Kärkäs Markus D, Åkermark Björn
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 106 91, Stockholm, Sweden.
Chem Rec. 2016 Apr;16(2):940-63. doi: 10.1002/tcr.201500254. Epub 2016 Mar 15.
Artificial photosynthesis represents an attractive way of converting solar energy into storable chemical energy. The H2O oxidation half-reaction, which is essential for producing the necessary reduction equivalents, is an energy-demanding transformation associated with a high kinetic barrier. Herein we present a couple of efficient Ru-based catalysts capable of mediating this four-proton-four-electron oxidation. We have focused on the incorporation of negatively charged ligands, such as carboxylate, phenol, and imidazole, into the catalysts to decrease the redox potentials. This account describes our work in designing Ru catalysts based on this idea. The presence of the negatively charged ligands is crucial for stabilizing the metal centers, allowing for light-driven H2O oxidation. Mechanistic details associated with the designed catalysts are also presented.
人工光合作用是将太阳能转化为可储存化学能的一种有吸引力的方式。水氧化半反应是产生必要还原当量所必需的，是一种与高动力学势垒相关的能量需求型转化。在此，我们展示了几种能够介导这种四质子-四电子氧化反应的高效钌基催化剂。我们专注于将带负电荷的配体，如羧酸盐、苯酚和咪唑，引入催化剂中以降低氧化还原电位。本报告描述了我们基于这一理念设计钌催化剂的工作。带负电荷配体的存在对于稳定金属中心、实现光驱动水氧化至关重要。还介绍了与设计的催化剂相关的机理细节。
