Mao Jun, Liu Huan, Li Yanan, Gao Meng, Zhang Yunlong, Song Yao, Zhang Mo, Xu Guilan, Zhou Wu, Yu Liang, Cui Xiaoju, Deng Dehui
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
J Am Chem Soc. 2025 Apr 30;147(17):14530-14540. doi: 10.1021/jacs.5c01515. Epub 2025 Apr 15.
The oriented conversion of CH to CHCOOH at low temperature, even room temperature, is both scientifically significant and industrially applicable for CH utilization, yet it is extremely challenging due to the difficulties associated with efficient CH activation and controllable C-C coupling. In this study, we for the first time achieve the room-temperature conversion of CH to CHCOOH using molecular O and CO over MoS-confined Rh-Fe sites, which delivers an unprecedented CHCOOH selectivity of 90.3% and a productivity of 26.2 μmol g h at 25 °C. Furthermore, the productivity of CHCOOH can be enhanced to 105.6 μmol g h at 80 °C, while maintaining a high selectivity of 95.6%. Comprehensive experimental and theoretical investigation reveal the critical role of Rh-Fe synergy in the selective formation of CHCOOH. The confined Fe sites in MoS enable the activation of O to generate highly reactive Fe═O center for CH dissociation to CH species at room temperature, which then readily couple with adsorbed CO on adjacent Rh sites to form the key CHCO intermediate for CHCOOH production. The unique structure of Rh-Fe sites offers synergistic catalytic properties that effectively balance C-H activation and C-C coupling, successfully addressing the trade-off between activity and selectivity in the carbonylation of CH to CHCOOH under mild conditions.
在低温甚至室温下将CH定向转化为CHCOOH，对于CH的利用而言，在科学上具有重要意义且在工业上具有应用价值，但由于高效CH活化和可控C-C偶联存在困难，这一过程极具挑战性。在本研究中，我们首次利用分子O₂和CO在MoS₂限制的Rh-Fe位点上实现了CH到CHCOOH的室温转化，在25℃下提供了前所未有的90.3%的CHCOOH选择性和26.2 μmol g⁻¹ h⁻¹的产率。此外，在80℃时CHCOOH的产率可提高到105.6 μmol g⁻¹ h⁻¹，同时保持95.6%的高选择性。全面的实验和理论研究揭示了Rh-Fe协同作用在CHCOOH选择性形成中的关键作用。MoS₂中受限的Fe位点能够活化O₂以生成高活性的O中心，用于在室温下将CH解离为CH物种，然后该物种易于与相邻Rh位点上吸附的CO偶联，形成用于生产CHCOOH的关键CHCO中间体。Rh-Fe位点的独特结构提供了协同催化性能，有效地平衡了C-H活化和C-C偶联，成功解决了在温和条件下将CH羰基化转化为CHCOOH过程中活性与选择性之间的权衡问题。
