Efficient electrochemical methane coupling enabled by stabilized oxygen species during oxygen evolution in a solid oxide electrolyzer integrated with CO2 electrolysis

Chunsong Li , Lingxiu Li , Fan Bai , Hui Gao , Yunzhu Liu , Zhongyuan Liu , Shixian Zhang , Yuhui Jin , Wenxi Ji , Longgui Zhang , Yifeng Li , Bo Yu

Front. Energy ›› 2025, Vol. 19 ›› Issue (4) : 521 -533.

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Front. Energy ›› 2025, Vol. 19 ›› Issue (4) : 521 -533. DOI: 10.1007/s11708-025-1016-2
RESEARCH ARTICLE

Efficient electrochemical methane coupling enabled by stabilized oxygen species during oxygen evolution in a solid oxide electrolyzer integrated with CO2 electrolysis

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Abstract

The electrochemical oxidative coupling of methane (EOCM), integrated with CO2 electrolysis enabled by high-temperature electrolysis technology, represents a promising pathway for methane utilization and carbon neutrality. However, progress in methane activation remains hindered by low C2 product selectivity and limited reaction activity, primarily due to the lack of efficient and stable catalysts and rational design strategies. A critical focus of current research is the development of catalysts capable of stabilizing reactive oxygen species to facilitate C–H bond activation and subsequent C–C bond formation. Herein, an easily fabricated composite electrode consisting of perovskite La0.6Sr0.4MnO3–δ and Ce-Mn-W materials with (Ce0.90Gd0.10)O1.95 as the support was developed, demonstrating efficient activate methane activation. Combined theoretical and experimental investigations reveal that the designed composite electrode stabilizes active oxygen species during the oxygen evolution reaction (OER) while exhibiting superior methane adsorption capability. This design, leveraging oxygen species engineering and interfacial synergy, significantly enhances electrochemical methane coupling efficiency, establishing a strategic framework for advancing high-performance catalyst development.

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Keywords

electrochemical oxidative coupling of methane (EOCM) / solid oxide electrolysis cell (SOEC) / methane to ethylene / composite electrode / CO2 electrolysis

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Chunsong Li, Lingxiu Li, Fan Bai, Hui Gao, Yunzhu Liu, Zhongyuan Liu, Shixian Zhang, Yuhui Jin, Wenxi Ji, Longgui Zhang, Yifeng Li, Bo Yu. Efficient electrochemical methane coupling enabled by stabilized oxygen species during oxygen evolution in a solid oxide electrolyzer integrated with CO2 electrolysis. Front. Energy, 2025, 19(4): 521-533 DOI:10.1007/s11708-025-1016-2

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References

[1]

Schwach P, Pan X, Bao X. Direct conversion of methane to value-added chemicals over heterogeneous catalysts: challenges and prospects. Chemical Reviews, 2017, 117(13): 8497–8520

[2]

Arinaga A M, Ziegelski M C, Marks T J. Alternative oxidants for the catalytic oxidative coupling of methane. Angewandte Chemie International Edition, 2021, 60(19): 10502–10515

[3]

Gambo Y, Jalil A A, Triwahyono S. . Recent advances and future prospect in catalysts for oxidative coupling of methane to ethylene: A review. Journal of Industrial and Engineering Chemistry, 2018, 59: 218–229

[4]

Zhong J, Han J, Wei Y. . Catalysts and shape selective catalysis in the methanol-to-olefin (MTO) reaction. Journal of Catalysis, 2021, 396: 23–31

[5]

Yang M, Fan D, Wei Y. . Recent progress in methanol-to-olefins (MTO) catalysts. Advanced Materials, 2019, 31(50): 1902181

[6]

Wang S, Wang P, Shi D. . Direct conversion of syngas into light olefins with low CO2 emission. ACS Catalysis, 2020, 10(3): 2046–2059

[7]

Jiao F, Li J, Pan X. . Selective conversion of syngas to light olefins. Science, 2016, 351(6277): 1065–1068

[8]

Liu J, Yue J, Lv M. . From fundamentals to chemical engineering on oxidative coupling of methane for ethylene production: A review. Carbon Resources Conversion, 2022, 5(1): 1–14

[9]

Ortiz-Bravo C A, Chagas C A, Toniolo F S. Oxidative coupling of methane (OCM): An overview of the challenges and opportunities for developing new technologies. Journal of Natural Gas Science and Engineering, 2021, 96: 104254

[10]

Thyssen V V, Vilela V B, de Florio D Z. . Direct conversion of methane to C2 hydrocarbons in solid-state membrane reactors at high temperatures. Chemical Reviews, 2022, 122(3): 3966–3995

[11]

Otsuka K, Suga K, Yamanaka I. Oxidative coupling of methane applying a solid oxide fuel cell system. Catalysis Today, 1990, 6(4): 587–592

[12]

Appamana W, Khammona K, Wiyaratn W. . Oxidative coupling of methane over YSZ support catalysts for application in C2 hydrocarbon production. Engineering Journal, 2015, 19: 1–11

[13]

Li F, Li Y, Chen H. . Impact of strain-induced changes in defect chemistry on catalytic activity of Nd2NiO4+δ electrodes. ACS Applied Materials & Interfaces, 2018, 10(43): 36926–36932

[14]

Fan L, Luo W, Fan Q. . Status and outlook of solid electrolyte membrane reactors for energy, chemical, and environmental applications. Chemical Science, 2025, 16(16): 6620–6687

[15]

Zhu C, Hou S, Hu X. . Electrochemical conversion of methane to ethylene in a solid oxide electrolyzer. Nature Communications, 2019, 10(1): 1173

[16]

Xu X, Li H, Han X. . Enhancing electrochemical methane coupling in solid oxide cells by tuning oxygen species in the catalyst. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2024, 12(9): 5115–5123

[17]

CaravacaA, de Lucas-Consuegra A, González-CobosJ, et al. Simultaneous production of H2 and C2 hydrocarbons by gas phase electrocatalysis. Applied Catalysis B: Environmental, 2012, 113–114: 192–200

[18]

Zheng Y, Zhao C, Wu T. . Enhanced oxygen reduction kinetics by a porous heterostructured cathode for intermediate temperature solid oxide fuel cells. Energy and AI, 2020, 2: 100027

[19]

Liu D, Shang H, Zhou C. . Active Cu and Fe nanoparticles codecorated Ruddlesden–Popper-type perovskite as solid oxide electrolysis cells cathode for CO2 splitting. Energy & Environmental Materials, 2024, 7(5): e12717

[20]

Wang W, Li H, Park K Y. . Enhancing direct electrochemical CO2 electrolysis by introducing A-site deficiency for the dual-phase Pr(Ca)Fe(Ni)O3−δ cathode. Energy & Environmental Materials, 2024, 7(5): e12715

[21]

Denoyer L H, Benavidez A, Garzon F H. . Highly stable doped barium niobate based electrocatalysts for effective electrochemical coupling of methane to ethylene. Advanced Materials Interfaces, 2022, 9(27): 2200796

[22]

Kodama S, Kikuchi R, Fujiwara N. . Oxidative coupling of methane in solid oxide electrolysis cell. ECS Transactions, 2019, 91(1): 2697–2705

[23]

Pujare N U, Sammells A F. Methane activation to C2 hydrocarbon species in solid oxide fuel cell. Journal of the Electrochemical Society, 1988, 135(10): 2544–2545

[24]

WhiteJ. The electrochemical oxidative dimerization of methane. Solid State Ionics, 1992, 53–56: 149–161

[25]

Otsuka K, Suga K, Yamanaka I. Electrochemical enhancement of oxidative coupling of methane over LiCl-doped NiO using stabilized zirconia electrolyte. Catalysis Letters, 1988, 1(12): 423–428

[26]

Ye L, Shang Z, Xie K. Selective oxidative coupling of methane to ethylene in a solid oxide electrolyser based on porous single-crystalline CeO2 monoliths. Angewandte Chemie International Edition, 2022, 61(32): e202207211

[27]

Kresse G, Furthmuller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B: Condensed Matter, 1996, 54(16): 11169–11186

[28]

Kresse G, Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 1996, 6(1): 15–50

[29]

Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868

[30]

Dudarev S L, Botton G A, Savrasov S Y. . Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study. Physical Review B: Condensed Matter, 1998, 57(3): 1505–1509

[31]

Chen H T, Raghunath P, Lin M C. Computational investigation of O2 reduction and diffusion on 25% Sr-doped LaMnO3 cathodes in solid oxide fuel cells. Langmuir, 2011, 27(11): 6787–6793

[32]

Polfus J M, Yildiz B, Tuller H L. Origin of fast oxide ion diffusion along grain boundaries in Sr-doped LaMnO3. Physical Chemistry Chemical Physics, 2018, 20(28): 19142–19150

[33]

Grimme S, Antony J, Ehrlich S. . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. Journal of Chemical Physics, 2010, 132(15): 154104

[34]

Monkhorst H J, Pack J D. Special points for Brillouin-zone integrations. Physical Review. B, Solid State, 1976, 13(12): 5188–5192

[35]

Wang V, Xu N, Liu J C. . VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code. Computer Physics Communications, 2021, 267: 108033

[36]

Piskunov S, Jacob T, Spohr E. Oxygen adsorption atLa1−xSrxMnO3(001) surfaces: Predictions from first principles. Physical Review B: Condensed Matter and Materials Physics, 2011, 83(7): 073402

[37]

Yang Z, Woo T K, Baudin M. . Atomic and electronic structure of unreduced and reduced CeO2 surfaces: A first-principles study. Journal of Chemical Physics, 2004, 120(16): 7741–7749

[38]

Lyons D M, Ryan K M, Morris M A. Preparation of ordered mesoporous ceria with enhanced thermal stability. Journal of Materials Chemistry, 2002, 12(4): 1207–1212

[39]

Lyons D M, McGrath J P, Morris M A. Surface studies of ceria and mesoporous ceria powders by solid-state 1H MAS NMR. Journal of Physical Chemistry B, 2003, 107(19): 4607–4617

[40]

Kiani D, Sourav S, Wachs I E. . A combined computational and experimental study of methane activation during oxidative coupling of methane (OCM) by surface metal oxide catalysts. Chemical Science, 2021, 12(42): 14143–14158

[41]

Kiani D, Sourav S, Taifan W. . Existence and properties of isolated catalytic sites on the surface of β-cristobalite-supported, doped tungsten oxide catalysts (WOx/β-SiO2, Na-WOx/β-SiO2, Mn-WOx/β-SiO2) for oxidative coupling of methane (OCM): A combined periodic DFT and experimental study. ACS Catalysis, 2020, 10(8): 4580–4592

[42]

Zou S, Li Z, Zhou Q. . Surface coupling of methyl radicals for efficient low-temperature oxidative coupling of methane. Chinese Journal of Catalysis, 2021, 42(7): 1117–1125

[43]

Song Y, Zhou Z, Zhang X. . Pure CO2 electrolysis over an Ni/YSZ cathode in a solid oxide electrolysis cell. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(28): 13661–13667

[44]

Chen M, Liu Y L, Bentzen J J. . Microstructural degradation of Ni/YSZ electrodes in solid oxide electrolysis cells under high current. Journal of the Electrochemical Society, 2013, 160(8): F883–F891

[45]

Yu B, Zhang W, Xu J. . Preparation and electrochemical behavior of dense YSZ film for SOEC. International Journal of Hydrogen Energy, 2012, 37(17): 12074–12080

[46]

Carda M, Budáč D, Paidar M. . Current trends in the description of lanthanum strontium manganite oxygen electrode reaction mechanism in a high-temperature solid oxide cell. Current Opinion in Electrochemistry, 2022, 31: 100852

[47]

Lin Q, Bian L, Liu C. . Improved La0.8Sr0.2MnO3‒δ oxygen electrode activity by introducing high oxygen ion conductor oxide for solid oxide steam electrolysis. International Journal of Hydrogen Energy, 2024, 49: 616–624

[48]

Zhao Z, Wang X, Tang S. . High-performance oxygen electrode Ce0.9Co0.1O2‒δ-LSM-YSZ for hydrogen production by solid oxide electrolysis cells. International Journal of Hydrogen Energy, 2021, 46(50): 25332–25340

[49]

Song J, Ren Y, Gao X. . Ce-Driven Ce-MnOx/Na2WO4/SiO2 composite catalysts for low-temperature oxidative coupling of methane. ACS Catalysis, 2024, 14(7): 5116–5131

[50]

Gholipour Z, Malekzadeh A, Hatami R. . Oxidative coupling of methane over (Na2WO4 + Mn or Ce)/SiO2 catalysts: In situ measurement of electrical conductivity. Journal of Natural Gas Chemistry, 2010, 19(1): 35–42

[51]

Chen K, Ai N, Jiang S P. Performance and structural stability of Gd0.2Ce0.8O1.9 infiltrated La0.8Sr0.2MnO3 nano-structured oxygen electrodes of solid oxide electrolysis cells. International Journal of Hydrogen Energy, 2014, 39(20): 10349–10358

[52]

Kim H Y, Lee S W, Lee S H. . Accelerating the electrochemical performance of solid oxide fuel cells using a Ce(Gd, Bi, Yb)O2−δ diffusion barrier layer acting as an oxygen reservoir at high-current loading conditions. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2025, 13(5): 3474–3483

[53]

Tao Y, Shao J, Cheng S. Electrochemically scavenging the silica impurities at the Ni-YSZ triple phase boundary of solid oxide cells. ACS Applied Materials & Interfaces, 2016, 8(27): 17023–17027

[54]

Jensen K. Effect of impurities on structural and electrochemical properties of the Ni–YSZ interface. Solid State Ionics, 2003, 160(1-2): 27–37

[55]

Liu F, Chen Z, Zhou H. . Highly efficient CH4-assisted CO2 electrolysis for syngas production in a quasi-symmetric Ni-ceramic electrolyzer. Journal of Power Sources, 2024, 609: 234703

[56]

Lu J, Zhu C, Pan C. . Highly efficient electrochemical reforming of CH4/CO2 in a solid oxide electrolyser. Science Advances, 2018, 4(3): 5100

[57]

Cui C, Wang Y, Tong Y. . Syngas production through CH4-assisted co-electrolysis of H2O and CO2 in La0.8Sr0.2Cr0.5Fe0.5O3‒δ-Zr0.84Y0.16O2‒δ electrode-supported solid oxide electrolysis cells. International Journal of Hydrogen Energy, 2021, 46(39): 20305–20312

[58]

Xu H, Chen B, Irvine J. . Modeling of CH4-assisted SOEC for H2O/CO2 co-electrolysis. International Journal of Hydrogen Energy, 2016, 41(47): 21839–21849

[59]

Wang Y, Liu T, Lei L. . Methane assisted solid oxide co-electrolysis process for syngas production. Journal of Power Sources, 2017, 344: 119–127

[60]

Stempien J P, Liu Q, Ni M. . Physical principles for the calculation of equilibrium potential for co-electrolysis of steam and carbon dioxide in a Solid Oxide Electrolyzer Cell (SOEC). Electrochimica Acta, 2014, 147: 490–497

[61]

Liu K, Zhao J, Zhu D. . Oxidative coupling of methane in solid oxide fuel cell tubular membrane reactor with high ethylene yield. Catalysis Communications, 2017, 96: 23–27

[62]

Jodaian V, Mirzaei M. Ce-promoted Na2WO4/TiO2 catalysts for the oxidative coupling of methane. Inorganic Chemistry Communications, 2019, 100: 97–100

[63]

Gu S, Kang J, Lee T. . Na2WO4/Mn supported on all-silica delaminated zeolite for the optimal oxidative coupling of methane via the effective stabilization of tetrahedral WO4: Elucidating effects of support precursors with different crystal structures, Al-addition, and morphologies. Chemical Engineering Journal, 2023, 457: 141057

[64]

Werny M J, Wang Y, Girgsdies F. . Fluctuating storage of the active phase in a Mn-Na2WO4/SiO2 catalyst for the oxidative coupling of methane. Angewandte Chemie International Edition, 2020, 59(35): 14921–14926

[65]

TagawaT, Kyaw Moe K, HiramatsuT, et al. Design of electrode for solid oxide fuel cells reactor. Solid State Ionics, 1998, 106(3‒4): 227–235

[66]

Ramaiyan K P, Denoyer L H, Benavidez A. . Selective electrochemical oxidative coupling of methane mediated by Sr2Fe1.5Mo0.5O6‒δ and its chemical stability. Communications Chemistry, 2021, 4(1): 139

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