Preparation of anodic catalysts via in situ exsolution of Pt nanoparticles for a methane oxidation enhanced SOEC process

doi:10.1016/j.cjche.2025.07.015

Chinese Journal of Chemical Engineering ›› 2025, Vol. 86 ›› Issue (10): 13-24.DOI: 10.1016/j.cjche.2025.07.015

Previous Articles Next Articles

Preparation of anodic catalysts via in situ exsolution of Pt nanoparticles for a methane oxidation enhanced SOEC process

Liming Zhou¹, Kejing Wu², Qiang Hu³, Houfang Lu^1,2, Bin Liang^1,2

1. School of Chemical Engineering, Sichuan University, Chengdu 610065, China;
2. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610207, China;
3. Sichuan Energy Internet Research Institute Tsinghua University, Chengdu 610299, China

Received:2025-03-23 Revised:2025-07-30 Accepted:2025-07-30 Online:2025-08-23 Published:2025-10-28
Contact: Bin Liang,E-mail:liangbin@scu.edu.cn
Supported by:
This work was supported by the Key Program of National Natural Science Foundation of China (22138008), the financial support provided by the State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC), the Program of National Natural Science Foundation of China (22478257) and Sichuan Province Advanced Building Materials Production-Education Integration Innovation Demonstration Platform (Chuancaijiao [2022] No. 106).

Preparation of anodic catalysts via in situ exsolution of Pt nanoparticles for a methane oxidation enhanced SOEC process

Liming Zhou¹, Kejing Wu², Qiang Hu³, Houfang Lu^1,2, Bin Liang^1,2

1. School of Chemical Engineering, Sichuan University, Chengdu 610065, China;
2. Institute of New Energy and Low-Carbon Technology, Sichuan University, Chengdu 610207, China;
3. Sichuan Energy Internet Research Institute Tsinghua University, Chengdu 610299, China

通讯作者: Bin Liang,E-mail:liangbin@scu.edu.cn
基金资助:
This work was supported by the Key Program of National Natural Science Foundation of China (22138008), the financial support provided by the State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC), the Program of National Natural Science Foundation of China (22478257) and Sichuan Province Advanced Building Materials Production-Education Integration Innovation Demonstration Platform (Chuancaijiao [2022] No. 106).

Abstract

Abstract: Introducing methane at the anode side of a solid oxide electrolysis cell (SOEC) has been proven to effectively suppress the oxygen evolution reaction (OER), thereby enabling hydrogen production at significantly lower voltages. In this work, a double perovskite oxide, Sr₂Fe_1.4Pt_0.1Mo_0.5O_6-δ (abbreviated as Pt-SFM), was successfully synthesized by a liquid-phase method and employed as both an electronic conductor and a catalyst for methane oxidation at the SOEC anode. Following high-temperature treatment under a reducing atmosphere, platinum (Pt) nanoparticles were exsolved from the perovskite lattice and uniformly dispersed on the oxide surface. These exsolved Pt nanoparticles act as highly active sites for methane adsorption and oxidation. Electrochemical performance tests were conducted at 1123.15 K, and the results demonstrated that the Pt-SFM cell treated for 20 h (Pt-SFM 20 h) achieved a current density of 0.85 A·cm^-2 at an applied voltage of 1.40 V. This performance corresponds to a 102.4% enhancement compared to the undoped SFM 20 h cell. The superior performance is attributed to the presence of exsolved Pt, which significantly improves the catalyst's ability to adsorb and dissociate methane molecules. Electrochemical impedance spectroscopy (EIS) analysis under open-circuit conditions revealed that the polarization impedance of the Pt-SFM 20 h cell was 1.25 Ω·cm², which is 49.2% lower than that of the SFM 20 h cell. Furthermore, a 45-h long-term stability test showed that the Pt-SFM 20 h cell maintained a stable performance, with a low voltage degradation rate of only 0.67 mV·h^-1.

Key words: Methane, Hydrogen production, Perovskite, Catalyst, Electrolysis

摘要： Introducing methane at the anode side of a solid oxide electrolysis cell (SOEC) has been proven to effectively suppress the oxygen evolution reaction (OER), thereby enabling hydrogen production at significantly lower voltages. In this work, a double perovskite oxide, Sr₂Fe_1.4Pt_0.1Mo_0.5O_6-δ (abbreviated as Pt-SFM), was successfully synthesized by a liquid-phase method and employed as both an electronic conductor and a catalyst for methane oxidation at the SOEC anode. Following high-temperature treatment under a reducing atmosphere, platinum (Pt) nanoparticles were exsolved from the perovskite lattice and uniformly dispersed on the oxide surface. These exsolved Pt nanoparticles act as highly active sites for methane adsorption and oxidation. Electrochemical performance tests were conducted at 1123.15 K, and the results demonstrated that the Pt-SFM cell treated for 20 h (Pt-SFM 20 h) achieved a current density of 0.85 A·cm^-2 at an applied voltage of 1.40 V. This performance corresponds to a 102.4% enhancement compared to the undoped SFM 20 h cell. The superior performance is attributed to the presence of exsolved Pt, which significantly improves the catalyst's ability to adsorb and dissociate methane molecules. Electrochemical impedance spectroscopy (EIS) analysis under open-circuit conditions revealed that the polarization impedance of the Pt-SFM 20 h cell was 1.25 Ω·cm², which is 49.2% lower than that of the SFM 20 h cell. Furthermore, a 45-h long-term stability test showed that the Pt-SFM 20 h cell maintained a stable performance, with a low voltage degradation rate of only 0.67 mV·h^-1.

关键词: Methane, Hydrogen production, Perovskite, Catalyst, Electrolysis

Liming Zhou, Kejing Wu, Qiang Hu, Houfang Lu, Bin Liang. Preparation of anodic catalysts via in situ exsolution of Pt nanoparticles for a methane oxidation enhanced SOEC process[J]. Chinese Journal of Chemical Engineering, 2025, 86(10): 13-24.

References

[1] K.L. Li, S. Chen, M.B. Li, L.L. Liu, Y.J. Li, G.B. Yang, H. Guo, E.T. Xu, F. Wang, Plasma catalytic ammonia synthesis in a fluidized-bed DBD reactor over M/Al(2)O(3): Enhancement of plasma-catalyst surface interaction, J. Colloid Interface Sci. 683 (Pt 1) (2025) 652-662.
[2] K. Lu, Y.H. Xu, H. Yuan, J.P. Liang, H.L. Wang, J. Zhang, Y.N. Li, D.Z. Yang, Non-thermal plasma synergistic Ni/Al₂O₃ for ammonia synthesis: Configuration and optimization of a double dielectric barrier discharge reactor, Int. J. Hydrog. Energy 97 (2025) 835-844.
[3] H.D. Cai, L.L. Zhang, J.S. Xu, J.H. Huang, X.L. Wei, L. Wang, Z.Y. Song, W. Long, Cobalt-free La_0.5Sr_0.5Fe_0.9Mo_0.1O_3-δ electrode for symmetrical SOFC running on H₂ and CO fuels, Electrochim. Acta 320 (2019) 134642.
[4] L.M. Zhou, K.J. Wu, D.T. Li, Q. Hu, H.F. Lu, B. Liang, Hydrogen production at a low voltage of 0.46 V @ 0.4 A/Cm² at 850 °C in SOECs enhanced by anode oxidation of methane, Ind. Eng. Chem. Res. 63 (47) (2024) 20497-20509.
[5] B.B. He, L. Zhao, S.X. Song, T. Liu, F.L. Chen, C.R. Xia, Sr₂Fe_1.5Mo_0.5O_6-δ-Sm_0.2Ce_0.8O_1.9 Composite anodes for intermediate-temperature solid oxide fuel cells, J. Electrochem. Soc. 159 (5) (2012) B619-B626.
[6] P. Qiu, S.C. Sun, J. Li, L.C. Jia, A review on the application of Sr₂Fe_1.5Mo_0.5O₆-based oxides in solid oxide electrochemical cells, Sep. Purif. Technol. 298 (2022) 121581.
[7] J. Lu, Y.B. Hu, M.M. Zhang, Q. Hu, J. Wu, Optimization of Pt infiltrated Sr₂Fe_2-xMoxO_6-δ-Ce_0.8Sm_0.2O_1.9 oxygen electrode for reversible solid oxide cell and CH₄-assisted electrolysis process, Int. J. Hydrog. Energy 55 (2024) 786-795.
[8] D. Ding, X.X. Li, S.Y. Lai, K. Gerdes, M.L. Liu, Enhancing SOFC cathode performance by surface modification through infiltration, Energy Environ. Sci. 7 (2) (2014) 552-575.
[9] P.A. Connor, X.L. Yue, C.D. Savaniu, R. Price, G. Triantafyllou, M. Cassidy, G. Kerherve, D.J. Payne, R.C. Maher, L.F. Cohen, R.I. Tomov, B.A. Glowacki, R.V. Kumar, J.T.S. Irvine, Tailoring SOFC electrode microstructures for improved performance, Adv. Energy Mater. 8 (23) (2018) 1800120.
[10] T.H. Zhang, Y.Q. Zhao, X.Y. Zhang, H. Zhang, N. Yu, T. Liu, Y. Wang, Thermal stability of an in situ exsolved metallic nanoparticle structured perovskite type hydrogen electrode for solid oxide cells, ACS Sustainable Chem. Eng. 7 (21) (2019) 17834-17844.
[11] J.H. Lu, C.L. Zhu, C.C. Pan, W.L. Lin, J.P. Lemmon, F.L. Chen, C.S. Li, K. Xie, Highly efficient electrochemical reforming of CH(4)/CO(2) in a solid oxide electrolyser, Sci. Adv. 4 (3) (2018) eaar5100.
[12] C.L. Dong, F.K. Jiang, L. Yang, C.L. Wang, K. Xie, Enhancing electrocatalytic reforming of CO₂/CH₄ with in situ exsolved metal-oxide interfaces in a solid oxide electrolysis cell, Sep. Purif. Technol. 299 (2022) 121714.
[13] Y. Patcharavorachot, S. Thongdee, D. Saebea, S. Authayanun, A. Arpornwichanop, Performance comparison of solid oxide steam electrolysis cells with/without the addition of methane, Energy Convers. Manag. 120 (2016) 274-286.
[14] B.D. Mukri, U.V. Waghmare, M.S. Hegde, Platinum ion-doped TiO₂: high catalytic activity of Pt²⁺ with oxide ion vacancy in Ti⁴⁺_1-xPt²⁺_xO_2-x compared to Pt⁴⁺ without oxide ion vacancy in Ti⁴⁺_1-xPt^4+xO₂, Chem. Mater. 25 (19) (2013) 3822-3833.
[15] A. Gili, M.F. Bekheet, F. Thimm, B. Bischoff, M. Geske, M. Konrad, S. Praetz, C. Schlesiger, S. Selve, A. Gurlo, F. Rosowski, R. Schomacker, One-pot synthesis of iron-doped ceria catalysts for tandem carbon dioxide hydrogenation, Catal. Sci. Technol. 14 (15) (2024) 4174-4186.
[16] J.H. Chen, H. Arandiyan, X. Gao, J.H. Li, Recent advances in catalysts for methane combustion, Catal. Surv. Asia 19 (3) (2015) 140-171.
[17] W.F. Li, M.J. Xiao, J.T. Jiang, Y.Q. Li, X. Zhang, S.M. Li, X.M. Lin, D.L. Peng, S.W. Or, S.H. Sun, Z.Y. Xing, Co₄N nanoparticles embedded in N-doped carbon pores: Advanced interlayer material for lithium-sulfur batteries, Nano Energy 142 (2025) 111140.
[18] Holzwarth, U, & Gibson, N, The scherrer equation versus the ‘Debye-scherrer equation’, Nat. Nanotechnol. 6 (2011) 534.
[19] L. Cheng, C.H. Ma, W.Q. Lu, X. Wang, H.J. Yue, D. Zhang, Z.Y. Xing, A graphitized hierarchical porous carbon as an advanced cathode host for alkali metal-selenium batteries, Chem. Eng. J. 433 (2022) 133527.
[20] X.A. Xi, X.W. Wang, Y. Fan, Q. Wang, Y. Lu, J. Li, L. Shao, J.L. Luo, X.Z. Fu, Efficient bifunctional electrocatalysts for solid oxide cells based on the structural evolution of perovskites with abundant defects and exsolved CoFe nanoparticles, J. Power Sources 482 (2021) 228981.
[21] W.C. Cui, M.J. Ma, J.X. Sun, R.Z. Ren, C.M. Xu, J.S. Qiao, W. Sun, K.N. Sun, Z.H. Wang, Sr₂Fe_1.5Mo_0.4Ti_0.1O_6-δperovskite anode for high-efficiency coal utilization in direct carbon solid oxide fuel cells, J. Power Sources 557 (2023) 232562.
[22] J. Xie, S. Wang, F.G. Wang, Photo-induced thermal effect on Pt/CeO₂ surface for promoting formaldehyde oxidation performance by photothermal catalysis, Appl. Surf. Sci. 644 (2024) 158709.
[23] Y.L. Lee, A. Mnoyan, H.S. Na, S.Y. Ahn, K.J. Kim, J.O. Shim, K. Lee, H.S. Roh, Comparison of the effects of the catalyst preparation method and CeO₂ morphology on the catalytic activity of Pt/CeO₂ catalysts for the water-gas shift reaction, Catal. Sci. Technol. 10 (18) (2020) 6299-6308.
[24] Y.M. Ma, L.J. Zhang, K. Zhu, B.Z. Zhang, R.R. Peng, C.R. Xia, L. Huang, In³⁺-doped Sr₂Fe_1.5Mo_0.5O_6-δ cathode with improved performance for an intermediate-temperature solid oxide fuel cell, Nano Res. 17 (1) (2024) 407-415.
[25] H.G. Jiang, Z.M. Lu, B. Qian, S. Wang, B. Yin, Y.F. Zheng, L. Ge, H. Chen, C.Z. Zhang, Bi-doped La_1.5Sr_0.5Ni_0.5Mn_0.5O_4+δ as an efficient air electrode material for SOEC, Int. J. Hydrog. Energy 46 (73) (2021) 36037-36045.
[26] T. Liu, H. Liu, X.Y. Zhang, L.B. Lei, Y.X. Zhang, Z.H. Yuan, F.L. Chen, Y. Wang, A robust solid oxide electrolyzer for highly efficient electrochemical reforming of methane and steam, J. Mater. Chem. A 7 (22) (2019) 13550-13558.
[27] A. Hauch, A. Hagen, J. Hjelm, T. Ramos, Sulfur poisoning of SOFC anodes: effect of overpotential on long-term degradation, J. Electrochem. Soc. 161 (6) (2014) F734-F743.

Preparation of anodic catalysts via in situ exsolution of Pt nanoparticles for a methane oxidation enhanced SOEC process

Preparation of anodic catalysts via in situ exsolution of Pt nanoparticles for a methane oxidation enhanced SOEC process

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Zhenxing Feng, Bin Song, Zongcheng Zhan, Lei Xu, Hanlei Sun, Shuo Yao, Hongzhi Wang, Licheng Liu. The sulfur and water resistance improvement of Pt/TiO₂ catalyst for CO oxidation reaction by anatase and rutile TiO₂ crystal interfaces [J]. Chinese Journal of Chemical Engineering, 2025, 85(9): 128-139.
[2]	Hansheng Wang, Xintian Luo, Kaixuan Chen, Benduan Xiao, Xu Zhang, Qingjun Meng, Huibing He, Jing Xu, Yong Jin. Research progress on the copper-based catalyst design for dimethyl oxalate hydrogenation to ethylene glycol [J]. Chinese Journal of Chemical Engineering, 2025, 85(9): 189-205.
[3]	Xin Peng, Rong Huang, Wenran Wang, Jianxin Zhang, Zhenxiao Pan, Yueping Fang, Huashang Rao, Xinhua Zhong, Guizhi Zhang. Modulating titanium dioxide electron transport layer by self-doping for high-efficiency carbon-based perovskite solar cells [J]. Chinese Journal of Chemical Engineering, 2025, 85(9): 348-354.
[4]	Qingyu Wang, Duiping Liu, Yong Lu, Jibin Zhou, Xiangang Ma, Mao Ye. Deep learning approach for morphology classification and particle sizing of industrial methanol-to-olefins (MTO) catalyst [J]. Chinese Journal of Chemical Engineering, 2025, 84(8): 1-10.
[5]	Tiantong Zhang, Haolin Cheng, Yao Nian, Jinli Zhang, Qingbiao Li, You Han. Application of generative artificial intelligence in catalysis [J]. Chinese Journal of Chemical Engineering, 2025, 84(8): 86-95.
[6]	Zhi Ma, Peng Cui, Xu Wang, Lanyu Li, Haoxiang Xu, Adrian Fisher, Daojian Cheng. The integration of artificial intelligence and high-throughput experiments: An innovative driving force in catalyst design [J]. Chinese Journal of Chemical Engineering, 2025, 84(8): 117-132.
[7]	Xuehui Wang, Dan Dan, Xinyue Hao, Wei Lin, Edward Wright. Investigation on the reducing parameters of the Helmholtz energy equation of state for methane/methanol binary with VLE data [J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 160-170.
[8]	Yilun Dong, Kang Xue, Zexing He, Chongjun Li, Ruijie Gao, Zhenfeng Huang, Chengxiang Shi, Xiangwen Zhang, Lun Pan, Jijun Zou. Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions [J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 217-228.
[9]	Mika Sillanpää, Mohammad Reza kimiaei, Soheil Balsini Gavanaroudi, Nezamaddin Mengelizadeh, Najmeh Ahmadi, Davoud Balarak. Synthesis of magnetically separable and recyclable MnFe₂O₄@SiO₂@NH₂ nanocomposite coupled-acylated MWCNTS with enhanced photocatalytic performance under visible-light irradiation [J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 229-243.
[10]	Mingqiang Chen, Tingting Zhu, Yishuang Wang, Defang Liang, Chang Li, Haosheng Xin, Jun Wang. Catalytic oxidation of methane for methanol production over copper sepiolite: Effect of noble metals [J]. Chinese Journal of Chemical Engineering, 2025, 82(6): 1-14.
[11]	Bo Pan, Muneeb Ul Hassan Naseer, Hao Du, Shaona Wang, Yeqing Lyu, Biao Liu, Haixu Wang, Lanjie Li. Separation and recovery of V/W/Na from waste SCR catalyst leaching solution using membrane electrolysis—Ion morphology pretreatment solvent extraction-stripping method [J]. Chinese Journal of Chemical Engineering, 2025, 82(6): 153-164.
[12]	Baowei Wang, Jiangzhou Kong, Xiaoyan Li. Preparation of MoO₃/γ-Al₂O₃ sulfur-resistant methanation catalyst with segmented plasma fluidized bed [J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 142-150.
[13]	Mengting Chen, Minjie Zhu, Tingyu Zhou, Qifeng Zhong, Meihua Zhang, Yingxin Liu, Zuojun Wei. Enhanced activity and stability of SAPO-5 zeolite supported RuMn catalyst for aqueous-phase selective hydrodeoxygenation of guaiacol to cyclohexanol [J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 200-207.
[14]	Zhenhui Lv, Jianan Li, Tao Yang, Yibao Li, Chong Peng. Effect of carbon modifications on the performance of hydrogenation catalysts [J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 270-276.
[15]	Yaqi Qu, Hualiang An, Xinqiang Zhao, Yanji Wang. Heterogeneously catalyzed self-condensation of n-butanal [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 89-99.