Electronic semiconducting oxides as pH sensors

Limitations on the response of electronically-conducting oxides as pH sensors are demonstrated. PtO₂, IrO₂, RuO₂, OsO₂, Ta₂O₅ and TiO₂ showed near-Nernstian behavior in the pH range 2–12 in air-saturated solutions. Interferences from selected reducing and oxidizing agents and from some complexing anions were measured and catalogued. No interference from monovalent cations (Group IA) was observed. Several reaction mechanisms are proposed and discussed.     

Controlled growth of semiconducting oxides hierarchical nanostructures

Semiconducting ZnO hierarchical nanostructure, where ZnO nanonails were grown on ZnO nanowires, has been fabricated under control experiment with a mixture of ZnO nanopowders and Sn metal powders. Sn nanoparticles are located at or close to the tips of the nanowires and the growth branches, serving as the catalyst for the vapor-liquid-solid growth mechanism. The morphology and microstructure of ZnO nanowire and nanonail were measured by scanning electron microscopy and high-resolution transmission electron microscopy. The long and straight ZnO nanowires grow along [0001] direction. ZnO nanonails are aligned radially with respect to the surface the ZnO nanowire. The long axis direction of nanonails forms an angle of ∼30° to the [0001] direction.     

Methanol oxidation on copper-oxide catalysts

Complete oxidation of methanol on CuO and CuO/Al₂O₃ catalysts has been studied. The main kinetic parameters have been determined. A possible mechanism and the nature of the rate-determining step are discussed.

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CuO CuO/Al₂O₃. . .

     

Heterogeneous partial oxidation catalysis on metal oxides

This review paper presents an overview of heterogeneous selective ammoxidation and oxidative dehydrogenation (ODH) of light alkanes, particularly of ethane. The conversion of ethane to ethene is in great demand in the domestic and worldwide chemical industry. The review has been voluntarily restricted to metal oxide-type catalysts, as it is devoted to the special issue honouring Edmond Payen and is based on 30 years of experience and discussions with pioneering scientists in the field. The main key factors, designated by Grasselli as the “7 pillars”, have been emphasised: isolation of active sites, M–O bond strength, crystalline structure, redox features, phase cooperation, multifunctionality and the nature of the surface oxygen species. The main features and physical and chemical properties of solid catalysts for selective oxidation compared to total oxidation have also been emphasised. Several case studies have been presented to illustrate the concept and importance of the key factors of catalyst preparation and activation and of the catalytic atmosphere. Based on such analysis and recent discoveries and process developments perspective views are also given.     

Methanol decomposition on copper and manganese oxides supported on activated carbon

Copper and manganese oxides supported on activated carbon have been studied in the reaction of methanol decomposition to H₂ and CO. XRD, EPR, TPR with CO and magnetic measurements have been used for their characterization. The nature of the catalytically active complex is also discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Methanol oxidation process on the silver block catalysts

By means of physico-chemical and structural-mechanical characteristics optimization a new type of silver catalyst has been worked out, viz. a porous metal block with cellular structure (foam silver). Activity and selectivity of the foam silver catalyst have been investigated in selective methanol oxidation.     

Methanol oxidation to formaldehyde on bismuth phosphate-based catalysts

A bismuth (III) phosphate catalyst has been prepared by precipitation and characterized by X-ray diffraction, thermogravimetric analysis, and X-ray photoelectron and infrared spectroscopy. Its activity and selectivity toward selective methanol oxidation to formaldehyde has been studied by a flow method. A high selectivity has been found, similar to that reported for typical catalysts used for this reaction. The possible importance of the strength and covalency of the P–O bonds is discussed.     

Photoelectrolysis of water by irradiation of platinized n-type semiconducting metal oxides

The basic principles of semiconductor photoelectrochemistry as applied to light to chemical and/or electrical energy conversions are outlined. Special emphasis is on the photoelectrolysis of H₂O to H₂ and O₂. New results are presented which show that platinized n-type SrTiO₃ and KTaO₃ evolve H₂ and O₂ from alkaline aqueous solutions when irradiated with ultraviolet light. The irradiated portions of the metal oxide behave as the photoanode and the dark platinized portions behave as the cathode. The nonplatinized oxides are energetically capable of evolving H₂ and O₂ upon irradiation but the overvoltage for H₂ is too great. The general requirement for the “short-circuit” redox chemistry at the irradiated n-type semiconductor surface is that the dark cathodic reaction occur at a potential more positive than the anodic reaction upon irradiation. The role of the Pt coating is to reduce the H₂ overvoltage to meet this requirement. It is demonstrated that polished n-type TiO₂ and SrTiO₃ are both capable of oxidizing H₂O to evolve O₂ and reducing Cu²⁺ to plate out Cu upon irradiation in 0.5 M CuSO₄ (pH = 7). We discuss the importance of “short-circuit” redox chemistry and overvoltage in obtaining opencircuit photopotential in photoelectrochemical cells.     

The oxidation of toluene on transition metal oxides

The oxidation of toluene on pure vanadium and molybdenum oxides was found to follow independent paths; it was benzene ring oxidation on V₂O₅ and side chain oxidation on MoO₃. On mixed xV₂O₅ · yMoO₃ oxides, the main reaction was the addition at the double bond preferably positioned meta rather than one-electron oxidation.     

Selective oxidation of semiconducting single-wall carbon nanotubes by hydrogen peroxide

Selective oxidation of single-wall carbon nanotubes (SWCNTs) by H2O2 was conducted at varying heating times and monitored by UV-vis-NIR spectroscopy. A major increase in the relative absorption intensity indicated a higher than 80% concentration of metallic SWCNTs in the final product. Here, it is suggested that semiconducting SWCNTs are more reactive than metallic SWCNTs because of hole-doping by H2O2, resulting in faster oxidation.     

Gas-phase toluene oxidation over platinum-containing mixed oxides

The gas-phase toluene oxidation was studied over platinum-containing mixed oxides derived from hydrotalcite-like compounds with high specific surface area. Both the temperature of the reaction and toluene and oxygen initial concentrations proved to influence toluene oxidation rate. Activation energy of 107 and 248 kJ/mol was found for toluene and oxygen, respectively, with an oxygen dissociative model.     

The effect of metal oxides on the oxidation of polybutadiene

Carboxy-terminated polybutadiene (CTPB) was oxidised as a coating on various metal oxides by heating in air on a thermobalance. The oxidation was found to be free from diffusion control and was catalysed by certain of the oxides. The catalysis was shown to be independent of semiconductor type and to be associated with those oxides for which the width of the forbidden zone between the valence and conduction bands (U) is less than 1.9 eV. In general, low values of U result in high catalytic activity. It is proposed that catalysis occurs by a redox mechanism, viz. RO₂H + p → RO₂^. + H⁺, RO₂H + e → RO^. + OH^?.     

Selective oxidation of propylene over gold deposited on titanium-based oxides

Gold supported on titanium-based metal oxides can assist the selective partial oxidation of propylene at temperatures from 313 K to 573 K in a gas containing both H₂ and O₂. The preparation method was found to be crucial in controlling the selectivities. In general, impregnation and chemical vapor deposition methods do not produce selective catalysts. Only the deposition-precipitation method makes gold selective to propylene oxide or propanal, suggesting that a strong contact between the gold particles and the titanium ion sites on the support is important. The effect of changing the support was also dramatic; the use of the anatase form of TiO₂ and Ti-MCM-41 results in propylene oxide production, while the rutile structure of TiO₂ caused complete oxidation to CO₂. Microporous crystalline titanium silicates such as TS-1, TS-2, and Ti-β zeolite make gold relatively selective to propanal and of the three TS-1 gives the highest selectivity. These results indicate that the oxidation of propylene in the copresence of H₂ must involve the surface of the supports and that the reaction takes place at the interface perimeter around the gold particles.     

Methanol oxidation on unsupported and carbon supported Pt + Ru anodes

A novel Pt + Ru electrode material is shown to be highly active for the direct electro-oxidation of methanol in H₂SO₄ solutions and to show very little tendency to poison. X-ray photoelectron spectroscopy of this material before use as an anode showed that the ruthenium is oxidised and that there is an important surface concentration of oxidised platinum. After prolonged use as a methanol-oxidation anode, the concentration of oxidised platinum is somewhat increased and there is no evidence for any Pt-CO or Pt₂ = CO species; rather adsorbed formate is present. These data are consistent with Ru acting as a promoter of active surface oxygen. Dispersion of the Pt and Ru on a pure carbon support gives a much greater performance per gram of precious metal; however, the initial increase in overpotential is greater by over 100 mV. The differences in the catalytic behaviour of these two materials is discussed, and the importance of competing reactions is considered.     

过渡金属氧化物掺杂对铜锰氧化物催化CO氧化性能的影响

以乙酸铜和乙酸锰为铜锰前驱体,以NH₄HCO₃为沉淀剂,相应金属硝酸盐为掺杂剂,采用共沉淀法制备了不同过渡金属氧化物掺杂的铜锰氧化物催化剂.?采用N₂物理吸附、X射线衍射,氢气-程序升温还原和原位红外漫反射光谱等方法对催化剂进行了表征,考察了系列催化剂上CO反应性能.?结果表明,掺杂过渡金属氧化物可以调变催化剂对CO的吸附能力,进而影响催化剂性能.     

氧化镁上乙酸乙酯和乙酸丁酯氧化反应（英文）

采用新型无溶剂反应和回流的方法制得锰钾矿型氧化镁(K-OMS-2),同时采用常规方法制得氧化镁,并测试不同催化剂对工业排放气中有机挥发性物质(VOCs)中的模型化合物––乙酸乙酯和乙酸丁酯的催化氧性能.采用N2吸附-脱附、X射线衍射、扫描电镜、程序升温还原和X射线光电子能谱等技术对催化剂进行了表征.所有氧化镁样品均表现出很高的催化乙酸乙酯和乙酸丁酯氧化生成CO2的活性,且制备方法对催化剂性能起着重要作用.新型无溶剂法制得的K-OMS-2纳米棒样品比常规的回流法制得样品表现出更好的催化性能,含锰钾矿型氧化镁的样品比常规方法制得样品表现出更高的活性.性能最好的催化剂也表现出较高的稳定性,在213和202 oC条件下,可分别使90%的乙酸乙酯和乙酸丁酯转化为CO2.催化剂性能的显著差异清楚地表明,对于所选VOCs氧化反应,采用新型无溶剂法制得的K-OMS-2纳米棒样品比常规法制备的氧化镁混合物更好,这可能与样品结构中含有更高的Mn平均氧化态有关.本文表明了催化剂性能与其表面化学性质间存在显著的关联,显示了K-OMS-2内在性质决定了其高的催化性能.     

The role of surface oxides in formic acid oxidation on Au

Compared to Pt or Pd electrodes, Au is a poor catalyst for the direct anodic oxidation of HCOOH, but the formation of Au surface oxides in acidic solutions is accompanied by a fast oxidation of HCOOH. This fast reaction is not simply a secondary reaction of Au surface oxides since those oxides are kinetically stable in HCOOH solutions. They do oxidize HCOOH only via a slow and purely electrochemical process which occurs on free Au sites and is “driven” by oxide reduction. The fast HCOOH oxidation is due to a highly reactive intermediate which is able either to form stable Au oxides Au_nO_m or to react with HCOOH. Our results are consistent with the model that by the charge transfer step a reactive non-equilibrium {Au…O> species is formed which converts to stable equilibrium oxides Au_nO_m after migration and rearrangement steps. Pre-equilibrium <Au…O> oxidizes HCOOH and this oxidation is of lower order with respect to <Au…O> compared with the formation of Au_nO_m.     

Methanol dissociation and oxidation on single Fe atom supported on graphitic carbon nitride

Considering environmental protection and sustainable development, fuel cells have always been an ideal choice for clean energy. For the performance of fuel cells, the anode catalysts are a key consideration. In the work reported, we designed a new type of anode catalyst, in which graphitic carbon nitride was used as the substrate and transition metal iron as the supported atom. The calculation results were characterized by adsorption energy, reaction energy barrier, potential energy surface and charge analysis. Based on density functional theory, the gradual decomposition of methanol molecules on the catalyst is realized; the decomposition products are oxidized to reduce the formation of CO, and the efficiency of anode catalysis is improved, which provides a new idea for the design of anode materials for methanol fuel cells.