Dataset Information

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 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.

SUBMITTER: Ma Y

PROVIDER: S-EPMC10540182 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature

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

Ma Yujie Y Han Xue X Xu Shaojun S Li Zhe Z Lu Wanpeng W An Bing B Lee Daniel D Chansai Sarayute S Sheveleva Alena M AM Wang Zi Z Chen Yinlin Y Li Jiangnan J Li Weiyao W Cai Rongsheng R da Silva Ivan I Cheng Yongqiang Y Daemen Luke L LL Tuna Floriana F McInnes Eric J L EJL Hughes Lewis L Manuel Pascal P Ramirez-Cuesta Anibal J AJ Haigh Sarah J SJ Hardacre Christopher C Schröder Martin M Yang Sihai S

Journal of the American Chemical Society 20230918 38

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 C<s ...[more]

PMID: 37722104

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Project description:Methane (CH4), which is the main component of natural gas, is an abundant and widely available carbon resource. However, CH4 has a low energy density of only 36 kJ L-1 under ambient conditions, which is significantly lower than that of gasoline (ca. 34 MJ L-1). The activation and catalytic conversion of CH4 into value-added chemicals [e.g., methanol (CH3OH), which has an energy density of ca. 17 MJ L-1], can effectively lift its energy density. However, this conversion is highly challenging due to the inert nature of CH4, characterized by its strong C-H bonds and high stability. Consequently, the development of efficient materials that can optimize the binding and activation pathway of CH4 with control of product selectivity has attracted considerable recent interest. Metal-organic framework (MOF) materials have emerged as particularly attractive candidates for the development of efficient sorbents and heterogeneous catalysts due to their high porosity, low density, high surface area and structural versatility. These properties enable MOFs to act as effective platforms for the adsorption, binding and catalytic conversion of CH4 into valuable chemicals. Recent reports have highlighted MOFs as promising materials for these applications, leading to new insights into the structure-activity relationships that govern their performance in various systems. In this Account, we present analysis of state-of-the-art MOF-based sorbents and catalysts, particularly focusing on materials that incorporate well-defined active sites within confined space. The precise control of these active sites and their surrounding microenvironment is crucial as it directly influences the efficiency of CH4 activation and the selectivity of the resulting chemical products. Our discussion covers key reactions involving CH4, including its activation, selective oxidation of CH4 to CH3OH, dry reforming of CH4, nonoxidative coupling of CH4, and borylation of CH4. We analyze the role of active sites and their microenvironment in the binding and activation of CH4 using a wide range of experimental and computational studies, including neutron diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, infrared and X-ray absorption spectroscopies coupled to density functional theory calculations. In particular, neutron scattering has notable advantages in elucidating host-guest interactions and the mechanisms of the conversion and catalysis of CH4 and CD4. In addition to exploring current advances, the limitations and future direction of research in this area are also discussed. Key challenges include improvements in the stability, scalability, and performance of MOFs under practical conditions, as well as achieving higher selectivity and yields of targeted products. The ongoing development of MOFs and related materials holds great promise for the efficient and sustainable utilization of CH4, transforming it from a low-density energy source into a versatile precursor for a wide range of value-added chemicals. This Account summarizes the design and development of functional MOF and related materials for the adsorption and conversion of CH4.

Dataset Information

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

Publications

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

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