TP CH PHT TRIN KH&CN, TP 9, S 1 -2006

NGHIN CU IU CH VT LIU XC TC QUANG HA TiO2 T SA

KHONG ILMENITE. PHN III: NH GI HOT TNH QUANG HO
XC TC CA TiO2 TRONG PHN NG QUANG PHN HU
AXT ORANGE 10
Nguyn Vn Dng(1), Phm Th Thu Loan(2), o Vn Lng(3), Cao Th H(4)
(1) Phn Vin Khoa hc Vt liu ti Tp.HCM Vin Khoa hc v Cng ngh Vit Nam
(2) Trng i hc Khoa hc T nhin HQG-HCM
(3) S KH&CN Tp.H Ch Minh
(4)Trng i hc Khoa hc T nhin HQG-HN
(Bi nhn ngy 24 thng 11 nm 2005, hon chnh sa cha ngy 10 thng 02 nm 2006)
TM TT: Vi vic p dng qu trnh thu phn trong iu kin vi sng, bt TiO2 c
kch thc nanmt c iu ch thnh cng t nguyn liu ban u l tinh qung
ilmenite Vit Nam. Kch thc tinh th trung bnh ca pha anatase nm trong khong 940nm. Bi bo ny nhm nh gi hot tnh quang xc tc ca sn phm TiO2 thng qua
phn ng phn hu quang ho thuc nhum azo (Acid Orange 10). Kt qu nghin cu cho
thy rng, c mi tng quan gia tinh th ho ca pha anatase vi hot tnh quang ho
xc tc ca TiO2. Hot tnh quang ha tt nht thu c vi mu c tinh th ho cao vi
kch thc tinh th trung bnh ca pha anatase khong 20nm, tng ng vi mu c nung
nhit bt u xy ra s chuyn pha cu trc anatase-rutile.
1. GII THIU
Trong hai thp k gn y, qu trnh xc tc quang ho bn dn trn TiO2 c xem nh
l mt phng php hiu qu v c trin vng thay th cc phng php truyn thng x
l cc cc cht hu c trong mi trng nc hoc khng kh [1,2]. Khi cc ht bn dn TiO2
c chiu sng vi bc x UV c nng lng ln hn nng lng vng cm ca bn dn s
lm pht sinh ra cp in t v l trng (e-/h+) m sau cc cp e-/h+ ny c th di chuyn ra
b mt ca ht khi u cho nhng phn ng oxy ho kh i vi cc cht hu c c
hp ph trn b mt TiO2 v trong a s trng hp, qu trnh oxi ha kh ny dn n s v
c ha hon ton cht hu c thnh CO2 v H2O [1,2]. Mt trong nhng gii hn chnh ca
qu trnh quang ho xc tc l gi tr hiu sut lng t tng i thp do s ti hp ca cc
cp e-/h+ trc khi chng tham gia cc phn ng oxy ho kh vi c cht [3]. Nhm t c
hiu qu quang ho cao, cn thit phi hn ch cc qu trnh ti hp ca cc cp e-/h+. Cc yu
t quan trng nh hng n hiu sut lng t l kch thc ht, cu trc v mc tinh th
ho ca TiO2 [3-7]. V cc thng s ny thay i r rt ty thuc vo phng php iu ch
TiO2 [8].
Gn y chng ti thnh cng trong vic iu ch TiO2 kch thc nanmt t
ilmenite vi vic p dng qu trnh thu phn trong iu kin vi sng [9,10]. Bi bo ny
nhm ng gi hot tnh quang ha xc tc v nghin cu trong mi tng quan gia hot
tnh quang ho v vi cc yu t c trng ca sn phm TiO2.
2. THC NGHIM
Trang 25

Science & Technology Development, Vol 9, No.1 - 2006

Cc mu TiO2 thu c bng qu trnh thu phn dung dch titanyl sulfate th trong
iu kin vi sng [10]. Sn phm kt ta ca qu trnh thy phn c ra sch bng nc ct
v sau c nung cc nhit 450, 500, 550, 600, 650, 700, 750, 800, 850, v 9000C
cng mt thi gian nung 2 gi. K hiu cc mu TiO2 tng ng vi cc nhit nung trn
y ln lt l T450, T500, T550, T600, T650, T700, T750, T800, T850 v T900. Cc thng
s c trng cho cc mu TiO2 nghin cu c nu trong bng I.
Hot tnh quang ho ca cc mu TiO2 c nh gi thng qua hiu qu qu trnh phn
hu quang xc tc thuc nhum azo Acid Orange 10 (mc phn tch, Merck). Dung dch
thuc nhum AO 10 c chun b bng nc kh ion (EC= 5S/cm) bo ha oxy vi
nng ban u ca AO10 l 10-4mol/l.
Qu trnh quang ho c thc hin trong h phn ng tnh s dng cc cc thu tinh
250mL cha 200mL dung dch AO10. Mi cc dung dch phn ng c b sung mi mu
xc tc TiO2 khc nhau vi cng hm lng 1gTiO2/l. Mu TiO2 thng mi P-25 ca
Degussa (30% rutile, 30nm, 50m2/g) cng c s dng nhm mc ch so snh. Trc thi
im chiu UV, cc dung dch phn ng c khuy t trong ti trong thi gian 1 gi bo
ho hp ph AO10 trn b mt TiO2. Trong qu trnh chiu UV, h huyn ph c trn lin
tc bng my khuy t v c n nh nhit 3210C bng nc lm mt bn ngoi cc
cc phn ng. Ngun bc x UV-A dng trong phn ng c pht ra t 2 n hunh quang
15W c nh bc x 360nm (FL15BL-360, Mitsubishi/Osram), c t v tr 10 cm pha
trn b mt cc dung dch phn ng. Gi tr cng nh sng trung bnh trong khong bc
x 340-400nm c xc nh bng potassium ferrioxalate [11] trn b mt dung dch phn
ng bng 1.30mW/cm2. Trong qu trnh chiu UV, sau nhng khong thi gian xc nh, 5ml
mu dung dch phn ng c rt ra ly tm v lc qua giy lc 0.45m nhm tch ht TiO2
trc khi phn tch. Nng AO10 cn li trong dung dch c xc nh thng qua ph hp
thu, o bng thit b quang ph UV-VIS hai chm tia (JASCO V-550).
NaO3S

N=N
OH

NaO3S
Hnh 1.Cu to ca thuc nhum Acid Organe 10 (AO10)
(C16H10O7N2S2Na2; MW = 452,30 g/mol)
3. KT QU V THO LUN
Hnh 2 trnh by s thay i ph hp thu ca dung dch AO10 theo thi gian phn ng
khi s dng cc mu xc tc TiO2 khc nhau. Mt cch tng qut, cng hp thu trong
vng uv-vis (200-600nm) ca dung dch u suy gim theo thi gian chiu UV. S suy gim
cng vn hp thu di bc sng c trng ca AO10 (max = 482nm) nh ch ra trong
hnh tng ng vi s kh mu ca dung dch azo trong qu trnh phn ng. Nh vy, khi s
dng mu xc tc P-25, qu trnh kh mu hon ton dung dch AO10 t c sau 240 pht
chiu UV, v s kh mu hon ton cng t c i vi cc dung dch s dng mu xc tc
T650 v T700 sau 300 pht chiu UV. Vi cc dung dch s dng nhng mu xc tc cn li
s kh mu hon ton khng t c sau 300 pht chiu UV.

Trang 26

TP CH PHT TRIN KH&CN, TP 9, S 1 -2006

K hiu
mu TiO2
T450
T500
T550
T600
T650
T700
T750
T800
T850
T900
P-25

Hm lng
pha rutile, %
0
0
0
0
0
0
4.41
38.40
81.55
94.30
30

dXRD (anatase),
nm
8.98
10.79
12.42
15.00
18.40
19.50
28.25
33.89
38.06
40.76
30

SBET,
m2/g
46.36
54.79
70.54
48.75
34.23
29.92
50

Hiu sut phn

hu AO10 *), %
52
53
59
61
73
72
58
39
14
9
94

Bng 1.Cc thng s c trng ca cc mu TiO2 s dng

*)

Sau 180 pht chiu UV

Mt khc, t l thuyt v ph uv-vis , cc di ph hp thu ca cc hp cht hu c

mch nhnh hoc mch vng xut hin trong vng bc sng 200-300nm [12], do s suy
gim cng hp thu trong vng bc sng ny cung cp thng tin nh tnh v qu trnh
khong ho ca cc sn phm trung gian ca AO10 trong qu trnh phn ng. Hnh 2 cho thy
rng, cng hp thu trong di bc sng 200-300nm ca cc dung dch s dng cc mu
xc tc T650, T700 v P-25 u suy gim r rt theo thi gian chiu UV. Nh vy, vi vic
s dng cc mu xc tc ny, bn cnh vic kh mu hon ton qu trnh quang ho xc tc
cn c kh nng khong ho dung dch AO10 n cc sn phm v c.
T cc s liu ca ph uv-vis, hiu sut kh mu dung dch AO10 (hay l hiu sut
phn hu thum nhum AO10) sau 180 pht chiu UV ca cc qu trnh quang ho xc tc
trn y c trnh by trong bng I v hnh 3. Nh vy, hot tnh quang ho ca cc mu
TiO2 thay i khi c nung cc nhit khc nhau: Vi cc mu c nung di 7000C,
hot tnh quang ho tng dn theo nhit nung, v hot tnh quang ho gim dn theo nhit
nung i vi cc mu c nung cao hn 7000C. Nhiu nghin cu cho thy rng hot tnh
quang ho ca titania b nh hng bi phng php x l nhit v thnh phn cu trc tinh
th [3-5]. Trong trng hp ca nghin cu ny, do mc tinh th ho ca pha anatase tng
ln cng vi nhit nung [10], v vy vic tng hot tnh ca cc mu c nung di
7000C c th gii thch l do s tng mc tinh th ho ca pha anatase [6,7].
Mt khc, s gim hot tnh xc tc ca cc mu nung trn 7000C c th c gii
thch l do s xut hin ca pha rutile (bng I). Bn cnh , d khng c s liu v din tch
b mt ring, s pht trin nhy vt ca kch thc tinh th khi xut hin pha rutile ca cc
mu nung nhit cao hn 7000C [10] c th lm gim nhanh chng din tch b mt
ring ca TiO2, v iu ny cng l mt nguyn nhn quan trng dn n s suy gim hot
tnh xc tc ca cc mu ny.

Trang 27

Science & Technology Development, Vol 9, No.1 - 2006

T600

T650

T750

T700

T800

P-25

Hnh 2.S thay i ph UVVis ca dung dch AO10 trong qu trnh quang ho xc tc vi
cc mu TiO2 khc nhau. Cng hp thu ca cc ph suy gim theo hng t trn xung
tng ng vi cc thi gian chiu UV l 0, 30, 60, 120, 180, 240, 300 pht.
Hnh 3 cng cho thy mi tng quan gia hot tnh quang ho v kch thc tinh th
ca cc mu TiO2. i vi cc mu c nung di 7000C, ngha l trong giai on cha xy
ra s chuyn pha anatase- rutile, hot tnh quang ho tng dn cng vi s pht trin tinh th
anatase d rng s pht trin kch thc ht dn n s gim din tch b mt ring ca xc
tc (bng I). C th gii thch iu ny nh sau, vic tng tinh th ho lm gim ng k
cc khuyt tt trong th khi cng nh trn b mt ca cc ht TiO2 dn ti vic hn ch ng
k s ti hp ca cc ht mang in quang sinh v lm tng hiu sut lng t, iu lm
tng mt tm hot tnh trn b mt xc tc nn mc d din tch b mt ring gim nhng
hot tnh xc tc tng cng vn tng ln. Kt lun ny ph hp vi mt s tc gi khc khi
cho rng tinh th ho quan trng hn din tch b mt ring ca xc tc [6]. Khi bt u
xy ra s chuyn pha anatase-rutile (hn 7000C), hot tnh quang ho gim nhanh chng cng
vi s pht trin kch thc ca tinh th anatase. Nh vy, trong trng hp ca nghin cu
Trang 28

TP CH PHT TRIN KH&CN, TP 9, S 1 -2006

ny, kch thc ti u ca tinh th anatase i vi qu trnh quang phn hu AO10 trong mi
trng nc vo khong 20nm.

94

Hieu suat phan huy AO 10, %

100

60

40

73 72

80
52 53

59 61

45
35
30

58

25

39

40

20
15
14

20

10

Kch thc tinh the anatase, nm

50

P-25

T900

T850

T800

T750

T700

T650

T600

T550

T500

T450

Mau TiO 2

Hnh 3.Hiu sut phn hy AO10 sau 180 pht chiu UV ca cc qu trnh quang ho xc tc
c thc hin vi cc mu TiO2.
Hnh 3 cng cho thy rng, trong s cc mu TiO2 nghin cu, mu T650 c hot tnh
quang ho tt nht phn hu AO10 sau 180 pht phn ng t khong 77% so vi trng
hp ca mu P-25. Tuy nhin, hiu sut phn hu AO10 biu din trn hnh 3 c so snh
trong iu kin phn ng s dng cng hm lng xc tc (1gTiO2/l). V vy, khi chun ho
hiu sut phn hy AO10 theo din tch b mt ring ca cc mu xc tc s dng, hot tnh
quang ho ca mu T700 ln hn so vi mu T650. Hn th na, hiu sut phn hu AO10
ca cc mu T650 (SBET=34.23m2/g) v T700 (SBET=29.92m2/g) c th t n 113% v
128% tng ng so vi mu P-25 (SBET=50 m2/g).
4.KT LUN
Vi vic p dng qu trnh thu phn trong iu kin vi sng, bt TiO2 c kch thc
nanmt c iu ch thnh cng t nguyn liu ban u l tinh qung ilmenite Vit
Nam. Nhit nung l mt yu t quan trng kim sot hot tnh quang ho ca TiO2. Qu
trnh tng nhit nung sn phm thu phn di nhit chuyn pha anatase-rutile lm pht
trin tinh th ho ca pha anatase v tng cng hot tnh quang ho ca TiO2.

Trang 29

Science & Technology Development, Vol 9, No.1 - 2006

PREPARARTION OF PHOTOCATALYST TiO2 FROM ILMENITE ORE.

PART III: PHOTOCATALYTIC ACTIVITY FOR THE DECOMPOSITION
OF ACID ORANGE 10
Nguyen Van Dzung(1), Pham Thi Thuy Loan (2), Dao Van Luong (3) Cao The Ha (4),
(1) Institute of Materials Science_HCMC Branch VAST
(2) University of Natural Sciences VNU-HCM
(3) Science & Technology Service of HCM
(4) University of Natural Sciences VNU-HN

ABSTRACT: With the thermal hydrolysis process carried out with microwave heating,
Nano-sized powder of TiO2 has been prepared from ilmenite ore. The average crystalline size
of anatase phase was 9-40nm. In this study, the photoactivity of the prepared TiO2 powder
was evaluated by the photodegradation reaction of an azo-dye (Acid Orange 10) in water.
The results showed that there was a relationship between the crystallinity and the
photoactivity of titania. Among the studied powders, the sample calcined at 7000C with pure
anatase, highly crystallinity was shown to have the highest photoactivity for the
decomposition AO10.

TI LIU THAM KHO

[1]. Hoffmann M.R., Martin S.T., Choi W., Bahnemann D.W., Environmental applications
of semiconductor photocatalysis, Chem. Rev., 95, pp.69-96 (1995).
[2]. Legrini O., Oliveros E., Braun A. M., Photochemical processes for water treatment,
Chem. Rev., 93, 671-698 (1993).
[3]. Zhang Q., Gao L., Guo J., Effects of calcination on the photocatalytic properties of
nanosized TiO2 powders prepared by TiCl4 hydrolysis, Appl. Cat.B: Environ , 26, pp.
207215 (2000).
[4]. Zhang Z., Wang C.C., Zakaria R., Ying J.Y., Role of particle size in nanocrystalline
TiO2-Based photocatalysts, J. Phys. Chem. B, 102, pp.10871-10878 (1998).
[5]. Tsai S.-J., Cheng S., Effect of TiO2 crystalline structure in photocatalytic degradation
of phenolic contaminants, Catal. Today, 33, pp. 227-237 (1997).
[6]. Nishimoto S.-I., Ohtani B., Kajiwara H., Kagiya T., Correlation of the crystal
structure of titanium dioxide prepared from titanium tetra-2-propoxide with the
photocatalytic activity for redox reactions in aqueous propan-2-ol and silver salt
solution, J. Chem. Soc., Faraday Trans. I, 81, pp. 61-68 (1985).
[7]. Jung K.Y., Park S.B., Anatase-phase titania: preparation by embedding silica and
photocatalytic activity for the decomposition of trichloroethylene, J. Photochem.
Photobiol. A: Chem., 127, pp. 117-122 (1999).
[8]. Sclafani A., Palmisano L., Schiavello M., Influence of the preparation methods of
titanium dioxide on the photocatalytic degradation of phenol in aqueous dispersion, J.
Phys. Chem. 94, pp. 829-832 (1990).
[9]. Nguyn Vn Dng, Hong Hi Phong, Phm Th Thu Loan, o Vn Lng, Nghin
cu iu ch vt liu xc tc quang ha TiO2 t sa khong ilmenite. Phn I: nh
hng ca nng Ti(IV) trong dung dch thu phn n cc tnh cht b mt ca
TiO2 , Tp ch Pht Trin Khoa Hc & Cng Ngh, Tp 8, S 9, tr.22-26 (2005).
[10]. Nguyn Vn Dng, Hong Hi Phong, Phm Th Thu Loan, o Vn Lng, Nghin
cu iu ch vt liu xc tc quang ha TiO2 t sa khong ilmenite. Phn II: nh
Trang 30

TP CH PHT TRIN KH&CN, TP 9, S 1 -2006

hng ca nhit nung n cc tnh cht b mt ca TiO2, Tp ch Pht Trin Khoa

Hc & Cng Ngh, Tp 8, S 9, tr.27-33 (2005).
[11]. Hatchrd C.G., Parker C.A., A New Sensitive Chemical Actinometer, Proc. R.
Soc.London, Ser.A, 235, pp. 518- 536 (1956).
[12]. Nguyn Hu nh, Trn Th , ng dng mt s phng php ph nghin cu cu
trc phn t, NXB Gio Dc (1999).

Trang 31