Elucidating Solvent Effects in Biomass Conversion Reactions by means of Operando Spectroscopy

本研究旨在阐明控制生物质转化反应中催化剂的反应速率、选择性和稳定性的溶剂化效应背后的基本原理。了解生物质加工过程中溶剂化效应的兴趣源于这样一个事实，即高活性和功能化分子（如生物质衍生的中间体）的转化可能受到均相和/或非均相活性位点周围溶剂的影响。这些系统的复杂性需要一种范式转变和一种更大灵活性的变革方法，在现实的操作条件下，催化剂和溶剂在一个单一的光学反应器中以时间和空间分解的方式同时研究。提出的综合框架侧重于葡萄糖异构化反应，这被认为是纤维素生物质催化转化为生物燃料和化学品的主要瓶颈。该框架的发展可以使溶剂和催化剂的选择变得合理和可预测，并将对各个学科和行业产生巨大的影响。本项目的主要研究目的是研究催化剂的活性位点，并利用operando光谱技术阐明生物质反应的潜在机制。该提案旨在解决与实施催化生物精炼厂概念相关的基本挑战。尽管溶剂-溶质-催化剂的相互作用对催化剂的性能有深远的影响，但目前对它们的了解甚少。拟议的工作将侧重于设计和开发一种多功能多光谱光学电池反应器原型，该反应器允许生成与传统催化液相反应器相似的催化性能数据。该反应器将在实际工作条件下通过耦合研究葡萄糖异构化反应，首次在生物质加工中应用反应诱导差红外光谱（RIDIS）和拉曼光谱。该研究可为生物质转化反应的结构-功能关系提供分子水平的信息。建议的研究和教育的整合，旨在创造一个智力刺激的环境，培养学生在催化和反应工程。拟议的外展计划针对的是来自不同背景的学生和STEM领域代表性不足的人群。

The research aims at elucidating the underlying principles behind solvation effects that govern the reaction rates, selectivity and stability of catalysts in biomass conversion reactions. The interest in understanding solvation effects during biomass processing arises from the fact that the conversion of highly reactive and functionalized molecules, such as biomass derived intermediates, can be influenced by the solvent surrounding the homogeneous and/or heterogeneous active site(s). The complexity of these systems demands a paradigm shift and a transformative approach towards greater flexibility, where catalysts and solvents are studied simultaneously in one single optical reactor in a time- and spatially-resolved manner under realistic operating conditions. The proposed integrated framework focuses on the glucose isomerization reaction, which is considered the major bottleneck in the catalytic conversion of cellulosic biomass to biofuels and chemicals. The development of this framework can render solvent and catalyst selection rational and predictable and will have a tremendous impact on various disciplines and industries.The main research objective of this project is to investigate the active site(s) in a catalyst and elucidate the underlying mechanisms in biomass reactions by means of operando spectroscopy. The proposal aims to address the fundamental challenges associated with implementing the concept of catalytic bio-refineries. Despite their profound effect on catalyst performance, solvent-solute-catalyst interactions are currently poorly understood. The proposed work will focus on the design and development of a versatile prototype multi-spectroscopic optical cell-reactor that allows the generation of catalytic performance data similar to those achieved with conventional catalytic liquid phase reactors. This reactor will be utilized to study glucose isomerization reaction under real working conditions by coupling, for the first time in biomass processing, Reaction Induced Difference Infrared Spectroscopy (RIDIS) and Raman spectroscopy. The proposed research may provide molecular-level information on structure-function relationships in biomass conversion reactions. The proposed integration of research and education aims at creating an intellectually stimulating environment for training students on catalysis ad reaction engineering. The proposed outreach plan is targeting students from diverse backgrounds and underrepresented populations in STEM fields.