Flow-Through Hollow Fiber Gas Diffusion Electrodes with Morphology-Controlled In Situ Galvanic Grown Silver Catalysts for Enhanced CO Selectivity in CO₂ Electroreduction

Abstract

Electrochemical reduction of CO₂ (CO₂RR) into value-added products offers a promising strategy to reduce dependence on fossil fuels, particularly when powered by renewable electricity. However, CO₂RR faces challenges, including high activation energy barriers, competing side reactions, and limited CO₂ mass transport. Addressing these limitations requires not only the development of advanced electrocatalysts to enhance CO₂RR activity but also the design of electrodes to optimize gas-catalyst-electrolyte interfaces and facilitate efficient mass transport, thereby advancing CO₂RR toward industrial-scale applications. Herein, we developed flow-through hollow fiber gas diffusion electrodes (HFGDEs) featuring in situ galvanic growth of flower-like silver structures. The abundant ultrathin 2D nanosheets enhance active sites and CO₂RR activity, and the resulting electrode achieves a high Faradaic efficiency of CO of 91% at −1.2 (V vs RHE). Furthermore, the HFGDE configuration ensured sufficient CO₂ delivery to the active sites, enabling a partial current density of CO of 280.8 mA cm⁻². In situ Raman spectroscopy revealed that the in situ-grown silver flower structure promotes the adsorption of *COOH intermediate, thereby accelerating CO₂RR kinetics. Moreover, the robust CO₂ supply afforded by the HFGDE configuration is crucial to suppress competitive hydrogen evolution reaction (HER) and maintain high CO₂RR activity under industrially relevant current densities.

Keywords

electrochemical CO₂ reduction / galvanic replacement reaction / gas diffusion electrodes / hollow fiber / silver catalysts

References

[1] P. De Luna, C. Hahn, D. Higgins, S. A. Jaffer, T. F. Jaramillo, E. H. J. S. Sargent, Science 2019, 364, eaav3506.

[2] S. Cao, S. Zhou, H. Chen, S. Wei, S. Liu, X. Lin, X. Chen, Z. Wang, W. Guo, X. Lu, Energy Environ. Mater. 2022, 6, e12287.

[3] F. P. García de Arquer, C.-T. Dinh, A. Ozden, J. Wicks, C. McCallum, A. R. Kirmani, D.-H. Nam, C. Gabardo, A. Seifitokaldani, X. J. S. Wang, Scinece 2020, 36, 661.

[4] R. S. J. S. Haszeldine, Science 2009, 325, 1647.

[5] J. E. Huang, F. Li, A. Ozden, A. Sedighian Rasouli, F. P. García de Arquer, S. Liu, S. Zhang, M. Luo, X. Wang, Y. J. S. Lum, Science 2021, 372, 1074.

[6] W. J. Teh, M. J. Kolb, F. Calle-Vallejo, B. S. J. A. F. M. Yeo, Adv. Funct. Mater. 2022, 33, 2210617.

[7] H. Rabiee, B. Ma, Y. Yang, F. Li, P. Yan, Y. Wu, X. Zhang, S. Hu, H. Wang, L. J. A. F. M. Ge, Adv. Funct. Mater. 2025, 35, 2411195.

[8] Y. Liu, Z. Wei, X. Su, X. Shi, L. Liu, T. Wang, X. Xu, M. Zhao, Y. Zhai, H. B. J. A. F. M. Yang, Adv. Funct. Mater. 2025, 35, 2403547.

[9] Z. Yang, H. Wang, X. Bi, X. Tan, Y. Zhao, W. Wang, Y. Zou, H. Wang, H. Ning, M. Wu, Energy Environ. Mater. 2023, 7, e12508.

[10] L. Xiao, R. Zhou, T. Zhang, X. Wang, R. Zhou, P. J. Cullen, K. Ostrikov, Energy Environ. Mater. 2023, 7, e12656.

[11] A. Raya-Imbernón, A. A. Samu, S. Barwe, G. Cusati, T. s. Fődi, B. M. Hepp, C. J. A. E. L. Janáky, ACS Energy Lett. 2023, 9, 288.

[12] N. T. Nesbitt, T. Burdyny, H. Simonson, D. Salvatore, D. Bohra, R. Kas, W. A. J. A. C. Smith, ACS Catal. 2020, 10, 14093.

[13] Z. Wang, Y. Zhou, P. Qiu, C. Xia, W. Fang, J. Jin, L. Huang, P. Deng, Y. Su, R. J. A. M. Crespo-Otero, Adv. Mater. 2023, 35, 2303052.

[14] Y. Kuang, H. Rabiee, L. Ge, T. E. Rufford, Z. Yuan, J. Bell, H. Wang, Energy Environ. Mater. 2023, 6, e12596.

[15] S. Garg, M. Li, A. Z. Weber, L. Ge, L. Li, V. Rudolph, G. Wang, T. E. Rufford, J Mater Chem A 2020, 8, 1511.

[16] S. Jin, Z. Hao, K. Zhang, Z. Yan, J. Chen, Angew. Chem. Int. Ed. Engl. 2021, 60, 20627.

[17] D. Wu, F. Jiao, Q. Lu, ACS Catal. 2022, 12, 12993.

[18] Q. Sun, C. Jia, H. Lu, M. Yang, R. Liu, D. M. Villamanca, Y. Zhao, C. Zhao, Chem. Soc. Rev. 2025, 54, 6973.

[19] H. Rabiee, L. Ge, X. Zhang, S. Hu, M. Li, Z. Yuan, Energy Environ. Sci. 2021, 14, 1959.

[20] H. Rabiee, L. Ge, S. Hu, H. Wang, Z. Yuan, Chem. Eng. J. 2022, 450, 138476.

[21] G. Chen, H. Rabiee, M. Li, B. Ma, Y. Kuang, F. Dorosti, Z. Zhu, H. Wang, L. Ge, Adv. Mater. 2025, 37, e2420391.

[22] R. Kas, K. K. Hummadi, R. Kortlever, P. de Wit, A. Milbrat, M. W. Luiten-Olieman, N. E. Benes, M. T. Koper, G. Mul, Nat. Commun. 2016, 7, 10748.

[23] D. Liu, Y. Hu, E. Shoko, H. Yu, T. T. Isimjan, X. Yang, Electrochim. Acta 2021, 365, 137343.

[24] C. Zhu, G. Shen, W. Chen, X. Dong, G. Li, Y. Song, W. Wei, Y. Sun, J. Power Sources 2021, 495, 229814.

[25] C. Zhu, Y. Song, X. Dong, G. Li, A. Chen, W. Chen, G. Wu, S. Li, W. Wei, Y. Sun, Energy Environ. Sci. 2022, 15, 5391.

[26] C. Zhu, G. Wu, J. Mao, A. Chen, Y. Zhao, G. Feng, Y. Wei, X. Liu, S. Li, G. Li, X. Dong, Y. Song, W. Wei, W. Chen, Chem. Eng. J. 2024, 485, 150040.

[27] G. Chen, L. Ge, Y. Kuang, H. Rabiee, B. Ma, F. Dorosti, A. Kumar Nanjundan, Z. Zhu, H. Wang, Chem. Eng. J. 2024, 490, 151651.

[28] G. Chen, L. Ge, Y. Kuang, H. Rabiee, B. Ma, F. Dorosti, A. K. Nanjundan, Z. Zhu, H. Wang, Small Sci. 2024, 4, 2400184.

[29] G. Chen, L. Ge, B. Ma, Y. Kuang, H. Rabiee, F. Dorosti, A. K. Nanjundan, Z. Zhu, H. Wang, Appl. Catal. B Environ. Energy 2025, 363, 124803.

[30] Z. Meng, F. Wang, Z. Zhang, S. Min, Nanoscale 2024, 16, 2295.

[31] H. Rabiee, L. Ge, X. Zhang, S. Hu, M. Li, S. Smart, Z. Zhu, Z. Yuan, Appl. Catal. B Environ. 2021, 286, 119945.

[32] H. Rabiee, L. Ge, J. Zhao, X. Zhang, M. Li, S. Hu, S. Smart, T. E. Rufford, Z. Zhu, H. Wang, Z. Yuan, Appl. Catal. B Environ. 2022, 310, 121362.

[33] H. Rabiee, X. Zhang, L. Ge, S. Hu, M. Li, S. Smart, Z. Zhu, Z. Yuan, ACS Appl. Mater. Interfaces 2020, 12, 21670.

[34] S. Watmanee, T. Klinaubol, R. Nganglumpoon, P. Pinthong, A. R. Christian Serraon, M. ChiongIii, Y. Morikawa, J. Panpranot, Chem. Eng. J. 2024, 480, 148182.

[35] X. Wu, Y. Guo, Z. Sun, F. Xie, D. Guan, J. Dai, F. Yu, Z. Hu, Y. C. Huang, C. W. Pao, J. L. Chen, W. Zhou, Z. Shao, Nat. Commun. 2021, 12, 660.

[36] S. Yan, S. A. Mahyoub, J. Lin, C. Zhang, Q. Hu, J. Zhong, C. Chen, F. Zhang, Z. Cheng, J. Catal. 2022, 405, 224.

[37] X. Li, X. Lin, B. Liu, X. Zhao, H. Zhao, L. Wang, S. Cong, Appl. Phy. A 2019, 12, 492.

[38] Y. Xia, Y. Wu, T. Hang, J. Chang, M. Li, Langmuir 2016, 32, 3385.

[39] S. Yang, D. Slotcavage, J. D. Mai, F. Guo, S. Li, Y. Zhao, Y. Lei, C. E. Cameron, T. J. Huang, J. Mater, Chem. C 2014, 2, 8350.

[40] S. Li, W. Chen, X. Dong, C. Zhu, A. Chen, Y. Song, G. Li, W. Wei, Y. Sun, Nat. Commun. 2022, 13, 3080.

[41] S. Li, X. Dong, J. Mao, W. Chen, A. Chen, G. Wu, C. Zhu, G. Li, Y. Wei, X. Liu, J. Wang, Y. Song, W. Wei, Small 2023, 19, e2301338.

[42] Y. Kuang, G. Chen, D. H. Mudiyanselage, H. Rabiee, B. Ma, F. Dorosti, A. K. Nanjundan, Z. Zhu, H. Wang, L. Ge, Chem. Eur. J. 2024, 30, e202403251.

[43] Y. Kuang, G. Chen, H. Rabiee, B. Ma, F. Dorosti, A. K. Nanjundan, Z. Zhu, H. Wang, L. Ge, Energy Fuel 2024, 38, 10096.

[44] B. Ma, H. Rabiee, G. Chen, Y. Kuang, T. Zhu, P. Yan, L. Ge, Z. Zhu, Chem. Eng. J. 2025, 523, 168323.

[45] G. Chen, M. Hong, B. Ma, Y. Kuang, H. Rabiee, X. Xu, F. Dorosti, P. Yan, N. Shah, A. K. Nanjundan, Z. Zhu, H. Wang, L. Ge, Appl. Catal. B Environ. Energy 2026, 381, 125902.

RIGHTS & PERMISSIONS

2026 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.