Wang Jiong, Dou Shuo, Wang Xin
Institute of Advanced Synthesis, Northwestern Polytechnical University (NPU), Xi'an 710072, China.
Yangtze River Delta Research Institute of NPU, Taicang 215400, China.
Sci Adv. 2021 Mar 26;7(13). doi: 10.1126/sciadv.abf3989. Print 2021 Mar.
Heterogeneous molecular catalysts based on transition metal complexes have received increasing attention for their potential application in electrochemical energy conversion. The structural tuning of first and second coordination spheres of complexes provides versatile strategies for optimizing the activities of heterogeneous molecular catalysts and appropriate model systems for investigating the mechanism of structural variations on the activity. In this review, we first discuss the variation of first spheres by tuning ligated atoms; afterward, the structural tuning of second spheres by appending adjacent metal centers, pendant groups, electron withdrawing/donating, and conjugating moieties on the ligands is elaborated. Overall, these structural tuning resulted in different impacts on the geometric and electronic configurations of complexes, and the improved activity is achieved through tuning the stability of chemisorbed reactants and the redox behaviors of immobilized complexes.
基于过渡金属配合物的多相分子催化剂因其在电化学能量转换中的潜在应用而受到越来越多的关注。配合物第一和第二配位层的结构调控为优化多相分子催化剂的活性提供了多种策略，也为研究结构变化对活性的影响机制提供了合适的模型体系。在这篇综述中，我们首先讨论通过调节配位原子来改变第一配位层；随后，详细阐述通过在配体上附加相邻金属中心、侧基、吸电子/给电子基团以及共轭部分来对第二配位层进行结构调控。总体而言，这些结构调控对配合物的几何和电子构型产生了不同的影响，并且通过调节化学吸附反应物的稳定性和固定化配合物的氧化还原行为实现了活性的提高。
