Methane to high-value liquid fuel conversion is critical for enabling efficient utilization of abundant natural gas resources while overcoming challenges associated with methane storage and transportation.
1
However, the conventional industrial routes for converting methane into liquid products rely largely on indirect reforming processes that require high-temperature operation (> 800
o
C), multistep processing, and substantial energy input.
2
From a molecular perspective, the high bond dissociation energy of methane (104 kcal mol
-1
) imposes severe kinetic barriers to C-H activation, while the thermodynamic preference for complete oxidation drives partially oxidized intermediates toward CO
2
formation.
3
This intrinsic coupling of kinetic difficulty and thermodynamic over-oxidation fundamentally limits the simultaneous achievement of high activity and selectivity. Consequently, electrocatalytic partial oxidation of methane has attracted increasing interest, since electrochemical systems allow precise regulation of reaction potential and oxidation pathways under mild conditions.
4
Nevertheless, selectively activating methane while suppressing over-oxidation remains a fundamental challenge for current catalytic technologies.
5
In this work, a series of MOₓ (M = Fe, Cu, Ni) catalysts is designed to regulate methane electrocatalytic oxidation through controlled metal–oxide interactions. Tailoring the intrinsic redox properties of the metal oxides modulates oxygen vacancy formation energies, lattice oxygen participation, and interfacial charge transfer, thereby decoupling methane activation from over-oxidation pathways. This study elucidates the role of metal–oxide interactions in controlling methane oxidation behavior and demonstrates enhanced activity in three-electrode electrochemical systems. Beyond intrinsic catalytic insights, the metal oxide catalysts are further integrated into membrane–electrode assemblies (MEAs) to evaluate their performance and stability under device-relevant electrochemical conditions.
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Non-thermal plasma (NTP) is a promising approach for activating methane at room temperature, enabling its direct conversion to ethylene under mild conditions. However, the high energy consumption and the trade-off between methane conversion and ethylene selectivity limit its industrial application. Herein, we report a pure-silica self-pillared pentasil (SPP) zeolite catalyst that enables efficient methane conversion to ethylene under non-thermal plasma activation at room temperature. This plasma-catalytic system achieves an exceptional ethylene selectivity of 58.8% with an energy yield of 52 mmol/MJ at atmospheric pressure. Mechanistic studies reveal that isolated hydroxyl groups on the self-pillared pentasil catalyst stabilize gaseous methyl radicals, promoting carbon–carbon coupling and methane dissociation. The confined plasma between catalyst granules selectively suppresses further hydrogenation and methylation of the key C2H5 intermediate, thereby achieving high ethylene selectivity. By systematically adjusting boundary conditions, an ethylene yield of 40% is achieved, surpassing the benchmarks of both plasma and thermal catalytic processes. Non-thermal plasma (NTP) offers a low-temperature route for methane activation but is hindered by high energy consumption and limited ethylene selectivity. Here, the authors develop a pure-silica self-pillared pentasil zeolite that improves methane-to-ethylene conversion under NTP conditions.
Dry reforming of methane (DRM) converts two major greenhouse gases, CH4 and CO2, into syngas. The products (CO and H2) can be directly utilized as feedstock for chemical processes such as Fischer–Tropsch synthesis and methanol production. Transition metal-based catalysts stand as the most commonly employed for DRM on account of their low cost and excellent intrinsic activity. Nevertheless, the harsh high-temperature conditions readily trigger the sintering of metals and carbon deposition, resulting in rapid catalyst deactivation. This critical drawback severely restricts the large-scale industrial rollout of DRM. Relying on the synergistic effect of spatial confinement and interfacial electronic modulation, confined catalysts can efficiently suppress metal sintering and side reactions. In comparison, some confined catalysts achieve a CH4 conversion of over 90% at a lower temperature, and some catalysts nearly form no graphitic carbon during a long-term durability test of 120 h. In contrast, unconfined catalysts suffer from continuous activity deterioration. This review systematically summarizes recent research progress on confined catalysts for DRM. It thoroughly analyzes anti-coking mechanisms, design criteria and optimization strategies, and clarifies the intrinsic coupling rules among geometric confinement, interfacial electronic effects and multi-dimensional synergistic confinement mechanisms. A horizontal comparison is also conducted to evaluate the advantages and limitations of four categories of confined structures: carbon-based, zeolite-based, MOF-derived, and composite support catalysts. Forward-looking optimization directions are proposed by integrating advanced techniques. The conclusions obtained from this review can provide theoretical foundations and practical references for the rational development of high-performance confined catalysts and the industrial advancement of DRM.
Unknown authors· Industrial & Engineering...· 0 citations
The availability of the essential commodities that underpin modern industrialized society has been made possible by efficient and large-scale chemical manufacturing. However, overdependence on fossil fuels and substantial CO2 emissions associated with the conventional processes increasingly threaten global sustainability, motivating the search for low-carbon electrified alternatives. Electrocatalytic routes, particularly for CO2 conversion and N2 fixation, have emerged as promising strategies to transform captured waste streams into value-added chemicals while enabling long-term and transportable storage of renewable electricity. Despite significant progress, electrocatalysis remains constrained by fundamental limitations in energy efficiency, selectivity, production rate, stability, and the accessible product range. In parallel, non-thermal plasma offers non-equilibrium reaction environments for electrified chemical synthesis by triggering electron-driven molecular activation. However, it also is limited by low product selectivity and low energy efficiency, as well as difficulty in coupling the ionized gas with aqueous feedstocks.In this perspective, we propose that plasma coupling with electrocatalysis could potentially overcome key bottlenecks in electrochemical synthesis reactions. After outlining the limitations of separate electrocatalysis and non-thermal plasma processes, we examine plasma-assisted electrocatalysis systems for CO2 and N2 conversion with a focus on the underlying motivations, proposed mechanisms, and current challenges. Then, we discuss potential synergies arising from plasma-electrocatalytic coupling, mechanistic knowledge gaps, and key design principles to guide future research. Through this perspective, we introduce plasma-assisted electrocatalysis as a promising yet largely unexplored paradigm that can provide access to innovative reaction pathways and contribute to the successful electrification of chemical manufacturing.
Electrocatalytic upgrading of renewable biomass-derived glycerol represents a sustainable method to produce value-added chemicals, but the complex reaction network of key intermediates during the glycerol oxidation poses challenges to product selectivity. Herein, we report a nickel-doped tungsten oxide catalyst grown on nickel foam (Ni-WOx/NF) for the highly selective electrooxidation of glycerol to formic acid (FA). This optimized catalyst achieves an FA Faraday efficiency (FE) of 95.1% and operates stably for over 18 h, outperforming conventional non-precious metal catalysts. Mechanistic understanding revealed that nickel doping effectively modulates the valence states of tungsten, increasing the proportion of low-valent W4+ species. This promotes the desorption of FA from the catalytic interface, thereby inhibiting its over-oxidation and enhancing selectivity. Taking a step forward, an integrated electrocatalytic system coupling the anodic glycerol oxidation reaction (GOR) with the cathodic nitrate reduction reaction (NO3-RR) is constructed. This system enables the simultaneous coproduction of FA and ammonia (NH3), achieving a high FE for FA of 96.9% along with sustained stability over 12 h, demonstrating significant potential for practical applications. This work demonstrates a sustainable catalytic system for selective glycerol oxidation by precisely regulating the reaction pathways of key intermediates.
Lang Chen, Mei Li, Shen Yan et al.· Small· 0 citations
The direct conversion of methane into value‐added chemicals under mild conditions offers a sustainable pathway to utilize this abundant hydrocarbon feedstock and mitigate greenhouse gas emissions. However, the thermodynamic stability of the C─H bond and the propensity for product overoxidation pose formidable scientific challenges. This review systematically summarizes recent breakthroughs in electrocatalytic, photocatalytic, and photoelectrocatalytic strategies for methane valorization. We critically examine fundamental activation mechanisms, structure‐property relationships in catalyst design, and strategies to tune product selectivity toward liquid oxygenates and coupled hydrocarbons. Beyond material innovation, this review places particular emphasis on reactor engineering, elaborating on the evolution from conventional batch systems to advanced continuous flow architectures, such as gas convection electrodes and hierarchical triphase diffusion architectures, to overcome mass transfer limitations. Finally, we provide forward looking perspectives on emerging frontiers, including data‐driven catalyst discovery and integrated system design, to guide the transition from laboratory research to industrial implementation.
Heng-Shuo Liu, Liu Huang, Ziyan Fu et al.· Carbon Neutralization· 0 citations
The imperative to mitigate climate change has accelerated the development of Carbon Capture, Utilization, and Storage (CCUS) technologies, particularly CO2 hydrogenation into high-value chemicals and alternative fuels. This work evaluates the fundamental thermodynamic limitations and the primary directions of CO2 conversion, with a primary focus on methanation, alongside related pathways such as methanol synthesis and the reverse water-gas shift (RWGS) reaction. To overcome the high kinetic barriers of CO2 activation, various catalytic systems are analyzed. While noble metal catalysts exhibit high catalytic performance, nickel-based catalysts serve as a viable and cost-effective alternative. To overcome nickel’s susceptibility to thermal sintering and coking, advanced bimetallic and multimetallic formulations are being developed to enhance structural stability and selectivity. These advancements are crucial for producing Synthetic Natural Gas (SNG) and sustainable aviation fuels (SAF). Ultimately, the objective of this comprehensive review is to systematically summarize recent advancements in catalyst design, critically analyze the advantages and fundamental bottlenecks of distinct catalytic systems, and outline prospective paths for the efficient industrial-scale production of sustainable alternative fuels.
Kornelia Nejranowska, Agnieszka Szymaszek-Wawryca, M. Motak· Materials· 0 citations
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