Anticorrelation between Surface and Subsurface Point Defects and the Impact on the Redox Chemistry of TiO2(110)

By using a combination of scanning tunneling microscopy (STM), density functional theory (DFT), and secondary‐ion mass spectroscopy (SIMS), we explored the interplay and relative impact of surface versus subsurface defects on the surface chemistry of rutile TiO₂. STM results show that surface O vacancies (V_O) are virtually absent in the vicinity of positively charged subsurface point defects. This observation is consistent with DFT calculations of the impact of subsurface defect proximity on V_O formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O₂ was employed and was observed to be suppressed around them. DFT results attribute this to a perceived absence of intrinsic (Ti), and likely extrinsic interstitials in the nearest subsurface layer beneath inhibited areas. We also postulate that the entire nearest subsurface region could be devoid of any charged point defects, whereas prevalent surface defects (V_O) are largely responsible for mediation of the redox chemistry at the reduced TiO₂(110).     

Ba adsorption on the stoichiometric and defective TiO(2) (110) surface from first-principles calculations

A theoretical study on Ba adsorption on the rutile TiO(2) (110) surface has been carried out by means of plane-wave, plane augmented waves potential, density functional theory calculations. A model consisting on a (4 x 1) unit cell, which corresponds to coverage of 0.125 monolayer (ML), has been used and several potential adsorption sites on the stoichiometric surface have been tried. It has been found that the most stable site is with the Ba atom in a position where it is bound to two bridging oxygen atoms and an in-plane oxygen atom forming equivalent bonds (OB site). The adsorption energy is 0.71 eV referred to the formation of Ba bulk and is about 0.3 eV more stable than other adsorption sites. The Ba-surface interaction produces some surface relaxation in all cases. The OB site is stable at moderate temperatures; however, after extensive molecular dynamic calculations it is found that atoms diffuse on the surface by means of a jumping mechanism among several stable positions. The presence of bridging oxygen vacancies does not alter significantly this picture since the adsorption close to defects is not energetically favorable and the atoms tend to move away from vacancies. A strong covalent character has been found in the nature of the bonding, which contrasts with previous suggestions of the existence of Ba(2+) species on the surface. When the coverage is increased to 0.25 ML by adding a Ba atom to the supercell, there is a significant repulsion between Ba atoms that move away from each other to occupy OB sites. Thus, the adsorption energy values per atom diminish. For the stoichiometric surface two equivalent adsorption patterns are found, whereas only one is found for the defective surface.     

Defects in Surface Chemistry—Reductive coupling of Benzaldehyde on Rutile TiO2(110)

The surface chemistry of oxygen and oxygenates on Rutile TiO₂(110) is of great interest for various applications such as heterogeneous catalysis and photo catalysis. Though it is generally accepted that surface defects are active sites, the role of subsurface defects is under debate. We have therefore investigated the influence of the bulk defect density on the reductive coupling of benzaldehyde to stilbene as a model system. Using IRRAS we identify stilbene diolate as a reduction intermediate. The concentration of this intermediate is proportional to the bulk defect density, whereas adsorption of benzaldehyde at lower temperatures is not affected, which indicates a dominant role of Ti interstitials at temperatures above 400 K.     

Chemistry of NO2 on oxide surfaces: formation of NO3 on TiO2(110) and NO2<-->O vacancy interactions

Synchrotron-based high-resolution photoemission, X-ray absorption near-edge spectroscopy, and first-principles density functional (DF) slab calculations were used to study the interaction of NO(2) with a TiO(2)(110) single crystal and powders of titania. The main product of the adsorption of NO(2) on TiO(2)(110) is surface nitrate with a small amount of chemisorbed NO(2). A similar result is obtained after the reaction of NO(2) with polycrystalline powders of TiO(2) or other oxide powders. This trend, however, does not imply that the metal centers of the oxides are unreactive toward NO(2). An unexpected mechanism is seen for the formation of NO(3). Photoemission data and DF calculations indicate that the surface nitrate forms through the disproportionation of NO(2) on Ti sites (2NO(2,ads) --> NO(3,ads) + NO(gas)) rather than direct adsorption of NO(2) on O centers of titania. Complex interactions take place between NO(2) and O vacancies of TiO(2)(110). Electronic states associated with O vacancies play a predominant role in the bonding and surface chemistry of NO(2). The adsorbed NO(2), on its part, affects the thermochemical stability of O vacancies, facilitating their migration from the bulk to the surface of titania. The behavior of the NO(2)/titania system illustrates the importance of surface and subsurface defects when using an oxide for trapping or destroying NO(x)() species in the prevention of environmental pollution (DeNOx operations).     

CO2 adsorption on TiO2(101) anatase: a dispersion-corrected density functional theory study

Adsorption, diffusion, and dissociation of CO(2) on the anatase (101) surface were investigated using dispersion-corrected density functional theory. On the oxidized surface several different local minima were identified of which the most stable corresponds to a CO(2) molecule adsorbed at a five-fold coordinated Ti site in a tilted configuration. Surface diffusion is characterized by relatively small activation barriers. Preferential diffusion takes place along Ti rows and involves a cartwheel type of motion. The presence of a bridging oxygen defect or a surface interstitial Ti atom allows creation of several new strong binding configurations the most stable of which have bent CO(2) structures with simultaneous bonding to two surface Ti atoms. Subsurface oxygen vacancy or interstitial Ti defects are found to enhance the bonding of CO(2) molecules to the surface. CO(2) dissociation from these defect sites is calculated to be exothermic with barriers less than 21 kcal/mol. The use of such defects for catalytic activation of CO(2) on anatase (101) surface would require a mechanism for their regeneration.     

Adsorption and vibrational spectroscopy of ammonia at mordenite: ab initio study

The adsorption of ammonia at various active centers at the outer and inner surfaces of mordenite, involving Br?nsted acid (BA) sites, terminal silanol groups, and Lewis sites has been investigated using periodic ab initio density-functional theory. It is shown that ammonia forms an ammonium ion when adsorbed at strong BA sites. The calculated adsorption energies for different BA sites vary in the interval from 111.5 to 174.7 kJ/mol depending on the local environment of the adduct. The lowest adsorption energy is found for a monodentate complex in the main channel, the highest for a tetradentate configuration in the side pocket. At weak BA sites such as terminal silanol groups or a defect with a BA site in a two-membered ring ammonia is H bonded via the N atom. Additional weak H bonds are formed between H atoms of ammonia and O atoms of neighboring terminal silanol groups. The calculated adsorption energies for such adducts range between 61.7 and 70.9 kJ/mol. The interaction of ammonia with different Lewis sites is shown to range between weak (DeltaE(ads)=17.8 kJ/mol) and very strong (DeltaE(ads)=161.7 kJ/mol), the strongest Lewis site being a tricoordinated Al atom at the outer surface. Our results are in very good agreement with the distribution of desorption energies estimated from temperature-programmed desorption (TPD) and microcalorimetry experiments, the multipeaked structure of the TPD spectra is shown to arise from strong and weak Br?nsted and Lewis sites. The vibrational properties of the adsorption complexes are investigated using a force-constant approach. The stretching and bending modes of NH(4) (+) adsorbed to the zeolite are strongly influenced by the local environment. The strongest redshift is calculated for the asymmetric stretching mode involving the NH group hydrogen bonded to the bridging O atom of the BA site, the shift is largest for a monodentate and smallest for a tetradentate adsorption complex. The reduced symmetry of the adsorbate also leads to a substantial splitting of the stretching and bending modes. In agreement with experiment we show that the main vibrational feature which differentiates coordinatively bonded ammonia from a hydrogen-bonded ammonium ion is the absence of bending modes above 1630 cm(-1) and in the region between 1260 and 1600 cm(-1), and a low-frequency bending band in the range from 1130 to 1260 cm(-1). The calculated distribution of vibrational frequencies agrees very well with the measured infrared adsorption spectra. From the comparison of the adsorption data and the vibrational spectra we conclude that due to the complex adsorption geometry the redshift of the asymmetric stretching is a better measure of the acidity of an active sites than the adsorption energy.     

The importance of bulk Ti3+ defects in the oxygen chemistry on titania surfaces

The role of bulk defects in the oxygen chemistry on reduced rutile TiO(2)(110)-(1 × 1) has been studied by means of temperature-programmed desorption spectroscopy and scanning tunneling microscopy measurements. Following O(2) adsorption at 130 K, the amount of O(2) desorbing at ～410 K initially increased with increasing density of surface oxygen vacancies but decreased after further reduction of the TiO(2)(110) crystal. We explain these results by withdrawal of excess charge (Ti(3+)) from the TiO(2)(110) lattice to oxygen species on the surface and by a reaction of Ti interstitials with O adatoms upon heating. Important consequences for the understanding of the O(2)-TiO(2) interaction are discussed.     

First-principles study of the adsorption of formaldehyde on the clean and atomic oxygen covered Cu(1 1 1) surface

The interaction of formaldehyde with the clean and atomic oxygen-covered Cu(1 1 1) surfaces has been studied by means of cluster model density functional calculations in which Cu₂₂(14,8) is used to represent the perfect Cu(1 1 1) surface. The calculations point towards a η¹-H₂CO---O orientation with the oxygen atom almost on top of a copper surface atom. The formaldehyde adsorption energy is of 22–25 kJ/mol and the internal geometry of adsorbed formaldehyde is almost identical to that of the molecule in the gas-phase. The C---O bond is almost parallel to the surface and the conformation with the molecular plane normal to the surface is slightly preferred to the conformation with the molecular plane nearly parallel to the surface. A Cu₂₂---O model where atomic oxygen is adsorbed on a fcc hollow site was used to study the co-adsorption and reaction of formaldehyde with atomic oxygen. Oxygen co-adsorption has a dramatic effect on the formaldehyde adsorption energy which is increased by 50%. The calculated energy barrier for the formation of the dioxymethylene intermediate species through the H₂CO+O→H₂CO₂ reaction is of 36 kJ/mol.     

The electronic structure of intrinsic defects at TiO2 (110) surfaces: An ab initio molecular orbital study

We report on an isolated cluster approach to determine local electronic structures of TiO₂ surfaces before and after formation of intrinsic defects, i.e., oxygen vacancies, at different crystallographic sites. In particular, isolated oxygen vacancies at bridging sites, isolated oxygen vacancies at in-plane sites and aggregated oxygen vacancies at bridging sites have been treated which lead to changes in the coordination of the adjacent Ti atoms. We find that electronic band gap states are only formed in the presence of fourfold coordinated Ti surface atoms. © 1996 John Wiley & Sons, Inc.     

Electrical properties and defect chemistry of TiO2 single crystal. I. Electrical conductivity

The present work reports the electrical properties of high-purity single-crystal TiO(2) from measurements of the electrical conductivity in the temperature range 1073-1323 K and in gas phases of controlled oxygen activities in the range 10(-13) to 10(5) Pa. The effect of the oxygen activity on the electrical conductivity indicates that oxygen vacancies are the predominant defects in the studied ranges of temperature and oxygen activities. The electronic and ionic lattice charge compensations were revealed at low and high oxygen activities, respectively. The determined semiconducting quantities include: the activation energy of the electrical conductivity (E(sigma) = 125-205 kJ.mol(-1)), the activation energies of the electrical conductivity components associated with electrons (E(n) = 218 kJ.mol(-1)), electron holes (E(p) = 34 kJ.mol(-1)), and ions (E(i) = 227 kJ.mol(-1)), and the enthalpy of motion for electronic defects (DeltaH(m) = 4 kJ/mol). The electrical conductivity data are considered in terms of the components related to electrons, holes, and ions. The obtained data allow the determination of the n-p demarcation line in terms of temperature and oxygen activities. The band gap determined from the electronic component of the electrical conductivity is 3.1 eV.     

MIES and UPS(HeI) studies on reduced TiO2(110)

We have studied reduced TiO₂(110) surfaces by combining metastable impact electron spectroscopy (MIES) and UPS(HeI). The reduced Ti species were preparation‐induced: their number density was modified either by adsorption of K atoms or by a combined annealing/oxygen exposure procedure. The emission from the bandgap state (binding energy 0.9 eV), caused by reduced Ti³⁺ 3d species, was monitored. Bandgap emission is seen clearly with UPS(HeI) and thus can be used to monitor the number density of the near‐surface reduced species. A corresponding spectral structure cannot be seen with MIES. We propose that the excess charge density introduced either by preparation‐induced oxygen vacancies or by K adsorption is delocalized over several surface and subsurface Ti sites; this, together with the partial shielding of the reduced Ti species, prevents detection of the reduced Ti species with MIES. The re‐oxidation and restructuring of the reduced TiO₂(110) surface, caused by simultaneous oxygen exposure and annealing, was studied at temperatures between 400 and 770 K, again by recording the Ti³⁺ 3d emission (0.9 eV bandgap state) with UPS(HeI). The surface can be completely re‐oxidized by oxygen exposure at any selected annealing temperature in the range given above. Morphology changes, leading to a partially reduced surface, take place when the re‐oxidized surface is further annealed at T > 600 K under reducing conditions. The results give support to the assumption that the re‐oxidation is caused by the growth of additional titania whereby the Ti stems from the bulk and the oxygen originates from the gas. The restructuring of the re‐oxidized surface upon annealing under reducing conditions appears to be due to diffusion of Ti interstitials to the surface. Copyright © 2004 John Wiley & Sons, Ltd.     

Adsorption, diffusion, and dissociation of molecular oxygen at defected TiO2(110): a density functional theory study

The properties of reduced rutile TiO2(110) surfaces, as well as the adsorption, diffusion, and dissociation of molecular oxygen are investigated by means of density functional theory. The O2 molecule is found to bind strongly to bridging oxygen vacancies, attaining a molecular state with an expanded O-O bond of 1.44 A. The molecular oxygen also binds (with somewhat shortened bond lengths) to the fivefold coordinated Ti atoms in the troughs between the bridging oxygen rows, but only when vacancies are present somewhere in the surface. In all cases, the magnetic moment of O2 is lost upon adsorption. The expanded bond lengths reveal together with inspection of electron density and electronic density of state plots that charging of the adsorbed molecular oxygen is of key importance in forming the adsorption bond. The processes of O2 diffusion from a vacancy to a trough and O2 dissociation at a vacancy are both hindered by relative large barriers. However, we find that the presence of neighboring vacancies can strongly affect the ability of O2 to dissociate. The implications of this in connection with diffusion of the bridging oxygen vacancies are discussed.     

The mechanism of the water-gas shift reaction on Cu/TiO2(110) elucidated from application of density-functional theory

The Cu/TiO(2)(110) surface displays a great catalytic activity toward the water-gas shift reaction (WGSR), for which Cu is considered to be the most active metal on a TiO(2)(110)-supported surface. Experiments revealed that Cu nanoparticles bind preferentially to the terrace and steps of the TiO(2)(110) surface, which would not only affect the growth mode of the surface cluster but also enhance the catalytic activity, unlike Au nanoparticles for which occupancy of surface vacancies is favored, resulting in poorer catalytic performance than Cu. With density-functional theory we calculated some possible potential-energy surfaces for the carboxyl and redox mechanisms of the WGSR at the interface between the Cu cluster and the TiO(2) support. Our results show that the redox mechanism would be the dominant path; the resident Cu clusters greatly diminish the barrier for CO oxidation (22.49 and 108.68 kJ mol(-1), with and without Cu clusters, respectively). When adsorbed CO is catalytically oxidized by the bridging oxygen of the Cu/TiO(2)(110) surface to form CO(2), the release of CO(2) from the surface would result in the formation of an oxygen vacancy on the surface to facilitate the ensuing water splitting (barrier 34.90 vs. 50.49 kJ mol(-1), with and without the aid of a surface vacancy).     

First principles analysis of H2O adsorption on the (110) surfaces of SnO2, TiO2 and their solid solutions

Both associative and dissociative H(2)O adsorption on SnO(2)(110), TiO(2)(110), and Ti-enriched Sn(1-x)Ti(x)O(2)(110) surfaces have been investigated at low ((1)/(12) monolayer (ML)) and high coverage (1 ML) by density functional theory calculations using the Gaussian and plane waves formalism. The use of a large supercell allowed the simulation at low symmetry levels. On SnO(2)(110), dissociative adsorption was favored at all coverages and was accompanied by stable associative H(2)O configurations. Increasing the coverage from (1)/(12) to 1 ML stabilized the (associatively or dissociatively) adsorbed H(2)O on SnO(2)(110) because of the formation of intermolecular H bonds. In contrast, on TiO(2)(110), the adsorption of isolated H(2)O groups ((1)/(12) ML) was more stable than at high coverage, and the favored adsorption changed from dissociative to associative with increasing coverage. For dissociative H(2)O adsorption on Ti-enriched Sn(1-x)Ti(x)O(2)(110) surfaces with Ti atoms preferably located on 6-fold-coordinated surface sites, the analysis of the Wannier centers showed a polarization of electrons surrounding bridging O atoms that were bound simultaneously to 6-fold-coordinated Sn and Ti surface atoms. This polarization suggested the formation of an additional bond between the 6-fold-coordinated Ti(6c) and bridging O atoms that had to be broken upon H(2)O adsorption. As a result, the H(2)O adsorption energy initially decreased, with increasing surface Ti content reaching a minimum at 25% Ti for (1)/(12) ML. This behavior was even more accentuated at high H(2)O coverage (1 ML) with the adsorption energy decreasing rapidly from 145.2 to 101.6 kJ/mol with the surface Ti content increasing from 0 to 33%. A global minimum of binding energies at both low and high coverage was found between 25 and 33% surface Ti content, which may explain the minimal cross-sensitivity to humidity previously reported for Sn(1-x)Ti(x)O(2) gas sensors. Above 12.5% surface Ti content, the binding energy decreased with increasing coverage, suggesting that the partial desorption of H(2)O is facilitated at a high fractional coverage.     

Adsorption of small organic molecules on anatase and rutile surfaces: a theoretical study

The adsorption of several small organic molecules on rutile (110) and (100) as well as on anatase (101) surfaces was investigated by Car-Parrinello molecular dynamics in aqueous solution and a new approach to the calculation of adsorption energies is proposed, taking into account the potential energy fluctuation of larger systems. Acetylene and ethylene insert into twin oxygen vacancies in the surface and form polarized covalent Ti-C bonds. In one case spontaneous coupling of two acetylene molecules to a C(4)H(3) molecule with a structure similar to trans-butadiene was observed. Neutral catechol and the singly charged anion were not reactive on any titanium dioxide surface, but the twofold-charged anion attained stable mono- and bidentated geometries on anatase. Methanol, ethanol, formaldehyde and acetaldehyde adsorbed with their functional groups. Very stable geometries provide a Ti-O bond and have adsorption energies of 60-200 kJ/mol. The adsorbates compete with water molecules for similar adsorption sites in point defects as well as on perfect surfaces.     

Underpotential deposition of hydrogen on benzene-modified Pt(111) in aqueous H2SO4

The Pt(111) electrode is modified by an overlayer of C6H6 (ads) upon its cycling in the 0.05-0.80 V range in aq H2SO4 + 1 mM C6H6. The C6H6 (ads) overlayer significantly changes the underpotential-deposited H (H(UPD)) and anion adsorption, and cyclic-voltammetry (CV) profiles show a sharp cathodic peak and an asymmetric anodic one in the 0.05-0.80 V potential range. The C6H6 (ads) layer blocks the (bi)sulfate adsorption but facilitates the adsorption of one monolayer of H(UPD). Cycling of the benzene-modified Pt(111) in benzene-free aq 0.05 H2SO4 from 0.05 to 0.80 V results in a partial desorption of C6H6 (ads) and in a partial recovery of the CV profile characteristic of an unmodified Pt(111). The peak potential of the cathodic and anodic feature is independent of the scan rate, s (10 < or = s < or = 100 mV s(-1)), and the peak current density increases linearly with an increase of the scan rate. Temperature variation modifies the peak potential and current density but does not affect the charge density of the cathodic or anodic feature. Temperature-dependent studies allow us to determine the thermodynamic state function for the H(UPD) adsorption and desorption. Delta G degrees(ads)(H(UPD))assumes values from -4 to -12 kJ mol(-1), while has values from 9 to 14 kJ mol(-1). The values of delta Delta G degrees (delta Delta G degrees = delat Delta G degrees(ads) + delta Delta D degrees(des)) decrease almost linearly from 6 kJ mol(-1) at theta(H(UPD) --> 0 to 0 kJ mol(-1) at theta(H(UPD) --> 1. The nonzero values of delta Delta G degrees testify that the adsorbing and desorbing H(UPD) adatoms interact with an energetically different substrate. The lateral interactions changed from repulsive (omega = 29 kJ mol(-1) at theta(H(UPD) --> 0) to attractive (omega = -28 kJ mol(-1) at theta(H(UPD) --> 1) as the H(UPD) coverage increases. The values of delta S degrees(ads)(H(UPD)) increase from 19 to 56 J K(-1) mol(-1), while those of delta S degrees(des)(H(UPD)) decrease from 45 to -30 J K(-1) mol(-1) with an increase of H(UPD) coverage. The values of delta H degrees(des)(H(UPD)) and delta H degrees(des)(H(UPD)) vary from 0 to 27 kJ mol(-1). The Pt(111)-H(UPD) surface bond energy at the benzene-modified Pt(111) electrode falls in the 191-218 kJ mol(-1) range and is weaker than in the case of the unmodified Pt(111) electrode in the same electrolyte.     

甲醛在CeO2(111)表面吸附的密度泛函理论研究

采用基于第一性原理的密度泛函理论和周期平板模型, 研究了甲醛在以桥氧为端面的CeO2(111)稳定表面上的吸附行为. 通过对不同覆盖度, 不同吸附位的甲醛吸附构型、吸附能及电子态密度的分析发现, 甲醛在CeO2(111)表面存在化学吸附与物理吸附两种情况. 化学吸附结构中甲醛的碳、氧原子分别与表面的氧、铈原子发生相互作用, 形成CH2O2物种; 吸附能随着覆盖度的增加而减小. 与自由甲醛分子相比, 物理吸附的甲醛构型变化不大, 其吸附能较小. 利用CNEB(climbing nudged elastic band)方法计算了甲醛在CeO2(111)表面的初步解离反应活化能(约1.71 eV), 远高于甲醛脱附能垒, 这与甲醛在清洁CeO2(111)表面程序升温脱附实验中产物主要为甲醛的结果相一致.     

Computational study of ethanol adsorption and reaction over rutile TiO(2) (110) surfaces

Studies of the modes of adsorption and the associated changes in electronic structures of renewable organic compounds are needed in order to understand the fundamentals behind surface reactions of catalysts for future energies. Using planewave density functional theory (DFT) calculations, the adsorption of ethanol on perfect and O-defected TiO(2) rutile (110) surfaces was examined. On both surfaces the dissociative adsorption mode on five-fold coordinated Ti cations (Ti(4+)(5c)) was found to be more favourable than the molecular adsorption mode. On the stoichiometric surface E(ads) was found to be equal to 0.85 eV for the ethoxide mode and equal to 0.76 eV for the molecular mode. These energies slightly increased when adsorption occurred on the Ti(4+)(5c) closest to the O-defected site. However, both considerably increased when adsorption occurred at the removed bridging surface O; interacting with Ti(3+) cations. In this case the dissociative adsorption becomes strongly favoured (E(ads) = 1.28 eV for molecular adsorption and 2.27 eV for dissociative adsorption). Geometry and electronic structures of adsorbed ethanol were analysed in detail on the stoichiometric surface. Ethanol does not undergo major changes in its structure upon adsorption with its C-O bond rotating nearly freely on the surface. Bonding to surface Ti atoms is a σ type transfer from the O2p of the ethanol-ethoxide species. Both ethanol and ethoxide present potential hole traps on O lone pairs. Charge density and work function analyses also suggest charge transfer from the adsorbate to the surface, in which the dissociative adsorptions show a larger charge transfer than the molecular adsorption mode.     

Pinning mass-selected Agn clusters on the TiO2(110)-1x1 surface via deposition at high kinetic energy

We present the first scanning tunneling microscopy (STM) study of the deposition of mass-selected silver clusters (Ag(n),n=1, 2, 3) on a rutile TiO(2)(110)-1x1 surface at room temperature under hard-landing conditions. Under hard-landing conditions, only small features are observed on the surface in all cases without sintering or surface damage. This suggests that the high impact energy of the clusters mainly dissipates as thermal energy in the substrate, resulting in the recovery of any initial impact-induced surface damage and the formation of bound clusters on the surface near the impact point. STM images indicate that Ag(1) binds on the bridging oxygen rows twice as often as on the Ti rows. Density-functional Theory (DFT) calculations are consistent with Ag(1) binding at either bridging oxygen vacancies or with two adjacent bridging oxygen atoms in the same bridging oxygen row. STM images of Ag(2) and Ag(3) depositions indicate almost exclusive binding centered on the Ti-atom rows. DFT calculations suggest that the Ag(2) and Ag(3) clusters are bound between two bridging oxygen rows, which is consistent with the STM observations.     

Reactivity of sub 1 nm supported clusters: (TiO2)n clusters supported on rutile TiO2 (110)

Metal oxide clusters of sub-nm dimensions dispersed on a metal oxide support are an important class of catalytic materials for a number of key chemical reactions, showing enhanced reactivity over the corresponding bulk oxide. In this paper we present the results of a density functional theory study of small sub-nm TiO(2) clusters, Ti(2)O(4), Ti(3)O(6) and Ti(4)O(8) supported on the rutile (110) surface. We find that all three clusters adsorb strongly with adsorption energies ranging from -3 eV to -4.5 eV. The more stable adsorption structures show a larger number of new Ti-O bonds formed between the cluster and the surface. These new bonds increase the coordination of cluster Ti and O as well as surface oxygen, so that each has more neighbours. The electronic structure shows that the top of the valence band is made up of cluster derived states, while the conduction band is made up of Ti 3d states from the surface, resulting in a reduction of the effective band gap and spatial separation of electrons and holes after photon absorption, which shows their potential utility in photocatalysis. To examine reactivity, we study the formation of oxygen vacancies in the cluster-support system. The most stable oxygen vacancy sites on the cluster show formation energies that are significantly lower than in bulk TiO(2), demonstrating the usefulness of this composite system for redox catalysis.