Single-atom anchored on curved boron nitride fullerene surface as efficient electrocatalyst for carbon dioxide reduction

Electrocatalytic carbon dioxide reduction reaction (CO2RR) is currently one of the most promising methods for conversion of excessive CO2 emission. In this study, the electrocatalytic performance of transitional-metal atoms anchored on defective boron nitride fullerene of different size were systematically investigated by density functional theory study (TM= Sc, Ti, V, Cr, Mn, Fe, Ni, Zn, and Mo). The results showed Mn-B23N24 and Fe-B23N24 exhibited high activity and selectivity for CO2RR to CH4. Analysis of the high catalytic performance origin indicates the binding energy of *CO and *OH intermediates (Eb(*CO) and Eb(*OH)) can server as descriptors for the catalytic performance. The curvature effect of the boron nitride fullerene surface on the catalytic performance was analyzed by the so-called pyramidalization angle which shows TM-N3 center with the pyramidalization angle of about 26° exhibits the highest activity. The analysis of the coordination environment also reveals B defects are more favorable for regulating catalytic activity compared with N defects. Especially, compare with the Mn doped BN nanosheet, the limiting potential is significantly decreased from −0.64 V on the flat nanosheet to −0.25 V on TM doped B defective B24N24, highlighting the importance of the curvature effect on the CO2RR performance. This study demonstrated that metal-doped boron nitride fullerene with appropriate curvature is high potential to be efficient CO2RR catalysts, providing valuable insights for the rational design of CO2RR electrocatalysts with high-efficiency.