CAREER: SuSChEM: Experimental characterization of catalytic water oxidation reaction intermediates

职业：SuSChEM：催化水氧化反应中间体的实验表征

• 批准号: 1454086
• 负责人: Etienne Garand
• 金额: $ 61.2万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-04-01 至 2020-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1454086&HistoricalAwards=false
• 关键词: CAREER; SuSChEM; Experimental; characterization; catalytic

With this CAREER Award, the Chemical Structure, Dynamics & Mechanisms B program is supporting the research of Professor Etienne Garand of the University of Wisconsin-Madison. Professor Garand will use cryogenic ion infrared predissociation spectroscopy to characterize reaction complexes present in catalytic water oxidation reactions. First, a methodology will be developed to isolate catalytic reaction complexes generated under realistic electrochemical conditions as well as by controlled gas-phase reactions. The structures of these isolated complexes will then be characterized in detail using a method based on a unique combination of mass spectrometry and vibrational predissociation spectroscopy. Subsequent studies involving systematic variations of the catalyst structure will reveal the influence of ligand environment and metal center on the nature and electronic structure of the reaction complexes. The active control of the solvent network in promoting processes such as proton coupled electron transfer will also be probed in detail. The methodology developed here will allow for precise and systematic spectroscopic characterization of reactive species, providing a detailed description of the molecular level interactions involved in the water oxidation process and elucidating their relationship with the catalyst structure. Lastly, the results from these studies will also provide stringent benchmarks for theoretical methods used to understand the mechanisms of such molecular catalysts. The project will improve our understanding of the mechanism of catalytic water oxidation reactions, which will help the development of more efficient water oxidation catalysts. Water oxidation reactions play a significant role in the conversion of solar energy into chemical energy. Professor Garand will also initiate educational projects that interweave research and teaching. To demystify mass spectrometry for the general audiences, Professor Garand will develop demonstrations based on a mechanically rotating saddle analog of the Paul trap and a mass-selective quadrupole trap for macroscopic particles. These interactive apparati will illustrate basic concepts in mass spectrometry such as ion trapping, mass selection and collision activation. They will be integrated into a general chemistry class and distributed more broadly through online videos. Such visual and hands-on demonstrations of the concepts of mass spectrometry will have the potential to engage the interest of the general public and undergraduate students, providing them with a deeper understanding and appreciation for the sciences behind these widely used instruments. Professor Garand will also provide initiation to research for undergraduate students through integrated research in classes and summer internships. Such experiences can provide the students with a well-rounded educational experience as they decide their future paths.

通过这一职业奖，化学结构、动力学和机械B项目支持威斯康星大学麦迪逊分校的艾蒂安·加兰德教授的研究。加兰德教授将使用低温离子红外预解离光谱来表征催化水氧化反应中存在的反应络合物。首先，将开发一种方法来分离在现实的电化学条件下产生的催化反应络合物以及由受控的气相反应产生的络合物。然后，将使用一种基于质谱学和振动预解离光谱的独特组合的方法来详细表征这些分离的络合物的结构。后续关于催化剂结构系统变化的研究将揭示配体环境和金属中心对反应络合物的性质和电子结构的影响。还将详细探讨溶剂网络在促进质子耦合电子转移等过程中的主动控制。这里开发的方法将允许对活性物种进行精确和系统的光谱表征，详细描述水氧化过程中涉及的分子水平相互作用，并阐明它们与催化剂结构的关系。最后，这些研究的结果也将为用于理解此类分子催化剂机理的理论方法提供严格的基准。该项目将加深我们对催化水氧化反应机理的理解，这将有助于开发更高效的水氧化催化剂。水氧化反应在太阳能转化为化学能的过程中起着重要作用。加兰德教授还将发起将研究和教学相结合的教育项目。为了给普通观众揭开质谱学的神秘面纱，加兰德教授将开发基于机械旋转鞍形模拟保罗陷阱和用于宏观粒子的质量选择四极陷阱的演示。这些交互设备将说明质谱学中的基本概念，如离子捕获、质量选择和碰撞激活。他们将被整合到一堂普通化学课上，并通过在线视频更广泛地分发。这种直观和亲身实践的质谱学概念演示将有可能引起普通公众和本科生的兴趣，使他们对这些广泛使用的仪器背后的科学有更深的了解和欣赏。加兰德教授还将通过课堂综合研究和暑期实习为本科生提供研究启蒙。这样的经历可以为学生提供全面的教育体验，帮助他们决定未来的道路。