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Regulating oxygen activity of perovskites to promote NOx oxidation and reduction kinetics

Abstract

Understanding the adsorption and oxidation of NO on metal oxides is of immense interest to environmental and atmospheric (bio)chemistry. Here, we show that the surface oxygen activity, defined as the oxygen 2p-band centre relative to the Fermi level, dictates the adsorption and surface coverage of NOx and the kinetics of NO oxidation for La1−xSrxCoO3 perovskites. Density functional theory and ambient-pressure X-ray photoelectron spectroscopy revealed favourable NO adsorption on surface oxygen sites. Increasing the surface oxygen activity by increasing the strontium substitution led to stronger adsorption and greater storage of NO2, which resulted in more adsorbed nitrogen-like species and molecular nitrogen formed upon exposure to CO. The NO oxidation kinetics exhibited a volcano trend with surface oxygen activity, centred at La0.8Sr0.2CoO3 and with an intrinsic activity comparable to state-of-the-art catalysts. We rationalize the volcano trend by showing that increasing the NO adsorption enhances the oxidation kinetics, although NO adsorption that is too strong poisons the surface oxygen sites with adsorbed NO2 to impede the kinetics.

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Fig. 1: NOx adsorption energetics on La1−xSrxCoO3 surfaces.
Fig. 2: AP-XPS of NO and O2 on (001)-oriented La0.8Sr0.2CoO3.
Fig. 3: Isothermal and isobaric surface reactivity of NO and O2 on La1−xSrxCoO3.
Fig. 4: NOx reduction on La1−xSrxCoO3 thin films under CO.
Fig. 5: NO oxidation activity and reaction mechanism on La1−xSrxCoO3.

Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

The ALS beamlines 9.3.2 and 11.0.2 are supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and Materials Sciences Division of the US DOE at the Lawrence Berkeley National Laboratory under Contract DE-AC02-05CH11231. Some of the PLD film growth was conducted at the Center for Nanophase Materials Sciences, a DOE Office of Science User Facility. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231. This work also used resources of the Extreme Science and Engineering Discovery Environment (XSEDE)84, which is supported by National Science Foundation grant number ACI-1548562. X.R.W. acknowledges support from the Nanyang Assistant Professorship grant from Nanyang Technological University, Academic Research Fund Tier 1 (RG108/17) and (RG177/18) from the Singapore Ministry of Education.

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Y.S.-H., J.H. and R.R.R. conceived and designed the experiments of this projects. J.H., R.R.R., K.A., E.J.C. and H.B. performed the ambient-pressure XPS measurements. X.R.W. grew the epitaxial thin films. K.A. performed the plug-flow reactor measurements. L.G. conducted the density functional theory calculations. Y.S.-H., J.H., R.R.R. and L.G. wrote the manuscript. All authors discussed, commented on and revised the manuscript.

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Correspondence to Livia Giordano or Yang Shao-Horn.

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Peer review information Nature Catalysis thanks Juan González-Velasco and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–41, Tables 1–6 and Notes 1–3.

Supplementary Data 1

Atomic coordinates of optimized structures for DFT calculations conducted in this study.

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Hwang, J., Rao, R.R., Giordano, L. et al. Regulating oxygen activity of perovskites to promote NOx oxidation and reduction kinetics. Nat Catal 4, 663–673 (2021). https://doi.org/10.1038/s41929-021-00656-4

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