Abstract: The electrochemical reduction reaction of carbon dioxide (CO2) is an environmentally friendly,and commercially promising method to resolve the energy dilemma and accomplish carbon recycling.To date,with high efficiency and kinetic feasibility,copper-based electrode materials have been widely applied as "star materials" for CO2 reduction to hydrocarbons.This review firstly focuses on the mechanism of catalysts in the electrochemical reduction reaction of CO2.Simultaneously,the design strategy about electrocatalytic catalyst for CO2 reduction to ethylene is summarized on the basis of morphology control,defect engineering,oxide and alloy forming different structure or adjusting different composition of copper catalyst.Finally,challenges and perspectives are proposed for further improvement of CO2 electrochemical reduction technologies.
[1] Hori Y,Takahashi I,Koga O,et al.Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes[J].Journal of Molecular Catalysis A:Chemical,2003,199(1/2):39-47. [2] Hori Y.Electrochemical CO2 reduction on metal electrodes[M].Modern Aspects of Electrochemistry,Springer,2008:89-189. [3] Schouten K,Kwon Y,Van Der Ham C,et al.A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes[J].Chemical Science,2011,2(10):1902-1909. [4] Ou L.Chemical and electrochemical hydrogenation of CO2 to hydrocarbons on Cu single crystal surfaces:Insights into the mechanism and selectivity from DFT calculations[J].RSC Advances,2015,5(71):57361-57371. [5] Ou L,Long W,Chen Y,et al.New reduction mechanism of CO dimer by hydrogenation to C2H4 on a Cu (100) surface:Theoretical insight into the kinetics of the elementary steps[J].RSC Advances,2015,5(117):96281-96289. [6] Reske R,Mistry H,Behafarid F,et al.Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles[J].Journal of the American Chemical Society,2014,136(19):6978-6986. [7] Jeon H S,Kunze S,Scholten F,et al.Prism-shaped Cu nanocatalysts for electrochemical CO2 reduction to ethylene[J].ACS Catalysis,2018,8(1):531-535. [8] Hori Y,Murata A,Takahashi R.Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution[J].Journal of the Chemical Society,Faraday Transactions 1:Physical Chemistry in Condensed Phases,1989,85(8):2309-2326. [9] Kuhn A N,Zhao H,Nwabara U O,et al.Engineering silver-enriched copper core-shell electrocatalysts to enhance the production of ethylene and C2+ chemicals from carbon dioxide at low cell potentials[J].Advanced Functional Materials,2022,31(26):2101668.1-2101668.10. [10] Gao Y,Wu Q,Liang X,et al.Cu2O nanoparticles with both{100}and{111}facets for enhancing the selectivity and activity of CO2 electroreduction to ethylene[J].Advanced Science,2020,7(6):1902820. [11] Choi C,Kwon S,Cheng T,et al.Highly active and stable stepped Cu surface for enhanced electrochemical CO2 reduction to C2H4[J].Nature Catalysis,2020,3(10):804-812. [12] 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[J].Nature Catalysis,2020,3(6):478-487. [13] Kas R,Kortlever R,Yılmaz H,et al.Manipulating the hydrocarbon selectivity of copper nanoparticles in CO2 electroreduction by process conditions[J].ChemElectroChem,2015,2(3):354-358. [14] Kim T,Palmore G T R.A scalable method for preparing Cu electrocatalysts that convert CO2 into C2+ products[J].Nature Communications,2020,11(1):1-11. [15] Zhang B,Zhang J,Hua M,et al.Highly electrocatalytic ethylene production from CO2 on nanodefective Cu nanosheets[J].Journal of the American Chemical Society,2020,142(31):13606-13613. [16] De Luna P,Quintero-Bermudez R,Dinh C T,et al.Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction[J].Nature Catalysis,2018,1(2):103-110. [17] Jung H,Lee S Y,Lee C W,et al.Electrochemical fragmentation of Cu2O nanoparticles enhancing selective C-C coupling from CO2 reduction reaction[J].Journal of the American Chemical Society,2019,141(11):4624-4633. [18] Jiang Y,Choi C,Hong S,et al.Enhanced electrochemical CO2 reduction to ethylene over CuO by synergistically tuning oxygen vacancies and metal doping[J].Cell Reports Physical Science,2021,2(3):100356. [19] Ren X,Zhang X,Cao X,et al.Efficient electrochemical reduction of carbon dioxide into ethylene boosted by copper vacancies on stepped cuprous oxide[J].Journal of CO2 Utilization,2020,38:125-131. [20] Hou L,Han J,Wang C,et al.Ag nanoparticle embedded Cu nanoporous hybrid arrays for the selective electrocatalytic reduction of CO2 towards ethylene[J].Inorganic Chemistry Frontiers,2020,7(10):2097-2106. [21] Hoang T T,Verma S,Ma S,et al.Nanoporous copper-silver alloys by additive-controlled electrodeposition for the selective electroreduction of CO2 to ethylene and ethanol[J].Journal of the American Chemical Society,2018,140(17):5791-5797. [22] Xiong L,Zhang X,Yuan H,et al.Breaking the linear scaling relationship by compositional and structural crafting of ternary Cu-Au/Ag nanoframes for electrocatalytic ethylene production[J].Angewandte Chemie,2021,133(5):2538-2548. [23] Feng Y,Li Z,Liu H,et al.Laser-prepared CuZn alloy catalyst for selective electrochemical reduction of CO2 to ethylene[J].Langmuir,2018,34(45):13544-13549.