Harnessing Redox-Active Ligands and Cofactors to Facilitate Multi-electron Reactivity

通过这一奖项，化学系的化学催化计划资助加州大学欧文分校化学系的艾伦·海杜克教授开发将水分解为氢和氧的新型分子催化剂。风能和太阳能等间歇性替代能源的利用要求制定有效的转换战略来生产化学燃料。为了实现这一目标，水裂解提供氢气和氧气是一种有吸引力的储能反应，为了广泛应用，这些催化剂必须由廉价和富含地球的元素制成。该项目还为本科生和研究生的培训提供了途径，并包括了在科学界历来代表性不足的群体的强大代表性。Heyduk教授正在开发新的三齿氧化还原活性配体，这种配体可以在与金属结合时在三个氧化态之间穿梭，作为将多电子氧化还原功能引入金属络合物的一种方式。PI正在探索这些络合物在重要的多电子反应中的催化作用，如水氧化和质子还原。该项目的最终目标是基于地球上丰富的第一排过渡金属，为水分解反应的两个部分产生分子电催化剂。用于质子电化学还原为氢和将水电化学氧化为氧的新型分子催化剂的发展为人们提供了对有效分解水的机理和动力学障碍的深入了解。为了广泛应用，这些催化剂必须由廉价和富含稀土的元素制成，这些元素中控制多电子反应活性的因素尚不清楚。这一努力的成功将为将瞬时能源转化为可储存的、便携式的化学燃料提供新的途径，从而影响替代能源战略。

With this award, the Chemical Catalysis Program of the Division of Chemistry is funding Professor Alan Heyduk of the Department of Chemistry at the University of California, Irvine to develop new molecular catalysts for splitting water into hydrogen and oxygen. The utilization of intermittent alternative energy sources such as wind and solar requires that efficient conversion strategies be developed to generate chemical fuels. Water-splitting to afford hydrogen and oxygen is an attractive energy-storing reaction for this goal, and for widespread applicability, these catalysts must be made from inexpensive and earth-abundant elements. This project is also providing avenues for the training of students at both the undergraduate and graduate levels and includes strong representation from groups that are historically underrepresented in the sciences. Professor Heyduk is developing new tridentate, redox active ligands that can be shuttled among three oxidation states while bound to a metal, as a way to introduce multi-electron redox functionality to the metal complex. The PI is exploring the use of these complexes in the catalysis of important multi-electron reactions, such as water oxidation and proton reduction. The ultimate goal of the project is to generate molecular electrocatalysts for both halves of the water-splitting reaction and based upon earth abundant first row transition metals. The development of new molecular catalysts for the electrochemical reduction of protons to hydrogen and the electrochemical oxidation of water to oxygen provide insights into the mechanistic and kinetic barriers to efficient water splitting. For widespread applicability, these catalysts must be made from inexpensive and earth-abundant elements, where the factors governing multi-electron reactivity are yet to be elucidated. Success in this endeavor will impact alternative energy strategies by providing new avenues for the conversion of transient energy sources into storable, portable, chemical fuels.