A Review of CO2 Electroreduction to Ethanol: C–C Coupling Mechanistic Insights and Catalyst Design
Corresponding Author: Di Zhao
Nano-Micro Letters,
Vol. 18 (2026), Article Number: 313
Abstract
As a major contributor to climate change, CO2 has imposed severe detrimental effects on global ecosystems. Among various CO2 conversion strategies, the electrocatalytic CO2 reduction reaction (eCO2RR) stands out due to its ability to operate under mild conditions using renewable electricity. Compared to gaseous C2 products such as ethylene, ethanol as a liquid fuel demonstrates greater economic potential and broader market prospects. In recent years, copper-based electrocatalysts have emerged as leading materials for the electrochemical conversion of CO2-to-ethanol. Meanwhile, a number of non-copper-based electrocatalysts have also been developed to produce ethanol via C–C coupling pathways distinct from those on Cu-based materials. However, few reviews have systematically addressed the reaction mechanisms and material design principles specific to ethanol production through eCO2RR. In this review, we highlight the most recent advancements in this field of study. We begin by assessing the economic viability of ethanol as a CO2 reduction product. This is followed by a systematic summary of the reaction mechanisms and advanced characterization methods involved in ethanol production via eCO2RR across various pathways. Next, we discuss and compare the catalytic active sites and key electrochemical performance metrics for ethanol generation on different types of electrocatalysts. Finally, we propose several promising strategies to guide the rational design and synthesis of next-generation high-performance electrocatalysts for selective ethanol production. This review comprehensively summarizes the latest research progress in the field of ethanol production via eCO2RR from multiple dimensions, including the economic value of ethanol, reaction mechanisms, an introduction to various electrocatalysts and strategies for improving electrocatalysts. It not only promotes in-depth basic research, but also provides theoretical guidance for electrocatalyst design, reaction condition optimization, and industrial applications, making it of great research value and practical significance.
Highlights:
1 Focusing on the economic viability of ethanol products and the application value of eCO2RR, this research anchors its core from an industrial conversion perspective, combining academic depth with practical orientation.
2 Systematically integrating multipath reaction mechanisms, advanced characterization techniques, and the active sites and performance metrics of various electrocatalysts, a comprehensive knowledge framework has been established.
3 Proposing a rational design strategy for next-generation highly selective ethanol synthesis electrocatalysts, this work provides a clear research direction for this field.
Keywords
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- Z. Sun, Y. Hu, D. Zhou, M. Sun, S. Wang et al., Factors influencing the performance of copper-bearing catalysts in the CO2 reduction system. ACS Energy Lett. 6(11), 3992–4022 (2021). https://doi.org/10.1021/acsenergylett.1c01965
- X. Wang, W. Cai, Promoted CO2 reforming with bioethanol over TiO2-supported photothermal catalysts. Energy Mater. Adv. 6, 205 (2025). https://doi.org/10.34133/energymatadv.0205
- B. Huang, F. Zhao, J. Fu, L. Zheng, J. Zhang et al., A carbon-based single-atom Cu electrocatalyst for efficient conversion of CO2 to carbon products. Chem. Commun. 61(81), 15822–15825 (2025). https://doi.org/10.1039/d5cc04310g
- C. Wang, Y. Zhang, F. Zhao, D. Zhao, J. Zhang, Design principles of metal phthalocyanine for electrochemical CO2 reduction: from targeted molecular structures to atomic-level active sites. Small 21(25), e2502897 (2025). https://doi.org/10.1002/smll.202502897
- Y.-C. Liu, J.-R. Huang, H.-L. Zhu, X.-F. Qiu, C. Yu et al., Electrosynthesis of pure urea from pretreated flue gas in a proton-limited environment established in a porous solid-state electrolyte electrolyser. Nat. Nanotechnol. 20(7), 907–913 (2025). https://doi.org/10.1038/s41565-025-01914-3
- A.M. Abdellah, F. Ismail, O.W. Siig, J. Yang, C.M. Andrei et al., Impact of palladium/palladium hydride conversion on electrochemical CO2 reduction via in-situ transmission electron microscopy and diffraction. Nat. Commun. 15(1), 938 (2024). https://doi.org/10.1038/s41467-024-45096-3
- Q. Wang, K. Liu, K. Hu, C. Cai, H. Li et al., Attenuating metal-substrate conjugation in atomically dispersed nickel catalysts for electroreduction of CO2 to CO. Nat. Commun. 13(1), 6082 (2022). https://doi.org/10.1038/s41467-022-33692-0
- D. Zhao, K. Yu, P. Song, W. Feng, B. Hu et al., Atomic-level engineering Fe1N2O2 interfacial structure derived from oxygen-abundant metal–organic frameworks to promote electrochemical CO2 reduction. Energy Environ. Sci. 15(9), 3795–3804 (2022). https://doi.org/10.1039/d2ee00878e
- F. Yang, X. Ma, W.-B. Cai, P. Song, W. Xu, Nature of oxygen-containing groups on carbon for high-efficiency electrocatalytic CO2 reduction reaction. J. Am. Chem. Soc. 141(51), 20451–20459 (2019). https://doi.org/10.1021/jacs.9b11123
- W. Yang, Y. Zhao, Y. Chen, H. Ren, J. Sun et al., Constraining CO2 coverage on copper promotes CO2 electroreduction to multi-carbon products in strong acid. Angew. Chem. Int. Ed. Engl. 64(12), e202422082 (2025). https://doi.org/10.1002/anie.202422082
- L. Fan, C. Xia, P. Zhu, Y. Lu, H. Wang, Electrochemical CO2 reduction to high-concentration pure formic acid solutions in an all-solid-state reactor. Nat. Commun. 11, 3633 (2020). https://doi.org/10.1038/s41467-020-17403-1
- H. Yang, G.-X. Zhang, H.-J. Zhou, Y.-Y. Sun, H. Pang, Metal–organic frameworks meet MXene: new opportunities for electrochemical application. Energy Mater. Adv. 4, 33 (2023). https://doi.org/10.34133/energymatadv.0033
- M. Li, Z. Zhao, W. Zhang, M. Luo, L. Tao et al., Sub-monolayer YOx/MoOx on ultrathin Pt nanowires boosts alcohol oxidation electrocatalysis. Adv. Mater. 33(41), e2103762 (2021). https://doi.org/10.1002/adma.202103762
- S.-C. Lin, C.-C. Chang, S.-Y. Chiu, H.-T. Pai, T.-Y. Liao et al., operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction. Nat. Commun. 11(1), 3525 (2020). https://doi.org/10.1038/s41467-020-17231-3
- C.-P. Liang, J.-R. Huang, H.-L. Zhu, Z.-H. Zhao, C. Yu et al., Precisely tailoring the first coordination shell of metal centers in porous nitrogen-doped carbon promoting electroreduction of CO2 under neutral condition. CCS Chem. 6(8), 1978–1986 (2024). https://doi.org/10.31635/ccschem.023.202303333
- I. Kim, G.-B. Lee, S. Kim, H.D. Jung, J.-Y. Kim et al., Unveiling the reconstruction of copper bimetallic catalysts during CO2 electroreduction. Nat. Catal. 8(7), 697–713 (2025). https://doi.org/10.1038/s41929-025-01368-9
- Y. Guan, Y. Li, Z. Li, Y. Hou, L. Lei et al., Promotion of C─C coupling in the CO2 electrochemical reduction to valuable C2+ products: from micro-foundation to macro-application. Adv. Mater. 37(23), 2417567 (2025). https://doi.org/10.1002/adma.202417567
- D.-S. Huang, Y. Wang, Y. Tang, J.-R. Huang, P.-X. Li et al., Embedding a self-supporting MOF-based molecular sieve membrane into an electrolyzer for boosting electroreduction of CO2 in air and flue gas to HCOOH. Natl. Sci. Rev. 12(10), nwaf329 (2025). https://doi.org/10.1093/nsr/nwaf329
- H. Wang, X. Bi, Y. Yan, Y. Zhao, Z. Yang et al., Efficient electrocatalytic reduction of CO2 to ethanol enhanced by spacing effect of Cu–Cu in Cu2-xSe nanosheets. Adv. Funct. Mater. 33(25), 2214946 (2023). https://doi.org/10.1002/adfm.202214946
- H. Li, K. Gan, R. Li, H. Huang, J. Niu et al., Highly dispersed NiO clusters induced electron delocalization of Ni-N-C catalysts for enhanced CO2 electroreduction. Adv. Funct. Mater. 33(1), 2208622 (2023). https://doi.org/10.1002/adfm.202208622
- J. Wang, Z. Zhu, Y. Lin, Z. Li, W. Tang et al., Nano-engineering in zinc-based catalysts for CO2 electroreduction: Advances and challenges. Carbon Neutralization 3(3), 423–440 (2024). https://doi.org/10.1002/cnl2.131
- H.-L. Zhu, P.-Q. Liao, X.-M. Chen, Precise engineering of multimetal sites in metal–organic frameworks for efficient and selective electrochemical reduction of CO2 to C2 and urea products. Acc. Chem. Res. 58(23), 3530–3542 (2025). https://doi.org/10.1021/acs.accounts.5c00584
- Z. Yang, D. Ji, Z. Li, Z. He, Y. Hu et al., CeO2/CuS nanoplates electroreduce CO2 to ethanol with stabilized Cu+ species. Small 19(40), 2303099 (2023). https://doi.org/10.1002/smll.202303099
- M. Luo, Z. Wang, Y.C. Li, J. Li, F. Li et al., Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen. Nat. Commun. 10, 5814 (2019). https://doi.org/10.1038/s41467-019-13833-8
- Y. Da, J. Chen, L. Fan, R. Jiang, Y. Xiao et al., Selective and energy efficient electrocatalytic CO2-to-ethanol conversion through anion modulation. Angew. Chem. Int. Ed. 64(35), e202506867 (2025). https://doi.org/10.1002/anie.202506867
- G. Liu, P. Adesina, N. Nasiri, H. Wang, Y. Sheng et al., Elucidating reaction pathways of the CO2 electroreduction via tailorable tortuosities and oxidation states of Cu nanostructures. Adv. Funct. Mater. 32(36), 2204993 (2022). https://doi.org/10.1002/adfm.202204993
- Y. Yang, A. He, H. Li, Q. Zou, Z. Liu et al., Operando constructing Cu/Cu2O electrocatalysts for efficient CO2 electroreduction to ethanol: CO2-assisted structural evolution of octahedral Cu2O by operando CV activation. ACS Catal. 12(20), 12942–12953 (2022). https://doi.org/10.1021/acscatal.2c03833
- H. Xu, D. Rebollar, H. He, L. Chong, Y. Liu et al., Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper. Nat. Energy 5(8), 623–632 (2020). https://doi.org/10.1038/s41560-020-0666-x
- J. Albo, A. Irabien, Cu2O-loaded gas diffusion electrodes for the continuous electrochemical reduction of CO2 to methanol. J. Catal. 343, 232–239 (2016). https://doi.org/10.1016/j.jcat.2015.11.014
- Y. Zhang, K. Li, M. Chen, J. Wang, J. Liu, Cu/Cu2O nanops supported on vertically ZIF-L-coated nitrogen-doped graphene nanosheets for electroreduction of CO2 to ethanol. ACS Appl. Nano Mater. 3(1), 257–263 (2020). https://doi.org/10.1021/acsanm.9b01935
- S.C. Abeyweera, M. Simukaitis, Q. Wei, Y. Sun, Interfaced Ag/Cu nanostructures derived from metal thiolate nanoplates: a highly selective catalyst for electrochemical reduction of CO2 to ethanol. SmartMat 3(1), 173–182 (2022). https://doi.org/10.1002/smm2.1096
- J. Wang, H. Yang, Q. Liu, Q. Liu, X. Li et al., Fastening Br– ions at copper–molecule interface enables highly efficient electroreduction of CO2 to ethanol. ACS Energy Lett. 6(2), 437–444 (2021). https://doi.org/10.1021/acsenergylett.0c02364
- M. Rahaman, A. Dutta, A. Zanetti, P. Broekmann, Electrochemical reduction of CO2 into multicarbon alcohols on activated Cu mesh catalysts: an identical location (IL) study. ACS Catal. 7(11), 7946–7956 (2017). https://doi.org/10.1021/acscatal.7b02234
- P. Wang, T. Li, Q. Wu, R. Du, Q. Zhang et al., Molecular assembled electrocatalyst for highly selective CO2 fixation to C2+ products. “ACS Nano” 16(10), 17021–17032 (2022). https://doi.org/10.1021/acsnano.2c07138
- W. Xia, Y. Xie, S. Jia, S. Han, R. Qi et al., Adjacent copper single atoms promote C–C coupling in electrochemical CO2 reduction for the efficient conversion of ethanol. J. Am. Chem. Soc. 145(31), 17253–17264 (2023). https://doi.org/10.1021/jacs.3c04612
- A. Goyal, G. Marcandalli, V.A. Mints, M.T.M. Koper, Competition between CO2 reduction and hydrogen evolution on a gold electrode under well-defined mass transport conditions. J. Am. Chem. Soc. 142(9), 4154–4161 (2020). https://doi.org/10.1021/jacs.9b10061
- B. Chang, H. Pang, F. Raziq, S. Wang, K.-W. Huang et al., Electrochemical reduction of carbon dioxide to multicarbon (C2+) products: challenges and perspectives. Energy Environ. Sci. 16(11), 4714–4758 (2023). https://doi.org/10.1039/d3ee00964e
- X. Fu, J. Zhang, Y. Kang, Electrochemical reduction of CO2 towards multi-carbon products via a two-step process. React. Chem. Eng. 6(4), 612–628 (2021). https://doi.org/10.1039/d1re00001b
- B. Hu, D. Zhao, B. Tian, C. Chen, Z. Zou, Pressure-enhanced electrocatalysis for small-molecule conversion. Energy Mater. Adv. 6, 359 (2025). https://doi.org/10.34133/energymatadv.0359
- D. Johnson, Z. Qiao, A. Djire, Progress and challenges of carbon dioxide reduction reaction on transition metal based electrocatalysts. ACS Appl. Energy Mater. 4(9), 8661–8684 (2021). https://doi.org/10.1021/acsaem.1c01624
- L. Li, J. Su, J. Lu, Q. Shao, Recent advances of core-shell Cu-based catalysts for the reduction of CO2 to C2+ products. Chem. Asian J. 18(5), e202201044 (2023). https://doi.org/10.1002/asia.202201044
- X. Su, C. Wang, F. Zhao, T. Wei, D. Zhao et al., Size effects of supported Cu-based catalysts for the electrocatalytic CO2 reduction reaction. J. Mater. Chem. A 11(43), 23188–23210 (2023). https://doi.org/10.1039/d3ta04929a
- J. Wang, Y. Zhang, Y. Ma, J. Yin, Y. Wang et al., Electrocatalytic reduction of carbon dioxide to high-value multicarbon products with metal–organic frameworks and their derived materials. ACS Mater. Lett. 4(11), 2058–2079 (2022). https://doi.org/10.1021/acsmaterialslett.2c00751
- J.-W. Zhao, H.-Y. Wang, L. Feng, J.-Z. Zhu, J.-X. Liu et al., Crystal-phase engineering in heterogeneous catalysis. Chem. Rev. 124(1), 164–209 (2024). https://doi.org/10.1021/acs.chemrev.3c00402
- S. Nitopi, E. Bertheussen, S.B. Scott, X. Liu, A.K. Engstfeld et al., Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 119(12), 7610–7672 (2019). https://doi.org/10.1021/acs.chemrev.8b00705
- F. Pan, Y. Yang, Designing CO2 reduction electrode materials by morphology and interface engineering. Energy Environ. Sci. 13(8), 2275–2309 (2020). https://doi.org/10.1039/d0ee00900h
- M.B. Ross, P. De Luna, Y. Li, C.-T. Dinh, D. Kim et al., Designing materials for electrochemical carbon dioxide recycling. Nat. Catal. 2(8), 648–658 (2019). https://doi.org/10.1038/s41929-019-0306-7
- T.K. Todorova, M.W. Schreiber, M. Fontecave, Mechanistic understanding of CO2 reduction reaction (CO2RR) toward multicarbon products by heterogeneous copper-based catalysts. ACS Catal. 10(3), 1754–1768 (2020). https://doi.org/10.1021/acscatal.9b04746
- Z. Sun, T. Ma, H. Tao, Q. Fan, B. Han, Fundamentals and challenges of electrochemical CO2 reduction using two-dimensional materials. Chem 3(4), 560–587 (2017). https://doi.org/10.1016/j.chempr.2017.09.009
- H. Yang, S. Li, Q. Xu, Efficient strategies for promoting the electrochemical reduction of CO2 to C2+ products over Cu-based catalysts. Chin. J. Catal. 48, 32–65 (2023). https://doi.org/10.1016/S1872-2067(23)64429-8
- G. Jiang, D. Han, Z. Han, J. Gao, X. Wang et al., Rational manipulation of intermediates on copper for CO2 electroreduction toward multicarbon products. Trans. Tianjin Univ. 28(4), 265–291 (2022). https://doi.org/10.1007/s12209-022-00330-1
- K. Xiang, F. Shen, Y. Fu, L. Wu, Z. Wang et al., Boosting CO2 electroreduction towards C2+ products via CO* intermediate manipulation on copper-based catalysts. Environ. Sci. Nano 9(3), 911–953 (2022). https://doi.org/10.1039/d1en00977j
- J. Yu, J. Wang, Y. Ma, J. Zhou, Y. Wang et al., Recent progresses in electrochemical carbon dioxide reduction on copper-based catalysts toward multicarbon products. Adv. Funct. Mater. 31(37), 2102151 (2021). https://doi.org/10.1002/adfm.202102151
- T. Yan, X. Chen, L. Kumari, J. Lin, M. Li et al., Multiscale CO2 electrocatalysis to C2+ products: reaction mechanisms, catalyst design, and device fabrication. Chem. Rev. 123(17), 10530–10583 (2023). https://doi.org/10.1021/acs.chemrev.2c00514
- Y. Deng, J. Zhao, S. Wang, R. Chen, J. Ding et al., Operando spectroscopic analysis of axial oxygen-coordinated single-Sn-atom sites for electrochemical CO2 reduction. J. Am. Chem. Soc. 145(13), 7242–7251 (2023). https://doi.org/10.1021/jacs.2c12952
- F. Li, Y.C. Li, Z. Wang, J. Li, D.-H. Nam et al., Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces. Nat. Catal. 3(1), 75–82 (2020). https://doi.org/10.1038/s41929-019-0383-7
- F. Zhang, N. Cao, C. Wang, S. Wang, Y. He et al., In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1−x shield. Nat. Commun. 16(1), 6082 (2025). https://doi.org/10.1038/s41467-025-61189-z
- P. Huang, Z. Yang, K. Zhai, B. Huang, J. Zhou et al., Balancing *CHO/*CO intermediate flux via carbonyl-hydroxyl motif synergy enables high-selectivity ethanol electrosynthesis from dilute CO2. J. Am. Chem. Soc. 147(25), 22062–22071 (2025). https://doi.org/10.1021/jacs.5c05839
- S. Kuang, Y. Su, M. Li, H. Liu, H. Chuai et al., Asymmetrical electrohydrogenation of CO2 to ethanol with copper-gold heterojunctions. Proc. Natl. Acad. Sci. U.S.A. 120(4), e2214175120 (2023). https://doi.org/10.1073/pnas.2214175120
- L. Zhang, J. Feng, L. Wu, X. Ma, X. Song et al., Oxophilicity-controlled CO2 electroreduction to C2+ alcohols over lewis acid metal-doped Cuδ+ catalysts. J. Am. Chem. Soc. 145(40), 21945–21954 (2023). https://doi.org/10.1021/jacs.3c06697
- L. Ding, N. Zhu, Y. Hu, Z. Chen, P. Song et al., Over 70% faradaic efficiency for CO2 electroreduction to ethanol enabled by potassium dopant-tuned interaction between copper sites and intermediates. Angew. Chem. Int. Ed. 61(36), e202209268 (2022). https://doi.org/10.1002/anie.202209268
- S. Wang, F. Li, J. Zhao, Y. Zeng, Y. Li et al., Manipulating C-C coupling pathway in electrochemical CO2 reduction for selective ethylene and ethanol production over single-atom alloy catalyst. Nat. Commun. 15, 10247 (2024). https://doi.org/10.1038/s41467-024-54636-w
- D. Zhong, Q. Fang, R. Du, Y. Jin, C. Peng et al., Selective electrochemical CO2 reduction to ethylene or ethanol via tuning *OH adsorption. Angew. Chem. Int. Ed. 64(32), e202501773 (2025). https://doi.org/10.1002/anie.202501773
- Z. Liu, L. Song, X. Lv, M. Liu, Q. Wen et al., Switching CO2 electroreduction toward ethanol by delocalization state-tuned bond cleavage. J. Am. Chem. Soc. 146(20), 14260–14266 (2024). https://doi.org/10.1021/jacs.4c03830
- Y. Qiao, S. Shen, C. Mao, Y. Xiao, W. Lai et al., Interfacial oxygen vacancy-copper pair sites on inverse CeO2/Cu catalyst enable efficient CO2 electroreduction to ethanol in acid. Angew. Chem. Int. Ed. 64(13), e202424248 (2025). https://doi.org/10.1002/anie.202424248
- Z.-H. Zhao, J.-R. Huang, P.-Q. Liao, X.-M. Chen, Highly efficient electroreduction of CO2 to ethanol via asymmetric C–C coupling by a metal–organic framework with heterodimetal dual sites. J. Am. Chem. Soc. 145(49), 26783–26790 (2023). https://doi.org/10.1021/jacs.3c08974
- J. Ding, H. Yang, X.-L. Ma, S. Liu, W. Liu et al., A tin-based tandem electrocatalyst for CO2 reduction to ethanol with 80% selectivity. Nat. Energy 8(12), 1386–1394 (2023). https://doi.org/10.1038/s41560-023-01389-3
- C.Y.J. Lim, M. Yilmaz, J.M. Arce-Ramos, A.D. Handoko, W.J. Teh et al., Surface charge as activity descriptors for electrochemical CO2 reduction to multi-carbon products on organic-functionalised Cu. Nat. Commun. 14(1), 335 (2023). https://doi.org/10.1038/s41467-023-35912-7
- G. Wu, Y. Song, Q. Zheng, C. Long, T. Fan et al., Selective electroreduction of CO2 to n-propanol in two-step tandem catalytic system. Adv. Energy Mater. 12(36), 2202054 (2022). https://doi.org/10.1002/aenm.202202054
- L. Zaza, K. Rossi, R. Buonsanti, Well-defined copper-based nanocatalysts for selective electrochemical reduction of CO2 to C2 products. ACS Energy Lett. 7(4), 1284–1291 (2022). https://doi.org/10.1021/acsenergylett.2c00035
- S. Yu, S. Louisia, P. Yang, The interactive dynamics of nanocatalyst structure and microenvironment during electrochemical CO2 conversion. JACS. Au. 2(3), 562–572 (2022). https://doi.org/10.1021/jacsau.1c00562
- W. Ye, X. Guo, T. Ma, A review on electrochemical synthesized copper-based catalysts for electrochemical reduction of CO2 to C2+ products. Chem. Eng. J. 414, 128825 (2021). https://doi.org/10.1016/j.cej.2021.128825
- F. Ma, P. Zhang, X. Zheng, L. Chen, Y. Li et al., Steering the site distance of atomic Cu–Cu pairs by first-shell halogen coordination boosts CO2-to-C2 selectivity. Angew. Chem. Int. Ed. 63(46), e202412785 (2024). https://doi.org/10.1002/anie.202412785
- R. Purbia, S.Y. Choi, C.H. Woo, J. Jeon, C. Lim et al., Highly selective and low-overpotential electrocatalytic CO2 reduction to ethanol by Cu-single atoms decorated N-doped carbon dots. Appl. Catal. B Environ. Energy 345, 123694 (2024). https://doi.org/10.1016/j.apcatb.2024.123694
- D. Karapinar, N.T. Huan, N. Ranjbar Sahraie, J. Li, D. Wakerley et al., Electroreduction of CO2 on single-site copper-nitrogen-doped carbon material: selective formation of ethanol and reversible restructuration of the metal sites. Angew. Chem. Int. Ed. 58(42), 15098–15103 (2019). https://doi.org/10.1002/anie.201907994
- C. Guo, Y. Guo, Y. Shi, X. Lan, Y. Wang et al., Electrocatalytic reduction of CO2 to ethanol at close to theoretical potential via engineering abundant electron-donating Cδ+ species. Angew. Chem. Int. Ed. 61(32), e202205909 (2022). https://doi.org/10.1002/anie.202205909
- B. Yang, L. Chen, S. Xue, H. Sun, K. Feng et al., Electrocatalytic CO2 reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes. Nat. Commun. 13(1), 5122 (2022). https://doi.org/10.1038/s41467-022-32740-z
- Y. Zhu, P. Li, X. Yang, M. Wang, Y. Zhang et al., Confinement of SnCuxO2+x nanoclusters in zeolites for high-efficient electrochemical carbon dioxide reduction. Adv. Energy Mater. 13(24), 2204143 (2023). https://doi.org/10.1002/aenm.202204143
- Q. Chang, Y. Liu, J.-H. Lee, D. Ologunagba, S. Hwang et al., Metal-coordinated phthalocyanines as platform molecules for understanding isolated metal sites in the electrochemical reduction of CO2. J. Am. Chem. Soc. 144(35), 16131–16138 (2022). https://doi.org/10.1021/jacs.2c06953
- M. Esmaeilirad, A. Baskin, A. Kondori, A. Sanz-Matias, J. Qian et al., Gold-like activity copper-like selectivity of heteroatomic transition metal carbides for electrocatalytic carbon dioxide reduction reaction. Nat. Commun. 12(1), 5067 (2021). https://doi.org/10.1038/s41467-021-25295-y
- Y. Guo, X. He, Y. Su, Y. Dai, M. Xie et al., Machine-learning-guided discovery and optimization of additives in preparing Cu catalysts for CO2 reduction. J. Am. Chem. Soc. 143(15), 5755–5762 (2021). https://doi.org/10.1021/jacs.1c00339
- Z. Han, D. Han, Z. Chen, J. Gao, G. Jiang et al., Steering surface reconstruction of copper with electrolyte additives for CO2 electroreduction. Nat. Commun. 13, 3158 (2022). https://doi.org/10.1038/s41467-022-30819-1
- Q. Lei, L. Huang, J. Yin, B. Davaasuren, Y. Yuan et al., Structural evolution and strain generation of derived-Cu catalysts during CO2 electroreduction. Nat. Commun. 13(1), 4857 (2022). https://doi.org/10.1038/s41467-022-32601-9
- F. Scholten, K.C. Nguyen, J.P. Bruce, M. Heyde, B. Roldan Cuenya, Identifying structure–selectivity correlations in the electrochemical reduction of CO2: a comparison of well-ordered atomically clean and chemically etched copper single-crystal surfaces. Angew. Chem. Int. Ed. 60(35), 19169–19175 (2021). https://doi.org/10.1002/anie.202103102
- K.U.D. Calvinho, A.W. Alherz, K.M.K. Yap, A.B. Laursen, S. Hwang et al., Surface hydrides on Fe2P electrocatalyst reduce CO2 at low overpotential: steering selectivity to ethylene glycol. J. Am. Chem. Soc. 143(50), 21275–21285 (2021). https://doi.org/10.1021/jacs.1c03428
- Y. Liang, J. Zhao, Y. Yang, S.F. Hung, J. Li et al., Stabilizing copper sites in coordination polymers toward efficient electrochemical C–C coupling. Nat. Commun. 14, 474 (2023). https://doi.org/10.1038/s41467-023-35993-4
- X. Chen, J. Chen, N.M. Alghoraibi, D.A. Henckel, R. Zhang et al., Electrochemical CO2-to-ethylene conversion on polyamine-incorporated Cu electrodes. Nat. Catal. 4(1), 20–27 (2021). https://doi.org/10.1038/s41929-020-00547-0
- S. Ren, E.W. Lees, C. Hunt, A. Jewlal, Y. Kim et al., Catalyst aggregation matters for immobilized molecular CO2RR electrocatalysts. J. Am. Chem. Soc. 145(8), 4414–4420 (2023). https://doi.org/10.1021/jacs.2c08380
- T. Zhang, B. Yuan, W. Wang, J. He, X. Xiang, Tailoring H intermediate coverage on the CuAl2O4/CuO catalyst for enhanced electrocatalytic CO2 reduction to ethanol. Angew. Chem. Int. Ed. 62(29), e202302096 (2023). https://doi.org/10.1002/anie.202302096
- Y.N. Xu, B. Mei, Q. Xu, H.Q. Fu, X.Y. Zhang et al., In situ/operando synchrotron radiation analytical techniques for CO2/CO reduction reaction: from atomic scales to mesoscales. Angew. Chem. Int. Ed. 63(25), e202404213 (2024). https://doi.org/10.1002/anie.202404213
- Y. Yang, J. Feijóo, M. Figueras-Valls, C. Chen, C. Shi et al., operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction. Nat. Catal. 8(6), 579–594 (2025). https://doi.org/10.1038/s41929-025-01359-w
- Y. Liu, L. Gong, J. Liu, P. Xiao, B. Chen et al., Fabrication of interface with capping-bonding synergy to boost CO2 electroreduction to formate. Appl. Catal. B Environ. Energy 362, 124760 (2025). https://doi.org/10.1016/j.apcatb.2024.124760
- X. Shen, X. Liu, S. Wang, T. Chen, W. Zhang et al., Synergistic modulation at atomically dispersed Fe/Au interface for selective CO2 electroreduction. Nano Lett. 21(1), 686–692 (2021). https://doi.org/10.1021/acs.nanolett.0c04291
- Y. Wu, C. Chen, S. Liu, Q. Qian, Q. Zhu et al., Highly selective CO2 electroreduction to multi-carbon alcohols via amine modified copper nanops at acidic conditions. Angew. Chem. Int. Ed. 63(49), e202410659 (2024). https://doi.org/10.1002/anie.202410659
- F. Yang, A.O. Elnabawy, R. Schimmenti, P. Song, J. Wang et al., Bismuthene for highly efficient carbon dioxide electroreduction reaction. Nat. Commun. 11, 1088 (2020). https://doi.org/10.1038/s41467-020-14914-9
- X. Wang, N. Fu, J.-C. Liu, K. Yu, Z. Li et al., Atomic replacement of PtNi nanoalloys within Zn-ZIF-8 for the fabrication of a multisite CO2 reduction electrocatalyst. J. Am. Chem. Soc. 144(50), 23223–23229 (2022). https://doi.org/10.1021/jacs.2c11497
- A. Bagger, W. Ju, A.S. Varela, P. Strasser, J. Rossmeisl, Electrochemical CO2 reduction: a classification problem. ChemPhysChem 18(22), 3266–3273 (2017). https://doi.org/10.1002/cphc.201700736
- H. Jia, Y. Yang, T.H. Chow, H. Zhang, X. Liu et al., Symmetry-broken Au–Cu heterostructures and their tandem catalysis process in electrochemical CO2 reduction. Adv. Funct. Mater. 31(27), 2101255 (2021). https://doi.org/10.1002/adfm.202101255
- J. Huang, M. Mensi, E. Oveisi, V. Mantella, R. Buonsanti, Structural sensitivities in bimetallic catalysts for electrochemical CO2 reduction revealed by Ag–Cu nanodimers. J. Am. Chem. Soc. 141(6), 2490–2499 (2019). https://doi.org/10.1021/jacs.8b12381
- Y. Zheng, J. Zhang, Z. Ma, G. Zhang, H. Zhang et al., Seeded growth of gold–copper Janus nanostructures as a tandem catalyst for efficient electroreduction of CO2 to C2+ products. Small 18(19), 2201695 (2022). https://doi.org/10.1002/smll.202201695
- L. Xiong, X. Zhang, H. Yuan, J. Wang, X. Yuan et al., Breaking the linear scaling relationship by compositional and structural crafting of ternary Cu–Au/Ag nanoframes for electrocatalytic ethylene production. Angew. Chem. Int. Ed. 60(5), 2508–2518 (2021). https://doi.org/10.1002/anie.202012631
- M. Sun, W. Guan, C. Chen, C. Wu, X. Liu et al., Mechanistic insight into the synergy between nickel single atoms and nanops on N-doped carbon for electroreduction of CO2. J. Energy Chem. 100, 327–336 (2025). https://doi.org/10.1016/j.jechem.2024.08.058
- O. Zaytseva, G. Neumann, Carbon nanomaterials: production, impact on plant development, agricultural and environmental applications. Chem. Biol. Technol. Agric. 3, 17 (2016). https://doi.org/10.1186/s40538-016-0070-8
- F. Zhao, Y. Zhang, C. Wang, J. Zhang, D. Zhao, Modulating *CO coverage via the pyrrolic-N content on carbon for enhanced electrocatalytic CO2 reduction to CO. Catal. Sci. Technol. 15(9), 2898–2907 (2025). https://doi.org/10.1039/d5cy00100e
- H. Wang, Y.-K. Tzeng, Y. Ji, Y. Li, J. Li et al., Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface. Nat. Nanotechnol. 15(2), 131–137 (2020). https://doi.org/10.1038/s41565-019-0603-y
- H. Han, Y. Noh, Y. Kim, S. Park, W. Yoon et al., Selective electrochemical CO2 conversion to multicarbon alcohols on highly efficient N-doped porous carbon-supported Cu catalysts. Green Chem. 22(1), 71–84 (2020). https://doi.org/10.1039/c9gc03088c
- C. Cometto, A. Ugolotti, E. Grazietti, A. Moretto, G. Bottaro et al., Copper single-atoms embedded in 2D graphitic carbon nitride for the CO2 reduction. npj 2D Mater. Appl. 5, 63 (2021). https://doi.org/10.1038/s41699-021-00243-y
- Z. Lin, L. Zheng, W. Yao, S. Liu, Y. Bu et al., A facile route for constructing Cu–N–C peroxidase mimics. J. Mater. Chem. B 8(37), 8599–8606 (2020). https://doi.org/10.1039/d0tb01494j
- Z.-Q. Liang, T.-T. Zhuang, A. Seifitokaldani, J. Li, C.-W. Huang et al., Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO2. Nat. Commun. 9(1), 3828 (2018). https://doi.org/10.1038/s41467-018-06311-0
- F. Xu, B. Feng, Z. Shen, Y. Chen, L. Jiao et al., Oxygen-bridged Cu binuclear sites for efficient electrocatalytic CO2 reduction to ethanol at ultralow overpotential. J. Am. Chem. Soc. 146(13), 9365–9374 (2024). https://doi.org/10.1021/jacs.4c01610
- X. Su, Z. Jiang, J. Zhou, H. Liu, D. Zhou et al., Complementary operando spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol. Nat. Commun. 13(1), 1322 (2022). https://doi.org/10.1038/s41467-022-29035-8
- H. Hu, J.Z. Ou, X. Xu, Y. Lin, Y. Zhang et al., Graphene-assisted construction of electrocatalysts for carbon dioxide reduction. Chem. Eng. J. 425, 130587 (2021). https://doi.org/10.1016/j.cej.2021.130587
- A. Liu, W. Guan, K. Wu, X. Ren, L. Gao et al., Density functional theory study of nitrogen-doped graphene as a high-performance electrocatalyst for CO2RR. Appl. Surf. Sci. 540, 148319 (2021). https://doi.org/10.1016/j.apsusc.2020.148319
- D. Zang, X.J. Gao, L. Li, Y. Wei, H. Wang, Confined interface engineering of self-supported Cu@N-doped graphene for electrocatalytic CO2 reduction with enhanced selectivity towards ethanol. Nano Res. 15(10), 8872–8879 (2022). https://doi.org/10.1007/s12274-022-4698-3
- L. Hou, X. Cui, B. Guan, S. Wang, R. Li et al., Synthesis of a monolayer fullerene network. Nature 606(7914), 507–510 (2022). https://doi.org/10.1038/s41586-022-04771-5
- Y. Chen, Z. Huang, X. Gu, Z. Ma, J. Chen et al., Top-down synthesis strategies: maximum noble-metal atom efficiency in catalytic materials. Chin. J. Catal. 38(9), 1588–1596 (2017). https://doi.org/10.1016/S1872-2067(17)62778-5
- Z.-W. Deng, Y. Liu, J. Lin, W.-X. Chen, Rational design and energy catalytic application of high-loading single-atom catalysts. Rare Met. 43(10), 4844–4866 (2024). https://doi.org/10.1007/s12598-024-02727-4
- C. Xia, Y. Qiu, Y. Xia, P. Zhu, G. King et al., General synthesis of single-atom catalysts with high metal loading using graphene quantum dots. Nat. Chem. 13(9), 887–894 (2021). https://doi.org/10.1038/s41557-021-00734-x
- S. Zhang, S. Zhao, D. Qu, X. Liu, Y. Wu et al., Electrochemical reduction of CO2 toward C2 valuables on Cu@Ag core-shell tandem catalyst with tunable shell thickness. Small 17(37), e2102293 (2021). https://doi.org/10.1002/smll.202102293
- M.K. Birhanu, M.-C. Tsai, A.W. Kahsay, C.-T. Chen, T.S. Zeleke et al., Copper and copper-based bimetallic catalysts for carbon dioxide electroreduction. Adv. Mater. Interfaces 5(24), 1800919 (2018). https://doi.org/10.1002/admi.201800919
- P. Wang, H. Yang, C. Tang, Y. Wu, Y. Zheng et al., Boosting electrocatalytic CO2-to-ethanol production via asymmetric C–C coupling. Nat. Commun. 13(1), 3754 (2022). https://doi.org/10.1038/s41467-022-31427-9
- J. Feng, L. Wu, S. Liu, L. Xu, X. Song et al., Improving CO2-to-C2+ product electroreduction efficiency via atomic lanthanide dopant-induced tensile-strained CuOx catalysts. J. Am. Chem. Soc. 145(17), 9857–9866 (2023). https://doi.org/10.1021/jacs.3c02428
- X. Wu, X. Li, J. Lv, X. Lv, A. Wu et al., Pulsed electrolysis promotes CO2 reduction to ethanol on heterostructured Cu2O/Ag catalysts. Small 20(12), e2307637 (2024). https://doi.org/10.1002/smll.202307637
- Y. Shen, N. Fang, X. Liu, Y. Ling, Y. Su et al., Observation of metal-organic interphase in Cu-based electrochemical CO2-to-ethanol conversion. Nat. Commun. 16(1), 2073 (2025). https://doi.org/10.1038/s41467-025-57221-x
- J. Tang, E. Weiss, Z. Shao, Advances in cutting-edge electrode engineering toward CO2 electrolysis at high current density and selectivity: a mini-review. Carbon Neutralization 1(2), 140–158 (2022). https://doi.org/10.1002/cnl2.21
- L. Zhang, S. Yang, Y. Lai, H. Liu, Y. Fan et al., In-situ synthesis of monodispersed CuxO heterostructure on porous carbon monolith for exceptional removal of gaseous Hg0. Appl. Catal. B Environ. 265, 118556 (2020). https://doi.org/10.1016/j.apcatb.2019.118556
- S. Yang, Z. Liu, X. Yan, C. Liu, Z. Zhang et al., Catalytic oxidation of elemental mercury in coal-combustion flue gas over the CuAlO2 catalyst. Energy Fuels 33(11), 11380–11388 (2019). https://doi.org/10.1021/acs.energyfuels.9b02376
- H. Guzmán, F. Salomone, S. Bensaid, M. Castellino, N. Russo et al., CO2 conversion to alcohols over Cu/ZnO catalysts: prospective synergies between electrocatalytic and thermocatalytic routes. ACS Appl. Mater. Interfaces 14(1), 517–530 (2022). https://doi.org/10.1021/acsami.1c15871
- H. Zhang, Y. Sun, J. Wang, X. Gao, Z. Tang et al., Engineering COBridge adsorption in Cu2O-TiO2 heterojunction catalyst for selective electrochemical CO2 reduction to ethanol. ACS Appl. Energy Mater. 6(22), 11448–11457 (2023). https://doi.org/10.1021/acsaem.3c01463
- P. Song, B. Hu, D. Zhao, J. Fu, X. Su et al., Modulating the asymmetric atomic interface of copper single atoms for efficient CO2 electroreduction. “ACS Nano” 17(5), 4619–4628 (2023). https://doi.org/10.1021/acsnano.2c10701
- T. Stolar, A. Prašnikar, V. Martinez, B. Karadeniz, A. Bjelić et al., Scalable mechanochemical amorphization of bimetallic Cu–Zn MOF-74 catalyst for selective CO2 reduction reaction to methanol. ACS Appl. Mater. Interfaces 13(2), 3070–3077 (2021). https://doi.org/10.1021/acsami.0c21265
- B. Shao, D. Huang, R.-K. Huang, X.-L. He, Y. Luo et al., Metal–organic framework supported low-nuclearity cluster catalysts for highly selective carbon dioxide electroreduction to ethanol. Angew. Chem. Int. Ed. 63(45), e202409270 (2024). https://doi.org/10.1002/anie.202409270
- Y. Zang, T. Liu, P. Wei, H. Li, Q. Wang et al., Selective CO2 electroreduction to ethanol over a carbon-coated CuOx catalyst. Angew. Chem. Int. Ed. 61(40), e202209629 (2022). https://doi.org/10.1002/anie.202209629
- Y. Liu, Y. Yang, X. Lin, Y. Lin, Z. Zhuo et al., The geometric-electronic coupled design of diatomic catalyst towards oxygen reduction reaction. Nat. Commun. 16, 5158 (2025). https://doi.org/10.1038/s41467-025-60170-0
- A. Wang, X.Y. Liu, C.-Y. Mou, T. Zhang, Understanding the synergistic effects of gold bimetallic catalysts. J. Catal. 308, 258–271 (2013). https://doi.org/10.1016/j.jcat.2013.08.023
- C.-J. Chang, S.-C. Lin, H.-C. Chen, J. Wang, K.J. Zheng et al., Dynamic reoxidation/reduction-driven atomic interdiffusion for highly selective CO2 reduction toward methane. J. Am. Chem. Soc. 142(28), 12119–12132 (2020). https://doi.org/10.1021/jacs.0c01859
- Y. Jia, F. Li, K. Fan, L. Sun, Cu-based bimetallic electrocatalysts for CO2 reduction. Adv. Powder Mater. 1(1), 100012 (2022). https://doi.org/10.1016/j.apmate.2021.10.003
- Y.-L. Liao, H.-B. Huang, R.-Y. Zou, S.-L. Shen, X.-J. Liu et al., A review of the synthesis, characterization, and mechanism of bimetallic catalysts for electrocatalytic CO2 reduction. New Carbon Mater. 39(3), 367–387 (2024). https://doi.org/10.1016/S1872-5805(24)60860-7
- G. Wu, C. Zhu, J. Mao, G. Li, S. Li et al., Ampere-level CO2-to-ethanol conversion via boron-incorporated copper electrodes. ACS Energy Lett. 8(11), 4867–4874 (2023). https://doi.org/10.1021/acsenergylett.3c01901
- J.-D. Yi, R. Xie, Z.-L. Xie, G.-L. Chai, T.-F. Liu et al., Highly selective CO2 electroreduction to CH4 by In Situ generated Cu2O single-type sites on a conductive MOF: stabilizing key intermediates with hydrogen bonding. Angew. Chem. Int. Ed. 59(52), 23641–23648 (2020). https://doi.org/10.1002/anie.202010601
- M. Zheng, P. Wang, X. Zhi, K. Yang, Y. Jiao et al., Electrocatalytic CO2-to-C2+ with ampere-level current on heteroatom-engineered copper via tuning *CO intermediate coverage. J. Am. Chem. Soc. 144(32), 14936–14944 (2022). https://doi.org/10.1021/jacs.2c06820
- X. Lv, L. Shang, S. Zhou, S. Li, Y. Wang et al., Electron-deficient Cu sites on Cu3Ag1 catalyst promoting CO2 electroreduction to alcohols. Adv. Energy Mater. 10(37), 2001987 (2020). https://doi.org/10.1002/aenm.202001987
- Z. Wang, Q. Yuan, J. Shan, Z. Jiang, P. Xu et al., Highly selective electrocatalytic reduction of CO2 into methane on Cu–Bi nanoalloys. J. Phys. Chem. Lett. 11(17), 7261–7266 (2020). https://doi.org/10.1021/acs.jpclett.0c01261
- P. Iyengar, M.J. Kolb, J. Pankhurst, F. Calle-Vallejo, R. Buonsanti, Theory-guided enhancement of CO2 reduction to ethanol on Ag–Cu tandem catalysts via p-size effects. ACS Catal. 11(21), 13330–13336 (2021). https://doi.org/10.1021/acscatal.1c03717
- C. Peng, J. Ma, G. Luo, S. Yan, J. Zhang et al., (111) facet-oriented Cu2Mg intermetallic compound with Cu3-Mg sites for CO2 electroreduction to ethanol with industrial current density. Angew. Chem. Int. Ed. 63(17), e202316907 (2024). https://doi.org/10.1002/anie.202316907
- M.C.O. Monteiro, F. Dattila, N. López, M.T.M. Koper, The role of cation acidity on the competition between hydrogen evolution and CO2 reduction on gold electrodes. J. Am. Chem. Soc. 144(4), 1589–1602 (2022). https://doi.org/10.1021/jacs.1c10171
- Y.N. Xu, W. Li, H.Q. Fu, X.Y. Zhang, J.Y. Zhao et al., Tuning the microenvironment in monolayer MgAl layered double hydroxide for CO2-to-ethylene electrocatalysis in neutral media. Angew. Chem. Int. Ed. 62(19), e202217296 (2023). https://doi.org/10.1002/anie.202217296
- P. Li, J. Bi, J. Liu, Y. Wang, X. Kang et al., P–d orbital hybridization induced by p-Block metal-doped Cu promotes the formation of C2+ products in Ampere-Level CO2 electroreduction. J. Am. Chem. Soc. 145(8), 4675–4682 (2023). https://doi.org/10.1021/jacs.2c12743
- C.G. Morales-Guio, E.R. Cave, S.A. Nitopi, J.T. Feaster, L. Wang et al., Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst. Nat. Catal. 1(10), 764–771 (2018). https://doi.org/10.1038/s41929-018-0139-9
- X. Yang, H. Ding, S. Li, S. Zheng, J.-F. Li et al., Cation-induced interfacial hydrophobic microenvironment promotes the C–C coupling in electrochemical CO2 reduction. J. Am. Chem. Soc. 146(8), 5532–5542 (2024). https://doi.org/10.1021/jacs.3c13602
- P. Wei, D. Gao, T. Liu, H. Li, J. Sang et al., Coverage-driven selectivity switch from ethylene to acetate in high-rate CO2/CO electrolysis. Nat. Nanotechnol. 18(3), 299–306 (2023). https://doi.org/10.1038/s41565-022-01286-y
- J. Gao, H. Zhang, X. Guo, J. Luo, S.M. Zakeeruddin et al., Selective C–C coupling in carbon dioxide electroreduction via efficient spillover of intermediates as supported by operando Raman spectroscopy. J. Am. Chem. Soc. 141(47), 18704–18714 (2019). https://doi.org/10.1021/jacs.9b07415
- L. Wan, X. Zhang, J. Cheng, R. Chen, L. Wu et al., Bimetallic Cu–Zn catalysts for electrochemical CO2 reduction: phase-separated versus core–shell distribution. ACS Catal. 12(5), 2741–2748 (2022). https://doi.org/10.1021/acscatal.1c05272
- D. Choukroun, L. Pacquets, C. Li, S. Hoekx, S. Arnouts et al., Mapping composition–selectivity relationships of supported sub-10 nm Cu–Ag nanocrystals for high-rate CO2 electroreduction. ACS Nano 15(9), 14858–14872 (2021). https://doi.org/10.1021/acsnano.1c04943
- Y. Lum, J.W. Ager, Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu. Energy Environ. Sci. 11(10), 2935–2944 (2018). https://doi.org/10.1039/c8ee01501e
- P. Iyengar, M.J. Kolb, J.R. Pankhurst, F. Calle-Vallejo, R. Buonsanti, Elucidating the facet-dependent selectivity for CO2 electroreduction to ethanol of Cu–Ag tandem catalysts. ACS Catal. 11(8), 4456–4463 (2021). https://doi.org/10.1021/acscatal.1c00420
- L.R.L. Ting, O. Piqué, S.Y. Lim, M. Tanhaei, F. Calle-Vallejo et al., Enhancing CO2 electroreduction to ethanol on copper–silver composites by opening an alternative catalytic pathway. ACS Catal. 10(7), 4059–4069 (2020). https://doi.org/10.1021/acscatal.9b05319
- E. Robens, B. Hecker, H. Kungl, H. Tempel, R.-A. Eichel, Bimetallic copper–silver catalysts for the electrochemical reduction of CO2 to ethanol. ACS Appl. Energy Mater. 6(14), 7571–7577 (2023). https://doi.org/10.1021/acsaem.3c00985
- H. Tang, Y. Liu, Y. Zhou, Y. Qian, B.-L. Lin, Boosting the electroreduction of CO2 to ethanol via the synergistic effect of Cu–Ag bimetallic catalysts. ACS Appl. Energy Mater. 5(11), 14045–14052 (2022). https://doi.org/10.1021/acsaem.2c02595
- H. Mistry, A.S. Varela, C.S. Bonifacio, I. Zegkinoglou, I. Sinev et al., Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat. Commun. 7, 12123 (2016). https://doi.org/10.1038/ncomms12123
- X. Wang, K. Klingan, M. Klingenhof, T. Möller, J. Ferreira de Araújo et al., Morphology and mechanism of highly selective Cu(II) oxide nanosheet catalysts for carbon dioxide electroreduction. Nat. Commun. 12(1), 794 (2021). https://doi.org/10.1038/s41467-021-20961-7
- W. Sun, P. Wang, Y. Jiang, Z. Jiang, R. Long et al., V-doped Cu2Se hierarchical nanotubes enabling flow-cell CO2 electroreduction to ethanol with high efficiency and selectivity. Adv. Mater. 34(50), 2207691 (2022). https://doi.org/10.1002/adma.202207691
- Y.C. Li, Z. Wang, T. Yuan, D.-H. Nam, M. Luo et al., Binding site diversity promotes CO2 electroreduction to ethanol. J. Am. Chem. Soc. 141(21), 8584–8591 (2019). https://doi.org/10.1021/jacs.9b02945
- J. Park, E.-D. Kim, S. Kim, C. Lim, H. Kim et al., Deriving an efficient and stable microenvironment for a CO2 MEA electrolyzer by reverse osmosis. ACS Energy Lett. 9(7), 3342–3350 (2024). https://doi.org/10.1021/acsenergylett.4c00933
- N.-H. Tran, H.P. Duong, G. Rousse, S. Zanna, M.W. Schreiber et al., Selective ethylene production from CO2 and CO reduction via engineering membrane electrode assembly with porous dendritic copper oxide. ACS Appl. Mater. Interfaces 14(28), 31933–31941 (2022). https://doi.org/10.1021/acsami.2c06068
- K. Li, W. Leigh, P. Feron, H. Yu, M. Tade, Systematic study of aqueous monoethanolamine (MEA)-based CO2 capture process: techno-economic assessment of the MEA process and its improvements. Appl. Energy 165, 648–659 (2016). https://doi.org/10.1016/j.apenergy.2015.12.109
- S. Zhang, X. Yuan, H. Wang, W. Mérida, H. Zhu et al., A review of accelerated stress tests of MEA durability in PEM fuel cells. Int. J. Hydrog. Energy 34(1), 388–404 (2009). https://doi.org/10.1016/j.ijhydene.2008.10.012
- J. Yu, J. Xiao, Y. Ma, J. Zhou, P. Lu et al., Acidic conditions for efficient carbon dioxide electroreduction in flow and MEA cells. Chem Catal. 3(8), 100670 (2023). https://doi.org/10.1016/j.checat.2023.100670
- M. Fang, M. Wang, Z. Wang, Z. Zhang, H. Zhou et al., Hydrophobic, ultrastable Cuδ+ for robust CO2 electroreduction to C2 products at ampere-current levels. J. Am. Chem. Soc. 145(20), 11323–11332 (2023). https://doi.org/10.1021/jacs.3c02399
- Z. Zhang, X. Huang, Z. Chen, J. Zhu, B. Endrődi et al., Membrane electrode assembly for electrocatalytic CO2 reduction: principle and application. Angew. Chem. Int. Ed. 62(28), e202302789 (2023). https://doi.org/10.1002/anie.202302789
- X. Wang, Z. Jiang, P. Wang, Z. Chen, T. Sheng et al., Ag+-doped InSe nanosheets for membrane electrode assembly electrolyzer toward large-current electroreduction of CO2 to ethanol. Angew. Chem. Int. Ed. 62(48), e202313646 (2023). https://doi.org/10.1002/anie.202313646
- N. Huang, L. Zhai, D.E. Coupry, M.A. Addicoat, K. Okushita et al., Multiple-component covalent organic frameworks. Nat. Commun. 7, 12325 (2016). https://doi.org/10.1038/ncomms12325
- K. Geng, T. He, R. Liu, S. Dalapati, K.T. Tan et al., Covalent organic frameworks: design, synthesis, and functions. Chem. Rev. 120(16), 8814–8933 (2020). https://doi.org/10.1021/acs.chemrev.9b00550
- R.-B. Lin, B. Chen, Reducing CO2 with stable covalent organic frameworks. Joule 2(6), 1030–1032 (2018). https://doi.org/10.1016/j.joule.2018.05.017
- Y.-R. Wang, H.-M. Ding, X.-Y. Ma, M. Liu, Y.-L. Yang et al., Imparting CO2 electroreduction auxiliary for integrated morphology tuning and performance boosting in a porphyrin-based covalent organic framework. Angew. Chem. Int. Ed. 61(5), e202114648 (2022). https://doi.org/10.1002/anie.202114648
- Q. Wu, M.-J. Mao, Q.-J. Wu, J. Liang, Y.-B. Huang et al., Construction of donor–acceptor heterojunctions in covalent organic framework for enhanced CO2 electroreduction. Small 17(22), 2004933 (2021). https://doi.org/10.1002/smll.202004933
- A. Singh, S. Barman, F.A. Rahimi, A. Dey, R. Jena et al., Atomically dispersed Co2+ in a redox-active COF for electrochemical CO2 reduction to ethanol: unravelling mechanistic insight through operando studies. Energy Environ. Sci. 17(6), 2315–2325 (2024). https://doi.org/10.1039/d3ee02946h
- Y. Xia, Q. Zhang, F. Guo, J. Wang, W. Li et al., Ag@Cu with Cu–CuO interface prepared by air cold-plasma promoting the electrocatalytic reduction of CO2 to low-carbon alcohols. Vacuum 196, 110767 (2022). https://doi.org/10.1016/j.vacuum.2021.110767
- S. Liu, H. Tao, L. Zeng, Q. Liu, Z. Xu et al., Shape-dependent electrocatalytic reduction of CO2 to CO on triangular silver nanoplates. J. Am. Chem. Soc. 139(6), 2160–2163 (2017). https://doi.org/10.1021/jacs.6b12103
- W. Yang, W. Ma, Z. Zhang, C. Zhao, Ligament size-dependent electrocatalytic activity of nanoporous Ag network for CO2 reduction. Faraday Discuss. 210, 289–299 (2018). https://doi.org/10.1039/c8fd00056e
- J. Qin, T. Wang, M. Zhai, C. Wu, Y.A. Liu et al., Hydroxypillar [5] Arene-confined silver nanocatalyst for selective electrochemical reduction of CO2 to ethanol. Adv. Funct. Mater. 33(29), 2300697 (2023). https://doi.org/10.1002/adfm.202300697
- C.-J. Zou, Z.-Y. Du, W. Tang, Q. Liu, X.-B. Liu et al., Interfacial water on Ag/Ag2S nanowires enhancing the ethanol selectivity for CO2 electroreduction. Adv. Mater. 37(37), 2503010 (2025). https://doi.org/10.1002/adma.202503010
- J. Xiao, X. Pan, S. Guo, P. Ren, X. Bao, Toward fundamentals of confined catalysis in carbon nanotubes. J. Am. Chem. Soc. 137(1), 477–482 (2015). https://doi.org/10.1021/ja511498s
- X. Liu, Y. Hou, F. Yang, Y. Liu, H. Yu et al., Selective CO2 electroreduction to ethanol on encapsulated nickel nanops by N-doped carbon nanotubes. Carbon 201, 460–466 (2023). https://doi.org/10.1016/j.carbon.2022.09.010
- Y. Song, R. Peng, D.K. Hensley, P.V. Bonnesen, L. Liang et al., High-selectivity electrochemical conversion of CO2 to ethanol using a copper nanop/N-doped graphene electrode. ChemistrySelect 1(19), 6055–6061 (2016). https://doi.org/10.1002/slct.201601169
- J. Park, C. Jeong, M. Na, Y. Oh, K.-S. Lee et al., Subnanometer Cu clusters on porous Ag enhancing ethanol production in electrochemical CO2 reduction. ACS Catal. 14(5), 3198–3207 (2024). https://doi.org/10.1021/acscatal.3c03469
- M.-Z. Gu, Y. Min, L. Jiang, F. Zhou, Q. Chen et al., Subsurface engineering for directional-selective CO₂-to-ethanol electrocatalysis at industrial-level. Nat. Commun. 17(1), 488 (2025). https://doi.org/10.1038/s41467-025-67176-8
- N. Zhang, Y. Zhang, Stabilizing *CO intermediate on nitrogen-doped carbon-coated CuxOy derived from metal–organic framework for enhanced electrochemical CO2-to-ethylene. J. Mater. Chem. A 13(4), 2902–2910 (2025). https://doi.org/10.1039/d4ta06722c
- K. Xiang, Y. Liu, H. Yu, H. Liu, K. Li, Strategies to improve the performance of copper-based catalyst for electroreduction of CO2 to multi-carbon products. Chin. Sci. Bull. 65(31), 3360–3372 (2020). https://doi.org/10.1360/tb-2020-0014
- K. Rossi, R. Buonsanti, Shaping copper nanocatalysts to steer selectivity in the electrochemical CO2 reduction reaction. Acc. Chem. Res. 55(5), 629–637 (2022). https://doi.org/10.1021/acs.accounts.1c00673
- X. Su, B. Hu, Y. Zhang, C. Liu, C. Wang et al., Built-in axial electric field-driven electron-rich monomolecular co sites for promoting CO2 electroreduction to CO over ultrawide potential window. Angew. Chem. Int. Ed. 64(51), e202511671 (2025). https://doi.org/10.1002/anie.202511671
- Y. Yan, M. Wu, L. Zhou, W. Chen, L. Han et al., Enhancing electrocatalytic activity through targeted local electrolyte micro-environment. Adv. Funct. Mater. 35(19), 2419328 (2025). https://doi.org/10.1002/adfm.202419328
- Z. Jiang, X. Yang, J. Zhang, J. Yang, B. Sun et al., From conventional two-electron to emerging multi-electron zinc-iodine batteries: advantages, challenges, and future perspectives. Adv. Funct. Mater. 35(50), e11754 (2025). https://doi.org/10.1002/adfm.202511754
References
Z. Sun, Y. Hu, D. Zhou, M. Sun, S. Wang et al., Factors influencing the performance of copper-bearing catalysts in the CO2 reduction system. ACS Energy Lett. 6(11), 3992–4022 (2021). https://doi.org/10.1021/acsenergylett.1c01965
X. Wang, W. Cai, Promoted CO2 reforming with bioethanol over TiO2-supported photothermal catalysts. Energy Mater. Adv. 6, 205 (2025). https://doi.org/10.34133/energymatadv.0205
B. Huang, F. Zhao, J. Fu, L. Zheng, J. Zhang et al., A carbon-based single-atom Cu electrocatalyst for efficient conversion of CO2 to carbon products. Chem. Commun. 61(81), 15822–15825 (2025). https://doi.org/10.1039/d5cc04310g
C. Wang, Y. Zhang, F. Zhao, D. Zhao, J. Zhang, Design principles of metal phthalocyanine for electrochemical CO2 reduction: from targeted molecular structures to atomic-level active sites. Small 21(25), e2502897 (2025). https://doi.org/10.1002/smll.202502897
Y.-C. Liu, J.-R. Huang, H.-L. Zhu, X.-F. Qiu, C. Yu et al., Electrosynthesis of pure urea from pretreated flue gas in a proton-limited environment established in a porous solid-state electrolyte electrolyser. Nat. Nanotechnol. 20(7), 907–913 (2025). https://doi.org/10.1038/s41565-025-01914-3
A.M. Abdellah, F. Ismail, O.W. Siig, J. Yang, C.M. Andrei et al., Impact of palladium/palladium hydride conversion on electrochemical CO2 reduction via in-situ transmission electron microscopy and diffraction. Nat. Commun. 15(1), 938 (2024). https://doi.org/10.1038/s41467-024-45096-3
Q. Wang, K. Liu, K. Hu, C. Cai, H. Li et al., Attenuating metal-substrate conjugation in atomically dispersed nickel catalysts for electroreduction of CO2 to CO. Nat. Commun. 13(1), 6082 (2022). https://doi.org/10.1038/s41467-022-33692-0
D. Zhao, K. Yu, P. Song, W. Feng, B. Hu et al., Atomic-level engineering Fe1N2O2 interfacial structure derived from oxygen-abundant metal–organic frameworks to promote electrochemical CO2 reduction. Energy Environ. Sci. 15(9), 3795–3804 (2022). https://doi.org/10.1039/d2ee00878e
F. Yang, X. Ma, W.-B. Cai, P. Song, W. Xu, Nature of oxygen-containing groups on carbon for high-efficiency electrocatalytic CO2 reduction reaction. J. Am. Chem. Soc. 141(51), 20451–20459 (2019). https://doi.org/10.1021/jacs.9b11123
W. Yang, Y. Zhao, Y. Chen, H. Ren, J. Sun et al., Constraining CO2 coverage on copper promotes CO2 electroreduction to multi-carbon products in strong acid. Angew. Chem. Int. Ed. Engl. 64(12), e202422082 (2025). https://doi.org/10.1002/anie.202422082
L. Fan, C. Xia, P. Zhu, Y. Lu, H. Wang, Electrochemical CO2 reduction to high-concentration pure formic acid solutions in an all-solid-state reactor. Nat. Commun. 11, 3633 (2020). https://doi.org/10.1038/s41467-020-17403-1
H. Yang, G.-X. Zhang, H.-J. Zhou, Y.-Y. Sun, H. Pang, Metal–organic frameworks meet MXene: new opportunities for electrochemical application. Energy Mater. Adv. 4, 33 (2023). https://doi.org/10.34133/energymatadv.0033
M. Li, Z. Zhao, W. Zhang, M. Luo, L. Tao et al., Sub-monolayer YOx/MoOx on ultrathin Pt nanowires boosts alcohol oxidation electrocatalysis. Adv. Mater. 33(41), e2103762 (2021). https://doi.org/10.1002/adma.202103762
S.-C. Lin, C.-C. Chang, S.-Y. Chiu, H.-T. Pai, T.-Y. Liao et al., operando time-resolved X-ray absorption spectroscopy reveals the chemical nature enabling highly selective CO2 reduction. Nat. Commun. 11(1), 3525 (2020). https://doi.org/10.1038/s41467-020-17231-3
C.-P. Liang, J.-R. Huang, H.-L. Zhu, Z.-H. Zhao, C. Yu et al., Precisely tailoring the first coordination shell of metal centers in porous nitrogen-doped carbon promoting electroreduction of CO2 under neutral condition. CCS Chem. 6(8), 1978–1986 (2024). https://doi.org/10.31635/ccschem.023.202303333
I. Kim, G.-B. Lee, S. Kim, H.D. Jung, J.-Y. Kim et al., Unveiling the reconstruction of copper bimetallic catalysts during CO2 electroreduction. Nat. Catal. 8(7), 697–713 (2025). https://doi.org/10.1038/s41929-025-01368-9
Y. Guan, Y. Li, Z. Li, Y. Hou, L. Lei et al., Promotion of C─C coupling in the CO2 electrochemical reduction to valuable C2+ products: from micro-foundation to macro-application. Adv. Mater. 37(23), 2417567 (2025). https://doi.org/10.1002/adma.202417567
D.-S. Huang, Y. Wang, Y. Tang, J.-R. Huang, P.-X. Li et al., Embedding a self-supporting MOF-based molecular sieve membrane into an electrolyzer for boosting electroreduction of CO2 in air and flue gas to HCOOH. Natl. Sci. Rev. 12(10), nwaf329 (2025). https://doi.org/10.1093/nsr/nwaf329
H. Wang, X. Bi, Y. Yan, Y. Zhao, Z. Yang et al., Efficient electrocatalytic reduction of CO2 to ethanol enhanced by spacing effect of Cu–Cu in Cu2-xSe nanosheets. Adv. Funct. Mater. 33(25), 2214946 (2023). https://doi.org/10.1002/adfm.202214946
H. Li, K. Gan, R. Li, H. Huang, J. Niu et al., Highly dispersed NiO clusters induced electron delocalization of Ni-N-C catalysts for enhanced CO2 electroreduction. Adv. Funct. Mater. 33(1), 2208622 (2023). https://doi.org/10.1002/adfm.202208622
J. Wang, Z. Zhu, Y. Lin, Z. Li, W. Tang et al., Nano-engineering in zinc-based catalysts for CO2 electroreduction: Advances and challenges. Carbon Neutralization 3(3), 423–440 (2024). https://doi.org/10.1002/cnl2.131
H.-L. Zhu, P.-Q. Liao, X.-M. Chen, Precise engineering of multimetal sites in metal–organic frameworks for efficient and selective electrochemical reduction of CO2 to C2 and urea products. Acc. Chem. Res. 58(23), 3530–3542 (2025). https://doi.org/10.1021/acs.accounts.5c00584
Z. Yang, D. Ji, Z. Li, Z. He, Y. Hu et al., CeO2/CuS nanoplates electroreduce CO2 to ethanol with stabilized Cu+ species. Small 19(40), 2303099 (2023). https://doi.org/10.1002/smll.202303099
M. Luo, Z. Wang, Y.C. Li, J. Li, F. Li et al., Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen. Nat. Commun. 10, 5814 (2019). https://doi.org/10.1038/s41467-019-13833-8
Y. Da, J. Chen, L. Fan, R. Jiang, Y. Xiao et al., Selective and energy efficient electrocatalytic CO2-to-ethanol conversion through anion modulation. Angew. Chem. Int. Ed. 64(35), e202506867 (2025). https://doi.org/10.1002/anie.202506867
G. Liu, P. Adesina, N. Nasiri, H. Wang, Y. Sheng et al., Elucidating reaction pathways of the CO2 electroreduction via tailorable tortuosities and oxidation states of Cu nanostructures. Adv. Funct. Mater. 32(36), 2204993 (2022). https://doi.org/10.1002/adfm.202204993
Y. Yang, A. He, H. Li, Q. Zou, Z. Liu et al., Operando constructing Cu/Cu2O electrocatalysts for efficient CO2 electroreduction to ethanol: CO2-assisted structural evolution of octahedral Cu2O by operando CV activation. ACS Catal. 12(20), 12942–12953 (2022). https://doi.org/10.1021/acscatal.2c03833
H. Xu, D. Rebollar, H. He, L. Chong, Y. Liu et al., Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper. Nat. Energy 5(8), 623–632 (2020). https://doi.org/10.1038/s41560-020-0666-x
J. Albo, A. Irabien, Cu2O-loaded gas diffusion electrodes for the continuous electrochemical reduction of CO2 to methanol. J. Catal. 343, 232–239 (2016). https://doi.org/10.1016/j.jcat.2015.11.014
Y. Zhang, K. Li, M. Chen, J. Wang, J. Liu, Cu/Cu2O nanops supported on vertically ZIF-L-coated nitrogen-doped graphene nanosheets for electroreduction of CO2 to ethanol. ACS Appl. Nano Mater. 3(1), 257–263 (2020). https://doi.org/10.1021/acsanm.9b01935
S.C. Abeyweera, M. Simukaitis, Q. Wei, Y. Sun, Interfaced Ag/Cu nanostructures derived from metal thiolate nanoplates: a highly selective catalyst for electrochemical reduction of CO2 to ethanol. SmartMat 3(1), 173–182 (2022). https://doi.org/10.1002/smm2.1096
J. Wang, H. Yang, Q. Liu, Q. Liu, X. Li et al., Fastening Br– ions at copper–molecule interface enables highly efficient electroreduction of CO2 to ethanol. ACS Energy Lett. 6(2), 437–444 (2021). https://doi.org/10.1021/acsenergylett.0c02364
M. Rahaman, A. Dutta, A. Zanetti, P. Broekmann, Electrochemical reduction of CO2 into multicarbon alcohols on activated Cu mesh catalysts: an identical location (IL) study. ACS Catal. 7(11), 7946–7956 (2017). https://doi.org/10.1021/acscatal.7b02234
P. Wang, T. Li, Q. Wu, R. Du, Q. Zhang et al., Molecular assembled electrocatalyst for highly selective CO2 fixation to C2+ products. “ACS Nano” 16(10), 17021–17032 (2022). https://doi.org/10.1021/acsnano.2c07138
W. Xia, Y. Xie, S. Jia, S. Han, R. Qi et al., Adjacent copper single atoms promote C–C coupling in electrochemical CO2 reduction for the efficient conversion of ethanol. J. Am. Chem. Soc. 145(31), 17253–17264 (2023). https://doi.org/10.1021/jacs.3c04612
A. Goyal, G. Marcandalli, V.A. Mints, M.T.M. Koper, Competition between CO2 reduction and hydrogen evolution on a gold electrode under well-defined mass transport conditions. J. Am. Chem. Soc. 142(9), 4154–4161 (2020). https://doi.org/10.1021/jacs.9b10061
B. Chang, H. Pang, F. Raziq, S. Wang, K.-W. Huang et al., Electrochemical reduction of carbon dioxide to multicarbon (C2+) products: challenges and perspectives. Energy Environ. Sci. 16(11), 4714–4758 (2023). https://doi.org/10.1039/d3ee00964e
X. Fu, J. Zhang, Y. Kang, Electrochemical reduction of CO2 towards multi-carbon products via a two-step process. React. Chem. Eng. 6(4), 612–628 (2021). https://doi.org/10.1039/d1re00001b
B. Hu, D. Zhao, B. Tian, C. Chen, Z. Zou, Pressure-enhanced electrocatalysis for small-molecule conversion. Energy Mater. Adv. 6, 359 (2025). https://doi.org/10.34133/energymatadv.0359
D. Johnson, Z. Qiao, A. Djire, Progress and challenges of carbon dioxide reduction reaction on transition metal based electrocatalysts. ACS Appl. Energy Mater. 4(9), 8661–8684 (2021). https://doi.org/10.1021/acsaem.1c01624
L. Li, J. Su, J. Lu, Q. Shao, Recent advances of core-shell Cu-based catalysts for the reduction of CO2 to C2+ products. Chem. Asian J. 18(5), e202201044 (2023). https://doi.org/10.1002/asia.202201044
X. Su, C. Wang, F. Zhao, T. Wei, D. Zhao et al., Size effects of supported Cu-based catalysts for the electrocatalytic CO2 reduction reaction. J. Mater. Chem. A 11(43), 23188–23210 (2023). https://doi.org/10.1039/d3ta04929a
J. Wang, Y. Zhang, Y. Ma, J. Yin, Y. Wang et al., Electrocatalytic reduction of carbon dioxide to high-value multicarbon products with metal–organic frameworks and their derived materials. ACS Mater. Lett. 4(11), 2058–2079 (2022). https://doi.org/10.1021/acsmaterialslett.2c00751
J.-W. Zhao, H.-Y. Wang, L. Feng, J.-Z. Zhu, J.-X. Liu et al., Crystal-phase engineering in heterogeneous catalysis. Chem. Rev. 124(1), 164–209 (2024). https://doi.org/10.1021/acs.chemrev.3c00402
S. Nitopi, E. Bertheussen, S.B. Scott, X. Liu, A.K. Engstfeld et al., Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 119(12), 7610–7672 (2019). https://doi.org/10.1021/acs.chemrev.8b00705
F. Pan, Y. Yang, Designing CO2 reduction electrode materials by morphology and interface engineering. Energy Environ. Sci. 13(8), 2275–2309 (2020). https://doi.org/10.1039/d0ee00900h
M.B. Ross, P. De Luna, Y. Li, C.-T. Dinh, D. Kim et al., Designing materials for electrochemical carbon dioxide recycling. Nat. Catal. 2(8), 648–658 (2019). https://doi.org/10.1038/s41929-019-0306-7
T.K. Todorova, M.W. Schreiber, M. Fontecave, Mechanistic understanding of CO2 reduction reaction (CO2RR) toward multicarbon products by heterogeneous copper-based catalysts. ACS Catal. 10(3), 1754–1768 (2020). https://doi.org/10.1021/acscatal.9b04746
Z. Sun, T. Ma, H. Tao, Q. Fan, B. Han, Fundamentals and challenges of electrochemical CO2 reduction using two-dimensional materials. Chem 3(4), 560–587 (2017). https://doi.org/10.1016/j.chempr.2017.09.009
H. Yang, S. Li, Q. Xu, Efficient strategies for promoting the electrochemical reduction of CO2 to C2+ products over Cu-based catalysts. Chin. J. Catal. 48, 32–65 (2023). https://doi.org/10.1016/S1872-2067(23)64429-8
G. Jiang, D. Han, Z. Han, J. Gao, X. Wang et al., Rational manipulation of intermediates on copper for CO2 electroreduction toward multicarbon products. Trans. Tianjin Univ. 28(4), 265–291 (2022). https://doi.org/10.1007/s12209-022-00330-1
K. Xiang, F. Shen, Y. Fu, L. Wu, Z. Wang et al., Boosting CO2 electroreduction towards C2+ products via CO* intermediate manipulation on copper-based catalysts. Environ. Sci. Nano 9(3), 911–953 (2022). https://doi.org/10.1039/d1en00977j
J. Yu, J. Wang, Y. Ma, J. Zhou, Y. Wang et al., Recent progresses in electrochemical carbon dioxide reduction on copper-based catalysts toward multicarbon products. Adv. Funct. Mater. 31(37), 2102151 (2021). https://doi.org/10.1002/adfm.202102151
T. Yan, X. Chen, L. Kumari, J. Lin, M. Li et al., Multiscale CO2 electrocatalysis to C2+ products: reaction mechanisms, catalyst design, and device fabrication. Chem. Rev. 123(17), 10530–10583 (2023). https://doi.org/10.1021/acs.chemrev.2c00514
Y. Deng, J. Zhao, S. Wang, R. Chen, J. Ding et al., Operando spectroscopic analysis of axial oxygen-coordinated single-Sn-atom sites for electrochemical CO2 reduction. J. Am. Chem. Soc. 145(13), 7242–7251 (2023). https://doi.org/10.1021/jacs.2c12952
F. Li, Y.C. Li, Z. Wang, J. Li, D.-H. Nam et al., Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces. Nat. Catal. 3(1), 75–82 (2020). https://doi.org/10.1038/s41929-019-0383-7
F. Zhang, N. Cao, C. Wang, S. Wang, Y. He et al., In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1−x shield. Nat. Commun. 16(1), 6082 (2025). https://doi.org/10.1038/s41467-025-61189-z
P. Huang, Z. Yang, K. Zhai, B. Huang, J. Zhou et al., Balancing *CHO/*CO intermediate flux via carbonyl-hydroxyl motif synergy enables high-selectivity ethanol electrosynthesis from dilute CO2. J. Am. Chem. Soc. 147(25), 22062–22071 (2025). https://doi.org/10.1021/jacs.5c05839
S. Kuang, Y. Su, M. Li, H. Liu, H. Chuai et al., Asymmetrical electrohydrogenation of CO2 to ethanol with copper-gold heterojunctions. Proc. Natl. Acad. Sci. U.S.A. 120(4), e2214175120 (2023). https://doi.org/10.1073/pnas.2214175120
L. Zhang, J. Feng, L. Wu, X. Ma, X. Song et al., Oxophilicity-controlled CO2 electroreduction to C2+ alcohols over lewis acid metal-doped Cuδ+ catalysts. J. Am. Chem. Soc. 145(40), 21945–21954 (2023). https://doi.org/10.1021/jacs.3c06697
L. Ding, N. Zhu, Y. Hu, Z. Chen, P. Song et al., Over 70% faradaic efficiency for CO2 electroreduction to ethanol enabled by potassium dopant-tuned interaction between copper sites and intermediates. Angew. Chem. Int. Ed. 61(36), e202209268 (2022). https://doi.org/10.1002/anie.202209268
S. Wang, F. Li, J. Zhao, Y. Zeng, Y. Li et al., Manipulating C-C coupling pathway in electrochemical CO2 reduction for selective ethylene and ethanol production over single-atom alloy catalyst. Nat. Commun. 15, 10247 (2024). https://doi.org/10.1038/s41467-024-54636-w
D. Zhong, Q. Fang, R. Du, Y. Jin, C. Peng et al., Selective electrochemical CO2 reduction to ethylene or ethanol via tuning *OH adsorption. Angew. Chem. Int. Ed. 64(32), e202501773 (2025). https://doi.org/10.1002/anie.202501773
Z. Liu, L. Song, X. Lv, M. Liu, Q. Wen et al., Switching CO2 electroreduction toward ethanol by delocalization state-tuned bond cleavage. J. Am. Chem. Soc. 146(20), 14260–14266 (2024). https://doi.org/10.1021/jacs.4c03830
Y. Qiao, S. Shen, C. Mao, Y. Xiao, W. Lai et al., Interfacial oxygen vacancy-copper pair sites on inverse CeO2/Cu catalyst enable efficient CO2 electroreduction to ethanol in acid. Angew. Chem. Int. Ed. 64(13), e202424248 (2025). https://doi.org/10.1002/anie.202424248
Z.-H. Zhao, J.-R. Huang, P.-Q. Liao, X.-M. Chen, Highly efficient electroreduction of CO2 to ethanol via asymmetric C–C coupling by a metal–organic framework with heterodimetal dual sites. J. Am. Chem. Soc. 145(49), 26783–26790 (2023). https://doi.org/10.1021/jacs.3c08974
J. Ding, H. Yang, X.-L. Ma, S. Liu, W. Liu et al., A tin-based tandem electrocatalyst for CO2 reduction to ethanol with 80% selectivity. Nat. Energy 8(12), 1386–1394 (2023). https://doi.org/10.1038/s41560-023-01389-3
C.Y.J. Lim, M. Yilmaz, J.M. Arce-Ramos, A.D. Handoko, W.J. Teh et al., Surface charge as activity descriptors for electrochemical CO2 reduction to multi-carbon products on organic-functionalised Cu. Nat. Commun. 14(1), 335 (2023). https://doi.org/10.1038/s41467-023-35912-7
G. Wu, Y. Song, Q. Zheng, C. Long, T. Fan et al., Selective electroreduction of CO2 to n-propanol in two-step tandem catalytic system. Adv. Energy Mater. 12(36), 2202054 (2022). https://doi.org/10.1002/aenm.202202054
L. Zaza, K. Rossi, R. Buonsanti, Well-defined copper-based nanocatalysts for selective electrochemical reduction of CO2 to C2 products. ACS Energy Lett. 7(4), 1284–1291 (2022). https://doi.org/10.1021/acsenergylett.2c00035
S. Yu, S. Louisia, P. Yang, The interactive dynamics of nanocatalyst structure and microenvironment during electrochemical CO2 conversion. JACS. Au. 2(3), 562–572 (2022). https://doi.org/10.1021/jacsau.1c00562
W. Ye, X. Guo, T. Ma, A review on electrochemical synthesized copper-based catalysts for electrochemical reduction of CO2 to C2+ products. Chem. Eng. J. 414, 128825 (2021). https://doi.org/10.1016/j.cej.2021.128825
F. Ma, P. Zhang, X. Zheng, L. Chen, Y. Li et al., Steering the site distance of atomic Cu–Cu pairs by first-shell halogen coordination boosts CO2-to-C2 selectivity. Angew. Chem. Int. Ed. 63(46), e202412785 (2024). https://doi.org/10.1002/anie.202412785
R. Purbia, S.Y. Choi, C.H. Woo, J. Jeon, C. Lim et al., Highly selective and low-overpotential electrocatalytic CO2 reduction to ethanol by Cu-single atoms decorated N-doped carbon dots. Appl. Catal. B Environ. Energy 345, 123694 (2024). https://doi.org/10.1016/j.apcatb.2024.123694
D. Karapinar, N.T. Huan, N. Ranjbar Sahraie, J. Li, D. Wakerley et al., Electroreduction of CO2 on single-site copper-nitrogen-doped carbon material: selective formation of ethanol and reversible restructuration of the metal sites. Angew. Chem. Int. Ed. 58(42), 15098–15103 (2019). https://doi.org/10.1002/anie.201907994
C. Guo, Y. Guo, Y. Shi, X. Lan, Y. Wang et al., Electrocatalytic reduction of CO2 to ethanol at close to theoretical potential via engineering abundant electron-donating Cδ+ species. Angew. Chem. Int. Ed. 61(32), e202205909 (2022). https://doi.org/10.1002/anie.202205909
B. Yang, L. Chen, S. Xue, H. Sun, K. Feng et al., Electrocatalytic CO2 reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes. Nat. Commun. 13(1), 5122 (2022). https://doi.org/10.1038/s41467-022-32740-z
Y. Zhu, P. Li, X. Yang, M. Wang, Y. Zhang et al., Confinement of SnCuxO2+x nanoclusters in zeolites for high-efficient electrochemical carbon dioxide reduction. Adv. Energy Mater. 13(24), 2204143 (2023). https://doi.org/10.1002/aenm.202204143
Q. Chang, Y. Liu, J.-H. Lee, D. Ologunagba, S. Hwang et al., Metal-coordinated phthalocyanines as platform molecules for understanding isolated metal sites in the electrochemical reduction of CO2. J. Am. Chem. Soc. 144(35), 16131–16138 (2022). https://doi.org/10.1021/jacs.2c06953
M. Esmaeilirad, A. Baskin, A. Kondori, A. Sanz-Matias, J. Qian et al., Gold-like activity copper-like selectivity of heteroatomic transition metal carbides for electrocatalytic carbon dioxide reduction reaction. Nat. Commun. 12(1), 5067 (2021). https://doi.org/10.1038/s41467-021-25295-y
Y. Guo, X. He, Y. Su, Y. Dai, M. Xie et al., Machine-learning-guided discovery and optimization of additives in preparing Cu catalysts for CO2 reduction. J. Am. Chem. Soc. 143(15), 5755–5762 (2021). https://doi.org/10.1021/jacs.1c00339
Z. Han, D. Han, Z. Chen, J. Gao, G. Jiang et al., Steering surface reconstruction of copper with electrolyte additives for CO2 electroreduction. Nat. Commun. 13, 3158 (2022). https://doi.org/10.1038/s41467-022-30819-1
Q. Lei, L. Huang, J. Yin, B. Davaasuren, Y. Yuan et al., Structural evolution and strain generation of derived-Cu catalysts during CO2 electroreduction. Nat. Commun. 13(1), 4857 (2022). https://doi.org/10.1038/s41467-022-32601-9
F. Scholten, K.C. Nguyen, J.P. Bruce, M. Heyde, B. Roldan Cuenya, Identifying structure–selectivity correlations in the electrochemical reduction of CO2: a comparison of well-ordered atomically clean and chemically etched copper single-crystal surfaces. Angew. Chem. Int. Ed. 60(35), 19169–19175 (2021). https://doi.org/10.1002/anie.202103102
K.U.D. Calvinho, A.W. Alherz, K.M.K. Yap, A.B. Laursen, S. Hwang et al., Surface hydrides on Fe2P electrocatalyst reduce CO2 at low overpotential: steering selectivity to ethylene glycol. J. Am. Chem. Soc. 143(50), 21275–21285 (2021). https://doi.org/10.1021/jacs.1c03428
Y. Liang, J. Zhao, Y. Yang, S.F. Hung, J. Li et al., Stabilizing copper sites in coordination polymers toward efficient electrochemical C–C coupling. Nat. Commun. 14, 474 (2023). https://doi.org/10.1038/s41467-023-35993-4
X. Chen, J. Chen, N.M. Alghoraibi, D.A. Henckel, R. Zhang et al., Electrochemical CO2-to-ethylene conversion on polyamine-incorporated Cu electrodes. Nat. Catal. 4(1), 20–27 (2021). https://doi.org/10.1038/s41929-020-00547-0
S. Ren, E.W. Lees, C. Hunt, A. Jewlal, Y. Kim et al., Catalyst aggregation matters for immobilized molecular CO2RR electrocatalysts. J. Am. Chem. Soc. 145(8), 4414–4420 (2023). https://doi.org/10.1021/jacs.2c08380
T. Zhang, B. Yuan, W. Wang, J. He, X. Xiang, Tailoring H intermediate coverage on the CuAl2O4/CuO catalyst for enhanced electrocatalytic CO2 reduction to ethanol. Angew. Chem. Int. Ed. 62(29), e202302096 (2023). https://doi.org/10.1002/anie.202302096
Y.N. Xu, B. Mei, Q. Xu, H.Q. Fu, X.Y. Zhang et al., In situ/operando synchrotron radiation analytical techniques for CO2/CO reduction reaction: from atomic scales to mesoscales. Angew. Chem. Int. Ed. 63(25), e202404213 (2024). https://doi.org/10.1002/anie.202404213
Y. Yang, J. Feijóo, M. Figueras-Valls, C. Chen, C. Shi et al., operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction. Nat. Catal. 8(6), 579–594 (2025). https://doi.org/10.1038/s41929-025-01359-w
Y. Liu, L. Gong, J. Liu, P. Xiao, B. Chen et al., Fabrication of interface with capping-bonding synergy to boost CO2 electroreduction to formate. Appl. Catal. B Environ. Energy 362, 124760 (2025). https://doi.org/10.1016/j.apcatb.2024.124760
X. Shen, X. Liu, S. Wang, T. Chen, W. Zhang et al., Synergistic modulation at atomically dispersed Fe/Au interface for selective CO2 electroreduction. Nano Lett. 21(1), 686–692 (2021). https://doi.org/10.1021/acs.nanolett.0c04291
Y. Wu, C. Chen, S. Liu, Q. Qian, Q. Zhu et al., Highly selective CO2 electroreduction to multi-carbon alcohols via amine modified copper nanops at acidic conditions. Angew. Chem. Int. Ed. 63(49), e202410659 (2024). https://doi.org/10.1002/anie.202410659
F. Yang, A.O. Elnabawy, R. Schimmenti, P. Song, J. Wang et al., Bismuthene for highly efficient carbon dioxide electroreduction reaction. Nat. Commun. 11, 1088 (2020). https://doi.org/10.1038/s41467-020-14914-9
X. Wang, N. Fu, J.-C. Liu, K. Yu, Z. Li et al., Atomic replacement of PtNi nanoalloys within Zn-ZIF-8 for the fabrication of a multisite CO2 reduction electrocatalyst. J. Am. Chem. Soc. 144(50), 23223–23229 (2022). https://doi.org/10.1021/jacs.2c11497
A. Bagger, W. Ju, A.S. Varela, P. Strasser, J. Rossmeisl, Electrochemical CO2 reduction: a classification problem. ChemPhysChem 18(22), 3266–3273 (2017). https://doi.org/10.1002/cphc.201700736
H. Jia, Y. Yang, T.H. Chow, H. Zhang, X. Liu et al., Symmetry-broken Au–Cu heterostructures and their tandem catalysis process in electrochemical CO2 reduction. Adv. Funct. Mater. 31(27), 2101255 (2021). https://doi.org/10.1002/adfm.202101255
J. Huang, M. Mensi, E. Oveisi, V. Mantella, R. Buonsanti, Structural sensitivities in bimetallic catalysts for electrochemical CO2 reduction revealed by Ag–Cu nanodimers. J. Am. Chem. Soc. 141(6), 2490–2499 (2019). https://doi.org/10.1021/jacs.8b12381
Y. Zheng, J. Zhang, Z. Ma, G. Zhang, H. Zhang et al., Seeded growth of gold–copper Janus nanostructures as a tandem catalyst for efficient electroreduction of CO2 to C2+ products. Small 18(19), 2201695 (2022). https://doi.org/10.1002/smll.202201695
L. Xiong, X. Zhang, H. Yuan, J. Wang, X. Yuan et al., Breaking the linear scaling relationship by compositional and structural crafting of ternary Cu–Au/Ag nanoframes for electrocatalytic ethylene production. Angew. Chem. Int. Ed. 60(5), 2508–2518 (2021). https://doi.org/10.1002/anie.202012631
M. Sun, W. Guan, C. Chen, C. Wu, X. Liu et al., Mechanistic insight into the synergy between nickel single atoms and nanops on N-doped carbon for electroreduction of CO2. J. Energy Chem. 100, 327–336 (2025). https://doi.org/10.1016/j.jechem.2024.08.058
O. Zaytseva, G. Neumann, Carbon nanomaterials: production, impact on plant development, agricultural and environmental applications. Chem. Biol. Technol. Agric. 3, 17 (2016). https://doi.org/10.1186/s40538-016-0070-8
F. Zhao, Y. Zhang, C. Wang, J. Zhang, D. Zhao, Modulating *CO coverage via the pyrrolic-N content on carbon for enhanced electrocatalytic CO2 reduction to CO. Catal. Sci. Technol. 15(9), 2898–2907 (2025). https://doi.org/10.1039/d5cy00100e
H. Wang, Y.-K. Tzeng, Y. Ji, Y. Li, J. Li et al., Synergistic enhancement of electrocatalytic CO2 reduction to C2 oxygenates at nitrogen-doped nanodiamonds/Cu interface. Nat. Nanotechnol. 15(2), 131–137 (2020). https://doi.org/10.1038/s41565-019-0603-y
H. Han, Y. Noh, Y. Kim, S. Park, W. Yoon et al., Selective electrochemical CO2 conversion to multicarbon alcohols on highly efficient N-doped porous carbon-supported Cu catalysts. Green Chem. 22(1), 71–84 (2020). https://doi.org/10.1039/c9gc03088c
C. Cometto, A. Ugolotti, E. Grazietti, A. Moretto, G. Bottaro et al., Copper single-atoms embedded in 2D graphitic carbon nitride for the CO2 reduction. npj 2D Mater. Appl. 5, 63 (2021). https://doi.org/10.1038/s41699-021-00243-y
Z. Lin, L. Zheng, W. Yao, S. Liu, Y. Bu et al., A facile route for constructing Cu–N–C peroxidase mimics. J. Mater. Chem. B 8(37), 8599–8606 (2020). https://doi.org/10.1039/d0tb01494j
Z.-Q. Liang, T.-T. Zhuang, A. Seifitokaldani, J. Li, C.-W. Huang et al., Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO2. Nat. Commun. 9(1), 3828 (2018). https://doi.org/10.1038/s41467-018-06311-0
F. Xu, B. Feng, Z. Shen, Y. Chen, L. Jiao et al., Oxygen-bridged Cu binuclear sites for efficient electrocatalytic CO2 reduction to ethanol at ultralow overpotential. J. Am. Chem. Soc. 146(13), 9365–9374 (2024). https://doi.org/10.1021/jacs.4c01610
X. Su, Z. Jiang, J. Zhou, H. Liu, D. Zhou et al., Complementary operando spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol. Nat. Commun. 13(1), 1322 (2022). https://doi.org/10.1038/s41467-022-29035-8
H. Hu, J.Z. Ou, X. Xu, Y. Lin, Y. Zhang et al., Graphene-assisted construction of electrocatalysts for carbon dioxide reduction. Chem. Eng. J. 425, 130587 (2021). https://doi.org/10.1016/j.cej.2021.130587
A. Liu, W. Guan, K. Wu, X. Ren, L. Gao et al., Density functional theory study of nitrogen-doped graphene as a high-performance electrocatalyst for CO2RR. Appl. Surf. Sci. 540, 148319 (2021). https://doi.org/10.1016/j.apsusc.2020.148319
D. Zang, X.J. Gao, L. Li, Y. Wei, H. Wang, Confined interface engineering of self-supported Cu@N-doped graphene for electrocatalytic CO2 reduction with enhanced selectivity towards ethanol. Nano Res. 15(10), 8872–8879 (2022). https://doi.org/10.1007/s12274-022-4698-3
L. Hou, X. Cui, B. Guan, S. Wang, R. Li et al., Synthesis of a monolayer fullerene network. Nature 606(7914), 507–510 (2022). https://doi.org/10.1038/s41586-022-04771-5
Y. Chen, Z. Huang, X. Gu, Z. Ma, J. Chen et al., Top-down synthesis strategies: maximum noble-metal atom efficiency in catalytic materials. Chin. J. Catal. 38(9), 1588–1596 (2017). https://doi.org/10.1016/S1872-2067(17)62778-5
Z.-W. Deng, Y. Liu, J. Lin, W.-X. Chen, Rational design and energy catalytic application of high-loading single-atom catalysts. Rare Met. 43(10), 4844–4866 (2024). https://doi.org/10.1007/s12598-024-02727-4
C. Xia, Y. Qiu, Y. Xia, P. Zhu, G. King et al., General synthesis of single-atom catalysts with high metal loading using graphene quantum dots. Nat. Chem. 13(9), 887–894 (2021). https://doi.org/10.1038/s41557-021-00734-x
S. Zhang, S. Zhao, D. Qu, X. Liu, Y. Wu et al., Electrochemical reduction of CO2 toward C2 valuables on Cu@Ag core-shell tandem catalyst with tunable shell thickness. Small 17(37), e2102293 (2021). https://doi.org/10.1002/smll.202102293
M.K. Birhanu, M.-C. Tsai, A.W. Kahsay, C.-T. Chen, T.S. Zeleke et al., Copper and copper-based bimetallic catalysts for carbon dioxide electroreduction. Adv. Mater. Interfaces 5(24), 1800919 (2018). https://doi.org/10.1002/admi.201800919
P. Wang, H. Yang, C. Tang, Y. Wu, Y. Zheng et al., Boosting electrocatalytic CO2-to-ethanol production via asymmetric C–C coupling. Nat. Commun. 13(1), 3754 (2022). https://doi.org/10.1038/s41467-022-31427-9
J. Feng, L. Wu, S. Liu, L. Xu, X. Song et al., Improving CO2-to-C2+ product electroreduction efficiency via atomic lanthanide dopant-induced tensile-strained CuOx catalysts. J. Am. Chem. Soc. 145(17), 9857–9866 (2023). https://doi.org/10.1021/jacs.3c02428
X. Wu, X. Li, J. Lv, X. Lv, A. Wu et al., Pulsed electrolysis promotes CO2 reduction to ethanol on heterostructured Cu2O/Ag catalysts. Small 20(12), e2307637 (2024). https://doi.org/10.1002/smll.202307637
Y. Shen, N. Fang, X. Liu, Y. Ling, Y. Su et al., Observation of metal-organic interphase in Cu-based electrochemical CO2-to-ethanol conversion. Nat. Commun. 16(1), 2073 (2025). https://doi.org/10.1038/s41467-025-57221-x
J. Tang, E. Weiss, Z. Shao, Advances in cutting-edge electrode engineering toward CO2 electrolysis at high current density and selectivity: a mini-review. Carbon Neutralization 1(2), 140–158 (2022). https://doi.org/10.1002/cnl2.21
L. Zhang, S. Yang, Y. Lai, H. Liu, Y. Fan et al., In-situ synthesis of monodispersed CuxO heterostructure on porous carbon monolith for exceptional removal of gaseous Hg0. Appl. Catal. B Environ. 265, 118556 (2020). https://doi.org/10.1016/j.apcatb.2019.118556
S. Yang, Z. Liu, X. Yan, C. Liu, Z. Zhang et al., Catalytic oxidation of elemental mercury in coal-combustion flue gas over the CuAlO2 catalyst. Energy Fuels 33(11), 11380–11388 (2019). https://doi.org/10.1021/acs.energyfuels.9b02376
H. Guzmán, F. Salomone, S. Bensaid, M. Castellino, N. Russo et al., CO2 conversion to alcohols over Cu/ZnO catalysts: prospective synergies between electrocatalytic and thermocatalytic routes. ACS Appl. Mater. Interfaces 14(1), 517–530 (2022). https://doi.org/10.1021/acsami.1c15871
H. Zhang, Y. Sun, J. Wang, X. Gao, Z. Tang et al., Engineering COBridge adsorption in Cu2O-TiO2 heterojunction catalyst for selective electrochemical CO2 reduction to ethanol. ACS Appl. Energy Mater. 6(22), 11448–11457 (2023). https://doi.org/10.1021/acsaem.3c01463
P. Song, B. Hu, D. Zhao, J. Fu, X. Su et al., Modulating the asymmetric atomic interface of copper single atoms for efficient CO2 electroreduction. “ACS Nano” 17(5), 4619–4628 (2023). https://doi.org/10.1021/acsnano.2c10701
T. Stolar, A. Prašnikar, V. Martinez, B. Karadeniz, A. Bjelić et al., Scalable mechanochemical amorphization of bimetallic Cu–Zn MOF-74 catalyst for selective CO2 reduction reaction to methanol. ACS Appl. Mater. Interfaces 13(2), 3070–3077 (2021). https://doi.org/10.1021/acsami.0c21265
B. Shao, D. Huang, R.-K. Huang, X.-L. He, Y. Luo et al., Metal–organic framework supported low-nuclearity cluster catalysts for highly selective carbon dioxide electroreduction to ethanol. Angew. Chem. Int. Ed. 63(45), e202409270 (2024). https://doi.org/10.1002/anie.202409270
Y. Zang, T. Liu, P. Wei, H. Li, Q. Wang et al., Selective CO2 electroreduction to ethanol over a carbon-coated CuOx catalyst. Angew. Chem. Int. Ed. 61(40), e202209629 (2022). https://doi.org/10.1002/anie.202209629
Y. Liu, Y. Yang, X. Lin, Y. Lin, Z. Zhuo et al., The geometric-electronic coupled design of diatomic catalyst towards oxygen reduction reaction. Nat. Commun. 16, 5158 (2025). https://doi.org/10.1038/s41467-025-60170-0
A. Wang, X.Y. Liu, C.-Y. Mou, T. Zhang, Understanding the synergistic effects of gold bimetallic catalysts. J. Catal. 308, 258–271 (2013). https://doi.org/10.1016/j.jcat.2013.08.023
C.-J. Chang, S.-C. Lin, H.-C. Chen, J. Wang, K.J. Zheng et al., Dynamic reoxidation/reduction-driven atomic interdiffusion for highly selective CO2 reduction toward methane. J. Am. Chem. Soc. 142(28), 12119–12132 (2020). https://doi.org/10.1021/jacs.0c01859
Y. Jia, F. Li, K. Fan, L. Sun, Cu-based bimetallic electrocatalysts for CO2 reduction. Adv. Powder Mater. 1(1), 100012 (2022). https://doi.org/10.1016/j.apmate.2021.10.003
Y.-L. Liao, H.-B. Huang, R.-Y. Zou, S.-L. Shen, X.-J. Liu et al., A review of the synthesis, characterization, and mechanism of bimetallic catalysts for electrocatalytic CO2 reduction. New Carbon Mater. 39(3), 367–387 (2024). https://doi.org/10.1016/S1872-5805(24)60860-7
G. Wu, C. Zhu, J. Mao, G. Li, S. Li et al., Ampere-level CO2-to-ethanol conversion via boron-incorporated copper electrodes. ACS Energy Lett. 8(11), 4867–4874 (2023). https://doi.org/10.1021/acsenergylett.3c01901
J.-D. Yi, R. Xie, Z.-L. Xie, G.-L. Chai, T.-F. Liu et al., Highly selective CO2 electroreduction to CH4 by In Situ generated Cu2O single-type sites on a conductive MOF: stabilizing key intermediates with hydrogen bonding. Angew. Chem. Int. Ed. 59(52), 23641–23648 (2020). https://doi.org/10.1002/anie.202010601
M. Zheng, P. Wang, X. Zhi, K. Yang, Y. Jiao et al., Electrocatalytic CO2-to-C2+ with ampere-level current on heteroatom-engineered copper via tuning *CO intermediate coverage. J. Am. Chem. Soc. 144(32), 14936–14944 (2022). https://doi.org/10.1021/jacs.2c06820
X. Lv, L. Shang, S. Zhou, S. Li, Y. Wang et al., Electron-deficient Cu sites on Cu3Ag1 catalyst promoting CO2 electroreduction to alcohols. Adv. Energy Mater. 10(37), 2001987 (2020). https://doi.org/10.1002/aenm.202001987
Z. Wang, Q. Yuan, J. Shan, Z. Jiang, P. Xu et al., Highly selective electrocatalytic reduction of CO2 into methane on Cu–Bi nanoalloys. J. Phys. Chem. Lett. 11(17), 7261–7266 (2020). https://doi.org/10.1021/acs.jpclett.0c01261
P. Iyengar, M.J. Kolb, J. Pankhurst, F. Calle-Vallejo, R. Buonsanti, Theory-guided enhancement of CO2 reduction to ethanol on Ag–Cu tandem catalysts via p-size effects. ACS Catal. 11(21), 13330–13336 (2021). https://doi.org/10.1021/acscatal.1c03717
C. Peng, J. Ma, G. Luo, S. Yan, J. Zhang et al., (111) facet-oriented Cu2Mg intermetallic compound with Cu3-Mg sites for CO2 electroreduction to ethanol with industrial current density. Angew. Chem. Int. Ed. 63(17), e202316907 (2024). https://doi.org/10.1002/anie.202316907
M.C.O. Monteiro, F. Dattila, N. López, M.T.M. Koper, The role of cation acidity on the competition between hydrogen evolution and CO2 reduction on gold electrodes. J. Am. Chem. Soc. 144(4), 1589–1602 (2022). https://doi.org/10.1021/jacs.1c10171
Y.N. Xu, W. Li, H.Q. Fu, X.Y. Zhang, J.Y. Zhao et al., Tuning the microenvironment in monolayer MgAl layered double hydroxide for CO2-to-ethylene electrocatalysis in neutral media. Angew. Chem. Int. Ed. 62(19), e202217296 (2023). https://doi.org/10.1002/anie.202217296
P. Li, J. Bi, J. Liu, Y. Wang, X. Kang et al., P–d orbital hybridization induced by p-Block metal-doped Cu promotes the formation of C2+ products in Ampere-Level CO2 electroreduction. J. Am. Chem. Soc. 145(8), 4675–4682 (2023). https://doi.org/10.1021/jacs.2c12743
C.G. Morales-Guio, E.R. Cave, S.A. Nitopi, J.T. Feaster, L. Wang et al., Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst. Nat. Catal. 1(10), 764–771 (2018). https://doi.org/10.1038/s41929-018-0139-9
X. Yang, H. Ding, S. Li, S. Zheng, J.-F. Li et al., Cation-induced interfacial hydrophobic microenvironment promotes the C–C coupling in electrochemical CO2 reduction. J. Am. Chem. Soc. 146(8), 5532–5542 (2024). https://doi.org/10.1021/jacs.3c13602
P. Wei, D. Gao, T. Liu, H. Li, J. Sang et al., Coverage-driven selectivity switch from ethylene to acetate in high-rate CO2/CO electrolysis. Nat. Nanotechnol. 18(3), 299–306 (2023). https://doi.org/10.1038/s41565-022-01286-y
J. Gao, H. Zhang, X. Guo, J. Luo, S.M. Zakeeruddin et al., Selective C–C coupling in carbon dioxide electroreduction via efficient spillover of intermediates as supported by operando Raman spectroscopy. J. Am. Chem. Soc. 141(47), 18704–18714 (2019). https://doi.org/10.1021/jacs.9b07415
L. Wan, X. Zhang, J. Cheng, R. Chen, L. Wu et al., Bimetallic Cu–Zn catalysts for electrochemical CO2 reduction: phase-separated versus core–shell distribution. ACS Catal. 12(5), 2741–2748 (2022). https://doi.org/10.1021/acscatal.1c05272
D. Choukroun, L. Pacquets, C. Li, S. Hoekx, S. Arnouts et al., Mapping composition–selectivity relationships of supported sub-10 nm Cu–Ag nanocrystals for high-rate CO2 electroreduction. ACS Nano 15(9), 14858–14872 (2021). https://doi.org/10.1021/acsnano.1c04943
Y. Lum, J.W. Ager, Sequential catalysis controls selectivity in electrochemical CO2 reduction on Cu. Energy Environ. Sci. 11(10), 2935–2944 (2018). https://doi.org/10.1039/c8ee01501e
P. Iyengar, M.J. Kolb, J.R. Pankhurst, F. Calle-Vallejo, R. Buonsanti, Elucidating the facet-dependent selectivity for CO2 electroreduction to ethanol of Cu–Ag tandem catalysts. ACS Catal. 11(8), 4456–4463 (2021). https://doi.org/10.1021/acscatal.1c00420
L.R.L. Ting, O. Piqué, S.Y. Lim, M. Tanhaei, F. Calle-Vallejo et al., Enhancing CO2 electroreduction to ethanol on copper–silver composites by opening an alternative catalytic pathway. ACS Catal. 10(7), 4059–4069 (2020). https://doi.org/10.1021/acscatal.9b05319
E. Robens, B. Hecker, H. Kungl, H. Tempel, R.-A. Eichel, Bimetallic copper–silver catalysts for the electrochemical reduction of CO2 to ethanol. ACS Appl. Energy Mater. 6(14), 7571–7577 (2023). https://doi.org/10.1021/acsaem.3c00985
H. Tang, Y. Liu, Y. Zhou, Y. Qian, B.-L. Lin, Boosting the electroreduction of CO2 to ethanol via the synergistic effect of Cu–Ag bimetallic catalysts. ACS Appl. Energy Mater. 5(11), 14045–14052 (2022). https://doi.org/10.1021/acsaem.2c02595
H. Mistry, A.S. Varela, C.S. Bonifacio, I. Zegkinoglou, I. Sinev et al., Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat. Commun. 7, 12123 (2016). https://doi.org/10.1038/ncomms12123
X. Wang, K. Klingan, M. Klingenhof, T. Möller, J. Ferreira de Araújo et al., Morphology and mechanism of highly selective Cu(II) oxide nanosheet catalysts for carbon dioxide electroreduction. Nat. Commun. 12(1), 794 (2021). https://doi.org/10.1038/s41467-021-20961-7
W. Sun, P. Wang, Y. Jiang, Z. Jiang, R. Long et al., V-doped Cu2Se hierarchical nanotubes enabling flow-cell CO2 electroreduction to ethanol with high efficiency and selectivity. Adv. Mater. 34(50), 2207691 (2022). https://doi.org/10.1002/adma.202207691
Y.C. Li, Z. Wang, T. Yuan, D.-H. Nam, M. Luo et al., Binding site diversity promotes CO2 electroreduction to ethanol. J. Am. Chem. Soc. 141(21), 8584–8591 (2019). https://doi.org/10.1021/jacs.9b02945
J. Park, E.-D. Kim, S. Kim, C. Lim, H. Kim et al., Deriving an efficient and stable microenvironment for a CO2 MEA electrolyzer by reverse osmosis. ACS Energy Lett. 9(7), 3342–3350 (2024). https://doi.org/10.1021/acsenergylett.4c00933
N.-H. Tran, H.P. Duong, G. Rousse, S. Zanna, M.W. Schreiber et al., Selective ethylene production from CO2 and CO reduction via engineering membrane electrode assembly with porous dendritic copper oxide. ACS Appl. Mater. Interfaces 14(28), 31933–31941 (2022). https://doi.org/10.1021/acsami.2c06068
K. Li, W. Leigh, P. Feron, H. Yu, M. Tade, Systematic study of aqueous monoethanolamine (MEA)-based CO2 capture process: techno-economic assessment of the MEA process and its improvements. Appl. Energy 165, 648–659 (2016). https://doi.org/10.1016/j.apenergy.2015.12.109
S. Zhang, X. Yuan, H. Wang, W. Mérida, H. Zhu et al., A review of accelerated stress tests of MEA durability in PEM fuel cells. Int. J. Hydrog. Energy 34(1), 388–404 (2009). https://doi.org/10.1016/j.ijhydene.2008.10.012
J. Yu, J. Xiao, Y. Ma, J. Zhou, P. Lu et al., Acidic conditions for efficient carbon dioxide electroreduction in flow and MEA cells. Chem Catal. 3(8), 100670 (2023). https://doi.org/10.1016/j.checat.2023.100670
M. Fang, M. Wang, Z. Wang, Z. Zhang, H. Zhou et al., Hydrophobic, ultrastable Cuδ+ for robust CO2 electroreduction to C2 products at ampere-current levels. J. Am. Chem. Soc. 145(20), 11323–11332 (2023). https://doi.org/10.1021/jacs.3c02399
Z. Zhang, X. Huang, Z. Chen, J. Zhu, B. Endrődi et al., Membrane electrode assembly for electrocatalytic CO2 reduction: principle and application. Angew. Chem. Int. Ed. 62(28), e202302789 (2023). https://doi.org/10.1002/anie.202302789
X. Wang, Z. Jiang, P. Wang, Z. Chen, T. Sheng et al., Ag+-doped InSe nanosheets for membrane electrode assembly electrolyzer toward large-current electroreduction of CO2 to ethanol. Angew. Chem. Int. Ed. 62(48), e202313646 (2023). https://doi.org/10.1002/anie.202313646
N. Huang, L. Zhai, D.E. Coupry, M.A. Addicoat, K. Okushita et al., Multiple-component covalent organic frameworks. Nat. Commun. 7, 12325 (2016). https://doi.org/10.1038/ncomms12325
K. Geng, T. He, R. Liu, S. Dalapati, K.T. Tan et al., Covalent organic frameworks: design, synthesis, and functions. Chem. Rev. 120(16), 8814–8933 (2020). https://doi.org/10.1021/acs.chemrev.9b00550
R.-B. Lin, B. Chen, Reducing CO2 with stable covalent organic frameworks. Joule 2(6), 1030–1032 (2018). https://doi.org/10.1016/j.joule.2018.05.017
Y.-R. Wang, H.-M. Ding, X.-Y. Ma, M. Liu, Y.-L. Yang et al., Imparting CO2 electroreduction auxiliary for integrated morphology tuning and performance boosting in a porphyrin-based covalent organic framework. Angew. Chem. Int. Ed. 61(5), e202114648 (2022). https://doi.org/10.1002/anie.202114648
Q. Wu, M.-J. Mao, Q.-J. Wu, J. Liang, Y.-B. Huang et al., Construction of donor–acceptor heterojunctions in covalent organic framework for enhanced CO2 electroreduction. Small 17(22), 2004933 (2021). https://doi.org/10.1002/smll.202004933
A. Singh, S. Barman, F.A. Rahimi, A. Dey, R. Jena et al., Atomically dispersed Co2+ in a redox-active COF for electrochemical CO2 reduction to ethanol: unravelling mechanistic insight through operando studies. Energy Environ. Sci. 17(6), 2315–2325 (2024). https://doi.org/10.1039/d3ee02946h
Y. Xia, Q. Zhang, F. Guo, J. Wang, W. Li et al., Ag@Cu with Cu–CuO interface prepared by air cold-plasma promoting the electrocatalytic reduction of CO2 to low-carbon alcohols. Vacuum 196, 110767 (2022). https://doi.org/10.1016/j.vacuum.2021.110767
S. Liu, H. Tao, L. Zeng, Q. Liu, Z. Xu et al., Shape-dependent electrocatalytic reduction of CO2 to CO on triangular silver nanoplates. J. Am. Chem. Soc. 139(6), 2160–2163 (2017). https://doi.org/10.1021/jacs.6b12103
W. Yang, W. Ma, Z. Zhang, C. Zhao, Ligament size-dependent electrocatalytic activity of nanoporous Ag network for CO2 reduction. Faraday Discuss. 210, 289–299 (2018). https://doi.org/10.1039/c8fd00056e
J. Qin, T. Wang, M. Zhai, C. Wu, Y.A. Liu et al., Hydroxypillar [5] Arene-confined silver nanocatalyst for selective electrochemical reduction of CO2 to ethanol. Adv. Funct. Mater. 33(29), 2300697 (2023). https://doi.org/10.1002/adfm.202300697
C.-J. Zou, Z.-Y. Du, W. Tang, Q. Liu, X.-B. Liu et al., Interfacial water on Ag/Ag2S nanowires enhancing the ethanol selectivity for CO2 electroreduction. Adv. Mater. 37(37), 2503010 (2025). https://doi.org/10.1002/adma.202503010
J. Xiao, X. Pan, S. Guo, P. Ren, X. Bao, Toward fundamentals of confined catalysis in carbon nanotubes. J. Am. Chem. Soc. 137(1), 477–482 (2015). https://doi.org/10.1021/ja511498s
X. Liu, Y. Hou, F. Yang, Y. Liu, H. Yu et al., Selective CO2 electroreduction to ethanol on encapsulated nickel nanops by N-doped carbon nanotubes. Carbon 201, 460–466 (2023). https://doi.org/10.1016/j.carbon.2022.09.010
Y. Song, R. Peng, D.K. Hensley, P.V. Bonnesen, L. Liang et al., High-selectivity electrochemical conversion of CO2 to ethanol using a copper nanop/N-doped graphene electrode. ChemistrySelect 1(19), 6055–6061 (2016). https://doi.org/10.1002/slct.201601169
J. Park, C. Jeong, M. Na, Y. Oh, K.-S. Lee et al., Subnanometer Cu clusters on porous Ag enhancing ethanol production in electrochemical CO2 reduction. ACS Catal. 14(5), 3198–3207 (2024). https://doi.org/10.1021/acscatal.3c03469
M.-Z. Gu, Y. Min, L. Jiang, F. Zhou, Q. Chen et al., Subsurface engineering for directional-selective CO₂-to-ethanol electrocatalysis at industrial-level. Nat. Commun. 17(1), 488 (2025). https://doi.org/10.1038/s41467-025-67176-8
N. Zhang, Y. Zhang, Stabilizing *CO intermediate on nitrogen-doped carbon-coated CuxOy derived from metal–organic framework for enhanced electrochemical CO2-to-ethylene. J. Mater. Chem. A 13(4), 2902–2910 (2025). https://doi.org/10.1039/d4ta06722c
K. Xiang, Y. Liu, H. Yu, H. Liu, K. Li, Strategies to improve the performance of copper-based catalyst for electroreduction of CO2 to multi-carbon products. Chin. Sci. Bull. 65(31), 3360–3372 (2020). https://doi.org/10.1360/tb-2020-0014
K. Rossi, R. Buonsanti, Shaping copper nanocatalysts to steer selectivity in the electrochemical CO2 reduction reaction. Acc. Chem. Res. 55(5), 629–637 (2022). https://doi.org/10.1021/acs.accounts.1c00673
X. Su, B. Hu, Y. Zhang, C. Liu, C. Wang et al., Built-in axial electric field-driven electron-rich monomolecular co sites for promoting CO2 electroreduction to CO over ultrawide potential window. Angew. Chem. Int. Ed. 64(51), e202511671 (2025). https://doi.org/10.1002/anie.202511671
Y. Yan, M. Wu, L. Zhou, W. Chen, L. Han et al., Enhancing electrocatalytic activity through targeted local electrolyte micro-environment. Adv. Funct. Mater. 35(19), 2419328 (2025). https://doi.org/10.1002/adfm.202419328
Z. Jiang, X. Yang, J. Zhang, J. Yang, B. Sun et al., From conventional two-electron to emerging multi-electron zinc-iodine batteries: advantages, challenges, and future perspectives. Adv. Funct. Mater. 35(50), e11754 (2025). https://doi.org/10.1002/adfm.202511754