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Reaction product-driven restructuring and assisted stabilization of a highly dispersed Rh-on-ceria catalyst

Abstract

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 (Rhm(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 Rhm(CO)n sites, while in situ/operando spectroscopy revealed a reversible restructuring between Rh3(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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Fig. 1: Evolution of the coordination environment of Rh.
Fig. 2: Surface chemistry of Ce and O during H2 reduction and catalysis.
Fig. 3: Structure and stability of the CeO2(111) surface under gas pressure of H2 and H2O vapour.
Fig. 4: Structure and stability of Rh active sites.
Fig. 5: Relative stability of Rhm(CO)n sites in the reaction environment.
Fig. 6: Reversible restructuring of Rh active sites.

Data availability

The atomic structures of CeO2(111) surfaces in Fig. 3a and CeO2(111)-supported Rh clusters used to construct Fig. 4a are available in Supplementary data. Other data that support the findings within this paper and of this study are available from the corresponding author(s) on reasonable request. Information requests regarding experimental and theoretical data should be addressed to F.T. and P.S., respectively.

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Acknowledgements

The experimental part of this study was supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy under grant no. DE-SC0014561, and by US National Science Foundation under grant no. NSF-CHE-1462121 and NSF-CHE-1800577; the computational part (P.S. and G.Y.) was supported by the NSF Award no. NSF-CHE-1800601. Yuting Li was partially supported by the National Science Foundation under grant no. NSF-OIA-1539105. We thank Fuzhou University (FZU) for the large amount of machine time and assistance provided in performing various TEM studies and spectroscopic studies for characterizations of samples. The calculations in this work used computational and storage services associated with the Hoffman2 shared computational cluster located at University of California Los Angeles. This work also used the Extreme Science and Engineering Discovery Environment, which is supported by National Science Foundation grant no. ACI-1548562 (ref. 69). Specifically, the systems Bridges, Bridges-2 and Comet were used. The Bridges system is supported by NSF award no. ACI-1445606, at the Pittsburgh Supercomputing Center70. The offer of valuable beam time from Y. Iwasawa, Director of the Innovation Research Center for Fuel Cells at The University of Electro-Communications in Tokyo, Japan is highly appreciated.

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P.S. and F.T. conceptualized and supervised the work. G.Y. performed computational studies. Y.T., Yuting Li, Yixiao Li and L.N. performed experiments. Y.T., L.N., T.S. and K.H. contributed to EXAFS experiments. F.T. guided experimental studies. The draft was prepared and edited by G.Y., Y.T., F.T. and P.S.

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Correspondence to Franklin Feng Tao or Philippe Sautet.

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Nature Catalysis thanks Mie Andersen, Christoph Rameshan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Notes 1–13, Figs. 1–29, Tables 1–11 and references.

Supplementary Data

Atomic positions of structures in Fig. 3a and structures used to construct Fig. 4.

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Yan, G., Tang, Y., Li, Y. et al. Reaction product-driven restructuring and assisted stabilization of a highly dispersed Rh-on-ceria catalyst. Nat Catal 5, 119–127 (2022). https://doi.org/10.1038/s41929-022-00741-2

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