Cobalt‐Doped Bismuth Nanosheet Catalyst for Enhanced Electrochemical CO₂ Reduction to Electrolyte‐Free Formic Acid

Electrochemical carbon dioxide (CO 2 ) reduction reaction (CO 2 RR) to valuable liquid fuels, such as formic acid/formate (HCOOH/HCOO − ) is a promising strategy for carbon neutrality. Enhancing CO 2 RR activity while retaining high selectivity is critical for commercialization. To address this, we developed metal‐doped bismuth (Bi) nanosheets via a facile hydrolysis method. These doped nanosheets efficiently generated high‐purity HCOOH using a porous solid electrolyte (PSE) layer. Among the evaluated metal‐doped Bi catalysts, Co‐doped Bi demonstrated improved CO 2 RR performance compared to pristine Bi, achieving ~90 % HCOO − selectivity and boosted activity with a low overpotential of ~1.0 V at a current density of 200 mA cm −2 . In a solid electrolyte reactor, Co‐doped Bi maintained HCOOH Faradaic efficiency of ~72 % after a 100‐hour operation under a current density of 100 mA cm −2 , generating 0.1 M HCOOH at 3.2 V. Density functional theory (DFT) results revealed that Co‐doped Bi required a lower applied potential for HCOOH generation from CO 2 , due to stronger binding energy to the key intermediates OCHO* compared to pure Bi. This study shows that metal doping in Bi nanosheets modifies the chemical composition, element distribution, and morphology, improving CO 2 RR catalytic activity performance by tuning surface adsorption affinity and reactivity.