng hp

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2.3.2. Qu trnh tng hp gel graphene t GO bng phng php kh

tnh.
Qu trnh kh GO c thc hin ln lt bng cc cht kh Ammoniac,
Vitamin C v HI thng qua phng php kh tnh. Mc ch ca qu trnh ny l
to cc h gel graphene , t chun b cho qu trnh to xp graphene. Cc mu
rGO sau khi tng hp c kho st cc tnh cht thng qua cc phng php TGA,
FT-IR, XRD thy c kh nng kh ca tng cht.

Hnh 2.8 Hn hp Graphene oxide v cht

Hnh 2.9 H autoclave

kh trc khi phn ng

2.3.2.1. Quy trnh kh tnh GO s dng cht kh l ammoniac (rGO- NH3) [12]

Qu trnh c thc hin nh sau:

Cn 0,057g GO cho vo bnh phn ng, sau thm 25,00 ml nc ri em
hn hp nh siu m (siu m thanh) cho n khi GO phn tn hon ton trong
nc. Sau thm 12,00 ml Ammoniac (tng th tch dung dch nc +
ammoniac=37ml). Sau hn hp c nh siu m ( my nh siu m bn)
trong 25 pht. Sau khi nh siu m xong, hn hp c a vo bnh thp kn ( h
autoclave) v tng nhit ln 180 C trong 24 gi. Sau 24 gi, gel GO c ly ra v
ra sch bng nc ct v pH= 7. Cui cng, gel rGO-NH3 em i ng c thu sn
phm.

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Hnh 2.10 S kh tnh s dng cht kh ammoniac

2.3.2.2. Quy trnh kh tnh GO s dng cht kh Vitamin C (rGO- VitC)

[15]

[23]

Quy trnh c thc hin nh sau:

Bt u cn 0.060g GO vo ly thy tinh sau thm 30,0ml nc. Dung
dch c nh siu m (siu m thanh) cho n khi phn tn hon ton GO trong
nc. Sau thm vo dung dch mt vi git ammoniac iu chnh pH dung
dch 10. Tip tc thm 0.30g vitamin C vo dung dch. Sau dung dch c a
vo bnh phn ng 30ml kn ri nng nhit ln T = 95 C trong 3 gi. Sau thi gian
kt thc phn ng, mu c ly ra v ra sch v pH= 6. Sau cng mu c em
i ng c (T= -44 C, p = 0.001bar) thu sn phm.

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Hnh 2.11 S kh thy nhit s dng cht kh Vitamin C

2.3.2.3. Quy trnh kh tnh GO s dng cht kh HI. (rGO- HI) [15] [24]
Quy trnh c thc hin nh sau:
Cn 0.057g GO vo ly thy tinh sau thm 20 ml Acetic acid. Sau nh
siu m ( s dng siu m bn) hn hp cho n khi GO phn tn tng i trong
acid. Thm tip 2,00 ml HI vo dung dch GO/ Acetic acid. Tip dung dch a
vo bnh phn ng 30 ml ri nng nhit ln T = 95 C trong 3 gi. Kt thc phn ng
mu c ra bng NaHC

O v Aceton cho n khi ht acid v pH dung dch

bng 6. Sau khi ra sch, mu c em i ng c (T= -44 C, p = 0.001bar). Sau

cng, khi kt thc qu trnh ng c thu c sn phm.

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Hnh 2.12 S kh tnh s dng cht kh HI

2.3.4. Tng hp xp graphene t gel graphene bng phng php ng
c
Cc gel graphene sau khi tng hp t qu trnh trn s c ng c to xp
graphene. Xp graphene thu c sau qu trnh ng c s c kho st cc tnh
cht thng qua vic o din tch b mt (BET) v hnh chp SEM.

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Phn 3. Kt qu v bn lun
3.1. Kt qu tng hp graphite oxide theo phng php Hummers
3.1.1. Gin XRD ca mu graphite v GO

Hnh 3.1 Ph XRD ca mu GO v graphite

Gin XRD ca graphite c mi gc 2

= 26,50 v d002 = 3,3721 .

Cng mi rt cao cho thy graphite ban u c kt tinh cao, cu trc tinh th
gn nh hon ho. Trong khi , gin XRD ca GO cho thy c s di mi v
gc 2 = 11,50 v cng mi kh thp so vi graphite cho thy GO khng cn
cu trc tinh th cao nh graphite. Khong cch d002 ca GO tng ln 7.7920

iu c d on l do sau qu trnh oxy ha, trn b mt graphite c nh ln

cc nhm phn cc nh Hydroxyl, Carboxylic, Epoxide to thnh graphite oxide.
Chnh cc nhm chc ny nong rng khong cch gia cc lp ca GO.

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3.1.2. Kt qu ph FT-IR ca mu GO

Hnh 3.2 Ph FT-IR ca mu GO

Ph FT-IR ca graphite oxide cho thy mi t rng 3382 cm-1 c trng
cho nhm hydroxyl OH. Do tn hiu mi rng v hp thu su, chng t cc
nhm hydroxyl c lin kt hydrogen vi nhau, hoc lin kt vi nc vn cn trong
khoang ca GO. Tip theo mi v tr 1724 cm-1 l dao ng ca nhm carbonyl
C=O v c th l nhm chc carboxylic. Mi 1615 cm-1l dao ng ca ni i
C=C ca carbon trn lp GO. Bn cnh cn xut hin cc mi 1070 1230
cm-1 c trng cho dao ng lin kt C-O, C-O-C ca nhm epoxide, C-OH.
Thng qua ph FT-IR mt ln na khng nh chnh cc nhm phn cc
Hydroxyl, Carboxylic, Epoxide lm gia tng khong cch gia cc lp trn
graphite oxide, c chng minh trn gin XRD trn.

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3.1.3. Gin TGA ca mu GO v graphite

Hnh 3.3 Gin TGA ca GO v graphite

Kt qu phn tch nhit trng lng ca graphite cho thy graphite b gim
cp, tuy nhin tng khi lng st gim khng ng k (2,7%). Mt d graphite
c bit n vi kh nng bn nhit cao, nhng trn graphite ban u vn c cc
nhm tp nh OH, metyl bin, . Cho nn kt qu TGA cho thy graphite vn
c s gim khi lng khi a ln hn 800 oC.
i vi graphite oxide gin TGA c s khc bit r rt, qu trnh gim
cp nhit bt u xy ra khi nhit ln n khong 500C v cho n 1100C khi
lng st gim l 8,57%. S st gim khi lng ny c cho l bay hi ca nc
trong cc khoang ca GO. c bit, s st gim khi lng cc i ti 222 oC vi
khi lng gim 34,2% . l s phn hy ca cc nhm carboxylic, hydroxyl,
peroxide trn b mt. Trong khong nhit tip theo c s gim lin tc khi
lng, iu ny do qu trnh gim cp ca cc lp graphite oxide (cu trc ca cc
lp graphite oxide khng c bn vng nh graphite).

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Kt qu phn tch TGA tng thch vi kt qu ca qu trnh phn tch

FT-IR cng nh kt qu XRD.
3.2. Kt qu phn tch tng hp cc cht kh trong qu trnh ch to gel

Hnh 3.4 Graphene oxide trc khi kh (a);

gel graphene to thnh sau khi kh (b)
3.2.1 Hnh nh cc mu gel GO c tng hp sau qu kh tnh

Hnh 3.5 Gel graphene sau qu trnh

Hnh 3.6 Gel graphene sau qu trnh

kh bng NH3

kh bng Vitamin C (VitC)

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Hnh 3.7 Gel graphene sau qu trnh kh bng HI

Nhn xt: gel graphene c tng hp thnh cng bng phng php kh
tnh s dng cht kh. Gel graphene to thnh c cu trc dng xp hnh tr. Khung
ca xp l cc tm graphene xp chng, phn th tch trng cn li trong xp do
nc chim gi.

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3.2.2. Cc kt qu phn tch cc mu rGO sau qu trnh kh

3.2.2.1 Gin XRD ca mu GO v cc mu GO sau qu trnh kh (rGO)

Hnh 3.8 Gin XRD ca mu GO, rGO-HI, rGO-VitC, rGO-NH3

T gin XRD cho thy, GO sau khi b kh bi cc cht ch HI,
Ammoniac, Vitamin C mt mi c c trng gc 2 = 11,5 v khng cn xut
hin mi c cng cao. iu ny c gii thch nh sau: khi qu trnh kh xy
ra, cc nhm chc trn b cc tm graphene oxide s gim dn, tnh k nc cng
tng ln. Do cc tm graphene oxide s c xu hng t tp li v xp chng ln
nhau. Qu trnh xp chng cc tm graphene oxide khng tun theo trt t, cc tm
ny c th xp song song hoc xin cho dn n xp graphene c cu trc v nh
hnh v khng xut hin mi c trng trn ph XRD.

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3.2.2.2. Ph FT-IR ca mu GO v rGO.

Hnh 3.9 Ph FT-IR ca mu GO, rGO-HI, rGO-VitC, rGO-NH3

T ph FT-IR cho thy qua qu trnh kh, cc mi c trng ca GO vn
xut hin nh mi t khong 3400cm-1 ca nhm OH, mi v tr 1724 cm-1 l
dao ng ca nhm carbonyl C=O ca nhm chc carboxylic. Mi 1615 cm-1l dao
ng ca ni i C=C ca carbon trn lp GO. Mi t 1000 cm-1 1300 cm-1 l dao
ng ca nhm C-O-C. Ngoi ra s xut hin mi CO2 cng cao trn mu rGOVitC v rGO-NH3 c th c l gii nh sau: trong qu trnh thc nghim, 2 mu
u c s dng NH3 lm tc nhn kh (vi mu rGO-NH3) hay to mi trng phn
ng (vi mu rGO-VitC), NH3 trong dung dch s phn ng vi CO2 (H2CO3) sinh
ra ngay trong qu trnh kh to mui (NH4)2CO3. Mui amonium cacbonate bm
trn sn phm kh v d b phn hy khin cho mi CO2 xut hin vi cng
cao trn ph FT-IR.

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Bn cnh , vic xut hin cc mi dao ng c trng trn ph FT-IR cho

thy qu trnh kh khng hon ton, mt s nhm chc a nc vn cn trn b
mt ca tm graphene. V th gel graphene sau khi tng hp vn gi nc trong cu
trc thng qua lin kt hydro gia cc nhm chc trn.
3.2.2.3. Ph tn x Raman ca graphite, GO v rGO

(b)
(a)
Hnh 3.10 Ph raman ca Graphite, GO v ca cc mu rGO
phn ny, s dng kt qu ph Raman nhm tm ra s khc bit nhn
danh rGO, thng qua vic so snh ph raman ca cc mu RGO vi GO v graphit.
i vi graphit, cc mi G (~1570 cm-1), D (~1330 cm-1) v 2D (~2700 cm-1) c
tm thy trn ph . Cng mi D c mi tng quan vi s hin din ca cc
khuyt tt xut hin trn tm graphit. Cng mi D cng ln tng ng vi t l
ID/ IG cng ln, xut hin nhiu khuyt tt trn mng. Tnh cht ny cng p dng
tng t i vi GO v rGO. Da vo gin (a), ta thy rng mi tn hiu D ca
Graphit c cng yu hn so vi GO v cc mu RGO. y l mt c im
quan trng nhm phn bit graphit vi GO v rGO. GO v rGO c cng mi D
ln chng t trong qu trnh oxi ha v kh c nhng bin i tc ng vo mng
cu trc gy ra nhiu khuyt tt. Theo nh kt qu thu c cng mi D ca 4
mu rGO kh u ln hn GO, iu ny mt ln na chng minh rng cc qu
trnh kh GO bn cnh loi b cc nhm phn cc trn GO th ng thi li

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nhiu sai hng dn n cc khuyt tt trn tm RGO. y cng l mt nhc

im ln nht ca qu trnh tng hp rGO t graphite oxide. Cc mu kh rGO thu
c u c t l ID/ IG ln, cho thy bt n trong cu trc ca mu cao, xut
hin nhiu khuyt tt trong cu trc.D dng nhn thy t l ID / IG ca rGO-HI l
cao nht , xut hin nhiu khuyt tt hn so vi hai mu kh cn li.
Bn cnh mi 2D (gin b) ca hu ht cc mu kh u c cng
cao hn so vi mu GO. iu ny chng t, qu trnh kh c hin tng ti cu
trc lin hp trn graphen nn xut hin mi 2D. Tuy nhin cc mi 2D khng cao,
y l nhc im kh ha hc cha hon ton, li nhiu khuyt tt.

Hnh 3.11 Biu t l cng ID/IG

3.2.2.4. Gin TGA ca mu GO v cc mu rGO sau qu trnh kh

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Hnh 3.12 Gin TGA ca cc mu GO v rGO-HI, rGO-VitC, rGO-NH3.

Theo gin TGA c th thy mt khi lng trong khong t nhit 150
C ti 400 C ca mu rGO-HI l thp nht so vi cc mu rGO-NH3, rGO-VitC v
GO. y l khong nhit din ra s phn hy mnh m ca cc nhm chc trn
GO. Ngoi ra, lng tro ca mu rGO-HI (74.25%) ln nht so vi mu rGO-NH3
(73.78%), mu rGO- VitC (53.11%) v thp nht l mu GO (38.66%). Do lng
tro thp hn cng nh ht gim khi lng cho thy cc nhm chc cn li trn
rGO-HI t hn mu rGO cn li. T c th kt lun rng HI l cht kh tt nht
trong s cc tc nhn kh.
3.2.2.5. Kt qu o dn in ca mu GO v rGO.
Mt trong nhng tnh cht quan trng nht, mang tnh quyt nh, l
dn in (hay thng qua in tr mt). dn in l bng chng thuyt phc
nht v kh nng kh ca mt tc nhn kh, ca mt phng php s dng.
dn in ca rGO khng ch ph thuc vo tnh hon ho ca b mt (cng hng

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lin tc, khng b khuyt tt) m cn ph thuc ln vo kch thc tm RGO v

phng php ch to mu trc khi o. Di tc dng ca qu trnh oxy ha kh
nhiu giai on, lm cho tm rGO b x vn, cho kch thc nh hn so vi
graphit ban u (1 lp graphit).
Trong ti ny, cc mu rGO c p vin v o dn bng my o 4 u d.

Hnh 3.13 Mu p vin i o d dn in

Bng 3.1: dn in v in tr mt ca cc mu.
Tn mu dy vin d (mm)
vin

in tr mt RS
(/o)

dn in
(S/m)

GO

0.18

rt ln

0.00

rGO-NH3

0.19

17.7

296.57

rGO-VitC

0.21

14.2

335.10

rGO-HI

0.18

3.23

1718.94

* dn in c xc nh bng cng thc: =1/(Rs x d), trong d c

n v l m, Rs n v l / th c n v l S/m. Nu d c n v l cm th c
n v l S/cm.
Rt d nhn bit c GO v rGO c kh t GO. GO hu nh khng dn
in do vi phm yu t cng dng in, cng dng qu b gn nh khng
c dng i qua cc tm GO. T bng s liu trn c th nhn thy rng mu rGO-HI
c dn in cao gp 5 ln so vi 2 mu rGO-NH3 v rGO-VitC. iu ny cho

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thy h thng in t pi ca tm graphene sau khi kh bng HI c phc hi v

lin hp tt. Qua ph Raman cho thy HI l tc nhn kh li nhiu khuyt tt.
Song ph Raman li khng cung cp thng tin nh lng v kh nng kh nhiu
hay t nn c th a ra gi thuyt rng: khi xt trn ton tm graphene, h thng
in t pi vn kt ni khng b t qung, nn cho dn cao. T c th khng
nh rng HI l tc cht kh tt hn NH3 v Vitamin C. Kt qu ny ph hp vi
kt qu TGA trc .
3.2.2.6. Kt qu tng hp xp graphene t gel graphene sau qu trnh ng c

Hnh 3.14 Cc mu rGO-NH3, rGO-HI, rGOVitaminC (vitC) sau khi ng c.

Nhn xt: Qua qu trnh ng c, ch c mu gel graphene kh bng HI l
to thnh xp graphene. Cc mu rGO kh bng Vitamin C v NH3 sau khi ng
c, gel graphene khng cn gi c cu trc dng khi, sn phm thu c c
dng bt.
Lp lun: Trong 3 mu gel graphene ch c mu rGO-HI l tng hp xp
thnh cng, chng t lin kt gia cc tm graphene trong gel graphene ca rGO-HI
bn hn rGO-NH3 v rGO-VitC. Trong xp graphene, lc lin kt gia cc tm
graphene l lin kt vt l gm tng tc [20], lc Vander Walls (khuch tn)
v lin kt hydrogen (gia cc nhm chc cn tn ti trn tm graphene sau qu
trnh kh) [13].

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Hnh 3.15. M hnh in t trn benzen (d) v 3 cu hnh sp xp ca vng

thm theo tng tc , kiu song song (a),
kiu xp cho (lch) (b), kiu ch T (c).
V cc tm graphene l mng nguyn t cacbon trng thi Csp2 vi h thng
rng khp nn tng tc c nh hng ln nht n bn ca gel
graphene. Do , khi qu trnh kh c hiu qu xy ra, cc nhm chc trn b mt
tm graphene b mt i cng nhiu th h thng lin hp ca c khi phc
cng ln, tng tc gia cc tm cng s tng ln khin xp graphene bn
hn. Bn cnh , phn ng kh cng ng thi lm tng tnh k nc cc tm
graphene khin lc khuch tn gia chng tng ln, gp phn lm tng bn ca
lc lin kt gia cc tm graphene.
T nhng nhn nh trn c th thy rng, kh nng kh ca cc tc nhn
kh s quyt nh n bn ca xp graphene. Theo , tc nhn kh hiu qu s
cho sn phm xp graphene bn. HI l mt tc nhn kh mnh hn NH3 v Vitamin
C, (iu ny c chng minh bng ph IR v gin TGA pha trn) vy nn
xp rGO-HI bn hn rGO-NH3 v rGO-VitC.
Xp rGO-HI sau khi tng hp thnh cng s c kho st cc tnh cht v
cu trc thng qua nh chp SEM v o din tch b mt BET.
3.3. Cc kt qu kho st xp graphene (rGO-HI)

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Hnh 3.16 Xp graphene rGO-HI sau ng c.

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3.3.1 Kt qu chp SEM xp graphene rGO-HI

Hnh 3.17 Hnh chp SEM mu xp rGO-HI cc kch thc khc nhau.
T kt qu chp SEM cc kch thc khc nhau cho thy xp graphene c
cu trc xp v nh hnh vi kch thc l xp c micromet (ph hp vi kt qu
XRD). iu ny c gii thch da trn tng tc gia cc tm graphene .

Hnh 3.18 M hnh in t ca vng thm theo tng tc , kiu song

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song (a), kiu xp chp (lch) (b), kiu ch T (c). [25]

Theo tng tc , cc tm graphene c th xp theo kiu song song, ch
T v kiu xp cho. Trong , nng lng lin kt ca kiu song song (sandwich)
khong -2.0 kcal/mol, kiu xp cho (parallel displaced) khong -2.8 kcal/mol, kiu
ch T (T-shaped) khong -2.7 kcal/mol [20] .Do khi qu trnh kh xy ra, cc tm
graphene s kt t li v c xu hng xp theo 2 kiu ch T hay kiu xp cho hn
l xp song song v c u tin hn v nng lng. Chnh s sp xp ny to nn
cu trc khung 3D v nh hnh ca xp graphene thay v cu trc lp trt t nh
graphite ban u.
3.3.2 Kt qu o din tch b mt ca xp graphene rGO-HI.
Din tch b mt ca xp graphene rGO-HI (dng bt) o c l 456,520
m2/g cn dng xp l 735.947 m/g [ph lc]. Din tch b mt ca xp rGO-HI
cao hn so vi xp c din tch b mt 426m2/g c ch to bi cc nh khoa hc
Trung Quc (mc 1.4.2.3). Vi din tch b mt cao m ra hng ng dng trong
lnh vc vt liu hp ph, xc tc cho xp rGO-HI. Theo kho st s b ca ti,
xp rGO-HI hp ph hn 70 ln khi lng du so vi khi lng ban u ca xp
(wt/wt = 70) . Kt qu ny cao hn rt nhiu so vi vt liu hp ph du hin nay
nh polymer (wt/wt =18) hay khong st (wt/wt = 14 18)[21] [12].
Bng 3.2 kho st khi lng hp ph du diezen ca xp rGO-HI
Ln
kho

Kh nng hp
Khi lng xp trc khi Khi lng xp sau khi
hp ph du diezen (g)

ph du W

st

hp ph du diezen (g)

0.0059

0.4613

77.19

0.0053

0.3471

64.49

0.0063

0.5131

80.44

0.0034

0.2663

77.32

0.0031

0.2191

69.68

(wt/wt)

Kh nng hp ph du trung bnh: 73 6

Kh nng hp ph du (W) = khi lng xp sau hp ph/ khi lng xp trc

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hp ph (wt/wt) [22]

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Phn 4. Kt lun v kin ngh

4.1. Kt lun
1/ tng hp Graphit Oxide t graphite bng phng php Hummers.
2/ tng hp gel graphene bng phng php kh tnh thng qua cc tc
nhn kh Vitamine C, NH3, HI. Trong cc tc nhn kh kho st, tc nhn kh HI
cho kt qu kh tt nht.
3/ thc hin qu trnh ch to xp graphene t gel graphene bng phng
php ng c. Kt qu thc nghim cho thy vi cc phng php kh tnh thy
nhit bng cc tc nhn kh Vit C, NH3, HI; ch c phng php kh GO bng HI
l c kh nng to xp. Kh nng kh cng cao th tng tc trong cu trc
r-GO cng tt , t lm tng kh nng to xp.
4/ kho st s b kh nng hp ph du ca xp graphene, kh nng ny
cao hn cc vt liu hp ph du hin ang s dng trong cng nghip.
4.2. Kin ngh
Do thi gian thc hin ti c hn, chng ti xin a ra mt s kin ngh
cho hng nghin cu ny. T c th m rng tim nng ng dng ca
ti trong thc tin.
Kho st, tng kh nng nn dn ca xp graphene t ng dng trong
vt liu hp ph du m.
Kho st cc tnh cht sinh hc t ng dng lm vt liu m, cht nn
s dng trong k thut nui cy t bo.
Kho st tnh cht in, nhit ng dng trong vt liu cm ng, dn in
v ch to t in.

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TI LIU THAM KHO

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Polymer Nanocomposites. Macromolecules 2010, 43, 6515- 6530.
[3]. Daniel R. Dreyer, Sungjin Park, Christopher W. Bielawski and Rodney S.
Ruo, The chemistry of graphene oxide,Chem.Soc.Rev 39, p 228-240, 2010.
[4]. G.I. Titelman, V. Gelman, S. Bron, R.L. Khaln, Y. Cohen, H. Bianco-Peled,
Characteristics and microstructure of aqueous colloidal dispersions, Carbon 43, p
641-649, 2005
[5]. C.Nethralvathi, Michael Rajamathi, Delamination, Colloidal dispersion and
reassembly of alkylamine intercalated graphitee oxide in alcohols, Carbon 44,2006,
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[6]. Dan Li, Richard B. Kaner, Graphenee-based meterials, materials science, 2008
[7]. Seung Hun Huh, (2010), Thermal Reduction of Graphenee Oxide,
Nanotechnology Convergence Lab, Korea Institute of Ceramic Engineering and
Technology (KICET), South Korea.
[8]. HN Lim, NM Huang, SS Lim, I Harrison, CH Chia4. Fabrication and
characterization of graphene hydrogel via hydrothermal approach as a scaffold for
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[9]. Z. H. Tang, S. L. Shen, J. Zhuang and X. Wang, Angew. Chem., Int.Ed., 2010,
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[10]. Z. S. Wu, S. B. Yang, Y. Sun, K. Parvez, X. L. Feng and K.Mullen, J.Am.
Chem. Soc., 2012, 134, 90829085
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[12]. Hengchang Bi , Xiao Xie , Kuibo Yin , Yilong Zhou , Shu Wan , Longbing He
, Feng Xu ,Florian Banhart , Litao Sun , Rodney S. Ruoff . Spongy Graphene as a

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Highly Efficient and Recyclables Sorbent for Oils and Organic Solvents, Adv.
Funct. Mater.2012
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