Rational Design of Selective Hydrodeoxygenation Catalysts for Organic Acids

美国国家科学基金会化学部的化学催化项目支持Andreas Heyden教授和联合PI教授John R。Monnier和Christopher T.来自南卡罗来纳州大学的威廉姆斯研究了基础科学，该科学可以导致开发高度选择性的催化材料，用于使用木质纤维素生物质的快速热解来升级生物油。 计算和实验相结合的研究方法将（a）获得对气相和液相（水和正丁醇）环境中有机酸在第VIII族过渡金属催化剂上的非均相催化加氢脱氧（HDO）的反应机理的基本理解和（B）合理设计用于将有机酸选择性转化为醇和烷烃的新型负载金属催化剂。该研究方法严格整合了（a）最先进的计算多相催化工具，如平面波密度泛函理论（DFT）、隐式连续溶剂化模型、d带模型、Brønsted-Evans-Polanyi（BEP）关系、标度关系、微动力学建模、坎贝尔的速率和选择性控制程度，和多维火山曲线，以及（B）结合新的催化剂合成方法的实验程序（无电极沉积）与结构和电子表征技术，原位振动光谱，和使用现有技术的单程流动反应器和高压间歇反应器的动力学评价。 计算研究将产生激发新实验的假设，而实验观察将证实理论发现并激发新的计算研究。 将生物质转化为有用的燃料和化学品是可持续化学的一个基本目标。本项目的基本目标是为合理设计新型非均相催化剂建立科学基础，该催化剂具有上级活性和选择性，用于与从木质纤维素生物质中获得的生物油升级相关的有机酸的HDO。其目的是增加对HDO反应机理的理解，并减少设计新的非均相催化剂所需的时间和财政资源，以满足资源有限的世界不断变化的需求。 最后，参与该项目的博士生将成为计算和实验催化的实践和整合方面的专家。 来自代表性不足群体的研究生将通过南加州大学化学工程学院正在进行的斯隆少数族裔研究生奖学金和东南研究生教育联盟和教授（SEAGEP）项目来吸引。 此外，研究成果将被整合到联合研究生和本科生选修课“多尺度建模：从电子到化学反应器”和“催化”和核心化学工程课程。

The Chemical Catalysis Program in the Chemistry Division at the National Science Foundation supports Professor Andreas Heyden and co-PIs Professor John R. Monnier and Professor Christopher T. Williams from the University of South Carolina to investigate the underlying science that can lead to the development of highly selective, catalytic materials for upgrading of bio-oils using fast pyrolysis of lignocellulosic biomass. A combined computational and experimental research approach will (a) obtain fundamental understanding of the reaction mechanism of the heterogeneous, catalytic hydrodeoxygenation (HDO) of organic acids on Group VIII transition metal catalysts in both a gas phase and liquid phase (water and n-butanol) environment and (b) rationally design novel supported metal catalysts for the selective conversion of organic acids into alcohols and alkanes. The research approach rigorously integrates (a) state-of-the-art computational heterogeneous catalysis tools such as plane wave density functional theory (DFT), implicit continuum solvation models, d-band models, Brønsted-Evans-Polanyi (BEP) relationships, scaling relations, microkinetic modeling, Campbell's degree of rate and selectivity control, and multi-dimensional volcano curves with (b) an experimental program that combines a novel bimetallic catalyst synthesis methodology (electrode less deposition) with structural and electronic characterization techniques, in-situ vibrational spectroscopy, and kinetic evaluation using state of the art single pass flow reactors and high pressure batch reactors. The computational studies will lead to hypotheses that motivate new experiments, while experimental observations will confirm theoretical findings and inspire new computational investigations. The conversion of biomass to useful fuels and chemicals is an essential goal of sustainable chemistry. The fundamental objective of this project is to establish a scientific basis for the rational design of novel heterogeneous catalysts with superior activity and selectivity for the HDO of organic acids relevant for upgrading of bio-oils obtained from lignocellulosic biomass. The aim is to increase the understanding of HDO reaction mechanisms and reduce the time and financial resources needed for the design of new heterogeneous catalysts tailored to meet the changing needs of a world with limited resources. Finally, the PhD students involved in this project will become experts in the practice and integration of computational and experimental catalysis. Graduate students from underrepresented groups will be attracted through the ongoing Sloan Minority Graduate Fellowship and Southeast Alliance for Graduate Education and the Professoriate (SEAGEP) programs that are available within Chemical Engineering at USC. Also, the research results will be integrated into the joint graduate and undergraduate electives"Multiscale Modeling: From Electrons to Chemical Reactors" and "Catalysis" and the core chemical engineering curriculum.