Sustaining metal–organic frameworks for water–gas shift catalysis by non-thermal plasma

Abstract

The limited thermal and water stability of metal–organic frameworks (MOFs) often restricts their applications in conventional catalysis that involve thermal treatment and/or use of water. Non-thermal plasma (NTP) is a promising technique that can overcome barriers in conventional catalysis. Here we report an example of an NTP-activated water–gas shift reaction (WGSR) over a MOF (HKUST-1). Significantly, the exceptional stability of HKUST-1 was sustained under NTP activation and in the presence of water, which led to a high specific rate of 8.8 h−1. We found that NTP-induced water dissociation has a twofold promotion effect in WGSR, as it facilitates WGSR by supplying OH and sustains the stability and hence activity of HKUST-1. In situ characterization of HKUST-1 revealed the critical role of open Cu sites in the binding of substrate molecules. This study paves the way to utilize MOFs for a wider range of catalysis.

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Fig. 1: Effect of Ar NTP treatment on HKUST-1.
Fig. 2: Catalytic WGSR by thermal and NTP activation.
Fig. 3: In situ DRIFTS characterization.
Fig. 4: Comparison of the pristine and used HKUST-1 by power XRD and N2 physisorption.

Data availability

All the figures presented in this paper are associated with raw data. The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

X.F. thanks The Royal Society (RG160031) for financial support. P.A.M. and S.X. acknowledge the support from the European Community’s Seventh Framework (FP7)/People-Marie Curie Actions Programme (RAPID under Marie Curie Grant agreement no. 606889). The UK Catalysis Hub is thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC (Portfolio Grant nos EP/K014706/2, EP/K014668/1, EP/K014854/1, EP/K014714/1 and EP/I019693/1). We thank S. Yang, A. Walton, R. Saunders and T. Vetter for their advice and help in improving the manuscript.

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Contributions

X.F. and S.X. conceived the idea. S.X. designed the NTP reactor under the guidance of P.A.M., carried out the catalytic tests and characterization of the materials using N2 sorption, XRD, scanning electron microscopy and FTIR spectroscopy under the guidance of X.F., performed in situ DRIFTS experiments and data analysis and took part in the initial discussion of the data under the guidance of X.F. and P.A.M. C.S. and S.C. designed and performed the in situ DRIFTS experiments and discussed the data with S.X. under the guidance of C.H. and X.F. K.W., B.I. and A.G. developed the in situ DRIFTS flow cell in collaboration with C.H. S.F.R.T. performed the XPS characterization and analysis under the guidance of C.H. N.A.-J. helped with the dynamic water vapour adsorption experiments under the guidance of X.F. X.F wrote the manuscript. All the authors contributed to the preparation of the manuscript.

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Correspondence to Christopher Hardacre or Philip A. Martin or Xiaolei Fan.

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Supplementary Information

Supplementary Methods; Supplementary Figures 1–34; Supplementary Tables 1–5; Supplementary Notes 1–6; Supplementary References

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Xu, S., Chansai, S., Stere, C. et al. Sustaining metal–organic frameworks for water–gas shift catalysis by non-thermal plasma. Nat Catal 2, 142–148 (2019). https://doi.org/10.1038/s41929-018-0206-2

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