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Structural selectivity of supported Pd nanoparticles for catalytic NH3 oxidation resolved using combined operando spectroscopy

Abstract

The selective catalytic oxidation of NH3 to N2 presents a promising solution for the abatement of unused NH3-based reductants from diesel exhaust after treatment. Supported Pd nanoparticle catalysts show selectivity to N2 rather than NOx, which is investigated in this work. The link between Pd nanoparticle structure and surface reactivity was found using operando X-ray absorption fine structure spectroscopy, diffuse reflectance infrared Fourier-transformed spectroscopy and on-line mass spectrometry. Nitrogen insertion into the metallic Pd nanoparticle structure at low temperatures (<200 °C) was found to be responsible for high N2 selectivity, whereas the unfavourable formation of NO is linked to adsorbed nitrates, which form at the surface of bulk PdO nanoparticles at high temperatures (>280 °C). Our work demonstrates the ability of combined operando spectroscopy and density functional theory calculations to characterize a previously unidentified PdNx species, and clarify the selectivity-directing structure of supported Pd catalysts for the selective catalytic oxidation of NH3 to N2.

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Fig. 1: Catalytic activity of supported Pd catalysts for NH3 oxidation at increasing temperatures.
Fig. 2: In situ Pd L3-edge XANES spectra of 1.5 wt% Pd/γ-Al2O3 in different gas environments.
Fig. 3: Operando Pd K-edge XANES and EXAFS spectra of Pd/γ-Al2O3 under different reaction conditions.
Fig. 4: Operando Pd K-edge XANES spectra of 1.5 wt% Pd/γ-Al2O3 under different reaction conditions.
Fig. 5: Operando DRIFTS spectrum of 1.5 wt% Pd/γ-Al2O3 during NH3 oxidation.

Data availability

The data that support the findings of this study are available from the University of Southampton repository with the identifier https://doi.org/10.5258/SOTON/D0709, or from the authors upon reasonable request.

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Acknowledgements

We acknowledge UCL and the EPSRC for the iCASE studentship of E.K.D; the beamline scientists at the Swiss Light Source and staff at the Paul Scherrer Institut for the provision of beamtime (proposal 20160396); and the beamline scientists at XMaS, European Synchrotron Radiation Facility, for the provision of beamtime (experiment 28-01-1213). XMaS is a UK national facility supported by EPSRC. We recognize staff at the University of Warwick and University of Liverpool for support in facilitating the beamtime. We also acknowledge the RCaH for the use of facilities, and Johnson Matthey for providing catalyst precursor materials and testing facilities. We thank the UK Catalysis Hub for resources and support provided via our membership of the UK Catalysis Hub Consortium (portfolio grants EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1 and EP/I019693/1). Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing service (http://www.archer.ac.uk). We acknowledge the use of Athena at HPC Midlands+, which was funded by the EPSRC (grant EP/P020232/1), in this research, via the EPSRC RAP call of spring 2018. We also thank HPC Wales for the computing time.

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The experiments on SuperXAS were performed by P.P.W., E.K.D., E.K.G., R.H.B., M.N. and A.G. The experiments on XMaS at the European Synchrotron Radiation Facility were performed by P.P.W., E.K.D., G.F.T., P.T. and S.M.R. The catalysts were prepared by E.K.D. and A.R., with routine characterization performed by E.K.D. The X-ray absorption spectroscopy data were interpreted by P.P.W., E.K.D., A.K. and E.K.G. XPS measurements were performed and analysed by E.K.D., S.F.R.T. and T.E.E. The computational work was performed by A.C. and C.D.Z.-Y. The work was conceived and designed by P.P.W., C.R.A.C., A.G., P.C. and C.H. The manuscript was written by P.P.W., E.K.D., A.C. and A.G.

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Correspondence to Alexandre Goguet or Peter P. Wells.

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Supplementary Figures 1–22; Supplementary Tables 1–10; Supplementary Note 1

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Dann, E.K., Gibson, E.K., Blackmore, R.H. et al. Structural selectivity of supported Pd nanoparticles for catalytic NH3 oxidation resolved using combined operando spectroscopy. Nat Catal 2, 157–163 (2019). https://doi.org/10.1038/s41929-018-0213-3

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