Spectroscopic Identification of Transition-Metal M[η 2 -(O,O)C] Species for Highly-Efficient CO 2 Activation

作者：Huijun Zheng, Xiangtao Kong, Chong Wang, Tiantong Wang, Dong Yang, Gang Li, Hua Xie, Zhi Zhao, Ruili Shi, Haiyan Han, Hongjun Fan, Xueming Yang, Ling Jiang · 发表于：The Journal of Physical Chemistry Letters · 年份：2020 · DOI：10.1021/acs.jpclett.0c03379 · 被引用次数：12 · 研究领域：Carbon dioxide utilization in catalysis、CO2 Reduction Techniques and Catalysts、Catalytic Processes in Materials Science

The CO 2 activation by transition metals is important in CO 2 utilization but has proven to be challenging for experimental targets. Here we report first synthesis and spectroscopic characterization of transition-metal M[η 2 -(O,O)C] species with bidentate double oxygen metal-CO 2 coordination in the [ZrO(CO 2 ) n ≥4 ] + complexes. The Zr[η 2 -(O,O)C] species yields a CO 2 – radical ligand, showing a high efficiency in CO 2 activation. We find that two important prerequisites are demanded for certain metals to form this intriguing M[η 2 -(O,O)C] species. One is that the metal center has high reduction capability, and the other is that the oxidation state of the metal center is lower than its highest one by 1. This study highlights the pivotal roles played by the M[η 2 -(O,O)C] species in CO 2 activation and also open new avenues toward the development of related single-atom catalysts with isolated transition-metal atoms dispersed on supports.