Fang 2013

Article
pubs.acs.org/JPCA
Computational Study of H2 and O2 Production from Water Splitting

by Small (MO2)n Clusters (M = Ti, Zr, Hf)
Zongtang Fang and David A. Dixon*
Department of Chemistry, The University of Alabama, Shelby Hall, Box 870336, Tuscaloosa, Alabama 35487-0336, United States
*
S Supporting Information
ABSTRACT: Coupled cluster [CCSD(T)] theory and density

functional theory (DFT) have been used to study the production of
H2 and O2 from hydrolysis products generated from H2O addition to
(MO2)n (M = Ti, Zr, Hf, n = 13) clusters on both the lowest singlet
and triplet potential energy surfaces (PESs). H2 production occurs via
the formation of an MH containing intermediate followed by HH
recombination and H2 desorption from MnO2n(OH)2 and MnO2n+2.
The hydrogen transfer reactions to form the MH bond are the rate
determining steps and can be considered to be proton coupled,
electron transfer (PCET) reactions with one or two electrons being
transferred. Oxygen is produced by breaking two weak MO bonds in
an atomic oxygen saturated metal oxide from an M n O2n O2
intermediate. On the triplet PES, the activation energies for the rst
and second H transfer to the metal are calculated to be 10 to 50 kcal/mol and 75 to 90 kcal/mol depending on the size of the
clusters and the metal. The barriers on the singlet surface for the rst and the second H transfer are predicted to be 110 to 140
kcal/mol, in general larger than the HO bond dissociation energy. The activation barriers for the step of HH recombination
are 15 to 50 kcal/mol, and the H2 desorption energies are less than 10 kcal/mol on the singlet and triplet PESs. The oxygen
desorption energies follow the order Ti < Zr < Hf for the triplets and Ti < Zr Hf for the singlets. The oxygen desorption
energy is approximately independent of the size of the cluster for the same metal. The water splitting reactions prefer to take
place on the triplet surface. A low excess potential energy is needed to generate 2H2 and O2 from 2H2O after the endothermicity
of the reaction is overcome on the triplet PES.
INTRODUCTION
Since Fujishima and Honda rst used TiO2 as the photocatalyst
many experiments dealing with the evolution rate and the
quantum yield eciency, the details of the H2 evolution
for water splitting to generate H2 and O2 under UV light in mechanism are not as well-understood. Generally it is believed
1971,1,2 solar splitting of water with TiO2 has been extensively that H2 production is due to the reduction potential of an
studied. The other two group 4 transition metal dioxides, excited electron which is sucient to reduce H+ ions to H2.13
zirconia (ZrO2) and hafnia (HfO2), also have been used as The detailed mechanism including the reaction intermediates
photocatalysts for water splitting to generate H2 and O2.36 and reaction barriers for the photodecomposition of water on
Water splitting into H2 and O2 (2H2O(g) 2H2(g) + O2(g)) crystal TiO2 and TiO2 nanoclusters is still not well-established.
is an endothermic reaction with a reaction enthalpy of 115.6 To overcome the high overpotential of oxygen evolution
kcal/mol using the heat of formation of H2O at 298 K (57.8 from water splitting and improve the eciency, a photo-
0.2 kcal/mol),7 which roughly corresponds to two 500 nm electrochemical catalytic approach has been used for water
visible photons. splitting. The presence of an electric eld at the interface
Hydrogen evolution from water splitting can be achieved prevents the recombination of photogenerated electrons and
without an external circuit by using TiO2 nanoparticles or TiO2 cationic holes.14,15 The mechanism of photoreduction in the
powder as the photocatalyst under visible light.811 In the waterTiO2 system is still controversial. Early work predicted
photocatalytic process, noble metals such as Pt or Ru serve as the formation of several radicals during the reaction. Fujishima
the catalyst and electric donors such as diethanolamine (DEA) and co-workers found that photogenerated holes can produce
or triethanolamine (TEA) are required to produce the H2. The hydroxyl (OH) radicals in both the gas phase16 and aqueous
photogeneration of H2 also can be achieved on a crystalline environment17,18 on the hydrated TiO2 anode surface. The
surface. A Pt-loaded TiO2 hierarchical photonic crystal formation of HO2, O2, and O33 radical intermediates
photocatalyst shows enhanced catalytic activity and can double
the hydrogen evolution in comparison with the rate obtained Received: February 8, 2013
by using nanocrystalline TiO2 due to improved light capture Revised: March 29, 2013
and multiple scattering among segments.12 Although there are Published: April 1, 2013
2013 American Chemical Society 3539 dx.doi.org/10.1021/jp401443x | J. Phys. Chem. A 2013, 117, 35393555
The Journal of Physical Chemistry A Article
were detected with EPR under UV irradiation of hydrated measure of the ability of a surface to bind oxygen.32 Vojovodic
anatase TiO2 in an oxygen environment.19 Salvador and and Nrskov33 veried this hypothesis by DFT calculations of
Gutierrez proposed the formation of H2O2 from the coupling the appropriate densities of states.
of OH radicals.20,21 On the basis of results from in situ FTIR Small TiO2 clusters (Ti2O4) have been used to study34
spectroscopy measurements, Nakato and co-workers22 pre- electrochemical water splitting for one and two water molecules
dicted that O2 evolution is initiated by the formation of a with a combination of DFT at the B3LYP/TZV(d,p) level
surface peroxo (TiOOTi) intermediate on the TiO2 followed by coupled cluster single and double (CCSD) single-
(rutile) surface. In acidic solution, TiOOH is formed by point energy calculations. Reactions in solution were modeled
protonation of TiOOTi by H2O. Without an external by a polarizable continuum model. Proton and electron
electric eld, oxygen evolution has only been reported with the removal is predicted to be very endothermic in both the gas
assistance of an electron acceptor, such as Ag+ in solution.2325 and aqueous phases. OO bond formation is predicted to
Transient absorption spectroscopy has been used to study the proceed through peroxides and takes place after the removal of
kinetics of oxygen evolution where O2 is produced in the two electrons.
aqueous phase using a nanocystalline PtTiO2 lm under UV The mechanism of H2 and O2 evolution using ZrO2 and
irradiation.24 That study predicted that four photogenerated HfO2 as photocatalysts has not been reported. In our previous
holes are required for 1 mol of oxygen production and that work, we predicted that water should readily react with small
there are three possible unidentied reaction paths for the (MO2)n (M = Ti, Zr, Hf) clusters to form hydroxides.35,36 H2
formation of oxygen. The same spectroscopic method was used and O2 evolution would then take place in subsequent steps
to detect the lifetime of photoholes in nitrogen-doped, with breaking of the MOH bonds. In the current study, we
nanocrystalline TiO2 lms.25 Oxygen production requires the use electronic structure theory at both the DFT and correlated
lifetime of the photoholes to be at least 0.4 s. molecular orbital theory coupled cluster (CCSD(T)) levels to
Computational research on water splitting has been focused study the H2 and O2 production mechanism of photocatalytic
on the electrochemical mechanism. The photoelectrochemical water splitting by (MO2)n (M = Ti, Zr, Hf, n = 13) clusters.
oxidation of water on the rutile TiO2 (110) surface was studied In our study, we do not employ a separate moiety to produce
by Valdes et al.26 with density functional theory (DFT)27 with the H2 as currently practiced and described above. Rather, we
the generalized gradient approximation (GGA) RPBE func- focus on the ability of a cluster to split water into both H2 and
tional. They based their mechanism on four one-electron O2. Both the lowest energy singlet and triplet potential energy
transfers and predicted the rate limiting step for water splitting surfaces were calculated. Starting from the initial hydrolysis
to be the formation of an adsorbed hydroxyl group based on products, the MOH bond is broken rst leading to the
thermodynamic correlations. In a neutral environment, an formation of a metal hydride before the formation of H2 and
overpotential of at least 0.78 V is needed for both H2 and O2 then MO bonds are broken to generate O2. Dehydrogenation
evolution. O2 evolution was predicted to take place via an and deoxygenation reaction energies and barriers are calculated
intermediate HOO adsorbed on the crystal surface. Part of this using the B3LYP functional.37,38 The DFT potential energy
group subsequently28 modeled water oxidation on a rutile TiO2 surfaces for the monomer and dimer were benchmarked by
(110) surface by using a (TiO2)26 cluster and found a similar comparison to the energies calculated at the CCSD(T) level.
oxygen evolution mechanism.29 Nrskov and co-workers30
reported the same oxygen evolution mechanism on transition
metal doped rutile TiO2 (110) surfaces. A lower overpotential
COMPUTATIONAL METHODS
Geometry optimization and frequency calculations were
for the oxygen evolution reaction was predicted for the doped performed at the DFT level with the B3LYP37,38 exchange-
surface as compared to the undoped surface. Liu and co- correlation functional. This functional was chosen, as it is the
workers31 studied oxygen evolution on dierent TiO2 anatase same method used for our study of the hydrolysis of (MO2)n
surfaces in an aqueous environment with DFT with the (M = Ti, Zr, Hf, n = 14) clusters where reasonable results
generalized gradient approximation (GGA) PBE exchange- were found in comparison to CCSD(T) calculations.35,36 The
correlation functional. They modeled oxygen evolution by DFT optimized DZVP2 based set was used for the reaction of
adding two H2O molecules to the crystal surface and then H2O with TiO2 clusters.39 For the reaction of H2O with ZrO2
removed the four protons step-by-step. After the rst H2O and HfO2 clusters, the aug-cc-pVDZ basis sets were used for O
decomposed on the crystal surface with formation of a hydroxyl and H40 and pseudopotential (PP)-based aug-cc-pVDZ-PP
group, a surface bridging TiOOTi moiety is formed by basis sets were used for Zr and Hf.41,42 For simplicity, we
loss of the proton from the OH group. The second H2O denote these combined basis sets as aD. Vibrational frequencies
adsorbs at the same Ti atom and production of the second OH were calculated to characterize the stationary points on the
group induces the evolution of O2. In the chemisorption potential energy surfaces and to obtain zero-point energy
reaction of the second water, the structure of surface bridging corrections as well as the thermal and free energy corrections at
OO changes from peroxide to superoxide. For the overall 298 K, the latter values using the normal statistical mechanical
reaction, the removal of the rst proton requires the highest expressions.43 The synchoronous transit-guided quasi-Newton
overpotential in comparison to the following steps in their (STQN) method was used for the transition state optimiza-
mechanism. A TiOH bond is formed instead of a OH tions.44 For the potential energy surfaces for the monomer and
radical, and no adsorbed OOH and HOOH species were the dimer, the B3LYP geometries were used in single-point
identied in the oxygen evolution reaction. They studied the energy calculations with the coupled cluster [CCSD(T)]
(101), (001), and (102) surfaces and did not nd signicant theory4547 with the aD basis set for all atoms.4850 The
dierences in terms of the overpotential. Further work on the open-shell calculations were performed with the R/UCCSD(T)
oxygen evolution reaction led to the proposal that the approach where a restricted open shell HartreeFock (ROHF)
occupation of the eg orbitals of the active metal in perovskites calculation was initially performed and the spin constraint was
was a descriptor of the reaction eciency, as it provides a then relaxed in the coupled cluster calculation.51
3540 dx.doi.org/10.1021/jp401443x | J. Phys. Chem. A 2013, 117, 35393555
Figure 1. Potential energy surfaces for Ti(OH)4 (1b) TiO2 (1a) + 2H2 + O2 at 0 K. Relative energies calculated at the CCSD(T)/aD//B3LYP/
DZVP2 (in blue) and B3LYP/DZVP2 (in black) levels in kcal/mol. The O atoms are given in red, Ti atoms in dark blue, and H atoms in gray-white.
The DFT calculations were carried out with the Gaussian 09 Molecular visualization was carried out using the AGUI
program package.52 All CCSD(T) calculations were performed graphics interface from the AMPAC program package.54
with the MOLPRO 2010.1 program.53 The calculations were
performed on local Xeon and Opteron based Penguin
Computing clusters, the Xeon based Dell Linux cluster at the
RESULTS
The structures of the optimized intermediates and transition
University of Alabama, the Opteron and Xeon based Dense states for M = Ti are shown in Figures 15. The total energies,
Cartesian coordinates, and pictures of the molecules for the
Memory Cluster (DMC) and Itanium 2 based SGI Altix
potential energy surfaces (PESs) for the reaction of H2O on
systems at the Alabama Supercomputer Center, and the M3O6 (M = Zr, Hf) are given as Supporting Information
Opteron based HP Linux cluster at the Molecular Science including atom numbering where appropriate. In our previous
Computing Facility at Pacic Northwest National Laboratory. study of the hydrolysis of M3O6 (M = Zr, Hf),36 we did not
Figure 2. Potential energy surfaces for Ti2O2(OH)4 (2b) Ti2O4 (2a) + 2H2 + O2 at 0 K. Relative energies calculated at the CCSD(T)/aD//
B3LYP/DZVP2 (in blue) and B3LYP/DZVP2 (in black) levels in kcal/mol.
study the reaction of the addition of a second H2O with the dimer reactions. The triplet state is used as a model for the
clusters. In the current work, we calculated the reaction of the excited state of the cluster, as it is not really possible to study
second H2O addition and the PESs are shown in the the excited open shell singlet states using current density
Supporting Information. functional theory approaches. Our prior work on the cluster
Potential Energy Surfaces. The calculated PESs for H2 excitation energies shows that the singlettriplet splitting is on
and O2 production on the monomer and the dimer of TiO2 the order of 0.1 eV.55 This small dierence in energy between
clusters at both the CCSD(T) and B3LYP levels are given in the rst open shell singlet and the triplet state does not change
Figures 1 and 2. The PESs for MO2 (M = Zr, Hf) and M2O4 the conclusions.
(M = Zr, Hf) are shown in the Supporting Information. The Monomers. The PES for H2 and O2 production for 3TiO2
PESs for the trimers at the B3LYP level are given in Figures (1a) starting from the hydrolysis product, 3Ti(OH)4, calculated
35. In the following sections, the CCSD(T) energy results are at the CCSD(T)/aD level is shown in Figure 1. 3Ti(OH)4 can
used for the discussion of the energetics for the monomer and be formed by 1Ti(OH)4 absorbing 84 kcal/mol of energy or by
Figure 3. Potential energy surfaces for M3O4(OH)4 (3b) M3O6 (3a) + 2H2 + O2 at 0 K. Relative energies calculated at the B3LYP/DZVP2 (in
black) level for M = Ti, the B3LYP/aD (in green) level for M = Zr, and the B3LYP/aD (in purple) level for M = Hf in kcal/mol.
excitation of TiO2 by a visible photon (555 nm) with 52 reaction starts with an endothermic H migration from a
kcal/mol of energy followed by the reaction of two H2O hydroxyl group forming a TiH bond with a reaction barrier of
molecules. As discussed above, the excited singlettriplet 37.4 kcal/mol. The formation of the MH bond is followed by
splitting is small so we approximate the photon absorption the recombination of two hydrogens to form H2, one from a
energy by the energy needed to generate the triplet. The TiH bond and the other an adjacent H atom in the hydroxyl
group. This step is also endothermic with a reaction barrier of energy. For the formation of the second metal hydride, the
32.3 kcal/mol. The H2 molecule is released from the complex barriers are 103.3 and 84.6 kcal/mol for M = Zr and M = Hf,
TiO2(OH)2H2 with a desorption energy of only 2.8 kcal/mol. respectively. The barriers for HH recombination and the H2
The process for the production of the second H2 is the same desorption energies are comparable to those for 3TiO2. The
as for the rst H2 molecule. The reaction barriers for TiH oxygen desorption energies on 3MO2 are 51.7 and 48.3 kcal/
bond formation and HH recombination are 78.7 and 34.6 mol for M = Zr and M = Hf, respectively. The alternative
kcal/mol, respectively. After the release of two H2 molecules, a reaction path for the release of O2 before the release of the
triplet oxygen molecule is readily desorbed from the 3TiO2O2 second H2 from the intermediate 3HMO3(OH) (M = Zr, Hf) is
(1l) species and 1TiO2 is regenerated. The calculated similar to that for TiO2. The reaction barriers for HH
desorption energy of 3O2 is 6.3 kcal/mol. If this reaction recombination are 39.1 and 44.0 kcal/mol for M = Zr and M =
were to take place on an excited singlet, then a singlettriplet Hf, respectively, slight larger than that for M = Ti. The path
crossing would need to occur, which could raise the barrier or proceeding in the order H2 release, O2 release, and H2 release
decrease the rate. The potential energy surface calculated at the (H2O2H2 path) has a higher energy prole than the path
B3LYP/DZVP2 level is in semiquantitative agreement in discussed above in the order H2 release, H2 release, and O2
comparison with the CCSD(T)/aD results with dierences of release (H2H2O2 path) especially for M = Zr, Hf although,
relative energies being less than 5 kcal/mol. for M = Ti, the two paths have more similar energies. For the
The PES for reactions on 1TiO2 at the CCSD(T)/aD level is H2O2H2 path, the highest potential energy along the PES is
also shown in Figure 1. The reaction process is similar to that still smaller than or equal to the endothermicity of the reaction
for 3TiO2, and the H2 release follows the same process, TiH 2H2O 2H2 + O2, even though it is higher in energy than the
bond formation, HH recombination, and H2 desorption. Due H2H2O2 path.
to the high exothermicity of the hydrolysis reaction on the Dimers. The PESs for H2 and O2 production on Ti2O4 (2a)
singlet cluster, the reaction barrier for the formation of the clusters are shown in Figure 2, and the PESs for the H2O2
titanium hydride, 1HTiO(OH)3 (1d) is high, 115.3 kcal/mol, H2 path on Ti2O4 and M2O4 (M = Zr, Hf) are given in the
which is larger than the average water HO bond energy of Supporting Information. The H2 production process for the
110 kcal/mol or the H2 bond energy of 104 kcal/mol.56 This reaction on the dimer is consistent with the reaction on the
barrier is also much larger than the excitation energy needed to monomer. For both the triplet and singlet, the OH bond in
form 3HTiO(OH)3. The barrier for HH recombination and M2O2(OH)4 is broken rst to form a metal hydride containing
the H2 desorption energy for the rst H2 release are 19.3 and species and the reaction is followed by a HH recombination
3.9 kcal/mol, comparable to the values for the triplet surface. step and H2 release. After the release of the rst H2, the
For the release of the second H2 from the singlet, the reaction intermediate 3M2O4(OH)2 undergoes a structural trans-
barriers for H transfer to Ti and HH recombination are 96.7 formation with modest energy input and two terminal MO
and 32.7 kcal/mol, respectively, and the H2 desorption energy oxygen atoms bond together as shown in 3M2O4(OH)2 (2g)
is 9.1 kcal/mol. The barrier to form the second TiH bond on leading to a structure that is favorable for O2 evolution. The
the singlet surface is also higher than that on the triplet surface. process for the release of the second H2 is the same as that for
Breaking the TiO bond in 1TiO2 O2 (1l) to generate 3TiO2 the rst one. For O2 formation, an intermediate M2O4O2
and 3O2 requires 33.4 kcal/mol if there is no surface crossing to (2n), which contains a ve-coordinate metal and an OO
form 1TiO2. The presence of a singlettriplet surface crossing bond, is formed by an O atom transfer to the adjacent metal
leads to an exothermic channel to form the 1TiO2. Again, the atom via the path shown for 2l 2n. The MO bond in the
B3LYP/DZVP2 results for the singlet potential energy surface atomic oxygen saturated intermediate is much weaker than a
are similar to those calculated at the CCSD(T)/aD level. normal MO bond,48 so only modest energy input is needed to
An alternative reaction path for the release of O2 and the break the MO bond to produce O2 and the dimer isomer,
second H2 is the conversion of 1m 1a. Oxygen is released M2O4 (C3v, 2o). The ground singlet state isomer 1M2O4 (C2h,
rst by breaking a TiO bond in 3HTiO3(OH) (1i). The O2 2a) is regenerated by a structural transformation reaction with a
desorption energy is 7.5 kcal/mol at the CCSD(T)/aD level. small barrier.
The nal step is H2 production with a barrier of 34.6 kcal/mol The barriers for the reactions on 3Ti2O4 for forming two Ti
and a H2 desorption energy of 6.3 kcal/mol on 1TiO2. H bonds are calculated to be 37.9 and 92.0 kcal/mol,
The processes for H2 and O2 release from the hydrolysis comparable to those for 3TiO2. The reaction barriers for the
product M(OH)4 (M = Zr, Hf) are the same as those for two HH recombination reactions are 23.4 and 17.6 kcal/mol,
Ti(OH)4. Consistent with the TiO2 results, the highest reaction slightly smaller than those for 3TiO2. Again, much smaller
barrier takes place in the formation of the metalhydrogen energies than the two reaction barriers are needed for H2
bond for the release of the second H2 on the triplet surface. For desorption. The reaction barrier for the formation of the
M = Zr, the reaction barriers for the formation of the two Zr oxygen saturated species is predicted to be 8.1, and 15.2 kcal/
H bonds are 14.4 and 84.5 kcal/mol at the CCSD(T)/aD level. mol is needed to break the weak TiO bond in 3Ti2O4O2
The corresponding energies are 12.1 and 87.9 kcal/mol for M = (2n). The isomer relaxation of 1Ti2O4 (C3v, 2o) to the ground
Hf. The reaction barriers for the two HH recombination singlet state 1Ti2O4 (C2h, 2a) is exothermic with a small barrier.
reactions are 44.9 and 27.5 kcal/mol for M = Zr and 50.4 and For the reaction on 1Ti2O4, the reaction barriers for hydrogen
30.8 kcal/mol for M = Hf. A much lower energy, generally 2 to transfer to the Ti atom are calculated to be 126.4 and 126.9
6 kcal/mol, is needed for the desorption of the rst and second kcal/mol, much larger than those for 3Ti2O4. The reaction
H2. The energy input to break the MO bonds are 19.5 and barriers for HH recombination, the H2 desorption energy,
33.2 for M = Zr and M = Hf respectively. On the singlet cluster, and the O2 desorption energy are comparable with those for
the reaction barrier for the formation of the rst MH bonds
3
Ti2O4. The barrier for the formation of 1Ti2O4O2 (2n) from
1
are 127.1 and 127.9 kcal/mol for M = Zr and M = Hf, Ti2O6 (2l) is 40.9 kcal/mol at the B3LYP/aD level, much
respectively, which are larger than the OH bond dissociation larger than that for triplet 2l 2m.
Figure 4. Potential energy surfaces for M3O4(OH)4 (3o) M3O6 (3a) + 2H2 + O2 at 0 K. Relative energies calculated at the B3LYP/DZVP2 (in
The reaction mechanisms for Zr2O4 and Hf2O4 are bond energy. In comparison with the large barrier for H
essentially the same as that for Ti2O4. On 3Zr2O4 and transfer to the metal, the HH recombination barriers, the H2
3
Hf2O4, the major energy consuming step is the formation of desorption energy, and the O2 desorption energy are much
the second metal hydride. For the reactions on 1Zr2O4 and smaller on both the singlet and triplet potential energy surfaces.
After formation of HM2O5(OH), the reaction can generate
1
Hf2O4, both the rst and the second H transfers to the metal the complex HM2O3(OH)O2 rst via rotation of the O atom
require signicant energy input. The barriers to form adjacent to the MH bond to bond to the other metal. Then
1 3
HM2O2(OH)3 (2d) are calculated to be 118.4 and 119.9 O2 is released by breaking two weak MO bonds followed by
kcal/mol for M = Zr and M = Hf, both larger than the HO HH recombination. After the release of the second H2, M2O4
Figure 5. Potential energy surfaces for M3O4(OH)4 (3aa) M3O6 (3a) + 2H2 + O2 at 0 K. Relative energies calculated at the B3LYP/DZVP2 (in
(C2h, 2a) is regenerated. For M = Ti, the energy needed to kcal/mol for both the triplet and singlet, 10 kcal/mol larger
release the second H2 from HM2O5(OH) is >25 kcal/mol than that from the triplet and singlet HTi2O5(OH). For M =
energy less than the energy needed to form the complex Zr, Hf, on the triplet surface, slightly more energy is needed to
HM2O3(OH)O2 for 3O2 release on both the triplet and singlet regenerate the ground state 1M2O4 for the H2O2H2 path
potential energy surfaces. The reaction barrier for HH than for the H2H2O2 path. On the singlet surface for M =
recombination from HTi2O3(OH) are predicted to be 30 Zr, Hf, >30 kcal/mol of additional energy are required to form
Table 1. Calculated Metal Hydrogen Bond Distance in at the B3LYP Levela

Ti Zr Hf
moleculeb singlet triplet singlet triplet singlet triplet
HMO(OH)3 (1d) 1.686 1.851 1.867 2.100 1.851 2.088
HMO3(OH) (1i) 1.711 1.724 1.873 1.865 1.857 1.844
HMO(OH) (1m) 1.720 1.894 1.864
HM2O3(OH)3 (2d) 1.699 1.900 1.884 2.151 1.869 2.129
HM2O5(OH) (2i) 1.696 1.689 1.878 1.874 1.864 1.857
HM3O5(OH)3 (3d) 1.682 2.202 1.865 2.558 1.849 2.441
HM3O7(OH) (3i) 1.680 1.679 1.864 1.857 1.879 1.842
HM3O5(OH)3 (3q) 1.681 2.332 1.868 2.122 1.850 2.094
HM3O7(OH) (3v) 1.691 1.680 1.871 1.859 1.851 1.843
HM3O5(OH)3 (3ac) 1.706 1.975 1.898 2.190 1.880 2.151
HM3O7(OH) (3ah) 1.713 1.682 1.882 1.859 1.861 1.868
a
DZVP2 basis set for M = Ti and aD basis set for M = Zr, Hf. bSee Figures 15 and Supporting Information for the molecular structures.
an oxygen complex compared to HH recombination from desorption energy from the complex of 3Ti3O6O2 (3n) is
1
HM2O5(OH). The activation barriers for HH recombination calculated to 22.1 kcal/mol.
are predicted to be 30 to 40 kcal/mol for both the triplet and On the singlet potential energy surface, the formation of the
singlet, 10 to 15 kcal/mol larger than the barriers in the second rst metal hydrogen containing species has large reaction
H2 production on the H2H2O2 path. barriers for all three dierent reactions as shown in Figures
Trimers. The PESs for hydrogen and oxygen production on 35. The barriers for the formation of a second metal hydrogen
the M3O6 (3a) cluster at the B3LYP/aD level are shown in containing singlet species are predicted to be 110 to 130
Figures 35. For both the triplet and singlet potential energy kcal/mol, much larger than on the triplet potential energy
surfaces, the reactions can start from three dierent hydrolysis surfaces. The reaction barriers and desorption energies for the
products, M3O4(OH)4 (3b, 3o, 3aa). All four hydrogen atoms H2 and O2 release steps are comparable with those on the
are bonded to a terminal O in M3O4(OH)4 (3b). There are one triplet potential energy surfaces. For M = Zr and Hf, the
or two hydrogen atoms bonded to a bridge O in the isomers of reaction barriers for forming the metal hydrogen containing
3o and 3aa, respectively. For the reaction shown in Figure 3, species and the HH recombination reaction as well as the H2
the H2 release step is similar to that for the monomers and and O2 desorption energies can dier by up to 20 kcal/mol as
dimers. After the release of two H2 molecules, the intermediate compared to the reactions with Ti3O6 on the triplet surface. On
is M3O8 (3l), in which there is a ve-coordinate metal bonded the singlet surface, those energy dierences are less than 5 kcal/
with four bridge O atoms and one terminal one. From this mol.
species, one bridge oxygen atom rotates to bond with the Cluster Geometries and Frequencies. The MH bond
terminal oxygen and form a dioxygen complex M3O6O2 (3n) lengths for the metal hydrogen containing intermediates
in which the two oxygens in an OO bond and M3O6 (3a) are predicted at the B3LYP/DZVP2 level for M = Ti and at the
connected by two weak MO bonds. O2 is released by B3LYP/aD level for M = Zr and Hf are given in Table 1 for
breaking the two weak MO bonds. both singlets and triplets; the corresponding vibrational
As shown in Figure 4, the two H atoms which are bonded to frequencies are given as Supporting Information. The calculated
terminal O atoms are released rst after hydrogen transfer to a MH bond distances for both the triplet and singlet states are
metal and the reaction is followed by the production of the similar in HMnO2n+1(OH) (n = 13). In the metal hydrogen
second H2, which contains the H atom bonded to a bridge O containing HMnO2n1(OH)3 (n = 13) molecules, the MH
bond distances in the triplet can be longer by up to 0.7 than
atom. On 3M3O6, after the release of H2 from the complex
in the singlet depending on the structure. This happens for the
3
M3O8H2 (3x), the oxygen saturated species relaxes to form
rst metal hydrogen containing species, where the MH bond
3
M3O6O2 (3n), which is ready for oxygen release. On 1M3O6, is elongated in comparison with the singlet but not for the
a structural transformation step is still needed to form the second metal hydrogen molecules. The MH bond distances
oxygen complex, 1M3O6O2 (3n). The same process takes in the singlet state molecules are predicted to be 1.69 to 1.72
place in the O2 production reactions shown in Figure 5 for for Ti, 1.86 to 1.90 for Zr, and 1.85 to 1.88 for Hf.
water splitting from M3O4(OH)4 (3aa). The H2 production The calculated TiH bond distances are slightly longer than
process is similar to the previous reactions. the TiH bond distance of 1.68 in TiH4.57 For the
In terms of the energetics, on the triplet potential energy HMnO2n1(OH)3 (n = 13) species, the TiH bond in the
surface starting from the hydrolysis product 3Ti3O4(OH)4 (3b) triplet is much longer than in the singlet and is similar to the
shown in Figure 3, the barrier for the formation of dierence in the TiH bond distances in the triplet and singlet
3
HTi3O5(OH)3 (3d) is 48.8 kcal/mol, much lower than that states of the HTiO+ cation.58,59 For the ZrH and HfH
for the formation of 3HTi3O7(OH) (3i) which is 97.2 kcal/mol. bonds, the bond distances are slight shorter than in MH4, which
As shown in Figures 4 and 5, the reaction barrier for the second are 1.912 and 1.907 for M = Zr and M = Hf respectively.60,61
H transfer is also much larger than the rst one. The HH The structures with long MH bonds suggest that the
recombination barriers fall into the range of 20 to 35 kcal/ excitation is at least partially localized in this region in the
mol, and the H2 desorption energies are predicted to be <8 triplets.
kcal/mol. For the oxygen production step, 30.1 kcal/mol is The MH stretching frequencies in the singlets change up to
needed to form the oxygen complex from 3M3O8 (3l). The O2 50 cm1 in comparison with those of the corresponding MH4
Table 2. Lowest Calculated Reaction Barriers (kcal/mol) for the Formation of MH bonds at 298 K
triplet singlet
reaction level Ti Zr Hf Ti Zr Hf
M(OH)4 (1b) HMO(OH)3 (1d) CCSD(T) 37.0 14.4 11.5 114.5 125.3 126.2
B3LYP 38.0 15.5 15.5 114.8 123.1 126.0
MO2(OH)2 (1g) HMO3(OH) (1i) CCSD(T) 89.0 84.5 74.5 95.6 102.6 84.1
B3LYP 88.7 73.5 75.4 94.8 92.3 77.4
M2O2(OH)4 (2b) HM2O3(OH)3 (2d) CCSD(T) 37.2 3.8 1.8 125.4 134.2 136.4
B3LYP 41.3 13.0 10.6 124.2 133.2 135.3
M2O4(OH)2 (2g) HM2O5(OH) (2i) CCSD(T) 91.7 88.9 86.3 126.1 135.2 138.2
B3LYP 93.1 85.5 86.5 125.3 134.6 137.3
M3O4(OH)4 (3b) HM3O5(OH)3 (3d) B3LYP 48.7 59.4 25.4 113.2 111.4 111.4
M3O6(OH)2 (3g) HM3O7(OH) (3i) B3LYP 97.7 122.2 124.8 110.5 110.3 111.0
M3O4(OH)4 (3o) HM3O5(OH)3 (3q) B3LYP 55.4 51.4 52.8 125.3 129.7 131.8
M3O6(OH)2 (3t) HM3O7(OH) (3v) B3LYP 79.3 77.9 81.6 126.5 123.9 121.5
M3O4(OH)4 (3aa) HM3O5(OH)3 (3ac) B3LYP 39.8 21.0 20.6 118.6 120.8 122.1
M3O6(OH)2 (3af) HM3O7(OH) (3ah) B3LYP 78.5 86.2 90.3 125.9 126.6 124.8
Table 3. Lowest Calculated Reaction Barriers (kcal/mol) for H2 Recombination and H2 Desorption Energies at 298 K
triplet singlet
reaction process level Ti Zr Hf Ti Zr Hf
HMO(OH)3 (1d) MO2(OH)2 (1g) + H2 HH recombination CCSD(T) 31.8 45.0 49.7 18.6 28.3 33.4
B3LYP 41.5 52.7 56.5 21.7 28.5 32.4
H2 desorption CCSD(T) 2.0 4.9 3.4 5.0 5.1 7.1
B3LYP 7.8 3.4 0.1 3.0 4.4 6.5
HMO3(OH) (1i) MO2O2 (1l) + H2 HH recombination CCSD(T) 34.2 25.3 30.3 32.3 35.5 41.7
B3LYP 33.1 27.7 30.7 31.2 35.4 39.7
B3LYP 5.8 5.3 7.2 5.3 5.9 8.4
HMO(OH) (1m) MO2(1a) + H2a HH recombination CCSD(T) 34.2 24.7 30.3
B3LYP 33.6 27.7 30.7
H2 desorption CCSD(T) 5.3 5.4 8.4
B3LYP 6.0 5.3 7.2
HM2O3(OH)3 (2d) M2O4(OH)2 (2i) + H2 HH recombination CCSD(T) 22.4 21.4 23.6 18.5 19.1 22.7
B3LYP 15.7 19.4 21.3 19.7 19.8 21.4
B3LYP 0.7 1.1 3.9 2.0 4.5 4.8
HM2O5(OH) (2i) M2O6 (2l) + H2 HH recombination CCSD(T) 17.0 28.1 18.0 19.2 20.4 24.0
B3LYP 20.1 23.7 26.0 20.7 21.1 22.4
B3LYP 0.0 1.0 1.5 2.4 3.7 5.3
HM3O5(OH)3 (3d) M3O6(OH)2 (3g) + H2 HH recombination B3LYP 30.8 18.5 19.3 23.2 29.9 35.2
H2 desorption B3LYP 0.0 0.0 0.1 2.0 5.2 8.0
HM3O7(OH) (3i) M3O8 (3l) + H2 HH recombination B3LYP 25.2 28.7 33.2 24.9 31.6 18.3
HM3O5(OH)3 (3q) M3O6(OH)2 (3t) + H2 HH recombination B3LYP 15.2 19.6 21.8 26.1 33.0 37.3
HM3O7(OH) (3v) M3O8 (3y) + H2b HH recombination B3LYP 26.9 24.6 24.7 13.6 17.7 19.3
H2 desorption B3LYP 0.0 4.5 3.8
HM3O5(OH)3 (3ac) M3O6(OH)2 (3af) + H2 HH recombination B3LYP 14.3 16.3 12.3 21.6 28.6 30.8
HM3O7(OH) (3ah) M3O8 (3ak) + H2c HH recombination B3LYP 12.7 14.2 15.2 27.3 13.4 27.4
H2 desorption B3LYP 0.5 3.4 4.1
a
The reaction takes place after desorption of 3O2 rst on the triplet potential energy surface. bAfter H2 release from the complex of 3M3O8H2 (3x),
the metal oxides 3 M3O8 relaxes to oxygen complex 3M3O6O2 (3n) automatically. cAfter H2 release from the complex of 3M3O8H2 (3j), the metal
oxides 3 M3O8 relaxes to oxygen complex 3M3O6O2 (3n) automatically.
molecules.62 The MH stretching frequencies in the singlet spin changes from singlet to triplet. The decreased MH
state are close to that in the triplet state HMnO2n+1(OH) (n = stretching frequencies are associated with the elongated MH
13) with the dierences being less than 40 cm1. The bond distances. The TiH, ZrH, and HfH stretching
frequencies change in HMnO2n1(OH)3 (n = 13) when the frequencies in the singlet MH containing intermediates fall
into the range of 1600 to 1750 cm1, 1600 to 1700 cm1, Ti, Zr, and Hf, respectively. These large activation energies are
and 1600 to 1700 cm1 respectively. The MH stretching due to the stable tetrahedral structure coordination environ-
frequency can decrease up to 1000 cm1 in the triplet of ment in 3g, and more energy input is needed to change this
HMnO2n1(OH)3 (n = 13). saturated coordination environment by H migration to the
Triplet Atomic Spin Densities. The Mulliken atomic spin metal especially for M = Zr and Hf.
densities of the triplet states for the reactants and reaction For the HH recombination reactions for the triplets, the
intermediates are given in the Supporting Information. Figures activation energies are calculated to be 30 to 45 kcal/mol for
for which atom numbers are needed are in the Supporting the monomers and the barriers for the production of the
Information. For the metal hydrogen containing species, the second H2 are slightly larger than those for the rst H2. The
excess spin density of 3HMO(OH)3 (1c) is on the terminal O energies for the dimers are 20 to 30 kcal/mol depending on
atom and the H bonded to the metal. For 3HMO3(OH) (1i), M, smaller than those for the monomers. The barriers for the
the excess spin is localized in the OO bond. The H bonded trimers are in the range of 15 to 30 kcal/mol. Generally, the
to the metal has excess spin density in the triplet of HH recombination barriers on the monomers are larger than
3
HMnO2n1(OH)3 (n = 2, 3). For 3HM2O3(OH)3 (2d) and those for the dimers and trimers. The energy dierences
HM3O5(OH)3 (3d), the excitation also involves the terminal O between the barriers for the rst and second HH
atom. Terminal atoms O(6) and O(14) have excess spin recombinations are less than 15 kcal/mol. For the H2
density in 3HM3O5(OH)3 (3q) and 3HM3O5(OH)3 (3ac). The desorption step, the energies are generally smaller than 8
excess spin in 3HMnO2n+1(OH) (n = 2, 3) does not involve the kcal/mol and much smaller than the activation energies for H
H atom. In 3HM2O5(OH) (2i), one excess spin is on the O H recombination. The dierences in the H2 desorption energies
atom and the other spin is localized on the two O atoms in the from the dierent substrates, either 3MnO2n(OH)2 or 3MnO2n+2,
OO bond. For 3HM3O7(OH) (3i), the terminal O(9) are less than 5 kcal/mol and also do not show much
atom and the other two bridge O(11, 13) atoms have excess dependence on the metal.
spin density. One terminal O and the two atoms in the O For the alternative reaction path for the second H2 release,
O bond have the excess spin density in 3HM3O7(OH) (3v) and 1m 1l for the monomers, the barriers for the HH
3
HM3O7(OH) (3ah). The excess spin is on the two terminal recombination reactions are 25 to 35 kcal/mol which are
O atoms for both 3MO2(OH)2(1g) and 3M2O4 (OH)2 (2g). consistent with those in the reactions of 1d 1g and 1i 1l.
The excitation sites are dierent for the three 3M3O6(OH)2 The H2 desorption energies from 1MO2 are 5 to 8 kcal/mol,
structures. The excess spin in 3M3O6(OH)2 (3g) is on two consistent with the H2 desorption energies from both triplet
bridge O (3, 6) atoms and one terminal O(13) atom, and singlet MO2(OH)2 or MO4.
whereas the spin in 3M3O6(OH)2 (3t) and 3M3O6(OH)2 (3af) Singlet States. For the monomers, the formation of the
is on two O atoms. For 3M2O6(2l), the excess spin is on two second MH bond requires slightly less energy than that for
terminal O atom and in the OO bond, and in 3M3O8 (3l), the formation of the rst MH bond. The reaction barriers for
the spin is on two O atoms around the oxygen saturated these two steps are similar for the dimers and trimers. Except
metal center and the adjacent terminal O atom. The OO for the reaction barriers in the reactions of the second H
bond contains the excess spin in all oxygen complex species, transfer to the metal on the monomers, all of the other reaction
3
(MO2)nO2 (n = 13), and for n = 2 and 3, the excess spin is barriers are larger than the average water HO bond energy of
on the terminal O atom. In general, the MH bond 110 kcal/mol. This suggests that the H atom would dissociate
distance correlates with the H atomic spin density with longer from the hydroxyl group and then bond to an adjacent metal.
MH bond distances having larger spin densities consistent Generally the barriers on the zirconium and hafnium clusters
with localization of the excitation in this region. are slightly larger than those for the titanium clusters. The
reaction barriers for the rst H transfer on the singlet potential
DISCUSSION
Hydrogen Production. The calculated reaction barriers for
energy surface are much larger than those on the triplet
potential energy surface. The dierences in the reaction barriers
are predicted to be generally larger than 70 kcal/mol and range
the formation of metal hydrogen containing intermediates and up to 130 kcal/mol. For the second H transfer reactions, the
HH recombination as well as the H2 desorption energies on reaction barriers are smaller for the triplet than for the singlet
the (MO2)n (n = 13) clusters at 298 K are summarized in with dierences of 10 to 15 kcal/mol for the monomers and
Tables 2 and 3. As the H2O2H2 path requires more energy 20 to 50 kcal/mol for the dimers and trimers.
than the H2H2O2 path and the H2 and O2 production The HH recombination barriers on the singlet potential
mechanisms are similar, we focus on the lower energy H2H2 energy surface are 20 to 35 kcal/mol, slightly smaller than on
O2 path. the triplet potential energy surface for the monomers. The
Triplet States. On the triplet potential energy surfaces, the dierences of HH recombination barriers between the singlet
reaction barriers for the formation of 3HTinO2n1(OH)3 (n = and the triplet dimers are less than 5 kcal/mol. For the trimers,
13) are calculated to be 35 to 50 kcal/mol. Substantially the barriers are in the range of 15 to 35 kcal/mol. For the
more energy is needed to form the second TiH containing monomers, the reaction barriers for the second HH
intermediates 3HTinO2n+1(OH) (n = 13) with generally 75 recombination reaction are slightly larger than those the rst
to 95 kcal/mol except for the reaction 3g 3i. The formation recombination. Again, the energy dierences of the reaction
of 3HMnO2n1(OH)3 (n = 13) has a broader range of reaction barriers for the second and the rst HH recombination
barriers, 10 to 50 kcal/mol for M = Zr and Hf. The reaction reactions are less than 15 kcal/mol. The H2 desorption energies
barrier energies for the second H transfer to the metal for M = are consistent with those on the triplet surfaces and, again, are
Zr and Hf dier by up to 10 kcal/mol in comparison with those much smaller than the activation barriers.
for M = Ti depending on the reaction. The barriers for the Metal Hydrogen Bond Formation Mechanism. The
reaction 3g 3i are 97.7, 122.2, and 124.8 kcal/mol for M = calculated Mulliken charges on the metal as well as the bond
distances in the optimized molecular structures are shown in In terms of the formation of the second TiH intermediate
the Supporting Information. As an example, the partial charges HTiO3(OH), the metal hydrogen atoms in both singlet and
of the atoms in the intermediate molecules 1b, 1d, 1g, and 1i Ti triplet HTiO(OH)3 (1i) behave as hydrides. A hydroxyl radical
monomer are shown in Figure 6. In 1HTiO(OH)3 (1d), the H is not observed in 1HTiO(OH)3 (1i) and the two O atoms in
the two MO bonds behave as oxy-radicals. In 3HTiO(OH)3
(1i), one hydroxyl radical and one oxy-radical are formed.
Thus, the reactions 1g1i for both the singlet and triplet are
two electron transfer redox reactions. For the triplet reaction,
one proton in a hydroxyl group transfers to Ti coupled with
two electron transfer, whereas it is the proton in the hydroxyl
radical that transfers to Ti metal in the singlet reaction. This
helps to explain why there is only a modest dierence in the
activation barriers for both the triplet and singlet.
The mechanism for the formation of metal hydrogen
containing species for the potential energy surface on TiO2
can be extended to the reactions on the dimers and trimers as
well as the other two transition metals, Zr and Hf. Generally the
formation of metal hydrogen intermediates are PCET reactions
involving two electrons except for the rst triplet metal
hydrogen species, 3HMnO2n1(OH)3 (M = Ti, Zr, Hf, n = 1
3). The presence of only one electron transfer in the formation
of 3HMnO2n1(OH)3 results in much smaller activation barriers
in comparison to the others. Both hydroxyl radicals and oxy-
radicals are found on the PESs.
The calculated d orbital energies and orbital types for the
reactants, transition states, and products in the formation of
metal hydrogen intermediates for M = Ti are given in the
Supporting Information. For example, the transfer of H to form
1
HTiO(OH)3 from Ti(OH)4 leads to a destabilization in the
highest occupied orbital with signicant d contributions from
0.37 to 0.29 au. In contrast to the destabilization of the
dominant d orbital energy for the formation of 1HTiO(OH)3,
hydrogen transfer from 3Ti(OH)4 to form 3HTiO(OH)3 is
associated with a stabilization of the dominant d orbital energy
from 0.19 to 0.36 au for -spin orbitals. The same results
are found for the dimer and the trimer. The activation barrier
on the triplet potential energy surface for the formation of the
rst metal hydrogen intermediate is lower than that for the
singlet. The larger reaction barrier energy for the singlet
correlates with a destabilization of the d orbitals during the
formation of 1HTinO2n1(OH)3 (n = 13). In contrast, the d
Figure 6. Partial charge analysis for the reactant and product orbitals are stabilized in the triplet and the reaction barrier is
molecules for the formation of metal hydrogen intermediates for the lower. The dominant d orbital energy in the transition state is
reaction on TiO2. destabilized as compared to the reactant for both the singlet
and the triplet for the formation of the second metal hydrogen-
transfer intermediate HTinO2n+1(OH). Both of the reaction
in the TiH bond behaves as a hydride63 based on the TiH barriers are also much larger than the reaction barrier for the
bond distance and the charges. The bond distances of the M formation of the rst triplet metal hydrogen intermediate, again
O bond and one of the MOH bonds are longer than normal showing a correlation with the destabilization of the d orbitals
and can be regarded as a hydroxyl radical and an oxy-radical, in the transition state. The relationship between the d orbital
respectively. Thus the reaction of singlet 1b 1d can be energy and the reaction barrier energy is also applicable to the
considered to be a proton coupled, electron transfer (PCET) Zr and Hf clusters.
reaction, and two electrons are transferred to the hydrogen The HH recombination reactions have much more modest
atom in TiH. In 3HTiO(OH)3 (1d), the H bonded to Ti acts barriers than does the H transfer barrier to form the metal
as a hydrogen atom.64 The O atom in MO bond can be hydride. This is expected as a protic OH hydrogen is reacting
considered to be an oxy-radical. Thus the reaction of triplet with a hydridic MH hydrogen. Such a four-center HH
1b1d is also a PCET reaction. In contrast to the singlet recombination is known to have modest barriers when protic
reaction, only one electron is transferred from the reactant 1b and hydridic hydrogens can react as found in BH3NH3 with an
to the product 1d. This explains the large dierence in reaction energy barrier of 36 kcal/mol at the CCSD(T)/complete basis
barriers on the singlet and triplet potential energy surfaces for set level in contrast to H2 elimination from C2H6 with a barrier
the formation of the rst TiH containing intermediate. The of 116 kcal/mol.65
absorption of a photon to create the triplet eectively provides H2 Production Mechanism. The detailed mechanism of H2
the energy needed for an electron transfer process. production from water splitting catalyzed by MO2 clusters is via
Table 4. Calculated Lowest Maximum Structural Transformation Reaction Barriers and Desorption Energies for O2 Production
at 298 K in kcal/mol
triplet singlet
reaction reaction type level Ti Zr Hf Ti Zr Hf
M2O6 (2l) M2O4O2 (2n) transformation CCSD(T) 7.4 3.5 8.9
B3LYP 8.8 23.2 17.2 48.0 57.5 46.2
M3O8 (3l) M3O6O2 (3n) transformation B3LYP 30.8 22.5 15.3 38.4 31.2 25.2
M3O8 (3y) M3O6O2 (3n) transformation B3LYP 27.8 21.6 17.2
M3O8 (3ak) M3O6O2 (3n) transformation B3LYP 17.4 11.5 40.7
MO2O2 (1l) MO2 (1a) + O2 O2 desorption CCSD(T) 34.5 24.3 33.2 36.3 49.8 49.6
B3LYP 21.2 35.8 44.0 29.6 40.4 33.2
M2O4O2 (2n) M2O4 (2o) + O2 O2 desorption CCSD(T) 10.2 22.8 32.5
B3LYP 15.2 23.0 31.7 29.5 48.3 43.5
M3O6O2 (3n) M3O6 (3a) + O2 O2 desorption B3LYP 13.7 34.2 44.3 37.4 44.6 44.5
the formation of an intermediate with a metal hydrogen bond predicted an activation barrier of 29 kcal/mol for the formation
followed by a HH recombination reaction and H2 desorption of the ZrH bond, slightly larger than our prediction on a ZrO2
from the adsorption substrate. The barriers for H transfer to the cluster of 24.7 kcal/mol.71 Generally, the previous work on the
metal for the triplets are smaller than that for the singlets. On reaction barriers for H2 desorption on an MO2 surface (M = Ti,
the triplet potential energy surface, the barriers for the second Zr) are consistent with our calculated values on the metal oxide
H transfer to the metal are larger than those for the rst clusters. In addition, we predict that H2 chemisorption can take
transfer, whereas there is not much dierence in the reaction place on other substrates such as MnO2n(OH)2 or MnO2n+2 (M
barrier between the rst and the second H transfer to the metal = Ti, Zr, Hf, n = 13) via the formation of MH bonds.
for the singlets. The barriers for the HH recombination Oxygen Production. The calculated reaction barriers and
reactions on both singlet and triplet potential energy surfaces desorption energies for the O2 production step at 298 K are
range from 15 to 50 kcal/mol depending on the size of the given in Table 4.
clusters and the metal. The H2 desorption energies are mostly Triplet States. For the monomers, after the release of two H2
below 8 kcal/mol, far smaller than the barriers of the previous molecules, the 3O2 molecule is produced by breaking two weak
steps. On the singlet surface, the rate determining step is the MO bonds in the complex of 3MO2O2 (1l). The desorption
formation of the MH bond due to the large reaction barriers. energies for the dierent metals follow the order Ti < Zr < Hf.
The substantial barriers to transfer a protic hydrogen from For the dimers, generally less than 10 kcal/mol is needed to
oxygen to generate a metal hydride via a PCET reaction, form the oxygen saturated intermediates via structural trans-
especially on the singlet surface, are consistent with the general formations. The O2 desorption energies on dierent metal
need to use a separate catalyst for the production of H2 or a clusters follow the same order as the monomers. For the
sacricial reactant. trimers, 3M3O4(OH)4 (3b) is the only hydrolysis product from
The formation of intermediates containing metal hydrogen which the O2 release step requires a structural transformation
bonds is also observed in catalytic H2 production reactions with to form the oxygen complex. The barriers for 3M3O8 (3l)
other transition metals under both experimental and theoretical structual transformations are 30.8, 22.5, and 15.3 kcal/mol for
study.66,67 A Mo-oxo complex has been used as a catalyst for H2 M = Ti, Zr, Hf. Again, the desorption energies for the three
evolution from the electrocatalysis of H2O, and it is predicted metals follow the same order as the monomer and dimers,
that the H2 is produced via the formation of a MoH suggesting that the weak MO bond in the triplet oxygen
intermediate by DFT with the B3LYP, BP86, and B97 complex is TiO < Zr O < HfO, consistent with the order
functionals.66 A Co complex catalyzes hydrogen evolution in previously predicted for these types of bonds.48 For the same
acidic solution, and the CoH bond was characterized with metal, the weak MO bond energy in the species of 3M3O6O2
NMR spectroscopy as one of the reactive intermediates.67 An (3n) is slightly larger than that in 3 M2O4O2 (2n) and
experimental study of H2 adsorption on the TiO2 (110) 3
MO2O2 (1l).
crystalline surface also suggested the formation of a TiH bond Singlet States. On the singlet PESs, the release of 3O2 from
after molecular adsorption of H2 based on scanning tunneling 1
MnO2nO2 will produce 3MnO2n, if there is no surface crossing
microscopy (STM) combined with electron stimulated as discussed above for the monomer. The presence of a
desorption (ESD). 68 Thermal desorption spectroscopy singlettriplet surface crossing leads to an exothermic channel
(TDS), together with electron paramagnetic resonance (EPR) to form the 1MnO2n. The barrier for structural transformations
spectroscopy, has been used to study the H2 adsorption for the dimers and trimer are larger than that for the triplet.
mechanism on the TiO2 (110) surface in a UHV chamber.69 The energy barriers are predicted to be 45 to 60 kcal/mol for
Chemisorption of hydrogen forms TiH bonds at 300 K. The the dimers, depending on the metal. The barriers are calculated
activation energy for H2 desorption from TiO2 is 25 kcal/mol, to be 10 to 40 kcal/mol, depending on the metal and reaction
slightly lower than our predicted reaction barrier on a TiO2 for the trimers. The desorption energies for the singlets do not
cluster of 34 kcal/mol. The chemisorption of H2 on the TiO2 follow the order found on the triplet PESs for the dierent
surface in these studies takes place on the defect sites. On the t- metals and are larger than those for the triplets. The energies
ZrO2 (101) surface, DFT studies with the PW91 functional needed to desorb O2 from 3(MO2)n (M = Zr, Hf, n = 13)
predicted chemisorption of H2 after physisorption to proceed clusters are similar and are between 40 to 50 kcal/mol
via formation of an ionic ZrH bond.70 Early ab initio SCF depending on the size of the clusters. The 3O2 release energy
calculations of H2 desorption on the c-ZrO2 (110) surface from 1TinO2nO2 (n = 13) is found to be 10 to 15 kcal/mol
smaller than that for the other two metals. Consistent with the the clusters can be excited to this state and if the lifetime of the
triplets, the oxygen desorption energy for the same metal does state is long enough. The energy input for the production of the
not change much with increasing the size of the clusters, rst H2 molecule is generally less than the adiabatic excitation
generally with a dierence of less than 5 kcal/mol. energy for the cluster to an excited triplet. As noted above, the
O2 Production Mechanism. After the release of two H2 rst excited singlet state should be close in energy to the triplet.
molecules for both the triplets and singlets, 3O2 is produced by More energy is consumed for the second H2 production
breaking two weak MO bonds in the oxygen-rich complex of coupled with the formation of an oxygen complex, an atomic
MnO2nO2. This process can occur directly on the triplet, but oxygen saturated metal oxide. As to the photocatalytic activities
formation of the singlet metal oxide cluster will require a of dierent sized clusters, the monomers show slightly higher
singlettriplet crossing to occur. For the dimers and trimers, catalytic abilities based on the smaller potential energies in
structural transformations are needed to form MnO2nO2 from comparison with the dimers and trimers. For reactions on the
the intermediate MnO2n+2. The barriers for the structural trimers, the dehydrogenation and deoxygenation reactions
transformations are predicted to be 10 to 30 kcal/mol for the starting with the hydrolysis products containing the H atom
triplets and 10 to 60 kcal/mol for the singlets. The 3O2 bonded to a bridge oxygen atom have smaller energy
desorption energies are predicted to be 10 to 15 kcal/mol for requirements than those with all of the H atoms bonded to a
M = Ti, 20 to 35 kcal/mol for M = Zr, and 30 to 45 kcal/ terminal oxygen. This is because the charge on the H atom
mol for M = Hf for the triplets. The desorption energies of 3O2 bonded with a bridge oxygen atom is less positive than the one
from the clusters follow the order Ti < Zr < Hf. On the singlet bonded with a terminal oxygen atom. Less energy is needed to
PESs, the desorption energies from the Zr and Hf clusters are break such OH bonds in M3O4(OH)4 (3o) and M3O4(OH)4
comparable, and both are larger than those for the Ti clusters. (3aa) because there is less electron transfer. For the water
Those energies fall in the range of 30 to 50 kcal/mol splitting reaction catalyzed by the M3O6 cluster, the hydrolysis
depending on the metal and the size of the cluster. The size of step prefers to proceed by H transfer to a bridge oxygen atom
the cluster does not have a dramatic eect on the O2 desorption instead of a terminal oxygen atom.35,36
energy for the same metal. Thus, 3O2 production is through the Our results can be compared to the theoretical study on the
formation of a MnO2nO2 intermediate as shown in the gures, electrochemical mechanism of water splitting on a Ti2O4 (C2h)
which is consistent with the previous water splitting mechanism cluster at the B3LYP/TZV(d,p) and CCSD levels.34 The
studies on the bulk TiO2 crystal surface.22,31 previous predictions in terms of physisorption energies,
Water Splitting Excess Potential Energy. For the pure reaction barriers, and chemisorption energies for the hydrolysis
water splitting reaction, we dene the excess potential energy step are consistent with our previous work on small TiO2
corresponds to any energy required that is more than the clusters.35 These authors34 studied the reaction mechanism for
endothermicity of the reaction 2H2O 2H2 + O2. For the MO2 the catalytic reaction 2H2O 4H+ + 4e + O2 by the removal
monomer, there is no excess potential energy on the triplet PES of an electron and a proton step by step from the hydrolysis
for M = Ti, Zr, Hf in terms of the energetics if the triplet states product, titanium hydroxide. They predict that OO bond
are long-lived. A modest excess potential energy of 15 kcal/ formation takes place after the removal of two electrons
mol is needed on the TiO2 singlet potential energy surface if consistent with our prediction of the formation of Ti2O4(OH)2
1
TiO2O2 can relax to the ground singlet state 1TiO2 after the (2g) in which an OO bond is formed after the release of rst
release of 3O2. There is also no excess potential energy required H2. These authors34 predicted that O2 production occurs via an
for the singlet ZrO2 and HfO2 monomers if the relaxation takes atomic oxygen saturated singlet titanium oxide Ti2O6, whereas
place in the nal step to produce 1MO2. For Ti2O4 and Zr2O4, we predict O2 release takes place from a triplet Ti2O6 (2l) with
15 and 25 kcal/mol of excess potential energy is needed if lower energy than the singlet. In their study,34 1Ti2O6 has a
the dimers can be excited to the lowest energy triplet excited lower energy than the triplet and the dierence is due to
state. No excess potential energy is required on the triplet dierent structures for 3Ti2O6. The O2 desorption energy is
Hf2O4 PES. If the reaction takes place on the singlet M2O4 (M predicted to be 78.4 kcal/mol without the additional step of
= Ti, Zr, Hf) PES, excess potential energies of 30 to 50 kcal/ structural transformation from 1Ti2O6, much higher than our
mol are required. For the trimers, the reactions on the triplet result of 29.5 kcal/mol for the 3O2 desorption energy with a
PESs shown in Figures 4 and 5 require an excess potential 48.0 kcal/mol activation barrier for the structural trans-
energy of 10 kcal/mol for M = Ti and there is no excess formation. Also in our work, the barrier and 3O2 desorption
potential energy required for M = Zr, Hf. For the triplet PES in energy from 3Ti2O6 are 10.2 and 7.4 kcal/mol, much lower than
Figure 3, the excess potential energies are predicted to be 50 those from the singlet. For the OO bond distances in 1Ti2O6,
kcal/mol for Ti, 25 kcal/mol for Zr, and 5 kcal/mol for Hf. our prediction of 1.47 is close to their result of 1.44 . The
The reactions for the singlets are predicted to require larger OO bond length in the singlet is much longer than that in
3
excess potential energies than for the triplets, 40 to 55 kcal/ Ti2O6 (2l), 1.33 , which is closer to the 3O2 bond length of
mol, depending on the hydrolysis product and the metal. The 1.21 .
predicted gas phase excess potential energies for the 3Ti2O4 and
3
Ti3O6 PESs are consistent with previous predictions of an
overpotential of 0.78 eV in the gas phase on the rutile TiO2
CONCLUSIONS
Coupled cluster [CCSD(T)] theory and density functional
(110) surface26,28 and an overpotential of 0.7 eV in the aqueous theory (DFT) were used to study the production of H2 and O2
phase on anatase TiO2 (101), (001), and (102) surfaces.31 from hydrolysis products starting from (MO2)n (M = Ti, Zr,
Due to the much larger excess potential energies on the Hf, n = 13) clusters. Instead of direct HH recombination
singlet potential energy surface than on the triplet potential from two H atoms on a hydroxyl group, the H2 molecule is
energy surface and the exothermicity of the hydrolysis reactions produced via an intermediate step of H transfer to the metal
of the clusters, the water splitting reaction to generate H2 and followed by HH recombination and H2 desorption from
O2 prefers to take place predominantly on the triplet surface if MnO2n(OH)2 and MnO2n+2. The H transfer steps have the
The Journal of Physical Chemistry A

Article
largest barriers. The formation of metal hydrogen intermediates ASSOCIATED CONTENT

takes place via a PCET reaction. The rate-determining step lies *
S Supporting Information
in the formation of the second metal hydrogen containing Complete author lists for refs 29, 52, and 53. Figures: Potential
intermediate for the further step of breaking the MOH bond. energy surfaces for the second H2O hydrolysis on M3O6 (3a)
After the release of two H2 molecules, the oxygen is produced (M = Zr, Hf) clusters; Potential energy surface for H2O2H2
by breaking two weak MO bonds in an oxygen complex step on Ti2O4; Potential energy surfaces for M(OH)4 MO2
which is an atomic oxygen saturated metal oxide MnO2nO2. + 2H2 + O2 and M2O2(OH)4 M2O4 + 2H2 + O2 at 0 K (M =
The large barriers for the PCET reactions are consistent with Zr, Hf); Calculated bond distances and Mulliken charges on the
experimental observations of the need for a separate catalyst for metal in the optimized molecular structures for the reaction on
the production of H2. the monomers and the dimers; Atomic spin density for the
The activation energies for the rst and second H transfer to triplet states of the metal hydrogen containing intermediates
the metal are calculated to be 10 to 50 kcal/mol and 75 to and oxygen complexes; Optimized molecular structures of the
90 kcal/mol on the triplet potential energy surface. For the Zr and Hf molecules in Figures 35. Tables: Calculated metal
singlets, the barriers for the rst and the second H transfer to hydrogen stretching frequencies; Calculated atomic spin
metal are similar and 110 to 140 kcal/mol. For the HH density of all the triplet state intermediates and metal atomic
recombination, the activation energies are 15 to 50 kcal/mol charges for the singlet and triplet intermediates; T1 Diagnostics
depending on the metal and the size of the cluster. The lower calculated at the CCSD(T)/aD level; Calculated molecular d
HH recombination barriers are due to the presence of a orbital energies (au) on the metal for the formation of metal
hydridic and a protic proton. The H2 desorption energies are hydrogen intermediates; B3LYP and Zero-Point energies for all
predicted to be generally less than 10 kcal/mol on both reactants, transition states, and products; CCSD(T) energies at
surfaces. The results suggest that small zirconium and hafnium the CCSD(T)/aD level for the molecules on the potential
oxide clusters may prove to be very useful for water splitting energy surfaces of the monomers and the dimers; and Cartesian
using solar radiation in addition to small TiO2 clusters. coordinates in angstroms for all reactants, transition states, and
Photocatalytic water splitting reactions using small group products. This material is available free of charge via the
IVB transitional metal oxide clusters as catalysts should proceed Internet at http://pubs.acs.org.
by rst exciting the ground state clusters to an excited state
(modeled here as the triplet) and then continue to take place
on the excited state surface. There is no excess potential energy
AUTHOR INFORMATION
Corresponding Author
for the monomers on the triplet PES. For M2O4, excess *E-mail: dadixon@bama.ua.edu.
potential energies of 15 kcal/mol for Ti, 25 kcal/mol for Zr, Notes
and 0 kcal/mol for Hf are predicted. For the trimers, there are The authors declare no competing nancial interest.

reaction sequences with an excess potential energy of 10 kcal/
mol for M = Ti and no excess potential energy for M = Zr, Hf. ACKNOWLEDGMENTS
The singlets have much higher excess potential energy
requirements for these gas phase processes. Overall, the results This work was supported by the Chemical Sciences, Geo-
show that the excitation of small (MO2)n clusters can lead to sciences and Biosciences Division, Oce of Basic Energy
the production of 2H2 and O2 from 2H2O with a very low Sciences, U.S. Department of Energy (DOE) under Grant No.
excess potential energy above the endothermicity of the DE-FG02-03ER15481 (Catalysis Center Program). D.A.D. also
reaction (two 500 nm photons) on the triplet surface. This thanks the Robert Ramsay Chair Fund of The University of
of course means that all of the visible photon energy needs to Alabama for support. Part of this work was performed on the
be used in the reaction and is not dissipated as heat to other computers in the Molecular Sciences Computing Facility at the
W. R. Wiley Environmental Molecular Sciences Laboratory, a
sites. If the lifetime of the excited state is long enough, then the
national scientic user facility sponsored by the DOEs Oce
photon energy can be used to overcome the reaction barrier.
of Biological and Environmental Research and located at Pacic
For the release of the rst H2, this is possible as the barriers are
Northwest National Laboratory, operated for the DOE by
all lower than the energy provided by the absorption of the
Battelle.

photon. For the elimination of the second H2, the barriers are
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Article

Computational Study of H2 and O2 Production from Water Splitting

ABSTRACT: Coupled cluster [CCSD(T)] theory and density

Table 1. Calculated Metal Hydrogen Bond Distance in at the B3LYP Levela

largest barriers. The formation of metal hydrogen intermediates ASSOCIATED CONTENT

3553 dx.doi.org/10.1021/jp401443x | J. Phys. Chem. A 2013, 117, 35393555

3554 dx.doi.org/10.1021/jp401443x | J. Phys. Chem. A 2013, 117, 35393555

3555 dx.doi.org/10.1021/jp401443x | J. Phys. Chem. A 2013, 117, 35393555

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