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

在国家科学基金会化学部化学催化项目的这一奖项下，佛罗里达国际大学的Raphael Raptis教授开发了新型的、受生物启发的水氧化电催化剂。这项研究是基于这样一个想法，即可以对导致氧气还原为水的催化剂(例如在具有三拷贝加氧酶的酶中观察到的催化剂)进行适当的修饰，以催化水到氧气的氧化。具体地说，工作计划包括努力合成六核铜-吡唑醇支架，该支架将能够两次去质子化水，形成配位的氧离子，并在氧化时以氧-氧键的形成为模板。这项合成工作将以理论为导向，旨在调整铜-氧代组件的氧化还原性能，使其有利于氧基氧化而不是铜基氧化。新配合物的结构、光谱、磁学和电化学研究将指导这一过程的热力学参数的计算。这种新型的电催化剂将被固定在电极表面，以评估其电化学性能。本研究将致力于开发利用富含稀土的金属铜的低成本电催化剂，以实现在低氧化还原电位下将水氧化为二氧化氧。这将使水的裂解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了当代多学科研究领域的培训机会，使他们同时接触到我们当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联活动完成的。

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.