Synergistic effect and high performance of transition metal-anchored boron-doped graphyne electrocatalyst applied in the electroreduction of CO2 to C1 products: A DFT study

It continues to be challenging to develop low-cost, high-efficiency electrocatalysts for CO2 electrochemical reduction reaction (CRR). In this work, the electrocatalytic performance of several transition metal (TM = Ti, V, Cr, Mn, and Fe) anchored boron co-doped graphyne (GY) is systematically examined by first-principle calculations. Among them, MnB1@GY exhibits the most excellent CRR performance with low limit potential of -0.21 V and high selectivity for the generation of CH4. A deep investigation into the high-performance origin by comparative analysis of single atom doped Mn@GY and MB1@GY reveals that due to the synergistic effect of codoped B and TM atoms which can break the linear-scaling relation of single atom catalyst, the selectivity is significantly improved. B in MnB1@GY regulates the charge transfer of the reaction, and the strong binding of *CHO with both B and Mn atom lower the energy required for the protonation step of *CO?*CHO, reducing the energy barrier of the rate determining steps and leading to the high performance of MnB1@GY. This work suggests that the synergistic effect of co-doped B and metal atoms can effectively enhance the catalytic activity, which can hopefully provide a potential strategy for the rational design of efficient CRR electrocatalysts.

Automated summary

In this study, the electrocatalytic performance of several transition metal (TM = Ti, V, Cr, Mn, and Fe) anchored boron co-doped graphyne (GY) for CO2 electrochemical reduction reaction (CRR) was systematically examined by first-principle calculations. The results showed that MnB1@GY exhibited the best CRR performance, with low limit potential and high selectivity for the generation of CH4. The synergistic effect of codoped B and TM atoms in MnB1@GY significantly improved the selectivity by breaking the linear-scaling relation of single atom catalyst.