光、电催化是与世界能源和环境问题紧密相关的一个核心科研方向。当前一个重要的技术瓶颈是阳极材料活性太低（水氧化反应的超电势过高），有鉴于此，本项目拟发展一个新颖的计算方法来研究氧化物电极界面上的水氧化反应。该方法结合量子力学和统计力学的技巧来计算质子和电子转移反应的自由能。采用该新方法能够让我们首次计算固液界面上水氧化反应中的质子/电子转移，从而有助于我们更深刻地理解反应机理和超电势的根源。一个重要亟待解决的问题是阳极材料的活性与其电子能带结构是如何关联的。本项目将对具有完全不同电子结构的半导体光电催化剂（如二氧化钛）和金属态电催化剂（如二氧化钌）进行系统地研究，进而从电子结构的角度理解光催化和电催化的相同与不同之处。最终目标是建立阳极材料的构效（电子结构与活性）关系，为实验寻找高性能光电催化剂提供必要的理论基础。

(Photo-)electro-catalysis is one of the key research areas that are closely related to the world energy and environmental issues. In view that an important bottleneck of the current technology is the low activity of anode materials (i.e. high overpotential for water oxidation), this proposal attempts to develop a new computational method to study water oxidation on oxide electrode surfaces. This method combines quantum mechanical and statistical mechanical techniques for computation of free energies of electron/proton transfer. It allows us to study, for the first time, water oxidation at oxide water interfaces from a unique perspective of proton coupled electron transfer. This will help to understand reaction mechanism and overpotential at a deeper level compared to traditional computational methods. A crucial question to be addressed is how to relate the activity of anode materials to their electronic structures. In the proposed research, a semiconducting photocatalyst (i.e. titanium dioxide) and metallic electrocatalyst (i.e. ruthenium dioxide), both with very different electronic structures, will be systematically investigated in order to understand the differences and similarities between photocatalysis and electrocatalysis at a fundamental electronic structure level. The ultimate goal is to establish the (electronic) structure-activity relation of anode materials to provide theoretical basis for searching for new catalytic materials with better efficiency.