Direct conversion of methane to ethylene and acetylene over an iron-based metal–organic framework

DOI: 10.1021/jacs.3c03935

Authors: Yujie Ma (University of Manchester) , Xue Han (University of Manchester; Beijing Normal University) , Shaojun Xu (University of Manchester) , Zhe Li (The Francis Crick Institute) , Wanpeng Lu (University of Manchester) , Bing An (University of Manchester) , Daniel Lee (University of Manchester) , Sarayute Chansai (University of Manchester) , Alena M. Sheveleva (University of Manchester) , Zi Wang (University of Manchester) , Yinlin Chen (University of Manchester) , Jiangnan Li (University of Manchester) , Weiyao Li (University of Manchester) , Rongsheng Cai (University of Manchester) , Ivan Da Silva (ISIS Facility) , Yongqiang Cheng (Oak Ridge National Laboratory) , Luke L. Daemen (Oak Ridge National Laboratory) , Floriana Tuna (University of Manchester) , Eric J. L. Mcinnes (University of Manchester) , Lewis Hughes (University of Manchester) , Pascal Manuel (ISIS Facility) , Anibal J. Ramirez-Cuesta (Oak Ridge National Laboratory) , Sarah J. Haigh (University of Manchester) , Christopher Hardacre (University of Manchester) , Martin Schroeder (University of Manchester) , Sihai Yang (University of Manchester; Peking University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: September 2023
Diamond Proposal Number(s): 19850

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.

Subject Areas: Materials, Chemistry


Instruments: B18-Core EXAFS

Other Facilities: WISH at ISIS

Added On: 21/09/2023 21:30

Documents:
jacs.3c03935.pdf

Discipline Tags:

Physical Chemistry Chemistry Materials Science Chemical Engineering Engineering & Technology Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Spectroscopy X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS)