Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework

Yujie Ma; Xue Han; Shaojun Xu; Zhe Li; Wanpeng Lu; Bing An; Daniel Lee; Sarayute Chansai; Alena M. Sheveleva; Zi Wang; Yinlin Chen; Jiangnan Li; Weiyao Li; Rongsheng Cai; Ivan da Silva; Yongqiang Cheng; Luke L. Daemen; Floriana Tuna; Eric J.L. McInnes; Lewis Hughes; Pascal Manuel; Anibal J. Ramirez-Cuesta; Sarah J. Haigh; Christopher Hardacre; Martin Schröder; Sihai Yang

doi:10.1021/jacs.3c03935

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework

Yujie Ma, Xue Han, Shaojun Xu, Zhe Li, Wanpeng Lu, Bing An, Daniel Lee, Sarayute Chansai, Alena M. Sheveleva, Zi Wang, Yinlin Chen, Jiangnan Li, Weiyao Li, Rongsheng Cai, Ivan da Silva, Yongqiang Cheng, Luke L. Daemen, Floriana Tuna, Eric J.L. McInnes, Lewis HughesPascal Manuel, Anibal J. Ramirez-Cuesta, Sarah J. Haigh, Christopher Hardacre, Martin Schröder, Sihai Yang

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Abstract

Conversion of methane (CH₄) to ethylene (C₂H₄) and/or acetylene (C₂H₂) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH₄ controllably, and separating C₂₊ products from unreacted CH₄ can be challenging. Here, we report the direct conversion of CH₄ to C₂H₄ and C₂H₂ driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal-organic framework material, MFM-300(Fe). The selectivity for the formation of C₂H₄ and C₂H₂ reaches 96% with a high time yield of 334 μmol g_cat^-1 h^-1. At a conversion of 10%, the selectivity to C₂₊ hydrocarbons and time yield exceed 98% and 2056 μmol g_cat^-1 h^-1, respectively, representing a new benchmark for conversion of CH₄. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe-O(H)-Fe sites in activating CH₄ and stabilizing reaction intermediates via the formation of an Fe-O(CH₃)-Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C₂H₄ and C₂H₂ from unreacted CH₄ for direct use. Integrating the processes of CH₄ activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

Original language	English
Pages (from-to)	20792-20800
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	145
Issue number	38
DOIs	https://doi.org/10.1021/jacs.3c03935
State	Published - Sep 27 2023

Funding

We thank the EPSRC (EP/I011870, EP/V056409), the Royal Society and the University of Manchester for funding, and the EPSRC for funding of the EPSRC National EPR Facility at Manchester. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 742401, NANOCHEM). We are grateful to the STFC/ISIS Facility for access to Beamline WISH. We acknowledge the Diamond Light Source beamline staff and the UK catalysis Hub Block Allocation Group (BAG) Programme Mode Application for provision of beamtime at B18 (Experiment SP19850) for collection of the data presented in this work and the initial discussion of the data. The UK Catalysis Hub is kindly thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC grant: EP/R026939/1, EP/R026815/1, EP/R026645/1, EP/R027129/1 or EP/M013219/1 (biocatalysis). The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. A.M.S. was supported by the Royal Society Newton International Fellowship, and Y.M. thanks the China Scholarship Council (CSC) for funding. X.H. was supported by a Dame Kathleen Ollerenshaw Fellowship. We thank E. Novak from ORNL for the help with INS experiments.

Funders	Funder number
Compute and Data Environment for Science
ISIS	SP19850
Office of Science
Oak Ridge National Laboratory
Laboratory Directed Research and Development
Horizon 2020 Framework Programme	EP/M013219/1, EP/R026645/1, EP/R027129/1, EP/R026815/1, EP/R026939/1, 742401
Engineering and Physical Sciences Research Council	EP/V056409, EP/I011870
Science and Technology Facilities Council
Royal Society
University of Manchester
European Research Council
China Scholarship Council

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Ma, Y., Han, X., Xu, S., Li, Z., Lu, W., An, B., Lee, D., Chansai, S., Sheveleva, A. M., Wang, Z., Chen, Y., Li, J., Li, W., Cai, R., da Silva, I., Cheng, Y., Daemen, L. L., Tuna, F., McInnes, E. J. L., ... Yang, S. (2023). Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework. Journal of the American Chemical Society, 145(38), 20792-20800. https://doi.org/10.1021/jacs.3c03935

@article{20aed07299a742e7b146cbd47deefeaf,

title = "Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework",

abstract = "Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal-organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 μmol gcat-1 h-1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 μmol gcat-1 h-1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe-O(H)-Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe-O(CH3)-Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.",

author = "Yujie Ma and Xue Han and Shaojun Xu and Zhe Li and Wanpeng Lu and Bing An and Daniel Lee and Sarayute Chansai and Sheveleva, {Alena M.} and Zi Wang and Yinlin Chen and Jiangnan Li and Weiyao Li and Rongsheng Cai and {da Silva}, Ivan and Yongqiang Cheng and Daemen, {Luke L.} and Floriana Tuna and McInnes, {Eric J.L.} and Lewis Hughes and Pascal Manuel and Ramirez-Cuesta, {Anibal J.} and Haigh, {Sarah J.} and Christopher Hardacre and Martin Schr{\"o}der and Sihai Yang",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

year = "2023",

month = sep,

day = "27",

doi = "10.1021/jacs.3c03935",

language = "English",

volume = "145",

pages = "20792--20800",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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Ma, Y, Han, X, Xu, S, Li, Z, Lu, W, An, B, Lee, D, Chansai, S, Sheveleva, AM, Wang, Z, Chen, Y, Li, J, Li, W, Cai, R, da Silva, I, Cheng, Y, Daemen, LL, Tuna, F, McInnes, EJL, Hughes, L, Manuel, P, Ramirez-Cuesta, AJ, Haigh, SJ, Hardacre, C, Schröder, M & Yang, S 2023, 'Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework', Journal of the American Chemical Society, vol. 145, no. 38, pp. 20792-20800. https://doi.org/10.1021/jacs.3c03935

TY - JOUR

T1 - Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework

AU - Ma, Yujie

AU - Han, Xue

AU - Xu, Shaojun

AU - Li, Zhe

AU - Lu, Wanpeng

AU - An, Bing

AU - Lee, Daniel

AU - Chansai, Sarayute

AU - Sheveleva, Alena M.

AU - Wang, Zi

AU - Chen, Yinlin

AU - Li, Jiangnan

AU - Li, Weiyao

AU - Cai, Rongsheng

AU - da Silva, Ivan

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Hughes, Lewis

AU - Manuel, Pascal

AU - Ramirez-Cuesta, Anibal J.

AU - Haigh, Sarah J.

AU - Hardacre, Christopher

AU - Schröder, Martin

AU - Yang, Sihai

PY - 2023/9/27

Y1 - 2023/9/27

N2 - Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal-organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 μmol gcat-1 h-1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 μmol gcat-1 h-1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe-O(H)-Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe-O(CH3)-Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

AB - Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal-organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 μmol gcat-1 h-1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 μmol gcat-1 h-1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe-O(H)-Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe-O(CH3)-Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

UR - http://www.scopus.com/inward/record.url?scp=85172712123&partnerID=8YFLogxK

U2 - 10.1021/jacs.3c03935

DO - 10.1021/jacs.3c03935

M3 - Article

C2 - 37722104

AN - SCOPUS:85172712123

SN - 0002-7863

VL - 145

SP - 20792

EP - 20800

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 38

ER -

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework

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