Boron Dopant Induced Electron‐Rich Bismuth for Electrochemical CO₂ Reduction with High Solar Energy Conversion Efficiency

Abstract

Electrochemical CO 2 reduction to formate offers a mild and feasible pathway for the utilization of CO 2 , and bismuth is a promising metal for its unique hydrogen evolution reaction inhibition. Reported works of Bi-based electrodes generally exhibit high selectivity while suffering from relatively narrow working potential range. From the perspective of electronic modification engineering, B-doped Bi is prepared by a facile chemical reduction method in this work. With B dopant, above 90% Faradaic efficiency for formate over a broad window of working potential of −0.6 to −1.2 V (vs. reversible hydrogen electrode) is achieved. In situ Raman spectroscopy, X-ray adsorption spectroscopy, and computational analysis demonstrate that the B dopant induces the formation of electron-rich bismuth, which is in favor of the formation of formate by fine-tuning the adsorption energy of *OCHO. Moreover, full-cell electrolysis system coupled with photovoltaic device is constructed and achieves the solar-to-formate conversion efficiency as high as 11.8%.

Enhanced electrocatalytic reduction of CO2to formateviadoping Ce in Bi2O3nanosheets

“…Sn, S, and B) can modify the electronic structures of the active sites and result in optimal adsorption energy of the reaction intermediates. [37][38][39][40] Cerium-based and ceria oxide-based catalysts are not ideal ECR electrocatalysts because of their poor intrinsic activity and the existence of the competitive HER. But some reports have proved that the activity of some ECR electrocatalysts can be effectively improved by combining with ceria through rational regulation.…”

Understanding the water molecule effect in metal-free B-based electrocatalysts for electrochemical CO2 reduction

“…40 The two-dimensional material bismuthene has the advantages of electrochemical stability and abundant defective unsaturated sites, and exhibits unique catalytic properties. 41,42 Hence, it is considered a suitable substrate for stabilizing a single atom. Additionally, the high cost and low abundance of noble metals have signicantly hindered the industrialization of SACs.…”

Modulating p‐Orbital of Bismuth Nanosheet by Nickel Doping for Electrocatalytic Carbon Dioxide Reduction Reaction

“…[11b,12] The introduction of the electron-rich atom has been proved to be effective in increasing the electronic density state and delocalization degree of Bi p-orbitals, shifting the p-orbital electronic density states toward the Fermi level and, thus, facilitating the CO 2 activation step. [13] The low-valence 3d transition metals, such as cobalt, nickel and copper, have been extensively investigated as typical electron-rich atoms to modify the electronic structure of the electrocatalysts. [14] For example, Ni was introduced into Pt catalyst to form PtNi alloy for the oxygen reduction reaction (ORR).…”