The role of low-coordinate oxygen on Co3O4(110) in catalytic CO oxidation

A complete catalytic cycle for carbon monoxide (CO) oxidation to carbon dioxide (CO(2)) by molecular oxygen on the Co(3)O(4)(110) surface was obtained by density functional theory plus the on-site Coulomb repulsion (DFT + U). Previously observed high activity of Co(3)O(4) to catalytically oxidize CO at very low temperatures is explained by a unique twofold-coordinate oxygen site on Co(3)O(4)(110). The CO molecule extracts this oxygen with a computed barrier of 27 kJ/mol. The extraction leads to CO(2) formation and an oxygen vacancy on Co(3)O(4)(110). Then, the O(2) molecule dissociates without a barrier between two neighboring oxygen vacancies (which are shown to have high surface mobility), thereby replenishing the twofold-coordinate oxygen sites on the surface and enabling the catalytic cycle. In contrast, extracting the threefold-coordinate oxygen site on Co(3)O(4)(110) has a higher barrier. Our work furnishes a molecular-level mechanism of Co(3)O(4)'s catalytic power, which may help understand previous experimental results and oxidation catalysis by transition metal oxides.     

Density functional theory study of CO catalytic oxidation on Co_2B_2/TiO_2（110） surface

Titanium dioxide with CoB amorphous alloys nanoparticles deposited on the surface is known to exhibit higher catalytic activity than the CoB amorphous. A study of the structure of such system is necessary to understand this effect. A quantum chemical study of Co2B2 on the TiO2 (110) surface was studied using periodic slab model within the framework of density functional theory (DFT). The results of geometry optimization indicated that the most stable model of adsorption was Co2B2 cluster adsorbed on the hollow site of TiO2.The adsorption energy calculated for Co2B2 on the hollow site was 439.3 kJ/mol.The adsorption of CO and O2 was further studied and the results indicated that CO and O2 are preferred to adsorb on the Co2 site. Co-adsorption of CO and O2 shows that Co2B2/TiO2 is a good catalyst for the oxidation of CO to carbon dioxide in the presence of oxygen.     

Modification of the size of supported clusters by coadsorption of an organic compound: gold and L-cysteine on rutile TiO2(110)

Using X-ray photoelectron spectroscopy we studied the coadsorption of the amino acid L-cysteine and gold on a rutile TiO(2)(110) surface under ultrahigh vacuum conditions. Irrespective of the deposition order, i.e., irrespective of whether L-cysteine or gold is deposited first, the primary interaction between L-cysteine and the gold clusters formed at the surface takes place through the deprotonated thiol group of the molecule. The deposition order, however, has a profound influence on the size of the gold clusters as well as their location on the surface. If L-cysteine is deposited first the clusters are smaller by a factor two to three compared to gold deposited onto the pristine TiO(2)(110) surface and then covered by L-cysteine. Further, in the former case the clusters cover the molecules and thus form the outermost layer of the sample. We also find that above a minimum gold cluster size the gold cluster/L-cysteine bond is stronger than the L-cysteine/surface bridging oxygen vacancy bond, which, in turn, is stronger than the gold cluster/vacancy bond.     

Cu_2O(111)催化水煤气变换反应机理的理论研究

采用密度泛函理论结合周期平板模型方法系统地研究了水煤气变换反应在Cu_2O(111)表面上的反应机理,包括氧化还原机理、羧基机理和甲酸根机理.结果表明,在Cu_2O(111)表面,羧基机理和甲酸根机理均可行,且甲酸根机理更为有利,其最佳反应途径为H_2O~*→H~*+OH~*;CO(g)+H~*+OH~*→trans-HCOOH~*(1)→cis-HCOOH~*→CO_2~*+H_2(g).其中trans-HCOOH~*(1)→cis-HCOOH~*为其决速步,该基元反应的能垒仅为59 kJ·mol~(-1).羧基机理的最优反应路径同样是以H_2O的解离反应开始,随后CO(g)+OH~*→cis-COOH~*→trans-COOH~*→CO_2(g)+H~*,最后产生的两个吸附的H原子先迁移再结合生成H_2,整个反应的控速步骤为H原子的迁移,迁移能垒为96 kJ·mol~(-1).氧化还原机理则由于OH解离需要越过一个很高的能垒(254 vs.187 kJ·mol~(-1))而不可行.     

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.     

The mechanism of emerging catalytic activity of gold nano-clusters on rutile TiO2(110) in CO oxidation reaction

This paper reveals the fact that the O adatoms (O(ad)) adsorbed on the 5-fold Ti rows of rutile TiO(2)(110) react with CO to form CO(2) at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO(2)(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of ～1.5 nm and two-atomic layer height corresponding to ～50 Au atoms∕cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO(2)(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O(2) adsorption on the surface and also enhance the reaction of CO with the O(ad) atoms to form CO(2) owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.     

Effect of the TiO2 reduction state on the catalytic CO oxidation on deposited size-selected Pt clusters

The catalytic activity of deposited Pt(7) clusters has been studied as a function of the reduction state of the TiO(2)(110)-(1 × 1) support for the CO oxidation reaction. While a slightly reduced support gives rise to a high catalytic activity of the adparticles, a strongly reduced one quenches the CO oxidation. This quenching is due to thermally activated diffusion of Ti(3+) interstitials from the bulk to the surface where they deplete the oxygen adsorbed onto the clusters by the formation of TiO(x) (x ? 2) structures. This reaction is more rapid than the CO oxidation. The present results are of general relevance to heterogeneous catalysis on TiO(2)-supported metal clusters and for reactions involving oxygen as intermediate.     

同步辐射光电了能谱研究在团簇存金红石相TiO2-（1×1）表面的生长和稳定性

利用同步辐射高分辨光电子能谱研究了金团簇在部分还原TiO2-（1×1）表面的生长和稳定性．价带谱实验结果观察到非常少量金团簇的沉积导致了Ti^3＋的3d峰完全消失,表明金团簇成核在TiO2-（1×1）表面的氧缺陷位．Au4f芯电子光电子能谱实验结果证明了TiO2-（1×1）表面氧缺陷位向金团簇转移电荷．还对比研究了化学剂量比和部分还原的TiO2-（1×1）表面上金团簇的热稳定性．当金团簇尺寸相近时部分还原的TiO2-（1×1）表面上金团簇要比化学剂量比的TiO2-（1×1）面上金团簇稳定;在相同的表面上尺寸大的金团簇要比尺寸小的金团簇稳定．     

The role of weakly bound on-top oxygen in the catalytic CO oxidation reaction over RuO2(110)

RuO(2)-based catalysts are much more active in the oxidation of CO than related metallic Ru catalysts. This high catalytic activity (or low activation barrier) is attributed to the weak oxygen surface bonding of bridging O atoms on RuO(2)(110) in comparison with the strongly chemisorbed oxygen on Ru(0001). Since the RuO(2)(110) surface is able to stabilize an even more weakly bound on-top oxygen species, one would anticipate that the catalytic activity will increase further under oxidizing conditions. We will show that this view is far too simple to explain our temperature-programmed reaction experiments, employing isotope labeling of the potentially active surface oxygen species on RuO(2)(110). Rather, both surface O species on RuO(2)(110) reveal similar activities in oxidizing CO.     

Pd(Cu)在MgO(100)表面吸附CO和O2的理论研究

采用固体镶嵌势能模型和DFT/B3LYP方法研究了在Pd/MgO和Cu/MgO表面吸附CO和O₂分子的电子性质. 计算结果表明, 在完美MgO(100)表面Pd原子对CO和O₂的吸附能分别为206.5和84.8 kJ/mol, 因此可知Pd原子更容易吸附CO分子; 而当Pd原子附着于有氧缺陷的MgO表面时, 它对两种分子的吸附都非常弱. 相反, 附着于MgO表面的Cu原子对O₂分子的吸附更为有利, 其吸附能在140～155 kJ/mol之间. 研究结果还表明, 对于双分子吸附体系, 即CO＋CO, CO＋O₂, O₂＋O₂体系, 双分子之间的结合力可减小完美MgO表面上Pd原子与被吸附分子的相互作用, 使吸附能减少了46～96 kJ/mol. 而对于在MgO表面上的Cu原子, 只有O₂＋O₂ 体系使吸附能减少了大约50～71 kJ/mol.     

Growth mechanism of palladium clusters on rutile TiO2 （110） surface

Oxide-supported transition metal systems have been the subject of enormous interest due to the improvement of catalytic properties relative to the separate metal.Thus in this paper,we embark on a systematic study for Pd n (n=1-5) clusters adsorbed on TiO2 (110) surface based on DFT-GGA calculations utilizing periodic supercell models.A single Pd adatom on the defect-free surface prefers to adsorb at a hollow site bridging a protruded oxygen and a five-fold titanium atom along the [110] direction,while Pd dimer is located on the channels with the Pd-Pd bond parallel to the surface.According to the transition states (TSs) search,the adsorbed Pd trimer tends to triangular growth mode,rather than linear mode,while the Pd4 and Pd5 clusters prefer three-dimensional (3D) models.However,the oxygen vacancy has almost no influence on the promotion of Pd n cluster nucleation.Additionally,of particular significance is that the Pd-TiO2 interaction is the main driving force at the beginning of Pd nucleation,whereas the Pd-Pd interaction gets down to control the growth process of Pd cluster as the cluster gets larger.It is hoped that our theoretical study would shed light on further designing high-performance TiO2 supported Pd-based catalysts.     

Electron-induced dissociation of CO2 on TiO2(110)

The electron-induced dissociation of CO(2) adsorbed at the oxygen vacancy defect on the TiO(2)(110) surface has been investigated at the single-molecular level using scanning tunneling microscopy (STM). Electron injection from the STM tip into the adsorbed CO(2) induces the dissociation of CO(2). The oxygen vacancy defect is found to be healed by the oxygen atom released during the dissociation process. Statistical analysis shows that the dissociation of CO(2) is one-electron process. The bias-dependent dissociation yield reveals that the threshold energy for electron-induced dissociation of CO(2) is 1.4 eV above the conduction-band minimum of TiO(2). The formation of a transient negative ion by the injected electron is considered to be the key process in CO(2) dissociation.     

Theoretical investigation of water gas shift reaction catalyzed by iron group carbonyl complexes M(CO)5 (M = Fe, Ru, Os)

We have investigated the mechanism of M(CO)(5) (M = Fe, Ru, Os) catalyzed water gas shift reaction (WGSR) by using density functional theory and ab initio calculations. Our calculation results indicate that the whole reaction cycle consists of six steps: 1 → 2 → 3 → 4 → 5 → 6 → 2. In this stepwise mechanism the metals Fe, Ru, and Os behave generally in a similar way. However, crucial differences appear in steps 3 → 4 → 5 which involve dihydride M(H)(2)(CO)(3)COOH(-) (4') and/or dihydrogen complex MH(2)(CO)(3)COOH(-) (4). The stability of the dihydrogen complexes becomes weaker down the iron group. The dihydrogen complex 4_Fe is only 11.1 kJ/mol less stable than its dihydride 4'_Fe at the B3LYP/II(f)++//B3LYP/II(f) level. Due to very low energy barrier it is very easy to realize the transform from 4_Fe to 4'_Fe and vice versa, and thus for Fe there is no substantial difference to differentiate 4 and 4' for the reaction cycle. The most possible key intermediate 4'_Ru is 38.2 kJ/mol more stable than 4_Ru. However, the barrier for the conversion 3_Ru → 4'_Ru is 23.8 kJ/mol higher than that for 3_Ru → 4_Ru. Additionally, 4'_Ru has to go through 4_Ru to complete dehydrogenation 4'_Ru → 5_Ru. The concerted mechanism 4'_Ru → 6_Ru, in which the CO group attacks ruthenium while H(2) dissociates, can be excluded. In contrast to Fe and Ru, the dihydrogen complex of Os is too unstable to exist at the level of theory. Moreover, we predict Fe and Ru species are more favorable than Os species for the WGSR, because the energy barriers for the 4 → 5 processes of Fe and Ru are only 38.9 and 16.2 kJ/mol, respectively, whereas 140.5 kJ/mol is calculated for the conversion 4' → 5 of Os, which is significantly higher. In general, the calculations are in good agreement with available experimental data. We hope that our work will be beneficial to the development and design of the WGSR catalyst with high performance.     

Surface studies of gas sensing metal oxides

The relation of surface science studies of single crystal metal oxides to gas sensing applications is reviewed. Most metal oxide gas sensors are used to detect oxidizing or reducing gases and therefore this article focuses on surface reduction processes and the interaction of oxygen with these surfaces. The systems that are discussed are: (i) the oxygen vacancy formation on the surface of the ion conductor CeO(2)(111); (ii) interaction of oxygen with TiO(2) (both adsorption processes and the incorporation of oxygen into the TiO(2)(110) lattice are discussed); (iii) the varying surface composition of SnO(2)(101) and its consequence for the adsorption of water; and (iv) Cu modified ZnO(0001)-Zn surfaces and its interaction with oxygen. These examples are chosen to give a comprehensive overview of surface science studies of different kinds of gas sensing materials and to illustrate the potential that surface science studies have to give fundamental insight into gas sensing phenomena.     

New Cu-based catalysts supported on TiO2 films for Ullmann S(N)Ar-type C-O coupling reactions

New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)).     

Dimethyl methylphosphonate decomposition on Cu surfaces: supported Cu nanoclusters and films on TiO2(110)

The thermal decomposition of dimethyl methylphosphonate (DMMP), which is a simulant molecule for organophosphorus nerve agents, has been investigated on Cu clusters as well as on Cu films deposited on a TiO(2)(110) surface. Scanning tunneling microscopy studies were conducted to characterize the cluster sizes and surface morphologies of the deposited Cu clusters and films. Temperature-programmed desorption experiments demonstrated that the surface chemistry of DMMP is not sensitive to the size of the Cu clusters over the range studied in this work. DMMP reaction on an annealed 40 monolayer Cu film resulted in the desorption of H(2), methane, methyl, formaldehyde, methanol, and molecular DMMP, and reaction on the small (4.4 +/- 0.9 nm diameter, 1.8 +/- 0.6 nm height) and large (10.7 +/- 1.9 nm diameter, 4.8 +/- 1.0 nm height) Cu clusters generated similar products. Formaldehyde and methane production is believed to occur via a methoxy intermediate on the Cu surface. These products are favored on the higher coverage Cu films that completely cover the TiO(2) surface since competing reaction pathways on TiO(2) are suppressed. X-ray photoelectron spectroscopy studies showed that DMMP begins to decompose on the Cu clusters upon adsorption at room temperature and that atomic carbon, atomic phosphorus, and PO(x) remain on the surface after DMMP decomposition.     

Mechanisms investigation of the WGSR catalyzed by single noble metal atoms supported on vanadium oxide clusters

The redox and carbonyl mechanisms of the water gas shift reaction (WGSR) catalyzed by the single noble metal (NM) atoms of Ru, Rh, Pd, Ag (from the 4d row) and Os, Ir, Pt, Au (from the 5d row) supported on vanadium oxide cluster ion V₂O₆⁺ have been firstly investigated through the density functional theory (DFT) calculations. Natural population analysis (NPA) shows NMs possess positive charges in the model systems and usually act as reactant molecule trapper and an effective electron store to accept or release electrons. The carbonyl mechanism avoiding the oxygen vacancy (O_v) formation and directing NM‐H bond cleavage is strongly preferred over the redox mechanism. Our computations identified single‐atom catalysts (SAC), especially RhV₂O₆⁺ and PdV₂O₆⁺ exhibit improved overall catalytic performance because of the lower rate‐control step activation barriers via the associate carbonyl mechanism. This work aims to provide some detailed insights into the effects of NM in bimetallic oxide clusters for WGSR at a molecular level, and serves as a starting point for further theoretical studies on the mechanisms of related SAC catalytic reactions.     

Density functional study of the charge on Aun clusters (n=1-7) supported on a partially reduced rutile TiO2(110): are all clusters negatively charged?

It is widely believed that small gold clusters supported on an oxide surface and adsorbed at the site of an oxygen vacancy are negatively charged. It has been suggested that this negative charge helps a gold cluster adsorb oxygen and weakens the O-O bond to make oxidation reactions more efficient. Given the fact that an oxygen vacancy is electron rich and that Au is a very electronegative element, the assumption that the Au cluster will take electron density from the vacancy is plausible. However, the density functional calculations presented here show that the situation is more complicated. The authors have used the Bader method to examine the charge redistribution when a Aun cluster (n=1-7) binds next to or at an oxygen vacancy on rutile TiO2(110). For the lowest energy isomers they find that Au1 and Au3 are negatively charged, Au5 and Au7 are positively charged, and Au2, Au4, and Au6 exchange practically no charge. The behavior of the Aun isomers having the second-lowest energy is also unexpected. Au2, Au3, Au5, and Au7 are negatively charged upon adsorption and very little charge is transferred when Au4 and Au6 are adsorbed. These observations can be explained in terms of the overlap between the frontier molecular orbitals of the gold cluster and the eigenstates of the support. Aun with even n becomes negatively charged when the lowest unoccupied molecular orbital has a lobe pointing in the direction of the oxygen vacancy or towards a fivefold coordinated Ti (5c-Ti) located in the surface layer; otherwise it stays neutral. Aun with odd n becomes negatively charged when the singly occupied molecular orbital has a lobe pointing in the direction of a 5c-Ti located at the vacancy site or in the surface layer, otherwise it donates electron density into the conduction band of rutile TiO2(110) becoming positively charged.