In situ XAS and VtC-XES Studies of Electrocatalytic Water Oxidation Mechanisms in Dimeric Copper(pyalc) Complexes

In situ XAS and VtC-XES experiments will be performed under electrocatalytic conditions for a dimeric copper-pyalc complex to unravel the mechanistic pathways of the Cu-complex for efficient water oxidation. This proposal aims to provide for the first time experimental understanding into the electrochemically generated in situ active catalytic species for water oxidation in a dinuclear Cu(pyalc) complex under real operando conditions. To this end, we propose the realization of in situ HERFD-XANES, EXAFS, VtC-XES experiments on our newly discovered Cu(pyalc) complex under bulk electrolysis condition. This study offers an excellent opportunity to directly monitor surface structure-transformations, evolution of the local-coordination, metal ligand interactions, changes in the electronic states and Cu valence state. These results will offer new insight into the mechanistic pathways in dimeric Cu-complexes for the design of efficient water oxidation catalysts.

针对二聚铜-pyalc配合物，将在电催化条件下开展原位X射线吸收光谱（XAS, X-ray Absorption Spectroscopy）与变温变浓度X射线发射光谱（VtC-XES, Variable Temperature and Concentration X-ray Emission Spectroscopy）实验，以揭示该铜配合物实现高效水氧化的机理路径。本研究方案旨在首次从实验层面阐明，在真实操作（operando）条件下，双核Cu(pyalc)配合物中经电化学原位生成的水氧化活性催化物种的特性。为此，我们拟在本体电解（bulk electrolysis）条件下，对新发现的Cu(pyalc)配合物开展原位高能量分辨率荧光检测X射线吸收近边结构（HERFD-XANES, High Energy Resolution Fluorescence Detected X-ray Absorption Near Edge Structure）、扩展X射线吸收精细结构（EXAFS, Extended X-ray Absorption Fine Structure）及VtC-XES实验。本研究为直接监测表面结构转变、局部配位环境演变、金属-配体相互作用、电子态变化及铜价态变化提供了绝佳契机。这些结果将为二聚铜配合物的机理路径研究及高效水氧化催化剂的设计提供新的见解。