Laine Tanja M, Kärkäs Markus D, Liao Rong-Zhen, Siegbahn Per E M, Åkermark Björn
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91 Stockholm (Sweden).
Key Laboratory for Large-Format Battery Materials and System, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074 (P.R. China).
Chemistry. 2015 Jul 6;21(28):10039-48. doi: 10.1002/chem.201406613. Epub 2015 Apr 29.
Insight into how H2 O is oxidized to O2 is envisioned to facilitate the rational design of artificial water oxidation catalysts, which is a vital component in solar-to-fuel conversion schemes. Herein, we report on the mechanistic features associated with a dinuclear Ru-based water oxidation catalyst. The catalytic action of the designed Ru complex was studied by the combined use of high-resolution mass spectrometry, electrochemistry, and quantum chemical calculations. Based on the obtained results, it is suggested that the designed ligand scaffold in Ru complex 1 has a non-innocent behavior, in which metal-ligand cooperation is an important part during the four-electron oxidation of H2 O. This feature is vital for the observed catalytic efficiency and highlights that the preparation of catalysts housing non-innocent molecular frameworks could be a general strategy for accessing efficient catalysts for activation of H2 O.
深入了解H₂O如何被氧化为O₂有望促进人工水氧化催化剂的合理设计，而人工水氧化催化剂是太阳能到燃料转换方案中的关键组成部分。在此，我们报道了一种基于双核钌的水氧化催化剂的相关机理特征。通过结合使用高分辨率质谱、电化学和量子化学计算研究了所设计的钌配合物的催化作用。基于所得结果，表明钌配合物1中设计的配体支架具有非惰性行为，其中金属-配体协同作用是H₂O四电子氧化过程中的重要部分。这一特征对于所观察到的催化效率至关重要，并突出表明制备具有非惰性分子骨架的催化剂可能是获得用于活化H₂O的高效催化剂的通用策略。
