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Synthesis and Structure of Nanocrystalline TiO

2
with
Lower Band Gap Showing High Photocatalytic Activity
K. Nagaveni ,

M. S. Hegde,*
,
N. Ravi shankar,

G. N. Subbanna,

and
Gi ri dhar Madras

Solid Stateand Structural Chemistry Unit, I ndian I nstituteof Science, Bangalore-560012,


I ndia, Materials Research Centre, I ndian I nstituteof Science, Bangalore-560012, I ndia, and
Department of Chemical Engineering, I ndian I nstituteof Science, Bangalore-560012, I ndia
Received September 24, 2003. I n Final Form: J anuary 21, 2004
Nanocrystal l i ne Ti O2 was synthesi zed by the sol uti on combusti on method usi ng ti tanyl ni trate and
vari ous fuel s such as gl yci ne, hexamethyl enetetrami ne, and oxal yl di hydrazi de. These catal ysts are acti ve
under vi si bl e l i ght, have opti cal absorpti on wavel engths bel ow 600 nm, and show superi or photocatal yti c
acti vi ty for the degradati on of methyl ene bl ue and phenol under UV and sol ar condi ti ons compared to
commerci al Ti O
2, Degussa P-25. The hi gher photocatal yti c acti vi ty i s attri buted to the structure of the
catal yst. Vari ous studi es such as X-ray di ffracti on, Raman spectroscopy, Brunauer-Emmett-Tel l er surface
area, thermogravi metri c-di fferenti al thermal anal ysi s, FT-I R spectroscopy, NMR, UV-vi s spectroscopy,
and surface aci di ty measurements were conducted. I t was concl uded that the pri mary factor for the enhanced
acti vi ty of combusti on-synthesi zed catal yst i s a l arger amount of surface hydroxyl groups and a l owered
band gap. The l ower band gap can be attri buted to the carbon i ncl usi on i nto the Ti O2 gi vi ng Ti O2-2xCx
V
O
2

.
Introduction
The presence of several organi c pol l utants i n i ndustri al
wastewater resul ts i n a seri ous envi ronmental probl em.
Photocatal yti c oxi dati on usi ng semi conductors i s one of
the advanced oxi dati on processes for the qui ck removal
of such organi c pol l utants. Al though several semi conduc-
tors such as ZnO, Fe
2
O
3
, WO
3
, and CdS have been used,
Ti O
2
has been the photocatal yst of choi ce due to i ts
photostabi l i ty, nontoxi ci ty, l ow cost, redox effi ci ency, and
avai l abi l i ty.
1-5
I n general , i t i s found that the ruti l e form
of Ti O
2
i s l ess photoacti ve than anatase.
3,5,6
Si nce the
acti vi ty of amorphous ti tani a i s negl i gi bl e, an anatase
powder wi th a hi gh degree of crystal l i ni ty wi th hi gh surface
area i s i mportant to i mprove the photocatal yti c acti vi ty.
7
I n most of the studi es, commerci al l y avai l abl e ti tani a
powder, Degussa P-25, was empl oyed. The probl em wi th
the P-25 powder i s that the Ti O
2
di sperses i n water formi ng
a whi te col l oi dal sol uti on and i t i s di ffi cul t to separate
from the reacti on mi xture for reuse. Fi l trati on i s energy
i ntensi ve, and therefore, i t woul d be desi rabl e to have a
powder that settl es easi l y and can be reused.
Several attempts have been made to i mprove the
performance of Ti O
2
as a photocatal yst under UV i l -
l umi nati on and to extend i ts absorpti on and conversi on
capaci ty i nto the vi si bl e porti on of the sol ar spectrum.
8-14
Choi et al .
10
conducted a systemati c study of 21 metal i ons
dopi ng i n quantum-si zed Ti O
2
, but noappreci abl e change
i n the band-gap energy of Ti O
2
was observed. Dopi ng of
ani ons has al so been i nvesti gated. Khan et al .
11
reported
a chemi cal l y modi fi ed, carbon-substi tuted Ti O
2
absorbi ng
l i ght at wavel engths bel ow 535 nm and havi ng a l ower
band gap. Asahi et al .
12
reported that Ti O
2-x
N
x
shows a
shi ft i n i ts opti cal absorpti on and photodegradati on of
methyl ene bl ue and gaseous acetal dehyde i n the vi si bl e
regi on of < 500 nm.
Nanosi ze ti tani a powders have been synthesi zed by
vari ous methods such as the aerosol process,
15,16
the sol -
gel method,
17,18
i nert gas condensati on,
19
and the hydro-
thermal process.
20,21
The aerosol process yi el ds hi gh-puri ty
products and does not i nvol ve mul ti pl e steps, but the hi gh
temperature empl oyed i n the aerosol process l eads to
aggregati on of the parti cl es. On the other hand, the sol -
gel process empl oys costl y chemi cal s and i nvol ves mul ti pl e
steps. I n the case of the i nert gas condensati on process,
gas condensati on i s carri ed out compl etel y under ul trahi gh
* To whom correspondence shoul d be addressed. E-mai l :
mshegde@sscu.i i sc.ernet.i n. Fax: +91-80-3601310.

Sol i d State and Structural Chemi stry Uni t.

Materi al s Research Centre.

Department of Chemi cal Engi neeri ng.


(1) Hoffmann, M. R.; Marti n, S. T.; Choi , W.; Bahnemann, D. W.
Chem. Rev. 1995, 95, 69.
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(5) Ol l i s, D. F.; Al -Ekabi , H. PhotocatalyticPurificationandTreatment
of Water and Air; El sevi er: Amsterdam, 1993.
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(10) Choi , W.; Termi n, A.; Hoffmann, M. R. J . Phys. Chem. 1994, 98,
13669.
(11) Khan, S. U. M.; Al -Shahry, M.; I ngl er, W. B., Jr. Science2002,
297, 2243.
(12) Asahi , R.; Mori kawa, T.; Ohwaki , T.; AoKi , K.; Taga, Y. Science
2001, 293, 269.
(13) Yu, J. C.; Yu, J. G.; Ho, W. K.; Ji ang, Z. T.; Zhang, L. Z. Chem.
Mater. 2002, 14, 3808.
(14) Hattori , A.; Shi moda, K.; Tada, H.; I to, S. Langmuir 1999, 15,
5422.
(15) Tewi l l i nger, C. D.; Chi ang, Y. M. Nanostruct. Mater. 1993, 2, 37.
(16) Akhtar, M. K.; Pratsi ni s, S. E.; Mastrangel o, S. V. R. J . Am.
Ceram. Soc. 1992, 75, 3408.
(17) Schnei der, M.; Bai ker, A. J . Mater. Chem. 1992, 2, 587.
(18) Campbel l , L. K.; Na, B. K.; Ko, E. I . Chem. Mater. 1992, 4 (6),
1329.
(19) Rubi o, J.; Oteo, J. L.; Vi l l egas, M.; Duran, P. J . Mater. Sci. 1997,
32, 643.
(20) Masui , T.; Fuji wara, K.; Machi da, K.; Adachi , G. Chem. Mater.
1997, 9 (10), 2197.
(21) Stathatos, E.; Li anos, P.; Del Monte, F.; Levy, D.; Tsi ourvas, D.
Langmuir 1997, 13, 4296.
2900 Langmuir 2004, 20, 2900-2907
10.1021/l a035777v CCC: $27.50 2004 Ameri can Chemi cal Soci ety
Publ i shed on Web 02/19/2004
vacuum condi ti ons and the cost of producti on i s hi gh. The
hydrothermal processi ng has shown great promi se, pro-
duci ng parti cl es at a rel ati vel y l ower temperature at
around 300 C. However, even these parti cl es requi re
cal ci nati on at a hi gher temperature of 550-600 Ctoreach
thei r photocatal yti c potenti al .
The sol uti on combusti on method has been found togi ve
hi ghl y crystal l i ne fi ne parti cl es/l arge surface area oxi de
materi al s such as al umi na, ceri a, ti tani a, and zi rconi a.
22,23
The fl ame pyrol ysi s of Ti metal gi ves carbon-substi tuted
Ti O
2-x
C
x
wi th l ower band gap energy.
11
Therefore, we
consi dered i t worthwhi l e to i nvesti gate whether the
sol uti on combusti on method wi th fuel s such as gl yci ne,
hexamethyl enetetrami ne (HMT), and oxal yl di hydrazi de
wi l l gi ve such chemi cal l y modi fi ed Ti O
2
wi th l ower band
gap. Herei n we report the synthesi s of hi gh surface area,
nanocrystal l i ne l ower band gap anatase Ti O
2
by the
sol uti on combusti on method and show that carbi de i on
substi tuted Ti O
2
i s a hi ghl y effi ci ent photocatal yst both
i n UV and sol ar condi ti ons for vari ous reacti ons. The
acti vi ty i s much hi gher than that of commerci al Ti O
2
,
Degussa P-25.
Experimental Section
Synthesis.Nanosi ze ti tani a was obtai ned by the combusti on
of aqueous sol uti ons contai ni ng stoi chi ometri c amounts of Ti O-
(NO3)2 and fuel s such as gl yci ne (Merck), hexamethyl enetetra-
mi ne (S.D. Fi ne Chemi cal s, I ndi a), and oxal yl di hydrazi de (ODH).
The control l ed hydrol ysi s of ti tani um i sopropoxi de under i ce-
col d (4 C)condi ti ons wi th vi gorous sti rri ng gi ves whi te preci pi tate
of Ti O(OH)
2. The preci pi tate was washed several ti mes i n di sti l l ed
water and then di ssol ved i n ni tri c aci d toget a cl ear, transparent
ti tanyl ni trate [Ti O(NO
3)2] sol uti on. Thi s sol uti on was used as
the precursor for the synthesi s of Ti O2. Further detai l s of the
preparati on have been descri bed el sewhere.
23
The product was
yel l ow i n col or when gl yci ne was used as a fuel [hereafter cal l ed
Ti O
2(G)], and i t was cl ear whi te wi th HMT [Ti O2(H)] and pal e
yel l ow wi th ODH [Ti O2(O)]. As-synthesi zed Ti O2 i s used i n
photochemi cal reacti ons.
Characterizationof theCombustionProduct.The X-ray
di ffracti on (XRD)patterns of ti tani a were recorded on a Si emens
D-5005 di ffractometer usi ng Cu KR radi ati on i n the 2 range
from 5 to 100 wi th a scanni ng rate of 1/mi n. The crystal l i ni ty
was anal yzed by Raman spectroscopy (Bruker RFS 100/S).
Transmi ssi on el ectron mi croscopy (TEM)of powders was carri ed
out usi ng a JEOL JEM-200CXtransmi ssi on el ectron mi croscope
operated at 200 kV. The surface area of the ti tani a was determi ned
wi th a standard Brunauer-Emmett-Tel l er (BET) apparatus
(NOVA-1000, Quantachrome). X-ray photoel ectron spectra of
these materi al s were recorded wi th ESCA-3 Mark I I spectrometer
(VG Sci enti fi c Ltd., U.K.) usi ng Al KR radi ati on (1486.6 eV).
Temperature-programmed desorpti on studi es of as-prepared Ti O2
were carri ed out, and the desorbed speci es were anal yzed wi th
quadrupol e mass spectrometer QXK300 (VG Sci enti fi c). The as-
synthesi zed Ti O2 was subjected to thermogravi metri c-di f-
ferenti al thermal anal ysi s (TGA-DTA) (Perki n-El mer-Pyri s
Di amond) to determi ne the adsorbed water. FT-I R studi es were
carri ed out i n the 400-4000 cm
-1
frequency range i n the
transmi ssi on mode (Perki n-El mer, FTI R-Spectrum-1000). UV-
vi s absorpti on spectra of Ti O2 powders were obtai ned usi ng a
UV-vi s spectrophotometer (GBC Ci ntra 40, Austral i a)between
270 and 800 nm. Each sampl e was dry-pressed i nto a 10 mm
di ameter round di sk contai ni ng about 150 mg of mass. Absorpti on
spectra were referenced to BaSO4. The aci di ty of the ti tani a was
determi ned by temperature-programmed desorpti on (TPD) of
ammoni a usi ng a thermal conducti vi ty detector.
CatalyticStudies.The photocatal yti cacti vi ty of combusti on-
synthesi zed Ti O2 was eval uated by measuri ng degradati on rates
of methyl ene bl ue (MB) and phenol i n sol ar and UV condi ti ons.
The acti vi ty of thi s catal yst was compared wi th that of commerci al
Ti O
2, Degussa P-25. Al l the experi ments were carri ed out usi ng
a cyl i ndri cal annul ar batch photoreactor. The desi gn, the
operati on of the reactor, and the characteri zati on of the l amp
have been di scussed i n detai l el sewhere.
23
Al l degradati ons were
performed i n an open system wherei n the top surface of the
photoreactor was open to ai r. Thi s i ndi cates that atmospheri c
ai r provi ded enough oxygen for the oxi dati ve degradati on of
pol l utants.
Al l the sol ar experi ments were carri ed out i n a cyl i ndri cal
borosi l i cate gl ass reactor wi th i .d. of 8 cm and 400 cm
3
vol ume.
Di rect sunl i ght was used i n the present study, and the average
sol ar i ntensi ty was 0.753 kW/m
2
. Sampl es were col l ected at
regul ar i nterval s for subsequent anal ysi s by a UV/vi si bl e
spectrophotometer (Shi madzu, UV-2100). Chemi cal anal ysi s of
the fi l trate was carri ed out i n a HPLC system (Waters I nc., USA).
Results
Photocatalytic Activity. I t was observed that no
detectabl e degradati on of the pol l utants occurs wi thout
Ti O
2
or i rradi ati on (UV and sol ar) al one. The adsorpti on
capaci ty of the combusti on-synthesi zed ti tani a for MBand
phenol was eval uated, and the resul ts i ndi cate that there
was no measurabl e amount of adsorpti on of MB as wel l
as phenol over combusti on-synthesi zed catal ysts. Hence,
the i ni ti al concentrati on was taken to be C
0
i n al l the
cases. The effects of catal yst l oadi ng and the i ni ti al
concentrati on on photocatal yti cdegradati on were studi ed,
and the opti mal catal yst l oadi ng of 1 kg/m
3
and i ni ti al
concentrati on of 100 ppm of dye and 0.5 mM/L phenol
were empl oyed throughout the study.
Fi gure 1a shows the degradati on profi l e of MB i n sol ar
i rradi ati on wi th an i ni ti al concentrati on of 100 ppm wi th
the 1 kg/m
3
(100 mg/100 mL) catal yst l oadi ng. The
compl ete degradati on of the dye was observed i n 220 mi n
wi th Ti O
2
(G), and the conversi on was essenti al l y compl ete
at 300 mi n over Ti O
2
(H). However, when the degradati on
was catal yzed by Degussa, an i ni ti al decrease i n the
concentrati on up to 50 ppm and no further degradati on
(22) Pati l , K. C.; Amar Sekar, M. M. I nt. J . Self-Propag. High-Temp.
Synth. 1994, 3, 181.
(23) Si val i ngam, G.; Nagaveni , K.; Hegde, M. S.; Madras, G. Appl.
Catal., B 2003, 45, 23.
Figure1. Degradati on profi l es of methyl ene bl ue wi th an i ni ti al
concentrati on of 100 ppm and a catal yst l oadi ng of 1 kg/m
3
wi th
combusti on-synthesi zed and Degussa P-25 Ti O2 under (a)sol ar
and (b) UV condi ti ons.
Synthesis and Structureof NanocrystallineTiO
2
Langmuir, Vol. 20, No. 7, 2004 2901
of MB was observed. Even though Ti O
2
(H) and Ti O
2
(O)
show compl ete degradati on of MB, the i ni ti al rate of
degradati on was l ess compared to the rate of degradati on
wi th Ti O
2
(G). The i ni ti al rates of the reacti on are
determi ned by conducti ng a seri es of concentrati on versus
ti me experi ments at di fferent i ni ti al concentrati ons, and
each run i s extrapol ated back to the i ni ti al condi ti ons.
24
The i ni ti al rates of degradati on of MB are 0.153, 0.027,
0.024, and 0.018 mol L
-1
s
-1
for Ti O
2
(G), Ti O
2
(H), Ti O
2
-
(O), and Degussa P-25 Ti O
2
, respecti vel y.
Experi ments were al so carri ed out under UV wi th the
same i ni ti al concentrati on and catal yst l oadi ng over Ti O
2
-
(G) and compared wi th resul ts for Degussa P25. The
resul ts are shown i n Fi gure 1b. Di sappearance of MB was
compl ete i n 50 mi n over Ti O
2
(G), whi l e the concentrati on
of the dye remai ned at 4.5 ppm wi th Degussa P25 even
at 120 mi n. The i ni ti al rate of degradati on of dye was
0.427 and 0.271 mol L
-1
s
-1
wi th Ti O
2
(G) and Degussa
P-25 Ti O
2
, respecti vel y. For hi gher i ni ti al concentrati ons
(200 ppm), compl ete degradati on of MB was observed i n
65 mi n under UV when catal yzed by Ti O
2
(G). However,
the concentrati on of MB shows onl y an i ni ti al decrease up
to 100 ppm and then there i s no further degradati on of
the dye when catal yzed by Degussa P25, as seen from the
i nset of the fi gure.
We al so eval uated the photodecomposi ti on of phenol
wi th the combusti on-synthesi zed Ti O
2
i n sol ar and UV
condi ti ons. Fi gure 2a shows the degradati on profi l e of
phenol wi th an i ni ti al concentrati on of 0.5 mM/L (48 ppm)
and a catal yst l oadi ng of 1 kg/m
3
i n sol ar condi ti ons. The
phenol compl etel y degrades when catal yzed by Ti O
2
(G),
and the photoacti vi ty of Ti O
2
(H) was comparabl e wi th
that of Ti O
2
(G), whi l e the concentrati on shows saturati on
at 30 ppm when catal yzed by Degussa P25. The Ti O
2
(O)
al soshows degradati on of phenol , but the i ni ti al degrada-
ti on rate i s l ess compared to the i ni ti al degradati on rate
of phenol by Ti O
2
(G) and Ti O
2
(H). The i ni ti al rates of
degradati on of phenol over di fferent catal ysts are i n the
fol l owi ng order: Ti O
2
(G) >Ti O
2
(H) >Ti O
2
(O) >Degussa
P-25 Ti O
2
.
The acti vi ty of combusti on-synthesi zed ti tani a was
hi gher i n UV condi ti ons, as seen from Fi gure 2b. The
compl ete degradati on of phenol was observed at 120 mi n
wi th combusti on-synthesi zed Ti O
2
(G), whi l e the concen-
trati on of phenol shows saturati on around 38 ppm wi th
Degussa P-25. The i ni ti al rates of degradati on of phenol
i n UV wi th combusti on-synthesi zed Ti O
2
and Degussa
P-25 are 0.023 and 0.012 mol L
-1
s
-1
, respecti vel y, whi ch
i s about 2 ti mes hi gher than that of Degussa P-25 Ti O
2
.
HPLC anal ysi s of the sol uti on from phenol degradati on
wi th combusti on-synthesi zed Ti O
2
showed no i ntermedi -
ates such as catechol (CC) or hydroqui none (HQ) duri ng
the reacti on, and the concentrati on of phenol conti nuousl y
decreased wi th ti me. However, when the degradati on of
phenol was conducted wi th Degussa P-25, twomajor peaks
for CC and HQ were detected and the concentrati on of
HQ and CC i ncreased wi th the decrease i n phenol
concentrati on. I t appears that secondary hydroxyl ati on
and ri ng-openi ng reacti ons for phenol are extremel y fast
wi th the combusti on-synthesi zed catal yst. Most of the
phenol i c speci es i ncl udi ng CC and HQ are al so water
pol l utants. Si nce no si gni fi cant amounts of these speci es
are formed when phenol i s degraded by combusti on-
synthesi zed Ti O
2
, thi s reduces the degree of pol l uti on i n
the water bodi es compared to the commerci al materi al
Degussa P-25. These resul ts demonstrate the hi gher
photocatal yti c acti vi ty of combusti on-synthesi zed Ti O
2
under UV and sol ar exposure compared to the photo-
catal yti c acti vi ty of Degussa P-25 under i denti cal experi -
mental condi ti ons. I n addi ti on to hi gher photocatal yti c
acti vi ty, the combusti on-synthesi zed ti tani a i s easi er to
separate from water. Degussa P25 Ti O
2
forms a mi l ky
whi te turbi d suspensi on i n aqueous medi a. Though the
combusti on-synthesi zed Ti O
2
crystal l i tes are 6-10 nm i n
si ze, they do not form a turbi d suspensi on. Further, thi s
catal yst settl es faster and i t i s easi er to separate from the
reacti on mi xture by centri fugati on. The hi gh catal yti c
acti vi ty of combusti on-synthesi zed Ti O
2
must be attri buted
to i ts structure, and therefore we have exami ned the
structure i n detai l .
Structural Analysis of the Catalyst
XRDStudies.XRDpatterns of Ti O
2
(G), Ti O
2
(H), Ti O
2
-
(O), and commerci al Ti O
2
, Degussa P25, are shown i n
Fi gure 3. The pattern can be i ndexed toTi O
2
i n the anatase
phase onl y. The ruti l e and brooki te phases of Ti O
2
were
not observed. The crystal l i te si ze i s determi ned from each
101 peak i n the XRD pattern usi ng the Sherrer formul a,
and the si zes are 6, 7, 9, and 32 nm for Ti O
2
(G, H, O) and
Degussa P25 Ti O
2
, respecti vel y.
Ri etvel d refi nements of the di ffracti on profi l es of
combusti on-synthesi zed ti tani a were carri ed out usi ng the
Ful l prof-98 program, and a good agreement between
cal cul ated and observed patterns was observed (see the
Supporti ng I nformati on, Fi gure S1). The background of
the X-ray pattern (Fi gure 3 and Fi gure S1) i s fl at,
i ndi cati ng that combusti on-synthesi zed Ti O
2
i s crystal l i ne.
For Ti O
2
(G), the R
Bragg
, R
F
, and R
P
val ues are 4.67, 3.36,
and 9.32%, respecti vel y. The l atti ce parameters for Ti O
2
-
(G) are a ) 3.7865 (5) and c ) 9.509 (1) . The total
oxygen i n al l the Ti O
2
sampl es was 2. Refi nements of Ti O
2
-
(H) and Ti O
2
(O) al so showed a good agreement wi th the
cal cul ated pattern, and no si gni fi cant vari ati on i n the
l atti ce parameters and oxygen content i s observed.
(24) Levenspi el , O. Chemical Reaction Engineering, 2nd ed.; John
Wi l ey & Sons: New York, 1995; p 70.
Figure 2. Degradati on profi l es of phenol wi th an i ni ti al
concentrati on of 0.5 mM (48 ppm) and a catal yst l oadi ng of 1
kg/m
3
wi th combusti on-synthesi zed and Degussa P-25 Ti O2
under (a) sol ar and (b) UV condi ti ons.
2902 Langmuir, Vol. 20, No. 7, 2004 Nagaveni et al.
After photocatal yti c reacti ons, XRD patterns of the
catal ysts were recorded and there was no change i n the
structure and the l i ne wi dth of the peaks. To fi nd the
stabi l i ty of combusti on-synthesi zed Ti O
2
, sampl es were
heated at 400 C for 48 h. Even after heat treatment of
Ti O
2
, onl y the anatase phase wi th i ncreased crystal l i te
si ze from 6 to 15 nm was observed. The col or of Ti O
2
(G)
changed from yel l ow to whi te.
RamanStudies.The Raman spectrum of Ti O
2
(G)(see
the Supporti ng I nformati on, Fi gure S2) shows that the
materi al i s wel l crystal l i zed i n the anatase phase wi thout
any ruti l e i mpuri ty. The spectrum shows a strong sharp
band at 146 cm
-1
, three mi d-i ntensi ty bands at 396, 516,
and 641 cm
-1
, and a weak band at 200 cm
-1
, whi ch
correspond to the fundamental vi brati onal modes of
anatase ti tani a. Ti O
2
(H) and Ti O
2
(O) al so show onl y the
anatase phase.
TEM Studies. Bri ght-fi el d i mages recorded i n the
transmi ssi on el ectron mi croscope of Ti O
2
(G), Ti O
2
(H), and
Ti O
2
(O) are shown i n Fi gure 4a-c. Si nce i t was di ffi cul t
to i denti fy the separate crystal l i tes usi ng bri ght-fi el d
i mages of combusti on-synthesi zed ti tani a, dark-fi el d
i magi ng was al socarri ed out and the crystal l i te si zes were
determi ned from the dark-fi el d i mages. The crystal l i te
si zes are 6-8, 7-9, and 11-13 nm for Ti O
2
(G), Ti O
2
(H),
and Ti O
2
(O), respecti vel y. The si zes obtai ned from the
dark-fi el d i mages are i n cl ose agreement wi th the XRD
val ues. The bri ght-fi el d i mage of Degussa P25 Ti O
2
i s
shown i n Fi gure 4d for compari son. Cl earl y the si zes of
these crystal l i tes are i n the range of 100-150 nm. The
si zes obtai ned i n TEM are si gni fi cantl y hi gher than that
cal cul ated usi ng the Sherrer formul a for Degussa P25.
The el ectron di ffracti on studi es i ndi cate that combusti on-
synthesi zed ti tani a i s hi ghl y crystal l i ne, as the pattern
coul d be i ndexed to the anatase phase onl y (Fi gure 4e).
The d spaci ng cal cul ated from the el ectron di ffracti on
pattern matches the val ues obtai ned from XRD patterns.
The crystal l i ne nature of the combusti on-synthesi zed
ti tani a i s evi dent from the absence of the di ffuse hal o
normal l y associ ated wi th the presence of amorphous
phases. Anal ysi s of the l atti ce fri nges of i ndi vi dual smal l
crystal l i tes i n the hi gh-resol uti on i mage of Ti O
2
(G) (see
the Supporti ng I nformati on, Fi gure S3)showed the l atti ce
spaci ng of 3.5 ( 0.1 , whi ch i s i n good agreement wi th
the anatase (101) l atti ce spaci ng of 3.52 . There i s no
evi dence for the presence of amorphous phases i n these
hi gh-resol uti on i mages, further corroborati ng that the
combusti on-synthesi zed ti tani a i s ful l y crystal l i ne.
Surface Area. The BET surface areas measured for
combusti on-synthesi zed Ti O
2
parti cl es are 246, 164, and
143 m
2
/g for Ti O
2
(G), Ti O
2
(H), and Ti O
2
(O), respecti vel y,
whi l e the surface area of commerci al Ti O
2
, Degussa P-25,
was 50 m
2
/g. The surface area for Ti O
2
(G) cal cul ated by
assumi ng al l the parti cl es are cubi c wi th si ze of 6 nm and
densi ty of 3.84 g/m
2
i s 260 m
2
/g. Thi s val ue i s cl ose to the
measured val ue of 246 m
2
/g. Thus, Ti O
2
(G) i s i ndeed a
nanocrystal l i ne, hi gh surface area materi al .
XPS Studies. Ti (2p) core l evel spectra of the Ti O
2
(G,
H, and O) and Degussa P25 were recorded (see the
Supporti ng I nformati on, Fi gure S4). The two peaks
observed at 459.0 and 464.8 eV are due to Ti
4+
(2p
3/2
) and
Ti
4+
(2p
1/2
), respecti vel y. There was noTi
3+
speci es observed
i n XPS. The l i ne wi dth of Ti (2p
3/2
) of Degussa P25 Ti O
2
i s sl i ghtl y hi gher compared to that of the Ti O
2
prepared
here.
25
Thi s may suggest that Degussa P25 i s not as
crystal l i ne as the Ti O
2
prepared here. The total Ti (2p)
i ntensi ty of Degussa P25 Ti O
2
i s much hi gher than that
of the Ti O
2
synthesi zed here. Obvi ousl y, the densi ty of Ti
i n the Degussa P25 pel l et i s hi gher than that of combus-
ti on-synthesi zed ti tani a, suggesti ng a hi gher crystal l i te
si ze of Degussa P25 whi ch agrees wel l wi th XRDand TEM.
Fi gure 5a shows the oxygen core l evel spectra of
combusti on-synthesi zed and Degussa P25 Ti O
2
. The O(1s)
core l evel spectrum of Ti O
2
(G) shows two peaks at 530.1
and 532.4 eV. The peak at 532.4 eV can be attri buted to
the surface hydroxyl groups or chemi sorbed water mol -
ecul es on the ti tani a, whi l e the 530.1 eV peak i s due to
O
2-
i on. Ti O
2
(H) and Ti O
2
(O) al so show a shoul der to the
mai n O(1s) peak at hi gher bi ndi ng energy, but the
i ntensi ti es are l ow. Thus Ti O
2
(G)contai ns more adsorbed
water.
The C(1s) spectra of the combusti on-synthesi zed Ti O
2
show a peak at 285.5 eVwhi ch can be assi gned tographi ti c
carbon as shown i n Fi gure 5b. Ti O
2
(G)has a l ower bi ndi ng
energy peak at 284.3 eV unl i ke Ti O
2
(H), Ti O
2
(O), and
Degussa P25. Thi s l ower bi ndi ng energy peak can be
assi gned to a carbi di c speci es. To test thi s, Ti O
2
(G) was
heated i n a furnace for 48 h at 400 C. The col or of the
Ti O
2
(G) pel l et changed from yel l ow to whi te. The l ow
bi ndi ng energy C(1s) peak vani shes upon heati ng Ti O
2
-
(G) [see Fi gure 5b]. Therefore, XPS of Ti O
2
(G) i s di fferent
compared to that of Ti O
2
(H)and Ti O
2
(O)i n terms of more
adsorbed water and the presence of carbi de speci es.
To i nvesti gate any ni trogen i ncorporati on, the N(1s)
core l evel spectra were recorded for al l the sampl es (see
(25) Nanda, J.; Kuruvi l l a, B. A.; Sharma, D. D. Phys. Rev. B 1999,
59, 7473.
Figure 3. X-ray di ffracti on patterns of (i ) Degussa P-25
Ti O2, (i i ) Ti O2(G), (i i i ) Ti O2(H), and (i v) Ti O2(O).
Synthesis and Structureof NanocrystallineTiO
2
Langmuir, Vol. 20, No. 7, 2004 2903
the Supporti ng I nformati on, Fi gure S5). I n al l the sampl es,
a N(1s) peak of si gni fi cant i ntensi ty i s observed at 400 (
0.5 eV whi ch can be assi gned to chemi sorbed -N
2
.
26
The
i ntensi ty rati o of N(1s)/Ti (2p
3/2
) i s 0.066 for Ti O
2
(H) and
Ti O
2
(O) compared to 0.057 for Degussa P25 Ti O
2
. The
val ue i s 0.37 i n Ti O
2
(G). General l y, N(1s) of N
3-
i on i s
observed at 398 (0.5 eV. From the N(1s)bi ndi ng energy,
the total ni trogen i n these materi al s i s not i n the N
3-
state and i t can be assi gned to -NH-l i ke speci es on the
surface. However, the i ntensi ty of N(1s)i n Ti O
2
(G)i s 5-6
ti mes hi gher. The N(1s)peak i s broad, and i t may contai n
a suffi ci ent amount of N
3-
at 398.5-399 eV i n addi ti on
to -NH-l i ke speci es.
TPD Studies. Thermal desorpti on studi es of the
combusti on-synthesi zed ti tani a from room temperature
to 500 C i n a vacuum were carri ed out, and the resul ts
reveal that the pri nci pl e speci es to l eave the surface of
Ti O
2
i s water. The appearance of two water desorpti on
peaks (see the Supporti ng I nformati on, Fi gure S6) i ndi -
cates that twotypes of water exi st on the surface of ti tani a.
I n the l ower temperature regi on (<150 C), for Ti O
2
(G)an
i ntense peak was observed due todesorpti on of mol ecul arl y
adsorbed (or physi sorbed) speci es (peak I ), and at hi gher
temperatures the dehydroxyl ati on of the H-bonded hy-
droxyl occurs. For temperatures around 450 C, under a
vacuum nearl y al l the H-bonded hydroxyl groups are
removed from the surface. Thus progressi ve heat treat-
ments dehydrate and dehydroxyl ate the ti tani a surface.
Evi dence of CO
2
desorpti on occurs above 300 C. Ti O
2
(H)
and Ti O
2
(O) al so show two water peaks, but the amount
of desorpti on i s rel ati vel y l ess. The CO
2
desorpti on was
much l ess i n the case of Ti O
2
(H) and Ti O
2
(O).
TGAStudies. TGA of combusti on-synthesi zed ti tani a
was carri ed out, and the total wei ght l oss i n the whol e
temperature range i s 14.4% for Ti O
2
(G), 11.5% for Ti O
2
-
(H), 6.3%for Ti O
2
(O), and 1.8%for Degussa P-25 ti tani a.
There are three regi ons of wei ght l oss i n the case of
combusti on-synthesi zed Ti O
2
(see the Supporti ng I nfor-
mati on, Fi gure S7). The fi rst regi on i s bel ow 150 C, over
whi ch the mass l oss of 10% was observed i n the case of
Ti O
2
(G), due to the l oss of physi cal l y adsorbed water, and
that i n the regi on of 150-500 C, where the mass l oss i s
4%due tothe removal of strongl y bound water or surface
hydroxyl groups. The thi rd stage i s from 500 to 800 C,
where the mass l oss i s about 0.4%and then mass remai ns
constant. Thi s can be attri buted to carbon, whi ch i s
i ncorporated duri ng combusti on. The Ti O
2
(H) and Ti O
2
-
(O)al soshow three regi ons of wei ght l oss. The commerci al
catal yst Degussa P-25 shows 0.8%wei ght l oss from room
temperature to 150 C, 0.9%wei ght l oss between 150 and
500 C, and no wei ght l oss thereafter. From the TGA
studi es, i t i s cl ear that surface hydroxyl groups are much (26) Saha, N. C.; Tompki ns, H. G. J . Appl. Phys. 1992, 72, 3072.
Figure4. Transmi ssi on el ectron mi crographs of (a) Ti O2(G), (b) Ti O2(H), (c) Ti O2(O), and (d) Degussa P25 Ti O2 and (e) el ectron
di ffracti on of Ti O2(G).
2904 Langmuir, Vol. 20, No. 7, 2004 Nagaveni et al.
hi gher i n combusti on-synthesi zed Ti O
2
. Among the Ti O
2
sampl es prepared here, Ti O
2
(G) has the hi ghest surface
hydroxyl ati on. The surface area of Ti O
2
(G) i s 5 ti mes
hi gher than that of Degussa P25. But the wei ght l oss due
to dehydroxyl ati on i s 8.5 ti mes hi gher. Therefore, the
i ncrease i n total H
2
O/OH
-
adsorpti on i s not purel y due to
i ncrease i n surface area al one.
FT-IR and NMR Studies. FT-I R spectra of combus-
ti on-synthesi zed Ti O
2
recorded i n the frequency range of
400-4000 cm
-1
show a very broad band at 3400 cm
-1
,
that resul ts from a superposi ti on of the vi brati on bands
of hydroxyl groups and the stretchi ng vi brati ons of
adsorbed water mol ecul es. A band at 1636 cm
-1
i s due to
bendi ng of mol ecul ar water (see the Supporti ng I nforma-
ti on, Fi gure S8). Cl earl y there i s a noti ceabl e di fference
between Ti O
2
(G) and Ti O
2
(H and O). There i s a consi der-
abl e area reducti on for the very l arge band at 3400 cm
-1
and for the 1640 cm
-1
band. I t can be seen from the fi gure
that the area of thi s band i s much l ess for Degussa P25
Ti O
2
compared to Ti O
2
prepared here. Combusti on-
synthesi zed ti tani a catal ysts were heated at 400 C, and
utmost care was taken toavoi d any absorpti on of moi sture.
The I R spectra of the catal yst recorded after heat
treatment al so showed a strong peak at 3400 cm
-1
. Thi s
can be attri buted to the presence of chemi sorbed water or
surface hydroxyl groups. A peak at around 2300 cm
-1
i s
due toCO
2
adsorbed on the ti tani a surface. The TPDstudy
al so confi rms the presence of a very smal l amount of
adsorbed CO
2
on the catal ysts.
The proton NMR spectra of Degussa P25 show a broad
peak wi th a ful l wi dth at hal f-maxi mum (fwhm)of 1.9938,
whi l e combusti on-synthesi zed ti tani a shows narrow peaks
wi th fwhms of 1.291 and 0.9346 for Ti O
2
(G) and Ti O
2
(H),
respecti vel y (see the Supporti ng I nformati on, Fi gure S9).
Thus, the protons of Ti O
2
(G and H)are much more mobi l e
than that i n Degussa P25.
27
The chemi cal shi ft of Degussa
P25 i s 4.98, whi l e the chemi cal shi fts for Ti O
2
(G and H)
are 5.73 ppm. Thi s i ncrease i n the chemi cal shi ft can be
attri buted to the i nteracti on between surface hydroxyl
groups, because a much l arger amount of H
2
O/OH
-
i s
present over combusti on-synthesi zed Ti O
2
.
UV-VisSpectroscopy.Fi gure 6 shows the UV-vi si bl e
absorpti on spectra of combusti on-synthesi zed Ti O
2
. The
band gap energi es (E
g
) are as fol l ows: for Ti O
2
(O), the
absorpti on edge i s at 415 nm (2.98 eV), for Ti O
2
(H) i t i s
435 nm (2.85 eV), and for commerci al Ti O
2
, Degussa P-25,
i t i s 400 nm (3.10 eV). Ti O
2
(G)shows twoopti cal absorpti on
threshol ds at 560 and 435 nm that correspond tothe band
gap energi es of 2.21 and 2.85 eV, respecti vel y. Ti O
2
(G)
absorbs appreci abl y at wavel engths l ess than 600 nm.
(27) Xu, W.; Raftery, D. J . Phys. Chem. B 2001, 105, 4343.
Figure 5. (a) O(1s) core l evel spectra of Ti O2; (b) C(1s) core l evel spectra of Ti O2.
Synthesis and Structureof NanocrystallineTiO
2
Langmuir, Vol. 20, No. 7, 2004 2905
Cl earl y the band gap of the Ti O
2
synthesi zed here i s l ower
than that of Degussa P25 Ti O
2
. On heati ng Ti O
2
(G)at 400
C for 48 h, the band at 570 nm di sappears and the
absorpti on spectrum i s si mi l ar to that of Ti O
2
(H).
The sol ar wavel ength spectrum measured here has
maxi mum i rradi ance at the wavel ength regi on of 450-
480 nm. Si nce the combusti on synthesi s Ti O
2
band gap
corresponds to thi s regi on, i t can absorb rel ati vel y hi gher
photon fl ux compared to Degussa P-25. The i rradi ances
correspondi ng to the wavel engths of 400, 467, and 570
nm are 1.556, 1.962, and 1.799 W m
-2
nm
-1
, respecti vel y.
The absorbed photon fl ux rati ofor combusti on-synthesi zed
Ti O
2
i s 1.62 and 2.35 ti mes hi gher than that of Degussa
P-25 Ti O
2
for the absorpti on threshol ds of 467 and 570
nm, respecti vel y.
Acidity Measurement. The TPD of ammoni a was
carri ed out over combusti on-synthesi zed Ti O
2
and Degussa
P25 Ti O
2
. The peak area i s l arger for combusti on-
synthesi zed Ti O
2
than for the Degussa P25 (see the
Supporti ng I nformati on, Fi gure S10). The strength and
amount of aci di c si tes are refl ected i n the desorpti on
temperature and the peak area, respecti vel y, i n a TPD
pl ot. Al though i t i s di ffi cul t to express the strength i n a
defi ni te scal e and to count the number of si tes quanti -
tati vel y, the rel ati ve strength and the rel ati ve number of
aci di c si tes are hi gher for combusti on-synthesi zed Ti O
2
.
The broad desorpti on range of Ti O
2
i ndi cates a wi de range
of aci d strength di stri buti on i n the sampl e.
Elemental Analysis. To confi rm the carbi de speci es
i n combusti on-synthesi zed ti tani a, the el emental anal ysi s
of the combusti on-synthesi zed Ti O
2
was carri ed out. The
Ti O
2
(G) showed 0.4% of carbon, 9.3 10
-5
% of ni trogen,
and 5.1 10
-5
%of hydrogen, whi l e Ti O
2
(H) and Ti O
2
(O)
di d not show any carbon.
Discussion
I n the present study, the sol uti on combusti on method
provi des a nanocrystal l i ne anatase phase ti tani a i n a si ngl e
step. Thi s method i nvol ves a rapi d heati ng of an aqueous
sol uti on contai ni ng stoi chi ometri c amounts of Ti O(NO
3
)
2
and fuel s such as gl yci ne, HMT, and ODH. Duri ng
combusti on, the temperature reached i s about 650 C for
a short peri od (1-2 mi n)maki ng thi s materi al crystal l i ne.
Si nce suffi ci ent ti me i s not al l owed, growth i n the si ze of
Ti O
2
and the phase transi ti on to ruti l e are hi ndered.
Evol uti on of a l arge amount of gases duri ng the process
hel ps to di ssi pate the heat and i nhi bi t the si nteri ng of the
parti cl es, and thi s i s the reason for the l arge surface area
of combusti on-synthesi zed ti tani a. The properti es of oxi des
prepared by the combusti on of redox mi xtures depend on
the fuel used. The combusti on method thus provi des faster
processi ng ti me for obtai ni ng a hi ghl y crystal l i ne materi al
wi th nanoscal e si ze and hi gh surface area.
Several studi es have shown
3,5,6
that the anatase phase
of ti tani um oxi de has a hi gher photocatal yti cacti vi ty than
the ruti l e phase, whi ch cannot be ascri bed to a smal l
di fference (0.2 eV) between thei r respecti ve band gaps,
but i t can possi bl y be due toanatase havi ng a hi gher degree
of surface hydroxyl ati on.
The fi rst step i n photocatal yti c oxi dati on i s absorpti on
of l i ght of a wavel ength hi gher than i ts band gap (h g
E
g
)3.2 eV)by Ti O
2
semi conductor, resul ti ng i n transi ti on
of an el ectron from the val ence band (VB)tothe conducti on
band (CB), l eavi ng a hol e behi nd:
The most i mportant of these reacti ons i s trappi ng of
adsorbed water or hydroxi de i ons by hol es (h
VB
+
) to
produce

OH radi cal s, whi ch are known to be the most
oxi di zi ng speci es.
El ectrons (e
CB
-
) are trapped at the surface by the reacti on
wi th adsorbed mol ecul ar oxygen to produce superoxi de
ani on radi cal s, whi ch then form more

OH radi cal s. The
reacti on of these

OH radi cal s wi th the organi c pol l utants
l eads to the mi neral i zati on of the compounds.
The surface hydroxyl groups accept hol es generated by
UV and sol ar i rradi ati on to form hydroxyl radi cal s and
prevent el ectron-hol e recombi nati on.
28-30
Therefore, i t
i s expected that a greater number of hydroxyl groups yi el d
a hi gher reacti on rate. Thus hi gh photocatal yti c acti vi ty
of Ti O
2
(G) i ndeed correl ates wi th a l arge amount of
hydroxyl speci es on the surface.
Besi des the surface area and crystal structure and
crystal l i ni ty, the photoacti vi ty of ti tani a powders i s al so
i nfl uenced by thei r surface aci di ty. A l i near rel ati onshi p
between photocatal yti c acti vi ty and surface aci di ty was
observed for Ti O
2
sampl es.
31
The resul ts of ammoni a
uptake i ndi cate that the total amount of aci d si tes i s
si gni fi cantl y hi gher for combusti on-synthesi zed Ti O
2
.
Fi nal l y, the other term for expl ai ni ng the hi gh photo-
acti vi ty of combusti on-synthesi zed ti tani a i s rel ated to
the band structure. Here, the combusti on-synthesi zed
ti tani a sampl es show a red shi ft i n thei r UV absorpti on
spectra, whi ch can be attri buted to the carbi de i on
substi tuti on i n the form of Ti O
2-2x
C
x
[V
O
2

]
x
, where [V
O
2

]
x
(28) Sato, S. Langmuir 1988, 4, 1156.
(29) Boonstra, A. H.; Mutsaera, C. A. H. A. J . Phys. Chem. 1975, 79,
1694.
(30) Lawl ess, D.; Serpone, N.; Mei sel , D. J . Phys. Chem. 1991, 95,
5166.
(31) Papp, J.; Sol ed, S.; Dwi ght, K.; Wol d, A. Chem. Mater. 1994, 6,
496.
Figure6. UV-vi s absorpti on spectra of combusti on-synthe-
si zed Ti O2 and Degussa P-25 Ti O2.
Ti O
2
+ h f h
VB
+
+ e
CB
-
(1)
h
VB
+
+ 2OH
-
(ads)
f OH
-
+

OH (3)
e
CB
-
+ O
2
f O
2
-
(4)
2O
2
-
+ 2H
2
O f 2

OH + 2OH
-
+ O
2
(5)
2906 Langmuir, Vol. 20, No. 7, 2004 Nagaveni et al.
i s the oxi de i on vacancy created for charge bal ance. The
oxi de i on vacancy thus created shoul d form si tes for H
2
O
adsorpti on. The carbi de (2p) band has a l ower bi ndi ng
energy (3-4 eV) than the O
2-
(2p) band (6-7 eV).
Therefore the C
4-
(2p) band shoul d l i e above the O
2-
(2p)
band. Hence, substi tuti on of carbi de i on (C
4-
)for an oxi de
i on i n ti tani a shoul d reduce the band gap because the
opti cal transi ti ons can occur from the carbon 2p

to Ti d
xy
(conducti on band), i nstead of from O 2p

to Ti d
xy
of the
ti tani a.
12
The presence of carbi de i on i n Ti O
2
(G) i s
confi rmed from XPS and el emental anal ysi s. Ti O
2
(H)and
Ti O
2
(O) al so show a sl i ght red shi ft i n the UV absorpti on
compared to the normal anatase; possi bl y, the extent of
dopi ng by carbi de i on i n these sampl es i s l ow compared
tothat of Ti O
2
(G). The above resul ts stress the i mportance
of the preparati on method. Si nce combusti on-synthesi zed
materi al s have hi gh crystal l i ni ty, hi gher surface area,
l arger amounts of surface hydroxyl groups, and l ower band
gap, they exhi bi t superi or photocatal yti c acti vi ty both i n
UV and sol ar condi ti ons compared to Degussa P25.
Acknowledgment. Fi nanci al support from the De-
partment of Sci ence and Technol ogy, Government of I ndi a,
i s grateful l y acknowl edged.
SupportingInformation Available: Ri etvel d refi ne-
ment of the XRDpattern of combusti on-synthesi zed Ti O2 (Fi gure
S1); Raman spectrum of Ti O2(G) (Fi gure S2); Hi gh-resol uti on
i mage of Ti O2(G) (Fi gure S3); Ti (2p) core l evel spectra of Ti O2
(Fi gure S4) and core l evel spectra of N(1s) (Fi gure S5). Tem-
perature-programmed desorpti on of Ti O
2(G)i n a vacuum (Fi gure
S6); TGA of combusti on-synthesi zed and Degussa P-25 Ti O2
(Fi gure S7); FT-I R and NMR spectra of combusti on-synthesi zed
and Degussa P-25 Ti O
2 (Fi gure S8 and S9); NH3-TPD curves of
Ti O2(G)and Degussa P25 (Fi gure S10). Thi s materi al i s avai l abl e
free of charge vi a the I nternet at http://pubs.acs.org.
LA035777V
Synthesis and Structureof NanocrystallineTiO
2
Langmuir, Vol. 20, No. 7, 2004 2907