Hydrangea-like Superstructured Micro/Nanoreactor of Topotactically Converted Ultrathin Bismuth Nanosheets for Highly Active CO2 Electroreduction to Formate

An electrocatalytic carbon dioxide reduction reaction (CO2RR) is an appealing route to obtain the value-added feedstocks and alleviate the energy crisis. However, how to achieve high-performance electrocatalysts for CO2 reduction to formate is challenging owing to the poor intrinsic activity, insufficient conductivity, and low surface density of active sites. Herein, we fabricated an extremely active and selective hydrangealike superstructured micro/nanoreactor of ultrathin bismuth nanosheets through an in situ electrochemical topotactic transformation of hierarchical bismuth oxide formate (BiOCOOH). The resulted bismuth nanosheet superstructure is in the form of three-dimensional intercrossed networks of ultrathin nanosheets, forming an ordered open porous structure through self-assembly, which can be used as a micro/nanoreactor to enable a large electrochemically active surface area as well as high atomic utilization. Such a distinctive nanostructure endows the material with high electrocatalytic performances for CO2 reduction to formate with near-unity Faradaic selectivity (>95%) in a wide potential window from -0.78 to -1.18 V. Furthermore, this micro/nanoreactor can give the high current densities over 300 mA cm(-2) at low applied potentials without compromising selectivity in a flow cell reactor. Density functional theory (DFT) and in situ attenuated total reflection-infrared spectroscopy (in situ ATR-IR) were further conducted to interpret the CO2RR mechanisms.

Automated summary

By fabricating an extremely active and selective ultra-thin bismuth nanosheet nano-reactor, high-efficiency electrochemical reduction of carbon dioxide to formate with nearly 100% Faraday selectivity can be achieved. The reactor can maintain high current densities at low applied potentials without compromising selectivity.