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.

生物质衍生的资源的化学反应，以提供可以按照产生或进一步转化为一系列化学物质或燃料的平台分子的化学反应，这是可持续化学工业的关键，可以最大程度地减少碳排放。催化在生物质的价值中起关键作用。脱氧脱水（DODH）是一类有希望的化学反应，用于将生物质衍生的二醇化学物质转化为烯烃 - 后者在化学制造中具有广泛应用，目前主要由化石资源产生。目前，该领域缺乏有效的DODH催化剂。这项研究将提高人们对DODH催化的基本理解，并利用该理解来设计更有效的催化剂和最佳部署这些催化剂在现实世界化学制造过程中的方法。将通过与技术的研究人员合作 - 以色列海法的以色列技术研究所来实现项目目标。该项目的目标旨在获得机械知识，然后设计催化材料，以与各种底物和还原一起使用，以开发出可以有效地“嵌套无人驾驶和挑战的纽带组合”的高级支持，并探索效率融合的纽带，并构成了效率的融合，并构成了效率的组合，好处。具体而言，该项目将利用完整的专业知识，并在催化和动力学，有机和无机合成以及催化剂表征的国际团队之间培养协同作用。协作实验方法由四个工作包组成：（i）一种新的详细的催化剂评估方法，该方法通过单独测量的脱氧脱氧二氢循环的关键步骤来代替整体产量，并结合了对活动金属状态的分析，从而提供了深度机械机械的洞察力；（ii）设计和合成具有浓缩配体的新型，稳定的rhenium催化剂，对于固体和固定催化剂或属于表面相相应改性的载体的无机配体，它们可能是有机氧化还原稳定的配体；（iii）发达的分子和支持的催化剂的表征；（iv）探索主动部分的临时和部分固定，以此作为具有异质催化分离特征的同质过程的一种手段。综上所述，这项研究将确定新的固体和固体催化剂用于脱氧脱水，以及在复杂的多步周期中基准催化剂性能的新方法。更广泛地说，结果将推动目标应用的商业前景，生物质衍生的原料的脱氧脱水。新的支持和合成它们的方法将适用于其他催化剂和其他化学物质，动力学分析的新方法也适用。除了技术方面，该项目还将为研究生和本科生提供有关催化和反应工程，材料合成和材料表征的培训。国际学生交流将在材料设计和合成，均质和异质催化和动力学以及原位和操作方法方面，促进群体之间的交叉施肥。研究人员将将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性本科生以及对UMASS的两个计划 - Sengi和工程和计算职业日的妇女的贡献 - 以及以色列合作者向海法的当地高中进行宣传。这一奖项反映了NSF的法定任务，并通过评估律师的范围来表现出色的企业。