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Amy Linsebigler received her B.S. degree in Chemistry from Seton Hill Professor John T. Yates. Jr. began his research in surface chemistry as
College in 1989. She is currently completing her Ph.D. in Chemistry at a graduate student at MIT. He continued this work from 1963 to 1982 at
the Univenity 01 Pittsburgh under the direction of Professor John T. Yates, the National Bureau of Standards. In 1982 he founded the Surface
Jr. During her doctoral studies she has examined several technologically Science Center at the University of Pittsburgh where he was appointed
important surface science systems. Her research includes the chemical R.K. Mellon Professor. He now holds a joint appointment in the
reactivity of environmentally important adsorbates on metal surfaces. Departments of Chemistry and Physics. Work on metallic, semiconducting,
electronic modification of metal surfaces with thin metal films, and currently, and insulator surfaces is now underway using modern surface measure-
the molecular level photochemistry and thermal chemistry of small probe ment techniques. His work with students and postdoctorals is focused
molecules on metal oxide single-crystal surfaces. on the use of electronic excitation to probe surface phenomena as well
as the use 01 a range of surface vibrational spectroscopies and other
methods for understanding surface processes.
Electron
Transfer D’ A-
---+ -I-
..
Guangquan Lu was born on Juiy 24. 1965. in Shandong, the People’s
Republic of China. He received his B.S. in Chemistry from Shandong
University in 1985, and his Ph.D. in Chemistry from the University of
Exchange -
California at San Diego in 1992. His primary research interests are the
kinetics and dynamics 01 thermal and photochemical processes on
semiconductor surfaces. He has been involved in a broad range of
research projects including the surface characterizations of SiiGe chemical
I A- -7 -+I
vapor depositions, the surface chemistry of photocatalytic reactions on
TiOZ. and the surface and interface characterizations of advanced electronic
materials processing. He is the recipient of the CGP scholarship from
the Chinese Education Commission (1985), the American Vacuum Society Figure 1.1. Electron transfer and energy transfer pro-
Student Prize (1990). and the Russell and Sigurd Varian Fellow Award cesses.
(1990).
An electron transfer process is a one-electron
excitation takes place in the catalyst substrate and reaction in which an electron jumps from an occupied
the photoexcited catalyst then transfers an electron orbital of the donor reactant to the empty orbital of
or energy into a ground state molecule, the process
is referred to as a sensitized photoreaction.
The initial excitation of the system is followed by -
place in either the donor molecule (D D*)or the
acceptor molecule (A A*). The electron transfer
-
the acceptor reactant. The initial excitation may take
subsequent electron transfer and/or energy transfer. process requires the overlap between the occupied
It is the subsequent deexcitation processes (via donor orbital and the acceptor orbital which may be
electron transfer or energy transfer) that leads to empty or half-filled. The electron transfer results in
chemical reactions in the heterogeneous photocataly- an ion pair of the donor cation (D+)and the acceptor
sis process. By using the electronic population anion (A-).
changes in the molecular orbitals, Figure 1.1 sche- An energy transfer process takes place by electron
matically illustrates the different interactions be- exchange or dipole-dipole resonant coupling. These
tween one reactive center in the excited state and two processes operate through two fundamentally
another reactive center in the ground state. A different mechanisms. Electron exchange occurs by
reactive center can be a molecule or a surface reactive two independent one-electron transfer steps-one in
site. each direction. Both electron transfer and electron
Photocatalysis on TiOn Surfaces Chemical Reviews, 1995, Vol. 95, No. 3 737
exchange require orbital overlap between the inter- expected to have no absorption intensity +if = 0), and
acting centers. When both processes are thermody- it will therefore be unlikely to cause photochemical
namically allowed, electron transfer predominates conversions which involve the excitation of such a
since the electron exchange process requires simul- transition.
taneous overlap of two orbital pairs, whereas only one The probability of an electronic transition can be
such overlap is necessary for electron t r a n ~ f e r . ~ calculated, using quantum mechanics purturbation
Dipole-dipole coupling occurs by a Coulombic reso- theory, as being proportional to the square of the
nance interaction in which the oscillating dipole of amplitude of the radiation field, EO,and the square
an excited state molecule is coupled with the induced of the transition dipole moment, IPiflz20s21
dipole in a ground state quencher molecule. This
coupling process does not require effective orbital
overlap between the two interacting centers and can
operate over a distance range from less than 10 A to Here pif = (YfIplYi)is the transition dipole moment
as large as 100 A.10 for an electronic excitation process from the initial
There exists a vast body of literature dealing with state Yi to the final state Yf. While the radiation
the electron transfer and energy transfer processes field can be controlled by varying the light intensity,
in photocatalytic reactions. A detailed description of the transition dipole moment is an intrinsic property
these processes is beyond the scope of this review. of the molecular structure.
Several excellent review articles and books already According to the Born-Oppenheimer approxima-
exist.11-19 Here, we tend to focus on interfacial tion, the molecular wave function Y can be expressed
processes and to summarize some of the operating as the products of the electronic spatial wave function
principles of heterogeneous photocatalysis. In section p,the electronic spin wave function 5, and the nuclear
2, we will first look at the electronic excitation wave function b?:20,21
processes in a molecule and in a semiconductor
substrate. The electronic interaction between the Y=q'G'K (2)
adsorbate molecule and the catalyst substrate will Then,
be discussed in terms of the catalyzed or sensitized
photoreactions. In section 3, thermal and photocata- Pif = P'fIPIYJ = (qfI,4qJ (SflSi) (KfIHi) (3)
lytic studies on Ti02 are summarized with emphasis
on the common characteristics and fundamental
principles of the TiOs-based photocatalysis systems. Now the transition dipole moment may be regarded
In section 4,we will address the research effort in as the product of the electronic transition moment,
the electronic modification of the semiconductor the electron spin wave function overlap, and the
catalysts and its effect on the photocatalytic ef- nuclear wave function overlap. The transition dipole
ficiency. Several representative examples will be moment, pif, will be zero if any of these three
presented including the Schottky barrier formation contributions become zero. This gives the selection
and modification at metal-semiconductor interfaces. rules for an electronic excitation process.
Some concluding remarks and future research direc- The electronic transition moment term (VfIPlqi)
tions will be given in the final section. depends on the nature of the electron distributions
in the initial and final electronic spatial wave func-
2. Electronic Processes in Photocatalysis tions. By examining the overall symmetry property
of the spatial wave function^,^^*^^ one can easily
2.1, Molecular Electronic Excitation determine if this integral is zero. When this term is
zero, the transition dipole moment pif is zero. Then
2.1.1. Molecular Spectroscopy and Photochemistry the transition is a symmetry-forbidden transition.
Photocatalysis processes involve the initial absorp- The overlap integral of the spin wave functions
tion of photons by a molecule or the substrate to ( d a ) can be evaluated using the orthornormal prop-
produce highly reactive electronically excited states. erty of the electron spin wave functions,20that is,
The efficiency of the photoinduced chemistry is
controlled by the system's light absorption charac-
teristics. In this section, we want to examine the Here a and p correspond to the only two spin
factors that control the light absorption intensity by configurations, spin-up ( a )and spin-down CP). The
the molecule or by the substrate. We will first electron spin functions maintain their orthogonality
discuss the electronic excitation of a molecule upon and normalization properties even when the electrons
photon absorption. The band-gap excitation of the under consideration are described by different spatial
semiconductor substrate will then be discussed and wave functions. Using these properties, we can
interfacial electron transfer will be reviewed. easily derive that the original spin orientation si must
Molecular electronic spectroscopy is a useful tool be preserved in the final excited state in order to keep
to determine where photochemistry may potentially the term (sfla) nonzero. Therefore, singlet-singlet
occur.11J2 Most importantly, we can determine what and triplet- triplet transitions are spin-allowed,while
photon energy will most likely induce an electronic a singlet- triplet transition is spin-forbidden. Excep-
transition in a molecule based on whether the transi- tions to this rule are often found among complex
tion dipole moment pif will be zero for a transition organic molecules containing heavy atoms (such as
from the initial state "i" to the final state "f". A Br or I). Spin-orbit coupling induces weakly allowed
transition that is forbidden by the selection rules is singlet-triplet transitions in these systems.
738 Chemical Reviews, 1995, Vol. 95, No. 3 Linsebigler et al.
Internuclear Distance -
Figure 2.1. Vibronic transitions in a diatomic molecule.
deexcitation channel is dominant, as discussed below.
2.1.2. Molecular Excitation and Deexcitafion Events
The allowable excitation and deexcitation processes
The nuclear overlap integral (KflKi) has to do with for a molecule are given in the energy level diagram
the nuclear motion (vibrational wave fuctions) during in Figure 2.2. The ground state singlet energy level
the electronic transition. Generally, the electronic of the molecule is represented by SOand illustrates
transition induced by the absorption of a photon the energy of the molecule at room temperature in
occurs much more rapidly than the nuclear motion. solution. The ground vibrational states for the three
The nuclei remain essentially frozen at the equilib- excited electronic states shown in Figure 2.2 for the
rium configuration of the ground state molecule molecule are represented as SZand SI for the singlet
during the transition. This is the Franck-Condon states and TI for the triplet state. The triplet excited
principle and is schematically illustrated in Figure state for the molecule is less energetic than the
2.laZ1Depending on the shape and spatial distribu- singlet excited state of the molecule. The respective
tion of the nuclear wave functions of the initial and energy levels of the excited states of the molecule are
final states, the excited state can be produced with important when dealing with the photosensitization
different vibrational and rotational levels. Then the of semiconductors via dye molecule excitation. Nu-
nuclear overlap integral (HflKi) can be used to deter- merous vibrational energy levels associated with the
mine which of the possible vibrational levels in the electronic energy levels exist but are not shown to
electronically excited state will be most likely popu- simplify the figure. Absorption of radiation results
lated during the transition. For a molecule with in the excitation of the molecule from the ground
similar nuclear geometries in the ground and excited state to one of the excited singlet states. The excita-
states, the largest overlap occurs when the vibra- tion to the second singlet state Sa (requiring a shorter
tional quantum number (no)in the ground state and wavelength than excitation to SI) is illustrated in
in the excited state remain the same (An = 0). For Figure 2.2. The selection rules for an electronic
a molecule that possesses a very different equilibrium excitation process imply that direct photoexcitation
nuclear geometry in the excited state, the largest from the singlet ground state to the triplet excited
overlap will occur at a different vibrational level. state is spin forbidden [(&) = 01. The absorption
Singlet Excited State Triplet Excited State
lnternol
r Conversion
Intersystem
Crossing
Absorption Internol
W Fluorescence ond
Phosphorescence
(to-'- t65S) Rodiotionless (to-', 10%
Conversion
C hemicol
SO V \ Reoc tion
Ground
State (16'O- to- 5s)
Figure 2.2. Excitation and deexcitation processes in a molecule.
Photocatalysis on Ti02 Surfaces Chemical Reviews, 1995, Vol. 95, No. 3 739
of a photon of radiation occurs very rapidly, on the become unpaired. Intersystem crossing is illustrated
order of s.24a Deexcitation events are much in Figure 2.2 between the S1 and TI excited states.
slower. This process is the result of vibrational states over-
The deexcitation of the excited molecule favors the lapping. The time required for such a process is in
route which will minimize the lifetime of the excited the range of lop6 s.24a Once intersystem crossing
state. Whether it occurs via emission of radiation occurs from a singlet to a triplet excited state, the
such as fluorescence or phosphorescence, or a radia- molecule undergoes deactivation by phosphorescence.
tionless decay, indicated in Figure 2.2 as curvy lines, The time scale for the radiative phosphorescence
depends upon the competition between different process is on the order of to s.24a
decay channels. The lifetime of the excited state for Relaxation of the excited singlet and triplet states
fluorescence emission is to s.24a can also occur by decomposition of the excited species
After the excitation of a molecule from the ground to form new chemical species. Such reactions include
state to a higher nondissociative excited state occurs, photoinduced fragmentation, intramolecular trans-
radiationless internal conversion transitions to the formation, and intermolecular and interfacial elec-
lower excited states usually take place before any tron or energy transfer. The photochemical reactions
radiative emission processes.25 The conversion is occur on a time scale of to s.24b
observed when the upper electronic energy levels are
close together and the vibrational energy levels 2.2. Semiconductor Electronic Excitation
overlap. The transition process from SZ to S1 is 2.2.1. Band-Gap Photoexcitation
isoenergetic through overlay between vibrational
levels. Once the transition occurs, the molecule Unlike metals which have a continuum of elec-
undergoes vibrational relaxations to the ground tronic states, semiconductors possess a void energy
vibrational state of the SI electronic excited state at region where no energy levels are available to pro-
a significant rate. Therefore, the SZto SI transition mote recombination of an electron and hole produced
in Figure 2.2 represents a loss of energy for the by photoactivation in the solid. The void region
internal conversion process. The time scale for which extends from the top of the filled valence band
internal conversion is to s . Internal
~ ~ ~as to the bottom of the vacant conduction band is called
well as external conversions can also occur from the the band gap. Once excitation occurs across the band
lowest excited states SI and TI t o the ground state gap there is a sufficient lifetime, in the nanosecond
SO. External conversions are the result of energy regime,26for the created electron-hole pair to un-
transfer to solvent or solute molecules and are dergo charge transfer to adsorbed species on the
usually only from the lowest excited states. If semiconductor surface from solution or gas phase
overlapping vibrational energy levels exist, deactiva- contact. If the semiconductor remains intact and the
tion via internal conversion to the ground state can charge transfer to the adsorbed species is continuous
occur faster than that involved in fluorescence emis- and exothermic the process is termed heterogeneous
sion. photocatalysis.
Figure 2.2 represents excitation to bound upper The initial process for heterogeneous photocatalysis
electronic states for the purpose of illustrating the of organic and inorganic compounds by semiconduc-
various classes of electronic transitions which are tors is the generation of electron-hole pairs in the
possible. Other upper states may involve chemical semiconductor particles. The enlarged section of
changes such as dissociation and are not shown here. Figure 2.3 shows the excitation of an electron from
Intersystem crossing is a process in which the spin the valence band to the conduction band initiated by
of the excited electron is reversed and the electrons light absorption with energy equal to or greater than
0
e--.
.
Sur face
I
- .-...-
I
~
Recombination /
r,
the fate of the separated electron and hole can follow
several pathways. Figure 2.3 illustrates some of the
deexcitation pathways for the electrons and holes.
The photoinduced electron transfer to adsorbed
organic or inorganic species or to the solvent results Go P
from migration of electrons and holes to the semi- c Sic
conductor surface. The electron transfer process is
more efficient if the species are preadsorbed on the ;aCJ- 4 I F -
surface.27While at the surface the semiconductor can
donate electrons to reduce an electron acceptor (usu- W
ally oxygen in an aerated solution) (pathway C); in
turn, a hole can migrate to the surface where an -6 t
electron from a donor species can combine with the
surface hole oxidizing the donor species (pathway D).
The probability and rate of the charge transfer
processes for electrons and holes depends upon the
respective positions of the band edges for the conduc-
tion and valence bands and the redox potential levels
-8 I
of the adsorbate species. Figure 2.4. Energies for various semiconductorsin aque-
In competition with charge transfer to adsorbed ous electrolytes at pH = 1.
species is electron and hole recombination. Recom-
bination of the separated electron and hole can occur carrier traps are used to promote the trapping of
in the volume of the semiconductor particle (pathway electrons and holes at the surface leading to a more
B) or on the surface (pathway A) with the release of efficient charge transfer process. For photooxidation
heat. The process of back-donation after charge processes on TiOz, n, > ps, because the electron
transfer from the adsorbed species t o the semicon- transfer process to molecular oxygen trapped at
ductor surface can occur but is not illustrated in defect sites is relatively slow.28
Figure 2.3. Obviously electron and hole recombination is det-
The efficiency of the photocatalytic process is rimental to the efficiency of a semiconductor photo-
measured as a quantum yield which is defined as the catalyst. Modifications to semiconductor surfaces
number of events occurring per photon absorbed. The such as addition of metals, dopants, or combinations
ability to measure the actual absorbed light is very with other semiconductors are beneficial in decreas-
difficult in heterogeneous systems due to scattering ing the electron and hole recombination rate and
of light by the semiconductor surface. It is usually thereby increasing the quantum yield of the photo-
assumed that all the light is absorbed and the catalytic process. Such semiconductor modifications
efficiency is quoted as an apparent quantum yield. will be discussed in detail in section 4 later in the
If several products are formed from the photocatalytic review.
reaction then the efficiency is sometimes measured
as the yield of a particular product. 2.2.2.Band-Edge Positions
To determine the efficiency or quantum yield, a The ability of a semiconductor to undergo photo-
combination of all the pathway probabilities for the induced electron transfer to adsorbed species on its
electron and hole must be considered. The quantum surface is governed by the band energy positions of
yield for an ideal system, 4, given by the simple the semiconductor and the redox potentials of the
relationship: adsorbate. The relevant potential level of the accep-
tor species is thermodynamically required to be below
' OC
kCT
+
kc, k ,
(more positive than) the conduction band potential
of the semiconductor. The potential level of the donor
needs to be above (more negative than) the valence
band position of the semiconductor in order to donate
is proportional to the rate of the charge transfer an electron to the vacant hole.
processes ( ~ c T and
) inversely proportional to the sum
of the charge transfer rate ( ~ c T )and the electron- The band edge positions of several semiconductors
hole recombination rate ( k ~(bulk
) and surface). It are presented in Figure 2.4. The internal energy
is assumed that diffusion of the products into the scale is given on the left for comparison to the
solution occurs quickly without the reverse reaction vacuum level and on the right for comparison to
of electrons recombining with donors and holes normal hydrogen electrode (NHE). The positions are
recombining with acceptors. Without recombination derived from the flat band potentials in a contact
the quantum yield would take on the ideal value of solution of aqueous electrolyte at pH = 1. The pH of
1for the photocatalytic process. In this case the rate the electrolyte solution influences the band edge
of charge transfer would be dependent on the diffu- positions of the various semiconductors compared to
sion of charge carriers to the surface in the absence the redox potentials for the adsorbate.
of excess surface charge. However, this is an ideali- 2.2.3. Charge Carrier Trapping
zation. In a real system recombination does occur
and the concentration of electrons (n,) and holes (p,) Recombination of the photoexcited electron-hole
at the surface is not For example, charge pair needs to be retarded for an efficient charge
Photocatalysis on Ti02 Surfaces Chemical Reviews, 1995, Vol. 95, No. 3 741
quantization and increase in effective band gap is Flat Accumulation Depletion Inversion
observed experimentally as a blue shift in the ab- -
Band Layer -
Layer Layer
sorption and emission spectra for CdS. The energy
shift in the band gap, AE, as a function of particle
size can be predicted by the three dimensional
confinement model based on the effective mass
approximati~n:~~,~~,~~-~~
m=-,+,
h22 1
2R2[m, di 1.786e2
0.248ERY (6)
aligned as shown in Figure 2.8. The electrical contact processes on wide band-gap oxide semiconductor
has formed a space charge layer. The surface of the surfaces, and is the focus of the rest of this review.
metal acquires an excess negative charge while the Figure 2.91, part D shows a common excitation
semiconductor exhibits an excess positive charge as scheme observed for adsorbates on metals. When the
a result of electron migration away from the barrier metal is irradiated, a hot electron is generated at a
region. The bands of the semiconductor bend upward level above the Fermi edge and this electron then
toward the surface, and the layer is said to be tunnels into an empty level in the adsorbate mol-
depleted. The barrier formed at the metal-semicon- ecule. Processes occurring by this type of electron
ductor interface is called the Schottky barrier. The transfer process have been reviewed recently.50
height of the barrier, b,is given by The interfacial electron transfer process has been
extensively investigated14J5and the dynamics of such
A = 4 m - E, processes continue to attract intensive research
- ~ ~rate constant for an interfacial
e f f ~ r t . ~ lThe
where E, is the electron affinity, measured from the electron transfer is found to be greater than 5 x 1O1O
conduction band edge to the vacuum level of the s-1,55,56 The driving force for the heterogeneous
semiconductor. The diagram in Figure 2.8 illustrates electron transfer is the energy difference between the
an ideal metal-semiconductor contact, i.e. no surface conduction band of the semiconductor and the reduc-
states exist on the semiconductor, etc. The Schottky tion potential of the acceptor redox couple, MA-, (hE
barrier produced at the metal-semiconductor inter- = E,b - EN*-). An excellent review of this subject
face can serve as an efficient electron trap preventing has been written by and applications of these
electron-hole recombination in photocatalysis as ideas are given in section 3.6 dealing with photooxi-
discussed in section 4.2. dation processes at the liquid-solid interface of TiOz.
1. PHOTOREACTION -
INITIAL EXCITATION OF ADSORBATE
A. Insulator
CB
VB
B. Semiconductor *
11. PHOTOREACTION -
I N I T I A L EXCITATION OF SOLID
C. Semiconductor or Insulator
A 1- A-
I .h I D+
D. Metal
Figure 2.9. (I) Catalyzed photoreaction, initial excitation of adsorbate, and (11)Sensitized photoreaction,initial excitation
of solid.
The electronic structure of the nearly perfect TiO,
surfaces is essentially identical to that of the bulk
-
The filled valence band at 6 eV is composed of 0
2p orbitals (as shown in the UPS spectrum) and the
rutile TiOz. Figure 3.3 shows the photoemission empty conduction band is composed of Ti 3d, 4s, and
spectra from vacuum-fractured (1101, (loo), and (001) 4p orbitals. The Ti 3d orbitals dominate the lower
faces of rutile Ti02.63 All three faces give spectra
similar to that of the bulk. The intense peak at 6
eV is due t o electron emission from the 0 2p obitals.
- portion of the conduction band. The weak emission
at -0.8 eV below the Fermi level is associated with
the defect induced-Ti 3d-derived levels. This state
The small emission peak near the Fermi level is due can be eliminated by surface oxidation.
to point defect oxygen vacancies. This feature is Few studies have been conducted on the structure
more clearly shown in Figure 3.4. Figure 3.4 shows of the anatase single crystal surface^.^^,^^@ A recent
the electronic band structure constructed from pho- photoemission study by Sanjines et al.65has shown
toemission (UPS) and inverse photoemission (IPS) that anatase TiOZ(101) and polycrystalline anatase
spectra for a slightly defective TiOB(110) surface.64 thin films exhibit similar electronic photoemission
Photocatalysis on TiOn Surfaces Chemical Reviews, 1995, Vol. 95, No. 3 745
0 = 4.593% 0=3.784a
=2.959 a c=9.515 A
Eg = 3.f eV Eg = 3.3 e V
p = 4 . 2 5 0 g/cm3 p = 3.894 g/cm3
AGdf =-212.6kcol/mole AGj =-211.4 kcol /mole
above 200 K.68 However, most of the adsorbed water activation energy to dissociate the H2 molecule is too
desorbs molecularly between 170-180 K. The hy- high, and no adsorption was observed.
droxyls were not completely removed from the sur- A recent study by Pan et al.69also reported a very
face until 350-400 K. low sticking probability for H2 adsorption on TiO2-
A recent XPS and TPD study by Hugenschmidt et (110). Low-energy H2+ ion bombardment was em-
al.70reported four different adsorption states for H2O ployed to enhance the hydrogen adsorption. Surface
on TiO2(110), a 500 K TPD peak due t o surface hydroxyl groups were generated upon hydrogen ion
hydroxyls bound to oxygen vacancies, a 375 K peak exposures. In addition, the surface Ti3+coverage was
due to dissociated H20, a 250-300 K feature due to found to increase with increasing hydrogen expo-
molecular H2O adsorbed at Ti4+ sites, a 170 K sures.
desorption feature due to molecular H2O bound to On powdered Ti02 surfaces, Beck et al.76reported
bridging-oxygen anion sites, and a 160 K mutilayer TPD spectra typical of weakly adsorbed molecular
state. The assignments of the 250-300 K and the hydrogen. I ~ a k observed
i ~ ~ different adsorption
170 K peaks are inconsistent with the results by the behavior for hydrogen on anatase and on rutile TiO2.
Madey group which attributed these two states to the On both types of Ti02 powders, chemisorption of
dissociated and first monolayer water adsorption, hydrogen took place only when hydrogen was intro-
respectively. A recent study by Lu et al.71demos- duced above 623 K.
trated that, in addition to the molecular and dis-
sociative adsorption, water molecules can be reduced 3.2.3.Oxygen Adsorption
at the Ti3+sites on the TiOa(110) surface to produce Partial charge transfer from the surface adsorption
hydrogen gas. The oxygen atom in the water mol- site to the oxygen molecule was found to play an
ecule is preferentially extracted by the substrate to important role for oxygen adsorption on Ti02(110).
fill the surface oxygen vacancies. This selective On the basis of conductivity (Ao) and surface poten-
reduction process (as well as others) can be used to tial ( A q ) measurements, Gopel et al.75proposed the
infer the relative coverage of oxygen vacancy defect formation of 0 2 - upon chemisorption of oxygen. This
sites.71 step requires the presence of surface defect sites, and
The interaction of water with other single-crystal is the precursor for further dissociative reactions
Ti02 surfaces as well as powdered Ti02 has also been between the adsorbed 0 2 and the surface or bulk
investigated. Bustillo et al.72and Lo et al.73studied
the thermal desorption of water from the Ti02(100)
surface and reported dissociative adsorption of water.
-
oxygen vacancies. The initial sticking coefficient is
8x
-
at 300 K. The maximum desorption rate
for oxygen thermal desorption occurs at 348 K.
On powdered T i 0 2 , three TPD peaks can be observed. Low-energy ion scattering study by Pan et
A poorly resolved doublet at -211 K was attributed indicated that oxygen adsorption on TiOz(110)occurs
to multilayer and monolayer adsorption. A 311 K at the surface oxygen vacancy sites. With the use of
desorption peak was assigned to a different form of isotope 1 8 0 2 adsorption, it was found that no oxygen
molecularly adsorbed H20, and a 568 K desorption adsorption would occur on a stoichiometric surface.
was thought to arise from dissociatively adsorbed Kurtz et a1.68reported that oxygen was dissociated
H20. The production of hydrogen gas was also on the surface at 400 K and that the surface Ti3+sites
detected for H2O adsorption on reduced Ti02 pow- can be eliminated upon oxygen exposure. Lu et al.78
der,74indicating that the reduction property is char- found that oxygen molecularly adsorbs on TiOd 110)
acteristic of the Ti3+defect sites. at 105 K, and all 0 2 molecules are dissociated above
400 K.
3.2.2. H2 Adsorption Beck et al. studied the adsorption of oxygen on
Gopel et al.75studied the adsorption of hydrogen powdered rutile Ti02 using thermal desorption mea-
on the TiOz(110) surface using temperature pro- ~ ~ different desorption states at 164
s u r e m e n t ~ .Three
grammed desorption (TPD), electron paramagnetic K, 416 and 445 K were identified. Isotope labeling
resonance (ESR), and measurements of surface con- experiments showed no involvement of lattice oxygen
ductivity (Ao) and work function (Acp). The surface in the 164 and 416 K desorption states, and only 7%
defect sites (oxygen vacancies) were found to act as lattice oxygen was detected in the high temperature
electron donors and are the specific sites for H2 peak. For oxygen adsorption on anatase Ti02 pow-
adsorption. Chemisorption of hydrogen at 300 K der, only the low temperature state was observed. A
forms ionic titanium hydride bonds Ti4+-H- after Hz recent thermal desorption study by Yanagisawa et
dissociative adsorption at the defect sites. This a1.80reported a similar thermal desorption profile for
0 2 on rutile TiO2. Two desorption features at 180
process involves the transfer of two electrons which
before adsorption were attributed to one oxygen and 470 K involved only the oxygen from gas adsorp-
vacancy site (with two Ti3+ present). These two tion while another desorption state at 520 K included
hydrogen atoms can easily recombine during subse- oxygen from both the gas and the lattice.
quent thermal desorption measurements, exhibiting 3.2.4. CO and CO2 Adsorption
first-order desorption kinetics. The adsorbed hydro-
gen atoms also diffise into the bulk at 300 K, causing Ab initio molecular orbital calculations by Koba-
a nearly linear increase in conductivity (Ao) when yashi et a1.81showed that CO weakly interacts with
the Ti02(110) crystal is exposed to a continuous flow a defect-free TiO2(110) surface. The presence of
of molecular hydrogen. An initial sticking coefficient oxygen vacancy defects strongly enhances such in-
of 1 x was reported for H2 adsorption on TiO2- teractions due to electron back-donation from surface
(110) at 300 K. In the absence of surface defects, the Ti3+into the JC*orbitals of molecular CO. CO does
Photocatalysis on TiOn Surfaces Chemical Reviews, 1995, Vol. 95, No. 3 747
not adsorb onto the surface oxygen atoms. Carbonate surface. Onishi et a1.86investigated the adsorption
ion type or colinear carbon dioxide precursor type of SO2 on TiOz(110) and (441) surfaces using X-ray
surface complexes do not exist on the Ti02 surface and ultraviolet photoemission spectroscopies (XPS
containing adsorbed CO. At 300 K, Gopel et al.75 and UPS). On the (441) surface, SO2 oxidized Ti3+
found that CO adsorbs only at the defect sites. A to Ti4+accompanied with the formation of S2- species.
small amount of CO2 can be formed due to the Only SOs2- was detected upon SO2 adsorption on the
reaction of adsorbed CO with an adjacent bridging- (110) surface at 300 K.
oxygen atom, resulting in an additional oxygen
vacancy. On a single-crystal Ti02(110) surface, Lu 3.2.6. NH3 and H2S Adsorption
et al.78reported a weakly bound CO state desorbing Diebold et al.87studied the NH3 adsorption on T i 0 2 -
at -150 K. No thermal dissociation or oxidation was
observed.
On a powdered rutile Ti02 surface, Beck et al.79
-
(110) using XPS and low-energy ion scattering (LEIS).
A saturation coverage of 0.16 ML [l ML = 1 NH3
per surface atom] was measured on the stoichiomet-
observed two CO desorption states at 175 and 437 ric surface. A slightly higher coverage (0.19 ML) was
K. These states were attributed to CO molecules observed on the highly defective surface. Ammonia
interacting with the surface oxygen anions through adsorbs on TiOz(110) in molecular form. Roman et
the C-end of CO and CO molecules interacting with a1.88investigated the same adsorption system using
the surface defect sites through the O-end of CO, synchrotron radiation UPS. It was found that am-
respectively. Infrared spectroscopic studies by Tana- monia weakly adsorbs at 300 K. The uptake was
ka and White82 observed two different molecularly reported to be slightly higher on the perfect surface
adsorbed CO species with vibrational frequencies at than on the defective surface. The surface species
2185 and 2115 cm-l. The lower frequency species are predominately molecular ammonia. A small
was more strongly bound to the surface. fraction possibly dissociates at the defect sites upon
Gopel et al.75also reported that C02 weakly ad- heating the surface t o higher temperatures. The
sorbed on the TiOz(110) surface and its adsorption saturation coverage is 0.1 ML at 300 K.
was not influenced by the density of surface defect Roman and de Segoviasg also investigated the
sites. In the presence of surface hydroxyl groups, adsorption of ammonia on the Ti02(001) surface
Tanaka and White82found that CO2 readily reacted using UPS and TPD. Similar to that found on the
to form bicarbonate species on a powdered anatase (110) surface, NH3 molecularly adsorbed on Ti02
Ti02 surface. (001) at 300 K. Molecular NH3 desorbed at -338 K
with first-order kinetics. Some ammonia was dis-
3.2.5.NO and SO2 Adsorption sociated to produce NH2 and OH species. Further
decomposition of these products yields desorption of
Lu et aL71 studied the adsorption of NO on the N2 and H2 at 343 and 364 K, respectively.
TiOa(110) surface and reported a weakly bound Smith et al.90studied the interaction of H2S with
molecular adsorption state desorbing at 120 K. In a highly defective TiO2(110) surface and identified
addition, the reduction product, N20, was observed two distinct adsorption states. At low coverages, H2S
to desorb at 169 and 250 K. The 169 K desorption dissociated to produce H and S atoms bound to
feature was observed only on defective surfaces and surface Ti cation sites. The presence of the adsorbed
its intensity was proportional to the surface defect sulfur atoms dramatically inhibited the oxidation of
coverage. This low-temperature N2O state was then Ti3+sites by oxygen adsorption. At high H2S expo-
+ -
associated with the NO reductive reaction at surface
oxygen vacancy sites, e.g., NO(,, vacancy N(a,
+
+
Olattlce; N(a) NO(,, -.+ NzO. These defect sites were
sures, molecular adsorption was observed. This
adsorption state can be thermally desorbed before
423 K. Beck et al.79studied the adsorption of H2S
completely removed upon oxidation by adsorbed NO on both anatase and rutile powders. Two molecularly
(to produce N2O). adsorbed states (multilayer and monolayer) were
Similar results were reported by Boccuzzi et al.83 observed in thermal desorption spectra on both
for NO adsorption on powdered Ti02 using FT-IR anatase and rutile. A third irreversible adsorption
measurements. NO weakly adsorbs on hlly oxidized state was observed only on rutile Ti02 and was
Ti02 at 300 K. On the reduced sample, several attributed to dissociative adsorption at bridge-bond-
molecular and dissociative adsorption states were ing defect sites.
identified. NO adsorption reoxidized the reduced
sample. Thermal desorption measurements by Pan- 3.2.7. Deoxygenation Reactions of Organic Molecules on
de et al.84observed both NO and N20 desorption from Ti02
NO-exposed T i 0 2 samples reduced at 523 K. Increas- On Ti02 surfaces, various coordinatively unsatur-
ing the reduction temperature (and therefore the ated Ti cations (Ti3+,Ti2+,and Ti1+)can be generated
defect density) resulted in a higher yield of reduction by vacuum annealing, Ar+ sputtering, or chemical
products (N20 and N2). Only N20 and N2 were It is the relative
reductions (using H2 or C0).68,s9,75,91
desorbed from an NO-exposed sample that was ease in producing such defect sites that makes the
reduced at 1073 K. Ti02 surface exhibit not only the acid-base proper-
Smith et al.85have shown that SO2 also reacts with ties of most metal oxides, but also oxidation-reduc-
and oxidizes the oxygen vacancy sites (Ti3+)on TiO2- tion reactivities. This is particularly true for the
(110) and Ti203(1012) surfaces. This reaction con- adsorption of oxygen-containing organic molecules
tinued until all such defect sites were removed by which commonly undergo dehydration, dehydroge-
SO2 dissociation. Very weak interaction was ob- nation, deoxygenation, and self-disproportionation
served for SO2 on the nearly perfect TiO2(110) reactions.
748 Chemical Reviews, 1995, Vol. 95, No. 3 Linsebigler et al.
r+l ,hu
A-
p - 4.2V---- H2/H20
02/H20
I "2'
hu
Pt-Ti02
,
Figure 3.6. Photosplitting of water in a photoelectro-
chemical cell.
Figure 3.5. Potential energy diagram for the H a 2 0 and
OZ/H20 redox couples relative to the band-edge positions
for TiOz.
On the fully oxidized (100) surface, formaldehyde Figure 3.7. Photosplitting of water on composite catalyst.
undergoes a Cannizzaro-type reaction to simulta-
neously produce adsorbed methoxide and formate been achieved under each of the following experi-
species.g1 The yield of each product is strongly mental conditions. Here, each experimental config-
dependent on the preparation procedure of the sur- uration is designed to effectively separate the pho-
face. The formation of dioxymethylene (-OCH20-) togenerated electrons and holes for maximum photo-
has been observed during formaldehyde adsorption reaction yield.
on Ti02.97,98Among all the above-mentioned adsorp- (1)A closed circuit photoelectrochemical cell em-
tion processes, the deposition or removal of surface ploying a Ti02 anode and a metal (Pt in most cases)
oxygen atoms play an essential role. cathode, as shown in Figure 3.6. Here, hydrogen
evolves from Pt and oxygen from TiO2. A small
3.3. Photochemistry of Small Inorganic Molecules externally applied electrical potential (> 0.25 V)lol
on Ti02 may be necessary but this is much smaller than that
required in an electrochemical cell for H2O electroly-
3.3.1. Photodecomposition of Water on Ti02 sis ( > 1.23 V). Such photoelectrochemical configura-
Even though Ti02 can be effectively photoexcited tions were extensively studied in the 1970s and early
under band-gap irradiation, H20 cannot be photode- - ~ system was designed to resemble an
1 9 8 0 ~ . ~The
composed on clean Ti02 surfaces. Figure 3.5 il- electrochemical reaction and to effectively separate
lustrates the band-edge positions of Ti02 relative to the photogenerated electrons and holes. The photo-
the electrochemical potentials of the Hfi20 redox excitation of T i 0 2 injects electrons from its valence
couple and the O a 2 0 redox couple.99 According to band into its conduction band. The electrons flow
this electron energy diagram, water photolysis is through the external circuit to the Pt cathode where
energetically favorable. However, due to the pres- water molecules are reduced to hydrogen gas and the
ence of a large overpotential for the evolution of H2 holes remain in the Ti02 anode where water mol-
and 0 2 on the Ti02 surface, Ti02 alone becomes ecules are oxidized to oxygen.
inactive. Although earlier studies by Schrauzer et (2)Ti02 powders with deposited metal particles
a1.lo0reported the photosplitting of water using Ti02, (such as Pt)for H2 evolution and metal oxide particles
Sat0 and White74 demonstrated that the hydrogen (such as RuO2) for 0 2 evolution,lo2as shown in Figure
evolution from wet Ti02 is not due to the photocata- 3.7. Here, this system behaves as a short-circuited
lytic splitting of water, but rather the photoassisted micro photoelectrochemical cell in which Pt is the
oxidation of the oxygen vacancy sites on reduced cathode and RuO2 is the anode. Band-gap excitation
TiO2. Sustained photodecomposition of water has in the Ti02 substrate injects negatively charged
Photocatalysis on TiOn Surfaces Chemical Reviews, 1995, Vol. 95, No. 3 749
I H2° hv
TiO, ' H,+ f0,
I
I tope exchange reactions. Bickley et a1.1°8 and Mu-
nuera et al.104J09studied the photoadsorption of
oxygen on rutile Ti02 surfaces and found that the
presence of adsorbed water enhances the photoad-
sorption of oxygen by trapping the photogenerated
Figure 3.8. Photosplitting of water: sacrificial donor
effect.
+ +
by electron trapping (H+ 0 2 2e- -
holes at OH- sites. The formation of surface HO2-
HO2-1 and
0 3 - by hole trapping reactions (02-(lattice) + 0 2 +
electrons into the Pt particles and positively charged
- h+
0 3 - ) is the primary route for 0 2 photoadsorption.
Oxygen adsorption is an important step for the
holes into the RuO2 particles. Trapped electrons in
Pt reduce water to hydrogen and trapped holes in photocatalytic oxidation of organics on TiO2. Anpo
et al.l1° showed that 0 3 - was formed by the reaction
RuO2 oxidize water t o oxygen. The presence of Pt
and RuO2 significantly reduces the overpotential for
+ -
of 0- (hole trap, 02-(lattice) hf 0-)with adsorbed
oxygen molecules, as discussed above. These authors
H2 and 0 2 production, respectively. also demonstrated the exclusive incorporation of gas
(3) The use of sacrificial species to remove one of
the photodecomposition products so that the reaction
equilibrium is shifted toward further decomposition,
-
phase oxygen into the CO2 product upon CO photo-
+
oxidation on TiO2, that is, I s 0 2 Cl60 2C160180.
No lattice oxygen was involved. Their calculations
as shown in Figure 3.8. Here, the sacrificial species implied that the photoactivation of oxygen occurred
may be oxidized by the hole-reaction product (pre- by the formation of a 03-(180-180-160-) species in
sumably 0 2 ) or reduced by the electron-reaction which the 0-0 bond in the original 0 2 molecule is
product (presumably H2). For example, when alco- significantly weakened.
hols such as CH30H are added to a Ti02 aqueous
suspension, sustained H2 production is observed upon Oxygen photodesorption from powdered Ti02 was
W irradiation and the alcohol molecules are oxidized recently studied by Yanagisawa and OtaeaOIt was
to C02.103 Additional examples about the photooxi- found that the photodesorption occurs only when
dation and reduction processes in aqueous Ti02 photon energy above the Ti02 band gap was deliv-
systems will be given later in this section. ered. Oxygen desorbed molecularly, and no isotopic
The detailed mechanism for the photodecomposi- exchange with the lattice was observed. The photo-
tion of water on Ti02 and the photooxidation or desorption signal followed t-l" decay kinetics, similar
reduction reactions involving the water-Ti02 system to that observed for COSphotodesorption from ZnO.lll
remains a controversial issue today. A number of These rate kinetics were attributed to the recombina-
researchers have reported the observation of several tion of adsorbed 0 2 - (or C02- on ZnO) with the
radical species using EPR measurements. Gonzalez- photogenerated holes.
Elipe et al.lo4reported the formation of HO2' and '0- Lu et al.78studied the adsorption of oxygen on a
or *023- species generated by W irradiation of TiOz(l10) surface and similar desorption behavior
hydrated anatase Ti02 in oxygen. Anpo and co- was observed. No isotopic mixing was detected
worker~ ~ ~ ~ 'OH radicals at 77 K on hydrated
observed during the photodesorption experiments even when
anatase under band-gap irradiation. Jaeger and a mixture of 1 8 0 2 and 1 6 0 2 was adsorbed on the
Bard reported the formation of HO2' and 'OH radicals surface.
in aqueous suspensions of Ti02,99 Howe and Grat-
ze131observed that surface hydration of anatase has 3.3.3.Photooxidation and Photoreduction of Molecular
a significant influence on the reactivity of holes and
Nitrogen
electrons generated upon band-gap irradiation. The photocatalytic activity of Ti02 for N2 oxidation
Trapped electrons are readily scavenged by adsorbed and reduction have been observed by several re-
oxygen. Trapped holes are much less reactive, and searchers. Schrauzer et al.loOfirst reported the
they react with surface hydroxyl groups above 77 K photoreduction of N2 by an iron-doped Ti02 catalyst.
to produce ' 0 2 - . Hydroxyl radicals are not the Adsorbed water was photodecomposed to yield oxy-
primary products and their existence is transient. gen, and at the same time nitrogen was reduced t o
produce NH3 and N2H4. The hydrogenation of un-
3.3.2. Photoadsorption and Photodesorption of Oxygen on saturated hydrocarbons was also achieved photocata-
Ti02 lytically in the same study.
The photoadsorption and photodesorption of 0 2 on Bickley and co-workers112studied the photooxida-
Ti02 have been investigated in an effort to under- tion of Nz on Ti02 at the gas-solid interface. Ther-
750 Chemical Reviews, 1995, Vol. 95, No. 3 Linsebigler et al.
Apertured QMS co
10 /
hv - Intermediate
H O CH2O
\ 0 Uactle.)
CH2O
Figure 3.11. Summary of CH$1 photooxidation on TiOz-
(110).
10.03 C'aOcI,
C,CI,H"O
e,
0
c
0
90
v)
further TCE photooxidation; the presence of water ing power of the conduction band energy and the
(either vapor or liquid) helped to remove these holes have the oxidizing power of the valence band
surface species. energy. From the band-edge positions of the valence
band and conduction band, as discussed in section
3.5.4. 4-Chlorophenol (4-CP) 2.2.2, the redox capability of a photoexcited semicon-
Photodegradation of 4-chlorophenol has been in- ductor particle in the aqueous solution can be esti-
vestigated in gas in aqueous suspen- mated. The bulk photoelectrons and photoholes can
si011,l~l-l~~and on e1e~trodes.l~~ The molecule is of recombine to produce thermal energy, or rapidly
interest due to its benzene ring structure which migrate to the surface and react with adsorbed
allows the capture of radical intermediates (such as species at the surface. In a steady state photocata-
'OH) or the direct interaction with an electron. A lytic reaction, the rate of oxidation by the holes has
recent FT-IR study of the gas phase reaction by to be balanced by the rate of reduction by the
Stafford et al.130 found that in the absence of water electrons. Either of these reactions can be rate
vapor, 4-CP was photooxidized possibly by reacting determining.
with the photogenerated ' 0 2 - radical species. Addi- Although the above physical events are generally
tion of water vapor to the system dramatically accepted as the initial step for the photooxidation
enhanced the rate and extent of photooxidation. process, the subsequent chemical events at the
However, the exact cause for this change was not liquid-solid interface remain an ambiguous and
determined. Direct reaction of 4-CP with photoge- controversial issue. The trapped holes have been
nerated electrons was also observed. 4-CP accepts proposed to directly oxidize adsorbate molecules,117
one electron and releases one C1- ion, resulting in or t o react with surface hydroxyl groups to produce
hydroquinone formation. Futher photooxidation re- hydroxyl radicals which are strong oxidizing agents.137
quired the presence of oxygen. From these results, The chemical identification of hydroxylated oxidation
the authors pointed out that hydroxyl radicals ('OH) intermediates and the ESR detection of hydroxyl
may not be exclusively responsible for the photooxi- radicals appear to support the hydroxyl radical
dation of 4-CP and the role of oxygen is more than mechanism. However, these data do not permit the
that of merely an electron scavenger. unambiguous delineation of the 'OH-driven mecha-
nism versus the direct hole oxidation mechanism
3.6. Photooxidation at the Liquid-Solid Interface since similar reaction intermediates are expected
on Ti02 Catalysts from these two schemes in an aqueous system. A
recent diffuse reflectance flash photolysis experiment
3.6.1. Introduction in nonaqueous solution presented evidence in favor
By using Ti02 as a catalyst, the photooxidation of of the direct hole oxidation route.l17 The trapped
organics may be used for decontamination treatment electrons are believed to react with preadsorbed
in polluted waters. Such applications have inspired molecular oxygen to produce 0 2 - and 0 z 2 - anions.
a vast amount of research. The solid photocatalysts However, the ultimate fate of these activated oxygen
studied include colloidal particles, high surface area species was not determined. They may directly
powders, and single-crystal surfaces. The complexity oxidize organic species, protonate to generate hydro-
of the liquid-solid interface presents many more peroxide radicals and hydroxyl radicals, or further
variables (in comparison t o the gas-solid system) to react with more trapped electrons to eventually form
be dealt with in kinetics studies. Such parameters water. Recent studies of 4-chlorophenol (4-CP) deg-
include the surface composition, surface area, prepa- radation in a T i 0 2 slurry suggested that oxygen plays
ration procedures, and concentration of the photo- a specific role during photooxidation in addition to
catalyst; the pH of the solution and its effect on the scavenging the trapped e l e c t r o n ~ . ~ ~It~ was
J~~J~~
surface structure; the concentration of the reactants; found that 4-CP degradation only occurs to a small
the solvent environment; the partial presure of extent (20%)in the presence of an alternative elec-
oxygen; the diffusion rate in solution and near the tron acceptor capable of sweeping up trapped elec-
surface, etc. Care must be taken with the control- trons as readily as oxygen, while complete photo-
lable parameters, or discrepencies will occur in the mineralization is achieved in a similar time frame
experimental results. For instance, chlorobenzene when oxygen is present.
was first reported not to undergo complete mineral-
ization over Ti02.135 However, experiments with a 3.6.3. The Dynamics of Charge Carrier Trapping,
differently prepared Ti02 catalyst and with a higher Recombination, and Interfacial Electron Transfer
oxygen pressure demonstrated that total photooxi- In an aqueous solution, picosecond and nanosecond
dation of chlorobenzene may be achieved.136 The laser photolysis was employed to investigate the
various kinetic parameters in the liquid-solid pho-
tooxidation systems have been discussed in several
recent reviews.14-19
tion in -
dynamics of charge carrier trapping and recombina-
60 8, colloidal particles of Ti02.30 The
trapping of the conduction band electrons is a very
rapid process and occurs within 30 ps. By contrast,
3.6.2. The Primary Events of Photooxidation at the the trapping of the valence band holes is a much
LiquicCSolid Interface slower process requiring an average time of 250 ns.
Continuous band-gap irradiation of an aqueous The recombination of trapped electrons with free or
semiconductor dispersion excites an electron from the trapped holes takes place in the to s time
valence band to the conduction band, creating an domain. At low charge carrier concentration, the
electron-hole pair. The electrons possess the reduc- mean lifetime of a single electron-hole pair is -30
754 Chemical Reviews, 1995, Vol. 95, No. 3 Linsebigler et at.
Trap Barrier
Semiconductor
\
Figure 4.3. Photoexcitation in composite semiconductor-
semiconductor photocatalyst.
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