Abstract
Electrochemical carbon dioxide reduction (ECO2R) is an attractive pathway to store carbon and renewable energy as chemical bonds in multi-carbon products. However, the complex multi-step reaction processes set huge obstacles for the direct conversion of CO2 to C2+ products. A strategy that uses carbon monoxide (CO) as a “transfer station” to produce C2+ at improved selectivity and reaction rates via the tandem ECO2R to CO and electrochemical CO reduction (ECOR) has attracted a lot attention. In this review, we focus on the design strategy of Cu-based electrocatalysts toward the formation of specific C2+ products in ECOR. Representative design strategies for catalysts engineering are summarized in various aspects, and the most recent research in the improvement of electrolysis reactor is included. Finally, the main challenges and the future prospects in this research field are expounded. These insights and perspectives offer meaningful guidance for designing Cu-based electrocatalytic system with enhanced C2+ product selectivity.
摘要
电化学二氧化碳还原(ECO2R)是一种将碳和可再生能源的能量 储存在多碳产品(C2+)的化学键中的有效途径. 然而, 反应涉及的复杂步 骤为CO2直接转化为C2+设置了巨大的障碍. 一种利用CO作为“中转站”, 通过串联ECO2R和电化学CO还原(ECOR)以提高生产C2+的选择性和反 应速率的策略引起了人们的广泛关注. 本文总结了铜基电催化剂在 ECOR中催化特定C2+生成的设计策略. 其次, 从各个方面总结了催化剂 工程的代表性设计策略, 并介绍了电解反应器改进方面的最新进展. 最 后, 阐述了该研究领域面临的主要挑战和未来前景. 这些见解和观点将 为铜基电催化剂的设计提供有益指导.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Birdja YY, Pérez-Gallent E, Figueiredo MC, et al. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels. Nat Energy, 2019, 4: 732–745
Wang Y, Liu J, Zheng G. Designing copper-based catalysts for efficient carbon dioxide electroreduction. Adv Mater, 2021, 33: 2005798
Zheng Y, Vasileff A, Zhou X, et al. Understanding the roadmap for electrochemical reduction of CO2 to multi-carbon oxygenates and hydrocarbons on copper-based catalysts. J Am Chem Soc, 2019, 141: 7646–7659
Nitopi S, Bertheussen E, Scott SB, et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem Rev, 2019, 119: 7610–7672
Fu J, Li P, Lin Y, et al. Fight for carbon neutrality with state-of-the-art negative carbon emission technologies. Eco-Environ Health, 2022, 1: 259–279
Liu J, Zhu C, Liu X, et al. Nonmicrobial mechanisms dominate the release of CO2 and the decomposition of organic matter during the short-term redox process in paddy soil slurry. Eco-Environ Health, 2023, 2: 227–234
Zaidi SAH, Hussain M, Uz Zaman Q. Dynamic linkages between financial inclusion and carbon emissions: Evidence from selected OECD countries. Resources Environ Sustainability, 2021, 4: 100022
Wang F, Liu J, Qin G, et al. Coastal blue carbon in China as a nature-based solution toward carbon neutrality. Innovation, 2023, 4: 100481
Hui S, Jiang Y, Jiang Y, et al. Cathode materials in microbial electrosynthesis systems for carbon dioxide reduction: Recent progress and perspectives. Energy Mater, 2023, 3: 300055
Chen JM. Carbon neutrality: Toward a sustainable future. Innovation, 2021, 2: 100127
Wang F, Harindintwali JD, Yuan Z, et al. Technologies and perspectives for achieving carbon neutrality. Innovation, 2021, 2: 100180
Jiang Y, Tian S, Li H, et al. Harnessing microbial electrosynthesis for a sustainable future. TIMS, 2023, 1: 100008
Cao C, Zhou S, Zuo S, et al. Si doping-induced electronic structure regulation of single-atom Fe sites for boosted CO2 electroreduction at low overpotentials. Research, 2023, 6: 0079
Zhu W, Fu J, Liu J, et al. Tuning single atom-nanoparticle ratios of Ni-based catalysts for synthesis gas production from CO2. Appl Catal B-Environ, 2020, 264: 118502
Liu LX, Zhou Y, Chang YC, et al. Tuning Sn3O4 for CO2 reduction to formate with ultra-high current density. Nano Energy, 2020, 77: 105296
Zhu W, Michalsky R, Metin Ö, et al. Monodisperse Au nanoparticles for selective electrocatalytic reduction of CO2 to CO. J Am Chem Soc, 2013, 135: 16833–16836
Masood ul Hasan I, Peng L, Mao J, et al. Carbon-based metal-free catalysts for electrochemical CO2 reduction: Activity, selectivity, and stability. Carbon Energy, 2021, 3: 24–49
Li X, Chen Y, Zhan X, et al. Strategies for enhancing electrochemical CO2 reduction to multi-carbon fuels on copper. TIMS, 2023, 1: 100014
Wu Y, Du H, Li P, et al. Heterogeneous electrocatalysis of carbon dioxide to methane. Methane, 2023, 2: 148–175
Wang X, Li P, Cao Y, et al. Techno-economic analysis and industrial application prospects of single-atom materials in CO2 catalysis. Chem J Chin U, 2022, 43: 20220347
Ross MB, De Luna P, Li Y, et al. Designing materials for electrochemical carbon dioxide recycling. Nat Catal, 2019, 2: 648–658
Lu X, Tong D, He K. China’s carbon neutrality: An extensive and profound systemic reform. Front Environ Sci Eng, 2023, 17: 14
Yang H, Huang X, Hu J, et al. Achievements, challenges and global implications of China’s carbon neutral pledge. Front Environ Sci Eng, 2022, 16: 111
Li L, Zhao ZJ, Zhang G, et al. Neural network accelerated investigation of the dynamic structure–performance relations of electrochemical CO2 reduction over SnOx surfaces. Research, 2023, 6: 0067
Dinh CT, García de Arquer FP, Sinton D, et al. High rate, selective, and stable electroreduction of CO2 to CO in basic and neutral media. ACS Energy Lett, 2018, 3: 2835–2840
Kim JYT, Zhu P, Chen FY, et al. Recovering carbon losses in CO2 electrolysis using a solid electrolyte reactor. Nat Catal, 2022, 5: 288–299
Xie L, Jiang Y, Zhu W, et al. Cu-based catalyst designs in CO2 electroreduction: Precise modulation of reaction intermediates for high-value chemical generation. Chem Sci, 2023, 14: 13629–13660
Zhu W, Zhang YJ, Zhang H, et al. Active and selective conversion of CO2 to CO on ultrathin Au nanowires. J Am Chem Soc, 2014, 136: 16132–16135
Cai Y, Fu J, Zhou Y, et al. Insights on forming N,O-coordinated Cu single-atom catalysts for electrochemical reduction CO2 to methane. Nat Commun, 2021, 12: 586
Cho JH, Ma J, Kim SY. Toward high-efficiency photovoltaics-assisted electrochemical and photoelectrochemical CO2 reduction: Strategy and challenge. Exploration, 2023, 3: 20230001
Zhu F, Ge J, Gao Y, et al. Molten salt electro-preparation of graphitic carbons. Exploration, 2023, 3: 20210186
Jin S, Hao Z, Zhang K, et al. Advances and challenges for the electrochemical reduction of CO2 to CO: From fundamentals to industrialization. Angew Chem Int Ed, 2021, 60: 20627–20648
Chen Z, Wang C, Zhong X, et al. Achieving efficient CO2 electrolysis to CO by local coordination manipulation of nickel single-atom catalysts. Nano Lett, 2023, 23: 7046–7053
Zhu W, Kattel S, Jiao F, et al. Shape-controlled CO2 electrochemical reduction on nanosized Pd hydride cubes and octahedra. Adv Energy Mater, 2019, 9: 1802840
Song RB, Zhu W, Fu J, et al. Electrode materials engineering in electrocatalytic CO2 reduction: Energy input and conversion efficiency. Adv Mater, 2020, 32: 1903796
Chen Y, Zhang J, Yang L, et al. Recent advances in non-precious metal–nitrogen–carbon single-site catalysts for CO2 electroreduction reaction to CO. Electrochem Energy Rev, 2022, 5: 11
Nguyen DLT, Kim Y, Hwang YJ, et al. Progress in development of electrocatalyst for CO2 conversion to selective CO production. Carbon Energy, 2020, 2: 72–98
Yan C, Yuan H, Wang X, et al. Sn-doping stabilizes residual oxygen species to promote intermediate desorption for enhanced CO2 to CO conversion. Sci China Mater, 2023, 66: 3547–3554
Jiao F, Li J, Pan X, et al. Selective conversion of syngas to light olefins. Science, 2016, 351: 1065–1068
Xu M, Qin X, Xu Y, et al. Boosting CO hydrogenation towards C2+ hydrocarbons over interfacial TiO2−x/Ni catalysts. Nat Commun, 2022, 13: 6720
Liang X, Meng X, Yang J, et al. Liquid viscosity and density of squalane and squalane with dissolved carbon dioxide at temperatures from (298.15 to 548.15) K. Int J Thermophys, 2023, 44: 168
Zhou W, Cheng K, Kang J, et al. New horizon in C1 chemistry: Breaking the selectivity limitation in transformation of syngas and hydrogenation of CO2 into hydrocarbon chemicals and fuels. Chem Soc Rev, 2019, 48: 3193–3228
Wentrup J, Pesch GR, Thöming J. Dynamic operation of Fischer-Tropsch reactors for power-to-liquid concepts: A review. Renew Sustain Energy Rev, 2022, 162: 112454
Wu HK, Zhang F, Li JY, et al. Photo-driven Fischer–Tropsch synthesis. J Mater Chem A, 2020, 8: 24253–24266
Du H, Fu J, Liu LX, et al. Recent progress in electrochemical reduction of carbon monoxide toward multi-carbon products. Mater Today, 2022, 59: 182–199
Kim JYT, Sellers C, Hao S, et al. Different distributions of multicarbon products in CO2 and CO electroreduction under practical reaction conditions. Nat Catal, 2023, 6: 1115–1124
Jouny M, Hutchings GS, Jiao F. Carbon monoxide electroreduction as an emerging platform for carbon utilization. Nat Catal, 2019, 2: 1062–1070
Overa S, Crandall BS, Shrimant B, et al. Enhancing acetate selectivity by coupling anodic oxidation to carbon monoxide electroreduction. Nat Catal, 2022, 5: 738–745
Li J, Chang K, Zhang H, et al. Effectively increased efficiency for electroreduction of carbon monoxide using supported polycrystalline copper powder electrocatalysts. ACS Catal, 2019, 9: 4709–4718
Ma M, Deng W, Xu A, et al. Local reaction environment for selective electroreduction of carbon monoxide. Energy Environ Sci, 2022, 15: 2470–2478
Ozden A, García de Arquer FP, Huang JE, et al. Carbon-efficient carbon dioxide electrolysers. Nat Sustain, 2022, 5: 563–573
Yu SH, Antonietti M. Creative and relevant materials innovation. TIMS, 2023, 1: 100002
Xiang Y, Sun Y, Liu Y, et al. Computational design of a two-dimensional copper carbide monolayer as a highly efficient catalyst for carbon monoxide electroreduction to ethanol. ACS Appl Mater Interfaces, 2023, 15: 13033–13041
Ji Y, Guan A, Zheng G. Copper-based catalysts for electrochemical carbon monoxide reduction. Cell Rep Phys Sci, 2022, 3: 101072
Zhang H, Li J, Cheng MJ, et al. CO electroreduction: Current development and understanding of Cu-based catalysts. ACS Catal, 2019, 9: 49–65
Yu J, Wang J, Ma Y, et al. Recent progresses in electrochemical carbon dioxide reduction on copper-based catalysts toward multicarbon products. Adv Funct Mater, 2021, 31: 2102151
Jin J, Wicks J, Min Q, et al. Constrained C2 adsorbate orientation enables CO-to-acetate electroreduction. Nature, 2023, 617: 724–729
Gao A, Gu L. Insight into materials science from a reductionist perspective. TIMS, 2023, 1: 100009
Duong HP, Rivera de la Cruz JG, Tran NH, et al. Silver and copper nitride cooperate for CO electroreduction to propanol. Angew Chem Int Ed, 2023, 62: e202310788
Liu J, You F, He B, et al. Directing the architecture of surface-clean Cu2O for CO electroreduction. J Am Chem Soc, 2022, 144: 12410–12420
Shi Q, Zhu W, Zhong H, et al. Highly dispersed platinum atoms on the surface of AuCu metallic aerogels for enabling H2O2 production. ACS Appl Energy Mater, 2019, 2: 7722–7727
Luo M, Ozden A, Wang Z, et al. Coordination polymer electro-catalysts enable efficient CO-to-acetate conversion. Adv Mater, 2023, 35: 2209567
Du H, Liu LX, Cai Y, et al. In situ formed N-containing copper nanoparticles: A high-performance catalyst toward carbon monoxide electroreduction to multicarbon products with high faradaic efficiency and current density. Nanoscale, 2022, 14: 7262–7268
Lai J, Zhang Z, Yang> X, et al. Opening the black box: Insights into the restructuring mechanism to steer catalytic performance. TIMS, 2023, 1: 100020
Wu ZZ, Zhang XL, Yang PP, et al. Gerhardtite as a precursor to an efficient CO-to-acetate electroreduction catalyst. J Am Chem Soc, 2023, 145: 24338–24348
Hou J, Chang X, Li J, et al. Correlating CO coverage and CO electroreduction on Cu via high-pressure in situ spectroscopic and reactivity investigations. J Am Chem Soc, 2022, 144: 22202–22211
Yang W, Liu H, Qi Y, et al. Boosting C–C coupling to multicarbon products via high-pressure CO electroreduction. J Energy Chem, 2023, 85: 102–107
Du J, Chen A, Hou S, et al. CNT modified by mesoporous carbon anchored by Ni nanoparticles for CO2 electrochemical reduction. Carbon Energy, 2022, 4: 1274–1284
Ruqia B, Tomboc GM, Kwon T, et al. Recent advances in the electrochemical CO reduction reaction towards highly selective formation of CX products (X = 1–3). Chem Catal, 2022, 2: 1961–1988
De Luna P, Hahn C, Higgins D, et al. What would it take for renewably powered electrosynthesis to displace petrochemical processes? Science, 2019, 364: eaav3506
Yi JD, Gao X, Zhou H, et al. Design of Co-Cu diatomic site catalysts for high-efficiency synergistic CO2 electroreduction at industrial-level current density. Angew Chem Int Ed, 2022, 61: e202212329
Martin AJ, Larrazábal GO, Pérez-Ramírez J. Towards sustainable fuels and chemicals through the electrochemical reduction of CO2: Lessons from water electrolysis. Green Chem, 2015, 17: 5114–5130
Li J, Wang Z, McCallum C, et al. Constraining CO coverage on copper promotes high-efficiency ethylene electroproduction. Nat Catal, 2019, 2: 1124–1131
Ma G, Syzgantseva OA, Huang Y, et al. A hydrophobic Cu/Cu2O sheet catalyst for selective electroreduction of CO to ethanol. Nat Commun, 2023, 14: 501
Niu W, Chen Z, Guo W, et al. Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion. Nat Commun, 2023, 14: 4882
Yin Z, Peng H, Wei X, et al. An alkaline polymer electrolyte CO2 electrolyzer operated with pure water. Energy Environ Sci, 2019, 12: 2455–2462
Lagadec MF, Grimaud A. Water electrolysers with closed and open electrochemical systems. Nat Mater, 2020, 19: 1140–1150
Möller T, Ju W, Bagger A, et al. Efficient CO2 to CO electrolysis on solid Ni–N–C catalysts at industrial current densities. Energy Environ Sci, 2019, 12: 640–647
Wei P, Li H, Lin L, et al. CO2 electrolysis at industrial current densities using anion exchange membrane based electrolyzers. Sci China Chem, 2020, 63: 1711–1715
She X, Wang Y, Xu H, et al. Challenges and opportunities in electrocatalytic CO2 reduction to chemicals and fuels. Angew Chem Int Ed, 2022, 61: e202211396
Xiang SQ, Shi JL, Gao ST, et al. Thermodynamic and kinetic competition between C–H and O–H bond formation pathways during electrochemical reduction of CO on copper electrodes. ACS Catal, 2021, 11: 2422–2434
Montoya JH, Shi C, Chan K, et al. Theoretical insights into a CO dimerization mechanism in CO2 electroreduction. J Phys Chem Lett, 2015, 6: 2032–2037
Goodpaster JD, Bell AT, Head-Gordon M. Identification of possible pathways for C–C bond formation during electrochemical reduction of CO2: New theoretical insights from an improved electrochemical model. J Phys Chem Lett, 2016, 7: 1471–1477
Garza AJ, Bell AT, Head-Gordon M. Mechanism of CO2 reduction at copper surfaces: Pathways to C2 products. ACS Catal, 2018, 8: 1490–1499
Wang L, Nitopi SA, Bertheussen E, et al. Electrochemical carbon monoxide reduction on polycrystalline copper: Effects of potential, pressure, and pH on selectivity toward multicarbon and oxygenated products. ACS Catal, 2018, 8: 7445–7454
Lin Y, Wang T, Zhang L, et al. Tunable CO2 electroreduction to ethanol and ethylene with controllable interfacial wettability. Nat Commun, 2023, 14: 3575
Ma W, Xie S, Liu T, et al. Electrocatalytic reduction of CO2 to ethylene and ethanol through hydrogen-assisted C–C coupling over fluorine-modified copper. Nat Catal, 2020, 3: 478–487
Cheng T, Xiao H, Goddard WA. Nature of the active sites for CO reduction on copper nanoparticles; suggestions for optimizing performance. J Am Chem Soc, 2017, 139: 11642–11645
Pérez-Gallent E, Figueiredo MC, Calle-Vallejo F, et al. Spectroscopic observation of a hydrogenated CO dimer intermediate during CO reduction on Cu(100) electrodes. Angew Chem Int Ed, 2017, 56: 3621–3624
Calle-Vallejo F, Koper MTM. Theoretical considerations on the electroreduction of CO to C2 species on Cu(100) electrodes. Angew Chem Int Ed, 2013, 52: 7282–7285
Chen R, Su H, Liu D, et al. Highly selective production of ethylene by the electroreduction of carbon monoxide. Angew Chem Int Ed, 2020, 59: 154–160
Lum Y, Cheng T, Goddard III WA, et al. Electrochemical CO reduction builds solvent water into oxygenate products. J Am Chem Soc, 2018, 140: 9337–9340
Ni F, Yang H, Wen Y, et al. N-modulated Cu+ for efficient electrochemical carbon monoxide reduction to acetate. Sci China Mater, 2020, 63: 2606–2612
Sun Q, Zhao Y, Tan X, et al. Atomically dispersed Cu–Au alloy for efficient electrocatalytic reduction of carbon monoxide to acetate. ACS Catal, 2023, 13: 5689–5696
Jouny M, Lv JJ, Cheng T, et al. Formation of carbon–nitrogen bonds in carbon monoxide electrolysis. Nat Chem, 2019, 11: 846–851
Jouny M, Luc W, Jiao F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat Catal, 2018, 1: 748–755
Wei P, Gao D, Liu T, et al. Coverage-driven selectivity switch from ethylene to acetate in high-rate CO2/CO electrolysis. Nat Nanotechnol, 2023, 18: 299–306
Pang Y, Li J, Wang Z, et al. Efficient electrocatalytic conversion of carbon monoxide to propanol using fragmented copper. Nat Catal, 2019, 2: 251–258
Xiao H, Cheng T, Goddard III WA. Atomistic mechanisms underlying selectivities in C1 and C2 products from electrochemical reduction of CO on Cu(111). J Am Chem Soc, 2017, 139: 130–136
Zhuang TT, Pang Y, Liang ZQ, et al. Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide. Nat Catal, 2018, 1: 946–951
Liu C, Zhang M, Li J, et al. Nanoconfinement engineering over hollow multi-shell structured copper towards efficient electrocatalytical C–C coupling. Angew Chem Int Ed, 2022, 61: e202113498
Du M, Li X, Pang H, et al. Alloy electrocatalysts. EnergyChem, 2023, 5: 100083
Zhu W, Tackett BM, Chen JG, et al. Bimetallic electrocatalysts for CO2 reduction. Top Curr Chem (Z), 2018, 376: 41
Zhang J, Yu P, Peng C, et al. Efficient CO electroreduction to methanol by CuRh alloys with isolated Rh sites. ACS Catal, 2023, 13: 7170–7177
Chen T, Liu T, Shen X, et al. Synergistically electronic tuning of metalloid CdSe nanorods for enhanced electrochemical CO2 reduction. Sci China Mater, 2021, 64: 2997–3006
Zhang J, Sui R, Xue Y, et al. Direct synthesis of parallel doped N-MoP/ N-CNT as highly active hydrogen evolution reaction catalyst. Sci China Mater, 2019, 62: 690–698
Zhou Y, Zhou Z, Chen M, et al. Doping and alloying for improved perovskite solar cells. J Mater Chem A, 2016, 4: 17623–17635
Huang H, Jia H, Liu Z, et al. Understanding of strain effects in the electrochemical reduction of CO2: Using Pd nanostructures as an ideal platform. Angew Chem Int Ed, 2017, 56: 3594–3598
Wang L, Higgins DC, Ji Y, et al. Selective reduction of CO to acetaldehyde with CuAg electrocatalysts. Proc Natl Acad Sci USA, 2020, 117: 12572–12575
Wang X, Wang Z, Zhuang TT, et al. Efficient upgrading of CO to C3 fuel using asymmetric C–C coupling active sites. Nat Commun, 2019, 10: 5186
Li J, Xu A, Li F, et al. Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption. Nat Commun, 2020, 11: 3685
Dorakhan R, Grigioni I, Lee BH, et al. A silver–copper oxide catalyst for acetate electrosynthesis from carbon monoxide. Nat Synth, 2023, 2: 448–457
Li J, Xiong H, Liu X, et al. Weak CO binding sites induced by Cu–Ag interfaces promote CO electroreduction to multi-carbon liquid products. Nat Commun, 2023, 14: 698
Mu Z, Han N, Xu D, et al. Critical role of hydrogen sorption kinetics in electrocatalytic CO2 reduction revealed by on-chip in situ transport investigations. Nat Commun, 2022, 13: 6911
Shen H, Wang Y, Chakraborty T, et al. Asymmetrical C–C coupling for electroreduction of CO on bimetallic Cu–Pd catalysts. ACS Catal, 2022, 12: 5275–5283
Ji Y, Chen Z, Wei R, et al. Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu–Pd sites. Nat Catal, 2022, 5: 251–258
Nørskov JK, Bligaard T, Rossmeisl J, et al. Towards the computational design of solid catalysts. Nat Chem, 2009, 1: 37–46
Yuan X, Zhang L, Li L, et al. Ultrathin Pd–Au shells with controllable alloying degree on Pd nanocubes toward carbon dioxide reduction. J Am Chem Soc, 2019, 141: 4791–4794
Wang X, Ou P, Ozden A, et al. Efficient electrosynthesis of n-propanol from carbon monoxide using a Ag–Ru–Cu catalyst. Nat Energy, 2022, 7: 170–176
Dong H, Zhang X, Li J, et al. Construction of morphology-controlled nonmetal 2D/3D homojunction towards enhancing photocatalytic activity and mechanism insight. Appl Catal B-Environ, 2020, 263: 118270
Shakeel M, Arif M, Yasin G, et al. Layered by layered Ni-Mn-LDH/g-C3N4 nanohybrid for multi-purpose photo/electrocatalysis: Morphology controlled strategy for effective charge carriers separation. Appl Catal B-Environ, 2019, 242: 485–498
Hu Q, Qin Y, Wang X, et al. Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate-ammonia conversion. Energy Environ Sci, 2021, 14: 4989–4997
Meng X, Yang Y, Chen L, et al. A control over hydrogenation selectivity of furfural via tuning exposed facet of Ni catalysts. ACS Catal, 2019, 9: 4226–4235
Zhang M, Xiao C, Yan X, et al. Efficient removal of organic pollutants by metal–organic framework derived Co/C yolk-shell nanoreactors: Size-exclusion and confinement effect. Environ Sci Technol, 2020, 54: 10289–10300
Liu W, Qi J, Bai P, et al. Utilizing spatial confinement effect of N atoms in micropores of coal-based metal-free material for efficiently electrochemical reduction of carbon dioxide. Appl Catal B-Environ, 2020, 272: 118974
Raciti D, Cao L, Livi KJT, et al. Low-overpotential electroreduction of carbon monoxide using copper nanowires. ACS Catal, 2017, 7: 4467–4472
Luc W, Fu X, Shi J, et al. Two-dimensional copper nanosheets for electrochemical reduction of carbon monoxide to acetate. Nat Catal, 2019, 2: 423–430
Du H, Liu LX, Li P, et al. Enriching reaction intermediates in multishell structured copper catalysts for boosted propanol electrosynthesis from carbon monoxide. ACS Nano, 2023, 17: 8663–8670
Li F, Thevenon A, Rosas-Hernández A, et al. Molecular tuning of CO2-to-ethylene conversion. Nature, 2020, 577: 509–513
Zhou X, Shan J, Zheng M, et al. Tuning molecular electrophilicity on Cu catalysts to steer CO2 electroreduction selectivity. Sci China Mater, 2023, doi: https://doi.org/10.1007/s40843-023-2676-y
Ji Y, Yang C, Qian L, et al. Promoting electrocatalytic carbon monoxide reduction to ethylene on copper-polypyrrole interface. J Colloid Interface Sci, 2021, 600: 847–853
Wang Y, Zhao J, Cao C, et al. Amino-functionalized Cu for efficient electrochemical reduction of CO to acetate. ACS Catal, 2023, 13: 3532–3540
Piqué O, Viñes F, Illas F, et al. Elucidating the structure of ethanol-producing active sites at oxide-derived Cu electrocatalysts. ACS Catal, 2020, 10: 10488–10494
Obasanjo CA, Zeraati AS, Shiran HS, et al. In situ regeneration of copper catalysts for long-term electrochemical CO2 reduction to multiple carbon products. J Mater Chem A, 2022, 10: 20059–20070
Hu Y, Wang X, Zhang J, et al. In situ engineering 3D conductive core-shell nano-networks and electronic structure of bismuth alloy nanosheets for efficient electrocatalytic CO2 reduction. Sci China Mater, 2023, 66: 2266–2273
Zhao Q, Wang J, Zhuang Y, et al. In situ reconstruction of Bi nano-particles confined within 3D nanoporous Cu to boost CO2 electroreduction. Sci China Mater, 2024, 67: 796–803
Sang J, Wei P, Liu T, et al. A reconstructed Cu2P2O7 catalyst for selective CO2 electroreduction to multicarbon products. Angew Chem Int Ed, 2022, 61: e202114238
Long C, Liu X, Wan K, et al. Regulating reconstruction of oxide-derived Cu for electrochemical CO2 reduction toward n-propanol. Sci Adv, 2023, 9: eadi6119
Wang S, Wang D, Tian B, et al. Synergistic Cu+/Cu0 on Cu2O-Cu interfaces for efficient and selective C2+ production in electrocatalytic CO2 conversion. Sci China Mater, 2023, 66: 1801–1809
Deng B, Huang M, Li K, et al. The crystal plane is not the key factor for CO2-to-methane electrosynthesis on reconstructed Cu2O micro-particles. Angew Chem Int Ed, 2022, 61: e202114080
Mu S, Lu H, Wu Q, et al. Hydroxyl radicals dominate reoxidation of oxide-derived Cu in electrochemical CO2 reduction. Nat Commun, 2022, 13: 3694
Gandionco KA, Kim J, Bekaert L, et al. Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates. Carbon Energy, 2024, 6: e410
Lum Y, Ager JW. Stability of residual oxides in oxide-derived copper catalysts for electrochemical CO2 reduction investigated with 18O labeling. Angew Chem Int Ed, 2018, 57: 551–554
Li CW, Ciston J, Kanan MW. Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper. Nature, 2014, 508: 504–507
Jiang K, Huang Y, Zeng G, et al. Effects of surface roughness on the electrochemical reduction of CO2 over Cu. ACS Energy Lett, 2020, 5: 1206–1214
Mariano RG, McKelvey K, White HS, et al. Selective increase in CO2 electroreduction activity at grain-boundary surface terminations. Science, 2017, 358: 1187–1192
Long C, Wan K, Chen Y, et al. Steering the reconstruction of oxide-derived Cu by secondary metal for electrosynthesis of n-propanol from CO. J Am Chem Soc, 2024, 146: 4632–4641
Martić N, Reller C, Macauley C, et al. Ag2Cu2O3—A catalyst template material for selective electroreduction of CO to C2+ products. Energy Environ Sci, 2020, 13: 2993–3006
Rong Y, Liu T, Sang J, et al. Directing the selectivity of CO electrolysis to acetate by constructing metal-organic interfaces. Angew Chem Int Ed, 2023, 62: e202309893
Wang Q, Lei Y, Wang D, et al. Defect engineering in earth-abundant electrocatalysts for CO2 and N2 reduction. Energy Environ Sci, 2019, 12: 1730–1750
Shah SSA, Sufyan Javed M, Najam T, et al. Metal oxides for the electrocatalytic reduction of carbon dioxide: Mechanism of active sites, composites, interface and defect engineering strategies. Coord Chem Rev, 2022, 471: 214716
Cui B, Liu C, Zhang J, et al. Waste to wealth: Defect-rich Ni-incorporated spent LiFePO4 for efficient oxygen evolution reaction. Sci China Mater, 2021, 64: 2710–2718
Yan X, Zhuang L, Zhu Z, et al. Defect engineering and characterization of active sites for efficient electrocatalysis. Nanoscale, 2021, 13: 3327–3345
Zhang Y, Tao L, Xie C, et al. Defect engineering on electrode materials for rechargeable batteries. Adv Mater, 2020, 32: 1905923
Zhu K, Shi F, Zhu X, et al. The roles of oxygen vacancies in electrocatalytic oxygen evolution reaction. Nano Energy, 2020, 73: 104761
Jiang W, Loh H, Low BQL, et al. Role of oxygen vacancy in metal oxides for photocatalytic CO2 reduction. Appl Catal B-Environ, 2023, 321: 122079
Yang T, Lin L, Lv X, et al. Interfacial synergy between the Cu atomic layer and CeO2 promotes CO electrocoupling to acetate. ACS Nano, 2023, 17: 8521–8529
Zhang J, Wang Y, Li Z, et al. Grain boundary-derived Cu+/Cu0 interfaces in CuO nanosheets for low overpotential carbon dioxide electroreduction to ethylene. Adv Sci, 2022, 9: 2200454
van Swygenhoven H, Farkas D, Caro A. Grain-boundary structures in polycrystalline metals at the nanoscale. Phys Rev B, 2000, 62: 831–838
Wang J, Cheng C, Huang B, et al. Grain-boundary-engineered La2CuO4 perovskite nanobamboos for efficient CO2 reduction reaction. Nano Lett, 2021, 21: 980–987
Feng X, Jiang K, Fan S, et al. A direct grain-boundary-activity correlation for CO electroreduction on Cu nanoparticles. ACS Cent Sci, 2016, 2: 169–174
Thirathipviwat P, Sato S, Song G, et al. A role of atomic size misfit in lattice distortion and solid solution strengthening of TiNbHfTaZr high entropy alloy system. Scripta Mater, 2022, 210: 114470
Dholabhai PP, Uberuaga BP. Beyond coherent oxide heterostructures: Atomic-scale structure of misfit dislocations. Advcd Theor Sims, 2019, 2: 1900078
Li Z, Fu JY, Feng Y, et al. A silver catalyst activated by stacking faults for the hydrogen evolution reaction. Nat Catal, 2019, 2: 1107–1114
Lv J, Yin R, Zhou L, et al. Microenvironment engineering for the electrocatalytic CO2 reduction reaction. Angew Chem Int Ed, 2022, 61: e202207252
Chen J, Wang L. Effects of the catalyst dynamic changes and influence of the reaction environment on the performance of electrochemical CO2 reduction. Adv Mater, 2022, 34: 2103900
Jiang H, Luo R, Li Y, et al. Recent advances in solid-liquid-gas three-phase interfaces in electrocatalysis for energy conversion and storage. EcoMat, 2022, 4: e12199
Fei H, Dong J, Chen D, et al. Single atom electrocatalysts supported on graphene or graphene-like carbons. Chem Soc Rev, 2019, 48: 5207–5241
van Deelen TW, Hernández Mejía C, de Jong KP. Control of metal-support interactions in heterogeneous catalysts to enhance activity and selectivity. Nat Catal, 2019, 2: 955–970
Yue P, Fu Q, Li J, et al. Triple-phase electrocatalysis for the enhanced CO2 reduction to HCOOH on a hydrophobic surface. Chem Eng J, 2021, 405: 126975
Zhou L, Li C, Lv J, et al. Synergistic regulation of hydrophobicity and basicity for copper hydroxide-derived copper to promote the CO2 electroreduction reaction. Carbon Energy, 2023, 5: e328
Park S, Grigioni I, Alkayyali T, et al. High carbon efficiency in CO-to-alcohol electroreduction using a CO reservoir. Joule, 2023, 7: 2335–2348
Duan GY, Li XL, Ding GR, et al. Highly efficient electrocatalytic CO2 reduction to C2+ products on a poly(ionic liquid)-based Cu0-CuI tandem catalyst. Angew Chem Int Ed, 2022, 61: e202110657
Duan GY, Li XQ, Chen JW, et al. Poly(ionic liquid) boosts overall performance of electrocatalytic reduction of low concentration of CO gas. Chem Eng J, 2023, 451: 138491
Rabiee H, Ge L, Zhang X, et al. Gas diffusion electrodes (GDEs) for electrochemical reduction of carbon dioxide, carbon monoxide, and dinitrogen to value-added products: A review. Energy Environ Sci, 2021, 14: 1959–2008
Nguyen TN, Dinh CT. Gas diffusion electrode design for electrochemical carbon dioxide reduction. Chem Soc Rev, 2020, 49: 7488–7504
Wakerley D, Lamaison S, Wicks J, et al. Gas diffusion electrodes, reactor designs and key metrics of low-temperature CO2 electrolysers. Nat Energy, 2022, 7: 130–143
Xu Q, Xu A, Garg S, et al. Enriching surface-accessible CO2 in the zero-gap anion-exchange-membrane-based CO2 electrolyzer. Angew Chem Int Ed, 2023, 62: e202214383
Weng LC, Bell AT, Weber AZ. Towards membrane-electrode assembly systems for CO2 reduction: A modeling study. Energy Environ Sci, 2019, 12: 1950–1968
Hasa B, Cherniack L, Xia R, et al. Benchmarking anion-exchange membranes for electrocatalytic carbon monoxide reduction. Chem Catal, 2023, 3: 100450
Rabinowitz JA, Ripatti DS, Mariano RG, et al. Improving the energy efficiency of CO electrolysis by controlling Cu domain size in gas diffusion electrodes. ACS Energy Lett, 2022, 7: 4098–4105
Ripatti DS, Veltman TR, Kanan MW. Carbon monoxide gas diffusion electrolysis that produces concentrated C2 products with high singlepass conversion. Joule, 2019, 3: 240–256
Higgins D, Hahn C, Xiang C, et al. Gas-diffusion electrodes for carbon dioxide reduction: A new paradigm. ACS Energy Lett, 2018, 4: 317–324
Lees EW, Mowbray BAW, Parlane FGL, et al. Gas diffusion electrodes and membranes for CO2 reduction electrolysers. Nat Rev Mater, 2022, 7: 55–64
Xu Q, Garg S, Moss AB, et al. Identifying and alleviating the durability challenges in membrane-electrode-assembly devices for high-rate CO electrolysis. Nat Catal, 2023, 6: 1042–1051
Wang Q, Dong H, Yu H, et al. Enhanced performance of gas diffusion electrode for electrochemical reduction of carbon dioxide to formate by adding polytetrafluoroethylene into catalyst layer. J Power Sources, 2015, 279: 1–5
Rabiee H, Heffernan JK, Ge L, et al. Tuning flow-through Cu-based hollow fiber gas-diffusion electrode for high-efficiency carbon monoxide (CO) electroreduction to C2+ products. Appl Catal B-Environ, 2023, 330: 122589
Ji Y, Shi Y, Liu C, et al. Plasma-regulated N-doped carbon nanotube arrays for efficient electrosynthesis of syngas with a wide CO/H2 ratio. Sci China Mater, 2020, 63: 2351–2357
Qiu N, Li J, Wang H, et al. Emerging dual-atomic-site catalysts for electrocatalytic CO2 reduction. Sci China Mater, 2022, 65: 3302–3323
Wang Z, Zou G, Park JH, et al. Progress in design and preparation of multi-atom catalysts for photocatalytic CO2 reduction. Sci China Mater, 2024, 67: 397–423
Yang C, Gao Z, Wang D, et al. Bimetallic phthalocyanine hetero-structure used for highly selective electrocatalytic CO2 reduction. Sci China Mater, 2022, 65: 155–162
Yang M, Sun J, Qin Y, et al. Hollow CoFe-layered double hydroxide polyhedrons for highly efficient CO2 electrolysis. Sci China Mater, 2022, 65: 536–542
Gong L, Zhang D, Lin CY, et al. Catalytic mechanisms and design principles for single-atom catalysts in highly efficient CO2 conversion. Adv Energy Mater, 2019, 9: 1902625
Yang Z, Gao W, Jiang Q. A machine learning scheme for the catalytic activity of alloys with intrinsic descriptors. J Mater Chem A, 2020, 8: 17507–17515
Vasilyev DV, Shyshkanov S, Shirzadi E, et al. Principal descriptors of ionic liquid co-catalysts for the electrochemical reduction of CO2. ACS Appl Energy Mater, 2020, 3: 4690–4698
Yuan H, Li Z, Zeng XC, et al. Descriptor-based design principle for two-dimensional single-atom catalysts: Carbon dioxide electroreduction. J Phys Chem Lett, 2020, 11: 3481–3487
Gao W, Xu Y, Xiong H, et al. CO binding energy is an incomplete descriptor of Cu-based catalysts for the electrochemical CO2 reduction reaction. Angew Chem, 2023, 135: e202313798
Yin Z, Yu J, Xie Z, et al. Hybrid catalyst coupling single-atom Ni and nanoscale Cu for efficient CO2 electroreduction to ethylene. J Am Chem Soc, 2022, 144: 20931–20938
Feng J, Zhang L, Liu S, et al. Modulating adsorbed hydrogen drives electrochemical CO2-to-C2 products. Nat Commun, 2023, 14: 4615
Zhang L, Yang X, Yuan Q, et al. Elucidating the structure-stability relationship of Cu single-atom catalysts using operando surface-enhanced infrared absorption spectroscopy. Nat Commun, 2023, 14: 8311
Jordaan SM, Wang C. Electrocatalytic conversion of carbon dioxide for the Paris goals. Nat Catal, 2021, 4: 915–920
Chang F, Xiao M, Miao R, et al. Copper-based catalysts for electrochemical carbon dioxide reduction to multicarbon products. Electrochem Energy Rev, 2022, 5: 4
Wang X, Hu Q, Li G, et al. Recent advances and perspectives of electrochemical CO2 reduction toward C2+ products on Cu-based catalysts. Electrochem Energy Rev, 2022, 5: 28
Dai Y, Kong F, Tai X, et al. Advances in graphene-supported singleatom catalysts for clean energy conversion. Electrochem Energy Rev, 2022, 5: 22
Kou Z, Li X, Wang T, et al. Fundamentals, on-going advances and challenges of electrochemical carbon dioxide reduction. Electrochem Energy Rev, 2022, 5: 82–111
Li L, Liu Z, Yu X, et al. Achieving high single-pass carbon conversion efficiencies in durable CO2 electroreduction in strong acids via electrode structure engineering. Angew Chem Int Ed, 2023, 62: e202300226
Ma Z, Yang Z, Lai W, et al. CO2 electroreduction to multicarbon products in strongly acidic electrolyte via synergistically modulating the local microenvironment. Nat Commun, 2022, 13: 7596
Gu J, Liu S, Ni W, et al. Modulating electric field distribution by alkali cations for CO2 electroreduction in strongly acidic medium. Nat Catal, 2022, 5: 268–276
Kurihara R, Nagita K, Ohashi K, et al. Carbon monoxide reduction reaction to produce multicarbon products in acidic electrolytes using gas diffusion electrode loaded with copper nanoparticles. Adv Mater Inter, 2024, 11: 2300731
Acknowledgements
Zhao W would like to acknowledge the support from the Natural Science Foundation of Jiangsu Province (BK20210189), the National Natural Science Foundation of China (22176086), the State Key Laboratory of Pollution Control and Resource Reuse, the Fundamental Research Funds for the Central Universities (021114380183, 021114380189, and 021114380199), the Research Funds from Frontiers Science Center for Critical Earth Material Cycling of Nanjing University, the Research Funds for Jiangsu Distinguished Professor, and the Carbon Peaking and Carbon Neutrality Technological Innovation Foundation of Jiangsu Province (BE2022861). Sun X Would like to thank the support from the National Natural Science Foundation of China (82272138 and 81971738) and Jiangsu Province Outstanding Youth Fund (BK20220086). Lin R would like to thank the support from the National Natural Science Foundation of China (52276177).
Author information
Authors and Affiliations
Contributions
Author contributions Zhu W supervised the project and organized the collaboration. Zhao W wrote the manuscript and Liu J, Wang G, Wang X, Yang C, Li J, Wang Y, Sun X, Lin R and Zuo G revised the manuscript. All authors discussed, edited and commented on the manuscript.
Corresponding author
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Wen Zhao is pursuing a Master degree at the School of the Environment, Nanjing University, under the supervision of Prof. Wenlei Zhu. Her research focuses on the electrochemical reduction of carbon monoxide.
Wenlei Zhu is a professor at the School of the Environment, Nanjing University. He obtained his BSc and PhD degrees from Nanjing University and Brown University, respectively, followed by postdoc at Washington University in St. Louis, Columbia University in the City of New York and University of Delaware for several years. His current research interests focus on resource utilization of greenhouse gases.
Rights and permissions
About this article
Cite this article
Zhao, W., Liu, J., Wang, G. et al. Copper-based catalysts for carbon monoxide electroreduction to multicarbon products. Sci. China Mater. 67, 1684–1705 (2024). https://doi.org/10.1007/s40843-023-2884-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-023-2884-8