47

Tp ch Ha hc, T. 42 (1), Tr. 47 - 51, 2004

MT S YU T NH HNG N HOAT TNH QUANG
XC TC PHN HY PHENOL TRN MANG TiO
2
/ KNH
n Ta son 10-4-2003
L Th Hoi Nam
1
, Bi Tin Dng
1
, Trn Th c
2
, Nguyn Th Dung
3
,
Nguyn Xun Ngha
4
1
Vin Ha hc, Vin Khoa hc v$ Cng ngh Vit Nam
2
Vin Vt l ng dng v$ Thit b khoa hc, Vin Khoa hc v$ Cng ngh Vit Nam
3
Vin Cng ngh ha hc, Vin Khoa hc v$ Cng ngh Vit Nam
4
Vin Khoa hc vt liu, Vin Khoa hc v$ Cng ngh Vit Nam

SUMMARY
Titanium dioxide (TiO
2
) membranes on glasses were prepared by sol-gel method. Raman
and AFM spectroscopies mainly characterized them. The catalytic activity was tested in the
degradation of phenol as a model compound. It was shown that all TiO
2
membranes had
good photocatalytic activity and the influential parameters such as the phenol concentration,
the particle size and the adding amount of ZnO have been investigated.

I - m u
Gn y rt nhiu cng trnh a ra kh
nng quang xc tc ca TiO
2
trong vic phn
hy hp cht hu c c hi trong nc v3 kh
cho sn phm cui cng l3 CO
2
v3 H
2
O [1, 2].
Vi kh nng quang ha tt ca TiO
2
, cc nh3
khoa hc khng ngng nghin cu ng dng
kt qu n3y cho mc ch bo v v3 x l mi
trng.
Song song vi vic nghin cu trin khai p
dng m3ng TiO
2
v3o thc t, vic nghin cu
c bn v phn ng quang ha v3 phng php
to nn m3ng bn vng iu kin thng vn
rt cn thit v3 ang l3 mc ch theo ui ca
nhiu nh3 khoa hc trn th gii.
TiO
2
c s dng dng bt cng nh
dng m3ng. Mc d TiO
2
dng bt c cu
trc anatas c coi l3 c hot tnh cao nht
cho nhiu phn ng quang xc tc khc nhau,
nhng vn hn ch c th p dng thc
tin l3 phi tch loi chng ra khi mi trng
sau phn ng. khc phc nhc im trn
ngi ta tin h3nh ch to m3ng TiO
2
trn
cc dng mang khc nhau [3, 4], ngo3i ra
cn a thm mt s cc oxit kim loi khc vi
h3m lng nh cng vi TiO
2
nhm tng hot
tnh ca m3ng trong di ph nh sng v3 thun
li trong vic thu hi v3 ti sinh xc tc.
Chng ti th3nh cng trong vic ch to
cc m3ng TiO
2
/ knh theo phng php sol-gel
ti phng th nghim. Trn cc m3ng n3y chng
ti tin h3nh nghin cu nh hng ca mt
s yu t nh nng phenol, kch thc ht
TiO
2
v3 cht pha thm ZnO n hot tnh quang
xc tc kh phenol trong mi trng nc.
II - Thc nghim
1. Ch to cc dng mng
a. Nguyn liu dng cho to m$ng TiO
2
Bt TiO
2
thng mi k hiu ST-01 (Nht
Bn) c kch thc ht trung bnh 7 nm v3 din
48
tch b mt 138 m
2
/g v3 TiO
2
Degussa P
25
(c)
c kch thc ht trung bnh 25 nm v3 din tch
b mt 50 m
2
/g.
- Cc ha cht khc nh tetrabutyl ortho
titanat, isopropanol, oxit km (Trung Quc).
b. Quy trnh to sol v$ m$ng mng TiO
2
trong
sut (sol-gel)
nh lng tetrabutyl ortho titanat (TBOT)
ha tan trong isopropanol (IP), dung dch thu
c k hiu l3 DI. Sau cho thm hp cht
amin v3o trong dung dch DI v3 khuy cho tan
ho3n to3n. Dung dch sol thu c phi trong
sut, k hiu l3 TiD. to m3ng TiO
2
trn
mang ta dng dung dch TiD (theo phng
php nhng ph), sau khi lp ph kh, em
sy kh m3ng 100
0
C trong 1 gi v3 nung
550
0
C trong 1 gi.
c. To m$ng TiO
2
t bt TiO
2
thJng mi ST-01
v$ P
25
trn cc knh
Ngo3i vic to m3ng TiO
2
t sol, chng ti
cn tin h3nh to m3ng TiO
2
t dng bt thng
mi sn c nh ST-01, P
25
trn knh. Sau qu
trnh x l nhit phi m bo c bm dnh
ca cc ngun TiO
2
thng mi trn knh.
d. Kim tra tnh cht vt l ca cc dng m$ng
S ch to
Cc m3ng TiO
2
c c trng bng hai
phng php chnh l3 quang ph Raman v3
knh hin vi lc nguyn t .
Ph Raman ca cc mu c o ti nhit
phng trn my vi quang ph Raman
LABRAM-1B (JOBIN-YVON, Php). nh hin
vi lc nguyn t c chp trn my hin vi lc
nguyn t AFM3.
2. Hot tnh quang xc tc ca mng TiO
2
trong phn ng kh phenol
Th nghim c tin h3nh nhit
phng trong bnh phn ng dng hnh hp ch
nht c kch thc 7,5 20 2 (cm) c l3m
t thy tinh pyrex, c cha m3ng xc tc (m3ng
TiO
2
dng trong l3m t sol, dng c t ST-01,
P
25
v3 ST-01 + 5%ZnO) v3 n UV (n thy
ngn UV spechonic BLE (USA) 8 W c cng
cc i bc sng 365 nm). Th tch dung
dch trong mi ln phn ng l3 80 ml. d3y
ca lp cht lng l3 6 mm.
Trc khi chiu n dung dich c sc
khng kh trong thi gian 30 pht phenol
hp ph bo ha trn b mt m3ng TiO
2
. Trong
qu trnh phn ng mu c ly ra theo tng
thi im phn tch cc ch tiu COD v3
nng phenol nh gi hiu qu quang xc
tc ca tng dng m3ng TiO
2
.
Phenol c phn tch bng phng php so
m3u trn my DR-2000 (HACH) vi cht hin
m3u 4-amino antipirine bc sng 510 nm v3
ph UV-vis c xc nh trn my JASCO-
V530 (Nht) vi s hin din ca 2 pic c trng
cho phenol bc sng 212 nm v3 267 nm.
Ch s COD c xc nh bng phng
php Bicromat trn my so m3u DR-2000
bc sng 600 nm.
chuyn ha phenol:

phenol
(%) = (C
0
C
t
).100/C
0
.
Trong : C
0
l3 nng phenol ban u (thi
im 0), C
t
l3 nng phenol thi im kho
st, l3 chuyn ha.
Tc phn ng c xc nh theo
phng trnh bc 1 biu kin theo phenol
R = ln (C
t
/ C
0
) = k t.
Trong : k l3 hng s tc biu kin, t l3 thi
gian phn ng.
III - Kt qu v tho lun
1. Kt qu to mu
Bng cc phng php to m3ng trn chng
ti to c mt s m3ng sau:
- M3ng TiO
2
trong sut (sol-gel).
- M3ng TiO
2
(ST-01): i t nguyn liu ST-01.
- M3ng TiO
2
(P
25
): i t nguyn liu P
25
.
- M3ng TiO
2
(P
25
) + 5% ZnO: i t nguyn
liu P
25
v3 ZnO.
2. Kt qu quang ph Raman v knh hin vi
lc nguyn t (AFM)
Cc hnh di y l3 kt qu thu c trn
m3ng TiO
2
dng sol v3 ST-01.
49
Hnh 1 v3 2 l3 ph tn x Raman ca 2
dng m3ng: m3ng l3m t sol v3 m3ng l3m t
ST-01. Hai dng m3ng trn u qua cc khu
x l nhit nh nhau. Qua hai ph thu c v3
so vi ph chun ta nhn thy TiO
2
tn ti
dng anatas ng thi khng b ln tp cc pha
khc, iu n3y ph hp vi mc ch t ra.
Vi m3ng TiO
2
(P
25
) cng c ph TiO
2
dng
anatas tng t.
Hnh 3 l3 nh hin vi lc nguyn t ca mu
m3ng TiO
2
iu ch t dng sol trn knh, qua
nh ta thy c g gh ca b mt m3ng v3
kch thc ht trung bnh khong 75 nm.
Hnh 1: Ph Raman ca m3ng TiO
2
l3m t bt ST-01
Hnh 2: Ph Raman ca m3ng mng
TiO
2
trong sut
Hnh 3: nh AFM ca m3ng mng TiO
2
trong sut
3. nh h3ng ca nng phenol ban u
nh hng ca nng phenol ban u
n chuyn ha phenol c a ra trn
hnh 4, 5, 6 trn 3 dng m3ng TiO
2
.Nhn v3o
hnh n3y ta c th thy l3 khi nng phenol
gim th chuyn ha tng vi cc mu c
tin h3nh cng iu kin phn ng. iu n3y c
th c gii thch nh sau: Trong iu kin
chiu sng bng mt loi n UV khng i c
ngha l3 s photon pht ra l3 khng i, khi
nng phenol tng c ngha l3 mt cc
phn t phenol trong dung dch tng, dn n
cng tia chiu khi truyn ti cc tm xc
tc TiO
2
gim do nh hng trc tip n
hiu qu quang xc tc. Nh vy trong trng
hp n3y nng phenol thch hp nht trong
khong 50 - 70 mg/l.
0
20
40
60
80
100

c
h
u
y

n
h

a
(
%
)
0 30 60 90 150 210
Thi gian (pht)
100
80
60
40
20
0
50
Hnh 4: th biu din nh hng ca nng
phenol ln hot tnh ca m3ng TiO
2
(P
25
)
0
20
40
60
80
100
120
0 30 60 90 150 210

Hnh 5: th biu din nh hng ca nng
phenol ln hot tnh ca m3ng
TiO
2
(P
25
) + 5% ZnO
0
20
40
60
80
100
0 30 60 90 150 210

Hnh 6: th biu din nh hng ca nng
phenol ln hot tnh ca m3ng
TiO
2
(sol-gel)
4. nh h3ng ca kch th3c ht TiO
2
Hot tnh quang xc tc ca cc m3ng TiO
2
c ch to t TiO
2
cc dng bt thng mi v3
m3ng ch to theo phng php sol-gel c s
khc nhau.
Kt qu nghin cu nh hng ca kch
thc ht TiO
2
n hot tnh quang xc tc trong
phn ng phn hy phenol c a ra trong
bng 1.
Cc s liu trong bng 1 cho thy tc
phn hy phenol sau 60 pht phn ng i vi
cc m3ng TiO
2
c kch thc ht khc nhau
thay i rt khc nhau, trong m3ng TiO
2
ch
to t bt TiO
2
ST-01 c tc cao nht gp 2
ln so vi TiO
2
P
25
v3 3 ln so vi m3ng TiO
2
sol-gel. Nh vy trong phn ng n3y kch thc
ht c nh hng rt ln n hot tnh quang
xc tc. Kch thc ht c3ng nh, hot tnh
c3ng cao. iu n3y kh ph hp vi nhng kt
qu nghin cu trc y ca cc tc gi [1, 3]
v3 c gii thch bi cc hiu ng b mt,
phn tn xc tc v3 hiu sut lng t ca
cc ht c kch thc khc nhau.
Bng 1: Kt qu xc nh nh hng ca kch thc ht (nng phenol 72 mg/l)
Dng m3ng TiO
2
Kch thc ht
(nm)
Tc phn hy ring phenol sau 30 pht
(mg/pht.g TiO
2
)
sol-gel 75 2,79
P-25 25 4,74
ST-01 7 10,37
5. nh h3ng ca vic 3a thm ZnO
Vic a thm cc kim loi ph gia v3o h
TiO
2
nhm mc ch tng hot tnh ca xc tc
trong di ph rng ca nh sng c
nghin cu vi kim loi km. Kt qu nghin
cu c trnh b3y trong bng 2.
T cc s liu COD v3 chuyn ha
Phenol

c
h
u
y

n
h

a
(
%
)
0 30 60 90 150 210
Thi gian (pht)
120
100
80
60
40
20
0

c
h
u
y

n
h

a
(
%
)
100
80
60
40
20
0
0 30 60 90 150 210
Thi gian (pht)
51
bng 2 ta nhn thy vic a thm ZnO kt
hp vi TiO
2
, l3m tng hot tnh quang xc
tc trong phn ng kh phenol. Sau 3 gi phn
ng, hu nh phenol chuyn ha trn 99% trong
trng hp c pha thm 5% ZnO v3o h xc tc,
gim ch s COD cng tng. Tuy vy s tng
hot tnh n3y khng r rt, c 2 thng s ch tng
khong 5%.
Bng 2: Kt qu xc nh nh hng ca vic a thm ZnO
M3ng TiO
2
(P
25
), nng phenol ban
u 72,0 mg/l
M3ng TiO
2
(P
25
) + 5% ZnO, nng
phenol ban u 73,1 mg/l
t
(pht)
[C]
phenol

Phenol
COD
COD
[C]
phenol

Phenol
COD
COD
0 72 197 73,1 179,8
30 51,7 28,19 182 7,61 59,2 19,02 164,9 8,29
60 45,5 36,81 160 18,78 47,2 35,43 142,5 20,75
90 24,4 66,11 133 32,49 30,7 58,00 122,7 31,76
150 16,9 76,53 88 55,33 8,2 88,78 70,6 60,73
210 2,3 96,81 43,3 78,02 0,05 99,93 30,9 82,81
Vic tm hiu vai tr ca ZnO s c
chng ti tip tc nghin cu trong nhng
cng trnh ti nhng di ph nh sng khc
nhau.
IV - Kt lun
ch to th3nh cng m3ng TiO
2
theo
phng php d l3m, r tin v3 c bn cao.
Cc dng m3ng TiO
2
u c hot tnh
trong phn ng kh phenol.
nghin cu cc thng s nh hng n
hiu qu quang xc tc: kch thc ht TiO
2
,
nng phenol ban u, kim loi pha thm
ZnO v3o h TiO
2
.
Nng phenol thch hp cho phn ng
l3 50 - 70 mg/l.
Kch thc ht c3ng nh hot tnh c3ng
cao.
Kim loi pha thm ZnO l3m tng hot tnh
ca xc tc, nhng khng ng k trong vng
nh sng UV.
Li cm n: Nhm tc gi trn th$nh cm n s
h tr ca Vin Khoa hc v$ Cng ngh Vit
Nam, Vin Vt l ng dng, ChJng trnh h tr
nghin cu c bn KT-04 v$ t$i nghin cu c
bn mS s 55.03.01.
Ti liu tham kho
1. Amy L. Linsebigler, Guangquan Lu, and T.
John. Photocatalysis on TiO
2
. Surfaces.
Principles, Mechanisms, and Selected Results,
Chem. Rev. (1995).
2. Michael R. Hoffmann, Scot T. Martin,
Wonyong Choi, and Detlef W. Bahnemann.
Environmental Application of Semiconduc-
tor Photocatalysis, Chem. Rev. (1995).
3. Srinivasan Sampath, Hiroyuki Uchida, and
Hiroshi Yoneyama. Journal of Catalysis, Vol.
149, P. 189 - 194 (1994).
4. S. Horikoshi, N. Watanabe, H. Onishi, H.
Hidaka, and N. Serpone. Applied Catalysis B:
Environmental, Vol. 37, P. 117 - 129 (2002).