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包括将原材料分解为含有结构单元化学品混合物的生物原油。 在溶剂和固体催化剂的帮助下，结构单元化学品可以进一步精制成更高价值的产品，通常在液相中。 该项目将研究其中一种结构单元化学品3-羟基丁内酯（3 HBA）转化为几种更高价值的化学品。 将理论分析和实验方法相结合，以了解溶剂如何影响催化剂的性能，促进转化为所需的产品3 HBA。 该研究的结果可以更广泛地应用于其他生物基化学品，以支持与向可再生化学品生产过渡相关的不断增长的生物精炼行业。 该项目将为生物质加工领域训练有素的专家队伍做出贡献，同时也增加了美国在化学品生物制造方面的技术优势。 多相催化研究的一个主要目标是确定活性位点，并了解它们如何与反应物，产物和本体环境相互作用，以促进化学转化。 虽然大多数催化剂研究都集中在催化剂的发现上，但从重新设计中受益最多的往往是本体反应环境。近年来，随着生物质液相催化加工技术的发展，对多相催化中溶剂化效应的关注也在不断扩大。受这一转变的推动，该项目的重点是开发催化处理可再生含氧化合物的溶剂系统的合理设计所需的科学基础。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钌（Ru）催化剂在3-HBA还原胺化形成2-氨基-3-羟基四氢呋喃和3-氨基四氢呋喃过程中的活性和选择性。计算和实验研究的拟议组合是围绕（1）最先进的密度泛函理论计算，（2）用于加速复杂反应网络研究的机器学习工具，（3）各种实验反应条件下的微动力学反应器建模，（4）气相催化剂评价和动力学同位素效应研究，（5）水凝聚相中的催化剂评价，乙醇，1，4-二氧六环和环己烷，和（6）通过贝叶斯统计分析的实验数据与计算模型的系统相关性。提出了一个迭代的研究循环，实验观察导致的假设，激发新的计算，而计算模型将合理化实验结果，并指导新的调查。该研究计划包括本科生外展，研究成果将被整合到本科生和研究生选修课，以及锡拉丘兹大学和南卡罗来纳州大学的核心化学工程课程。该奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。