High performance CO reduction at electrolyzer stack level through system optimization

Abstract

This study demonstrates the electrochemical reduction of carbon monoxide (COR) at high current densities in a zero-gap electrolyzer cell and cell stack. By systematically optimizing both the commercially available membrane electrode assembly components (including binder content and gas diffusion layer) and the operating conditions, we could perform COR at current densities up to 1.4 A cm⁻² with a maximum C₂₊ selectivity of 90%. We demonstrated the scale-up to a 3 × 100 cm² electrolyzer stack that can sustain stable operation at 1 A cm⁻² for several hours without significant performance decay and with a total C₂₊ selectivity of ~80% and an ethylene selectivity of ~40%. We provide critical insights into the holistic optimization of key system parameters, without using special catalysts or surface additives, which can pave the way for scalable and industrially viable COR processes.

Keywords

CO reduction / electrolysis / membrane electrode assembly / scale-up

References

[1] De Luna P, Hahn C, Higgins D, Jaffer SA, Jaramillo TF, Sargent EH. What would it take for renewably powered electrosynthesis to displace petrochemical processes? Science. 2019; 364(6438): eaav3506.

[2] Kuhl KP, Cave ER, Abram DN, Jaramillo TF. New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces. Energy Environ Sci. 2012; 5(5): 7050.

[3] Li CW, Kanan MW. CO₂ reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu₂O films. J Am Chem Soc. 2012; 134(17): 7231-7234.

[4] Dinh CT, Burdyny T, Kibria MG, et al. CO₂ electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science. 2018; 360(6390): 783-787.

[5] O'Brien CP, Miao RK, Shayesteh Zeraati A, Lee G, Sargent EH, Sinton D. CO₂ electrolyzers. Chem Rev. 2024; 124(7): 3648-3693.

[6] Zheng Y, Vasileff A, Zhou X, Jiao Y, Jaroniec M, Qiao SZ. Understanding the roadmap for electrochemical reduction of CO₂ to multi-carbon oxygenates and hydrocarbons on copper-based catalysts. J Am Chem Soc. 2019; 141(19): 7646-7659.

[7] Jouny M, Hutchings GS, Jiao F. Carbon monoxide electroreduction as an emerging platform for carbon utilization. Nat Catal. 2019; 2(12): 1062-1070.

[8] Larrazábal GO, Strøm-Hansen P, Heli JP, et al. Analysis of mass flows and membrane cross-over in CO₂ reduction at high current densities in an MEA-type electrolyzer. ACS Appl Mater Interfaces. 2019; 11(44): 41281-41288.

[9] El-Nagar GA, Haun F, Gupta S, Stojkovikj S, Mayer MT. Unintended cation crossover influences CO₂ reduction selectivity in Cu-based zero-gap electrolysers. Nat Commun. 2023; 14(1): 2062.

[10] Schellekens MP, Raaijman SJ, T. M. Koper M, Corbett PJ. Temperature-dependent selectivity for CO electroreduction on copper-based gas-diffusion electrodes at high current densities. Chem Eng J. 2024; 483: 149105.

[11] Ozden A, Wang Y, Li F, et al. Cascade CO₂ electroreduction enables efficient carbonate-free production of ethylene. Joule. 2021; 5(3): 706-719.

[12] Overa S, Feric TG, Park AHA, Jiao F. Tandem and hybrid processes for carbon dioxide utilization. Joule. 2021; 5(1): 8-13.

[13] Möller T, Filippi M, Brückner S, Ju W, Strasser P. A CO₂ electrolyzer tandem cell system for CO₂-CO co-feed valorization in a Ni-N-C/Cu-catalyzed reaction cascade. Nat Commun. 2023; 14(1): 5680.

[14] Alkayyali T, Zargartalebi M, Ozden A, et al. Pathways to reduce the energy cost of carbon monoxide electroreduction to ethylene. Joule. 2024; 8(5): 1478-1500.

[15] Kim JYT, Sellers C, Hao S, Senftle TP, Wang H. Different distributions of multi-carbon products in CO₂ and CO electroreduction under practical reaction conditions. Nat Catal. 2023; 6(12): 1115-1124.

[16] Jouny M, Luc W, Jiao F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat Catal. 2018; 1(10): 748-755.

[17] Wei P, Gao D, Liu T, et al. Coverage-driven selectivity switch from ethylene to acetate in high-rate CO₂/CO electrolysis. Nat Nanotechnol. 2023; 18(3): 299-306.

[18] Xu Q, Garg S, Moss AB, et al. Identifying and alleviating the durability challenges in membrane-electrode-assembly devices for high-rate CO electrolysis. Nat Catal. 2023; 6(11): 1042-1051.

[19] Li J, Wang Z, McCallum C, et al. Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction. Nat Catal. 2019; 2(12): 1124-1131.

[20] Watkins NB, Schiffer ZJ, Lai Y, et al. Hydrodynamics change tafel slopes in electrochemical CO₂ reduction on copper. ACS Energy Lett. 2023; 8(5): 2185-2192.

[21] Ma W, Xie S, Zhang B, et al. Copper lattice tension boosts full-cell CO electrolysis to multi-carbon olefins and oxygenates. Chem. 2023; 9(8): 2161-2177.

[22] Wang X, Chen Y, Li F, et al. Site-selective protonation enables efficient carbon monoxide electroreduction to acetate. Nat Commun. 2024; 15(1): 616.

[23] Dorakhan R, Grigioni I, Lee BH, et al. A silver-copper oxide catalyst for acetate electrosynthesis from carbon monoxide. Nat Synth. 2023; 2(5): 448-457.

[24] Yao K, Li J, Ozden A, et al. In situ copper faceting enables efficient CO₂/CO electrolysis. Nat Commun. 2024; 15(1): 1749.

[25] Henckel D, Saha P, Intia F, et al. Elucidation of critical catalyst layer phenomena toward high production rates for the electrochemical conversion of CO to ethylene. ACS Appl Mater Interfaces. 2024; 16(3): 3243-3252.

[26] Monis Ayyub M, Kormányos A, Endrődi B, Janáky C. Electrochemical carbon monoxide reduction at high current density: cell configuration matters. Chem Eng J. 2024; 490: 151698.

[27] Li H, Wei P, Liu T, et al. CO electrolysis to multicarbon products over grain boundary-rich Cu nanoparticles in membrane electrode assembly electrolyzers. Nat Commun. 2024; 15(1): 4603.

[28] Crandall BS, Ko BH, Overa S, et al. Kilowatt-scale tandem CO₂ electrolysis for enhanced acetate and ethylene production. Nat Chem Eng. 2024; 1(6): 421-429.

[29] Xu Q, Liu S, Longhin F, Kastlunger G, Chorkendorff I, Seger B. Impact of anodic oxidation reactions in the performance evaluation of high-rate CO₂/CO electrolysis. Adv Mater. 2024; 36(2): 2306741.

[30] Nesbitt NT, Burdyny T, Simonson H, et al. Liquid-solid boundaries dominate activity of CO₂ reduction on gas-diffusion electrodes. ACS Catal. 2020; 10(23): 14093-14106.

[31] Moore T, Xia X, Baker SE, Duoss EB, Beck VA. Elucidating mass transport regimes in gas diffusion electrodes for CO₂ electroreduction. ACS Energy Lett. 2021; 6(10): 3600-3606.

[32] Kormányos A, Endrődi B, Zhang Z, et al. Local hydrophobicity allows high-performance electrochemical carbon monoxide reduction to C₂₊ products. EES Catal. 2023; 1(3): 263-273.

[33] Endrődi B, Kecsenovity E, Samu A, et al. High carbonate ion conductance of a robust PiperION membrane allows industrial current density and conversion in a zero-gap carbon dioxide electrolyzer cell. Energy Environ Sci. 2020; 13(11): 4098-4105.

[34] Samu AA, Szenti I, Kukovecz Á, Endrődi B, Janáky C. Systematic screening of gas diffusion layers for high performance CO₂ electrolysis. Commun Chem. 2023; 6(1): 41.

[35] Etzi M, Dangbegnon J, Chiodoni A, Pirri CF. Impact of gas diffusion layer architecture on the performances of Cu-based electrodes for CO₂ electroreduction to ethylene in flow reactors. J CO2 Util. 2024; 83: 102772.

[36] Endrődi B, Kecsenovity E, Samu A, et al. Multilayer electrolyzer stack converts carbon dioxide to gas products at high pressure with high efficiency. ACS Energy Lett. 2019; 4(7): 1770-1777.

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2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.