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NSF-BSF: Mechanism-Guided Design of Deoxydehydration Catalysts

NSF-BSF：脱氧脱水催化剂的机理引导设计

基本信息

批准号：
2227945
负责人：
Friederike Jentoft
金额：
$ 36.27万
依托单位：
University of Massachusetts Amherst
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2022
资助国家：
美国
起止时间：
2022-09-01 至 2025-08-31
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2227945&HistoricalAwards=false
关键词：
NSF BSF Mechanism Guided Design

项目摘要

Chemical reaction of biomass-derived resources to give platform molecules that can be used either as produced, or further converted into a range of chemicals or fuels, is key to a sustainable chemical industry that minimizes carbon emissions. Catalysis plays a key role in the valorization of biomass. Deoxydehydration (DODH) is a promising class of chemical reactions for converting biomass-derived diol chemicals to olefins – the latter having wide application in chemical manufacturing, and currently produced primarily from fossil resources. At present, the field lacks efficient DODH catalysts. The study will advance fundamental understanding of DODH catalysis, and use that understanding to design more efficient catalysts and ways of best deploying those catalysts in real-world chemical manufacturing processes. The project objectives will be achieved through collaboration with researchers at the Technion – Israel Institute of Technology in Haifa, Israel.The objectives of the project are to gain mechanistic knowledge and thereupon design catalytic materials for use with various substrates and reductants, to develop advanced supports that can efficiently "nest" the active moiety with no leaching, and to explore innovative approaches to bridge homogeneous and heterogeneous catalysis and combine their benefits. Specifically, the project will leverage complementary expertise and cultivate synergies between the international teams in the areas of catalysis and kinetics, organometallic and inorganic synthesis, and catalyst characterization. The collaborative experimental approach consists of four work packages: (i) A new and detailed catalyst evaluation approach that replaces overall yields by separately measured kinetics of the key steps in the deoxydehydration cycle and incorporates analysis of the state of the active metal by in situ spectroscopy, thus providing deep mechanistic insights; (ii) design and synthesis of new, stable rhenium catalysts with strongly complexing ligands, which may be organic redox-stable ligands for both soluble and immobilized catalysts, or inorganic ligands belonging to a surface-phase modified support; (iii) characterization of the developed molecular and supported catalysts; and (iv) exploration of temporary and partial immobilization of active moieties as a means to arrive at a homogeneous process with the separation characteristics of heterogeneous catalysis. Taken together, the research will identify new soluble and solid catalysts for deoxydehydration, and new methods for benchmarking catalyst performance in complex multistep cycles. More broadly, the results will advance the commercial prospects of the target application, deoxydehydration of biomass-derived feedstocks. The new supports and the methods to synthesize them will be applicable for other catalysts and other chemistries, as will novel approaches to kinetics analysis. Beyond the technical aspects, the project will provide training to both graduate and undergraduate students in cutting-edge methods of catalysis and reaction engineering, materials synthesis, and materials characterization. International student exchange will foster cross-fertilization between the groups with respect to materials design and synthesis, homogeneous and heterogeneous catalysis and kinetics, and in situ and operando methods. The researchers will integrate the state-of-the art information into their formal teaching. Broadened participation of underrepresented students will include recruiting of female undergraduate students and contributions to two programs at UMass - SENGI and the Women in Engineering and Computing Career Day - as well as outreach by the Israeli collaborator to local high schools in Haifa.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

生物质衍生资源的化学反应产生平台分子，这些分子可以在生产时使用，也可以进一步转化为一系列化学品或燃料，这是最大限度地减少碳排放的可持续化学工业的关键。催化剂在生物质的价值评估中起着关键作用。脱氧脱水（DODH）是用于将生物质衍生的二醇化学品转化为烯烃的一类有前途的化学反应，烯烃在化学制造中具有广泛的应用，并且目前主要由化石资源生产。目前，该领域缺乏有效的DODH催化剂。该研究将促进对DODH催化的基本理解，并利用这种理解来设计更有效的催化剂以及在现实世界的化学制造过程中最好地部署这些催化剂的方法。该项目的目标将通过与以色列海法的Technion -以色列理工学院的研究人员合作来实现。该项目的目标是获得机理知识，从而设计用于各种底物和还原剂的催化材料，开发能够有效地“嵌套”活性部分而不浸出的先进载体，并探索创新的方法来连接均相和多相催化并将它们的益处联合收割机结合起来。具体而言，该项目将利用互补的专业知识，培养国际团队在催化和动力学、有机金属和无机合成以及催化剂表征领域的协同作用。合作实验方法由四个工作包组成：㈠新的详细催化剂评价方法，用脱氧脱水循环中关键步骤的单独测量动力学取代总产率，并采用现场光谱法分析活性金属的状态，从而提供深入的机理见解;（ii）设计和合成具有强络合配体的新的、稳定的氧化还原催化剂，所述配体可以是用于可溶性和固定化催化剂的有机氧化还原稳定配体，或属于表面相改性载体的无机配体;（iii）表征所开发的分子和负载型催化剂;以及（iv）探索活性部分的暂时和部分固定化，作为达到具有多相催化的分离特征的均相过程的手段。总而言之，该研究将确定用于脱氧脱水的新型可溶性和固体催化剂，以及在复杂多步循环中对催化剂性能进行基准测试的新方法。更广泛地说，这些结果将推进目标应用的商业前景，生物质衍生原料的脱氧脱水。新的载体和合成它们的方法将适用于其他催化剂和其他化学品，以及新的动力学分析方法。除了技术方面，该项目还将为研究生和本科生提供催化和反应工程，材料合成和材料表征的尖端方法的培训。国际学生交流将促进材料设计和合成，均相和非均相催化和动力学，以及原位和操作方法之间的相互交流。研究人员将把最先进的信息整合到他们的正式教学中。扩大代表性不足的学生的参与将包括招募女本科生，并为马萨诸塞大学的两个项目---- SENGI和妇女在工程和计算职业日----做出贡献。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响进行评估，被认为值得支持审查标准。