Indian Journal of Chemistry

Vol. 51A, March 2012, pp. 411-419

Photocatalytic reduction of carbon dioxide by water on titania:

Role of photophysical and structural properties
K Rajalakshmi, V Jeyalakshmi, K R Krishnamurthy & B Viswanathan*
National Centre for Catalysis Research (NCCR), Indian Institute of Technology Madras,
Chennai 600 036, Tamil Nadu, India
Email: [email protected]

Received 1 November 2011; revised and accepted 13 January 2012

Photocatalytic reduction of carbon dioxide has been investigated on three different titania catalysts (two commercial titania,
De Gussa P-25 and UV-100 Hombikat and another catalyst prepared by sol-gel method under reverse micelle environment)
dispersed in aqueous alkaline medium under irradiation in visible region (300-700 nm) from Hg lamp. The catalysts have been
characterized by XRD, diffuse reflectance and fluorescence spectroscopic techniques and textural analysis. Methane, methanol
and ethanol are observed as the major products. Activity in terms of total hydrocarbons production and (methane + methanol)
yields during six hours run follows the order: P-25>RM-TiO2>UV-100. Ethanol is formed in significant amounts in the case of
UV-100 and RM-TiO2 but not with P-25. Probable reaction pathways that lead to the formation of these products have been
proposed. While the catalytic activity is governed by the generation and life span of photo-induced charge carriers, it is
envisaged that product selectivity is determined by the type of transformations that the transient surface species undergo on
titania. Surface Ti ions with singly or doubly vacant coordination sites (four or five coordinate Ti ions) act as active centres for
these transformations. The relative population of four/five coordinate Ti ions play a vital role in directing the transformations
and hence selectivity. The coordination environment of surface Ti atoms evolves during catalyst preparation. Photophysical
as well as structural properties of titania samples influence their overall catalyst performance.

Keywords: Photocatalytic reduction, Photophysical properties, Titania, Carbon dioxide reduction, Structural properties

Photocatalytic reduction of carbon dioxide with CO2. It is essential that the photo-generated electrons
water on semiconductor oxide catalyst surfaces and holes are spatially separated so that they have
using solar energy to yield fuels/chemicals (methane, sufficient life time to initiate redox reactions on
methanol, etc.) has the potential to become a viable titania surface. In this respect, the life time of the
and sustainable alternative energy source to fossil photogenerated electrons is a crucial factor for the
fuels1-3. The process involves two major steps, photo-reduction of water as well as CO2. The complex
splitting of water to yield hydrogen, which in turn sequence of process steps that follow, involving two,
helps in the reduction of carbon dioxide to different four, six or eight electrons for reduction, lead to the
hydrocarbon products in the second step. Design of formation of formic acid/CO, formaldehyde, methanol
effective catalysts for such a complex process, and methane respectively4,5, depending on the type of
involving multi-electron transfer steps, holds the catalyst and reaction conditions employed.
key for the viability of the process. Titania in various crystalline, morphological and
Ideal catalysts are expected to display maximum nanostructural (tubes, sheets, films, foams etc.) forms
efficiency towards solar energy absorption and modified by doping with metals and anions, titania
possess requisite band energy level characteristics to coupled with various semiconductor oxides and
drive the redox reactions on the semi-conducting binary/ternary oxides of titanium with oxides of
catalyst surface. Functionally, the catalysts should tantalum, niobium, alkaline earth and rare earth, has
have valence band top energy level suitable for been extensively studied as catalysts1-6. Intrinsic
splitting of water to generate hydrogen, which is the properties of titania, like, particle/crystallite size,
primary step. The second and the crucial step is the phase composition (anatase and rutile), surface area,
reduction of CO2 to hydrocarbons, which requires the surface hydroxyls, lattice defects and the type and
bottom energy level of the conduction band to be level of dopants (metals and non-metals) influence
more negative with respect to reduction potential for its performance1-6. Photocatalytic activity and phase
412 INDIAN J CHEM, SEC A, MARCH 2012

transition behavior of TiO2 are significantly influenced composites observed that the product
by the preparative conditions and methods7-10. profile/selectivity depends on the method of
One of the most interesting aspects of preparation of titania. While the titania prepared
photocatalysis by titania (for air and water by sol-gel route (mainly anatase) displays higher
purification, hydrogen generation from water and selectivity towards ethanol, that prepared via
reduction of CO2 by water) is the effect of its phase hydrothermal route (rutile phase) selectively yields
composition, mainly anatase and rutile contents, in a formic acid.
given titania sample. Divergent views prevail on the Selectivity/product profile is also governed by
activity of mixed phases of titania and the scientific the wavelength of the radiation used. Besides the
reasons therein. A number of studies11-15 conclude band–gap excitation, sub-band gap excitations (due
that a mixed phase titania with specific composition to lattice defects) and formation of charge transfer
(of anatase and rutile) is more active than pure anatase complexes with the reactants may affect the activity
or rutile, since the synergy between the phases15 is and the product selectivity as observed in the case of
said to be beneficial in reducing the recombination 2,4,5-trichlorophenol conversion on P-25, leading to
of photogenerated electrons and holes, thereby wavelength dependent reaction paths24. Thus, a clear
increasing their life time and utility. According picture of the role of intrinsic photo-physical and
to Hurum et al.16, mixed-phase titania catalysts structural properties of titania in governing the
show higher activity due to three factors: (1) the activity and selectivity for photocatalytic reactions
smaller band gap of rutile extends the useful range in general, and specifically for reduction of CO2 with
of photoactivity into the visible region, (2) the water, is yet to emerge.
stabilization of charge separation by electron transfer In this context, we have carried out investigations
from rutile to anatase slows recombination, and on photocatalytic reduction of CO2 with water
(3) the small size of the rutile crystallites facilitates on three titania samples (P-25, Hombikat-UV-100
this transfer, making catalytic hot spots at the and RM-TiO2) and attempted rationalization of the
rutile/anatase interface. observed activity/selectivity patterns in terms of their
Chen et al.17 carried out photocatalytic reduction photophysical and structural characteristics and the
of CO2 with water on a series of sputtered mixed probable mechanistic pathways.
phase titania films and observed that the film with
the composition of 70% anatase, 30% rutile proved Materials and Methods
to be far superior to the other compositions Preparation of catalysts
towards methane formation. Similarly, Li et al.18 have Commercial samples, P-25 (DeGussa) and
confirmed the positive synergy effect in mixed phase Hombikat-UV 100 (Sachtleben Chemie GmbH) were
titania nanocomposites prepared by hydrothermal used as such. RM-TiO2 was prepared by sol-gel
method for photo-oxidation of methylene blue as well method25, by slow drop-wise addition of titanium (IV)
as photoreduction of CO2. However, Ohtani et al.19, iso-propoxide into the hydrolysis medium consisting
on the basis of their studies involving separation of cyclohexane, anionic surfactant-Triton-X-114 and
and characterization of anatase and rutile phases distilled water, with vigorous stirring, under reverse
from P-25 and reconstruction of P-25 phase, micelle environment and ambient temperature.
concluded that there is no such synergy effect for Molar ratio of cyclohexane: Triton:water:titanium iso-
a set of reactions studied. propoxide was 11:1:1:1. The sol was stabilized for 15
Besides the life of the charge carriers, the minutes and then allowed to gel at ambient
concentration of surface hydroxyl groups and hence temperature for 24 hrs, followed by calcination in
the crystallite form and surface area of the titania air at 400 °C for 4 hours to obtain RM-TiO2.
also play a vital role as reported by Carniero et al.20-22 Characterization of catalysts
for selective photo-oxidation of cyclohexane, wherein The crystal phase of the catalysts was analyzed
the reaction medium, aqueous or non-aqueous, also by X-ray diffractometer (Rigaku-MiniFlex-II) using
influences the activity. CuKα radiation (λ = 1.54056 Å) in the scan range
Xia et al.23 in the course of their studies on of 2θ = 5-90° at a speed of 3°/min.. Crystallite sizes
photocatalytic reduction of CO2 with water on titania- were calculated by Scherrer’s formula, t = Kλ/ Cos,
multi-walled carbon nano tubes (MWCNT) where t is the crystallite size, K is the constant
 RAJALAKSHMI et al.: PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE ON TiO2 413

dependent on crystallite shape (0.9 for this case); dispersed in the medium by vigorous stirring.
λ = 1.54056 Å, β is the FWHM (full width at half Aqueous alkaline solution (at pH-13.0) was then
maximum) and θ is the Bragg’s angle. saturated with pure CO2 by continuous bubbling
The phase composition of TiO2 was analyzed for 30 minutes after which the pH turned 8.0.
using the relative peak intensity of anatase and Reactor inlet and outlet valves were then closed
rutile26, FA = 1/[1+ 1.26 (IR/IA)], where FA is the and irradiation with Hg lamp with 77 W power
fraction of anatase phase and IR and IA are the (from WACOM HX-500 lamp house) was started.
intensities of peaks due to rutile and anatase phases After every two hours, gas samples were taken out
respectively. with a 500 µl gas-tight syringe and analysed by
Diffuse reflectance absorption spectra of the gas chromatography (Perkin Elmer, Clarus 580 GC,
catalysts in the UV-visible region were recorded using Poroplot Q column and FID).
a Thermo Scientific Evolution 600 spectrophotometer Blank experiments (reaction with irradiation
equipped with a Praying Mantis diffuse reflectance without catalyst and reaction in dark with catalyst)
accessory. The fluorescence spectra of catalysts were were conducted to ensure that the product formed was
measured by a JY Fluorolog-3-11 spectrophotometer due to the photoreduction of CO2. No product in
at an excitation wavelength of 260 nm. Surface area measurable quantities could be detected in liquid
and pore volume of the catalysts were measured samples. The high rate of stirring (400 rpm)
using Micromeritics ASAP 2020. Samples were maintained to ensure good dispersion/suspension
degassed at 373 K for 2 h and at 423 K for 3 h. of titania in solution perhaps allows the products
Pure nitrogen at liquid nitrogen temperature (77 K) to escape into gas phase.
was used.
Results & Discussion
Photocatalytic reaction Characterization of catalysts
The photocatalytic reactor as shown in Fig. 1 X-ray diffraction patterns of the prepared and
was used to follow the reduction of CO2 by water commercial samples are given in Fig. 2. XRD peaks
under radiation in UV-visble range 300-700 nm at 2θ = 25.28°, 37.98°, 48.38°, 53.98°, 55.08°, 62.78°,
from a 250 W high pressure Hg lamp. A jacketed all- 68.98°, 70.18° and 75.58° were identified as due
glass reactor (620 mL) fitted with quartz window (5 to anatase phase, and those at 2θ = 27.58°, 36.18°,
cm dia.) was filled with 400 mL of aqueous 41.38° and 48.18° represented rutile phase (JCPDS
0.2 N NaOH solution and 0.4 g of the catalyst was data 89-4920 and 89-4921). Hombikat-UV-100 and
RM-TiO2 contain pure anatase phase, while P-25
consists of 85 % anatase and the rest rutile.
Diffuse reflectance spectra of the titania samples
in UV-visible region are presented in Fig. 3 and the

Fig. 1—Experimental setup for photocatalytic reduction of CO2 Fig. 2—XRD patterns for titania catalysts. [1, P25; 2, RM TiO2;
by water. 3, Hombikat].
414 INDIAN J CHEM, SEC A, MARCH 2012

Table 2—Photocatalytic reduction of CO2 by H2O

Catalyst Yielda (µmol/g) Total CO2
CH4 CH3OH C2H5OH consumed

P25 0.7 914 0 915

Hombikat 0.3 118 53 216
UV-100
RM TiO2 0.6 130 59 249
a
Yields after 6 h of irradiation.

stoichiometry. Methane and methanol are the major

products formed on all the three samples. Ethanol is
observed on Hombikat and RM-TiO2 but surprisingly
not on P-25, the most active amongst the three.
Fig. 3—Fluorescence spectra of titania catalysts. [1, RM TiO2; With UV radiation (365 nm), Xia et al.23 observed
2, Hombikat; 3, P25]. methane and formic acid as major products on (P-
Table 1—Physico-chemical characteristics of the catalysts 25 + MWCNT) composite, with very little ethanol (~
Sample Phase Surface Crystal Band gap
5 micro moles/g) but no methanol. Formation of
comp. (%) area (m2/g) size (nm) (eV) ethanol on TiO2 (anatase) has been observed earlier
by Mizuno et al.27, but at higher pressures of CO2.
P-25 Anatase (85) 50 22 3.02 Subrahmanyam et al.28 have reported that on acidic
Rutile (15) titania composites only C1 hydrocarbons are formed,
Hombikat Anatase 311 9 3.04 while on composites with basic character, C1-C3
UV-100
hydrocarbons including ethanol are observed. Thus,
RM-TiO2 Anatase 48 12 3.06
the basic characteristics of titania could be one of the
band gap values measured as per standard procedure factors responsible for formation of C2 hydrocarbons
are given in Table 1 along with other characteristics. like ethanol/acetaldehyde, etc. It is also known that
P-25 displays the lowest band gap value due to the titania contains both acidic as well as basic sites
presence of rutile phase in measurable proportions. and its reduction with the formation of Ti3+ generates
Significant variations however, are observed in basic sites29.
the fluorescence spectra of the samples (Fig. 3).
Lower fluorescence intensity for P-25 is due to the Activity versus photophysical properties
reduced number of recombination sites resulting in The major factors responsible for the higher
longer life-time of photoelectrons on the TiO2 surface, activity observed for P-25 in the present case are
thus leading to a higher photocatalytic activity. the stabilization of charge separation as evidenced
The reduction in recombination in P-25 is due to by the low intensity fluorescence spectrum and the
the co-existing rutile phase, whose valence band existence of positive synergy effect between anatase
and conduction band levels are slightly higher than and rutile phases, which has been substantiated
those for anatase15,16. At the anatase-rutile interface, by earlier work11-16. Both Hombikat-UV-100 and RM-
such energy levels promote charge separation, thereby TiO2 with higher charge recombination rates display
reducing fluorescence intensity. Both Hombikat UV- relatively lower activity, their lower particle sizes
100 & RM-TiO2 display intense fluorescence leading to an increase in the density of
indicating higher charge recombination rates. recombination centres25. Trends observed in methane
formation, which requires the maximum
Photocatalytic activity photogenerated electrons population for eight
The effects of such changes in the photophysical electrons transfer, are also in tune with this
properties are clearly seen in the activity pattern concept. Besides, Hombikat titania which is the least
for CO2 conversion, P-25> RMTiO2> Hombikat active, is known to adsorb water strongly30, which
(Table 2). Activity is expressed as micromoles of CO2 may adversely affect the adsorption/activation of
consumed in six hours, which is calculated as per the CO2/HCO3 and hence the overall activity.
 RAJALAKSHMI et al.: PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE ON TiO2 415

An interesting observation in the present work is Besides, CO as one of the reduction products has been
the product profile, especially for methanol and reported on titania and metal supported titania35.
ethanol formation. Maximum methanol formation is A different route (Mechanism B, Fig. 4) involving
observed with P-25, which surprisingly does not HCOOH as the primary intermediate has been
form ethanol in measurable quantities, while it proposed by Wu36 based on in situ IR spectroscopic
is formed in substantial amounts on RM-TiO2 and studies. IR absorption bands due to bicarbonate,
Hombikat, which are relatively less active for overall carbonate, formate, formaldehyde and methoxy
CO2 conversion. species on TiO2 surface have been observed.
Xia et al.23, who studied CO2 photoreduction Accordingly, methanol is formed through surface
on various titania-MWCNT composites, observed methoxy species and its further reduction results in
methane, formic acid and ethanol as major methane formation.
products, but not methanol. Possibly, the nature Similar reaction pathway have been proposed
of nanocarbon support, phase composition earlier by Subrahmanyam et al.28 for mixed oxides of
(anatase/rutile) of titania and the wavelength of titania and by Sasirekha et al.37 for Ru supported on
radiation used (365 nm) could be responsible TiO2 dispersed on SiO2. Formation of methane via
for driving the reaction along the specific path. methanol seems to be unlikely, since added methanol
Though ethanol formation has been observed does not lead to increase in methane formation38.
earlier31 on AgBr/P-25 with visible light at 420 nm Kinetic equations39,40 based on Mechanism A,
in 0.2 M KHCO3 solution saturated with CO2, the developed for photoreduction of CO2 with water on
elementary steps leading to its formation are not
clear. An understanding of the elementary reaction Mechanism A
steps is therefore needed to explain the observed CO2 + e- .CO2 …(7)
product profile for three titania samples.
.CO2 + .H CO +OH ...(8)
Reaction pathways  
The first step involving photocatalytic splitting of CO + e CO …(9)
water follows the well-accepted elementary steps as .CO + .H .C +OH …(10)
shown in Eqs (1) to (6):
.C +H+ +e .CH .CH2 .CH3 …(11)
TiO2 + hν e + h+ ...(1)
.CH3 + H+ + e CH4 …(12)
H2O H+ + OH …(2)
.CH3 + .OH CH3OH …(13)
H+ + e H. …(3)
OH-+ h+ OH ..................................... (4) Mechanism B

2 OH. H2O2 + h+ O 2+ 2H+ …(5)

O2 + h+ O2............................................(6)
The second step for activation and reduction
of CO2 could then follow different pathways.
Anpo et al.32 have identified ESR signals due to C and
H atoms, CH3 radicals and Ti3+ ions on powdered
titania catalysts in presence of CO2 and water at 77 K.
Accordingly, the following pathway (Mechanism A)
involving the formation of active surface carbon
and its reaction with H and OH radicals, have been
proposed by Anpo et al.
Observations by Yang et al.33 on the formation of
carbon residues and ESR evidence on hydrogen,
methyl and methoxy radicals and CO 3 anion radicals
by Dimitrijevic et al.34 on titania surface during CO2 Fig. 4—Reaction pathway for photocatalytic reduction of CO2 by
photoreduction lend credence to this mechanism. water on TiO2 (Mechanism B).
416 INDIAN J CHEM, SEC A, MARCH 2012

TiO2, could be validated with the experimental data Influence of structural properties of titania
indicating that it has better acceptability than Surface density and the coordination environment
Mechanism B. of individual Ti4+ ions are the two key parameters
In the present work, major products observed that govern the reactivity. Influence of surface
are methane, methanol and ethanol. Methyl radical structure of titania on activity and selectivity during
could be the common intermediate in the formation CO2 photoreduction was observed by Anpo et al.32
of methane/methanol. Population and lifetime of in their studies on TiO2(100) and TiO2(110) surfaces.
photogenerated electrons are the critical factors Overall CO2 conversion was high on TiO2 (100)
responsible for the formation of methane. In the surface with the formation of both methane and
present investigation, with aqueous alkali as the methanol (3.5 and 2.4 nanomoles/h/g cat respectively)
medium, the availability of surface hydroxyls and while lower conversion with only methanol
.OH radicals are responsible for methanol formation. (0.8 nanomoles/hr/g cat) was observed on TiO2(110)
Ethanol formation by CO2 photoreduction on surface. Higher atomic [Ti]/[O] ratio (proportional
titania/titania based catalysts has been observed to the number of active sites) on TiO2(100) surface
earlier23,27,28,41, though the pathway leading to its is suggested as the basis for the increase in activity.
formation is yet to be understood. Liu et al.42 have Surface cation (Ti4+) density that influences
reported selective ethanol formation on monoclinic the overall activity varies significantly in anatase
BiVO4, a photocatalyst for O2 production from and rutile phases. For low index planes like (101),
water and proposed dimerization of surface C1 species cation density is 5.2 versus 7.9 Ti atoms/nm2 and
as the route for ethanol formation. Formation of for (100) it is 2.8 versus 7.4 Ti atoms/nm2 for
ethanol may be envisaged to proceed through anatase and rutile respectively [46, 47]. Effect of
coupling of ethyl and methylene radicals as shown this factor is observed in the proportionately
below: higher aliphatic alcohols uptake by polycrystalline
rutile vis-à-vis anatase48. Thus, higher density
.CH3 + .CH2 + e CH3-CH2 +.OH CH3-CH2-OH of surface Ti atoms in rutile, which constitutes
...(14)
~1520 % in a typical P-25 phase, could be an
Such a pathway is in line with routes proposed additional factor contributing towards its higher
for formation of ethylene and ethane via dimerization activity, though moderated by easy charge re-
as observed on Cu/TiO2 and TiO2 and ZrO2 combination. In the case of pure rutile phase however,
respectively43,44. shorter life cycle of charge carriers due to facile
recombination, coupled with the presence of fewer
Ċ H3 + ˙CH3 CH3-CH3 …(15) surface hydroxyl groups relative to anatase, renders it
less reactive.
˙CH2 + ˙CH2 + 2e CH2=CH2 …(16)
Evidence for the presence of four and five
Surface structural features of titania that facilitate coordinated surface Ti4+ ion sites emerges from
such transformations are discussed later in this article. the in situ IR spectroscopic studies on adsorption
Since Mechanism A involves CO as one of the of water and CO249 and adsorption and
intermediates, in presence of H2 photocatalytic decomposition of primary alcohols (C1-C3)48 on
Fischer-Tropsch route to > C1 hydrocarbons that polycrystalline anatase and rutile surfaces. In the
proceed through surface carbides could be another case of anatase,49 two types of chemisorbed –OH
pathway45. In particular, when the reaction is species (corresponding to 3676 cm-1 on (001)
carried out under pressure so as to improve the plane and 3716 cm-1 on (100) and/or (010) plane)
limited solubility of CO and H2 in water, such and two types of molecularly adsorbed water
transformations are possible. Mizuno et al.27 did (3694 and 3495 cm-1 on (100) 3660 and 3465 cm-1
observe formation of > C1 hydrocarbons and ethanol on (010) planes) have been observed by Tanake
during CO2 photoreduction at higher pressures using and White49. While four coordinate Ti4+ ions act
TiO2 dispersed in aqueous alkaline solution. It is then as sites for both molecularly adsorbed water and
essential that the crystal structure of titania with –OH groups, the five coordinate Ti4+ sites adsorb
appropriate sites should facilitate bimolecular surface –OH only. CO2 forms bidentate carbonate and
reactions envisaged above. bicarbonate species on titania surface.
 RAJALAKSHMI et al.: PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE ON TiO2 417

According to Lusvardi et al.48 at room temperature, the process conditions/temperatures are different.
C1-C3 aliphatic alcohols get adsorbed in molecular CO2 photoreduction proceeds at room temperature
and dissociated forms, a behavior similar to that of and hence at very low rates. The probable surface
water. On dissociation, alcohols form alkoxides and transformations46,48 on four and five coordinated
hydroxyls on the surface. The behavior of adsorbed Ti ion sites are discussed below.
species is then governed by the coordination Scheme 1 presents the transformations on five
environment of surface Ti4+ ions. On heating up to coordinated Ti ion site, wherein the methane and/or
400 K the surface species recombine and desorb as methanol could be formed from methyl radical along
alcohols, while at higher temperatures several with ethane, to a limited extent, by dimerization.
decomposition products of alkoxides, like ethers, On four coordinated Ti ion sites, methylene
olefins and paraffins, aldehydes and ketones (C1- and methyl radicals on adjacent sites could couple to
C3) are formed through complex surface
form ethyl radical which gets transformed to ethanol
transformations46-48,50 involving dehydration and
(Scheme 2). Another possibility is the coupling of two
dehydrogenation on five coordinated Ti ions and
adjacent methoxy species or methoxy and methyl
bimolecular coupling/dimerization of surface species
species to form dimethyl ether, which can undergo
adsorbed on adjacent sites linked to four coordinated
further transformation [55] to methane and
Ti ions. Similar observations have been made
formaldehyde (Scheme 3).
earlier50,51 on TiO2 single crystals. With {114} faceted
(001) surface, which exposes four, five and six Thus, the local environment of surface Ti could
coordinated Ti cations, methanol desorbs as dimethyl play a key role in controlling the selectivity of
ether, formed, while coupling of adjacent methoxy the products. These proposals, yet to be substantiated
species bound to four coordinated Ti cations. by experimental observations, provide valuable
On {011} faceted (001) surface which exposes five clues/leads towards understanding and establishing
or six coordinated Ti ions, methane with highest the actual reaction mechanism in the light of the
selectivity is formed, while ether formation is fact that a comprehensive mechanistic path for CO2
not observed. Similar dependence on the local photoreduction is yet to emerge54.
cation environment was observed with carboxylic In short, while the energy values of the occupied
acids as well52 with {114} faceted (001) surface and unoccupied states of semiconductor show the
(Ti ions exposed in four and five coordination) possibility of photo-assisted process, molecular
yielding formaldehyde by coupling of formic acid. level sites on solid surface that are responsible for
This was not observed on {011} faceted (001) surface the activation of the reactants denote the feasibility
(Ti ions exposed in five and six coordination). of the reaction in the desired direction.
On similar grounds, water gets adsorbed It is well known that the evolution of such micro-
molecularly on (100) and (101) surfaces of rutile, environments on titania surface takes place during the
and dissociatively on (110) surface53, which can catalyst preparation and thermal
readily accommodate two–OH groups on adjacent
sites linked to surface Ti ion. Water adsorption
on anatase is expected to follow the same trend.
Such microstructural features of titania could have
a direct bearing on photocatalytic water splitting, and
adsorption of CO2 and the surface transformations
that follow during CO2 photoreduction with water.
The adsorbed water promotes the formation of
bidentate carbonate/bicarbonate on titania49.
Within a reasonable degree of agreement, the
transformations of alkoxide and hydroxyl species
formed on titania surfaces due to adsorption of
alcohols, could be compared with the possible
transformations that the adsorbed methylene,
methyl, methoxy and hydroxyl and species32-34 may Formation of methane, methanol and ethane
undergo during photoreduction of CO2, although Scheme 1
418 INDIAN J CHEM, SEC A, MARCH 2012

photo-induced charge carriers, it is envisaged that

product selectivity is determined by the coordination
environment of surface Ti ions (four/five
coordinated), which in turn evolve during catalyst
preparation. Photophysical as well as structural
properties influence the overall catalyst performance.

Acknowledgement
Authors gratefully acknowledge the Department of
Science & Technology, Govt. of India, New Delhi,
for the grant towards establishing NCCR at
IIT Madras, M/s Hindustan Petroleum Corporation
Formation of ethanol Limited, Mumbai for a funding the project on
Scheme 2 photocatalytic conversion of CO2 and M/s Sachtleben
Chemie GmbH, Germany for samples of Hombikat-
UV-100 for research studies.

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