UNS: Selective Catalytic Conversion of Syngas-Derived Dimethyl Oxalate to Ethylene Glycol: Mechanistic Insights from In-Situ Surface Vibrational Spectroscopy

1510157Williams, Christopher t .提议的工作将研究通过草酸二烷基中间体催化脱氢反应从合成气中生产乙二醇（EG）的反应。乙二醇是一种重要的工业化学品。这为利用煤、天然气和生物质能等非常规资源生产EG打开了大门，而不是利用石油资源生产环氧乙烷的传统工艺。虽然该技术已经使用了几十年，但新的催化剂配方以及适用于反应条件下分析的更先进的表征技术，为获得更详细的催化机理理解提供了机会，从而进一步发展催化剂技术。作为该项目的一部分，开发的技术将广泛适用于一系列催化过程，特别是在液体中进行的催化过程。首席研究员还将把国际研究机会和针对代表性不足群体的研究机会纳入项目。该项目将研究各种草酸二烷基在Cu、Ag、Au-Cu和Au-Ag催化剂上加氢的表面化学反应，包括负载和非负载催化剂，以及气相和液相。该项目的关键将是实施一种新的衰减全反射红外分光光度计（ATR-IR）作为主要工具，并通过设计一种新的高压和高温ATR-IR电池。新型ATR-IR电池的应用，以及在相同条件下得到的反应动力学，将为催化反应机理和影响催化剂稳定性和中毒的因素提供新的认识。该研究的一个独特之处在于，实验将在气相和液相环境中进行，条件接近于工业实践中使用的条件。该项目的基本性质，涉及相对复杂的有机化学品和多种反应途径，以及水相和气相环境下的反应，使其成为高压/高温ATR-IR电池提供的改进实验能力的重要试验台。从该研究中获得的信息将为从电催化到光催化以及生物质中间产品的催化转化等广泛的催化过程提供见解。在液相环境中的催化作用将特别适用于本项目所展示的工具和技术的研究。PI还将在拟议的研究项目中整合几个新的教育机会，包括为他的研究生提供国际研究经验，以及为研究生和本科生的代表性不足群体提供研究机会。

1510157Williams, Christopher TThe proposed work will examine the reactions involved in producing ethylene glycol (EG) - an important industrial chemical - from synthesis gas via catalytic dehydrogenation reactions of dialkyl oxalate intermediates. This opens the door to EG production from non-conventional sources such as coal, natural gas, and biomass instead of the conventional process based on ethylene oxide produced from petroleum resources. Although the technology has been used for several decades, new catalyst formulations, as well as more advanced characterization techniques suitable for analysis under reaction conditions, present an opportunity to obtain a more detailed understanding of the catalytic mechanism, and thereby further develop the catalyst technology. The techniques developed as part of the project will be broadly applicable to a range of catalytic processes - especially those carried out in liquids. The principal investigator will also integrate international research opportunities and research opportunities targeting underrepresented groups into the project.The project will examine the surface chemistry involved in the hydrogenation of various dialkyl oxalate species on Cu, Ag, Au-Cu, and Au-Ag catalysts - both supported and unsupported - and both in the gas and liquid phases. Critical to the project will be the implementation of a new attentuated total reflection infrared spectrophotometer (ATR-IR) as the primary tool and through design of a new high-pressure and high-temperature ATR-IR cell. Application of the new ATR-IR cell, together with reaction kinetics obtained under the same conditions, should shed new insight on the catalytic reaction mechanism and factors affecting catalyst stability and poisoning. A unique feature of the study is that experiments will be conducted in both gas phase and liquid phase environments under conditions close to those utilized in industrial practice.The fundamental nature of the project, involving relatively complex organic chemicals and multiple reaction pathways, as well as reaction in both aqueous and gas phase environments, makes it an important test-bed for the improved experimental capabilities offered by the high pressure/temperature ATR-IR cell. Information derived from the study should offer insight into a broad range of catalytic processes ranging from electrocatalysis to photocatalysis and to catalytic conversion of biomass intermediate products. Catalysis in liquid phase environments will be particularly amenable to study by the tools and techniques demonstrated in this project. The PI will also integrate several novel educational opportunities into the proposed research project, including an international research experience for his graduate students, and research opportunities for underrepresented groups at both the graduate and undergraduate levels.