Timmer Brian J J, Kravchenko Oleksandr, Zhang Biaobiao, Liu Tianqi, Sun Licheng
Department of Chemistry, KTH Royal Institute of Technology, 10044 Stockholm, Sweden.
Center of Artificial Photosynthesis for Solar Fuels, School of Science, Westlake University, 310024 Hangzhou, China.
Inorg Chem. 2021 Jan 18;60(2):1202-1207. doi: 10.1021/acs.inorgchem.0c03339. Epub 2020 Dec 31.
Water provides an ideal source for the production of protons and electrons required for generation of renewable fuels. Among the most-prominent electrocatalysts capable of water oxidation at low overpotentials are -type catalysts. Although many studies were dedicated to the investigation of the influence of structural variations, the true implication of the bda backbone on catalysis remains mostly unclarified. In this work, we further investigated if electronic effects are contributing to catalysis by or if the intrinsic catalytic activity mainly originates from the structural features of the ligand. Through introduction of pyrazines in the bda backbone, forming and , electronic differences were maximized while minimizing changes in the geometry and other intermolecular interactions. Through a combination of electrochemical analysis, chemical oxygen evolution, and density functional theory calculations, we reveal that the catalytic activity is unaffected by the electronic features of the backbone and that the unique bimolecular reactivity of the family of catalysts thus purely depends on the spatial geometry of the ligand.
水为生产可再生燃料所需的质子和电子提供了理想的来源。在能够在低过电位下进行水氧化的最突出的电催化剂中，有 - 型催化剂。尽管许多研究致力于研究结构变化的影响，但bda主链对催化作用的真正影响仍大多未阐明。在这项工作中，我们进一步研究了电子效应是否有助于 催化，或者内在催化活性是否主要源自配体的结构特征。通过在bda主链中引入吡嗪，形成 和 ，在最小化几何形状和其他分子间相互作用变化的同时，使电子差异最大化。通过电化学分析、化学析氧和密度泛函理论计算相结合，我们揭示催化活性不受主链电子特征的影响，因此 族催化剂独特的双分子反应性纯粹取决于配体的空间几何形状。
