TP CH KHOA HC V CNG NGH, I HC NNG - S 3(26).

2008

XC TC QUANG HA TIO2 MICRO NANO

COMPOSIT MANG TRN VT LIU NANO
CARBON C CU TRC
TIO2 MICRO NANO COMPOSITES PHOTOCATALYST
CARRIED ON NANO CARBON MATERIAL WITH
MACROSCOPIC STRUCTURE
NG TUN ANH - NGUYN NH LM
Trng i hc Bch Khoa, i hc Nng
TM TT
Xc tc quang ha trn c s composit TiO2/Cacbon nano hin ang c u
t nghin cu rt nhiu trn th gii bi hot tnh quang ha cao v c kh nng
hp th hu ht cc bc x t mt tri. Khi hp th cc photon, xc tc ny c
th -xy ha hon ton cc hp cht hu c, to sn phm cui cng l CO 2 v
H2O. Nghin cu ca chng ti hng n mt loi xc tc quang ha hon ton
mi trn c s composit TiO2 thng mi, TiO2 sol-gel v Carbon nano, c
mang trn vt liu c cu trc. Loi xc tc mi ny cho php tng cng hot
tnh quang ha v gim gi thnh xc tc. Xc tc ny c ng dng ti
phng th nghim trong h thng thit b phn ng quang ha lin tc phn
hy cc hp cht hu c nhim trong nc thi.
ABSTRACT
Composite TiO2/Carbon nano based photocatalysts are being investigated
widely in the world because of their high photoactivity and their capacity of
absorbing almost of suns irradiation. By absorbing a photon, these catalysts can
promote the total oxidation of organic compounds to CO2, H2O products. Our
researches are now focused on the new photocatalysts based on composite TiO 2
commercial, sol-gel / Carbon nano with macroscopic structure. This new type of
catalyst allows amplifying the photoactivity and reducing the cost. These catalysts
were successfully applied in our laboratory for continuous systems to degradate
organic compounds in waste water.

1. t vn
Trong nhng nm gn y, titan dioxit (TiO2) c s dng nh mt xc
tc quang ha x l nhng vn nhim mi trng, c bit l loi cc
hp cht c hi trong nc thi [1-3]. Tuy nhin, ch c nhng bc x t ngoi,
chim khong 4% bc x mt tri [4], ng vi cc photon c nng lng ln hn
3,2eV mi c hp th v to ra hiu qu quang ha. Do , cc hng nghin
cu v tng kh nng quang ha ca TiO2 trong vng nh sng kh kin c pht
trin mnh s dng c hiu qu hn c tnh quang ha loi vt liu ny.
Trong nhng nghin cu gn y, ngi ta c bit ch trng n vic p
dng cc dng Cacbon nano ng (CNT) v Cacbon nano si (CNF) nh vo cc
c tnh u vit ca n: kh nng dn in rt tt, ng knh c kch thc nano,
hp ph cao v en tuyt i [5] v khi kt hp vi TiO2 to ra hot tnh

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quang ha rt mnh [6]. Cc loi xc tc quang ha trn c s composit TiO2/CNT

v ang c nghin cu nhiu nhng ch dng li vic kho st trn h
thng phn ng gin on. Xc tc c tng hp di dng bt gy kh khn cho
vic ng dng vo thc t v chi ph cao cho h thng lc xc tc [7]. Hn na,
phng php ph bin hin nay a TiO2 ln CNT l phng php sol-gel i t
cc tin cht ca alkoxide titan. Gi thnh ca alkoxide titan rt cao, cng thm
cc iu kin khc nghit khi nung thiu kt nhit cao khin cho gi thnh
xc tc tng ln rt nhiu.
Vi nhng l do nh trn, nghin cu ca chng ti hng n vic tng
hp ra loi xc tc quang ha mi dng composit ca TiO2 v nano cacbon:
cacbon nano ng a lp MWNT v cacbon nano si CNF mang trn vt liu c
cu trc. Loi xc tc mi ca chng ti c hot tnh tng cng nhiu ln so vi
cc loi tng c cng b, ng thi gi thnh gim ng k nh vic tn
dng hot tnh cao ca pha anatase TiO2 thng mi c trong thnh phn xc tc.
Vic kim tra hot tnh quang ha ca xc tc c thc hin bng phn ng phn
hy methylen xanh di bc x nh sng mt tri trong h thng thit b phn ng
gin on v lin tc.
2. Tng hp xc tc
Xc tc c tng hp vi 3 hp phn: TiO2 thng mi, TiO2 sol-gel v
Cacbon nano ng a lp (MWNT) hoc Cacbon nano si (CNF). TiO2 thng
mi (99% dng anatase, kch thc ht trung bnh l 1,7 micromet) t tp on
SENSIENT c s dng trc tip. TiO2 sol-gel c tng hp bng phng php
sol-gel t tin cht Ti(OC3H7)3. MWNT v CNF c tng hp theo phng php
kt t ha hc trong pha hi (CVD). y l cc sn phm ca cng trnh nghin
cu v cacbon nano ca TS Nguyn nh Lm, trng i hc Bch Khoa, i
hc Nng. Hnh 1 m t hnh nh bn ngoi v cu trc ca CNF sau khi c
pht trin v nh hnh trn m carbon thu c t knh hin vi in t qut
(SEM).

Hnh 1: nh bn ngoi v cu trc ca CNF mang trn m carbon (nh SEM).

Chng ti tin hnh tng hp xc tc quang ha trn c s TiO2, vi tn
gi micro nano composit, bng cch dn TiO2 thng mi c kch thc trung

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bnh 1,7 micromet (TiO2 TM) ln MWNT v CNF vi qua lp TiO2 sol-gel cng
c chiu dy c nano. Tn gi cho cc loi xc tc khi dng MWNT v CNF trn
vt liu c cu trc ln lt l micro nano composit 1 v micro nano composit
2 vi cc t l thnh phn theo khi lng nh sau:.
- Xc tc Micro nano composit 1: TiO2(TM)/TiO2 sol-gel/MWNT = 1/0,25/0,05.
- Xc tc Micro nano composit 2: TiO2(TM)/TiO2 sol-gel/MWNT = 0,8/0,2/0,7
Pha anatase ca TiO2 thng mi c s dng vi vai tr l pha quang
hot chnh trong xc tc ca chng ti. iu ny lm gim ng k gi thnh xc
tc composit v s dng c hot tnh cao ca TiO2 thng mi.
3. nh gi hot tnh xc tc
Hot tnh quang ha ca xc tc c nh gi da trn kh nng phn hy
cc hp cht hu c di tc dng ca bc x nh sng.
3.1. Cht phn ng
Trong nghin cu ny, chng ti nh gi hot tnh qua kh nng phn hy
Methylen xanh. Cc thng tin ca Methylen xanh (MB) c trnh by trong bng
1. Methylen xanh dng bt ban u c pha vo nc ct theo cc nng cho
trc (50, 100 v 200mg/l).
Bng 1: Mt s thng s ca Methylen xanh
Cng thc

Cu trc

C16H18ClN3S

ha tan
trong nc

Mu

Bc sng
hp ph

50 g/l

Xanh da
tri

650nm

3.2. Ngun sng

Chng ti s dng 2 ngun bc x nh sng khc nhau: n cao p hi thy
ngn (Osram 250 W) - cng sng ti v tr trn b mt ng phn ng l 57 klux
tng ng vi 83,4 W/m2 v nh sng mt tri c dng t 10h n 15h hng
ngy, cng sng trung bnh ti b mt ng phn ng l 78 klux tng ng
vi 114,2 W/m2.
3.3. Thit b phn ng (TBP)
Trong h thng phn ng gin on, chng ti s dng TBP hnh tr
bng thy tinh, ng knh 100mm, dung tch 300ml. H thng TBP lin tc
c thit k v ch to ti phng th nghim Lc ha du, trng i hc Bch
khoa, i hc Nng, gm cc ng thy tinh c ng knh 6mm, b dy thnh
ng 0,4mm; c b tr gia h thng cc tm knh phn quang (hnh 2). Lu
lng x l qua TBP c iu khin bng valve.

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Hnh 2: H thng TNP lin tc c ch to ti

trng i hc Bch khoa, H Nng
3.4. Qui trnh phn ng v phn tch mu
3.4.1. H thng phn ng gin on:
Mt lng xc tc tng ng 0,2g TiO2 c cho vo TBP (TiO2 TM,
TiO2 sol-gel, TiO2 sol-gel/CNT v micro nano composit 1), sau thm 100ml
dung dch MB 200 mg/l iu chnh pH = 3. Hn hp c khuy t trong bng
ti trong 1h qu trnh hp ph t cn bng. Mu u tin c ly ra xc
nh nng MB ban u trc khi phn ng. Sau hn hp huyn ph c
chiu sng bng n cao p thy ngn v khuy t lin tc vi tc khng i.
Mu c ly ra theo chu k trong sut thi gian phn ng. Sau khi ly tm tch xc
tc, nng MB trong mu c xc nh bng hp th quang trn my UVVis (JENWAY 6305) bc sng 650nm v xc nh ch s COD theo ASTM
D1252 ti Trung tm ng dng Tin b Khoa hc v Cng ngh, S Khoa hc v
Cng ngh Nng.
3.4.2. H thng phn ng lin tc:
Mt lng xc tc tng ng 0,7g TiO2 (micro nano composit 2 v
TiO2 TM-TiO2 sol-gelcacbon hot tnh) c cho vo TBP dng ng v lp vo
h thng. Dung dch MB nng 50 mg/l c iu chnh pH = 3 c cho
chy qua h thng thit b phn ng vi lu lng c khng ch. Ton b cc
ng phn ng c chiu sng bng n hoc nh sng mt tri. Qu trnh phn
tch mu c thc hin tng t i vi h thng phn ng gin on.
4. Kt qu v tho lun
4.1. Cu trc micro nano composit 1 thu c t knh hin vi in t truyn
qua.
Cc nh TEM ca xc tc micro nano composit 1 thu c trn hnh 3
chng minh bn c hc cao h xc tc phc hp ny sau khi b phn tn trong

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dung mi di tc dng ca vi sng cng cao. Hon ton khng c ng nano

carbon no nm ring l cho thy ton b cc ng nano carbon c dn rt tt
trn b mt ht TiO2 thng mi bng lp TiO2 sol-gel. Ti mi v tr c nano
carbon u c TiO2 sol-gel (v tr c mu en m trn nh), v b dy lp sol-gel
c kch thc rt nh, cha n 50 nm.

Hnh 3: nh knh hin vi in t truyn qua (TEM)

ca xc tc "Micro Nano Composite 1"
iu ny cho thy phng php tng hp xc tc ca chng ti l hon
ton ng n v nh hot tnh xc tc rt cao c thc nghim chng
minh khi kho st phn ng phn hy MB di tc dng ca nh sng.
4.2. Phn hy Methylen xanh di tc dng ca xc tc quang ha trn h
thng phn ng gin on
Quan h gia chuyn ha v thi gian phn ng trn cc cht xc tc
khc nhau c th hin trn hnh 4. Kt qu cho thy rng chuyn ha ca
TiO2 sol-gel thp hn TiO2 thng mi (TiO2 TM) do kh nng hp ph km ca
n [17]. Vi mu TiO2/CNT, giai on u CNT hp ph mnh MB nn lm gim
mnh nng MB trong dung dch, tuy nhin khi chiu sng th nng MB gim
chm. chuyn ha ca xc tc micro nano composit 1 ln hn TiO2 TM
khong 10%, v t 98% sau 3h chiu sng. iu ny chng minh s tn ti ca
hiu ng synergic gia cacbon nano v TiO2.
Ngoi ra chng ti cng kho st s phn hy MB trong mi trng
CO2. Mt lng xc tc khc tng ng 0,2g TiO2 v 100ml dung dch MB 50
mg/l. Sau 1 gi phn ng, mu dung dch sau c ly tm tch xc tc v phn
tch COD. Kt qu c th hin trn hnh 5. Kt qu cho thy mu micro nano
composit 1 c kh nng phn hy trit hn TiO2 thng mi. Sau 1h chiu
sng th hu nh tt c cc hp cht hu c b oxi ha hon ton to CO2 v H2O.
Cn phi ch rng: iu kin thng (25oC 1 atm), lng oxi ha tan trong
nc bo ha 9 mg/l [10]. Nh vy c th c th khng nh rng cc nguyn t
Hydro v Oxi hot tnh sinh ra trn b mt xc tc t qu trnh quang in phn
nc ng vai tr chnh trong vic kh v oxi ha cc hp cht hu c.

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chuyn ha, %

TP CH KHOA HC V CNG NGH, I HC NNG - S 3(26).2008

Hp ph

1 - TiO2 thng mi
2- Micro composite

Chiu sng

Thi
pht

gian,

Hnh 4: Chuyn ha ca MB theo thi gian Hnh 5: COD trcv sau 1 gi phn ng
Phn tch kt qu thu c trn xc tc micro nano composit 2 cng cho
kt qu tng t, tuy nhin trn CNF hiu qu quang in phn cao hn do cc
tm kim loi tn ti nh ca si nano carbon nh c chng minh trn cc
nh thu c t knh hin vi in t truyn qua (TEM, hnh 6) v qut (SEM, hnh
7).

Hnh 7: nh SEM thu c ch

composit vt liu CNF/m Carbon,
Hnh 6: nh (TEM) m t s
chng minh cc tm xc tc Ni b y ra
pht trin ca CNF trn cc tm
khi b mt cht mang trong qu trnh
xc tc Ni [12]
pht trin CNF. [12]
T cc kt qu thc nghim trn, chng ti xut c ch hot ng ca
xc tc micro nano composit theo 4 phn ng nh sau:
Ni/MWNT/TiO2 + h Ni-/MWNT+/TiO2
(1)
+
+
Ni /MWNT /TiO2
Ni /MWNT/TiO2
(2)
+
+
o
2Ni /MWNT/TiO2 + H2O(hp ph) 2Ni/MWNT/TiO2 + 2H +2OH
(3)
2Ni-/MWNT/TiO2+ + H2O(hp ph)2Ni-/MWNT/TiO2+Oo+ 2H+
(4)

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Oxi nguyn t v Hydro mi sinh ny vi hot tnh rt mnh v s thc

hin cc qu trnh oxi ha v kh cc cht hu c b hp ph trn b mt xc tc.
Cc qu trnh ny c th c m t trn hnh 8. Theo c ch ny, b dy lp TiO2
sol-gel nh hng rt ln n kh nng chuyn electron, b dy cng nh th hiu
qu chuyn cng cao. iu ny c khng nh r rng khi chng ti tin hnh so
snh hot tnh ca 2 loi composit trn c s CNF v cacbon hot tnh trn h
thng lin tc, c trnh by phn tip theo.

Hnh 8: C ch hot ng ca micro composit

chuyn ha, %

chuyn ha, %

4.3. Phn hy Methylen xanh di tc dng ca xc tc quang ha trn h

thng phn ng lin tc
Trn h thng ny, thi gian lu t chuyn ha MB 100% l 21
pht v 24 pht tng ng vi trng hp chiu bng nh sng mt tri v chiu
n cao p thy ngn. Quan h gia thi gian lu v chuyn ha c th hin
trn hnh 9.
2

Thi gian chiu sng, h

Thi gian lu, pht

Hnh 9: chuyn ha di n v Hnh 10: chuyn ha theo thi gian hot

nh sng mt tri theo thi gian lu ng ca xc tc composit TiO2 TM-SG /
CA
Mt lng xc tc composit TiO2 TM SG cacbon hot tnh (CA) vi
phng php tng hp tng t c th hot tnh ng thi so snh. Kt qu
cho thy mu xc tc trn CA cho hiu qu quang ha rt thp, bn c hc km
v gim hot tnh nhanh chng (hnh 10).
nh gi bn ca xc tc, chng ti cho h thng hot ng thi
gian lu c nh 24 pht v ly mu phn tch nh k. Khi chuyn ha gim
xung cn 95%, chng ti s tin hnh ti sinh xc tc v ti s dng xc tc. Xc
tc c ti sinh ch bng cch cho chiu sng di dng nc ct chy lin tc

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trong 20h. S thay i chuyn ha theo thi gian s dng v s ln ti sinh

c th hin trn hnh 11.

chuyn ha, %

Chiu sng
80h

Ti sinh ln 1

Chiu sng

Ti sinh ln 2

20h

Chiu sng

Ti sinh ln 3

18h

Thi gian, h

Hnh 11: chuyn ha theo thi gian ca xc tc Micro Nano Composit 2

Nguyn nhn ca s gim hot tnh xc tc c th c gii thch do cc
sn phm trung gian sinh ra trong qu trnh phn ng b hp ph ln tm xc tc,
c th l cc hp cht cha N, S v cc cht khong (Na+, Cl-, SO42-)
[13,14,15,16]. Hot tnh ca xc tc c phc hi sau mi ln ti sinh c th
c gii thch nh vo vic phn hy hon ton cc hp cht hu c trung gian
bng oxi v hydro nguyn t trong qu trnh quang in phn nc.
5. Kt lun v xut
Vi nghin cu ny, chng ti to ra c mt loi xc tc quang ha
hon ton mi, trn c s t hp cc vt liu kch thc micro v nanomet, c
mang ln vt liu c cu trc. Hot tnh quang ha ca xc tc mnh v c th hot
ng n nh trong thi gian di. c bit, h xc tc ny c th c ng dng
trong h thng x l nc thi lin tc x l cc cht nhim hu c di tc
dng ca nh sng mt tri. Chi ph sn xut xc tc tnh cho 1 gam TiO2 c
gim i ng k do s dng c cc loi TiO2 thng mi vi pha anatase trong
thnh phn v gim c lng TiO2 sol-gel. Cn phi ch rng: Chi ph sn
xut TiO2 sol-gel rt ln bi gi ca alkoxide titan cao v chi ph vn hnh l nung
to dng anatase rt ln, do cn nhit nung cao (400-500oC) v mi trng
kh tr hoc chn khng trnh t chy carbon nano. Khi vn hnh trn h
thng nghin cu trong phng th nghim ca chng ti, kt qu x l rt tt v chi
ph vn hnh rt nh khi s dng nng lng mt tri, hu nh bng 0. Kt qu
y tim nng ca nghin cu ny c th c ng dng rng ri cho h thng
cng nghip trong vic phn hy cc hp cht hu c c trong nc thi m cc
phng php truyn thng khng th thc hin c.
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