Understanding and Controlling Reactivity of Functionalized Alcohols on Metal Surfaces

在这个由化学催化项目资助的项目中，科罗拉多大学博尔德分校的威尔·梅德林教授将研究官能醇在金属表面的反应。其目的是确定设计用于生物质衍生化合物选择性反应的固体催化剂的方法。表面光谱将与量子化学建模结合使用，以了解醇的分子结构如何控制它们在工业催化剂中通常用作活性成分的金属表面上的反应活性。分子结构的作用将与侧链官能团对C-OH键强度的影响以及对化学吸附的醇的几何形状的影响有关。为了控制反应的选择性，这项工作将研究表面改性剂的使用，这种表面改性剂有利于官能醇在金属表面上以特定的几何形状吸附。作为一个具有现实意义的特定模型系统，将使用糠醇选择性氢解来检验本项目中开发的催化剂设计原理。这项研究旨在为可再生生物质原料转化为燃料和化学品取得重要进展。从生物质衍生的糖可以大量生产功能醇，如呋喃醇和5-羟甲基呋喃甲醛。由于试剂的复杂性，对有选择地将这些中间体转化为所需产品的坚固固体催化剂的鉴定受到阻碍。通过制定这类催化剂的基本设计原则，这项工作可以带来生产燃料和有用化学品的新的、可持续的途径。研究生将为该项目进行研究，他们的研究影响将通过与国家可再生能源实验室的研究人员正在进行的合作而扩大。本科生还将在研究生研究的基础上，对自己的小规模项目进行独立研究。最后，将通过首席研究员发挥积极或领导作用的现有方案，组织面向普通受众的外联活动，这些方案包括可再生能源材料研究科学和工程中心、科罗拉多州生物精炼和生物燃料中心以及可再生和可持续能源研究所。

In this project funded by the Chemical Catalysis Program, Prof. Will Medlin of the University of Colorado at Boulder will investigate the reactions of functional alcohols on metal surfaces. The objective is to identify methods to design solid catalysts for selective reactions of biomass-derived compounds. Surface spectroscopy will be used in conjunction with quantum chemical modeling to understand how the molecular structure of alcohols controls their reactivity on the surfaces of metals that are commonly used as active components in industrial catalysts. The role of molecular structure will be linked to the influence of pendant functional groups on C-OH bond strength and on the geometry of the chemisorbed alcohol. For the purpose of controlling reaction selectivity, this work will investigate the use of surface modifiers that favor the adsorption of functional alcohols in specific geometries above metal surfaces. As a specific model system of real-world importance, the selective hydrogenolysis of furfuryl alcohol will be used to test the catalyst design principles developed in this project.This research is directed toward making important advances for the conversion of renewable biomass feedstocks to fuels and chemicals. Functional alcohols such as furfuryl alcohol and 5-hydroxymethylfurfural can be produced in large volumes from biomass-derived sugars. Identification of robust solid catalysts that selectively convert these intermediates to desired products is hampered by the complexity of the reagents. By developing fundamental design principles for such catalysts, this work can lead to new, sustainable pathways for production of fuels and useful chemicals. Graduate students will conduct research for the project, and the impact of their research will be extended from ongoing collaborations with researchers at the National Renewable Energy Laboratory. Undergraduate students will also conduct independent research on their own small-scale projects that build on the research of graduate students. Finally, outreach activities oriented toward a general audience will be organized through existing programs in which the principal investigator plays an active or leadership role, including the Renewable Energy Materials Research Science and Engineering Center, the Colorado Center for Biorefining and Biofuels, and the Renewable and Sustainable Energy Institute.