Bimetallic catalysts for "hydrogen-free" hydrogenation of furfural derivatives.

该项目与EPSRC资助的Chris Baddeley教授和Mark Keane教授（赫瑞瓦特大学化学工程）合作有关，旨在设计在连续流动操作中具有增强“无氢”选择性加氢催化活性的双金属催化剂。金已被证明是一种有效的超选择性氢化催化剂，但其催化活性受到H2解离步骤缓慢的限制。初步研究表明，在氧化负载的Au和Cu的物理混合物上，将2-丁醇脱氢（提供活性氢）与糠醛加氢（生成糠醇）偶联，可以显著提高偶联体系中H2的利用率，并且相对于单组分Au催化剂提高选择性加氢速率。铜的作用被认为是为脱氢步骤提供活性位点。这种耦合系统不需要在高压下使用H2，因此对大规模催化过程具有潜在的重要安全意义。糠醛是一种生物质衍生的杂环醛，可以作为一种非石油基的可再生原料。目标糠醇产品是一种高价值的化学品，用于制造树脂/橡胶/粘合剂，并作为药物合成的化学基石。该项目旨在通过一系列表面测量，包括扫描隧道显微镜（STM）、FTIR光谱、x射线光电子能谱（XPS）和中能离子散射（MEIS），对耦合脱氢/加氢过程的机制有一个基本的了解。金属纳米颗粒将沉积在平坦的氧化物表面上，以提供真实催化系统的模型，这些模型可以通过表面技术进行详细分析。研究了2-丁醇和糠醛在负载型Cu、Au和双金属CuAu纳米颗粒上的竞争吸附。这项工作将首先关注金属/载体界面和纳米颗粒组成对表面化学和催化反应性的影响。通过表面表征和确定气相试剂对表面组成的影响（哈德斯菲尔德大学的MEIS设施）提供的分子水平的机制理解将为支持Cu-Au双金属体系的合成提供信息。一项合理的催化剂设计计划将被实施，旨在实现催化剂配方，提供最佳的氢利用效率。请列出任何商定的培训要求：参加相关的学校座谈会；完成以下PG课程的选择：学术写作；先进光谱方法；表面化学;多相催化;电子结构计算的化学应用固态电化学ⅰ，离子传导，插层与电池；纳米材料

This project is related to an EPSRC funded collaboration between Prof Chris Baddeley and Prof Mark Keane (Chemical Engineering, Heriot-Watt University) that aims to design bimetallic catalysts with enhanced catalytic activity in "hydrogen free" selective hydrogenation in continuous flow operation. Au has been shown to be an effective catalyst for ultraselective hydrogenation, but its catalytic activity is limited by the slow H2 dissociation step. Preliminary studies show that coupling of 2-butanol dehydrogenation (to provide reactive hydrogen) with furfural hydrogenation (to furfuryl alcohol) over physical mixtures of oxide supported Au and Cu results in orders of magnitude enhanced H2 utilisation in the coupled system and elevated selective hydrogenation rate relative to the single component Au catalyst. The role of Cu is thought to be to provide active sites for the dehydrogenation step. This coupled system does not necessitate the use of H2 at high pressure, so has potentially important safety implications for large scale catalytic processes.Furfural is a biomass derived heterocyclic aldehyde that can serve as a non-petroleum based renewable feedstock. The target furfuryl alcohol product is a high value chemical used to manufacture resins/rubbers/adhesives and as a chemical building block for drug synthesis. The project sets out to gain a fundamental understanding of the mechanism of the coupled dehydrogenation/ hydrogenation process through a range of surface measurements including scanning tunnelling microscopy (STM) FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS) and medium energy ion scattering (MEIS). Metal nanoparticles will be deposited onto flat oxide surfaces to provide models of the real catalytic systems that can be analysed in detail by surface techniques. The competitive adsorption of 2-butanol and furfural will be examined on supported nanoparticles of Cu, Au and bimetallic CuAu. The work will first focus on the influence of the metal/support interface and nanoparticle composition on the surface chemistry and catalytic reactivity. The molecular-level mechanistic understanding provided by the surface characterisation coupled with a determination of the influence of gas phase reagents on surface composition (MEIS facility at the University of Huddersfield) will inform synthesis of supported Cu-Au bimetallic systems. A programme of rational catalyst design will be undertaken directed at achieving the catalyst formulation that delivers the optimum hydrogen utilisation efficiency.Please list any agreed training requirements:Attendance at relevant School ColloquiaCompletion of a selection of the following PG courses: Academic Writing; Advanced Spectroscopic Methods; Surface Chemistry; Heterogeneous Catalysis; Chemical Applications of Electronic Structure Calculations; Solid State Electrochemistry I, Ionic Conduction, Intercalation and Batteries; Nanostructured Materials