Spectroscopic Elucidation of Cu and Fe Active Sites in Zeolites

沸石中 Cu 和 Fe 活性位点的光谱解析

• 批准号: 1660611
• 负责人: Edward Solomon
• 金额: $ 55万
• 依托单位: Stanford University
• 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: 2017-07-01 至 2021-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1660611&HistoricalAwards=false
• 关键词: Spectroscopic; Elucidation; Cu; Fe; Active

Methane, by far the largest component of natural gas, is one of the most abundant fossil fuel resources, but it remains underutilized due to costs and dangers associated with transporting liquefied natural gas. This problem could be resolved by converting methane into methanol, an environmentally friendly liquid fuel that has been identified as the most promising application for natural gas in the transportation sector. The industrial-scale methane/methanol conversion in use today is energy intensive, however, requiring multiple steps at high temperatures and pressures to overcome the inherently low reactivity of methane. For methanol fuel derived from natural gas to be cost-effective, a more efficient method is required. With funding from the Chemical Catalysis Program of the Chemistry Division, Professor Solomon of Stanford University is studying a class of materials called zeolites that perform this challenging chemistry. Professor Solomon's research is revealing how these materials operate on the molecular level. This insight is important for understanding how to design improved catalysts for methane/methanol conversion, as well as other economically significant reactions. Professor Solomon's research is also coupled to outreach activities that serve K-12 students in the areas surrounding Stanford University. This includes developing a shadowing program that brings high school students in to experience research laboratories at Stanford.This project builds on Professor Solomon's current spectroscopic and computational studies of Fe and Cu zeolites, including their geometric/electronic structures, reactivity in selective hydrocarbon oxidation, and their correlation to Fe and Cu enzymes. It also extends this effort to metallozeolites that perform selective catalytic reduction (SCR) of NOx pollutants. These studies are providing detailed insight into reaction mechanisms, defining structural contributions to active site formation, as well as general principles of reactivity. The resulting insight may lead to improved catalysts for a number of economically significant chemical transformations, including the conversion of natural gas to CH3OH fuel, and the abatement of NOx pollutants generated by diesel engines. This proposal involves significant international collaboration, and Professor Solomon is involved in a number of directions to enhance knowledge in physical inorganic chemistry and spectroscopy. Professor Solomon's group has also taken a leadership role in outreach to local K-12 schools, including developing a shadowing program that brings high school students in to experience research laboratories at Stanford.

到目前为止，甲烷是天然气中最大的成分，是最丰富的化石燃料资源之一，但由于运输液化天然气的成本和危险，它仍然没有得到充分利用。这个问题可以通过将甲烷转化为甲醇来解决，甲醇是一种环境友好的液体燃料，已被确定为天然气在交通领域最有前途的应用。然而，目前使用的工业规模的甲烷/甲醇转化是能源密集型的，需要在高温和高压下进行多个步骤才能克服甲烷固有的低反应性。为了使从天然气中提取的甲醇燃料具有成本效益，需要一种更有效的方法。在化学系化学催化项目的资助下，斯坦福大学的所罗门教授正在研究一种名为沸石的材料，这种材料可以执行这种具有挑战性的化学任务。所罗门教授的研究揭示了这些材料是如何在分子水平上运作的。这一见解对于理解如何为甲烷/甲醇转化以及其他具有重大经济意义的反应设计改进的催化剂非常重要。所罗门教授的研究还与服务于斯坦福大学周边地区K-12学生的外展活动相结合。该项目建立在所罗门教授目前对铁和铜沸石的光谱和计算研究的基础上，包括它们的几何/电子结构、选择性碳氢化合物氧化的反应性，以及它们与铁和铜酶的相关性。它还将这一努力扩展到对NOx污染物执行选择性催化还原(SCR)的金属沸石。这些研究提供了对反应机理的详细见解，定义了对活性中心形成的结构贡献，以及反应性的一般原则。由此得出的见解可能会导致一些经济上重要的化学转化的催化剂得到改进，包括将天然气转化为CH3OH燃料，以及减少柴油发动机产生的NOx污染物。这项建议涉及重大的国际合作，所罗门教授参与了多个方向的工作，以增强物理、无机化学和光谱学方面的知识。所罗门教授的团队还在接触当地K-12学校方面发挥了领导作用，包括开发了一个跟踪项目，让高中生体验斯坦福大学的研究实验室。

项目成果

Reply to: Practical constraints on atmospheric methane removal

• DOI: 10.1038/s41893-020-0498-5
• 发表时间: 2020-03
• 期刊: Nature Sustainability
• 影响因子: 27.6
• 作者: R. Jackson;E. Solomon;J. Canadell;M. Cargnello;C. Field;S. Abernethy

Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

• DOI: 10.1073/pnas.1721717115
• 发表时间: 2018-04
• 期刊: Proceedings of the National Academy of Sciences
• 作者: Benjamin E. R. Snyder;L. Böttger;Max L. Bols;James J. Yan;Hannah M. Rhoda;A. Jacobs;Michael Y. Hu;Jiyong Zhao;E. Alp;B. Hedman;K. Hodgson;K. Hodgson;R. Schoonheydt;B. Sels;E. Solomon;E. Solomon

Coordination and activation of nitrous oxide by iron zeolites

• DOI: 10.1038/s41929-021-00602-4
• 发表时间: 2021-04-01
• 期刊: NATURE CATALYSIS
• 影响因子: 37.8
• 作者: Bols, Max L.;Snyder, Benjamin E. R.;Sels, Bert F.
• 通讯作者: Sels, Bert F.

Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites

• DOI: 10.1073/pnas.1813849115
• 发表时间: 2018-11
• 期刊: Proceedings of the National Academy of Sciences
• 作者: Benjamin E. R. Snyder;Max L. Bols;Hannah M. Rhoda;Pieter Vanelderen;Pieter Vanelderen;Lars H. Böttger