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

用于糠醛衍生物“无氢”加氢的双金属催化剂。

• 批准号: 1792108
• 金额: --
• 依托单位: University of St Andrews
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2016
• 资助国家: 英国
• 起止时间: 2016 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-1792108
• 关键词: Bimetallic; catalysts; hydrogen; free; hydrogenation

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

该项目与EPSRC资助的Chris Baddeley教授和Mark Keane教授（Heriot-Watt大学化学工程）之间的合作有关，旨在设计在连续流操作中具有增强催化活性的“无氢”选择性加氢的催化剂。Au已被证明是超选择性氢化的有效催化剂，但其催化活性受到缓慢的H2解离步骤的限制。初步研究表明，耦合2-丁醇脱氢（提供活性氢）与糠醛加氢（糠醇）的氧化物负载的Au和Cu的物理混合物的结果在数量级提高H2利用率在耦合系统和提高选择性加氢速率相对于单组分Au催化剂。Cu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，因此对于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，可以用作非石油基的可再生原料。目标糠醇产品是一种高价值化学品，用于制造树脂/橡胶/粘合剂，并作为药物合成的化学构件。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），从根本上了解耦合脱氢/氢化过程的机理。金属纳米颗粒将沉积在平坦的氧化物表面上，以提供可以通过表面技术详细分析的真实的催化系统的模型。研究了2-丁醇和糠醛在Cu、Au和Cu-Au-Au纳米粒子上的竞争吸附。这项工作将首先集中在金属/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。由表面表征提供的分子水平的机械理解，再加上气相试剂对表面组成的影响的测定（哈德斯菲尔德大学的MEIS设施），将为合成支持的Cu-Au纳米晶系统提供信息。一个合理的催化剂设计计划将直接实现催化剂配方，提供最佳的氢气利用效率。请列出任何商定的培训要求：参加相关的学校学术讨论会完成以下PG课程的选择：学术写作;高级光谱方法;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，嵌入和电池;纳米结构材料

项目成果

Structure and Reactivity of Cu-doped Au(111) Surfaces

Cu 掺杂 Au(111) 表面的结构和反应性

• DOI: 10.1380/ejssnt.2018.163
• 发表时间: 2018
• 期刊: e-Journal of Surface Science and Nanotechnology
• 影响因子: 0.7
• 作者: Grillo F

Thermal behaviour of Cu and Au nanoparticles grown on CeO2 thin films

• DOI: 10.1016/j.apsusc.2021.151656
• 发表时间: 2021-10
• 期刊: Applied Surface Science
• 影响因子: 6.7
• 作者: R. Megginson;F. Grillo;S. Francis;V. Z. C. Paes;H. Trombini;P. L. Grande;A. Rossall;J. van den Berg;C.J. Baddeley conceptualisation

Structural and electronic characterization of Cu/Au(111) near-surface alloys

• DOI: 10.7567/1347-4065/ab1b5b
• 发表时间: 2019-06
• 期刊: Japanese Journal of Applied Physics
• 影响因子: 1.5
• 作者: F. Grillo;R. Megginson;D. Batchelor;M. Muntwiler;C. Baddeley

Phenylacetylene hydrogenation coupled with benzyl alcohol dehydrogenation over Cu/CeO2: A consideration of Cu oxidation state

• DOI: 10.1016/j.jcat.2020.11.002
• 发表时间: 2020-11
• 期刊: Journal of Catalysis
• 影响因子: 7.3
• 作者: Chiara Pischetola;S. Francis;F. Grillo;C. Baddeley;F. Cárdenas-Lizana