New Approaches to Reversible Homogeneous Electrocatalysts

在这个由化学系化学催化项目资助的项目中，斯坦福大学的Robert Waymouth教授正在开发将醇电催化转化为酮的新实验方法。将化合物如醇转化为酮可以形成燃料电池的基础，燃料电池是传统电源的替代品。虽然醇/酮燃料电池非常有吸引力，但化学反应很困难。在该项目中，正在开发促进这种困难反应的新催化剂。这项研究为将化学燃料高效转化为有用的能源形式提供了新的手段。与斯坦福大学教授Richard Zare和Christopher Chidsey的合作研究增强了能源科学的实验和教育基础设施，并为教师，博士后，研究生和本科生提供了丰富的教育和合作研究机会。该项目的重点是均相催化剂轴承质子和氧化还原活性配体。它是由这样的假设，即已经开发的化学转移氢化催化，如金属配体双功能活化的基板，机械概念，可以应用于质子和氧化还原活性配体的行为，有效地介导多电子和质子转移。 实验方法利用均相配位络合物，并试图确定介导氢原子，质子和电子转移步骤在有效的电催化过程中的金属/配体配位环境的关键特征。 高分辨率质谱技术的开发和应用，连接到电化学电池是实验计划的一个创新方面。这为电催化反应过程中产生的中间体提供了新的机理见解。 这项工作的更广泛影响包括采用新的办法，以高能效的方式将化学燃料转化为有用的能源形式。

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor Robert Waymouth of Stanford University is developing new experimental approaches for the electrocatalytic conversion of alcohols into ketones. The conversion of chemical compounds such as alcohols into ketones can form the basis of fuel cells, which are alternatives to conventional power sources. While the alcohol/ketone fuel cells are very attractive, the chemical reaction is difficult. In this project, new catalysts that facilitate such difficult reactions are being developed. This research provides new means for the energy-efficient conversion of chemical fuels into useful forms of energy. Collaborative investigations with Professors Richard Zare and Christopher Chidsey at Stanford University enhance the experimental and educational infrastructure for energy science and provide faculty, postdoctoral, graduate, and undergraduate students with rich opportunities for education and collaborative research. This project focuses on homogeneous catalysts bearing proton and redox-active ligands. It is guided by the hypothesis that mechanistic concepts that have been developed for chemical transfer hydrogenation catalysis, such as metal-ligand bifunctional activation of substrates, can be applied to the behavior of proton- and redox-active ligands that are effective in mediating multi-electron and proton transfers. The experimental approach utilizes homogeneous coordination complexes and seeks to determine the key features of the metal/ligand coordination environments that mediate the hydrogen atom, proton and electron transfer steps in efficient electrocatalytic processes. The development and application of high resolution mass spectrometry techniques, interfaced to electrochemical cells is an innovative aspect of the experimental plan. These provide new mechanistic insights on the intermediates generated during electrocatalytic reactions. Broader impacts of this work include new approaches for the energy-efficient conversion of chemical fuels into useful forms of energy.