Conversion of Biorenewable Polyols over Supported Metal Catalysts

提案标题：生物可再生多元醇在负载型金属催化剂上的转化提案编号：CTS-0624608主要调查者：罗伯特·J·戴维斯研究所：弗吉尼亚大学主校区分析(决策的基本原理)：美国面临着重大的科学和技术挑战，以缓解其对石油和石油衍生产品日益增长的需求。全球石油产量将在本世纪达到峰值，实际上可能在未来50年内达到顶峰。要潜在地减少美国对进口石油的依赖，同时减少石油加工对环境的影响，一种战略是利用可再生的生物质衍生原料。将可再生分子转化为高价值的化学品需要各种多相催化剂。由于从生物质中获得的分子与石油中的碳氢化合物具有不同的性质，因此需要对中温下生物可再生原料在水环境中的催化转化进行新的研究。这项研究特别关注生物柴油合成的副产物甘油等可再生多元醇的催化反应。研究的主要假设是，通过添加第二种金属，可以合理地控制纳米Ru的氢解活性。双金属Ru-Pt和Ru-Re催化剂将通过表面氧化还原方法制备，即一种金属还原沉积在另一种还原纳米颗粒上。Ru-K、PtLIII和Re-LIII的原位X射线吸收光谱将用来评价高压下水相反应过程中金属的化学状态、局部结构和混合程度。高分辨率分析电子显微镜将被用来检查样品的均匀性和甘油反应引起的纳米级结构变化。对葡萄糖和巴豆醛氢化以及甘油氢解的详细动力学测量将有助于阐明双金属催化剂的基本结构-功能关系。该项目对人力资源开发的主要影响是对化学工程研究生和本科生的教育。一名研究生将在他或她的博士学习期间参与该项目。此外，至少有一名本科生将参与这一研究项目。该项目的研究生将在实验室指导本科生。这项研究的结果将在发表的期刊文章中报告，并在AIChE和ACS等组织的全国会议上发表，以及在与北美催化学会相关的国际会议上报告。除了本科生和研究生研究人员的培训外，弗吉尼亚大学还将提供一门新生水平的工程设计-建造入门课程，重点是生物可再生资源的催化转化。

AbstractProposal Title: Conversion of Biorenewable Polyols over Supported Metal Catalysts Proposal Number: CTS-0624608Principal Investigator: Robert J. DavisInstitution: University of Virginia Main CampusAnalysis (rationale for decision):The United States faces significant scientific and technical challenges to alleviate its growing demand for petroleum and petroleum-derived products. Worldwide production of petroleum will peak in this century and may actually occur within the next 50 years. One strategy to potentially diminish US reliance on imported oil while decreasing the environmental impact of petroleum processing involves the utilization of renewable, biomass-derived feedstocks. Transformation of renewable molecules to high value chemicals requires a variety of heterogeneous catalysts. Since the molecules obtained from biomass have different properties than hydrocarbons in petroleum, new research on the catalytic conversion of biorenewable feedstocks in aqueous environments at moderate temperatures is needed. This proposal focuses specifically on the catalytic reactions of a renewable polyol such as glycerol, a byproduct of biodiesel synthesis.The main hypothesis of the proposed research is that hydrogenolysis activity of Ru nanoparticles can be rationally manipulated by addition of a second metal. Bimetallic Ru-Pt and Ru-Re catalysts will be prepared by a surface redox method involving reductive deposition of one metal on reduced nanoparticles of the other. In situ X-ray absorption spectroscopy at the Ru K, Pt LIII, and Re LIII, will be used to evaluate the chemical state, local structure and degree of mixing of the metals during aqueous-phase reaction under high pressure. High-resolution analytical transmission electron microscopy will be used to examine sample uniformity and nanoscale structural changes resulting from reactions of the glycerol. Detailed kinetic measurements of the hydrogenation of glucose and crotonaldehyde, as well as the hydrogenolysis of glycerol will enable fundamental structure-function relationships to be elucidated for the bimetallic catalysts.The major impact of the project on development of human resources is the education of graduate and undergraduate chemical engineering students. One graduate student will participate in the project for the duration of his or her doctoral studies. In addition, at least one undergraduate student will participate in this research project. The graduate student on the project will be expected to mentor the undergraduate student in the laboratory. Results from this study will be reported in published journal articles and in presentations at national meetings of organizations like the AIChE and the ACS, as well as at international meetings such as those associated with the North American Catalysis Society. In addition to training of undergraduate and graduate researchers, a freshman-level Introduction to Engineering design-build course focusing on catalytic conversion of biorenewable resources will be offered at the University of Virginia.