Comparison of the activity of Au/CeO2 and Au/Fe2O3 catalysts for the CO oxidation and the water-gas shift reactions

We compare the activity and relevant gold species of nanostructured gold–cerium oxide and gold–iron oxide catalysts for the CO oxidation by dioxygen and water. Well dispersed gold nanoparticles in reduced form provide the active sites for the CO oxidation reaction on both oxide supports. On the other hand, oxidized gold species, strongly bound on the support catalyze the water-gas shift reaction. Gold species weakly bound to ceria (doped with lanthana) or iron oxide can be removed by sodium cyanide at pH ≥12. Both parent and leached catalysts were investigated. The activity of the leached gold–iron oxide catalyst in CO oxidation is approximately two orders of magnitude lower than that of the parent material. However, after exposure to H₂ up to 400 °C gold diffuses out and is in reduced form on the surface, a process accompanied by a dramatic enhancement of the CO oxidation activity. Similar results were found with the gold–ceria catalysts. On the other hand, pre-reduction of the calcined leached catalyst samples did not promote their water-gas shift activity. UV–Vis, XANES and XPS were used to probe the oxidation state of the catalysts after various treatments.     

Oxidation of benzyl alcohol using supported gold–palladium nanoparticles

A key discovery in the last two decades has been the realisation that gold, when prepared as supported nanoparticles, is exceptionally effective as an oxidation catalyst, particularly for the oxidation of alcohols. The catalytic efficacy is enhanced further by the alloying of gold with palladium. In this paper we study the effect of the method preparation of gold–palladium alloy nanoparticles supported on titania and investigate the activity of the materials for the selective oxidation of benzyl alcohol. We contrast impregnation and deposition–precipitation methods and demonstrate that the most active catalysts are prepared using the deposition–precipitation method.     

非贵金属催化5-羟甲基糠醛选择氧化的研究进展

5-羟甲基糠醛（HMF）作为一种连接生物质资源和精细化学品工业的多功能平台化合物,因含有醛基、羟甲基而具有非常活泼的化学性质。HMF催化选择氧化在生物质转化过程中具有十分重要的意义,近年来受到研究者们的广泛关注。其氧化产物如2,5-呋喃二甲醛（DFF）和2,5-呋喃二甲酸（FDCA）都是具有高附加值的精细化学品,可用于抗菌剂、医药中间体、合成聚酯等方面。非贵金属催化剂因具备低成本、资源丰富以及环境友好的优势,用于HMF选择氧化的相关报道已逐渐增多。阐述了HMF选择氧化的催化反应机理,着重从非贵金属催化剂的角度出发,对近年来HMF的不同催化氧化体系进行了总结和归纳。最后,展望了HMF选择氧化的研究前景,为构建绿色、高效的催化体系提供思路和参考。     

Silica-Supported Gold Catalyst Modified by Doping with Titania for Cyclohexane Oxidation

Amorphous silica was modified by doping with titania through a surface sol–gel process and applied as the support for depositing gold. These doped silica-supported gold catalysts were tested in the selective cyclohexane oxidation to cyclohexanone and cyclohexanol using oxygen. Under the oxidation conditions of 150 °C, 1.5 MPa and 3 h, a selectivity of 91.7% for cyclohexanone and cyclohexanol could be reached over the gold catalyst, affording a cyclohexane conversion of 8.4% and a turnover frequency up to 40,133 per hour. Moreover, the catalytic activity and selectivity could be well retained in 4 recycling oxidation reactions, showing a high stability of the gold catalyst supported on titania-doped silica.     

New approaches to designing selective oxidation catalysts: Au/C a versatile catalyst

Selective oxidation is of key importance in the synthesis of chemical intermediates. For many years a number of oxides and supported metal catalysts have been used. The key questions involved in the design of selective oxidation catalysts are discussed in the initial part of this paper. One of the most exciting recent developments in the field of selective oxidation has been the discovery that supported gold catalysts are active. The second part of the paper discusses Au/C catalysts, which are shown to be particularly versatile for oxidation reactions. Four examples of selective oxidation are described using molecular oxygen as oxidant: (a) selective oxidation of glycerol to glycerate in the presence of base; (b) the oxidation of cyclohexane to cyclohexanol and cyclohexanane in the presence of a radical initiator; (c) the oxidation of hydrogen to hydrogen peroxide, and (d) the oxidation of benzyl alcohol to benzaldehyde under solvent free conditions. In contrast, the Au/C catalysts are not active for oxidation of carbon monoxide at ambient temperature. These examples demonstrate that there exists a rich potential for Au/C as a selective oxidation catalyst and that research efforts should now be focussed on selective oxidation using supported gold catalysts.     

Use of renewables for the production of chemicals: Glycerol oxidation over carbon supported gold catalysts

As a renewable feedstock and due to its high functionality glycerol is an attractive reactant for the production of a large number of valuable compounds. We report on an environmentally friendly alternative to produce chemicals from the glycerol oxidation, which are currently produced either by stoichiometric oxidation processes or by enzymatic routes. We investigate the heterogeneously catalyzed liquid-phase oxidation of glycerol with carbon supported gold catalysts. The prepared nanosized gold catalysts are highly active, so that the reaction could be performed under atmospheric pressure. The influence of the preparation method of the catalysts has been investigated. Moreover, the support effect on the catalytic process has been studied and discussed in terms of pore structure of the investigated carbon materials. The promotor effect of platinum on Au/C catalysts was examined and it could be shown that the presence of Pt increases not only the catalyst activity but also the selectivity. By promoting the gold catalysts with platinum the selectivity to dihydroxyacetone could be increased from 26% (Au/C) to 36% (Au–Pt/C).     

Catalytic Processes for Biomass-Derived Platform Molecules Valorisation

Nowadays, biomass is an interesting raw material for chemical industry, and the valorisation of its derivatives becomes in a sustainable alternative against to the depletion of fossil sources necessary for the production of energy, fuels and chemicals. Different organic compounds, such as sugars, polyols, furanics, as well as several acids (i.e. levulinic acid, succinic acid, itaconic acid, 3-hydroxy-propionic acid, among others) can be obtained after a primary treatment of the lignocellulosic-type biomass. These bio-derived molecules can be used as “platform chemicals” for the synthesis of numerous chemical products (i.e. components and additives for fuels, solvents and paintings, new monomers for polymer industry, etc.). In this review, the possibilities of valorisation via novel catalytic processes of some of the most promising biomass(cellulose/hemicellulose)-derived intermediates and platform chemicals for obtaining both conventional and new high added-value chemicals for industry will be assessed, also including cascade-type (or “one-pot”) catalytic processes recently developed.

     

Systematic Study of the Oxidation of Methane Using Supported Gold Palladium Nanoparticles Under Mild Aqueous Conditions

The oxidation of methane using hydrogen peroxide has been studied using supported gold palladium catalysts prepared using the incipient wetness technique. The effect of reaction conditions and catalyst parameters has been investigated. The supported gold palladium nanoparticles produce methyl hydroperoxide as the primary reaction product which is subsequently converted to methanol with high selectivity, ca. 40–70 %. The selectivity to methanol is influenced by the oxidation state the palladium component of the catalyst. In contrast to homogeneous gold and palladium catalysts the heterogeneous gold palladium nanoalloys are reusable and affords high oxygenate selectivity (ca. 90 %).     

Oxidation of glycerol with hydrogen peroxide using silicalite and aluminophosphate catalysts

The oxidation of glycerol using a range of metal‐containing silicalite and aluminophosphate catalysts is described and discussed. Variation in reaction conditions (extent of conversion, temperature, glycerol/hydrogen peroxide ratio) or catalyst (silicalite containing Ti, V, Fe or AlPO‐5 containing Cr, V, Mn, Co) did not lead to the formation of partial oxidation products of glycerol. Formic acid and a mono‐formate ester of glycerol were observed to be the major products together with a complex mixture of acetals. Increasing the pore size of the catalyst was investigated for Ti‐containing materials and it was found that increasing the pore size from ca. 0.5 nm for TS‐1 to 15 nm for a titania–silica co‐gel significantly increased the formation of partial oxidation products of glycerol, namely glyceraldehyde, dihydroxyacetone and glyceric acid. This revised version was published online in July 2006 with corrections to the Cover Date.     

Liquid Phase Oxidation of Glycerol Using a Single Phase (Au–Pd) Alloy Supported on Activated Carbon: Effect of Reaction Conditions

The liquid phase oxidation of glycerol has been studied over gold–palladium nanoparticles supported on activated carbon and synthesized by using a one-protocol synthesis. The effect of pressure, catalyst amount and base has been examined by using an autoclave reactor with molecular oxygen as oxidant at mild conditions. By choosing the appropriate reaction conditions control of selectivity could be possible, whereas activity is strongly dependent on catalyst amount and concentration of base.     

From Renewable to Fine Chemicals Through Selective Oxidation: The Case of Glycerol

Catalytic selective oxidation of glycerol is presented in terms of catalytic systems and experimental conditions. Unsupported gold nanoparticles (AuNPs), AuNPs on carbon and on TiO₂ were employed and compared in terms of reaction selectivity and activity. The role of the base and the formed hydrogen peroxide has been considered. Gold based catalysts showed selectivity that is strongly dependent of the reaction conditions. In particular C–C scission products increases by increasing the reaction temperature but correlated only partially with the rate of degradation of the H₂O₂ formed under the operative conditions. Moreover, under neutral/acidic conditions glycerol can be oxidised also by increasing the temperature slightly, but it leads to a detrimental effect on selectivity and catalyst life.     

Production of Biomass-Derived Chemicals and Energy: Chemocatalytic Conversions of Glycerol

The growing production of biodiesel as a renewable source-based fuel leads to an increased amount of glycerol. Thus, it is a favorable starting material to obtain highly functionalized products. From a variety of catalytic reactions three examples, namely glycerol oxidation, glycerol hydrogenolysis and aqueous-phase reforming, were chosen for detailed studies in our group. The experimental focus for the oxidation of glycerol was set on preparation and detailed examination of supported Pt–Bi catalysts in batch reactions as well as in continuous experiments using a trickle bed reactor. For aqueous-phase reforming of glycerol to hydrogen the addition of tin to supported platinum catalysts was investigated. Ruthenium and copper based catalysts could be successfully applied in the hydrogenolysis of glycerol to 1,2-propanediol.     

Magnetron sputtering of gold nanoparticles onto WO3 and activated carbon

In this paper we describe the production and investigation of two supported gold catalyst systems prepared by magnetron sputtering: Au on WO₃ and Au on activated carbon. The magnetron sputtering technique entails using an argon plasma to sputter a high purity gold target producing a flux of gold atoms which are deposited onto a constantly tumbling support material. This technique offers a number of advantages over conventional chemical preparation methods. One advantage is the ability to create gold nanoparticles (diameters <3 nm) on unusual support materials, such as WO₃ and carbon, which are generally not accessible using the ubiquitous deposition-precipitation technique. We present data demonstrating the formation of catalytic gold nanoparticles with average diameters of 1.7 nm (Au/C) and 2.1 nm (Au/WO₃), as well as a substantial number of single atom species on the Au/C sample. Prototypical carbon monoxide oxidation (Au/WO₃) and glycerol oxidation (Au/C) reactions were performed in order to gauge the activity of these catalysts. The WO₃ supported catalyst exhibits substantial catalytic activity from room temperature to 135 °C (0.0018–0.082 mol CO/mol Au s) with an activation energy near 23 kJ/mol. The activity of the Au/C catalyst was compared to a Au/C catalyst prepared from a poly(vinyl alcohol) (PVA) sol. The smaller catalysts prepared by sputtering are more active than the large gold particles prepared using the PVA sol, however the larger gold nanoparticles are substantially more selective towards the production of intermediate products from the oxidation of glycerol.     

Oxidation and reduction effects of propane–oxygen on Pd–chlorine/alumina catalysts

Pd–chloride precursor salt was used to prepare Pd/Al₂O₃ catalysts. TPSR measurements showed three distinct reactions for the oxidation of propane on palladium surface under excess of hydrocarbon: complete oxidation, steam reforming and propane hydrogenolysis. Propane oxidation on palladium catalysts was related to the Pd²⁺ sites observed on Pd/Al₂O₃ through infrared of adsorbed carbon monoxide. In fresh catalysts reduced by H₂, the IR spectra showed the linear and bridge adsorbed CO species on the Pd⁰ surface. After propane reaction, a new band at 2130 cm^-1 related to CO adsorption on Pd²⁺ species was noted. Carbon monoxide species adsorbed on Pd⁰ were also observed in all samples after reaction. Our results suggest surface ratios of Pd⁰/PdO during the propane oxidation. On the other hand, time on stream conversions of the complete oxidation of propane were affected by either the water generated during the reaction or added as a reactant at 10 vol%. The water generated by the reaction helped to eliminate chlorine residues in the form of oxychloride species leading to an increasing of the activity. However, the presence of water into the reaction mixture caused a strong decreasing of the activity. The inhibition mechanism of propane oxidation in the presence of water consisted in the dissociative adsorption of water on palladium sites with the possible formation of palladium hydroxide (Pd–OH) at the surface, diminishing the number of active surface sites. Dynamic fluctuations into the reaction conditions supported the idea that a pseudo‐equilibrium adsorption–desorption of water was reached. After water removal or increasing in the reaction temperature the equilibrium was shifted to the direction of OH–Pd decomposition. This behavior suggests that the inhibitory effect of water is a reversible phenomenon, being a function of the amount of water and the reaction temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Promotional effect of hydroxyl on the aqueous phase oxidation of carbon monoxide and glycerol over supported Au catalysts

Gold particles supported on carbon and titania were explored as catalysts for oxidation of CO or glycerol by O₂ at room temperature in liquid-phase water. Although Au/carbon catalysts were not active for vapor phase CO oxidation at room temperature, a turnover frequency of 5 s⁻¹ could be achieved with comparable CO concentration in aqueous solution containing 1 M NaOH. The turnover frequency on Au/carbon was a strong function of pH, decreasing by about a factor of 50 when the pH decreased from 14 to 0.3. Evidently, a catalytic oxidation route that was not available in the vapor phase is enabled by operation in the liquid water at high pH. Since Au/titania is active for vapor phase CO oxidation, the role of water, and therefore hydroxyl concentration, is not as significant as that for Au/carbon. Hydrogen peroxide is also produced during CO oxidation over Au in liquid water and increasing the hydroxyl concentration enhances its formation rate. For glycerol oxidation to glyceric acid (C₃) and glycolic acid (C₂) with O₂ (1–10 atm) at 308–333 K over supported Au particles, high pH is required for catalysis to occur. Similar to CO oxidation in liquid water, H₂O₂ is also produced during glycerol oxidation at high pH. The formation of the C-C cleavage product glycolic acid is attributed to peroxide in the reaction.     

Supported gold and gold palladium catalysts for selective chemical synthesis

Catalysts based on gold are now well established as very active and selective for broad ranges of redox reactions. Although primarily known for selective and preferential oxidation reactions, gold catalysts are also highly effective for selective hydrogenation. Hydrogenation reactions provide the focus for this perspective paper that is based on a François Gault lecture given at the Sabatier Conference in 2007. In particular, two reactions will be discussed; namely, the use of supported gold catalysts for selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols, and the use of supported gold palladium alloys for the direct hydrogenation of molecular oxygen to form hydrogen peroxide in preference to water.     

Application of heterogeneous colloid catalysts for the preparation of fine chemicals

Preprepared nanometals stabilized by surfactants may be used as precursors for a new type of heterogeneous catalyst. Independent of the support these mono– or plurimetallic precursors may be optimized dependent on the size, composition, and structure of the particles. Further, the active metal surface may be shielded against poisons by the protective shell. In addition, doping agents may be used in order to enhance the catalytic performance. The cis–selective partial hydrogenation of 3–hexyn–1–ol giving leaf alcohol, a valuable fragrance, and the selective oxidation of glucose giving sodium gluconate are current examples for the application of supported nanometal colloids in fine chemicals catalysis. This revised version was published online in June 2006 with corrections to the Cover Date.     

生物质的电化学转化反应及反应器

生物质通过电化学转化合成燃料和高附加值化学品是未来化学工业发展的一个重要方向，也是现代社会实现可持续发展的重要保障。在可再生能源产能不断提升，而现阶段暂无成熟的大规模能源存储技术的背景下，如何有效地利用可再生能源所产电能进行生物质的电化学转化是目前学术界和工业界关注的一个热点。本文介绍了近年来该领域的研究进展，着重阐释了关键的电化学反应和相关反应器的设计。从生物质衍生的平台分子的电化学转化取得了一定的进展，然而从生物质到平台分子的电化学转化还面临较大的挑战。提高平台分子和生物质电化学反应的选择性有赖于合适的电极材料和催化剂，而将原位分离与电极反应耦合的设计能够提高产物的收率，特别是在生物质直接电化学转化的过程中。     

Conversion of biomass products to energy sources in the presence of nanocatalysts and membrane-catalyst systems

A particular role in the harmonious exploitation of raw materials is assigned to organic sources of fuels based on renewable biomass. The most promising feedstocks of major energy sources, such as hydrogen and organic components of motor fuels, include ethanol and other bioalcohols, i.e., the primary products of its conversion. In this work, we describe the results for new reactions of conversion of ethanol and a mixture of ethanol and glycerol, which are the major products of biomass, to the C₃–C₁₀ alkane-olefin fraction in the presence of nanoscale mono- and bimetal-containing active components supported on γ-Al₂O₃ (〈d〉 = 5–8 nm) and on the inner surface of microchannels of ceramic membranes (〈d〉 = 15–20 nm). Mono- and bimetallic alkoxide and acetate complexes are used as precursors. It is found that the selectivity for the ethanol conversion to aliphatic hydrocarbons, as well as the content of branched structures, heavily depends on the nuclearity and composition of metal-complex precursors supported on γ-Al₂O₃. It is found for the first time that glycerol exhibits high reactionary ability in the reaction of cross-condensation of the carbon skeleton of alcohols of different nature. In the presence of a Ta-Re-containing system, a mixture of ethanol and glycerol is converted to 60% of C₄–C₁₀₊ olefins, which contain up to 50% of branched structures. It is shown that by varying the composition of Pd-Zn-containing active components, it is possible to targetedly convert ethanol to the olefin, alkane, or alkane-olefin fraction. Porous membrane-catalyst systems are designed to produce hydrogen and syngas from biomass products; the systems exhibit high activity in the carbon dioxide and steam reforming of ethanol, a mixture of ethanol and glycerol, and acetic acid. A scheme for the production of a wide range of valuable organic products based on bioalcohols containing no toxic impurities and independent of crude oil is described. According to this scheme, alkanes derived from ethanol and other bioalcohols are the major components of motor fuels; a large number of organic synthesis products can be derived from olefins, hydrogen, and carbon monoxide in the carbonylation/hydrocarbonylation processes.     

催化合成典型5-羟甲基糠醛衍生物的研究进展

作为重要的生物基平台化合物之一, 5-羟甲基糠醛(HMF)可通过可再生的生物质碳水化合物脱水制备, 已获得广泛关注, HMF可以催化合成一系列重要的有机化工中间体, 这逐渐成为研究热点。本文综述了5-羟甲基糠醛制备2,5-二甲酰基呋喃(DFF)、2,5-呋喃二甲酸(FDCA)和1,6-己二醇(HDO)三种典型HMF衍生物的研究进展, 并着重分析了HMF选择氧化制备DFF和FDCA的催化体系。介绍了该三种重要有机化工中间体的相关应用, 分析其制备过程中的问题与难点, 对其今后的研究方向提供了建议, 并指出目前HMF未大规模工业生产导致其价格昂贵, 是制约下游产品发展的重要因素。采用生物质为原料, 通过5-羟甲基糠醛催化合成下游有机化工产品的研究具有广阔的前景。