TP CH HA HC T.

53(3) 289-294 THNG 6 NM 2015

DOI: 10.15625/0866-7144.2015-00131

NGHIN CU NG DNG PHN HY CHT MU CNG NGHIP

TRONG THC PHM BNG VT LIU XC TC QUANG HA
KH KIN Zn/ZnO/TiO2-Ag
Nguyn Th Minh Dip1, Trn Thu Qunh2, Hunh ng Chnh2, Nguyn Xun Trng2*
1
Khoa Dc, Trng Cao ng Dc Ph Th
2
Vin K thut Ha hc, Trng i hc Bch khoa H Ni
n Ta son 23-01-2015; Chp nhn ng 20-6-2015

Abstract
Ag-doped TiO2 amorphous composite film coupled with metal oxide semiconductor ZnO on Zn-slide as a novel
visible light photocatalyst is synthesized. The material is characterized using various analytical techniques such as X-
ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive X-ray
Spectroscopy (EDS) and Diffusive Reflectance Spectroscopy (DRS). It is indicated that the presence of the dopant, Ag,
on Zn/ZnO/TiO2 film enhances its catalytic activity in VIS region. For environmental application, the photocatalytic
activities of the material are evaluated by degradation of an artificial dye, tartazine, under sunlight. Furthermore, the
effect of pH and H2O2 as an oxidizing agent on the degradation efficiency of the material is also investigated. The
results show the optimal conditions for the photodegradation of the tartazine 0.5 mg sample are pH 5 and 3 ml H2O2
10 % in 6-hour irradiation.
Keywords. Visible light photocatalyst, photodegradation, tartazine, foods and drugs, Ag-doped Zn/ZnO/TiO2 film.

1. M U liu mng t hp ZnO/TiO2/Ag th hin hot tnh

X l nc nhim bng phng php oxi ha
tin tin s dng cht xc tc quang ha TiO2 v
ang c nghin cu nhiu nc trn th gii [1-
4, 8-12]. Tuy nhin, vic ng dng cht xc tc ny
loi b cc phm mu, cht bo qun trong ngnh
cng nghip thc phm v dc phm gn y mi
bt u c quan tm nghin cu. Mt khc, vt
liu TiO2 thng thng ch c hot tnh quang xc
tc khi b kch thch bi nh sng vng t ngoi v
kh thu hi xc tc sau phn ng [6, 7, 15].
Trong nghin cu ny, chng ti a ra kt qu
tng hp vt liu mng xc tc quang ha kh kin
Zn/ZnO/TiO2Ag. Cht bn dn oxit kim loi ZnO
v TiO2 u c nng lng vng cm rng [5, 15,
17]. Di s kch thch ca bc x UV, t l kt hp
in t - l trng cao nn hot tnh xc tc quang
thp. Tuy nhin, nu kt hp chng vi nhau s to
thnh loi vt liu cu trc nano a lp, dn n
gim s kt hp in t - l trng. ng thi s kt
hp ny c th ci thin s di chuyn ca cc in
t b mt do ci thin hot tnh quang xc tc ca
vt liu t hp ZnO-TiO2 [13, 16, 17]. Mt khc, s
c mt ca mt lng nh Ag trn mng bn dn c
tc dng lm gim rng vng cm v lm chm
li tc kt hp in t - l trng. Do vy, vt
quang xc tc cao trong vng nh sng kh kin
[8,14,18]. Mt u im khc l d dng thu hi xc
tc ti s dng i vi loi vt liu mng
Zn/ZnO/TiO2Ag.
Trong bi bo ny, chng ti cng a ra kt
qu nh gi kh nng ng dng vt liu
Zn/ZnO/TiO2Ag x l nc nhim c cha
phm mu cng nghip, thng qua hiu sut ca
phn ng quang phn hy cht mu tartazine (E102)
di tc dng ca nh sng mt tri.
2. PHNG PHP NGHIN CU
2.1. Ha cht v thit b
Ha cht: Tetra n-butyl octotitanat - TBOT
(Merck, c), etanol-EtOH (Merck, c), NaOH
(Trung Quc), HNO3 63 % (Trung Quc), AgNO3
tinh th (Trung Quc), H2O2 30% (Trung Quc),
km tm b dy 0,1 cm, nc ct 2 ln, tartazine
(dung dch 5 % trong nc v axit axetic).
Tartazine c cng thc ha hc
C16H9N4Na3O9S2, danh php quc t l trisodium
(4E)-5-oxo-1-(4-sulfonatophenyl)-4-[(4-
sulfonatophenyl) hydrazono]-3-pyrazole-
carboxylate, m s quc t E102, l mt cht to

289
TCHH, T. 53(3), 2015
mu vng chanh v c cng to mu kh cao,
ch mt lng rt nh c th to ra mt mu vng
kh m [12, 19].
Hnh 1: Cng thc cu to ca tartazine
Dng c v thit b: in cc titan, my khuy
t gia nhit, thit b in phn, thit b ph nhng
sol-gel, my o pH, cn phn tch, l nung.
Gin nhiu x tia X (XRD) c ghi trn h
nhiu x k SIEMENS D5005 (CHLB c) ti
Khoa Ha hc, Trng i hc Khoa hc T nhin
H Ni.
nh hin vi in t qut (SEM) v ph tn x
nng lng tia X (EDS) c ghi trn thit b
HRTEM Tecnai G2 F20 (FEI, M) ti Vin Tin
tin Khoa hc v Cng ngh, Trng i hc Bch
Khoa H Ni.
Ph hp th t ngoi-kh kin (UV-Vis) c
ghi trn trn my UV-Vis (Agilent 8453, M) ti
Vin K thut Ha hc, Trng i hc Bch Khoa
H Ni.
Ph tn x-phn x (DRS) c ghi trn my
quang ph Lambda 950 UV/VIS/NIR (Perkin-
Elmer, Anh) ti Vin Ha l v Ha l thuyt,
Trng i hc K thut Graz, Cng ha o.
2.2. Tng hp vt liu Zn/ZnO/TiO2Ag
2.2.1. Tng hp vt liu mang Zn/ZnO bng
phng php in ha
Mu Zn ra sch, nh bng bng giy rp ln
lt c th, c va v c mn.
Mu Zn sau c ra li bng nc ct,
nhng ngp phn din tch cn dng trong dung dch
HCl 10 %, sy kh v mc vo bnh in phn. Anot
l mu Zn, catot l in cc titan nguyn cht. in
phn vi mt dng 0,2 A/dm2 trong dung dch
NaOH 0,5 M trong thi gian 90 pht [10, 11].
2.2.2. Tng hp vt liu Zn/ZnO/TiO2-Ag bng
phng php nhng ph solgel
Trc ht, chun b dung dch sol theo t l v
mol nh sau: TBOT:H2O:EtOH:HNO3:AgNO3 =
1:08:8:0,08:0,02 [6, 7]. Theo t l mol ny, lng
Ag/TiO2-Ag tng ng v phn trm khi lng l
1,0 %. Hn hp lun c khuy u 0 oC. Sau
Nguyn Xun Trng v cng s
, nhng vt liu mang Zn/ZnO vo dung dch sol
vi tc 1cm/pht, nung 350 oC trong 10 pht.
Qu trnh nhng v nung c lp li 2 ln, nung
ln th 2 thc hin trong 10 pht.
2.3. nh gi hot tnh xc tc quang ha ca
vt liu
Hot tnh quang xc tc ca vt liu c nh
gi thng qua phn ng quang phn hy cht mu
tartazine. Phn km ph mng ZnO/TiO2-Ag vi
din tch 22 cm2 c nhng ngp trong cc thy
tinh cha 50 ml dung dch tartazine (0,5 mg
tartazine). Th nghim th hot tnh c thc hin
ngoi tri di iu kin chiu sng t nhin.
Hiu sut ca phn ng quang phn hy c
tnh theo cng thc:
A At
H (%) 0 100 .
A0
Trong A0 v At l hp th ca tartazine ban
u v ti thi im t.
hp th ca tartazine c xc nh theo
phng php o quang ti bc sng max = 429 nm.
3. KT QU V THO LUN
3.1. Cu trc ca vt liu mng Zn/ZnO/TiO2-Ag
Gin XRD ca vt liu mng Zn/ZnO/TiO2-
Ag c ch ra trn hnh 2. Trn gin , ch quan
st thy cc pic ca ZnO () v Zn (). Kt qu ch
ra rng mng to thnh ZnO/TiO2-Ag trn Zn c
cu trc v nh hnh.
3.2. nh hin vi in t qut FESEM
Hnh 3a cho thy cu trc ca lp mng ZnO c
xp rt cao v cc lp xp chng ln nhau vi
mt dy c. Cu trc l xp to thnh ny chnh
l c s cn thit v thun li cho s bm ph ca
dung dch sol v sau l mng TiO2Ag [4, 6, 7].
Quan st hnh 3b, sau khi ph lp dung dch sol vo
cc l xp ZnO v tin hnh nung luyn thu c
lp mng kh ng nht. dy ca lp mng t
hp ZnO/TiO2-Ag c 500 m (hnh 3c).
3.3. Ph tn x nng lng tia XEDS
Ph EDS ca mu Zn/ZnO/TiO2-Ag (hnh 4)
cho thy pic ca Ag cng vi pic ca cc nguyn t
c bn khc Ti, O v Zn. iu ny chng t phng
php nhng ph solgel pha tp thnh cng Ag
trn mng ZnO/TiO2.
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TCHH, T. 53(3), 2015 Nghin cu ng dng phn hy cht mu

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau 2

400

300

d=2.482
d=2.812
Lin (Cps)

d=2.603
200

d=1.485
d=2.092

d=1.627

d=1.378
100

d=1.911
0

10 20 30 40 50 60

2-Theta - Scale
File: Mau2.raw - Type: 2Th/Th locked - Start: 10.000 - End: 70.000 - Step: 0.030 - Step time: 0.3 s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 10.000 - Theta: 5.000 - Chi: 0.00 - Phi: 0.00
01-089-1397 (C) - Zinc Oxide - ZnO - Y: 28.90 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 3.25300 - b 3.25300 - c 5.21300 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P63mc (186) - 2 - 47.77
00-004-0831 (*) - Zinc, syn - Zn - Y: 9.93 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 2.66500 - b 2.66500 - c 4.94700 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - P63/mmc (194) - 2 - 30.4275

Hnh 2: Gin XRD ca vt liu Zn/ZnO/TiO2-Ag

(a) (b) (c)

Hnh 3: nh SEM b mt Zn/ZnO (a), Zn/ZnO/TiO2-Ag (b) v (c) dy lp mng ZnO/TiO2-Ag

nh sng mt tri trn hai mu vt liu: khng pha

tp Ag (M1) v c pha tp Ag 1 % (M2). Nhn thy,
vi s pha tp kim loi Ag, hiu sut (H) ca phn
ng quang phn hy tartazin tng ln r rt (H tng
gp ~ 2 ln, mi trng pH 5).
Zn/ZnO/TiO2-Ag
1,0 Zn/ZnO/TiO2
Reflectance

0,8
Hnh 4: nh EDS mu Zn/ZnO/TiO2-Ag

3.4. Ph tn x phn x - DRS

0,6

Kt qu ghi ph DRS (hnh 5) cho thy, vt liu

mng Zn/ZnO/TiO2-Ag c phn x gim vng 350 400 450 500 550 600 650
460-600 nm so vi vt liu Zn/ZnO/TiO2. Nh vy, wavelength / nm
c s tng hp th ca vt liu Zn/ZnO/TiO2-
Hnh 5: Ph DRS ca vt liu Zn/ZnO/TiO2 v
trong vng nh sng kh kin do s pha tp kim loi
Zn/ZnO/TiO2-Ag
Ag.
S tng mnh hiu sut phn ng ca vt liu
3.5. S c mt ca Ag nh hng n hot tnh
quang xc tc Zn/ZnO/TiO2-Ag c th c gii
quang xc tc
thch nh sau: kim loi chuyn tip Ag c a
vo mng ZnO-TiO2 c tc dng lm hp rng
Hnh 6 a ra kt qu kho st hiu sut ca
nng lng vng cm do s lai ha cc orbitan d
phn ng quang phn hy tartzine di tc dng ca

291
TCHH, T. 53(3), 2015
gia Ti v nguyn t Ag. Mt khc, hng ro
Schottky c hnh thnh gia kim loi Ag v cc
oxt bn dn, dn n c s chuyn ri electron gia
kim loi Ag v oxit bn dn. Do vy, s c mt ca
Ag s lm chm qu trnh ti t hp in t - l
trng. Chng ng vai tr nh cc by in t v
by l trng, tng cng s chia tch l trng
in t [4, 8, 14-16, 18]. Cc in t b mc kt trn
by in t tng tc vi O2 to thnh cc phn t
hot ng (O2, OH). Do lm tng hiu sut
phn ng quang xc tc phn hy tartazine.
65
60
55
50
45
40
35
H(%)
Nguyn Xun Trng v cng s
sau 6 gi chiu sng, lng Ag pha tp ln lt l
2,0 % v 3,0 % th H bt u gim nh so vi khi
pha tp 1,0 % Ag v hu nh khng tng thm sau 4
gi chiu sng. Nh vy, vi vt liu nghin cu
y, hm lng Ag pha tp 1,0 % cho hiu qu
quang xc tc ti u nht.
3.6. nh hng ca pH n hot tnh quang xc
tc
Nghin cu kho st nh hng ca pH n hiu
sut phn ng quang phn hy tartazine bi vt liu
M1
M2
Zn/ZnO/TiO2-Ag di tc dng ca nh sng mt
tri. Kt qu (hnh 8) cho thy tc v hiu sut
phn ng trong mi trng axit pH 5 cao hn so vi
trong mi trng axit mnh pH 2, trung tnh v mi
trng kim pH 10. Ti pH 5, sau 6 gi, H t ti

30
25
~61 %. Trong khi ti pH 7, H > 35 %, ti pH 10, H
20
15 > 4 % v mi trng axit mnh pH 2, H > 55 %.
10 Tc v hiu sut phn ng cao trong mi trng
axit l do tng cng s hp ph ca tartazine ln b
5
0
0 1 2 3
t (h)
4 5 6
mt TiO2 mang in dng. Trong mi trng axit
Hnh 6: S c mt ca Ag nh hng n hot tnh mnh pH 2, lp ZnO c th b ha tan phn no, do
quang xc tc ca vt liu. M1:Zn/ZnO/TiO2; c hot tnh thp hn. Trong mi trng trung
M2:Zn/ZnO/TiO2-Ag tnh v kim, hiu sut quang phn hy gim i do
kh nng to thnh Zn(OH)2 dn ti th ng ha b
Nhng mt khc, khi nng pha tp t n gi mt v lm gim hot tnh qu trnh quang xc tc
tr no th cc by in t li ng vai tr nh [10].
cc tm ti hp ca cc cp in t - l trng lm 70

gim kh nng quang xc tc ca vt liu [6, 16]. M1

Kt qu kho st s nh hng ca hm lng Ag

60 M2
M3
M4
pha tp n hot tnh quang xc tc ca vt liu 50

(hnh 7) cho thy, vi hm lng Ag pha tp 0,5%, 40

H ~52 %. Vi lng Ag pha tp 1,0 %, H > 61 %

H(%)

30

20
65
60 10
M1
55 M2 0
0 1 2 3 4 5 6
50 M3
pH
45 M4
M5
40
Hnh 8: nh hng ca pH n hot tnh
35
quang xc tc ca vt liu. M1: pH 2; M2: pH 5;
H(%)

30
25
M3: pH 7; M4: pH 10
20
15 3.7. nh hng ca H2O2 n hot tnh quang
10 xc tc
5
0
0 1 2 3 4 5 6 Hiu sut quang phn hy mu cha 0,5 mg
t (h) tartazin bng vt liu mng Zn/ZnO/TiO2-Ag (s = 4
Hnh 7: nh hng ca hm lng Ag pha tp n cm2) vi lng 3 ml H2O2 10 % l ti u (hnh 9).
hot tnh quang xc tc ca vt liu Nghin cu cho thy nu ch thm mt lng H2O2
M1:Zn/ZnO/TiO2; M2: Zn/ZnO/TiO2-0,5 % Ag; tng t (3 ml H2O2 10 %) vo mu m khng c
M3:Zn/ZnO/TiO2-1,0% Ag; M4:Zn/ZnO/TiO2-2,0 vt liu Zn/ZnO/TiO2-Ag, th H ch t ~ 20 % sau 6
% Ag; M5: Zn/ZnO/TiO2-3,0 % Ag gi. Mt khc, khi thm lng H2O2 nhiu hn, hiu
hiu sut khng cao hn v hu nh khng tng

292
TCHH, T. 53(3), 2015
thm sau 4 gi. Nguyn nhn l do s c mt ca
gc OH nhiu s dn ti s ti kt hp cc gc t
do O2-, OH, OH2, bn cnh H2O2 s tng tc
vi OH lm gim mt phn lng OH [9, 15, 19].
100
90 M1
M2
80
M3
M4
70
60
50
H(%)
40
30
20
10
0
0 1 2 3 4 5
t (h)
Hnh 9: nh hng ca H2O2n hot tnh quang
xc tc
M1: Zn/ZnO/TiO2 1,0 %Ag + 1,0ml H2O2 10 %
M2: Zn/ZnO/TiO2 1,0 %Ag + 2,0 ml H2O2 10 %
M3: Zn/ZnO/TiO2 1,0 %Ag + 3,0 ml H2O2 10 %
M4: Zn/ZnO/TiO2 1,0 %Ag + 4,0 ml H2O2 10 %
Kt qu (hnh 9) cho thy hiu sut phn hy
mu cha 0,5 mgtartazin t ti 92 % sau 6 gi
chiu sng t nhin khi s dng kt hp vt liu
mng xc tc Zn/ZnO/TiO2-Ag v thm 3 ml H2O2
10 % trong mi trng pH 5.
4. KT LUN
tng hp thnh cng vt liu mng
Zn/ZnO/TiO2-Ag, c hot tnh xc tc quang ha
trong vng nh sng kh kin. Cht mang Zn/ZnO
c tng hp bng phng php in ha c cu
trc l xp ng u, trt t cao. Mng TiO2-Ag
c tng hp bng phng php sol-gel c cu trc
v nh hnh. Vi lng pha tp ti u 1 % Ag, vt
liu th hin hot tnh quang xc tc cao trong vng
nh sng kh kin.
Vi 4 cm2 din tch b mt xc tc, vt liu
mng Zn/ZnO/TiO2-Ag cho hiu sut quang phn
hy mu cha 0,5 mg tartazine t ti 92 % trong
iu kin: mi trng axit pH 5, thm 3 ml H2O2 10
%, v sau 6h di nh sng mt tri. Vt liu rt c
trin vng s dng trong vic x l nc nhim
cha cc cht mu cng nghip.
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