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.

通过此职业奖，化学结构，动力学和机制B计划支持威斯康星大学麦迪逊分校的Etienne Garand教授的研究。 Garand教授将使用低温离子红外预性光谱法来表征催化水氧化反应中存在的反应复合物。 首先，将开发一种方法来隔离在现实的电化学条件以及受控气相反应下产生的催化反应复合物。 然后，这些分离的复合物的结构将使用基于质谱和振动前序列光谱的独特组合的方法进行详细表征。 随后涉及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复合物的性质和电子结构的影响。 溶剂网络在促进过程（例如质子耦合电子转移）中的主动控制也将进行详细探讨。 此处开发的方法将允许对反应性物种的精确和系统的光谱表征，从而详细描述了水氧化过程中涉及的分子水平相互作用，并阐明了它们与催化剂结构的关系。最后，这些研究的结果还将为用于理解这种分子催化剂机制的理论方法提供严格的基准。 该项目将提高我们对催化水氧化反应机制的理解，这将有助于开发更有效的水氧化催化剂。 水氧化反应在太阳能转化为化学能中起着重要作用。 Garand教授还将启动与研究和教学交织的教育项目。 为了揭开一般观众的质谱，Garand教授将基于保罗陷阱的机械旋转的马鞍类似物和宏观旋转四极杆陷阱进行示范。这些交互式设备将说明质谱中的基本概念，例如离子捕获，质量选择和碰撞激活。它们将被整合到一般化学课程中，并通过在线视频更广泛地分发。 这种对质谱概念的视觉和动手演示将有可能吸引公众和本科生的兴趣，从而使他们对这些广泛使用的乐器背后的科学有了更深入的了解和欣赏。 Garand教授还将通过课堂和暑期实习的综合研究为本科生提供研究。 这样的经历可以为学生决定未来的道路时提供全面的教育经验。