中国科学院大连化物所邓德会团队实现了MoS₂限制的Rh-Fe位点上甲烷温和转化为乙酸。相关论文于2025年4月15日发表在《美国化学会杂志》上。

在低温甚至室温下将CH₄定向转化为CH₃COOH在科学上具有重要意义，在工业上也适用于CH₄的利用，但由于与高效CH₄活化和可控C-C耦合相关的困难，这极具挑战性。研究组首次在MoS₂限制的Rh-Fe位点上使用分子O₂和CO实现了CH₄到CH₃COOH的室温转化，这提供了前所未有的90.3%的CH₃COOH选择性和在25°C下26.2μmol gcat^-1 h^-1的生产率。

此外，CH₃COOH的生产率可以提高到在80°C下105.6 μmol gcat^-1 h^-1，同时保持95.6%的高选择性。综合实验和理论研究揭示了Rh-Fe协同作用在CH₃COOH选择性形成中的关键作用。MoS₂中的受限Fe位点能够激活O₂，在室温下产生高活性的Fe═O中心，用于CH₄解离为CH₃物种，然后很容易与相邻Rh位点上吸附的CO结合，形成CH₃COOH生产的关键CH₃CO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，成功地解决了温和条件下CH₄羰基化制备CH₃COOH过程中活性和选择性之间的权衡问题。、

附：英文原文

Title: Mild-Condition Conversion of Methane to Acetic Acid over MoS2–Confined Rh–Fe Sites

Author: Jun Mao, Huan Liu, Yanan Li, Meng Gao, Yunlong Zhang, Yao Song, Mo Zhang, Guilan Xu, Wu Zhou, Liang Yu, Xiaoju Cui, Dehui Deng

Issue&Volume: April 15, 2025

Abstract: The oriented conversion of CH4 to CH3COOH at low temperature, even room temperature, is both scientifically significant and industrially applicable for CH4 utilization, yet it is extremely challenging due to the difficulties associated with efficient CH4 activation and controllable C–C coupling. In this study, we for the first time achieve the room-temperature conversion of CH4 to CH3COOH using molecular O2 and CO over MoS2-confined Rh–Fe sites, which delivers an unprecedented CH3COOH selectivity of 90.3% and a productivity of 26.2 μmol gcat.–1 h–1 at 25 °C. Furthermore, the productivity of CH3COOH can be enhanced to 105.6 μmol gcat.–1 h–1 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 CH3COOH. The confined Fe sites in MoS2 enable the activation of O2 to generate highly reactive Fe═O center for CH4 dissociation to CH3 species at room temperature, which then readily couple with adsorbed CO on adjacent Rh sites to form the key CH3CO intermediate for CH3COOH 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 CH4 to CH3COOH under mild conditions.

DOI: 10.1021/jacs.5c01515

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c01515