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


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.


  1. 1.

    Yaghi, O. M. & Li, H. Hydrothermal synthesis of a metal–organic framework containing large rectangular channels. J. Am. Chem. Soc. 117, 10401–10402 (1995).

  2. 2.

    Corma, A. et al. Engineering metal organic frameworks for heterogeneous catalysis. Chem. Rev. 110, 4606–4655 (2010).

  3. 3.

    Rowsell, J. L. C. & Yaghi, O. M. Metal–organic frameworks: a new class of porous materials. Microporous Mesoporous Mater. 73, 3–14 (2004).

  4. 4.

    Peterson, V. K. et al. Neutron powder diffraction study of D2 sorption in Cu3(1,3,5-benzenetricarboxylate)2. J. Am. Chem. Soc. 128, 15578–15579 (2006).

  5. 5.

    Chui, S. S. et al. A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n. Science 283, 1148–1150 (1999).

  6. 6.

    Al-Janabi, N. et al. Mapping the Cu-BTC metal–organic framework (HKUST-1) stability envelope in the presence of water vapour for CO2 adsorption from flue gases. Chem. Eng. J. 281, 669–677 (2015).

  7. 7.

    Alaerts, L. et al. Probing the Lewis acidity and catalytic activity of the metal–organic framework [Cu3(btc)2] (btc = benzene-1,3,5-tricarboxylate). Chem. Eur. J. 12, 7353–7363 (2006).

  8. 8.

    Luz, I. et al. Bridging homogeneous and heterogeneous catalysis with MOFs: Cu-MOFs as solid catalysts for three-component coupling and cyclization reactions for the synthesis of propargylamines, indoles and imidazopyridines. J. Catal. 285, 285–291 (2012).

  9. 9.

    Al-Janabi, N. et al. Underlying mechanism of the hydrothermal instability of Cu3(BTC)2 metal–organic framework. Front. Chem. Sci. Eng. 10, 103–107 (2016).

  10. 10.

    Al-Janabi, N. et al. Cyclic adsorption of water vapour on CuBTC MOF: sustaining the hydrothermal stability under non-equilibrium conditions. Chem. Eng. J. 333, 594–602 (2018).

  11. 11.

    Mehta, P. et al. Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis. Nat. Catal. 1, 269–275 (2018).

  12. 12.

    Stere, C. E. et al. Non-thermal plasma activation of gold-based catalysts for low-temperature water–gas shift catalysis. Angew. Chem. Int. Ed. 56, 5579–5583 (2017).

  13. 13.

    Gibson, E. K. et al. Probing the role of a non-thermal plasma (NTP) in the hybrid NTP catalytic oxidation of methane. Angew. Chem. Int. Ed. 56, 9351–9355 (2017).

  14. 14.

    Ashford, B. & Tu, X. Non-thermal plasma technology for the conversion of CO2. Curr. Opin. Green Sustainable Chem. 3, 45–49 (2017).

  15. 15.

    Bae, J. et al. Oxygen plasma treatment of HKUST-1 for porosity retention upon exposure to moisture. Chem. Commun. 53, 12100–12103 (2017).

  16. 16.

    Luo, J. et al. Water splitting in low-temperature ac plasmas at atmospheric pressure. Res. Chem. Intermed. 26, 849–874 (2000).

  17. 17.

    Decoste, J. B. et al. Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition. J. Am. Chem. Soc. 134, 1486–1489 (2012).

  18. 18.

    Decoste, J. B. et al. Hierarchical pore development by plasma etching of Zr-based metal–organic frameworks. Chem. Eur. J. 21, 18029–18032 (2015).

  19. 19.

    Sadakiyo, M. et al. A new approach for the facile preparation of metal–organic framework composites directly contacting with metal nanoparticles through arc plasma deposition. Chem. Commun. 52, 8385–8388 (2016).

  20. 20.

    Tao, L. et al. Creating coordinatively unsaturated metal sites in metal–organic frameworks as efficient electrocatalysts for the oxygen evolution reaction: insights into the active centers. Nano Energy 41, 417–425 (2017).

  21. 21.

    Bahri, M. et al. Metal organic frameworks for gas-phase VOCs removal in a NTP-catalytic reactor. Chem. Eng. J. 320, 308–318 (2017).

  22. 22.

    Junliang, W. et al. Chromium-based metal–organic framework MIL-101 as a highly effective catalyst in plasma for toluene removal. J. Phys. D. 50, 475202 (2017).

  23. 23.

    Xu, S. et al. CO2 conversion in a non-thermal, barium titanate packed bed plasma reactor: The effect of dilution by Ar and N2. Chem. Eng. J. 327, 764–773 (2017).

  24. 24.

    Drenchev, N. et al. CO as an IR probe molecule for characterization of copper ions in a basolite C300 MOF sample. Phys. Chem. Chem. Phys. 12, 6423–6427 (2010).

  25. 25.

    Al-Janabi, N. et al. Assessment of MOF’s quality: quantifying defect content in crystalline porous materials. J. Phys. Chem. Lett. 7, 1490–1494 (2016).

  26. 26.

    Cheetham, A. K. et al. Defects and disorder in metal organic frameworks. Dalton. Trans. 45, 4113–4126 (2016).

  27. 27.

    Holzer, F. et al. Combination of non-thermal plasma and heterogeneous catalysis for oxidation of volatile organic compounds: Part 1. Accessibility of the intra-particle volume. Appl. Catal. B 38, 163–181 (2002).

  28. 28.

    Roland, U. et al. Combination of non-thermal plasma and heterogeneous catalysis for oxidation of volatile organic compounds: Part 2. Ozone decomposition and deactivation of γ-Al2O3. Appl. Catal. B 58, 217–226 (2005).

  29. 29.

    Zhang, Y. R. et al. Can plasma be formed in catalyst pores? A modeling investigation. Appl. Catal. B 2016(185), 56–67 (2016).

  30. 30.

    Karra, J. R. & Walton, K. S. Effect of open metal sites on adsorption of polar and nonpolar molecules in metal–organic framework Cu-BTC. Langmuir 24, 8620–8626 (2008).

  31. 31.

    Jeong, D.-W. et al. Low-temperature water–gas shift reaction over supported Cu catalysts. Renew. Energy 65, 102–107 (2014).

  32. 32.

    Tanaka, Y. et al. Water gas shift reaction over Cu-based mixed oxides for CO removal from the reformed fuels. Appl. Catal. A 242, 287–295 (2003).

  33. 33.

    Gokhale, A. A. et al. On the mechanism of low-temperature water gas shift reaction on copper. J. Am. Chem. Soc. 130, 1402–1414 (2008).

  34. 34.

    Aranifard, S. et al. On the importance of the associative carboxyl mechanism for the water–gas shift reaction at Pt/CeO2 interface sites. J. Phys. Chem. C 118, 6314–6323 (2014).

  35. 35.

    Burch, R. Gold catalysts for pure hydrogen production in the water-gas shift reaction: activity, structure and reaction mechanism. Phys. Chem. Chem. Phys. 8, 5483–5500 (2006).

  36. 36.

    Szanyi, J. Well-studied Cu-BTC still serves surprises: evidence for facile Cu2+/Cu+ interchange. Phys. Chem. Chem. Phys. 14, 4383–4390 (2012).

  37. 37.

    Chen, C.-S. et al. Active sites on Cu/SiO2 prepared using the atomic layer epitaxy technique for a low-temperature water–gas shift reaction. J. Catal. 263, 155–166 (2009).

  38. 38.

    Ilinich, O. et al. Cu–Al2O3–CuAl2O4 water–gas shift catalyst for hydrogen production in fuel cell applications: mechanism of deactivation under start–stop operating conditions. J. Catal. 247, 112–118 (2007).

  39. 39.

    Wang, X. et al. In situ studies of the active sites for the water gas shift reaction over Cu−CeO2 catalysts: complex interaction between metallic copper and oxygen vacancies of ceria. J. Phys. Chem. B 110, 428–434 (2006).

  40. 40.

    Du, H. et al. In situ FTIR spectroscopic analysis of carbonate transformations during adsorption and desorption of CO2 in K-promoted HTlc. Chem. Mater. 22, 3519–3526 (2010).

  41. 41.

    Campbell, C. T. & Daube, K. A. A surface science investigation of the water–gas shift reaction on Cu(111). J. Catal. 104, 109–119 (1987).

  42. 42.

    Zhang, Z. et al. The most active Cu facet for low-temperature water gas shift reaction. Nat. Commun. 8, 488 (2017).

  43. 43.

    Baier, T. & Kolb, G. Temperature control of the water gas shift reaction in microstructured reactors. Chem. Eng. Sci. 62, 4602–4611 (2007).

  44. 44.

    Łaniecki, M. et al. Water–gas shift reaction over sulfided molybdenum catalysts. Appl. Catal. A 196, 293–303 (2000).

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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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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).

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