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.
Subscribe to Journal
Get full journal access for 1 year
only $8.67 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
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.
Yaghi, O. M. & Li, H. Hydrothermal synthesis of a metal–organic framework containing large rectangular channels. J. Am. Chem. Soc. 117, 10401–10402 (1995).
Corma, A. et al. Engineering metal organic frameworks for heterogeneous catalysis. Chem. Rev. 110, 4606–4655 (2010).
Rowsell, J. L. C. & Yaghi, O. M. Metal–organic frameworks: a new class of porous materials. Microporous Mesoporous Mater. 73, 3–14 (2004).
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).
Chui, S. S. et al. A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n. Science 283, 1148–1150 (1999).
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).
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).
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).
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).
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).
Mehta, P. et al. Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis. Nat. Catal. 1, 269–275 (2018).
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).
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).
Ashford, B. & Tu, X. Non-thermal plasma technology for the conversion of CO2. Curr. Opin. Green Sustainable Chem. 3, 45–49 (2017).
Bae, J. et al. Oxygen plasma treatment of HKUST-1 for porosity retention upon exposure to moisture. Chem. Commun. 53, 12100–12103 (2017).
Luo, J. et al. Water splitting in low-temperature ac plasmas at atmospheric pressure. Res. Chem. Intermed. 26, 849–874 (2000).
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).
Decoste, J. B. et al. Hierarchical pore development by plasma etching of Zr-based metal–organic frameworks. Chem. Eur. J. 21, 18029–18032 (2015).
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).
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).
Bahri, M. et al. Metal organic frameworks for gas-phase VOCs removal in a NTP-catalytic reactor. Chem. Eng. J. 320, 308–318 (2017).
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).
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).
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).
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).
Cheetham, A. K. et al. Defects and disorder in metal organic frameworks. Dalton. Trans. 45, 4113–4126 (2016).
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).
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).
Zhang, Y. R. et al. Can plasma be formed in catalyst pores? A modeling investigation. Appl. Catal. B 2016(185), 56–67 (2016).
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).
Jeong, D.-W. et al. Low-temperature water–gas shift reaction over supported Cu catalysts. Renew. Energy 65, 102–107 (2014).
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).
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).
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).
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).
Szanyi, J. Well-studied Cu-BTC still serves surprises: evidence for facile Cu2+/Cu+ interchange. Phys. Chem. Chem. Phys. 14, 4383–4390 (2012).
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).
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).
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).
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).
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).
Zhang, Z. et al. The most active Cu facet for low-temperature water gas shift reaction. Nat. Commun. 8, 488 (2017).
Baier, T. & Kolb, G. Temperature control of the water gas shift reaction in microstructured reactors. Chem. Eng. Sci. 62, 4602–4611 (2007).
Łaniecki, M. et al. Water–gas shift reaction over sulfided molybdenum catalysts. Appl. Catal. A 196, 293–303 (2000).
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.
The authors declare no competing interests.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
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
Journal of Physics D: Applied Physics (2020)
Kinetic Study of Nonthermal Plasma Activated Catalytic CO2 Hydrogenation over Ni Supported on Silica Catalyst
Industrial & Engineering Chemistry Research (2020)
ACS Catalysis (2020)
Effect of metal dispersion and support structure of Ni/silicalite-1 catalysts on non-thermal plasma (NTP) activated CO2 hydrogenation
Applied Catalysis B: Environmental (2020)
Plasma-assisted catalytic dry reforming of methane (DRM) over metal-organic frameworks (MOFs)-based catalysts
Applied Catalysis B: Environmental (2020)