CAREER: Toward unprecedented selectivities in C-O bond cleavage reactions using Fe-based bimetallic catalysts

职业生涯：使用铁基双金属催化剂实现 C-O 键裂解反应前所未有的选择性

• 批准号: 1351609
• 负责人: Jason Hicks
• 金额: $ 40万
• 依托单位: University of Notre Dame
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-07-01 至 2020-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1351609&HistoricalAwards=false
• 关键词: CAREER; Toward; unprecedented; selectivities; bond

Abstract Title: Selective, bimetallic non-noble metal phosphide catalysts for C-O bond cleavage reactions necessary for lignocellulosic biomass conversion.Abstract Content:Utilization of biomass for fuels and chemicals is an important component of a sustainable and secure national energy plan, but the design and development of new catalysts is needed to enable this aim. Specifically, catalysts that selectively cleave C-O bonds, which are ubiquitous in biomass, are needed to efficiently and effectively convert biomass to value-added liquid products and fuels. The novel, iron-based bimetallic catalysts developed by PI Jason Hicks at the University of Notre Dame address this need using earth abundant transition metals which are not only highly selective for these reactions but also offer environmental benefits over existing catalysts and technologies. Using this NSF CAREER award, Prof. Hicks will seek the optimum catalysts for the bond breakage reactions, and will seek some fundamental factors that will point directions for improvements in these catalysts. In addition to the specific research aims, this CAREER project also benefits student education by planning for research in the laboratory by undergraduate and high school students, and development of a new Heterogeneous Catalyst Design course and Graduate Research Symposium at the University of Notre Dame. These activities integrate research with education of future scientists to address the challenge of sustainable energy.The primary goals of this project are to thoroughly investigate the stability, reactivity, and selectivity of bimetallic Fe and Mo based phosphide catalysts for C-O bond cleavage reactions of biomass model compounds, targeting those bonds most relevant to bio-based feedstocks. Bimetallic catalysts often exhibit enhanced catalytic activity and/or selectivity compared to monometallic catalysts for many reactions, including the production of biofuels and bio-derived chemicals. The ability to tune the performance of a catalyst by incorporating another metal or additive can, therefore, have profound effects on the reaction pathway and provide more control over the catalytic selectivity. The CAREER proposal is focused primarily on transition metal phosphide catalysts for these important reactions. Metallic phosphides are a class of materials that have tunable structural and chemical characteristics based on the metals used, ratio of metals to phosphorus, and synthesis parameters. Phosphides can be synthesized as well-defined crystalline powders, nanoparticles, or supported catalysts, depending on the desired application. Experimental studies by the Hicks group on these catalytic materials indicate possible selectivities for C-O bond cleavage of phenolic model compounds greater than 90%. Based on these initial results, the proposed Project involves the synthesis of unique bimetallic phosphide catalysts with various metal compositions to ultimately control the catalyst performance. Additionally, reaction mechanisms for the hydrodeoxygenation of phenolic compounds using these catalysts, as well as other oxygenated compounds found in bio-oils, will be studied. Together with bulk and surface characterization techniques, catalyst structure/performance relationships will be determined to elucidate the properties of these catalytic materials. Ultimately, the PI aims to develop sustainable energy processes and pathways to cleaner fuels production by leveraging rational catalyst design to enhance the conversion of lignin and lignocellulosic materials to liquid transportation fuels and chemicals.

摘要标题：选择性，非贵金属磷化物催化剂的C-O键裂解反应所需的木质纤维素生物质conversion.Abstract Content：利用生物质的燃料和化学品是一个可持续的和安全的国家能源计划的重要组成部分，但需要设计和开发新的催化剂，使这一目标。具体而言，需要选择性裂解生物质中普遍存在的C-O键的催化剂来高效且有效地将生物质转化为增值的液体产物和燃料。圣母大学PI Jason Hicks开发的新型铁基催化剂使用地球上丰富的过渡金属来满足这一需求，这些金属不仅对这些反应具有高度选择性，而且还提供了比现有催化剂和技术更好的环境效益。利用这个NSF CAREER奖，希克斯教授将寻求键断裂反应的最佳催化剂，并将寻求一些基本因素，这些因素将为这些催化剂的改进指明方向。除了具体的研究目标，这个职业生涯项目也有利于学生教育的本科生和高中生在实验室的研究规划，并在圣母大学开发一个新的多相催化剂设计课程和研究生研究研讨会。这些活动将研究与未来科学家的教育相结合，以应对可持续能源的挑战。本项目的主要目标是彻底研究铁和钼基磷化物催化剂的稳定性，反应性和选择性，用于生物质模型化合物的C-O键裂解反应，目标是与生物基原料最相关的那些键。 对于许多反应，包括生物燃料和生物衍生化学品的生产，双金属催化剂与单金属催化剂相比通常表现出增强的催化活性和/或选择性。 因此，通过掺入另一种金属或添加剂来调节催化剂性能的能力可以对反应途径产生深远的影响，并对催化选择性提供更多的控制。 CAREER的建议主要集中在这些重要反应的过渡金属磷化物催化剂上。 金属磷化物是一类具有可调结构和化学特性的材料，其基于所使用的金属、金属与磷的比率以及合成参数。 磷化物可以合成为明确定义的晶体粉末，纳米颗粒或负载型催化剂，这取决于所需的应用。 Hicks小组对这些催化材料的实验研究表明，酚类模型化合物的C-O键断裂的选择性可能大于90%。 基于这些初步结果，拟议项目涉及合成具有各种金属成分的独特磷化物催化剂，以最终控制催化剂性能。 此外，还将研究使用这些催化剂对酚类化合物以及生物油中发现的其他含氧化合物进行加氢脱氧的反应机理。 连同本体和表面表征技术，催化剂的结构/性能的关系将被确定，以阐明这些催化材料的性能。 最终，PI旨在通过利用合理的催化剂设计来开发可持续的能源工艺和清洁燃料生产途径，以提高木质素和木质纤维素材料向液体运输燃料和化学品的转化。