Collaborative Research: SusChEM: Manipulation of Reaction Selectivity in the electrochemical environment for biomass-to-chemicals conversions

合作研究：SusChEM：生物质到化学品转化的电化学环境中反应选择性的操纵

• 批准号: 1665176
• 负责人: Adam Holewinski
• 金额: $ 43万
• 依托单位: University of Colorado at Boulder
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-09-01 至 2020-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665176&HistoricalAwards=false
• 关键词: Collaborative; Research; SusChEM; Manipulation; Reaction; Collaborative; Research; SusChEM; Manipulation; Reaction

Manipulation of reaction selectivity in the electrochemical environment for biomass-to-chemicals conversions Fuels and chemicals derived from plant matter (biomass) are a promising means to sustainably meet demands for energy and commodity products. Biomass is a "carbon neutral" feedstock because it grows by incorporating CO2 from the atmosphere while only consuming solar energy. This project is finding new and efficient outlets to generate useful chemicals from components of biomass that are currently difficult to process. While most biomass conversions are presently performed using catalysts and energy supplied by heat, this work is exploiting unique aspects of electricity-driven catalytic reactions in order to achieve synthesis of useful chemicals at low temperatures and pressures. The electricity required for these processes may, in turn, be derived from renewable sources such as wind and solar. A fundamental approach is being taken in which experimental techniques that probe the nature of the catalytic reactions are combined with computer simulations to build a comprehensive picture of the factors that govern reaction selectivity and to design more efficient processes. Insights from this work have broader application in extending the scope of green chemistry. This research is also being used to promote science education by involving undergraduate student researchers for summer internships, and the PI's are additionally developing a series of interactive educational modules related to understanding the physical processes governing electro-catalytic reactions. This project is investigating electrochemical control over selectivity in the conversion of biomass-derived feedstocks to desired chemical targets. Electrochemical conversions offer advantages in sustainable processing since they generally operate at low temperatures and utilize aqueous feedstocks directly. Using selective oxidation of furfural and 5-hydroxymethyl furfural over Pt electrodes as probe systems, this work focuses on determining the different mechanisms by which selectivity can be manipulated through control over electrode potential and composition. Mechanisms being explored include differentiation of charge-transfer reactions relative to neutral atom transfer reactions, variation in surface coverage of oxygen and organic species, and the role of promoters with specific reactivity or geometry. Three complementary research approaches are being integrated to characterize these effects. Measurement of electrochemical kinetics on metal catalysts is combined with in-situ spectroscopy to identify reaction pathways; surface science experiments are used on a model Pt(111) surface to study oxidation elementary steps in detail; and finally, density functional theory calculations are used to investigate the same surface chemistry, including simulation of electric potential effects and the water-metal interface. The three research thrusts provide complementary information and enrich the depth of understanding of the electrochemical environment. Insights from this work have broader application in extending the scope of green chemistry and electrochemical synthetic routes. This research is also being used to promote science education by involving undergraduate student researchers for summer internships, and the PI's are additionally developing a series of interactive educational modules related to understanding the physical processes governing electro-catalytic reactions.

在电化学环境中操纵反应选择性的生物质到化学物质转化燃料和源自植物质量的化学物质（生物量）是可持续地满足能源和商品产品需求的一种有希望的方法。生物质是一种“碳中性”原料，因为它通过仅消耗太阳能而在大气中掺入二氧化碳来生长。该项目正在寻找新的高效插座，以从目前难以处理的生物量的组成部分中生成有用的化学物质。 尽管目前使用热量催化剂和能量进行的大多数生物量转化次数均进行，但这项工作正在利用电力驱动的催化反应的独特方面，以实现在低温和压力下有用的化学物质的合成。这些过程所需的电力可能又来自可再生能源，例如风和太阳能。正在采用一种基本方法，其中将探测催化反应性质的实验技术与计算机模拟结合在一起，以构建控制反应选择性并设计更有效过程的因素的全面图片。这项工作的见解在扩展绿色化学范围方面具有更广泛的应用。这项研究还用于通过涉及本科生研究人员进行暑期实习来促进科学教育，而PI还在开发一系列与理解有关电流反应的物理过程有关的互动教育模块。 该项目正在研究对生物量衍生的原料转换为所需化学靶标的选择性的电化学控制。电化学转换在可持续加工方面具有优势，因为它们通常在低温下运行并直接利用水性原料。 将呋喃和5-羟基甲基呋喃的选择性氧化作为探针系统，这项工作着重于确定可以通过控制电极电位和组成来控制选择性的不同机制。探索的机制包括与中性原子转移反应，氧和有机物种的表面覆盖率变化以及具有特定反应性或几何形状的启动子的作用相对的电荷转移反应的分化。正在整合三种互补的研究方法以表征这些效果。金属催化剂上电化学动力学的测量与原位光谱相结合，以鉴定反应途径。表面科学实验用于PT模型（111）表面，以详细研究氧化基本步骤；最后，密度功能理论计算用于研究相同的表面化学，包括电势效应和水 - 金属界面的模拟。这三项研究推力提供了互补的信息，并丰富了对电化学环境的理解深度。 这项工作的见解在扩展绿色化学和电化学合成路线的范围方面具有更广泛的应用。这项研究还用于通过涉及本科生研究人员进行暑期实习来促进科学教育，而PI还在开发一系列与理解有关电流反应的物理过程有关的互动教育模块。