Boron Phosphide Nanoparticles: A Nonmetal Catalyst for High‐Selectivity Electrochemical Reduction of CO2 to CH3OH

Abstract Electrocatalysis has emerged as an attractive way for artificial CO 2 fixation to CH 3 OH, but the design and development of metal‐free electrocatalyst for highly selective CH 3 OH formation still remains a key challenge. Here, it is demonstrated that boron phosphide nanoparticles perform highly efficiently as a nonmetal electrocatalyst toward electrochemical reduction of CO 2 to CH 3 OH with high selectivity. In 0.1 m KHCO 3 , this catalyst achieves a high Faradaic efficiency of 92.0% for CH 3 OH at −0.5 V versus reversible hydrogen electrode. Density functional theory calculations reveal that B and P synergistically promote the binding and activation of CO 2 , and the rate‐determining step for the CO 2 reduction reaction is dominated by *CO + *OH to *CO + *H 2 O process with free energy change of 1.36 eV. In addition, CO and CH 2 O products are difficultly generated on BP (111) surface, which is responsible for the high activity and selectivity of the CO 2 ‐to‐CH 3 OH conversion process.