Journal
NATURE CATALYSIS
Volume 5, Issue 2, Pages 119-127Publisher
NATURE PORTFOLIO
DOI: 10.1038/s41929-022-00741-2
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Funding
- Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy [DE-SC0014561]
- US National Science Foundation [NSF-CHE-1462121, NSF-CHE-1800577]
- NSF [NSF-CHE-1800601]
- National Science Foundation [ACI-1548562, NSF-OIA-1539105]
- NSF at the Pittsburgh Supercomputing Center [ACI-1445606]
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Understanding the structural dynamics of catalysts under reaction conditions is essential for catalyst design. In this study, supported rhodium catalysts were found to undergo atomic-scale restructuring in response to carbon monoxide. The pressure of CO product stabilized CO-liganded rhodium clusters, and reversible restructuring between CO-ligand-free rhodium clusters and CO-liganded clusters was observed. These findings highlight the importance of considering product molecules in the atomic-scale understanding of catalytic active sites and mechanisms.
Understanding the structural dynamics of a catalyst under reaction conditions is challenging but crucial regarding catalyst design. Here, by a combination of in situ/operando characterization and first-principles modelling, we show that supported rhodium (Rh) catalysts undergo restructuring at the atomic scale in response to carbon monoxide (CO), a gaseous product formed during steam reforming of methane. Despite transformation of the initially prepared single-Rh-cation catalyst into Rh nanoparticles during hydrogen pretreatment, the formed Rh nanoparticles redispersed to low-nuclearity, CO-liganded Rh clusters (Rh-m(CO)(n) (m = 1-3, n = 2-4)) under catalytic conditions. Theoretical simulations under reaction conditions suggest that the pressure of the CO product stabilizes Rh-m(CO)(n) sites, while in situ/operando spectroscopy revealed a reversible restructuring between Rh-3(CO)(3) clusters and CO-ligand-free Rh clusters driven by CO pressure. Our findings demonstrate the importance of including product molecules in the atomic-scale understanding of catalytic active sites and mechanisms.
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