Catalyst deactivation via decomposition into single atoms and the role of metal loading

Abstract

In the high-temperature environments needed to perform catalytic processes, supported precious metal catalysts lose their activity severely over time. Generally, loss of catalytic activity is attributed to nanoparticle sintering or processes by which larger particles grow at the expense of smaller ones. Here, by independently controlling particle size and particle loading using colloidal nanocrystals, we reveal the opposite process as an alternative deactivation mechanism: nanoparticles rapidly lose activity for methane oxidation by high-temperature decomposition into inactive single atoms. This deactivation route is remarkably fast, leading to severe loss of activity in as little as 10 min. Importantly, this deactivation pathway is strongly dependent on particle density and the concentration of support defect sites. A quantitative statistical model explains how, for certain reactions, higher particle densities can lead to more stable catalysts.

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Fig. 1: Effect of different Pd nanoparticle densities on catalytic stability.
Fig. 2: Particle density-dependent conversion of Pd nanoparticles into Pd single atoms.
Fig. 3: Interface-limited atomic emission demonstrated by nanoparticle size control.
Fig. 4: Conditions of catalyst decomposition.
Fig. 5: Statistical mechanics model of density-dependent particle decomposition.

Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The authors acknowledge support from the US Department of Energy, Chemical Sciences, Geosciences and Biosciences Division of the Office of Basic Energy Sciences, via grant no. DE-AC02-76SF00515 to the SUNCAT Center for Interface Science and Catalysis. E.D.G. acknowledges support from the National Science Foundation Graduate Research Fellowship under grant no. DGE-1656518. M.C. acknowledges support from the School of Engineering at Stanford University and from a Terman Faculty Fellowship. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award no. ECCS-1542152. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76F00515. A.S.H. and S.R.B. acknowledge support from the Department of Energy, Basic Energy Sciences Funded Consortium for Operando and Advanced Catalyst Characterization via Electronic Spectroscopy and Structure (Co-ACCESS) at SLAC. O. Mueller is thanked for beamtime assistance. E.M.D. and P.N.P. acknowledge support from the state of Baden-Württemberg, Germany through bwHPC (bwunicluster and JUSTUS, RV bw16G001 and bw17D011) and financial support from the Helmholtz Association.

Author information

E.D.G. and M.C. conceived and designed the experiments. E.D.G. performed catalyst synthesis and testing. A.C.J.-P. performed HAADF-STEM characterization. E.M.D. performed DFT calculations with support from P.N.P. C.J.W. performed X-ray absorption spectroscopy analysis with support from A.S.H. and S.R.B. F.A.-P. contributed to the discussion of atomic energetics. E.D.G. and M.C. wrote the manuscript with contributions and discussions from all authors.

Correspondence to Matteo Cargnello.

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Supplementary Information

Supplementary Figs. 1–14; Supplementary Tables 1–3

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