Thermal‐driven Dispersion of Bismuth Nanoparticles among Carbon Matrix for Efficient Carbon Dioxide Reduction

The poor electrocatalytic stability and rapid deactivation of metal electrocatalysts are always present in the electrocatalytic conversion of carbon dioxide (CO2) due to the harsh reduction condition. Herein, we demonstrate the controllable dispersion of ultrafine bismuth nanoparticles among the hollow carbon shell (Bi@C‐700‐4) simply by a thermal‐driven diffusion process. The confinement effect of nitrogen‐doped carbon matrix is able to low the surface energy of bismuth nanoparticles against the easy aggregation commonly observed for the thermal treatment. On the basis of the synergistic effect and confinement effect between bismuth nanoparticles and carbon matrix, the highly dispersed active sites render the obviously improved electrocatalytic activity and stability for carbon dioxide reduction into formate. The in‐situ experimental observation on the reduction process and theoretical calculations reveal that the incorporation of bismuth nanoparticles with nitrogen‐doped carbon matrix would promote the activation of CO2 and the easy formation of key intermediate (*OCHO), thus leading the enhanced electrocatalytic activity, with a Faradaic Efficiency (FE) of formate about 94.8% and the long‐time stability. Furthermore, the coupling of an anode for 5‐hydroxymethylfurfural oxidation reaction (HMFOR) in solar‐driven system renders the high 2,5‐furandicarboxylic acid (FDCA) yield of 81.2%, presenting the impressive solar‐to‐fuel conversion.