Boosting CO<sub>2</sub> Hydrogenation to Formate over Edge‐Sulfur Vacancies of Molybdenum Disulfide
Zifeng Wang, Yiran Kang, Jingting Hu, Qinqin Ji, Zhixuan Lu, Guilan Xu, Yutai Qi, Mo Zhang, Wangwang Zhang, Rui Huang, Liang Yu, Zhong‐Qun Tian, Dehui Deng
Abstract
Abstract Synthesis of formate from hydrogenation of carbon dioxide (CO 2 ) is an atom‐economic reaction but is confronted with challenges in developing high‐performance non‐precious metal catalysts for application of the process. Herein, we report a highly durable edge‐rich molybdenum disulfide (MoS 2 ) catalyst for CO 2 hydrogenation to formate at 200 °C, which delivers a high selectivity of over 99 % with a superior turnover frequency of 780.7 h −1 surpassing those of previously reported non‐precious metal catalysts. Multiple experimental characterization techniques combined with theoretical calculations reveal that sulfur vacancies at MoS 2 edges are the active sites and the selective production of formate is enabled via a completely new water‐mediated hydrogenation mechanism, in which surface OH* and H* species in dynamic equilibrium with water serve as moderate hydrogenating agents for CO 2 with residual O* reduced by hydrogen. This study provides a new route for developing low‐cost high‐performance catalysts for CO 2 hydrogenation to formate.