Copper-based water-oxidation electrocatalysts; Design, synthesis and characterization

该奖项由美国国家科学基金会化学部化学催化项目颁发，来自佛罗里达国际大学的Raphael Raptis教授开发了新型生物水氧化电催化剂。这项研究是基于这样一种想法，即导致双氧到水的还原的催化剂（例如在具有三铜加氧酶的酶中观察到的）可以被明智地修饰以催化水到双氧的氧化。具体来说，这项工作计划包括努力合成一种六核铜-吡唑啉支架，这种支架将能够两次使水去质子化，形成协调的氧化离子，并在氧化时形成氧-氧键。合成工作将是理论驱动的，并将致力于调整铜-氧组件的氧化还原特性，以支持基于基氧化而不是基于铜的氧化。新的配合物的结构、光谱、磁和电化学研究将指导这一过程的热力学参数的计算。新的电催化剂将被固定在电极表面，以评估其电化学性能。这项研究的目标是利用地球上丰富的金属铜开发低成本的电催化剂，这将实现水在低氧化还原电位下氧化成双氧。这将使分解水成为一种经济上可行的生产氢燃料的方法。该项目还为参与者提供当代多学科研究领域的培训机会，使他们同时接触到我们本地和国际合作者的工作。项目成果的传播是通过一系列社区外展活动完成的。

With this award from the Chemical Catalysis Program of the Division of Chemistry of the National Science Foundation Professor Raphael Raptis from the Florida International University develop new, bio-inspired, water-oxidation electrocatalysts. This research is based on the idea that a catalyst leading to dioxygen-to-water reduction (such as that observed in an enzyme having a tricopper oxygenase) can be judiciously modified to catalyze the water-to-dioxygen oxidation. Specifically, the work plan consists of efforts to synthesize a hexanuclear copper-pyrazolato scaffold, which will be able to deprotonate water twice, forming coordinated oxide-ions, and template the formation of oxygen-oxygen bonds, upon oxidation. The synthetic work will be theory-driven and will aim at tuning the redox properties of the copper-oxo assembly as to favor O-based oxidation over a Cu-based one. Structural, spectroscopic, magnetic and electrochemical studies of the new complexes will guide the computation of the thermodynamic parameters for this process. The new electrocatalysts will be anchored on electrode surfaces in order to evaluate their electrochemical performance.This research will aim at low-cost electrocatalysts development using Earth-abundant metal, copper, which will achieve the oxidation of water to dioxygen at a low redox potential. This will make the splitting of water an economically viable means of producing hydrogen fuel. The project also provides its participants with training opportunities in a contemporary, multidisciplinary research field, exposing them at the same time to the work of our local and international collaborators. Dissemination of the project results is accomplished via a host of community outreach activities.