Research Progress in Copper-Based Tandem Catalysts for Electrocatalytic Reduction of Carbon Dioxide AITranslate

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY24010006

Chinese Library Classification Number:O643.36

Citation Information:

With the development of industrialization，the extensive use of fossil fuels has resulted in the accumulation of increasing amounts of carbon dioxide （CO₂） in the atmosphere. This has caused significant environmental problems （e.g.，global warming and rising sea levels，as well as an energy crisis）. The technology of CO₂ capture，transportation，and reuse or safe storage is helpful to realize the coordination and integration of energy conservation，waste utilization，and carbon reduction and establishing a new CO₂ circular economy industrial chain. The traditional methods of utilizing carbon dioxide include photocatalysis，thermal catalysis，biocatalysis，and electrocatalysis. Among these approaches，using renewable electricity to convert carbon dioxide into high-value hydrocarbons and oxygen-containing compounds is one of the important methods for realizing the resource utilization of carbon dioxide. Copper is a catalyst that can efficiently reduce CO₂ to produce multi-carbon products. Due to the complex thermodynamic and kinetic processes involved in electrocatalytic carbon dioxide reduction （CO₂RR），numerous reaction pathways，intermediates，and products are caused. Single-component copper catalysts cannot efficiently achieve C–C coupling. The deep reduction of CO₂ still faces challenges such as high overpotential，low Faraday efficiency，and current density of C₂₊ products，and industrial applications are limited. It is generally believed that the primary reason for the low Faraday efficiency and current density of C₂₊ products on Cu-based catalysts is that Cu is difficult to activate CO₂ to generate *CO. The introduction of a second catalyst improves the conversion efficiency of converting CO₂ to CO，enhances the local concentration of *CO at the interface （increased Faraday efficiency and current density），reduces the energy barrier of C−C coupling （reduce overpotential），and enhances the overall efficiency of the deep reduction of CO₂. CO is an important intermediate in the production of methane，methanol，ethylene，ethanol and other products. After the formation of a CO intermediate （*CO），the CO₂ reduction follows a similar path to the electrocatalytic CO reduction reaction （CORR）. Tandem catalysis can eliminate the need for purifying and separating intermediates at each step，and can effectively addressing the problem of complex CO₂RR reaction pathway and numerous intermediates. The entire catalytic process is divided into several stages，with each stage being carried out at different catalytic sites. This arrangement is beneficial for achieving the optimal binding energy at each stage of the reaction，reducing the thermodynamic reaction energy barrier，accelerating the reaction kinetics and achieving high selectivity，high current and fast rate to produce C₂₊ products. A variety of catalysts are capable of converting CO₂ to CO. However，further reduction of CO occurs almost exclusively on copper. Combining the catalyst that can efficiently produce CO with the Cu catalyst that effectively catalyzes the C−C coupling to form a tandem catalyst is an emerging design strategy. This strategy aims to break the linear proportional relationship and enhance the selectivity and formation rate of C₂₊ products. Due to the ligand effect，electronic effect，and geometric effect between different metal elements，the CO₂RR performance of Cu-based catalysts in CO₂ reduction reaction can be greatly improved by incorporating other metal elements （Au，Ag） in conjunction with Cu. However，precious metals have drawbacks such as high cost，poor long-term stability，and low natural reserves，which impede the commercialization process. Non-metallic materials，such as carbon-based materials，single atoms，and polymers，offer the advantages of excellent chemical stability，electrical conductivity，wide source of raw materials，and controllable structure. making them potential candidates for series connection with copper. Based on this design strategy，many series catalysts have been developed，and a series of research results have been achieved，which greatly promoted the development of CO₂RR. In this review，we first introduced the basic principles of electrocatalytic carbon dioxide reduction，explained its fundamental reaction mechanism and potential pathways to generate C₂₊ products，and elucidated the design principles and precautions of copper-based tandem catalysts. Secondly，the research progress of copper and metal components in series （alloy nanostructures，heterostructures，core-shell structures） and copper and non-metal components in series （copper-carbon，copper−M-N-C，copper-polymer） in the field of CO₂RR was systematically summarized and discussed，based on the different series components. The problems that should be paid attention in the design of copper-based series catalysts （such as low series current density，single series mode，easy desorption of CO，difficult further coupling） and the problems still existing in industrial applications （such as difficult separation of reduction products，low energy conversion efficiency，limited reaction device，and slow anode half reaction） were pointed out. Finally，future research challenges and opportunities were discussed.