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Selective CO2 reduction to formic acid or formate is the most technologically and economically viable approach to realize electrochemical CO2 valorization. Main group metal–based (Sn, Bi, In, Pb, and Sb) nanostructured materials hold great promise, but are still confronted with several challenges. Here, the current status, challenges, and future opportunities of main group metal–based nanostructured materials for electrochemical CO2 reduction to formate are reviewed. Firstly, the fundamentals of electrochemical CO2 reduction are presented, including the technoeconomic viability of different products, possible reaction pathways, standard experimental procedure, and performance figures of merit. This is then followed by detailed discussions about different types of main group metal–based electrocatalyst materials, with an emphasis on underlying material design principles for promoting the reaction activity, selectivity, and stability. Subsequently, recent efforts on flow cells and membrane electrode assembly cells are reviewed so as to promote the current density as well as mechanistic studies using in situ characterization techniques. To conclude a short perspective is offered about the future opportunities and directions of this exciting field. [ABSTRACT FROM AUTHOR]

Keywords: electrochemical CO2 reduction; formate; main group metals; nanostructures In article number 1902338, Youyong Li, Yanguang Li and co-workers review the current status, challenges and future opportunities of main-group-metal-based nanostructured materials for electrochemical CO SB 2 sb reduction to formate. Electrochemical CO2 reduction, formate, main group metals, nanostructures. [Extracted from the article]

The conversion of CO2 to value‐added products using electrical or solar energy represents an attractive means for the capture and utilization of atmospheric CO2. Formate is a popular product from CO2 reduction, but its reaction selectivity is usually unsatisfactory. Tin‐based materials have attracted the most attention for formate production at present. Unfortunately, most of them only exhibit moderate selectivity in a narrow and highly cathodic potential window. In this study, it is demonstrated that traditionally under‐explored bismuth has a much greater potential for formate production than tin or other materials. Mesoporous bismuth nanosheets are prepared here by the cathodic transformation of atomic‐thick bismuth oxycarbonate nanosheets. They enable the selective CO2 reduction to formate with large current density, excellent Faradaic efficiency (≈100%) over a broad potential window and great operation stability. Moreover, Bi nanosheets are integrated with an oxygen evolution reaction electrocatalyst in full cells, and achieve efficient and robust solar conversion of CO2/H2O to formate/O2. Cathodic transformation of atomic‐thick Bi2O2CO3 nanosheets to 2D mesoporous Bi nanosheets enables efficient CO2 reduction to formate with large current density, excellent selectivity over a broad potential window, and satisfactory stability. [ABSTRACT FROM AUTHOR]