Atomically Dispersed Rh–O–V Pairs Promote Methane Dry Reforming with Sustained Catalytic Activity
Yani Zhang, Ning Cao, Ke Wang, Yan Mi, Xingwang Zhang, Pengfei Xie
Abstract
Dry reforming of methane (DRM) offers an approach to promote natural gas utilization and mitigate climate change contributed by CH 4 and CO 2, but the development of high-performance and stable catalysts is challenging. Here, we load Rh single atoms on CeVO 3 perovskite surfaces enriched with oxygen vacancies to enhance the activity and resistance to carbon accumulation. The obtained catalyst not only improved the catalytic activity by interfacial synergism and achieved high CH 4 (74.92%) and CO 2 (80.67%) conversions at 650 °C, with a CH 4 reaction rate of 20.08 mmol CH4 ·g cat –1 ·min –1, but also suppressed catalyst deactivation due to carbon accumulation. A combination of in situ spectroscopic characterization and theoretical calculations revealed the unique local coordination and electronic environment of single-atom sites as intrinsically active centers, promoting CH 4 dissociation (rate-determining step) and formation of CH 2 O* intermediates to avoid coke formation. Meanwhile, CO 2 is activated as bidentate CO 3 2– dominant at the specific sites, providing a persistent supply of oxygen species for the reaction, which ensures the long-term stability of the catalyst. This work provides a catalyst design strategy for the high-value utilization of carbon resources.