Interfacial Engineering Toward Local Environment Modulation for Selective CO₂ Electroreduction

Abstract

Electrochemical CO₂ reduction (CO₂RR) holds promise for sustainable fuel and chemical production but faces fundamental challenges rooted in limited CO₂ availability and high activation reaction barriers. These issues manifest as slow kinetics, low selectivity, and poor stability under industrial operational conditions. While the catalyst/electrolyte interface engineering plays a decisive role in modulating the local microenvironment, which directly influences the kinetics and thermodynamics of CO₂RR, current understanding remains fragmented due to the complex interplay of interfacial factors. Herein, in this review, we address this gap by moving beyond conventional categorization by materials or products. We present a unified mechanism-oriented framework that directly links interfacial design strategies for tackling the core challenges of CO₂ availability, site accessibility, and reaction affordability. We systematically decouple the interface interactions and survey interfacial engineering strategies for CO₂ reduction, including mass-transport control, electrostatic microenvironment tuning, molecular functionalization, and device–interface engineering. By elucidating the mechanistic principles behind these strategies and their interconnections, this review provides actionable guidelines for engineering robust interfaces that break inherent trade-offs among activity, selectivity, and stability. We aim for this perspective to not only advance understanding of microenvironment modulation but also accelerate the development of scalable, carbon-neutral energy conversion technologies.

Keywords

electrocatalytic CO₂ reduction (CO₂RR) / interfacial engineering / microenvironment modulation / selectivity / surface functionalization

References

[1] S. Yang, W. Che, Y. Shao, et al., “Advancements and Prospects of Near-infrared-light Driven CO₂ Reduction Reaction,” Chemical Society Reviews 54 (2025): 7174–7215.

[2] IEA, Global Energy Review 2025 (Paris: IEA, 2025). Licence: CC BY 4.0, https://www.iea.org/reports/global-energy-review-2025.

[3] K. O. Yoro and M. O. Daramola, “CO₂ Emission Sources, Greenhouse Gases, and the Global Warming Effect,” in Advances in Carbon Capture, eds. M. R. Rahimpour, M. Farsi, and M. A. Makarem (Woodhead Publishing, 2020), 3–28, https://doi.org/10.1016/B978-0-12-819657-1.00001-3.

[4] Z. Liu, Z. Deng, G. He, et al., “Challenges and Opportunities for Carbon Neutrality in China,” Nature Reviews Earth & Environment 3 (2022): 141–155.

[5] D. Xu, K. Li, B. Jia, et al., “Electrocatalytic CO₂ Reduction Towards Industrial Applications,” Carbon Energy 5 (2023): e230.

[6] L. Li, X. Li, Y. Sun, and Y. Xie, “Rational Design of Electrocatalytic Carbon Dioxide Reduction for a Zero-Carbon Network,” Chemical Society Reviews 51 (2022): 1234–1252.

[7] Y. Chen, C. W. Li, and M. W. Kanan, “Aqueous CO₂ Reduction at Very Low Overpotential on Oxide-Derived Au Nanoparticles,” Journal of the American Chemical Society 134 (2012): 19969–19972.

[8] Y. Wang, C. Li, Z. Fan, et al., “Undercoordinated Active Sites on 4H Gold Nanostructures for CO₂ Reduction,” Nano Letters 20 (2020): 8074–8080.

[9] T. Xu, H. Yang, T. Lu, et al., “Microenvironment Engineering by Targeted Delivery of Ag Nanoparticles for Boosting Electrocatalytic CO₂ Reduction Reaction,” Nature Communications 16 (2025): 977.

[10] C. Kim, T. Eom, M. S. Jee, et al., “Insight into Electrochemical CO₂ Reduction on Surface-Molecule-Mediated Ag Nanoparticles,” ACS Catalysis 7 (2017): 779–785.

[11] E. L. Clark, S. Ringe, M. Tang, et al., “Influence of Atomic Surface Structure on the Activity of Ag for the Electrochemical Reduction of CO₂ to CO,” ACS Catalysis 9 (2019): 4006–4014.

[12] J. Rosen, G. S. Hutchings, Q. Lu, et al., “Mechanistic Insights into the Electrochemical Reduction of CO₂ to CO on Nanostructured Ag Surfaces,” ACS Catalysis 5 (2015): 4293–4299.

[13] D. Yao, C. Tang, A. Vasileff, X. Zhi, Y. Jiao, and S.-Z. Qiao, “The Controllable Reconstruction of Bi-MOFs for Electrochemical CO₂ Reduction Through Electrolyte and Potential Mediation,” Angewandte Chemie International Edition 60 (2021): 18178–18184.

[14] H. Shen, H. Jin, H. Li, et al., “Acidic CO₂-to-HCOOH Electrolysis With Industrial-Level Current on Phase Engineered Tin Sulfide,” Nature Communications 14 (2023): 2843.

[15] N. Han, P. Ding, L. He, Y. Li, and Y. Li, “Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO₂ Reduction to Formate,” Advanced Energy Materials 10 (2020): 1902338.

[16] T. Ren, Z. Miao, L. Ren, H. Xie, Q. Li, and C. Xia, “Nanostructure Engineering of Sn-Based Catalysts for Efficient Electrochemical CO₂ Reduction,” Small 19 (2023): 2205168.

[17] C.-T. Dinh, T. Burdyny, M. G. Kibria, et al., “CO₂ Electroreduction to Ethylene Via Hydroxide-Mediated Copper Catalysis at an Abrupt Interface,” Science 360 (2018): 783–787.

[18] M. Zhong, K. Tran, Y. Min, et al., “Accelerated Discovery of CO₂ Electrocatalysts Using Active Machine Learning,” Nature 581 (2020): 178–183.

[19] M. Zheng, J. Zhang, P. Wang, H. Jin, Y. Zheng, and S.-Z. Qiao, “Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper-Based Catalysts,” Advanced Materials 36 (2024): 2307913.

[20] J.-C. Yan, F.-M. Wang, S. Yin, J. Zhang, W. Jiang, and G.-G. Liu, “Copper/Metal Oxide Heterostructures for Electrochemical Carbon Dioxide Reduction,” Rare Metals 44 (2025): 2239–2267.

[21] J. Chen, X. Peng, Z. Li, et al., “Rational Modulation of Interface Microenvironment and Design of the Flow Electrolyzer for CO_x Electroreduction to Alcohol,” Advanced Materials 37 (2025): 2409106.

[22] W. Liu, Z. Lv, C. Wang, et al., “Industrial-Level Modulation of Catalyst-Electrolyte Microenvironment for Electrocatalytic CO₂ Reduction: Challenges and Advancements,” Advanced Energy Materials 14 (2024): 2402942.

[23] L. Yuan, S. Zeng, X. Zhang, X. Ji, and S. Zhang, “Advances and Challenges of Electrolyzers for Large-Scale CO₂ Electroreduction,” Materials Reports: Energy 3 (2023): 100177.

[24] A. Ozden, F. P. García de Arquer, J. E. Huang, et al., “Carbon-Efficient Carbon Dioxide Electrolysers,” Nature Sustainability 5 (2022): 563–573.

[25] D. Zhang, H. Cheng, X. Hao, et al., “Stable Seawater Oxidation at High-Salinity Conditions Promoted by Low Iron-Doped Non-Noble-Metal Electrocatalysts,” ACS Catalysis 13 (2023): 15581–15590.

[26] P.-P. Yang and M.-R. Gao, “Enrichment of Reactants and Intermediates for Electrocatalytic CO₂ Reduction,” Chemical Society Reviews 52 (2023): 4343–4380.

[27] Y. Zhang, B. Johannessen, P. Zhang, J. Gong, J. Ran, and S.-Z. Qiao, “Reversed Electron Transfer in Dual Single Atom Catalyst for Boosted Photoreduction of CO₂,” Advanced Materials 35 (2023): 2306923.

[28] Y.-R. Wang, H.-M. Ding, X.-Y. Ma, et al., “Imparting CO₂ Electroreduction Auxiliary for Integrated Morphology Tuning and Performance Boosting in a Porphyrin-based Covalent Organic Framework,” Angewandte Chemie International Edition 61 (2022): e202114648.

[29] D. Bagchi, J. Raj, A. K. Singh, et al., “Structure-Tailored Surface Oxide on Cu–Ga Intermetallics Enhances CO₂ Reduction Selectivity to Methanol at Ultralow Potential,” Advanced Materials 34 (2022): 2109426.

[30] P. Saha, S. Amanullah, and A. Dey, “Selectivity in Electrochemical CO₂ Reduction,” Accounts of Chemical Research 55 (2022): 134–144.

[31] J. Vavra, G. P. L. Ramona, F. Dattila, et al., “Solution-Based Cu₊ Transient Species Mediate the Reconstruction of Copper Electrocatalysts for CO₂ Reduction,” Nature Catalysis 7 (2024): 89–97.

[32] A. R. Woldu, Z. Huang, P. Zhao, L. Hu, and D. Astruc, “Electrochemical CO₂ Reduction (CO₂RR) to Multi-Carbon Products Over Copper-Based Catalysts,” Coordination Chemistry Reviews 454 (2022): 214340.

[33] M. Jiang, H. Wang, M. Zhu, et al., “Review on Strategies for Improving the Added Value and Expanding the Scope of CO₂ Electroreduction Products,” Chemical Society Reviews 53 (2024): 5149–5189.

[34] S.-J. Liu, T.-T. Hu, H.-Q. Chu, Z.-Z. Li, and W. Zhou, “Advances in Rare Metal Catalysis for Common CO₂ Reduction Reactions,” Rare Metals 44 (2025): 3622–3652.

[35] J. Li, G. Chen, Y. Zhu, et al., “Efficient Electrocatalytic CO₂ Reduction on a Three-Phase Interface,” Nature Catalysis 1 (2018): 592–600.

[36] L. Li, J. Chen, V. S. S. Mosali, et al., “Hydrophobicity Graded Gas Diffusion Layer for Stable Electrochemical Reduction of CO₂,” Angewandte Chemie International Edition 61 (2022): e202208534.

[37] Z. Xing, L. Hu, D. S. Ripatti, X. Hu, and X. Feng, “Enhancing Carbon Dioxide Gas-Diffusion Electrolysis by Creating a Hydrophobic Catalyst Microenvironment,” Nature Communications 12 (2021): 136.

[38] M. Sun, J. Cheng, and M. Yamauchi, “Gas Diffusion Enhanced Electrode With Ultrathin Superhydrophobic Macropore Structure for Acidic CO₂ Electroreduction,” Nature Communications 15 (2024): 491.

[39] F. Zhang and A. C. Co, “Direct Evidence of Local pH Change and the Role of Alkali Cation During CO₂ Electroreduction in Aqueous Media,” Angewandte Chemie International Edition 59 (2020): 1674–1681.

[40] W. Wu and Y. Wang, “The Role of Protons in CO₂ Reduction on Gold under Acidic Conditions,” Journal of the American Chemical Society 147 (2025): 11662–11666.

[41] S. Banerjee, C. S. Gerke, and V. S. Thoi, “Guiding CO₂RR Selectivity by Compositional Tuning in the Electrochemical Double Layer,” Accounts of Chemical Research 55 (2022): 504–515.

[42] J. Yang, J. Jiao, S. Liu, et al., “Switching Reaction Pathways of CO₂ Electroreduction by Modulating Cations in the Electrochemical Double Layer,” Angewandte Chemie International Edition 63 (2024): e202410145.

[43] B. Seger, G. Kastlunger, A. Bagger, and S. B. Scott, “A Perspective on the Reaction Mechanisms of CO₂ Electrolysis,” ACS Energy Letters 10 (2025): 2212–2227.

[44] Y. Zheng, A. Vasileff, X. Zhou, Y. Jiao, M. Jaroniec, and S.-Z. Qiao, “Understanding the Roadmap for Electrochemical Reduction of CO₂ to Multi-Carbon Oxygenates and Hydrocarbons on Copper-Based Catalysts,” Journal of the American Chemical Society 141 (2019): 7646–7659.

[45] X. Zhi, Y. Jiao, Y. Zheng, K. Davey, and S.-Z. Qiao, “Directing the Selectivity of CO₂ Electroreduction to Target C₂ Products Via Non-Metal Doping on Cu Surfaces,” Journal of Materials Chemistry A 9 (2021): 6345–6351.

[46] J. Ferreira de Araújo, J. Rossmeisl, H. Yin, X. Wang, A. Bagger, and P. Strasser, “Electrochemical CO₂ Valorization Pathways and Processes Toward C₂ to C₆ Products: Acetylene, Propylene, Butadiene, and Benzene,” ACS Energy Letters 10 (2025): 2532–2542.

[47] K. P. Kuhl, E. R. Cave, D. N. Abram, and T. F. Jaramillo, “New Insights Into the Electrochemical Reduction of Carbon Dioxide on Metallic Copper Surfaces,” Energy & Environmental Science 5 (2012): 7050–7059.

[48] J.-J. Li and Z.-C. Zhang, “K⁺-Enhanced Electrocatalytic CO₂ Reduction to Multicarbon Products in Strong Acid,” Rare Metals 41 (2022): 723–725.

[49] M. Du, F. Yu, S. Gong, and F. Liu, “Design of Electrocatalysts With High Performance Based on Thermodynamics and Kinetics: Progress and Prospects,” Advanced Functional Materials 35 (2025): 2413826.

[50] Y. Ji, J. Du, A. Chen, X. Gao, and M. Peng, “Transition Metal-Nitrogen-Carbon Single-Atom Catalysts Enhanced CO₂ Electroreduction Reaction: A Review,” ChemSusChem 18 (2025): e202401557.

[51] Y. Y. Birdja, E. Pérez-Gallent, M. C. Figueiredo, A. J. Göttle, F. Calle-Vallejo, and M. T. M. Koper, “Advances and Challenges in Understanding the Electrocatalytic Conversion of Carbon Dioxide to Fuels,” Nature Energy 4 (2019): 732–745.

[52] C. Chen, Y. Li, and P. Yang, “Address the “Alkalinity Problem” in CO₂ Electrolysis With Catalyst Design and Translation,” Joule 5 (2021): 737–742.

[53] Y. Jiang, L. Huang, C. Chen, Y. Zheng, and S.-Z. Qiao, “Catalyst–Electrolyte Interface Engineering Propels Progress in Acidic CO₂ Electroreduction,” Energy & Environmental Science 18 (2025): 2025–2049.

[54] Q. Wang, Y. Liu, Y. Tan, et al., “Enhanced Acidic CO₂-to-C₂₊ Reduction via Ionic Liquid Layer Modification,” Small 21 (2025): 2412293.

[55] R. Shi, J. Guo, X. Zhang, et al., “Efficient Wettability-Controlled Electroreduction of CO₂ to CO at Au/C Interfaces,” Nature Communications 11 (2020): 3028.

[56] J. Ryu and D. W. Lee, “Tailoring Hydrophilic and Hydrophobic Microenvironments for Gas–Liquid–Solid Triphase Electrochemical Reactions,” Journal of Materials Chemistry A 12 (2024): 10012–10043.

[57] X. Zhou, H. Liu, B. Y. Xia, K. Ostrikov, Y. Zheng, and S.-Z. Qiao, “Customizing the Microenvironment of CO₂ Electrocatalysis Via Three-Phase Interface Engineering,” SmartMat 3 (2022): 111–129.

[58] Z. Guo, P. Paciok, R. Zandonella, et al., “Visualizing Electrochemical CO₂ Reduction Reaction: Recent Progress of In Situ Liquid Cell Transmission Electron Microscopy,” Advanced Functional Materials 35 (2025): 2500915.

[59] T. N. Nguyen and C.-T. Dinh, “Gas Diffusion Electrode Design for Electrochemical Carbon Dioxide Reduction,” Chemical Society Reviews 49 (2020): 7488–7504.

[60] F. Pan and Y. Yang, “Designing CO₂ Reduction Electrode Materials by Morphology and Interface Engineering,” Energy & Environmental Science 13 (2020): 2275–2309.

[61] M. Colet-Lagrille, S. González-Poggini, C. Salazar-Espinoza, and B. Sánchez, “Gas Diffusion Electrodes (GDEs) for Carbon Dioxide (CO₂) Reduction in Microfluidic Cells: Towards a Fluid Dynamics Assisted Rational Design,” Journal of the Electrochemical Society 171 (2024): 044502.

[62] Z. Xing, X. Hu, and X. Feng, “Tuning the Microenvironment in Gas-Diffusion Electrodes Enables High-Rate CO₂ Electrolysis to Formate,” ACS Energy Letters 6 (2021): 1694–1702.

[63] J. Chen, H. Qiu, Y. Zhao, et al., “Selective and Stable CO₂ Electroreduction at High Rates Via Control of Local H₂O/CO₂ Ratio,” Nature Communications 15 (2024): 5893.

[64] Q. Chang, J. H. Lee, Y. Liu, et al., “Electrochemical CO₂ Reduction Reaction Over Cu Nanoparticles With Tunable Activity and Selectivity Mediated by Functional Groups in Polymeric Binder,” JACS Au 2 (2022): 214–222.

[65] T. H. M. Pham, J. Zhang, M. Li, et al., “Enhanced Electrocatalytic CO₂ Reduction to C₂₊ Products by Adjusting the Local Reaction Environment With Polymer Binders,” Advanced Energy Materials 12 (2022): 2103663.

[66] C. Chen, L. Huang, Y. Jiang, Y. Zheng, and S.-Z. Qiao, “Modulating Local Environment for Electrocatalytic CO₂ Reduction to Alcohol,” Nano Energy 126 (2024): 109656.

[67] Y. Wang, J. Zhang, J. Zhao, et al., “Strong Hydrogen-Bonded Interfacial Water Inhibiting Hydrogen Evolution Kinetics to Promote Electrochemical CO₂ Reduction to C₂₊,” ACS Catalysis 14 (2024): 3457–3465.

[68] T. Shao, K. Yang, S. Chen, et al., “Tackling the Proton Limit Under Industrial Electrochemical CO₂ Reduction by a Local Proton Shuttle,” Carbon Energy 6 (2024): e416.

[69] Y. Lin, T. Wang, L. Zhang, et al., “Tunable CO₂ Electroreduction to Ethanol and Ethylene With Controllable Interfacial Wettability,” Nature Communications 14 (2023): 3575.

[70] S. Yoo, S. Yoo, G. Deng, et al., “Nanocluster Surface Microenvironment Modulates Electrocatalytic CO₂ Reduction,” Advanced Materials 36 (2024): 2313032.

[71] L. Li, Z. Liu, X. Yu, and M. Zhong, “Achieving High Single-Pass Carbon Conversion Efficiencies in Durable CO₂ Electroreduction in Strong Acids via Electrode Structure Engineering,” Angewandte Chemie International Edition 62 (2023): e202300226.

[72] L. Xiong, X. Fu, Y. Zhou, P. Nian, Z. Wang, and Q. Yue, “Precise Site-Hydrophobicity Modulation for Boosting High-Performance CO₂ Electroreduction,” ACS Catalysis 13 (2023): 6652–6660.

[73] S. Shu, T. Song, C. Wang, H. Dai, and L. Duan, “[2+1] Cycloadditions Modulate the Hydrophobicity of Ni-N₄ Single-Atom Catalysts for Efficient CO₂ Electroreduction,” Angewandte Chemie International Edition 63 (2024): e202405650.

[74] T. Deng, S. Jia, C. Chen, et al., “Polymer Modification Strategy to Modulate Reaction Microenvironment for Enhanced CO₂ Electroreduction to Ethylene,” Angewandte Chemie International Edition 63 (2024): e202313796.

[75] M. Wang, L. Lin, Z. Zheng, et al., “Hydrophobized Electrospun Nanofibers of Hierarchical Porosity as the Integral Gas Diffusion Electrode for Full-pH CO₂ Electroreduction In Membrane Electrode Assemblies,” Energy & Environmental Science 16 (2023): 4423–4431.

[76] W. Ju, F. Jiang, H. Ma, et al., “Electrocatalytic Reduction of Gaseous CO₂ to CO on Sn/Cu-Nanofiber-Based Gas Diffusion Electrodes,” Advanced Energy Materials 9 (2019): 1901514.

[77] M. Filippi, T. Möller, R. Pastusiak, E. Magori, B. Paul, and P. Strasser, “Scale-Up of PTFE-Based Gas Diffusion Electrodes Using an Electrolyte-Integrated Polymer-Coated Current Collector Approach,” ACS Energy Letters 9 (2024): 1361–1368.

[78] S. Mu, L. Li, R. Zhao, H. Lu, H. Dong, and C. Cui, “Molecular-Scale Insights Into Electrochemical Reduction of CO₂ On Hydrophobically Modified Cu Surfaces,” ACS Applied Materials & Interfaces 13 (2021): 47619–47628.

[79] H.-Q. Liang, S. Zhao, X.-M. Hu, M. Ceccato, T. Skrydstrup, and K. Daasbjerg, “Hydrophobic Copper Interfaces Boost Electroreduction of Carbon Dioxide to Ethylene in Water,” ACS Catalysis 11 (2021): 958–966.

[80] T. Shi, D. Liu, H. Feng, Y. Zhang, and Q. Li, “Evolution of Triple-Phase Interface for Enhanced Electrochemical CO₂ Reduction,” Chemical Engineering Journal 431 (2022): 134348.

[81] S. Chang, J. Gao, Y. Xuan, D. Li, and K. Wang, “Amine Modification Enables Selective CO₂ Electroreduction to Ethanol Via Coupling of Carbon-Containing Intermediates,” Chem Catalysis 5 (2025): 101383.

[82] Y. Cheng, Q. Li, M. I. B. Salaman, et al., “Microenvironment Tailoring for Electrocatalytic CO₂ Reduction: Effects of Interfacial Structure on Controlling Activity and Selectivity,” Journal of the American Chemical Society 147 (2025): 12438–12448.

[83] Z.-Z. Niu, F.-Y. Gao, X.-L. Zhang, et al., “Hierarchical Copper With Inherent Hydrophobicity Mitigates Electrode Flooding for High-Rate CO₂ Electroreduction to Multicarbon Products,” Journal of the American Chemical Society 143 (2021): 8011–8021.

[84] J. Bi, P. Li, J. Liu, et al., “Construction of 3D Copper-Chitosan-Gas Diffusion Layer Electrode for Highly Efficient CO₂ Electrolysis to C₂₊ Alcohols,” Nature Communications 14 (2023): 2823.

[85] Q. Geng, L. Fan, H. Chen, et al., “Revolutionizing CO₂ Electrolysis: Fluent Gas Transportation Within Hydrophobic Porous Cu₂O,” Journal of the American Chemical Society 146 (2024): 10599–10607.

[86] C. Liu, H. Zang, X. Liu, H. Lu, N. Yu, and B. Geng, “Establishment of Gas–Liquid–Solid Interface on Multilevel Porous Cu₂O for Potential-Driven Selective CO₂ Electroreduction Toward C1 or C2 Products,” ACS Applied Materials & Interfaces 17 (2025): 6845–6856.

[87] C. Chen, X. Yan, Y. Wu, et al., “Boosting the Productivity of Electrochemical CO₂ Reduction to Multi-Carbon Products by Enhancing CO₂ Diffusion Through a Porous Organic Cage,” Angewandte Chemie International Edition 61 (2022): e202202607.

[88] M. Sassenburg, M. Kelly, S. Subramanian, W. A. Smith, and T. Burdyny, “Zero-Gap Electrochemical CO₂ Reduction Cells: Challenges and Operational Strategies for Prevention of Salt Precipitation,” ACS Energy Letters 8 (2023): 321–331.

[89] L. Zhang, J. Feng, L. Wu, et al., “Oxophilicity-Controlled CO₂ Electroreduction to C₂₊ Alcohols over Lewis Acid Metal-Doped Cu^δ+ Catalysts,” Journal of the American Chemical Society 145 (2023): 21945–21954.

[90] M. R. Singh, Y. Kwon, Y. Lum, J. W. Ager, and A. T. Bell, “Hydrolysis of Electrolyte Cations Enhances the Electrochemical Reduction of CO₂ Over Ag and Cu,” Journal of the American Chemical Society 138 (2016): 13006–13012.

[91] J. Gu, S. Liu, W. Ni, W. Ren, S. Haussener, and X. Hu, “Modulating Electric Field Distribution by Alkali Cations for CO₂ Electroreduction in Strongly Acidic Medium,” Nature Catalysis 5 (2022): 268–276.

[92] A. Murata and Y. Hori, “Product Selectivity Affected by Cationic Species in Electrochemical Reduction of CO₂ and CO at a Cu Electrode,” Bulletin of the Chemical Society of Japan 64 (2006): 123–127.

[93] S. Ringe, E. L. Clark, J. Resasco, et al., “Understanding Cation Effects in Electrochemical CO₂ Reduction,” Energy & Environmental Science 12 (2019): 3001–3014.

[94] M. R. Thorson, K. I. Siil, and P. J. A. Kenis, “Effect of Cations on the Electrochemical Conversion of CO₂ to CO,” Journal of the Electrochemical Society 160 (2012): F69–F74.

[95] M. Liu, Y. Pang, B. Zhang, et al., “Enhanced Electrocatalytic CO₂ Reduction Via Field-Induced Reagent Concentration,” Nature 537 (2016): 382–386.

[96] J. Resasco, L. D. Chen, E. Clark, et al., “Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide,” Journal of the American Chemical Society 139 (2017): 11277–11287.

[97] G. Hussain, L. Pérez-Martínez, J.-B. Le, et al., “How Cations Determine the Interfacial Potential Profile: Relevance for the CO₂ Reduction Reaction,” Electrochimica Acta 327 (2019): 135055.

[98] M. C. O. Monteiro, F. Dattila, B. Hagedoorn, R. García-Muelas, N. López, and M. T. M. Koper, “Absence of CO₂ Electroreduction on Copper, Gold and Silver Electrodes Without Metal Cations in Solution,” Nature Catalysis 4 (2021): 654–662.

[99] A. S. Malkani, J. Li, N. J. Oliveira, et al., “Understanding the Electric and Nonelectric Field Components of the Cation Effect on the Electrochemical CO Reduction Reaction,” Science Advances 6 (2020): eabd2569.

[100] V. J. Ovalle, Y.-S. Hsu, N. Agrawal, M. J. Janik, and M. M. Waegele, “Correlating Hydration Free Energy and Specific Adsorption of Alkali Metal Cations During CO₂ Electroreduction on Au,” Nature Catalysis 5 (2022): 624–632.

[101] X. Chen, I. T. McCrum, K. A. Schwarz, M. J. Janik, and M. T. M. Koper, “Co-Adsorption of Cations as the Cause of the Apparent pH Dependence of Hydrogen Adsorption on a Stepped Platinum Single-Crystal Electrode,” Angewandte Chemie International Edition 56 (2017): 15025–15029.

[102] Q. Zhu, S. K. Wallentine, G.-H. Deng, J. A. Rebstock, and L. R. Baker, “The Solvation-Induced Onsager Reaction Field Rather Than the Double-Layer Field Controls CO₂ Reduction on Gold,” JACS Au 2 (2022): 472–482.

[103] S.-J. Shin, H. Choi, S. Ringe, et al., “A Unifying Mechanism for Cation Effect Modulating C1 and C2 Productions From CO₂ Electroreduction,” Nature Communications 13 (2022): 5482.

[104] Z. Cui, A. J.-W. Wong, M. J. Janik, and A. C. Co, “Cation Effects on CO₂ Reduction Catalyzed by Single-crystal and Polycrystalline Gold Under Well-Defined Mass Transport Conditions,” Science Advances 11 (2025): eadr6465.

[105] Z. Zhang, H. Li, Y. Shao, et al., “Molecular Understanding of the Critical Role of Alkali Metal Cations in Initiating CO₂ Electroreduction on Cu(100) Surface,” Nature Communications 15 (2024): 612.

[106] W. Ren, A. Xu, K. Chan, and X. Hu, “A Cation Concentration Gradient Approach to Tune the Selectivity and Activity of CO₂ Electroreduction,” Angewandte Chemie International Edition 134 (2022): e202214173.

[107] Z. Li, L. Wang, L. Sun, and W. Yang, “Dynamic Cation Enrichment During Pulsed CO₂ Electrolysis and the Cation-Promoted Multicarbon Formation,” Journal of the American Chemical Society 146 (2024): 23901–23908.

[108] J. E. Huang, F. Li, A. Ozden, et al., “CO₂ Electrolysis to Multicarbon Products in Strong Acid,” Science 372 (2021): 1074–1078.

[109] X. Zi, Y. Zhou, L. Zhu, et al., “Breaking K⁺ Concentration Limit on Cu Nanoneedles for Acidic Electrocatalytic CO₂ Reduction to Multi-Carbon Products,” Angewandte Chemie International Edition 62 (2023): e202309351.

[110] J. Hou, B. Xu, and Q. Lu, “Influence of Electric Double Layer Rigidity on CO Adsorption and Electroreduction Rate,” Nature Communications 15 (2024): 1926.

[111] R. Yang, Y. Cai, Y. Qi, et al., “How Local Electric Field Regulates C–C Coupling at a Single Nanocavity in Electrocatalytic CO₂ Reduction,” Nature Communications 15 (2024): 7140.

[112] J.-M. McGregor, J. T. Bender, A. S. Petersen, et al., “Organic Electrolyte Cations Promote Non-Aqueous CO₂ Reduction by Mediating Interfacial Electric Fields,” Nature Catalysis 8 (2025): 79–91.

[113] Z. Mi, T. Wang, L. Xiao, G. Wang, and L. Zhuang, “Catalytic Peculiarity of Alkali Metal Cation-Free Electrode/Polyelectrolyte Interfaces Toward CO₂ Reduction,” Journal of the American Chemical Society 146 (2024): 17377–17383.

[114] D. Gao, F. Scholten, and B. Roldan Cuenya, “Improved CO₂ Electroreduction Performance on Plasma-Activated Cu Catalysts via Electrolyte Design: Halide Effect,” ACS Catalysis 7 (2017): 5112–5120.

[115] J. M. Yoo, J. Ingenmey, M. Salanne, and M. R. Lukatskaya, “Anion Effect in Electrochemical CO2Reduction: From Spectators to Orchestrators,” Journal of the American Chemical Society 146 (2024): 31768–31777.

[116] Z. Tan, J. Zhang, Y. Yang, et al., “Polymeric Ionic Liquid Promotes Acidic Electrocatalytic CO₂ Conversion to Multicarbon Products With Ampere Level Current on Cu,” Nature Communications 16 (2025): 1843.

[117] G.-Y. Duan, X.-Q. Li, Y.-R. Du, and B.-H. Xu, “Efficient Electrocatalytic Reduction of CO₂ to CO on Highly Dispersed Ag Nanoparticles Confined by Poly(Ionic) Liquid,” Chemical Engineering Journal 455 (2023): 140910.

[118] O. K. Coskun, S. Dongare, B. Doherty, A. Klemm, M. Tuckerman, and B. Gurkan, “Tailoring Electrochemical CO₂ Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors,” Angewandte Chemie International Edition 63 (2024): e202312163.

[119] S. Dongare, O. K. Coskun, E. Cagli, et al., “A Bifunctional Ionic Liquid for Capture and Electrochemical Conversion of CO₂ to CO Over Silver,” ACS Catalysis 13 (2023): 7812–7821.

[120] S. Hong, S. Lee, S. Kim, J. K. Lee, and J. Lee, “Anion Dependent CO/H₂ Production Ratio From CO₂ Reduction on Au Electro-Catalyst,” Catalysis Today 295 (2017): 82–88.

[121] A. S. Varela, W. Ju, T. Reier, and P. Strasser, “Tuning the Catalytic Activity and Selectivity of Cu for CO₂ Electroreduction in the Presence of Halides,” ACS Catalysis 6 (2016): 2136–2144.

[122] Y. Jiang, H. Li, C. Chen, Y. Zheng, and S.-Z. Qiao, “Dynamic Cu⁰/Cu⁺ Interface Promotes Acidic CO₂ Electroreduction,” ACS Catalysis 14 (2024): 8310–8316.

[123] T. Yuan, T. Wang, G. Zhang, et al., “The Effect of Specific Adsorption of Halide Ions on Electrochemical CO₂ Reduction,” Chemical Science 13 (2022): 8117–8123.

[124] V. J. Ovalle and M. M. Waegele, “Impact of Electrolyte Anions on the Adsorption of CO on Cu Electrodes,” Journal of Physical Chemistry C 124 (2020): 14713–14721.

[125] J. Wang, Y. Qin, S. Jin, et al., “Customizing CO₂ Electroreduction by Pulse-Induced Anion Enrichment,” Journal of the American Chemical Society 145 (2023): 26213–26221.

[126] M. C. O. Monteiro, F. Dattila, N. López, and M. T. M. Koper, “The Role of Cation Acidity on the Competition Between Hydrogen Evolution and CO₂ Reduction on Gold Electrodes,” Journal of the American Chemical Society 144 (2022): 1589–1602.

[127] D. F. Bruggeman, G. Rothenberg, and A. C. Garcia, “Investigating Proton Shuttling and Electrochemical Mechanisms of Amines in Integrated CO₂ Capture and Utilization,” Nature Communications 15 (2024): 9207.

[128] X. Chen, J. Chen, N. M. Alghoraibi, et al., “Electrochemical CO₂-to-Ethylene Conversion on Polyamine-Incorporated Cu Electrodes,” Nature Catalysis 4 (2021): 20–27.

[129] J. Cheng, L. Chen, X. Xie, et al., “Proton Shuttling by Polyaniline of High Brønsted Basicity for Improved Electrocatalytic Ethylene Production from CO₂,” Angewandte Chemie International Edition 62 (2023): e202312113.

[130] S. Liu, T. Wang, X. Liu, et al., “In Situ Dissociated Chalcogenide Anions Regulate the Bi-Catalyst/Electrolyte Interface With Accelerated Surface Reconstruction Toward Efficient CO₂ Reduction,” ACS Catalysis 14 (2024): 489–497.

[131] J. Y. T. Kim, C. Sellers, S. Hao, T. P. Senftle, and H. Wang, “Different Distributions of Multi-Carbon Products in CO₂ and CO Electroreduction Under Practical Reaction Conditions,” Nature Catalysis 6 (2023): 1115–1124.

[132] P. Wei, D. Gao, T. Liu, et al., “Coverage-Driven Selectivity Switch From Ethylene to Acetate in High-Rate CO₂/CO Electrolysis,” Nature Nanotechnology 18 (2023): 299–306.

[133] B. Bao, J. Hao, X. Bian, et al., “3D Porous Hydrogel/Conducting Polymer Heterogeneous Membranes With Electro-/pH-Modulated Ionic Rectification,” Advanced Materials 29 (2017): 1702926.

[134] S. Li, X. Dong, G. Wu, et al., “Ampere-Level CO₂ Electroreduction With Single-Pass Conversion Exceeding 85% in Acid Over Silver Penetration Electrodes,” Nature Communications 15 (2024): 6101.

[135] A. Wagner, C. D. Sahm, and E. Reisner, “Towards Molecular Understanding of Local Chemical Environment Effects in Electro- and Photocatalytic CO₂ Reduction,” Nature Catalysis 3 (2020): 775–786.

[136] Y. Yang, C. Zhang, C. Zhang, et al., “Ligand-Tuning Copper in Coordination Polymers for Efficient Electrochemical C–C Coupling,” Nature Communications 15 (2024): 6316.

[137] X. Zhou, J. Shan, M. Zheng, H. Li, B. Y. Xia, and Y. Zheng, “Tuning Molecular Electrophilicity on Cu Catalysts to Steer CO₂ Electroreduction Selectivity,” Science China Materials 67 (2024): 1858–1865.

[138] Y. Liu and C. C. L. McCrory, “Modulating the Mechanism of Electrocatalytic CO₂ Reduction by Cobalt Phthalocyanine Through Polymer Coordination and Encapsulation,” Nature Communications 10 (2019): 1683.

[139] X. Jiang, H. Li, J. Xiao, et al., “Carbon Dioxide Electroreduction Over Imidazolate Ligands Coordinated With Zn(II) Center in ZIFs,” Nano Energy 52 (2018): 345–350.

[140] S. Sung, X. Li, L. M. Wolf, et al., “Synergistic Effects of Imidazolium-Functionalization on fac-Mn(CO)₃ Bipyridine Catalyst Platforms for Electrocatalytic Carbon Dioxide Reduction,” Journal of the American Chemical Society 141 (2019): 6569–6582.

[141] M. L. Clark, A. Ge, P. E. Videla, et al., “CO₂ Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields,” Journal of the American Chemical Society 140 (2018): 17643–17655.

[142] Z. Cao, S. B. Zacate, X. Sun, et al., “Tuning Gold Nanoparticles With Chelating Ligands for Highly Efficient Electrocatalytic CO₂ Reduction,” Angewandte Chemie International Edition 57 (2018): 12675–12679.

[143] Y. Fang and J. C. Flake, “Electrochemical Reduction of CO₂ at Functionalized Au Electrodes,” Journal of the American Chemical Society 139 (2017): 3399–3405.

[144] J. Chen, X. Liu, S. Xi, et al., “Functionalized Ag With Thiol Ligand to Promote Effective CO₂ Electroreduction,” ACS Nano 16 (2022): 13982–13991.

[145] W. Ge, Y. Zhu, H. Wang, H. Jiang, and C. Li, “Anionic Surfactant-Tuned Interfacial Water Reactivity Promoting Electrocatalytic CO₂ Reduction,” ACS Catalysis 14 (2024): 18156–18166.

[146] Y. Chen, Y. Zhang, Z. Li, et al., “Amphipathic Surfactant on Reconstructed Bismuth Enables Industrial-Level Electroreduction of CO₂ to Formate,” ACS Nano 18 (2024): 19345–19353.

[147] Z.-Q. Zhang, S. Banerjee, V. S. Thoi, and A. Shoji Hall, “Reorganization of Interfacial Water by an Amphiphilic Cationic Surfactant Promotes CO₂ Reduction,” Journal of Physical Chemistry Letters 11 (2020): 5457–5463.

[148] T. Dong, H. Li, Z. Wang, et al., “Acidic Electroreduction CO₂ to Formic Acid Via Interfacial Modification of Bi Nanoparticles at Industrial-Level Current,” Nano Research 17 (2024): 5817–5825.

[149] J. Chen, Y. Wang, Y. Yu, et al., “Composite Materials Based on Covalent Organic Frameworks for Multiple Advanced Applications,” Exploration3 (2023): 20220144.

[150] S. Zheng, X. Liu, C. Wang, et al., “Quantitative Skeletal-Charge Engineering of Anion-Selective COF Membrane for Ultrahigh Osmotic Power Output,” Journal of the American Chemical Society 147 (2025): 15777–15786.

[151] W. Qin, D. Han, X. Zhang, et al., “Redox-Active Metal-Covalent Organic Frameworks for Dendrite-Free Lithium Metal Batteries,” Advanced Materials 37 (2025): 2418638.

[152] B.-C. Shi, M. Jin, Y. Zou, et al., “Cathodic Electrodeposition Activation of NiFe-Based Metal–Organic Frameworks for Enhanced Oxygen Evolution Reaction,” Rare Metals (2025), https://doi.org/10.1007/s12598-025-03446-0.

[153] G. Hai, X. Xue, S. Feng, Y. Ma, and X. Huang, “High-Throughput Computational Screening of Metal–Organic Frameworks as High-Performance Electrocatalysts for CO₂RR,” ACS Catalysis 12 (2022): 15271–15281.

[154] T. A. Al-Attas, N. N. Marei, X. Yong, et al., “Ligand-Engineered Metal–Organic Frameworks for Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide,” ACS Catalysis 11 (2021): 7350–7357.

[155] A. H. Mamaghani, J. Liu, Z. Zhang, et al., “Promises of MOF-Based and MOF-Derived Materials for Electrocatalytic CO₂ Reduction,” Advanced Energy Materials 14 (2024): 2402278.

[156] C. Qin, X. Li, T. Wang, Z. Xu, K.-J. Chen, and F. Pan, “Metal-Organic Frameworks-Based Copper Catalysts for CO₂ Electroreduction Toward Multicarbon Products,” Exploration 5, (2025): 270011.

[157] X. Zheng, S. Yang, D. Chen, et al., “Crown Ether Functionalization Boosts CO₂ Electroreduction to Ethylene on Copper-Based MOFs,” Chemical Communications 61 (2025): 2993–2996.

[158] M. Liu, Q. Xu, and G. Zeng, “Ionic Covalent Organic Frameworks in Adsorption and Catalysis,” Angewandte Chemie International Edition 63 (2024): e202404886.

[159] K. Yang, M. Li, T. Gao, et al., “An Acid-Tolerant Metal-Organic Framework for Industrial CO₂ Electrolysis Using a Proton Exchange Membrane,” Nature Communications 15 (2024): 7060.

[160] Y. Shen, N. Fang, X. Liu, et al., “Observation of Metal-Organic Interphase in Cu-Based Electrochemical CO₂-to-ethanol Conversion,” Nature Communications 16 (2025): 2073.

[161] Q.-J. Wu, D.-H. Si, Q. Wu, Y.-L. Dong, R. Cao, and Y.-B. Huang, “Boosting Electroreduction of CO₂ over Cationic Covalent Organic Frameworks: Hydrogen Bonding Effects of Halogen Ions,” Angewandte Chemie International Edition 62 (2023): e202215687.

[162] Y. Zhao, L. Hao, A. Ozden, et al., “Conversion of CO₂ to Multicarbon Products in Strong Acid by Controlling the Catalyst Microenvironment,” Nature Synthesis 2 (2023): 403–412.

[163] G. Shi, W. Zhang, Y. Kang, et al., “Nanoconfinement Promotes CO₂ Electroreduction to Methanol on a Molecular Catalyst,” Nature Communications 16 (2025): 7359.

[164] L. Xie, X. Yu, S. Wang, et al., “A Multiscale Strategy to Construct Cobalt Nanoparticles Confined within Hierarchical Carbon Nanofibers for Efficient CO₂ Electroreduction,” Small 18 (2022): 2104958.

[165] Z. Liu, L. Cao, M. Wang, Y. Zhao, M. Hou, and Z. Shao, “A Robust Ni Single-Atom Catalyst for Industrial Current and Exceptional Selectivity in Electrochemical CO₂ Reduction to CO,” Journal of Materials Chemistry A 12 (2024): 8331–8339.

[166] W. Wang, N. Zhao, K. Zhao, et al., “Multi-Heteroatom-Doped Porous Carbon Electrodes From 3D Printing and Conformal Carbonization of Ionic Liquids for Electrocatalytic CO₂ Conversion Into Syngas,” Communications Chemistry 8 (2025): 121.

[167] H. Wang, C. Ma, and Q. Lu, et al., “Precise Tuning of Functional Group Spatial Distribution on Porphyrin Rings for Enhanced CO₂ Electroreduction Selectivity,” Angewandte Chemie International Edition 64 (2025): e202501091.

[168] L.-Y. Li, X.-Y. Zhao, M.-H. Tang, et al., “Highly Efficient CO₂ Electroreduction in Artificial Seawater Electrolyte Catalyzed by Strong-Acid/Base-Resistant MOF,” Angewandte Chemie International Edition (2025): e202512100.

[169] X. Chen, R. Lu, C. Li, et al., “Activating Inert Non-Defect Sites in Bi Catalysts Using Tensile Strain Engineering for Highly Active CO₂ Electroreduction,” Nature Communications 16 (2025): 1927.

[170] X.-Y. Wu, J.-F. Lu, S. Zou, et al., “Reducing the Coordination Number of Bismuth Sites in Metal-Organic Framework to Enhance the Performance of Electrochemical CO₂ Reduction Over a Wide Potential Range,” Advanced Functional Materials 35 (2025): 2504928.

[171] D. Kim, S. Yu, F. Zheng, et al., “Selective CO₂ Electrocatalysis at the Pseudocapacitive Nanoparticle/Ordered-Ligand Interlayer,” Nature Energy 5 (2020): 1032–1042.

[172] S. Yu, S. Louisia, and P. Yang, “The Interactive Dynamics of Nanocatalyst Structure and Microenvironment During Electrochemical CO₂ Conversion,” JACS Au 2 (2022): 562–572.

[173] S. Yu, D. Kim, Z. Qi, et al., “Nanoparticle Assembly Induced Ligand Interactions for Enhanced Electrocatalytic CO₂ Conversion,” Journal of the American Chemical Society 143 (2021): 19919–19927.

[174] Y. Shan, X. Zhao, M. Fonseca Guzman, et al., “Nanometre-Resolved Observation of Electrochemical Microenvironment Formation at the Nanoparticle–Ligand Interface,” Nature Catalysis 7 (2024): 422–431.

[175] S. Sun, “Pocket the Difference,” Nature Energy 5 (2020): 943–944.

[176] Y. Chae, H. Kim, D. K. Lee, U. Lee, and D. H. Won, “Exploring the Critical Role of Binders in Electrochemical CO₂ Reduction Reactions,” Nano Energy 130 (2024): 110134.

[177] C. Kim, J. C. Bui, X. Luo, et al., “Tailored Catalyst Microenvironments for CO₂ Electroreduction to Multicarbon Products on Copper Using Bilayer Ionomer Coatings,” Nature Energy 6 (2021): 1026–1034.

[178] M. Zhuansun, Y. Liu, R. Lu, et al., “Promoting CO₂ Electroreduction to Multi-Carbon Products by Hydrophobicity-Induced Electro-Kinetic Retardation,” Angewandte Chemie International Edition 62 (2023): e202309875.

[179] W. Jung, S.-H. Shin, S. Park, et al., “Unveiling Key Descriptors of Ionomer Materials for Enhanced Electrochemical CO₂ Reduction,” ACS Energy Letters 10 (2025): 620–628.

[180] X. Du, P. Zhang, G. Zhang, et al., “Confinement of Ionomer for Electrocatalytic CO₂ Reduction Reaction via Efficient Mass Transfer Pathways,” National Science Review 11 (2023): nwad149.

[181] Y. Zhao, X. Zu, R. Chen, et al., “Industrial-Current-Density CO₂-to-C₂₊ Electroreduction by Anti-Swelling Anion-Exchange Ionomer-Modified Oxide-Derived Cu Nanosheets,” Journal of the American Chemical Society 144 (2022): 10446–10454.

[182] M. Fang, X. Miao, Z. Huang, et al., “Anionic Ionomer: Released Surface-Immobilized Cations and an Established Hydrophobic Microenvironment for Efficient and Durable CO₂-to-Ethylene Electrosynthesis at High Current over One Month,” Journal of the American Chemical Society 146 (2024): 27060–27069.

[183] S. Banerjee, Z.-Q. Zhang, A. S. Hall, and V. S. Thoi, “Surfactant Perturbation of Cation Interactions at the Electrode–Electrolyte Interface in Carbon Dioxide Reduction,” ACS Catalysis 10 (2020): 9907-9914.

[184] Y. Qin, C. Xia, T. Wu, et al., “Specific Adsorption of Alkaline Cations Enhances CO–CO Coupling in CO₂ Electroreduction,” Journal of the American Chemical Society 146 (2024): 32539–32549.

[185] L. Li, Y. Zhou, C. Wan, et al., “Neighboring Nonmetal Site as an Intermediate Modulator Switching CO₂ Electroreduction Pathway toward Multicarbons,” Joule 9 (2025): 101926.

[186] M. L. Frisch, L. Wu, C. Atlan, et al., “Unraveling the Synergistic Effects of Cu-Ag Tandem Catalysts During Electrochemical CO₂ Reduction Using Nanofocused X-Ray Probes,” Nature Communications 14 (2023): 7833.

[187] C. Du, J. P. Mills, A. G. Yohannes, et al., “Cascade Electrocatalysis Via AgCu Single-Atom Alloy and Ag Nanoparticles in CO₂ Electroreduction Toward Multicarbon Products,” Nature Communications 14 (2023): 6142.

[188] M. Wang, V. Nikolaou, A. Loiudice, I. D. Sharp, A. Llobet, and R. Buonsanti, “Tandem Electrocatalytic CO₂ Reduction With Fe-Porphyrins and Cu Nanocubes Enhances Ethylene Production,” Chemical Science 13 (2022): 12673–12680.

[189] C. Wang, Y. Sun, Y. Chen, et al., “In Situ Electropolymerizing Toward EP-CoP/Cu Tandem Catalyst for Enhanced Electrochemical CO₂-to-Ethylene Conversion,” Advanced Science 11 (2024): 2404053.

[190] M. Liu, Q. Wang, T. Luo, et al., “Potential Alignment in Tandem Catalysts Enhances CO₂-to-C₂H₄ Conversion Efficiencies,” Journal of the American Chemical Society 146 (2024): 468–475.

[191] X.-Q. Li, G.-Y. Duan, R. Wang, L.-J. Han, Y.-F. Wang, and B.-H. Xu, “Poly(Ionic Liquid)-Based Bimetallic Tandem Catalysts for Highly Efficient Carbon Dioxide Electroreduction,” Applied Catalysis, B: Environmental 313 (2022): 121459.

[192] A. Ghatak, G. S. Shanker, Y. Pearlmutter, A. Fryder, R. Shimoni, and I. Hod, “Dual Molecular Catalyst-Based Tandem That Enables Electrocatalytic CO₂−Formaldehyde−Methanol Cascade Conversion,” Journal of the American Chemical Society 147 (2025): 20329–20337.

[193] J. Li, J. Xiong, M. Sun, and F. Li, “Anodic Reactions Matter for Cathodic Electrocarboxylation With CO₂,” Chem Catalysis 5 (2025): 101263.

[194] Y. Yang and F. Li, “Reactor Design for Electrochemical CO₂ Conversion Toward Large-Scale Applications,” Current Opinion in Green and Sustainable Chemistry 27 (2021): 100419.

[195] J. Feng, H. Gao, L. Zheng, et al., “A Mn-N₃ Single-Atom Catalyst Embedded in Graphitic Carbon Nitride for Efficient CO₂ Electroreduction,” Nature Communications 11 (2020): 4341.

[196] Z. Chen, X. Zhang, W. Liu, et al., “Amination Strategy to Boost the CO₂ Electroreduction Current Density of M–N/C Single-Atom Catalysts to the Industrial Application Level,” Energy & Environmental Science 14 (2021): 2349–2356.

[197] G. Zeng, Y. He, D.-D. Ma, et al., “Reconstruction of Ultrahigh-Aspect-Ratio Crystalline Bismuth–Organic Hybrid Nanobelts for Selective Electrocatalytic CO₂ Reduction to Formate,” Advanced Functional Materials 32 (2022): 2201125.

[198] F. P. García de Arquer, C.-T. Dinh, A. Ozden, et al., “CO₂ Electrolysis to Multicarbon Products at Activities Greater Than 1 A Cm−2,” Science 367 (2020): 661–666.

[199] G. Wen, B. Ren, X. Wang, et al., “Continuous CO₂ Electrolysis Using a CO₂ Exsolution-Induced Flow Cell,” Nature Energy 7 (2022): 978–988.

[200] J. Lee, W. Lee, K. H. Ryu, et al., “Catholyte-Free Electroreduction of CO₂ for Sustainable Production of CO: Concept, Process Development, Techno-Economic Analysis, and CO₂ Reduction Assessment,” Green Chemistry 23 (2021): 2397–2410.

[201] F. Li, A. Thevenon, A. Rosas-Hernández, et al., “Molecular Tuning of CO₂-to-ethylene Conversion,” Nature 577 (2020): 509–513.

[202] Q. Sun, Y. Zhao, X. Tan, et al., “Atomically Dispersed Cu–Au Alloy for Efficient Electrocatalytic Reduction of Carbon Monoxide to Acetate,” ACS Catalysis 13 (2023): 5689–5696.

[203] T. Möller, M. Filippi, S. Brückner, W. Ju, and P. Strasser, “A CO₂ Electrolyzer Tandem Cell System for CO₂-CO Co-Feed Valorization in a Ni-N-C/Cu-Catalyzed Reaction Cascade,” Nature Communications 14 (2023): 5680.

[204] D. Wakerley, S. Lamaison, F. Ozanam, et al., “Bio-Inspired Hydrophobicity Promotes CO₂ Reduction on a Cu Surface,” Nature Materials 18 (2019): 1222–1227.

[205] S. Neyrizi, J. Kiewiet, M. A. Hempenius, and G. Mul, “What It Takes for Imidazolium Cations to Promote Electrochemical Reduction of CO₂,” ACS Energy Letters 7 (2022): 3439–3446.

[206] H. Rabiee, L. Ge, X. Zhang, S. Hu, M. Li, and Z. Yuan, “Gas Diffusion Electrodes (GDEs) for Electrochemical Reduction of Carbon Dioxide, Carbon Monoxide, and Dinitrogen to Value-Added Products: A Review,” Energy & Environmental Science 14 (2021): 1959–2008.

[207] J. Disch, L. Bohn, S. Koch, et al., “High-Resolution Neutron Imaging of Salt Precipitation and Water Transport in Zero-Gap CO₂ Electrolysis,” Nature Communications 13 (2022): 6099.

[208] S. Hao, A. Elgazzar, N. Ravi, et al., “Improving the Operational Stability of Electrochemical CO₂ Reduction Reaction Via Salt Precipitation Understanding and Management,” Nature Energy 10 (2025): 266–277.

[209] K. U. Hansen and F. Jiao, “Hydrophobicity of CO₂ Gas Diffusion Electrodes,” Joule 5 (2021): 754–757.

[210] T. Möller, T. Ngo Thanh, X. Wang, W. Ju, Z. Jovanov, and P. Strasser, “The Product Selectivity Zones in Gas Diffusion Electrodes during the Electrocatalytic Reduction of CO₂,” Energy & Environmental Science 14 (2021): 5995–6006.

[211] M. C. O. Monteiro, A. Mirabal, L. Jacobse, K. Doblhoff-Dier, S. C. Barton, and M. T. M. Koper, “Time-Resolved Local pH Measurements During CO₂ Reduction Using Scanning Electrochemical Microscopy: Buffering and Tip Effects,” JACS Au 1 (2021): 1915–1924.

[212] Y. Kim, S. Park, S.-J. Shin, et al., “Time-Resolved Observation of C–C Coupling Intermediates on Cu Electrodes for Selective Electrochemical CO₂ Reduction,” Energy & Environmental Science 13 (2020): 4301–4311.

[213] J. de Ruiter, V. R. M. Benning, S. Yang, et al., “Multiscale X-Ray Scattering Elucidates Activation and Deactivation of Oxide-Derived Copper Electrocatalysts for CO₂ Reduction,” Nature Communications 16 (2025): 373.

[214] A. B. Moss, S. Garg, M. Mirolo, et al., “In Operando Investigations of Oscillatory Water and Carbonate Effects in MEA-Based CO₂ Electrolysis Devices,” Joule 7 (2023): 350–365.

[215] S. Axnanda, E. J. Crumlin, B. Mao, et al., “Using ‘Tender’ X-Ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface,” Scientific Reports 5 (2015): 9788.

[216] O. J. Wahab, M. Kang, E. Daviddi, M. Walker, and P. R. Unwin, “Screening Surface Structure–Electrochemical Activity Relationships of Copper Electrodes under CO₂ Electroreduction Conditions,” ACS Catalysis 12 (2022): 6578–6588.

[217] K. Zhao, X. Jiang, X. Wu, et al., “Recent Development and Applications of Differential Electrochemical Mass Spectrometry in Emerging Energy Conversion and Storage Solutions,” Chemical Society Reviews 53 (2024): 6917–6959.

[218] S. Wang, Q. Gao, C. Xu, et al., “Molecular Surface Functionalization of In₂O₃ to Tune Interfacial Microenvironment for Enhanced Catalytic Performance of CO₂ Electroreduction,” Nano Research 17 (2024): 1242–1250.

[219] C. P. Cox, Q. Lyu, M. K. Wilsey, et al., “Interfacial Microenvironment Effects at Laser-Made Gold Nanoparticles Steer Carbon Dioxide Reduction Product Generation,” ACS Materials Au 5 (2025): 522–536.

[220] T. Zheng, K. Jiang, N. Ta, et al., “Large-Scale and Highly Selective CO₂ Electrocatalytic Reduction on Nickel Single-Atom Catalyst,” Joule 3 (2019): 265–278.

[221] J. J. Kaczur, H. Yang, Z. Liu, S. D. Sajjad, and R. I. Masel, “Carbon Dioxide and Water Electrolysis Using New Alkaline Stable Anion Membranes,” Frontiers in Chemistry 6 (2018), https://doi.org/10.3389/fchem.2018.00263.

[222] P. Zhu, Z.-Y. Wu, A. Elgazzar, et al., “Continuous Carbon Capture in an Electrochemical Solid-Electrolyte Reactor,” Nature 618 (2023): 959–966.

[223] D. Kim, W. Choi, H. W. Lee, et al., “Electrocatalytic Reduction of Low Concentrations of CO₂ gas in a Membrane Electrode Assembly Electrolyzer,” ACS Energy Letters 6 (2021): 3488–3495.

[224] H. Rabiee, A. Dutta, P. Yan, et al., “From Flue Gas to Syngas: Composite Electrode Based on Ionic Liquid and Microporous Polymer for MEA-Based CO₂ Electrolysis,” Angewandte Chemie International Edition 64 (2025): e202513103.

[225] M. Li, S. Fu, R. Kortlever, and J. R. van Ommen, “The Effects of SO₂ Impurities on CO₂ Electroreduction on Bare Silver and SiO₂ Coated Silver in Different Cell Geometries,” Catalysis Science & Technology 15 (2025): 2148–2159.

[226] C. Wang, B. Chen, Q. Wang, et al., “Dynamic Activation of Edge-Hosted Co–N₄ Sites for Energy-Efficient Electrochemical CO₂ Reduction at Industry-Level Current Density,” ACS Catalysis 15 (2025): 8540–8550.

[227] Q. Sun, C. Jia, H. Lu, et al., “Ampere-Level Electroreduction of CO₂ and CO,” Chemical Society Reviews 54 (2025): 6973–7016.

[228] Q. Wang, Y. Gong, X. Zi, et al., “Coupling Nano and Atomic Electric Field Confinement for Robust Alkaline Oxygen Evolution,” Angewandte Chemie International Edition 63 (2024): e202405438.

[229] N. S. Matin, D. A. Moreno, K. Abad, A. Omosebi, K. Liu, and J. Thompson, “Life Cycle Assessment of Charge Carrier Mediated Electrocatalytic Reduction of Carbon Dioxide to Formic Acid,” Journal of Environmental Chemical Engineering 13 (2025): 115184.

[230] M. Zheng, P. Wang, Y. Gao, C. Peng, Y. Zheng, and S.-Z. Qiao, “Tuning Interfacial *H Coverage and Aldehyde Adsorption Configuration for Selective Electrocatalytic Hydrogenation of Furfural,” Journal of Materials Chemistry A 13 (2025): 9135–9143.

[231] D. Yao, C. Liu, Y. Zhang, et al., “Modulating Selectivity and Stability of the Direct Seawater Electrolysis for Sustainable Green Hydrogen Production,” Materials Today Catalysis 8 (2025): 100089.

[232] X. Chen, D. Yao, L. Ji, and Y. Jin, “Recent Developments in CO₂ Permanent Storage Using Mine Waste Carbonation,” Materials Today Sustainability 29 (2025): 101070.

[233] M. Li, E. Irtem, H.-P. Iglesias van Montfort, M. Abdinejad, and T. Burdyny, “Energy Comparison of Sequential and Integrated CO₂ Capture and Electrochemical Conversion,” Nature Communications 13 (2022): 5398.

[234] P. Wang, A. Pei, Z. Chen, et al., “Integrated System for Electrolyte Recovery, Product Separation, and CO₂ Capture in CO₂ Reduction,” Nature Communications 16 (2025): 731.

[235] D. F. Bruggeman, G. Rothenberg, and A. C. Garcia, “Investigating Proton Shuttling and Electrochemical Mechanisms of Amines in Integrated CO₂ Capture and Utilization,” Nature Communications 15 (2024): 9207.

[236] Y. Kim, M. Namdari, A. M. L. Jewlal, et al., “Economic Viability of Integrated CO₂ Capture and Conversion,” ACS Energy Letters 10 (2025): 403–409.

[237] Z. Zhang, Y. Li, Y. Zhong, et al., “sp²/sp³–Hybridized Nitrogen–mediated Electrochemical CO₂ Capture and Utilization,” Science Advances 11 (2025): eadw6592.

[238] I. Sullivan, A. Goryachev, I. A. Digdaya, et al., “Coupling Electrochemical CO₂ Conversion With CO₂ Capture,” Nature Catalysis 4 (2021): 952–958.

RIGHTS & PERMISSIONS

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