Department of Chemistry, Organic Chemistry , KTH Royal Institute of Technology , SE-100 44 Stockholm , Sweden.
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Materials Chemistry and Service Failure, School of Chemistry and Chemical Engineering , Huazhong University of Science and Technology , Wuhan 430074 , China.
Inorg Chem. 2018 Sep 4;57(17):10881-10895. doi: 10.1021/acs.inorgchem.8b01527. Epub 2018 Aug 22.
Catalysts for oxidation of water to molecular oxygen are essential in solar-driven water splitting. In order to develop more efficient catalysts for this oxidatively demanding reaction, it is vital to have mechanistic insight in order to understand how the catalysts operate. Herein, we report the mechanistic details associated with the two Ru catalysts 1 and 2. Insight into the mechanistic landscape of water oxidation catalyzed by the two single-site Ru catalysts was revealed by the use of a combination of experimental techniques and quantum chemical calculations. On the basis of the obtained results, detailed mechanisms for oxidation of water by complexes 1 and 2 are proposed. Although the two complexes are structurally related, two deviating mechanistic scenarios are proposed with metal-ligand cooperation being an important feature in both processes. The proposed mechanistic platforms provide insight for the activation of water or related small molecules through nontraditional and previously unexplored routes.
用于水氧化为氧气的催化剂对于太阳能驱动的水分解至关重要。为了开发更有效的用于这种氧化要求高的反应的催化剂，深入了解催化剂的工作原理至关重要。在此，我们报告了与两个 Ru 催化剂 1 和 2 相关的机理细节。通过使用实验技术和量子化学计算的组合，揭示了由两个单原子 Ru 催化剂催化的水氧化的机理概况。基于获得的结果，提出了复合物 1 和 2 氧化水的详细机理。尽管这两个配合物在结构上相关，但提出了两种不同的机理情景，其中金属-配体协同作用是两个过程的重要特征。所提出的机理平台为通过非传统和以前未探索的途径激活水或相关小分子提供了深入了解。
