Collaborative Research: Understanding and manipulating the solvent microenvironment for selective, catalytic amination of renewable oxygenates

合作研究：了解和操纵溶剂微环境，用于可再生含氧化合物的选择性催化胺化

• 批准号: 1804843
• 负责人: Jesse Bond
• 金额: $ 22.5万
• 依托单位: Syracuse University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2021-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1804843&HistoricalAwards=false
• 关键词: Collaborative; Research; Understanding; manipulating; solvent

The initial steps of biomass refining involve breakdown of the raw material to a biocrude oil containing a mixture of building block chemicals. The building block chemicals can be further refined to higher value products, often in the liquid phase, with the aid of a solvent and a solid catalyst. This project will investigate the transformation of one of those building block chemicals, 3-hydroxybutryolactone (3HBA), to several higher-value chemicals. Theoretical analysis and experimental methods will be combined to understand how the solvent influences the performance of the catalyst in promoting conversion of 3HBA to the desired products. Results of the study can be applied more generally to other bio-based chemicals to support a growing bio-refining industry relevant for the transition to renewable chemical production. The project will contribute to a highly trained workforce of experts in biomass processing, while also adding to U.S. technical prominence in biomanufacturing of chemicals. A major goal of heterogeneous catalysis research is to identify active sites and to understand how they interact with reactants, products, and the bulk environment to facilitate chemical transformations. While most catalyst studies focus on catalyst discovery, it is often the bulk reaction environment that benefits most from redesign. The focus on solvation effects in heterogeneous catalysis has recently expanded with the trend toward liquid-phase, catalytic processing of biomass. Motivated by this shift, the project focuses on developing the scientific foundations needed for the rational design of solvent systems for catalytically processing renewable oxygenates. Specifically, the proposed research aims at understanding how the nature of the solvent microenvironment impacts activity and selectivity of ruthenium (Ru) catalysts during reductive amination of 3-HBA to form 2-amino-3-hydroxytetrahydrofuran and 3-aminotetrahydrofuran. The proposed combination of computational and experimental research is structured around (1) state-of-the-art density functional theory calculations, (2) machine learning tools for accelerating complex reaction network investigation, (3) microkinetic reactor modeling under various experimental reaction conditions, (4) vapor phase catalyst evaluation and kinetic isotope effect studies, (5) catalyst evaluations in condensed phases of water, ethanol, 1,4-dioxane, and cyclohexane, and (6) systematic correlation of experimental data with computational models through Bayesian statistical analysis. An iterative research loop is proposed, with experimental observations leading to hypotheses that motivate new computations, while computational models will rationalize experimental findings and guide new investigations. The research program includes undergraduate outreach, and research results will be integrated into undergraduate and graduate electives and the core chemical engineering curriculum at both Syracuse University and the University of South Carolina.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.

生物质精炼的初始步骤涉及将原材料分解为包含构建块化学物质混合物的生物乳油。 可以在溶剂和固体催化剂的帮助下，通常在液相中进一步完善构建块化学品。 该项目将调查其中一种基础化学物质，即3-羟基丁基酮（3HBA）向几种高价值化学物质的转化。 理论分析和实验方法将合并，以了解溶剂如何影响催化剂在促进3HBA转化为所需产品方面的性能。 该研究的结果可以更普遍地应用于其他基于生物的化学物质，以支持与可再生化学生产过渡相关的生物改造行业。 该项目将有助于训练有素的生物质加工专家劳动力，同时也增加了美国化学生物制造业的技术突出。 异质催化研究的一个主要目标是识别活跃的位点，并了解它们与反应物，产品和批量环境的相互作用，以促进化学转化。 尽管大多数催化剂研究都集中在催化剂发现上，但通常是重新设计的大量反应环境。在异质催化中，对溶剂化作用的重点最近随着液相，生物量的催化加工的趋势而扩展。在这一转变的驱动下，该项目着重于开发用于催化加工可再生氧合的溶剂系统所需的科学基础。具体而言，拟议的研究旨在了解溶剂微环境的性质如何影响3-HBA降低3-HBA时ruthenium（RU）催化剂的活性和选择性，以形成2-氨基-3-氨基-3-羟基甲状腺肿瘤和3-氨基甲基甲曲霉。 The proposed combination of computational and experimental research is structured around (1) state-of-the-art density functional theory calculations, (2) machine learning tools for accelerating complex reaction network investigation, (3) microkinetic reactor modeling under various experimental reaction conditions, (4) vapor phase catalyst evaluation and kinetic isotope effect studies, (5) catalyst evaluations in condensed phases of water, ethanol, 1,4-二恶烷和环己烷，以及（6）通过贝叶斯统计分析与计算模型的实验数据系统相关性。提出了一个迭代研究循环，实验性观察导致假设激发了新的计算，而计算模型将合理化实验发现并指导新的研究。该研究计划包括本科外展活动，研究结果将纳入本科和研究生选修课，以及锡拉丘兹大学和南卡罗来纳大学的核心化学工程课程。该奖项反映了NSF的法定任务，并被认为是通过基金会的智力功能和广泛影响的评估来评估CRETERIA的评估。