A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO2 to formic acid

Hu, Leiming; Wrubel, Jacob A.; Baez-Cotto, Carlos M.; Intia, Fry; Park, Jae Hyung; Kropf, Arthur Jeremy; Kariuki, Nancy; Huang, Zhe; Farghaly, Ahmed; Amichi, Lynda; Saha, Prantik; Tao, Ling; Cullen, David A.; Myers, Deborah J.; Ferrandon, Magali S.; Neyerlin, Kenneth C.

doi:10.1038/s41467-023-43409-6

Title: A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO₂ to formic acid

Journal Article · 22 November 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-43409-6 · OSTI ID:2217556

^[1]; Wrubel, Jacob A. ^[1];

^[1]; Intia, Fry ^[1]; Park, Jae Hyung ^[2];

^[2]; Kariuki, Nancy ^[2]; Huang, Zhe ^[1];

^[2]; Amichi, Lynda ^[3]; Saha, Prantik ^[1];

^[1];

^[3];

^[2]; Ferrandon, Magali S. ^[2];

^[1]

National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

The electrochemical reduction of carbon dioxide to formic acid is a promising pathway to improve CO₂ utilization and has potential applications as a hydrogen storage medium. In this work, a zero-gap membrane electrode assembly architecture is developed for the direct electrochemical synthesis of formic acid from carbon dioxide. The key technological advancement is a perforated cation exchange membrane, which, when utilized in a forward bias bipolar membrane configuration, allows formic acid generated at the membrane interface to exit through the anode flow field at concentrations up to 0.25 M. Having no additional interlayer components between the anode and cathode this concept is positioned to leverage currently available materials and stack designs ubiquitous in fuel cell and H₂ electrolysis, enabling a more rapid transition to scale and commercialization. The perforated cation exchange membrane configuration can achieve >75% Faradaic efficiency to formic acid at <2 V and 300 mA/cm² in a 25 cm² cell. More critically, a 55-hour stability test at 200 mA/cm² shows stable Faradaic efficiency and cell voltage. Technoeconomic analysis is utilized to illustrate a path towards achieving cost parity with current formic acid production methods.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO); USDOE

Grant/Contract Number:: AC36-08GO28308; AC02-06CH11357; AC05-00OR22725

OSTI ID:: 2217556

Alternate ID(s):: OSTI ID: 2228672; OSTI ID: 2278906; OSTI ID: 2481272

Report Number(s):: NREL/JA-5900-85814; MainId:86587; UUID:1c6e2981-ec3e-4ea4-8056-5eea034431b9; MainAdminID:71207

Journal Information:: Nature Communications, Vol. 14, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Continuous electrochemical reduction of carbon dioxide into formate using a tin cathode: Comparison with lead cathode Alvarez-Guerra, Manuel; Del Castillo, Andrés; Irabien, Angel Chemical Engineering Research and Design, Vol. 92, Issue 4 https://doi.org/10.1016/j.cherd.2013.11.002	journal	April 2014
High-Pressure Electrochemical Reduction of CO ₂ to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics Ramdin, Mahinder; Morrison, Andrew R. T.; de Groen, Mariette Industrial & Engineering Chemistry Research, Vol. 58, Issue 51 https://doi.org/10.1021/acs.iecr.9b03970	journal	November 2019
Anolyte Enhances Catalyst Utilization and Ion Transport Inside a CO₂ Electrolyzer Cathode Saha, Prantik; Henckel, Danielle; Baez-Cotto, Carlos Journal of The Electrochemical Society, Vol. 170, Issue 1 https://doi.org/10.1149/1945-7111/acb01d	journal	January 2023
Platinum and Palladium Monolayer Electrocatalysts for Formic Acid Oxidation Liang, Zhixiu; Song, Liang; Elnabawy, Ahmed O. Topics in Catalysis, Vol. 63, Issue 7-8 https://doi.org/10.1007/s11244-020-01264-5	journal	April 2020
Electrochemical CO2 reduction to high-concentration pure formic acid solutions in an all-solid-state reactor Fan, Lei; Xia, Chuan; Zhu, Peng Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17403-1	journal	July 2020
Formic-acid-induced depolymerization of oxidized lignin to aromatics Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J. Nature, Vol. 515, Issue 7526, p. 249-252 https://doi.org/10.1038/nature13867	journal	November 2014
Advances in electrochemical reduction of carbon dioxide to formate over bismuth-based catalysts Wang, Yu-Hong; Jiang, Wen-Jun; Yao, Wei Rare Metals, Vol. 40, Issue 9 https://doi.org/10.1007/s12598-021-01728-x	journal	May 2021
Electrochemical conversion of CO2 to formic acid utilizing Sustainion™ membranes Yang, Hongzhou; Kaczur, Jerry J.; Sajjad, Syed Dawar Journal of CO2 Utilization, Vol. 20 https://doi.org/10.1016/j.jcou.2017.04.011	journal	July 2017
The economic outlook for converting CO ₂ and electrons to molecules Huang, Zhe; Grim, R. Gary; Schaidle, Joshua A. Energy & Environmental Science, Vol. 14, Issue 7 https://doi.org/10.1039/D0EE03525D	journal	January 2021
A high performance dual electrolyte microfluidic reactor for the utilization of CO 2 Lu, Xu; Leung, Dennis Y. C.; Wang, Huizhi Applied Energy, Vol. 194 https://doi.org/10.1016/j.apenergy.2016.05.091	journal	May 2017
Green hydrogen storage and delivery: Utilizing highly active homogeneous and heterogeneous catalysts for formic acid dehydrogenation Younas, Mohammad; Rezakazemi, Mashallah; Arbab, Muhammad Saddique International Journal of Hydrogen Energy, Vol. 47, Issue 22 https://doi.org/10.1016/j.ijhydene.2022.01.184	journal	March 2022
An economic analysis of the role of materials, system engineering, and performance in electrochemical carbon dioxide conversion to formate Badgett, Alex; Ruth, Mark; Crow, Allison Journal of Cleaner Production, Vol. 351 https://doi.org/10.1016/j.jclepro.2022.131564	journal	June 2022
Transferring Electrochemical CO ₂ Reduction from Semi-Batch into Continuous Operation Mode Using Gas Diffusion Electrodes Kopljar, Dennis; Wagner, Norbert; Klemm, Elias Chemical Engineering & Technology, Vol. 39, Issue 11 https://doi.org/10.1002/ceat.201600198	journal	October 2016
Formate as a key intermediate in CO₂ utilization Schuler, Eric; Morana, Michele; Ermolich, Pavel A. Green Chemistry, Vol. 24, Issue 21 https://doi.org/10.1039/D2GC02220F	journal	January 2022
Electrochemical conversion of CO2 to HCOOH at tin cathode in a pressurized undivided filter-press cell Proietto, Federica; Schiavo, Benedetto; Galia, Alessandro Electrochimica Acta, Vol. 277 https://doi.org/10.1016/j.electacta.2018.04.159	journal	July 2018
Improving trade-offs in the figures of merit of gas-phase single-pass continuous CO2 electrocatalytic reduction to formate Díaz-Sainz, Guillermo; Alvarez-Guerra, Manuel; Ávila-Bolívar, Beatriz Chemical Engineering Journal, Vol. 405 https://doi.org/10.1016/j.cej.2020.126965	journal	February 2021
Nanostructured β‐Bi ₂ O ₃ Fractals on Carbon Fibers for Highly Selective CO ₂ Electroreduction to Formate Tran‐Phu, Thanh; Daiyan, Rahman; Fusco, Zelio Advanced Functional Materials, Vol. 30, Issue 3 https://doi.org/10.1002/adfm.201906478	journal	October 2019
The effect of catholyte and catalyst layer binders on CO2 electroreduction selectivity Chen, Yingying; Wrubel, Jacob A.; Vise, Ashlee E. Chem Catalysis, Vol. 2, Issue 2 https://doi.org/10.1016/j.checat.2022.01.011	journal	February 2022
Electroreduction of carbon dioxide to formate at high current densities using tin and tin oxide gas diffusion electrodes Sen, Sujat; Brown, Steven M.; Leonard, McLain Journal of Applied Electrochemistry, Vol. 49, Issue 9 https://doi.org/10.1007/s10800-019-01332-z	journal	July 2019
Sn nanoparticles on gas diffusion electrodes: Synthesis, characterization and use for continuous CO 2 electroreduction to formate Del Castillo, A.; Alvarez-Guerra, M.; Solla-Gullón, J. Journal of CO2 Utilization, Vol. 18 https://doi.org/10.1016/j.jcou.2017.01.021	journal	March 2017
Continuous production of pure liquid fuel solutions via electrocatalytic CO2 reduction using solid-electrolyte devices Xia, Chuan; Zhu, Peng; Jiang, Qiu Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0451-x	journal	September 2019
Recent Advances in Catalytic Transfer Hydrogenation with Formic Acid over Heterogeneous Transition Metal Catalysts Nie, Renfeng; Tao, Yuewen; Nie, Yunqing ACS Catalysis, Vol. 11, Issue 3 https://doi.org/10.1021/acscatal.0c04939	journal	January 2021
Techno-economic assessment of low-temperature carbon dioxide electrolysis Shin, Haeun; Hansen, Kentaro U.; Jiao, Feng Nature Sustainability https://doi.org/10.1038/s41893-021-00739-x	journal	July 2021
The formate bio-economy Yishai, Oren; Lindner, Steffen N.; Gonzalez de la Cruz, Jorge Current Opinion in Chemical Biology, Vol. 35 https://doi.org/10.1016/j.cbpa.2016.07.005	journal	December 2016
Continuous electroreduction of carbon dioxide to formate on Tin nanoelectrode using alkaline membrane cell configuration in aqueous medium Lei, Tao; Zhang, Xia; Jung, Joey Catalysis Today, Vol. 318 https://doi.org/10.1016/j.cattod.2017.10.003	journal	November 2018
Elucidating the Role of Hydroxide Electrolyte on Anion-Exchange-Membrane Water Electrolyzer Performance Liu, Jiangjin; Kang, Zhenye; Li, Dongguo Journal of The Electrochemical Society, Vol. 168, Issue 5 https://doi.org/10.1149/1945-7111/ac0019	journal	May 2021
Improving growth of Cupriavidus necator H16 on formate using adaptive laboratory evolution-informed engineering Calvey, Christopher H.; Sànchez i. Nogué, Violeta; White, Aleena M. Metabolic Engineering, Vol. 75 https://doi.org/10.1016/j.ymben.2022.10.016	journal	January 2023
Robust Operation of Fuel Cell Systems in Subfreezing Conditions: A Material-Based Solution to Achieve Better Anode Durability Hu, Leiming; Hong, Bo Ki; Oh, Jong-Gil ACS Applied Energy Materials, Vol. 2, Issue 10 https://doi.org/10.1021/acsaem.9b01108	journal	September 2019
Rapid Nondestructive Fractionation of Biomass (≤15 min) by using Flow‐Through Recyclable Formic Acid toward Whole Valorization of Carbohydrate and Lignin Zhou, Hao; Tan, Liping; Fu, Yingjuan ChemSusChem, Vol. 12, Issue 6 https://doi.org/10.1002/cssc.201802803	journal	February 2019
Fabrication of Bi/Sn bimetallic electrode for high-performance electrochemical reduction of carbon dioxide to formate Li, Zong; Feng, Yujie; Li, Yunfei Chemical Engineering Journal, Vol. 428 https://doi.org/10.1016/j.cej.2021.130901	journal	January 2022
A Robust, Scalable Platform for the Electrochemical Conversion of CO ₂ to Formate: Identifying Pathways to Higher Energy Efficiencies Chen, Yingying; Vise, Ashlee; Klein, W. Ellis ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00860	journal	May 2020
Performance and long-term stability of CO2 conversion to formic acid using a three-compartment electrolyzer design Yang, Hongzhou; Kaczur, Jerry J.; Sajjad, Syed Dawar Journal of CO2 Utilization, Vol. 42 https://doi.org/10.1016/j.jcou.2020.101349	journal	December 2020
Techno-Economic Assessment of Green H₂ Carrier Supply Chains Crandall, Bradie S.; Brix, Todd; Weber, Robert S. Energy & Fuels, Vol. 37, Issue 2 https://doi.org/10.1021/acs.energyfuels.2c03616	journal	December 2022
Electroreduction of CO₂: Advances in the Continuous Production of Formic Acid and Formate Fernández-Caso, Kevin; Díaz-Sainz, Guillermo; Alvarez-Guerra, Manuel ACS Energy Letters, Vol. 8, Issue 4 https://doi.org/10.1021/acsenergylett.3c00489	journal	March 2023
Bismuth Oxides with Enhanced Bismuth–Oxygen Structure for Efficient Electrochemical Reduction of Carbon Dioxide to Formate Deng, Peilin; Wang, Hongming; Qi, Ruijuan ACS Catalysis, Vol. 10, Issue 1 https://doi.org/10.1021/acscatal.9b04043	journal	November 2019
Metal-support interaction enhanced electrochemical reduction of CO2 to formate between graphene and Bi nanoparticles Wu, Dan; Chen, Wenyue; Wang, Xuewan Journal of CO2 Utilization, Vol. 37 https://doi.org/10.1016/j.jcou.2020.02.007	journal	April 2020
High current density electroreduction of CO2 into formate with tin oxide nanospheres Nguyen-Phan, Thuy-Duong; Hu, Leiming; Howard, Bret H. Scientific Reports, Vol. 12, Issue 1 https://doi.org/10.1038/s41598-022-11890-6	journal	May 2022
Catholyte-Free Electrocatalytic CO ₂ Reduction to Formate Lee, Wonhee; Kim, Young Eun; Youn, Min Hye Angewandte Chemie International Edition, Vol. 57, Issue 23 https://doi.org/10.1002/anie.201803501	journal	May 2018
Study of the Exchange Current Density for the Hydrogen Oxidation and Evolution Reactions Neyerlin, K. C.; Gu, Wenbin; Jorne, Jacob Journal of The Electrochemical Society, Vol. 154, Issue 7 https://doi.org/10.1149/1.2733987	journal	January 2007
CO2 electroreduction to formate: Continuous single-pass operation in a filter-press reactor at high current densities using Bi gas diffusion electrodes Díaz-Sainz, G.; Alvarez-Guerra, M.; Solla-Gullón, J. Journal of CO2 Utilization, Vol. 34 https://doi.org/10.1016/j.jcou.2019.05.035	journal	December 2019
Electrifying the production of sustainable aviation fuel: the risks, economics, and environmental benefits of emerging pathways including CO₂ Grim, R. Gary; Ravikumar, Dwarak; Tan, Eric C. D. Energy & Environmental Science, Vol. 15, Issue 11 https://doi.org/10.1039/D2EE02439J	journal	January 2022

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Title: A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO2 to formic acid

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Title: A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO₂ to formic acid