{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T16:53:29Z","timestamp":1790873609879,"version":"4.1.0"},"reference-count":120,"publisher":"MDPI AG","issue":"21","license":[{"start":{"date-parts":[[2025,10,30]],"date-time":"2025-10-30T00:00:00Z","timestamp":1761782400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Innovative Research Team (in Science and Technology) in University of Henan Province","award":["23IRTSTHN009"],"award-info":[{"award-number":["23IRTSTHN009"]}]},{"DOI":"10.13039\/501100011447","name":"Science and Technology Department of Henan Province","doi-asserted-by":"crossref","award":["252102240092"],"award-info":[{"award-number":["252102240092"]}],"id":[{"id":"10.13039\/501100011447","id-type":"DOI","asserted-by":"crossref"}]},{"name":"Education Key Projects of Henan Provincial Department","award":["25A530008"],"award-info":[{"award-number":["25A530008"]}]},{"name":"National Key Research and Development Program of China","award":["2025YFE0111200"],"award-info":[{"award-number":["2025YFE0111200"]}]},{"name":"Major Science and Technology Projects of Henan Province","award":["241100240400"],"award-info":[{"award-number":["241100240400"]}]},{"name":"Key R&D and Promotion Special Project (Scientific and Technological Research) of Henan Province","award":["252102241036"],"award-info":[{"award-number":["252102241036"]}]},{"name":"Key R&D and Promotion Special Project (Scientific and Technological Research) of Henan Province","award":["252102240069"],"award-info":[{"award-number":["252102240069"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>The renewable-energy-powered electrocatalytic CO2 reduction reaction (CO2RR) efficiently converts CO2 into high-value chemicals and fuels, offering a promising approach to addressing environmental and energy sustainability challenges. This process is of immense significance for constructing a sustainable artificial carbon cycle. Cu-based catalysts exhibit remarkable catalytic activity and broad product selectivity in CO2RR, which can be attributed to their excellent electrical conductivity, moderate adsorption energy, and unique electronic structure. This review comprehensively summarizes the advantages, practical applications, and mechanistic insights of Cu-based catalysts in CO2RR, with a systematic based on recent advances in tuning strategies via electronic effects and structural design. Specifically, it emphasizes the influence of electronic structure tuning (electron-donating\/-withdrawing effects and steric hindrance effects), active center tuning (single-atom catalysts, heterogeneous synergetic effects, and polymer modification), and surface structure (morphology effect, valence-state effect, and crystalline-facet effect) influences on catalytic performance. By rationally designing the catalyst structure, the adsorption behavior of reaction intermediates can be effectively regulated, thereby enabling the highly selective generation of target products. The objective of this paper is to provide a theoretical framework and actionable strategies for the structural design and catalytic performance optimization of Cu-based catalysts, with the ultimate goal of promoting the development and practical application of efficient CO2RR catalytic systems.<\/jats:p>","DOI":"10.3390\/ma18214964","type":"journal-article","created":{"date-parts":[[2025,10,31]],"date-time":"2025-10-31T03:33:07Z","timestamp":1761881587000},"page":"4964","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Enhancing CO2 Reduction Performance on Cu-Based Catalysts: Modulating Electronic Properties and Molecular Configurations"],"prefix":"10.3390","volume":"18","author":[{"given":"Huimin","family":"Han","sequence":"first","affiliation":[{"name":"School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Luxin","family":"Yang","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chao","family":"Han","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maosheng","family":"Bi","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongbo","family":"Li","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering, Luoyang Institute of Science and Technology, Luoyang 471023, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuwei","family":"Zeng","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering, Luoyang Institute of Science and Technology, Luoyang 471023, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kunming","family":"Pan","sequence":"additional","affiliation":[{"name":"School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471000, China"},{"name":"Longmen Laboratory, Luoyang 471000, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shengyu","family":"Yin","sequence":"additional","affiliation":[{"name":"Longbai Group Co., Ltd., Jiaozuo 454191, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5608-6649","authenticated-orcid":false,"given":"Fang","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Energy and Chemical Engineering, Luoyang Institute of Science and Technology, Luoyang 471023, China"},{"name":"Henan Key Laboratory of Green Building Materials Manufacturing and Intelligent Equipment, Luoyang 471023, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Saifei","family":"Pan","sequence":"additional","affiliation":[{"name":"College of Vehicle and Traffic Engineering, Henan University of Science and Technology, Luoyang 471003, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,10,30]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"3421","DOI":"10.1038\/s41467-025-58755-w","article-title":"Cu supraparticles with enhanced mass transfer and abundant C-C coupling sites achieving ampere-level CO2-to-C2+ electrosynthesis","volume":"16","author":"Ma","year":"2025","journal-title":"Nat. Commun."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"8311","DOI":"10.1038\/s41467-023-44078-1","article-title":"Elucidating the structure-stability relationship of Cu single-atom catalysts using operando surface-enhanced infrared absorption spectroscopy","volume":"14","author":"Zhang","year":"2023","journal-title":"Nat. Commun."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"243","DOI":"10.1007\/s10311-021-01335-3","article-title":"Bimetallic atomic site catalysts for CO2 reduction reactions: A Review","volume":"20","author":"Fu","year":"2022","journal-title":"Environ. Chem. Lett."},{"key":"ref_4","first-page":"2008068","article-title":"Co (II)-based molecular complexes for photochemical CO2 reduction","volume":"37","author":"Zhang","year":"2021","journal-title":"Acta Phys. Chim. Sin."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"4587","DOI":"10.1038\/s41467-021-24828-9","article-title":"Engineering single-atomic ruthenium catalytic sites on defective Nickel-Iron layered double hydroxide for overall water splitting","volume":"12","author":"Zhai","year":"2021","journal-title":"Nat. Commun."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"10651","DOI":"10.1002\/anie.202003623","article-title":"Rare-earth single erbium atoms for enhanced photocatalytic CO2 reduction","volume":"59","author":"Ji","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"151897","DOI":"10.1016\/j.scitotenv.2021.151897","article-title":"Electrochemical degradation of nanoplastics in water: Analysis of the role of reactive oxygen species","volume":"808","author":"Kiendrebeogo","year":"2022","journal-title":"Sci. Total Environ."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"e202500191","DOI":"10.1002\/anie.202500191","article-title":"Atomic-level elucidation of lattice-hydrogens in copper catalysts for selective CO2 electrochemical conversion toward C2 products","volume":"64","author":"Ma","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"e202424749","DOI":"10.1002\/anie.202424749","article-title":"Switching CO2 electroreduction toward C2+ products and CH4 by regulating the dimerization and protonation in platinum\/copper catalysts","volume":"64","author":"Hou","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2711","DOI":"10.1039\/D0CY00453G","article-title":"Integrated design for electrocatalytic carbon dioxide reduction","volume":"10","author":"Zhao","year":"2020","journal-title":"Catal. Sci. Technol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"388","DOI":"10.1021\/jz3021155","article-title":"Understanding trends in the electrocatalytic activity of metals and enzymes for CO2 reduction to CO","volume":"4","author":"Hansen","year":"2013","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"7485","DOI":"10.1021\/acscatal.6b02089","article-title":"Recent advances in heterogeneous photocatalytic CO2 conversion to solar fuels","volume":"6","author":"Li","year":"2016","journal-title":"ACS Catal."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3703","DOI":"10.1039\/c1cs15008a","article-title":"Recent advances in catalytic hydrogenation of carbon dioxide","volume":"40","author":"Wang","year":"2011","journal-title":"Chem. Soc. Rev."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"215802","DOI":"10.1016\/j.ccr.2024.215802","article-title":"Palladium-Copper bimetallic catalysts for electroreduction of CO2 and nitrogenous species","volume":"509","author":"Zhou","year":"2024","journal-title":"Coord. Chem. Rev."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"7694","DOI":"10.1021\/acscatal.1c01478","article-title":"Revealing the CO coverage-driven C-C coupling mechanism for electrochemical CO2 reduction on Cu2O nanocubes via Operando Raman Spectroscopy","volume":"11","author":"Zhan","year":"2021","journal-title":"ACS Catal."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"15438","DOI":"10.1038\/ncomms15438","article-title":"Understanding trends in electrochemical carbon dioxide reduction rates","volume":"8","author":"Liu","year":"2017","journal-title":"Nat. Commun."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"E4585","DOI":"10.1073\/pnas.1602984113","article-title":"Inhibited Proton transfer enhances Au-catalyzed CO2-to-fuels selectivity","volume":"113","author":"Wuttig","year":"2016","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"812","DOI":"10.1021\/acsenergylett.8b00273","article-title":"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","volume":"3","author":"Varela","year":"2018","journal-title":"ACS Energy Lett."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1052","DOI":"10.1007\/s11426-022-1419-y","article-title":"Defect engineering for advanced electrocatalytic conversion of nitrogen-containing molecules","volume":"66","author":"Wang","year":"2023","journal-title":"Sci. China Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"9326","DOI":"10.1021\/acscatal.3c01439","article-title":"Electrochemical CO2 reduction over copper phthalocyanine derived catalysts with enhanced selectivity for multicarbon products","volume":"13","author":"Zhang","year":"2023","journal-title":"ACS Catal."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"3266","DOI":"10.1002\/cphc.201700736","article-title":"Electrochemical CO2 reduction: A Classification Problem","volume":"18","author":"Bagger","year":"2017","journal-title":"ChemPhysChem"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"66211","DOI":"10.1021\/acsami.4c16847","article-title":"High-entropy metal sulfide nanoparticles promise high-performance carbon dioxide reduction","volume":"16","author":"Gong","year":"2024","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1695","DOI":"10.1246\/cl.1985.1695","article-title":"Production of CO and CH4 in electrochemical reduction of CO2 at metal electrodes in aqueous hydrogen-carbonate solution","volume":"14","author":"Hori","year":"1985","journal-title":"Chem Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"7975","DOI":"10.1021\/acsnano.0c10697","article-title":"Architectural design for enhanced C2 product selectivity in electrochemical CO2 reduction using Cu-based catalysts: A Review","volume":"15","author":"Xiao","year":"2021","journal-title":"ACS Nano"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"2103663","DOI":"10.1002\/aenm.202103663","article-title":"Enhanced electrocatalytic CO2 reduction to C2+ products by adjusting the local reaction environment with polymer binders","volume":"12","author":"Pham","year":"2022","journal-title":"Adv. Energy Mater."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"732","DOI":"10.1038\/s41560-019-0450-y","article-title":"Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels","volume":"4","author":"Birdja","year":"2019","journal-title":"Nat. Energy"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"2401530","DOI":"10.1002\/smll.202401530","article-title":"Surface facets reconstruction in copper-based materials for enhanced electrochemical CO2 reduction","volume":"20","author":"Xie","year":"2024","journal-title":"Small"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"12673","DOI":"10.1021\/acscatal.1c02319","article-title":"Atomically dispersed Ni\/Cu dual sites for boosting the CO2 reduction reaction","volume":"11","author":"Cheng","year":"2021","journal-title":"ACS Catal."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"22705","DOI":"10.1021\/jacs.5c04364","article-title":"Synergistic catalysis by Cu single atoms and atomically Cu-doped Au nanoparticles in a metal-organic framework for photocatalytic CO2 reduction to C2H6","volume":"147","author":"Chen","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1222","DOI":"10.1038\/s41563-019-0445-x","article-title":"Bio-inspired hydrophobicity promotes CO2 reduction on a Cu surface","volume":"18","author":"Wakerley","year":"2019","journal-title":"Nat. Mater."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2504292","DOI":"10.1002\/adma.202504292","article-title":"Polymer-halogen pockets steering *CO adsorption configurations for highly selective CO2 electroreduction","volume":"37","author":"Wu","year":"2025","journal-title":"Adv. Mater."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"13246","DOI":"10.1021\/acscatal.4c02718","article-title":"Restructuring of Cu-based catalysts during CO electroreduction: Evidence for the dominant role of surface defects on the C2+ product selectivity","volume":"14","author":"Rollier","year":"2024","journal-title":"ACS Catal."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"2470","DOI":"10.1039\/D1EE03838A","article-title":"Local reaction environment for selective electroreduction of carbon monoxide","volume":"15","author":"Ma","year":"2022","journal-title":"Energy Environ. Sci."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2502733","DOI":"10.1002\/smll.202502733","article-title":"Functional group engineering of single-walled carbon nanotubes for anchoring copper nanoparticles toward selective CO2 electroreduction to C2 products","volume":"21","author":"Wang","year":"2025","journal-title":"Small"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1455","DOI":"10.1002\/cssc.201702262","article-title":"Steric hindrance in sulfur vacancy of monolayer MoS2 boosts electrochemical reduction of carbon monoxide to methane","volume":"11","author":"Chen","year":"2018","journal-title":"ChemSusChem"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"e202507062","DOI":"10.1002\/anie.202507062","article-title":"Selective CO electroreduction to multi-carbon oxygenates over atomically dispersed Cu-Ag sites in alkaline membrane electrode assembly electrolyzer","volume":"64","author":"Guo","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"22580","DOI":"10.1021\/jacs.5c03158","article-title":"Copper\u2013carbon bond metal\u2013organic frameworks for highly efficient and stable CO2 electrochemical methanation","volume":"147","author":"Jia","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"123281","DOI":"10.1016\/j.apcatb.2023.123281","article-title":"Functionalizing Cu nanoparticles with fluoric polymer to enhance C2+ product selectivity in membrane CO2 reduction","volume":"340","author":"Zhao","year":"2024","journal-title":"Appl. Catal. B Environ."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"466","DOI":"10.1002\/anie.202011836","article-title":"Size-dependent activity and selectivity of atomic-level copper nanoclusters during CO\/CO2 electroreduction","volume":"60","author":"Rong","year":"2021","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"422","DOI":"10.1038\/s41560-024-01461-6","article-title":"Selective and energy-efficient electrosynthesis of ethylene from CO2 by tuning the valence of Cu catalysts through aryl diazonium functionalization","volume":"9","author":"Wu","year":"2024","journal-title":"Nat. Energy"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"e202415590","DOI":"10.1002\/anie.202415590","article-title":"Unravelling the effect of crystal facet of derived-copper catalysts on the electroreduction of carbon dioxide under unified mass transport condition","volume":"64","author":"Zhao","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"3603","DOI":"10.1039\/D2EE00472K","article-title":"Design strategies for markedly enhancing energy efficiency in the electrocatalytic CO2 reduction reaction","volume":"15","author":"Lai","year":"2022","journal-title":"Energy Environ. Sci."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1382","DOI":"10.1039\/D2CS00843B","article-title":"A rational design of functional porous frameworks for electrocatalytic CO2 reduction reaction","volume":"52","author":"Wang","year":"2023","journal-title":"Chem. Soc. Rev."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"15341","DOI":"10.1039\/D0TA02633F","article-title":"Catalyst design strategies for stable electrochemical CO2 reduction reaction","volume":"8","author":"Choi","year":"2020","journal-title":"J. Mater. Chem. A."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"e202113498","DOI":"10.1002\/anie.202113498","article-title":"Nanoconfinement engineering over hollow multi-shell structured copper towards efficient electrocatalytical C-C coupling","volume":"61","author":"Liu","year":"2022","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"198","DOI":"10.1016\/j.jechem.2022.07.011","article-title":"Mechanically induced Cu active sites for selective C-C coupling in CO2 electroreduction","volume":"74","author":"Chen","year":"2022","journal-title":"J. Energy Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"219","DOI":"10.1016\/j.jechem.2022.02.050","article-title":"Tandem catalysis on adjacent active motifs of copper grain boundary for efficient CO2 electroreduction toward C2 products","volume":"70","author":"Luo","year":"2022","journal-title":"J. Energy Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"1963","DOI":"10.1021\/acs.nanolett.1c04653","article-title":"Vertical Cu nanoneedle arrays enhance the local electric field promoting C2 hydrocarbons in the CO2 electroreduction","volume":"22","author":"Zhou","year":"2022","journal-title":"Nano Lett."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"9057","DOI":"10.1039\/D4NR04790G","article-title":"Cu-based bimetallic catalysts for electrochemical CO2 reduction: Before and beyond the tandem effect","volume":"17","author":"Luo","year":"2025","journal-title":"Nanoscale"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"159210","DOI":"10.1016\/j.cej.2025.159210","article-title":"Recent progress in Cu-based electrocatalysts for CO2 reduction","volume":"505","author":"Xiong","year":"2025","journal-title":"Chem. Eng. J."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"e202401750","DOI":"10.1002\/anie.202401750","article-title":"Elaborate modulating binding strength of intermediates via three-component covalent organic frameworks for CO2 reduction reaction","volume":"63","author":"Liu","year":"2024","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"160154","DOI":"10.1016\/j.cej.2025.160154","article-title":"Influence of electron-induced effect of ligand on electrocatalytic reduction of CO2 by copper phthalocyanine","volume":"506","author":"Fang","year":"2025","journal-title":"Chem. Eng. J."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"16114","DOI":"10.1021\/acscatal.3c02454","article-title":"Boosting electrochemical CO2 reduction via surface hydroxylation over Cu-based electrocatalysts","volume":"13","author":"Li","year":"2023","journal-title":"ACS Catal."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"2205730","DOI":"10.1002\/smll.202205730","article-title":"Promoting electrocatalytic CO2 reduction to CH4 by copper porphyrin with donor\u2013acceptor structures","volume":"19","author":"Yu","year":"2023","journal-title":"Small"},{"key":"ref_55","doi-asserted-by":"crossref","unstructured":"Wang, C.H., Zhou, W., Ma, J.M., Wang, Z., and Zhang, C.Y. (2025). Electronic modulation of Cu catalytic interfaces by functionalized ionic liquids for enhanced CO2 reduction. Molecules, 30.","DOI":"10.3390\/molecules30112352"},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"eado5000","DOI":"10.1126\/sciadv.ado5000","article-title":"Tuning catalyst-support interactions enable steering of electrochemical CO2 reduction pathways","volume":"11","author":"Wang","year":"2025","journal-title":"Sci. Adv."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"26038","DOI":"10.1021\/jacs.3c06888","article-title":"Enhanced CO2 reactive capture and conversion using aminothiolate ligand-metal interface","volume":"145","author":"Wan","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"e202409206","DOI":"10.1002\/anie.202409206","article-title":"Switching product selectivity in CO2 electroreduction via Cu\u2013S bond length variation","volume":"63","author":"Wei","year":"2024","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"125434","DOI":"10.1016\/j.apcatb.2025.125434","article-title":"In-situ construction of highly durable Cu\u03b4+ species boosting electrocatalytic reduction of CO2 to C2+ products","volume":"375","author":"Wang","year":"2025","journal-title":"Appl. Catal. B Environ."},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"e202501091","DOI":"10.1002\/anie.202501091","article-title":"Precise tuning of functional group spatial distribution on porphyrin rings for enhanced CO2 electroreduction selectivity","volume":"64","author":"Wang","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"e202508497","DOI":"10.1002\/anie.202508497","article-title":"Engineered spatial confinement of Cu single-atoms with diagonal N-Cu-N motifs for high-rate CO2 methanation","volume":"64","author":"Feng","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"13400","DOI":"10.1021\/acscatal.4c02823","article-title":"Confined intermediates boost C2+ selectivity in CO2 electroreduction","volume":"14","author":"Li","year":"2024","journal-title":"ACS Catal."},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"e202503417","DOI":"10.1002\/anie.202503417","article-title":"Steering the product selectivity of CO2 electroreduction by single-atom switching in isostructural copper nanocluster catalysts","volume":"64","author":"Han","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"196","DOI":"10.1016\/S1872-2067(25)64711-5","article-title":"Highly selective CO2 electroreduction to ethylene on long alkyl chains-functionalized copper nanowires","volume":"73","author":"Li","year":"2025","journal-title":"Chin. J. Catal."},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"2417247","DOI":"10.1002\/advs.202417247","article-title":"Highly Selective Electroreduction of CO2 to CH4 on Cu\u2013Pd alloy catalyst: The role of palladium-adsorbed hydrogen species and blocking effect","volume":"12","author":"Huang","year":"2025","journal-title":"Adv. Sci."},{"key":"ref_66","doi-asserted-by":"crossref","first-page":"19944","DOI":"10.1039\/D5TA01319D","article-title":"Tuning hydrocarbon selectivity in electrochemical CO2 reduction via copper-porphyrin immobilization on carbon nanotubes","volume":"13","author":"Esfandiari","year":"2025","journal-title":"J. Mater. Chem. A"},{"key":"ref_67","doi-asserted-by":"crossref","first-page":"8505","DOI":"10.1039\/D4NR03795B","article-title":"Activation and electrochemical reduction of carbon dioxide by transition metal atom-doped copper clusters","volume":"17","author":"Mohanta","year":"2025","journal-title":"Nanoscale"},{"key":"ref_68","doi-asserted-by":"crossref","first-page":"2214946","DOI":"10.1002\/adfm.202214946","article-title":"Efficient Electrocatalytic Reduction of CO2 to Ethanol Enhanced by Spacing Effect of Cu\u2212Cu in Cu2-xSe Nanosheets","volume":"33","author":"Wang","year":"2023","journal-title":"Adv. Funct. Mater."},{"key":"ref_69","doi-asserted-by":"crossref","first-page":"2001848","DOI":"10.1002\/adma.202001848","article-title":"Heterogeneous single-atom catalysts for electrochemical CO2 reduction reaction","volume":"32","author":"Li","year":"2020","journal-title":"Adv. Mater."},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"2000028","DOI":"10.1002\/smsc.202000028","article-title":"Recent advances in strategies for improving the performance of CO2 reduction reaction on single atom catalysts","volume":"1","author":"Wang","year":"2021","journal-title":"Small Sci."},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"18688","DOI":"10.1021\/acsnano.3c07307","article-title":"Insight on atomically dispersed Cu catalysts for electrochemical CO2 reduction","volume":"17","author":"Wang","year":"2023","journal-title":"ACS Nano"},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"65","DOI":"10.1038\/s41570-018-0010-1","article-title":"Heterogeneous single-atom catalysis","volume":"2","author":"Wang","year":"2018","journal-title":"Nat. Rev. Chem."},{"key":"ref_73","doi-asserted-by":"crossref","first-page":"1740","DOI":"10.1021\/ar300361m","article-title":"Single-atom catalysts: A new frontier in heterogeneous catalysis","volume":"46","author":"Yang","year":"2013","journal-title":"Acc. Chem. Res."},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"1902625","DOI":"10.1002\/aenm.201902625","article-title":"Catalytic mechanisms and design principles for single-atom catalysts in highly efficient CO2 conversion","volume":"9","author":"Gong","year":"2019","journal-title":"Adv. Energy Mater."},{"key":"ref_75","doi-asserted-by":"crossref","first-page":"164503","DOI":"10.1149\/1945-7111\/abc593","article-title":"Non-noble metal-based single-atom catalysts for efficient electrochemical CO2 reduction reaction","volume":"167","author":"Choi","year":"2020","journal-title":"J. Electrochem. Soc."},{"key":"ref_76","first-page":"44541","article-title":"High-density atomically dispersed copper sites with close distances on ultrathin n-doped carbon nanosheets as an efficient oxygen reduction catalyst","volume":"17","author":"Bi","year":"2025","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_77","doi-asserted-by":"crossref","first-page":"5913","DOI":"10.1038\/s41467-024-50118-1","article-title":"Contact-electro-catalytic CO2 reduction from ambient air","volume":"15","author":"Wang","year":"2024","journal-title":"Nat. Commun."},{"key":"ref_78","doi-asserted-by":"crossref","first-page":"17253","DOI":"10.1021\/jacs.3c04612","article-title":"Adjacent copper single atoms promote C-C coupling in electrochemical CO2 reduction for the efficient conversion of ethanol","volume":"145","author":"Xia","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"ref_79","doi-asserted-by":"crossref","first-page":"4615","DOI":"10.1038\/s41467-023-40412-9","article-title":"Modulating adsorbed hydrogen drives electrochemical CO2-to-C2 products","volume":"14","author":"Feng","year":"2023","journal-title":"Nat. Commun."},{"key":"ref_80","doi-asserted-by":"crossref","first-page":"7386","DOI":"10.1021\/acs.chemmater.9b02031","article-title":"Palladium separation by Pd-catalyzed gel formation via alkyne coupling","volume":"31","author":"Yang","year":"2019","journal-title":"Chem. Mater."},{"key":"ref_81","doi-asserted-by":"crossref","first-page":"7113","DOI":"10.1021\/acscatal.8b01014","article-title":"Single-atomic Cu with multiple oxygen vacancies on ceria for electrocatalytic CO2 reduction to CH4","volume":"8","author":"Wang","year":"2018","journal-title":"ACS Catal."},{"key":"ref_82","doi-asserted-by":"crossref","first-page":"623","DOI":"10.1038\/s41560-020-0666-x","article-title":"Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper","volume":"5","author":"Xu","year":"2020","journal-title":"Nat. Energy"},{"key":"ref_83","doi-asserted-by":"crossref","first-page":"24706","DOI":"10.1039\/D5TA03359D","article-title":"Compositional gradient Au-Cu bimetallic heterostructures for efficient electroreduction of CO2 to ethanol at low potential","volume":"13","author":"Xu","year":"2025","journal-title":"J. Mater. Chem. A"},{"key":"ref_84","doi-asserted-by":"crossref","first-page":"251","DOI":"10.1021\/jz201461p","article-title":"Activity Descriptors for CO2 electroreduction to methane on transition-metal catalysts","volume":"3","author":"Peterson","year":"2012","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_85","doi-asserted-by":"crossref","first-page":"016105","DOI":"10.1103\/PhysRevLett.99.016105","article-title":"Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces","volume":"99","author":"Greeley","year":"2007","journal-title":"Phys. Rev. Lett."},{"key":"ref_86","doi-asserted-by":"crossref","first-page":"143606","DOI":"10.1016\/j.cej.2023.143606","article-title":"Nitrogen-doped carbon confined Cu-Ag bimetals for efficient electroreduction of CO2 to high-order products","volume":"468","author":"Zou","year":"2023","journal-title":"Chem. Eng. J."},{"key":"ref_87","doi-asserted-by":"crossref","first-page":"14149","DOI":"10.1002\/anie.201808964","article-title":"Highly efficient electroreduction of CO2 to methanol on palladium-copper bimetallic aerogels","volume":"57","author":"Lu","year":"2018","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_88","doi-asserted-by":"crossref","first-page":"11103","DOI":"10.1021\/acscatal.1c02556","article-title":"Tunable selectivity for electrochemical CO2 reduction by bimetallic Cu-Sn catalysts: Elucidating the roles of Cu and Sn","volume":"11","author":"Zhang","year":"2021","journal-title":"ACS Catal."},{"key":"ref_89","doi-asserted-by":"crossref","first-page":"e202217569","DOI":"10.1002\/anie.202217569","article-title":"Electron-rich Bi nanosheets promote CO2\u2212 formation for high-performance and pH-universal electrocatalytic CO2 reduction","volume":"62","author":"Li","year":"2023","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_90","doi-asserted-by":"crossref","first-page":"e202417066","DOI":"10.1002\/anie.202417066","article-title":"Constructing Ag\/Cu2O interface for efficient neutral CO2 electroreduction to C2H4","volume":"64","author":"Wei","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_91","doi-asserted-by":"crossref","first-page":"2300186","DOI":"10.1002\/admi.202300186","article-title":"Recent progress in electrocatalytic conversion of CO2 to valuable C2 products","volume":"10","author":"Yan","year":"2023","journal-title":"Adv. Mater. Interfaces"},{"key":"ref_92","doi-asserted-by":"crossref","first-page":"e202417008","DOI":"10.1002\/anie.202417008","article-title":"Copper-catalysed electrochemical CO2 methanation via the alloying of single cobalt atoms","volume":"64","author":"Li","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_93","doi-asserted-by":"crossref","first-page":"2417567","DOI":"10.1002\/adma.202417567","article-title":"Promotion of C-C coupling in the CO2 electrochemical reduction to valuable C2+ products: From micro-foundation to macro-application","volume":"37","author":"Guan","year":"2025","journal-title":"Adv. Mater."},{"key":"ref_94","doi-asserted-by":"crossref","first-page":"474","DOI":"10.1038\/s41467-023-35993-4","article-title":"Stabilizing copper sites in coordination polymers toward efficient electrochemical C-C coupling","volume":"14","author":"Liang","year":"2023","journal-title":"Nat. Commun."},{"key":"ref_95","doi-asserted-by":"crossref","first-page":"6316","DOI":"10.1038\/s41467-024-50791-2","article-title":"Ligand-tuning copper in coordination polymers for efficient electrochemical C-C coupling","volume":"15","author":"Yang","year":"2024","journal-title":"Nat. Commun."},{"key":"ref_96","doi-asserted-by":"crossref","first-page":"2214062","DOI":"10.1002\/adfm.202214062","article-title":"Molecular modulation of sequestered copper sites for efficient electroreduction of carbon dioxide to methane","volume":"33","author":"Zhang","year":"2023","journal-title":"Adv. Funct. Mater."},{"key":"ref_97","doi-asserted-by":"crossref","first-page":"12119","DOI":"10.1021\/jacs.0c01859","article-title":"Dynamic reoxidation\/reduction-driven atomic interdiffusion for highly selective CO2 reduction toward methane","volume":"142","author":"Chang","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_98","doi-asserted-by":"crossref","first-page":"16131","DOI":"10.1021\/jacs.2c06953","article-title":"Metal-coordinated phthalocyanines as platform molecules for understanding isolated metal sites in the electrochemical reduction of CO2","volume":"144","author":"Chang","year":"2022","journal-title":"J. Am. Chem. Soc."},{"key":"ref_99","doi-asserted-by":"crossref","first-page":"406","DOI":"10.1126\/science.abo0356","article-title":"Physical mixing of a catalyst and a hydrophobic polymer promotes CO hydrogenation through dehydration","volume":"377","author":"Fang","year":"2022","journal-title":"Science"},{"key":"ref_100","doi-asserted-by":"crossref","first-page":"1795","DOI":"10.1007\/s12274-020-2661-8","article-title":"A mini-review on recent progress of new sensitizers for luminescence of lanthanide doped nanomaterials","volume":"13","author":"Zhang","year":"2020","journal-title":"Nano Res."},{"key":"ref_101","doi-asserted-by":"crossref","first-page":"14734","DOI":"10.1021\/acsami.8b22071","article-title":"Electrodeposited AgCu foam catalysts for enhanced reduction of CO2 to CO","volume":"11","author":"Kottakkat","year":"2019","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_102","doi-asserted-by":"crossref","first-page":"23651","DOI":"10.1039\/C7TA06247H","article-title":"Eutectic-directed self-templating synthesis of PtNi nanoporous nanowires with superior electrocatalytic performance towards the oxygen reduction reaction: Experiment and DFT calculation","volume":"5","author":"Wang","year":"2017","journal-title":"J. Mater. Chem. A"},{"key":"ref_103","doi-asserted-by":"crossref","first-page":"176","DOI":"10.1016\/j.jechem.2019.03.030","article-title":"Low-overpotential selective reduction of CO2 to ethanol on electrodeposited Cux Auy nanowire arrays","volume":"37","author":"Zhu","year":"2019","journal-title":"J. Energy Chem."},{"key":"ref_104","doi-asserted-by":"crossref","first-page":"2102293","DOI":"10.1002\/smll.202102293","article-title":"Electrochemical reduction of CO2 toward C2 valuables on Cu@Ag core-Shell tandem catalyst with tunable shell thickness","volume":"17","author":"Zhang","year":"2021","journal-title":"Small"},{"key":"ref_105","doi-asserted-by":"crossref","first-page":"5643","DOI":"10.1039\/D5EE01081K","article-title":"Highly dense atomic Fe-Ni dual metal sites for efficient CO2 to CO electrolyzers at industrial current densities","volume":"18","author":"Qi","year":"2025","journal-title":"Energy Environ. Sci."},{"key":"ref_106","doi-asserted-by":"crossref","first-page":"8078","DOI":"10.1021\/jacs.7b02736","article-title":"Ionic exchange of metal-organic frameworks to access single-nickel sites for efficient electroreduction of CO2","volume":"139","author":"Zhao","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"ref_107","doi-asserted-by":"crossref","first-page":"421","DOI":"10.1038\/s41929-018-0084-7","article-title":"Steering post-C-C coupling selectivity enables high efficiency electroreduction of carbon dioxide to multi-carbon alcohols","volume":"1","author":"Zhuang","year":"2018","journal-title":"Nat. Catal."},{"key":"ref_108","doi-asserted-by":"crossref","first-page":"601","DOI":"10.1021\/acs.jpclett.7b03180","article-title":"Is subsurface oxygen necessary for the electrochemical reduction of CO2 on copper?","volume":"9","author":"Garza","year":"2018","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_109","doi-asserted-by":"crossref","first-page":"2102142","DOI":"10.1002\/adfm.202102142","article-title":"Cu\/Cu2O interconnected porous aerogel catalyst for highly productive electrosynthesis of ethanol from CO2","volume":"31","author":"Kim","year":"2021","journal-title":"Adv. Funct. Mater."},{"key":"ref_110","doi-asserted-by":"crossref","first-page":"e202405733","DOI":"10.1002\/anie.202405733","article-title":"Synthesis of n-propanol from CO2 electroreduction on bicontinuous Cu2O\/Cu nanodomains","volume":"63","author":"Zhang","year":"2024","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_111","doi-asserted-by":"crossref","first-page":"2200454","DOI":"10.1002\/advs.202200454","article-title":"Grain boundary-derived Cu+\/Cu0 interfaces in CuO nanosheets for low overpotential carbon dioxide electroreduction to ethylene","volume":"9","author":"Zhang","year":"2022","journal-title":"Adv. Sci."},{"key":"ref_112","doi-asserted-by":"crossref","first-page":"211","DOI":"10.1016\/j.chempr.2023.08.027","article-title":"Engineering Cu(I)\/Cu(0) interfaces for efficient ethanol production from CO2 electroreduction","volume":"10","author":"Cai","year":"2024","journal-title":"Chem"},{"key":"ref_113","doi-asserted-by":"crossref","first-page":"e202209629","DOI":"10.1002\/anie.202209629","article-title":"Selective CO2 electroreduction to ethanol over a carbon-coated CuOx catalyst","volume":"61","author":"Zang","year":"2022","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_114","doi-asserted-by":"crossref","first-page":"258","DOI":"10.1016\/0039-6028(95)00441-6","article-title":"Adsorption of CO accompanied with simultaneous charge transfer on copper single crystal electrodes related with electrochemical reduction of CO2 to hydrocarbons","volume":"335","author":"Hori","year":"1995","journal-title":"Surf. Sci."},{"key":"ref_115","doi-asserted-by":"crossref","first-page":"2032","DOI":"10.1021\/acs.jpclett.5b00722","article-title":"Theoretical insights into a CO dimerization mechanism in CO2 electroreduction","volume":"6","author":"Montoya","year":"2015","journal-title":"J. Phys. Chem. Lett."},{"key":"ref_116","doi-asserted-by":"crossref","first-page":"1902820","DOI":"10.1002\/advs.201902820","article-title":"Cu2O Nanoparticles with Both {100} and {111} Facets for Enhancing the Selectivity and Activity of CO2 Electroreduction to Ethylene","volume":"7","author":"Gao","year":"2020","journal-title":"Adv. Sci."},{"key":"ref_117","doi-asserted-by":"crossref","first-page":"111","DOI":"10.1038\/s41929-017-0009-x","article-title":"Metal ion cycling of Cu foil for selective C-C coupling in electrochemical CO2 reduction","volume":"1","author":"Jiang","year":"2018","journal-title":"Nat Catal."},{"key":"ref_118","doi-asserted-by":"crossref","first-page":"4456","DOI":"10.1021\/acscatal.1c00420","article-title":"Elucidating the facet-dependent selectivity for CO2 electroreduction to ethanol of Cu-Ag tandem catalysts","volume":"11","author":"Iyengar","year":"2021","journal-title":"ACS Catal."},{"key":"ref_119","doi-asserted-by":"crossref","first-page":"2110607","DOI":"10.1002\/adma.202110607","article-title":"Confined growth of silver-copper janus nanostructures with {100} facets for highly selective tandem electrocatalytic carbon dioxide reduction","volume":"34","author":"Ma","year":"2022","journal-title":"Adv. Mater."},{"key":"ref_120","doi-asserted-by":"crossref","first-page":"75","DOI":"10.1038\/s41929-019-0383-7","article-title":"Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule-metal catalyst interfaces","volume":"3","author":"Li","year":"2020","journal-title":"Nat. Catal."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/18\/21\/4964\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,11,11]],"date-time":"2025-11-11T09:06:38Z","timestamp":1762851998000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/18\/21\/4964"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,10,30]]},"references-count":120,"journal-issue":{"issue":"21","published-online":{"date-parts":[[2025,11]]}},"alternative-id":["ma18214964"],"URL":"https:\/\/doi.org\/10.3390\/ma18214964","relation":{},"ISSN":["1996-1944"],"issn-type":[{"value":"1996-1944","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,10,30]]}}}