KHOA HC CNG NGH

TNG HP VT LIU NANO TIO2 T TITANIA THNG MI BNG PHNG

PHP THY NHIT
Nguyn Hong Lng Ngc, ng Thanh Phong

Trng i hc Cng nghip Thc Phm TP. H Ch Minh

TM TT

Ngy gi bi: 04/11/2015 Ngy chp nhn ng: 15/12/2015

Nano TiO2dng si c tng hp t bt titania thng mi bng phng php thy nhit, mu
cphn hy bng dung dch NaOH 10M trong autoclave. Cc tnh cht c trng ca TiO2 nano si c
nh gi bng cc phng php ha l hin i: nhiu x tia X (XRD), hp ph ng nhit N2 v xc nh b
mt ring theo l thuyt BET, knh hin vi in t qut (SEM) cho thy sn phm thu c c cu trc n pha
anatase, dng si phn b ng u, kch thc si t 10 - 20 nm, chiu di khong 250 - 300 nm c b mt
ring c tng cng t 71 m2/g. Vt liu TiO2nano si c hot tnh quang ha tt, c kim chng bng
qu trnh mt mu dung dch xanh metylen trong iu kin c chiu bc x UV, nh sng mt tri v ngay c
Halogen.
T kha: TiO2, si nano, hot tnh xc tc, vt liu composite

SYNTHESIZE TITANIUM OXIDE NANOROD FROM COMMERICAL TITANIUM OXIDE BY

HYDROTHERMAL METHOD

ABSTRACT

Titanium oxide nanorod was synthesized from commerical titanium oxide by hydrothermal method of 10
M NaOH solution in autoclave. The prepared samples were characterized by X-ray diffraction (XRD), scanning
electron microscopy (SEM), and nitrogen adsorption measurements (BET). The results showed that anatase
phase was dominant and its morphology consisted of uniform nanorod with 10 - 20 nm in scale,lengths of the
TiO2 nanorods were 250-300 nm, its surface area as high as 71 m2/g. TiO2 nanorod exhibited excellent photocalalytic activity for degradation of methylene blue under UV, sunlight and even halogen radition.
Keywords: TiO2; Nanorods; Photocatalytic activity; Composites.

1. T VN
Vt liu nano TiO2 rt bn, khng c, cc tnh cht quang hc v sinh hc cho php
chng c ng dng trong lnh vc x l mi trng, cc cht nhim v dit khun. c
bit, TiO2 dng anatase kch thc nano c hot tnh quang xc tc rt mnh [8]. Di tc
ng ca tia t ngoi vt liu nano TiO2 s lm pht sinh cc tc nhn xy ho cc mnh nh
H2O2, O2-, OH- c th phn hu hu ht cc hp cht hu c, kh thi c hi, vi khun, ru
mc bm trn b mt vt liu thnh nhng cht v hi nh CO2, H2O.
Vic iu ch nano TiO2 i t cc nguyn liu titanium alkoxide thu c sn phm
c cp ht ng u, kch thc ht c nanomet, c kh nng xc tc quang ha tt, lm mt
mu xanh metylen, metyl , oxi ha c phenol thnh CO2 v H2O. Tuy nhin, do cc
nguyn liu u rt t tin hn ch kh nng ng dng ca sn phm vo thc t. Gn
y, vic s dng cc ngun nguyn liu: qung ilmenite (FeTiO3) rutile (TiO2), trong t
nhin tng hp nano TiO2 c cc nh khoa hc quan tm. Tuy nhin, do i t qung
nn vic x l tp cht, m bo tinh khit ca vt liu kh phc phc tp [1], [5], [7].
Vic tng hp vt liu nano TiO2 t bt TiO2 cng nghip c tinh khit cao s gim
c nhiu cng on x l tp cht phc tp, m bo tinh khit ca vt liu. Bi bo
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ny trnh by nhng kt qu nghin cu tng hp vt liu t bt titania cng nghip bng
phng php thy nhit v kho st qu trnh quang xc tc ca vt liu thng qua qu trnh
lm mt mu dung dch xanh metylen.

2. THC NGHIM
Ly mt lng xc nh bt TiO2 cho vo bnh teflon dung tch 200 ml, thm vo 100
ml dung dch NaOH c nng thay i t 5M 10M. Khuy u mu trn my khuy t trong
2 gi, trnh cho bt khng b vn cc. Tin hnh thy nhit trong autoclave, qu trnh thy
nhit mu c thc hin nhit 120 - 180oC, trong thi gian 12 - 24 gi [2].
Sau khi thy nhit, ngui t t n nhit phng, hn hp phn ng thu c
dng sol trng, ra gn nhiu ln bng nc ct loi b bt lng NaOH d, trung ha
bng HCl 0,1M, tip tc ra kt ta bng nc ct n khi pH ca dch lc hu nh trung
tnh. Lc kt ta bng my ht chn khng v sy kh nhit 80oC trong 5 gi n khi
lng khng i. Sn phm c phn tn vo dung mi etanol, rung siu m trong 15 pht
vi cng sut 500W trn thit b Sonics & Materials (M). Mu c sy kh cho bay ht
dung mi sau nung mu trong khong nhit 450 - 600oC trong thi gian 45 pht thu
c sn phm nano TiO2.
Thnh phn tinh th ca mu c xc nh bng nhiu x tia X trn thit b D5005
(Siemens, c) vi bc x CuK ( = 1, 5406 ). Cp ht v hnh dng bn ngoi c quan
st bng hin vi in t qut (SEM) JSM Jeol 5410LV (Nht Bn).
Hot tnh quang xc tc ca vt liu c nghin cu thng qua qu trnh phn hy
xanh metylen trong iu kin c chiu bc x UV ( cng sut n 20W). Mt quang ca
dung dch c o trn thit b T89 UV/VIS spectrometer 665nm [9], [10].
3. KT QU V THO LUN.
3.1. Thnh phn pha v kch thc ht ca bt TiO2 thng mi
Hnh 1 trnh by gin XRD ca bt TiO2 thng mi, mu k hiu l T0. Kt qu
cho thy trn gin xut hin cc pic nhiu x c trng ca anatase vi cng b cc
gc nhiu x 25,3o tng ng vi mt (101), 37,8o (004) v 48,05o (200). Ngoi ra, trn gin
xut hin rt nhiu pic nhiu x c cng rt b. Kt qu ny cho thy: ngoi mt phn
tn ti dng tinh th anatase, phn ln TiO2 tn ti dng v nh hnh hoc vi tinh th.
Hnh thi v kch thc ht ca bt TiO2 thng mi c quan st bng hin vi in
t qut (SEM) c trnh by hnh 2. Kt qu cho thy: hnh thi ca ht TiO2 thng mi
c dng hnh cu, kt t thnh tng m, kch thc ht khng ng u, dao ng trong
khong t 150 - 350 nm.

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KHOA HC CNG NGH

110
100

80
70

d=3.522

Lin (Cps)

90

60

20

d=1.360

30

d=1.477

d=1.680

40

d=1.905

d=2.375

50

10
0

20

30

40

50

2-Theta- Scale

60

70

80

Hnh 1. Gin XRD bt TiO2thng mi

Hnh 2. nh SEM bt TiO2thng mi
3.2. Tng hp vt liu nano TiO2 bng phng php thy nhit
3.2.1. Cc yu t nh hng n qu trnh tng hp nano TiO2
Bng 1. iu kin tng hp nano TiO2 nng NaOH khc nhau
K hiu
Khi lng
Th tch
Nng
Nhit thy Thi gian thy
mu
bt TiO2 (g) NaOH (ml) NaOH (mol/l)
nhit (oC)
nhit (gi)
T-5M
2,0
100
5
180
24
T-10M
2,0
100
10
180
24
T-15M
2,0
100
15
180
24
iu kin tng hp nano TiO2 nhng nng NaOH khc nhau c trnh by bng
1, cc nhit thy nhit khc nhau c trnh by bng 2, cc thi gian thy nhit khc
nhau c trnh by bng 3.
File: HungHue M45.raw- Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 0.3s - Temp.: 25 C(Room) - Time Started: 12s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.00

Bng 2. iu kin tng hp nano TiO2 cc nhit thy nhit khc nhau
K hiu
Khi lng
Th tch
Nng
Nhit thy Thi gian thy
mu
bt TiO2 (g) NaOH (ml) NaOH (mol/l)
nhit (oC)
nhit (gi)
T-120
2,0
100
10
120
24
T-150
2,0
100
10
150
24
T-180
2,0
100
10
180
24
T-10M

T-5M

T-15M

Hnh 3. nh SEM ca cc mu nano TiO2 cc nng NaOH khc nhau

Bng 3. iu kin tng hp nano TiO2 cc thi gian thy nhit khc nhau
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KHOA HC CNG NGH

K hiu
Khi lng
Th tch
Nng
Nhit thy Thi gian thy
mu
bt TiO2 (g) NaOH (ml) NaOH (mol/l)
nhit (oC)
nhit (gi)
T-12H
2,0
100
10
180
12
T-18H
2,0
100
10
180
18
T-24H
2,0
100
10
180
24
Khi tng nng NaOH ln 15M (T-15M), cu trc si nano b ph v, cc ht TiO2
kch thc ln hn v c xu hng kt t thnh tng m, phn b khng ng u do s v
vn ca cc si nano.
T-120

T-150

T-180

Hnh 4. nh SEM ca cc mu nano TiO2 cc nhit thy nhit khc nhau

nh SEM hnh 4 cho thy: khi tng dn nhit thy nhit, hnh thi ca sn
phm chuyn t dng ht sang dng si kh r rng. Mu T-120, sn phm tn ti dng
ht vi kch thc khong 50 - 55 nm kt t li thnh tng m, hnh thnh cc tm mng.
Mu T-150: hnh thi ca sn phm tn ti dng si kh r rng, tuy nhin vn cn mt
lng ln sn phm dng ht. Mu T-180: cc si c cu trc ng u, chiu di cc si
nano ln hn so vi mu T-150, kch thc khong 10-20 nm v chiu di khong 250
300nm.
Vi cc thi gian thy nhit khc nhau, hnh thi sn phm thy nhit cng hon ton
khc nhau. mu T-12H: sn phm thu c l cc si nano. kch thc khng ng u,
ng knh cc si khong 25 - 40 nm, Khi tng thi gian thy nhit ln thnh 18 v 24 gi
(T-18H v T-24H): sn phm thu c dng si kch thc ng u hn. c bit mu T24H bao gm cc si nano vi phn tn cao, ng knh cc si nano trong mu ny
khong 10 - 20 nm, chiu di khong 250 - 300 nm, phn b ng u, b mt cc si nano
nhn.

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KHOA HC CNG NGH

T-12H

T-18H

T-24H

Hnh 5. nh SEM ca cc mu nano TiO2 vi cc thi gian thy nhit khc nhau

3.2.2. c trng vt liu nano TiO2 tng hp

A

A: anatase
A

C- ng nhiu x (cps)

T600

T450

T0
10

20

30

40

50

Gc nhiu x (2)

60

70

Hnh 6. Gin XRD ca mu nano TiO2

Hnh 7. ng ng nhit hp ph - kh
nung cc nhit khc nhau.
hp ph N2 mu T-10M
Hnh 6 trnh by gin XRD ca cc mu T450, T600 v T0. C th nhn thy
thnh phn pha ca cc mu T0 v T450 ch yu dng v nh hnh hoc vi tinh th. Cc
pic nhiu x c trng ca anatase xut ti cc gc nhiu x 25,3o, 37,8o v 48,05o tuy
nhin vi cng b. Khi tng nhit nung ln 600oC, cng cc pic nhiu x c
trng ca anatase tng ln r rt. iu ny chng t khi nung vt liu TiO2 600oC
chuyn TiO2 t dng v nh hnh thnh dng tinh th anatase.

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Th
tch
kh
hp
ph
Va
(cm3/
g)

400

Th
tch
kh
hp
ph
Va
(cm3
/g)

350
300
250
200
150
100
50
0
2

10

12

14

16

18

20

dy trung bnh ca lp hp ph t
dy trung bnh ca l p hp ph t

dy trung bnh ca lp hp ph t

Hnh 8. th biu din s ph

Hnh 9. th biu din s ph
thuc ca dy trung bnh ca lp
thuc tuyn tnh ca t v Va
hp ph t v th tch kh hp ph Va
Hnh 7 trnh gin ng ng nhit hp ph - kh hp ph N2 -196oC ca mu T10M cho thy, theo phn loi ca UIPAC, ng ng nhit hp ph - kh hp ph N2 ca
mu T-10M thuc loi IV c trng cho vt liu mao qun. im ngng t ca h p sut
P/Po kh cao kt hp vi dng iu, ng ng nhit c mt vng tr kiu H3, chng t vt
liu thu c c mao qun trung bnh bn tinh th (2 - 50 nm), mao qun ny l mao qun
gia cc si nano. Vi vng tr tri di t p sut tng i 0,82 n 1,0, vt liu c mao
qun dng hnh khe.
Cc thng s b mt ca vt liu c trnh by hnh 8, hnh 9 v bng 4.
Bng 4. Cc thng s c trng b mt ca vt liu nano TiO2
Thng s

Din tch b mt BET

Din tch mao qun TB

Din tch vi mao qun
Th tch vi mao qun

Th tch mao qun TB

ng knh mao qun TB

K hiu

n v

Gi tr

Spore

m2/g

66,2

SBET
Smic

Vmic

Vpore
Dpore

m /g
2

m /g
2

71,0
4,8

cm /g

0,0015

33

cm /g
3

0,59

3.3. Hot tnh quang xc tc ca vt liu TiO2

nghin cu kh nng xc tc quang ha ca nano TiO2 di bc x UV, bc x
mt tri, n halogen, chun b mt dy mu kho st cha dung dch xanh metylen vi b
dy l 15cm c nng 2,5 g/l, thm vo mi mu 10 mg vt liu nano TiO2 T-10M. Tin
hnh chiu bc x, thi gian chiu bc x thay i t 10 - 50 pht cho mi mu vi b dy
dung dch l 15cm. Mu M0 l dung dch xanh metylen ban u khng c nano TiO2, dng
so snh. Mu kho st sau khi chiu x c quay ly tm (3000 vng/pht) trong 10 pht
tch huyn ph. Mt quang ca dung dch c ghi bc sng 665 nm trn my trc
quang T80. Kt qu kho st kh nng xc tc quang ha ca nano TiO2 di bc x UV

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(n UV-20W), bc x mt tri (thi gian gia tra 10h-12h, nng gt), bc x halogen (n
Halogen EGK JM-500W).
Bng 5. chuyn ha xanh metylen ca vt liu T-10M di tc dng ca bc x UV
K hiu
mu
M0
M10UV
M20UV
M30UV
M40UV
M50UV

V dung dch xanh

metylen 2,5 mg/l (ml)
100
100
100
100
100
100

Khi lng Thi gian hp th chuyn

bt TiO2 (mg)
(pht)
quang
ha (%)
10
0
0,804
10
10
0,370
53,9
10
20
0,262
67,4
10
30
0,143
82,2
10
40
0,092
88,6
10
50
0,045
94,4
M0

0.8

Mt

quang

M10UV

0.6

M20UV

M30UV

0.4

M40UV

0.2

M50UV

0.0
500

550

600

650

B- c sng (nm)

700

Bc sng (nm)

750

800

Hnh 10. Ph UV-Vis ca xanh metylen vi vt liuT10M di tc dng ca bc x UV

M0 M10UV M20UV M30UV M40UV M50UV

Hnh 11. Cng mu kho st ca cc mu theo thi
gian chiu x UV
Kt qu cho thy khi chiu bc x UV, nh sng mt tri th hp th quang ca xanh
metylen gim rt mnh sau 10 pht. Khi tng thi gian chiu x, hp th quang ca dung

dch cng gim, mu sau khi chiu x 50 pht di bc x UV chuyn ha t trn 94%,
di nh sng mt tri th chuyn ha t 91,9%.
Bng 6. chuyn ha xanh metylen ca nano TiO2 tng hp theo phng php baz
di tc dng ca bc x mt tri
K hiu mu

V dung dch xanh

metylen 2,5 mg/l

Khi lng bt
TiO2 (mg)

Thi gian
(pht)

TP CH KHOA HC CNG NGH & THC PHM S 08/2016

hp chuyn
th quang ha (%)
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KHOA HC CNG NGH

(ml)
100
100
100
100
100
100

M0
M10UV-Vis
M20UV-Vis
M30UV-Vis
M40UV-Vis
M50UV-Vis

10
10
10
10
10
10

0
10
20
30
40
50

45,4
65,5
75,9
87,3
91,9

M0

0.8

Mt

quang

0,804
0,439
0,277
0,194
0,138
0,065

0.6

M10UV-Vis
M20UV-Vis

0.4

M30UV-Vis

M40UV-Vis

0.2

M50UV-Vis

0.0
500

550

600

650

700

B- sng
c sng
(nm)
Bc
(nm)

750

800

Hnh 12. Ph UV-Vis ca xanh metylen vi vt liu T-10M

di bc x mt tri
T hnh 12 v bng 6 nhn thy rng khi s dng nh sng mt tri chiu x, sau
10 pht th hp th quang ca xanh metylen gim nhanh, chuyn ha t gn 45%. Sau
thi gian 50 pht th chuyn ha t 91,9%. Chng t nano TiO2 tng hp bng phng
php baz c hot tnh quang xc tc tt di tc dng ca bc x mt tri. Mc d nh sng
mt tri ch cha 5% bc x UV, nhng chuyn ha xanh metylen ca TiO2 khi chiu bc
x mt tri t gn tng t vi bc x n UV.
Bng 7. chuyn ha xanh metylen ca vt liu T-10M di ca bc x Halogen

K hiu
mu

M0
M10Hal
M20Hal
M30Hal
M40Hal
M50Hal

V dung dch xanh

metylen 2,5 mg/l
(ml)
100
100
100
100
100
100

Khi lng bt
TiO2 (mg)
10
10
10
10
10
10

Thi gian
(pht)
0
10
20
30
40
50

hp th chuyn
quang
ha (%)

TP CH KHOA HC CNG NGH & THC PHM S 08/2016

0,804
0,572
0,482
0,396
0,202
0,095

28,8
40,1
50,7
75,9
88,2

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KHOA HC CNG NGH

M0

0.8

M20Hal

0.6

M30Hal

Mt quang

Mt

quang

M10Hal

0.4

M40Hal

M50Hal

0.2

0.0
500

550

600

650

700

B- c sng
Bc
sng(nm)
(nm)

750

800

Hnh 13. Ph UV-Vis ca xanh metylen vi vt liu T-10M

di bc x Halogen
Khi chiu x n Halogen, chuyn ha gim chm hn so vi bc x UV v nh
sng mt tri. Sau khi chiu x 50 pht, chuyn ha t 88%. Nh vy, nano TiO2 tng
hp c hot tnh quang ha tt di bc x UV v bc x mt tri, tng i tt di bc x
halogen.
Hnh 13 trnh by ph UV-Vis ca xanh metylen vi xc tc nano TiO2 tng hp khi
chiu x bng UV, nh sng mt tri, n Halogen trong thi gian 10 pht.
C th thy rng, cng mt lng xc tc nano TiO2 v thi gian chiu bc x nh
nhau, chuyn ha xanh metylen gim dn theo trt t UV > nh sng mt tri > n
Halogen.
M10Hal

0.6
0.5

Mt

quang

4.

M10UV-Vis

0.4
0.3

M10UV

0.2
0.1
0.0
500

550

600

650

700

Bc sng (nm)

750

800

Hnh 14. Ph UV-Vis ca xanh metylen vi vt liu T-10M

di tc dng ca 3 ngun bc x khc nhau
KT LUN
xc nh c cc iu kin thch hp tng hp vt liu TiO2 c cu trc nano
dng si. Vi nng NaOH 10M, nhit thy nhit 180oC trong autoclave, thi gian thy
nhit l 24 gi, sn phm thu c tn ti dng si phn b ng u, kch thc si dao
ng t 10 - 20 nm, chiu di khong 250 - 300 nm. Thnh phn pha tinh th ca sn phm

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thu c sau khi nung 600oC trong 45 pht ch yu l anatase, din tch b mt ca sn
phm t 71 m2/g. Vt liu nano TiO2 tng hp c c u c kh nng xc tc quang
ha tt lm mt mu dung dch xanh metylen di bc x UV, nh sng mt tri v ngay c
Halogen.

TI LIU THAM KHO

[1]. C. C. Tsai, J. N. Nian, H. Teng, Mesoporous nanotube aggregates obtained from
hydrothermally treating TiO2 with NaOH, Applied surface science, 253, pp. 1898-1902,
2006.
[2]. H. Yu, J. Yu, B. Cheng, J. Lin, Synthesis, characterization and photocatalytic activity of
mesoporous titania nanorod/titanate nanotube composites, Journal of Hazardous Materials,
147, pp. 581587, 2007
[3]. G. H. Du, K. Q. Chen, R. C. Che, Z. Y. Yuan, L. M. Peng, Preparation and structure
analysis of titanium oxide nanotubes, Appl. Phys. Lett., 79, pp. 3702-3704, 2001.
[4]. L.Xiong,Y.Yang,J.Mai,W.Sun,C.Zhang, D.Wei,Q.Chen,J.Ni, Adsorption behavier of
methylen blue into titanate nanotubes, Chemical Engneering Journal, 156, pp. 313-320,
2010.
[5]. L. Wu, J. C. Yu, X. Wang, L. Zhang, J. Yu, Characterization of mesoporous
nanocrystalline TiO2 Photocatalytic synthesized via a solvothermal process at a low
temperature, Tournal of Solid State Chemistry, 178, pp. 321-328, 2004.
[6]. S. Zhan, J. Yang, Y. Liu, N. Wang, J. Dai, H. Yu, X. Gao, Y. Li, Mesoporous Fe2O3doped TiO2 nano structurer fibers with higher photocatalytic activity, Journal of Colloid and
Interface Sicence, 355, pp. 328-333, 2011.
[7]. S. Kim , H. Park , C Kwak , M. Ji, M. Lee, J. Paik, B. Choi, Characterization of pore
structure of mesoporous hydrogen titanium oxide hydrates, Journal of Physics and
Chemistry of Solids, 69, pp. 1139-1141, 2008.
[8]. X. Chen, S. Mao, Titanium dioxide nanomaterials: synthesis, properties, modifications,
and application, Chem. Rev., 107, pp. 2891-2959, 2007.
[9]. W. Fumin, S. Zhansheng, G. Feng, J. Jinting, A. Motonari, J. Chin, Morphology
Control of Anatase TiO2 by Surfactant - assisted Hydrothermal Method, Chin. J. Chem. Eng.,
15(5), pp. 754 759, 2007.
[10]. Y. Jiang, P. Zhang, Z. Liu, F. Xu, The preparation of porous nano-TiO2 with high
activity and the discussion of the cooperation photocatalysis mechanism, Materials
Chemistry and Physics, 99, pp. 498-504, 2005.

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