Selectivity

Physics

Electrochemical energy conversion

Nanotechnology

Electrode

Organic chemistry

Metal-organic framework

Current density

Electrochemical reduction of carbon dioxide

Bismuth

Adsorption

Engineering

Catalysis

Physical chemistry

Chemistry

Metallurgy

Materials science

Formate

Carbon monoxide

Metal

Quantum mechanics

Chemical engineering

Electrochemistry

Angewandte Chemie International Edition

Electrochemical reduction of CO 2 to valuable fuels is appealing for CO 2 fixation and energy storage. However, the development of electrocatalysts with high activity and selectivity in a wide potential window is challenging. Herein, atomically thin bismuthene (Bi‐ene) is pioneeringly obtained by an in situ electrochemical transformation from ultrathin bismuth‐based metal–organic layers. The few‐layer Bi‐ene, which possesses a great mass of exposed active sites with high intrinsic activity, has a high selectivity (ca. 100 %), large partial current density, and quite good stability in a potential window exceeding 0.35 V toward formate production. It even deliver current densities that exceed 300.0 mA cm −2 without compromising selectivity in a flow‐cell reactor. Using in situ ATR‐IR spectra and DFT analysis, a reaction mechanism involving HCO 3 − for formate generation was unveiled, which brings new fundamental understanding of CO 2 reduction.

Metal–Organic Layers Leading to Atomically Thin Bismuthene for Efficient Carbon Dioxide Electroreduction to Liquid Fuel