Designing Membrane Electrode Assembly for Electrochemical CO₂ Reduction: a Review

Abstract

Currently, the electrochemical CO₂ reduction reaction (CO₂RR) can realize the resource conversion of CO₂, which is a promising approach to carbon resource use. Important advancements have been made in exploring the CO₂RR performance and mechanism because of the rational design of electrolyzer systems, such as H-cells, flow cells, and catalysts. Considering the future development direction of this technology and large-scale application needs, membrane electrode assembly (MEA) systems can improve energy use efficiency and achieve large-scale CO₂ conversion, which is considered the most promising technology for industrial applications. This review will concentrate on the research progress and present situation of the MEA component structure. This paper begins with the composition and construction of a gas diffusion electrode. Then, the application of ion-exchange membranes in MEA is introduced. Furthermore, the effects of pH and the anion and cation of the anolyte on MEA performance are explored. Additionally, we present the anode reaction type in MEA. Finally, the challenges in this field are summarized, and upcoming trends are projected. This review should offer researchers a clearer picture of MEA systems and provide important, timely, and valuable insights into rational electrolyzer design to facilitate further development of CO₂ electrochemical reduction.

Graphical Abstract

Keywords

CO₂ reduction / Electrocatalysis / Membrane electrode assembly

References

[1] Costentin C, Robert M, Savéant JM Catalysis of the electrochemical reduction of carbon dioxide. Chem Soc Rev, 2013, 42(6): 2423-2436.

[2] Schreier M, Héroguel F, Steier L, et al. Solar conversion of CO₂–CO using earth-abundant electrocatalysts prepared by atomic layer modification of CuO. Nat Energy, 2017, 2(7): 17087.

[3] Bushuyev OS, De Luna P, Dinh CT, et al. What should we make with CO₂ and how can we make it?. Joule, 2018, 2(5): 825-832.

[4] Gao D, Wei P, Li H, et al. Designing electrolyzers for electrocatalytic CO₂ reduction. Acta Phys Chim Sin, 2020, 37: 2009020-2009021.

[5] Voiry D, Shin HS, Loh KP, et al. Low-dimensional catalysts for hydrogen evolution and CO₂ reduction. Nat Rev Chem, 2018, 2: 105.

[6] Lees EW, Mowbray BAW, Parlane FGL, et al. Gas diffusion electrodes and membranes for CO₂ reduction electrolysers. Nat Rev Mater, 2022, 7: 55-64.

[7] Zhang S, Fan Q, Xia R, et al. CO₂ reduction: from homogeneous to heterogeneous electrocatalysis. Acc Chem Res, 2020, 53(1): 255-264.

[8] Pan F, Yang Y Designing CO₂ reduction electrode materials by morphology and interface engineering. Energy Environ Sci, 2020, 13(8): 2275-2309.

[9] Gu J, Hsu CS, Bai L, et al. Atomically dispersed Fe³⁺ sites catalyze efficient CO₂ electroreduction to CO. Science, 2019, 364(6445): 1091-1094.

[10] Cheng Y, Hou P, Wang X, et al. CO₂ electrolysis system under industrially relevant conditions. Acc Chem Res, 2022, 55(3): 231-240.

[11] Lin R, Guo J, Li X, et al. Electrochemical reactors for CO₂ conversion. Catalysts, 2020, 10(5): 473.

[12] Overa S, Ko BH, Zhao Y, et al. Electrochemical approaches for CO₂ conversion to chemicals: a journey toward practical applications. Acc Chem Res, 2022, 55(5): 638-648.

[13] Rabiee H, Ge L, Zhang X, et al. Gas diffusion electrodes (GDEs) for electrochemical reduction of carbon dioxide, carbon monoxide, and dinitrogen to value-added products: a review. Energy Environ Sci, 2021, 14(4): 1959-2008.

[14] Wakerley D, Lamaison S, Wicks J, et al. Gas diffusion electrodes, reactor designs and key metrics of low-temperature CO₂ electrolysers. Nat Energy, 2022, 7: 130-143.

[15] Reyes A, Jansonius RP, Mowbray BAW, et al. Managing hydration at the cathode enables efficient CO₂ electrolysis at commercially relevant current densities. ACS Energy Lett, 2020, 5(5): 1612-1618.

[16] Ma D, Jin T, Xie K, et al. An overview of flow cell architecture design and optimization for electrochemical CO₂ reduction. J Mater Chem A, 2021, 9(37): 20897-20918.

[17] Weng LC, Bell AT, Weber AZ Modeling gas-diffusion electrodes for CO₂ reduction. Phys Chem Chem Phys, 2018, 20(25): 16973-16984.

[18] Lapicque F, Belhadj M, Bonnet C, et al. A critical review on gas diffusion micro and macroporous layers degradations for improved membrane fuel cell durability. J Power Sources, 2016, 336: 40-53.

[19] Leonard ME, Clarke LE, Forner-Cuenca A, et al. Investigating electrode flooding in a flowing electrolyte, gas-fed carbon dioxide electrolyzer. Chemsuschem, 2020, 13(2): 400-411.

[20] Shi R, Guo J, Zhang X, et al. Efficient wettability-controlled electroreduction of CO₂ to CO at Au/C interfaces. Nat Commun, 2020, 11(1): 3028.

[21] Gabardo CM, O’Brien CP, Edwards JP, et al. Continuous carbon dioxide electroreduction to concentrated multi-carbon products using a membrane electrode assembly. Joule, 2019, 3(11): 2777-2791.

[22] Velayutham G, Kaushik J, Rajalakshmi N, et al. Effect of PTFE content in gas diffusion media and microlayer on the performance of PEMFC tested under ambient pressure. Fuel Cells, 2007, 7(4): 314-318.

[23] Kim B, Hillman F, Ariyoshi M, et al. Effects of composition of the micro porous layer and the substrate on performance in the electrochemical reduction of CO₂ to CO. J Power Sources, 2016, 312: 192-198.

[24] Zhong M, Tran K, Min Y, et al. Accelerated discovery of CO₂ electrocatalysts using active machine learning. Nature, 2020, 581(7807): 178-183.

[25] Orogbemi OM, Ingham DB, Ismail MS, et al. The effects of the composition of microporous layers on the permeability of gas diffusion layers used in polymer electrolyte fuel cells. Int J Hydrog Energy, 2016, 41(46): 21345-21351.

[26] Wang Z, Li Y, Zhao X, et al. Localized alkaline environment via in situ electrostatic confinement for enhanced CO₂-to-ethylene conversion in neutral medium. J Am Chem Soc, 2023, 145(11): 6339-6348.

[27] Liu M, Hu H, Kong Y, et al. The role of ionomers in the electrolyte management of zero-gap MEA-based CO₂ electrolysers: a Fumion versus Nafion comparison. Appl Catal B Environ, 2023, 335.

[28] Merino-Garcia I, Alvarez-Guerra E, Albo J, et al. Electrochemical membrane reactors for the utilisation of carbon dioxide. Chem Eng J, 2016, 305: 104-120.

[29] Weekes DM, Salvatore DA, Reyes A, et al. Electrolytic CO₂ reduction in a flow cell. Acc Chem Res, 2018, 51(4): 910-918.

[30] Salvatore DA, Gabardo CM, Reyes A, et al. Designing anion exchange membranes for CO₂ electrolysers. Nat Energy, 2021, 6: 339-348.

[31] Kibria MG, Edwards JP, Gabardo CM, et al. Electrochemical CO₂ reduction into chemical feedstocks: from mechanistic electrocatalysis models to system design. Adv Mater, 2019, 31(31

[32] Zheng Y, Jiao Y, Vasileff A, et al. The hydrogen evolution reaction in alkaline solution: from theory, single crystal models, to practical electrocatalysts. Angew Chem Int Ed Engl, 2018, 57(26): 7568-7579.

[33] Jiang K, Siahrostami S, Zheng T, et al. Isolated Ni single atoms in graphene nanosheets for high-performance CO₂ reduction. Energy Environ Sci, 2018, 11(4): 893-903.

[34] Yanagi R, Zhao T, Cheng M, et al. Photocatalytic CO₂ reduction with dissolved carbonates and near-zero CO₂(aq) by employing long-range proton transport. J Am Chem Soc, 2023, 145(28): 15381-15392.

[35] Hori Y, Ito H, Okano K, et al. Silver-coated ion exchange membrane electrode applied to electrochemical reduction of carbon dioxide. Electrochim Acta, 2003, 48(18): 2651-2657.

[36] Sassenburg M, Kelly M, Subramanian S, et al. Zero-gap electrochemical CO₂ reduction cells: challenges and operational strategies for prevention of salt precipitation. ACS Energy Lett, 2022, 8(1): 321-331.

[37] Xu Y, Miao RK, Edwards JP, et al. A microchanneled solid electrolyte for carbon-efficient CO₂ electrolysis. Joule, 2022, 6(6): 1333-1343.

[38] Pan B, Fan J, Zhang J, et al. Close to 90% single-pass conversion efficiency for CO₂ electroreduction in an acid-fed membrane electrode assembly. ACS Energy Lett, 2022, 7(12): 4224-4231.

[39] Lee W, Kim YE, Youn MH, et al. Catholyte-free electrocatalytic CO₂ reduction to formate. Angew Chem Int Ed Engl, 2018, 57(23): 6883-6887.

[40] Zhang Z, Huang X, Chen Z, et al. Membrane electrode assembly for electrocatalytic CO₂ reduction: principle and application. Angew Chem Int Ed Engl, 2023, 62(28

[41] Xie K, Miao RK, Ozden A, et al. Bipolar membrane electrolyzers enable high single-pass CO₂ electroreduction to multicarbon products. Nat Commun, 2022, 13(1): 3609.

[42] Blommaert MA, Aili D, Tufa RA, et al. Insights and challenges for applying bipolar membranes in advanced electrochemical energy systems. ACS Energy Lett, 2021, 6(7): 2539-2548.

[43] McDonald MB, Ardo S, Lewis NS, et al. Use of bipolar membranes for maintaining steady-state pH gradients in membrane-supported, solar-driven water splitting. Chemsuschem, 2014, 7(11): 3021-3027.

[44] Vargas-Barbosa NM, Geise GM, Hickner MA, et al. Assessing the utility of bipolar membranes for use in photoelectrochemical water-splitting cells. Chemsuschem, 2014, 7(11): 3017-3020.

[45] Li YC, Zhou D, Yan Z, et al. Electrolysis of CO₂ to syngas in bipolar membrane-based electrochemical cells. ACS Energy Lett, 2016, 1: 1149-1153.

[46] Yang K, Li M, Subramanian S, et al. Cation-driven increases of CO₂ utilization in a bipolar membrane electrode assembly for CO₂ electrolysis. ACS Energy Lett, 2021, 6(12): 4291-4298.

[47] Vermaas DA, Smith WA Synergistic electrochemical CO₂ reduction and water oxidation with a bipolar membrane. ACS Energy Lett, 2016, 1(6): 1143-1148.

[48] Nitopi S, Bertheussen E, Scott SB, et al. Progress and perspectives of electrochemical CO₂ reduction on copper in aqueous electrolyte. Chem Rev, 2019, 119(12): 7610-7672.

[49] Zhong H, Fujii K, Nakano Y, et al. Effect of CO₂ bubbling into aqueous solutions used for electrochemical reduction of CO₂ for energy conversion and storage. J Phys Chem C, 2015, 119(1): 55-61.

[50] Ma M, Clark EL, Therkildsen KT, et al. Insights into the carbon balance for CO₂ electroreduction on Cu using gas diffusion electrode reactor designs. Energy Environ Sci, 2020, 13(3): 977-985.

[51] Liu M, Pang Y, Zhang B, et al. Enhanced electrocatalytic CO₂ reduction via field-induced reagent concentration. Nature, 2016, 537(7620): 382-386.

[52] Bohra D, Chaudhry JH, Burdyny T, et al. Modeling the electrical double layer to understand the reaction environment in a CO₂ electrocatalytic system. Energy Environ Sci, 2019, 12(11): 3380-3389.

[53] Li Z, Sun B, Xiao D, et al. Electron-rich Bi nanosheets promote CO₂⋅^- formation for high-performance and pH-universal electrocatalytic CO₂ reduction. Angew Chem Int Ed Engl, 2023, 62(11

[54] Ma M, Djanashvili K, Smith WA Controllable hydrocarbon formation from the electrochemical reduction of CO₂ over Cu nanowire arrays. Angew Chem Int Ed Engl, 2016, 55(23): 6680-6684.

[55] Varela AS, Kroschel M, Leonard ND, et al. pH effects on the selectivity of the electrocatalytic CO₂ reduction on graphene-embedded Fe–N–C motifs: bridging concepts between molecular homogeneous and solid-state heterogeneous catalysis. ACS Energy Lett, 2018, 3(4): 812-817.

[56] Baricuatro JH, Kwon S, Kim YG, et al. Operando electrochemical spectroscopy for CO on Cu(100) at pH 1–13:validation of grand canonical potential predictions. ACS Catal, 2021, 11(5): 3173-3181.

[57] Sebastián-Pascual P, Petersen AS, Bagger A, et al. pH and anion effects on Cu–phosphate interfaces for CO electroreduction. ACS Catal, 2021, 11(3): 1128-1135.

[58] Lu X, Zhu C, Wu Z, et al. In situ observation of the pH gradient near the gas diffusion electrode of CO₂ reduction in alkaline electrolyte. J Am Chem Soc, 2020, 142(36): 15438-15444.

[59] Zhang Z, Melo L, Jansonius RP, et al. pH matters when reducing CO₂ in an electrochemical flow cell. ACS Energy Lett, 2020, 5(10): 3101-3107.

[60] She X, Zhai L, Wang Y, et al. Pure-water-fed, electrocatalytic CO₂ reduction to ethylene beyond 1000 h stability at 10 A. Nat Energy, 2024, 9: 81-91.

[61] O’Brien CP, Miao RK, Liu S, et al. Single pass CO₂ conversion exceeding 85% in the electrosynthesis of multicarbon products via local CO₂ regeneration. ACS Energy Lett, 2021, 6(8): 2952-2959.

[62] Kim C, Bui JC, Luo X, et al. Tailored catalyst microenvironments for CO₂ electroreduction to multicarbon products on copper using bilayer ionomer coatings. Nat Energy, 2021, 6: 1026-1034.

[63] Park J, Ko YJ, Lim C, et al. Strategies for CO₂ electroreduction in cation exchange membrane electrode assembly. Chem Eng J, 2023, 453.

[64] Le D, Rahman TS On the role of metal cations in CO₂ electrocatalytic reduction. Nat Catal, 2022, 5: 977-978.

[65] Bhugun I, Lexa D, Savéant JM Catalysis of the electrochemical reduction of carbon dioxide by iron (0) porphyrins synergistic effect of Lewis acid cations. J Phys Chem, 1996, 100(51): 19981-19985.

[66] Jin Z, Guo Y, Qiu C Electro-conversion of carbon dioxide to valuable chemicals in a membrane electrode assembly. Sustainability, 2022, 14(9): 5579.

[67] Murata A, Hori Y Product selectivity affected by cationic species in electrochemical reduction of CO₂ and CO at a Cu electrode. Bull Chem Soc Jpn, 1991, 64(1): 123-127.

[68] Endrődi B, Samu A, Kecsenovity E, et al. Operando cathode activation with alkali metal cations for high current density operation of water-fed zero-gap carbon dioxide electrolyzers. Nat Energy, 2021, 6(4): 439-448.

[69] Hsieh YC, Senanayake SD, Zhang Y, et al. Effect of chloride anions on the synthesis and enhanced catalytic activity of silver nanocoral electrodes for CO₂ electroreduction. ACS Catal, 2015, 5(9): 5349-5356.

[70] Resasco J, Lum Y, Clark E, et al. Effects of anion identity and concentration on electrochemical reduction of CO₂. ChemElectroChem, 2018, 5(7): 1064-1072.

[71] Deng B, Huang M, Zhao X, et al. Interfacial electrolyte effects on electrocatalytic CO₂ reduction. ACS Catal, 2021, 12(1): 331-362.

[72] Gabardo CM, Seifitokaldani A, Edwards JP, et al. Combined high alkalinity and pressurization enable efficient CO₂ electroreduction to CO. Energy Environ Sci, 2018, 11(9): 2531-2539.

[73] Ogura K, Ferrell JR, Cugini AV, et al. CO₂ attraction by specifically adsorbed anions and subsequent accelerated electrochemical reduction. Electrochim Acta, 2010, 56(1): 381-386.

[74] Lv X, Yang Y, Lv J, et al. Iodine-mediated C─C coupling in neutral flow cell for electrochemical CO₂ reduction. Adv Funct Mater, 2023, 34: 2311236.

[75] Varela AS, Ju W, Reier T, et al. Tuning the catalytic activity and selectivity of Cu for CO₂ electroreduction in the presence of halides. ACS Catal, 2016, 6(4): 2136-2144.

[76] Wang J, Qin Y, Jin S, et al. Customizing CO₂ electroreduction by pulse-induced anion enrichment. J Am Chem Soc, 2023, 145(48): 26213-26221.

[77] Wu QJ, Si DH, Wu Q, et al. Boosting electroreduction of CO₂ over cationic covalent organic frameworks: hydrogen bonding effects of halogen ions. Angew Chem Int Ed Engl, 2023, 62(7

[78] Yun H, Choi W, Shin D, et al. Atomic arrangement of AuAg alloy on carbon support enhances electrochemical CO₂ reduction in membrane electrode assembly. ACS Catal, 2023, 13(13): 9302-9312.

[79] Li D, Yang J, Lian J, et al. Recent advances in paired electrolysis coupling CO₂ reduction with alternative oxidation reactions. J Energy Chem, 2023, 77: 406-419.

[80] Chen H, Ding C, Kang C, et al. The design of alternative anodic reactions paired with electrochemical CO₂ reduction. Green Chem, 2023, 25(14): 5320-5337.

[81] Na J, Seo B, Kim J, et al. General technoeconomic analysis for electrochemical coproduction coupling carbon dioxide reduction with organic oxidation. Nat Commun, 2019, 10(1): 5193.

[82] Verma S, Lu S, Kenis PJA Co-electrolysis of CO₂ and glycerol as a pathway to carbon chemicals with improved technoeconomics due to low electricity consumption. Nat Energy, 2019, 4: 466-474.

[83] Wei X, Li Y, Chen L, et al. Formic acid electro-synthesis by concurrent cathodic CO₂ reduction and anodic CH₃OH oxidation. Angew Chem Int Ed Engl, 2021, 60(6): 3148-3155.

[84] Cao C, Ma DD, Jia J, et al. Divergent paths, same goal: a pair-electrosynthesis tactic for cost-efficient and exclusive formate production by metal-organic-framework-derived 2D electrocatalysts. Adv Mater, 2021, 33(25

[85] Zhou Y, Wang Z, Fang W, et al. Modulating O–H activation of methanol oxidation on nickel-organic frameworks for overall CO₂ electrolysis. ACS Catal, 2023, 13(3): 2039-2046.

[86] Xie K, Ozden A, Miao RK, et al. Eliminating the need for anodic gas separation in CO₂ electroreduction systems via liquid-to-liquid anodic upgrading. Nat Commun, 2022, 13: 3070.