Chemical Looping Steam Reforming of Methane under Mild Conditions via Non-Thermal Plasma

Zunrong Sheng; Donglong Fu; Tingting Yang; Xianhua Zhang; Zheyuan Ding; Chunlei Pei; Sai Chen; Zhi-Jian Zhao; Jinlong Gong

doi:10.1016/j.eng.2026.01.001

Engineering ›› :202601001 DOI: 10.1016/j.eng.2026.01.001

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Chemical Looping Steam Reforming of Methane under Mild Conditions via Non-Thermal Plasma

Zunrong Sheng ^a^,^b^,^c^,^d
, Donglong Fu ^a^,^b^,^c
, Tingting Yang ^a^,^b^,^c^,^e
, Xianhua Zhang ^a^,^b^,^c^,^e
, Zheyuan Ding ^a^,^b^,^c
, Chunlei Pei ^a^,^b^,^c^,^f^,^g
, Sai Chen ^a^,^b^,^c
, Zhi-Jian Zhao ^a^,^b^,^c^,^f^,^g
, Jinlong Gong ^a^,^b^,^c^,^h^,ⁱ^,^*

Author information +

^a Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

^b Collaborative Innovation Center for Chemical Science and Engineering, Tianjin 300072, China

^c International Joint Laboratory of Low-Carbon Chemical Engineering of Ministry of Education, Tianjin 300350, China

^d School of Electrical Engineering, Dalian University of Technology, Dalian 116024, China

^e Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China

^f Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China

^g National Industry-Education Platform for Energy Storage, Tianjin University, Tianjin 300350, China

^h State Key Laboratory of Synthetic Biology, Tianjin University, Tianjin 300072, China

ⁱ Tianjin Normal University, Tianjin 300387, China

Corresponding author:

^* jlgong@tju.edu.cn (Jinlong Gong)

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Abstract

The chemical looping steam reforming of methane (CL-SRM) holds immense potential for energy-efficient conversion of CH₄ into syngas and high-purity hydrogen. However, its large-scale implementation remains limited by high operating temperatures and substantial energy requirements. This paper describes a non-thermal plasma-mediated CL-SRM process based on CH₄/H₂O redox cycles over lanthanum-based perovskites under mild conditions. The developed process achieves efficient CH₄ activation at 600 °C, attaining 53.5% CH₄ conversion and 0.57 mmol∙g⁻¹ H₂ with 92% purity over La_0.5Ce_0.5FeO₃, while negligible conversion is observed under plasma-free conditions at the same furnace temperature. These performances surpass those observed under purely thermal conditions at 800 °C. Mechanistic insights reveal that plasma plays a crucial role in generating vibrationally excited CH₄^v species, thereby markedly lowering the reaction barrier for CH₄ activation. The plasma-mediated CL-SRM process delivers energy through voltage-induced electron transfer, offering the potential for adiabatic reactor designs that minimize energy consumption compared with conventional combustion-based systems suffering from heat transfer limitations.

Keywords

Non-thermal plasma / Redox chemistry / Steam reforming of methane

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Zunrong Sheng, Donglong Fu, Tingting Yang, Xianhua Zhang, Zheyuan Ding, Chunlei Pei, Sai Chen, Zhi-Jian Zhao, Jinlong Gong. Chemical Looping Steam Reforming of Methane under Mild Conditions via Non-Thermal Plasma. Engineering 202601001 DOI:10.1016/j.eng.2026.01.001

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References

Publishing order | Descend order by publishing year | Descend order by cited within

[1]	Wismann ST, Engbæk JS, Vendelbo SB, Bendixen FB, Eriksen WL, Aasberg-Petersen K, et al. Electrified methane reforming: a compact approach to greener industrial hydrogen production. Science 2019; 364(6442):756-9.

[2]	Ben-Mansour R, Azazul Haque MD, Harale A, Paglieri SN, Alrashed FS, Raghib Shakeel M, et al. Comprehensive parametric investigation of methane reforming and hydrogen separation using a CFD model. Energy Convers Manage 2021; 249:114838.

[3]	Song C, Liu Q, Ji N, Kansha Y, Tsutsumi A. Optimization of steam methane reforming coupled with pressure swing adsorption hydrogen production process by heat integration. Appl Energy 2015; 154:392-401.

[4]	Liu K, Pan C, Kuhn A, Nievergelt AP, Fantner GE, Milenkovic O, et al. Detecting topological variations of DNA at single-molecule level. Nat Commun 2019; 10:3.

[5]	Wang W, Chen S, Pei C, Luo R, Sun J, Song H, et al. Tandem propane dehydrogenation and surface oxidation catalysts for selective propylene synthesis. Science 2023; 381(6660):886-90.

[6]	Metcalfe IS, Ray B, Dejoie C, Hu W, de Leeuwe C, Dueso C, et al. Overcoming chemical equilibrium limitations using a thermodynamically reversible chemical reactor. Nat Chem 2019; 11(7):638-43.

[7]	Muhich CL, Evanko BW, Weston KC, Lichty P, Liang X, Martinek J, et al. Efficient generation of H₂ by splitting water with an isothermal redox cycle. Science 2013; 341(6145):540-2.

[8]	Huang J, Liu W, Yang Y, Liu B. High-performance Ni-Fe redox catalysts for selective CH₄ to syngas conversion via chemical looping. ACS Catal 2018; 8(3):1748-56.

[9]	Chen S, Zeng L, Tian H, Li X, Gong J. Enhanced lattice oxygen reactivity over Ni-modified WO₃-based redox catalysts for chemical looping partial oxidation of methane. ACS Catal 2017; 7(5):3548-59.

[10]	Kang Y, Han Y, Tian M, Huang C, Wang C, Lin J, et al. Promoted methane conversion to syngas over Fe-based garnets via chemical looping. Appl Catal B 2020; 278:119305.

[11]	Zhang X, Pei C, Chang X, Chen S, Liu R, Zhao ZJ, et al. FeO₆ octahedral distortion activates lattice oxygen in perovskite ferrite for methane partial oxidation coupled with CO₂ splitting. J Am Chem Soc 2020; 142(26):11540-9.

[12]	Liu R, Pei C, Zhang X, Chen S, Li H, Zeng L, et al. Chemical looping partial oxidation over FeWO_x/SiO₂ catalysts. Chin J Catal 2020; 41(7):1140-51.

[13]	Chang H, Bjørgum E, Mihai O, Yang J, Lein HL, Grande T, et al. Effects of oxygen mobility in La-Fe-based perovskites on the catalytic activity and selectivity of methane oxidation. ACS Catal 2020; 10(6):3707-19.

[14]	Kang Y, Tian M, Huang C, Lin J, Hou B, Pan X, et al. Improving syngas selectivity of Fe₂O₃/Al₂O₃ with yttrium modification in chemical looping methane conversion. ACS Catal 2019; 9(9):8373-82.

[15]	Zhang X, Liu R, Liu T, Pei C, Gong J. Redox catalysts for chemical looping methane conversion. Trends Chem 2023; 5(7):512-25.

[16]	Ma S, Chen S, Zhu M, Zhao Z, Hu J, Wu M, et al. Enhanced sintering resistance of Fe₂O₃/CeO₂ oxygen carrier for chemical looping hydrogen generation using core-shell structure. Int J Hydrogen Energy 2019; 44(13):6491-504.

[17]	Neal L, Shafiefarhood A, Li F. Effect of core and shell compositions on MeO_x@La_ySr_1-yFeO₃ core-shell redox catalysts for chemical looping reforming of methane. Appl Energy 2015; 157:391-8.

[18]	Zheng Y, Marek EJ, Scott SA. H₂ production from a plasma-assisted chemical looping system from the partial oxidation of CH₄ at mild temperatures. Chem Eng J 2020; 379:122197.

[19]	Ranganathan RV, Jony B, Fondriest SM, Liu Z, Wang R, Uddi M.Plasma-catalysis chemical looping CH₄ reforming with water splitting using ceria supported Ni based La-perovskite nano-catalyst. J CO₂ Util 2019; 32:11-20.

[20]	Gibson EK, Stere CE, Curran-McAteer B, Jones W, Cibin G, Gianolio D, et al. Probing the role of a non-thermal plasma (NTP) in the hybrid NTP catalytic oxidation of methane. Angew Chem Int Ed 2017; 56(32):9351-5.

[21]	Winter LR, Chen JG. Challenges and opportunities in plasma-activated reactions of CO₂ with light alkanes. J Energy Chem 2023; 84:424-7.

[22]	Loenders B, Michiels R, Bogaerts A. Is a catalyst always beneficial in plasma catalysis? Insights from the many physical and chemical interactions. J Energy Chem 2023; 85:501-33.

[23]	Wang L, Yi Y, Wu C, Guo H, Tu X. One-step reforming of CO₂ and CH₄ into high-value liquid chemicals and fuels at room temperature by plasma-driven catalysis. Angew Chem 2017; 129(44):13867-71.

[24]	Geng F, Haribal VP, Hicks JC.Non-thermal plasma-assisted steam methane reforming for electrically-driven hydrogen production. Appl Catal A 2022; 647:118903.

[25]	Bajpai A, Mehta S, Joshi K, Kumar S. Hydrogen from catalytic non-thermal plasma-assisted steam methane reforming reaction. Int J Hydrogen Energy 2023; 48(63):24328-41.

[26]	Zhu X, Liu X, Lian HY, Liu JL, Li XS. Plasma catalytic steam methane reforming for distributed hydrogen production. Catal Today 2019; 337:69-75.

[27]	Hrabovsky M, Hlina M, Kopecky V, Maslani A, Krenek P, Serov A, et al. Steam plasma methane reforming for hydrogen production. Plasma Chem Plasma Process 2018; 38(4):743-58.

[28]	Stere CE, Anderson JA, Chansai S, Delgado JJ, Goguet A, Graham WG, et al. Non-thermal plasma activation of gold-based catalysts for low-temperature water-gas shift catalysis. Angew Chem Int Ed 2017; 56(20):5579-83.

[29]	Mistry H, Varela AS, Bonifacio CS, Zegkinoglou I, Sinev I, Choi YW, et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat Commun 2016; 7:12123.

[30]	Mehta P, Barboun P, Herrera FA, Kim J, Rumbach P, Go DB, et al.Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis. Nat Catal 2018; 1(4):269-75.

[31]	Zheng Y, Grant R, Hu W, Marek E, Scott SA. H₂ production from partial oxidation of CH₄ by Fe₂O₃-supported Ni-based catalysts in a plasma-assisted packed bed reactor. Proc Combust Inst 2019; 37(4):5481-8.

[32]	Nozaki T, Okazaki K. Non-thermal plasma catalysis of methane: principles, energy efficiency, and applications. Catal Today 2013; 211:29-38.

[33]	Sheng Z, Watanabe Y, Kim HH, Yao S, Nozaki T. Plasma-enabled mode-selective activation of CH₄ for dry reforming: first touch on the kinetic analysis. Chem Eng J 2020; 399:125751.

[34]	Xing Y, Fan Y, Yan Z, Zhao B, Huang Y, Pan W. Core-shell LaOCl/LaFeO₃ nanofibers with matched impedance for high-efficiency electromagnetic wave absorption. Sci China Mater 2023; 66(4):1587-96.

[35]	Morgan WL. A critical evaluation of low-energy electron impact cross sections for plasma processing modeling. II: Cl₄, SiH₄, and CH₄. Plasma Chem Plasma Process 1992; 12(4):477-93.

[36]	Taylor FH, Buckeridge J, Catlow CRA. Defects and oxide ion migration in the solid oxide fuel cell cathode material LaFeO₃. Chem Mater 2016; 28(22):8210-20.

[37]	Jones A, Islam MS. Atomic-scale insight into LaFeO₃ perovskite: defect nanoclusters and ion migration. J Phys Chem C 2008; 112(12):4455-62.

[38]	Yang J, Bjørgum E, Chang H, Zhu KK, Sui ZJ, Zhou XG, et al. On the ensemble requirement of fully selective chemical looping methane partial oxidation over La-Fe-based perovskites. Appl Catal B 2022; 301:120788.

[39]	Kim DY, Ham H, Chen X, Liu S, Xu H, Lu B, et al. Cooperative catalysis of vibrationally excited CO₂ and alloy catalyst breaks the thermodynamic equilibrium limitation. J Am Chem Soc 2022; 144(31):14140-9.

[40]	Quan J, Muttaqien F, Kondo T, Kozarashi T, Mogi T, Imabayashi T, et al. Vibration-driven reaction of CO₂ on Cu surfaces via Eley-Rideal-type mechanism. Nat Chem 2019; 11(8):722-9.

[41]	Alharbi AA, Sackmann A, Weimar U, Bârsan N. Acetylene-and ethylene-sensing mechanism for LaFeO₃-based gas sensors: operando insights. J Phys Chem C 2020; 124(13):7317-26.

[42]	Shao S, Zhang H, Xiao R, Li X, Cai Y. Catalytic conversion of biomass-derivates by in situ DRIFTS: evolution of coke. J Anal Appl Pyrolysis 2017; 127:258-68.

[43]	Guo J, Hou Z, Gao J, Zheng X. DRIFTS study on adsorption and activation of CH₄ and CO₂ over Ni/SiO₂ catalyst with various Ni particle sizes. Chin J Catal 2007; 28(1):22-6.

[44]	Kuhn JN, Ozkan US.Surface properties of Sr-and Co-doped LaFeO₃. J Catal 2008; 253(1):200-11.

[45]	He F, Li X, Zhao K, Huang Z, Wei G, Li H. The use of La_1-xSr_xFeO₃ perovskite-type oxides as oxygen carriers in chemical-looping reforming of methane. Fuel 2013; 108:465-73.

[46]	Kim J, Kim YJ, Ferree M, Gunduz S, Co AC, Kim M, et al. In-situ exsolution of bimetallic CoFe nanoparticles on (La,Sr)FeO₃ perovskite: its effect on electrocatalytic oxidative coupling of methane. Appl Catal B 2023; 321:122026.

[47]	Wang Y, Hu P, Yang J, Zhu YA, Chen D. C-H bond activation in light alkanes: a theoretical perspective. Chem Soc Rev 2021; 50(7):4299-358.

[48]	Amrillah T, Supandi AR, Puspasari V, Hermawan A, Seh ZW. MXene-based photocatalysts and electrocatalysts for CO₂ conversion to chemicals. Trans Tianjin Univ 2022; 28(4):307-22.

[49]	Alharbi A, Junker B, Alduraibi M, Algarni A, Weimar U, Bârsan N. The role of different lanthanoid and transition metals in perovskite gas sensors. Sensors 2021; 21(24):8462.

[50]	Sheng Z, Kim HH, Yao S, Nozaki T. Plasma-chemical promotion of catalysis for CH₄ dry reforming: unveiling plasma-enabled reaction mechanisms. Phys Chem Chem Phys 2020; 22(34):19349-58.

[51]	Donat F, Müller CR. CO₂-free conversion of CH₄ to syngas using chemical looping. Appl Catal B 2020; 278:119328.

[52]	Sun X, Zhu L, Zhao W, Li F, Chen X. Ni-Fe bimetallic hexaaluminate for efficient reduction of O₂-containing CO₂ via chemical looping. Chem Eng J 2022; 441:136071.

[53]	Zeng L, Cheng Z, Fan JA, Fan LS, Gong J. Metal oxide redox chemistry for chemical looping processes. Nat Rev Chem 2018; 2(11):349-64.

[54]	Ngo SI, Lim YI, Kim W, Seo DJ, Yoon WL. Computational fluid dynamics and experimental validation of a compact steam methane reformer for hydrogen production from natural gas. Appl Energy 2019; 236:340-53.