Investigating the Potency of Boron Doping on Graphene Nanoclusters as Catalysts for CO Reduction Reaction

Abstract

Graphene materials exhibit significant potential as electrocatalysts for the CO reduction reaction (CORR), a crucial process for mitigating greenhouse gas emissions. This study investigates the impact of boron (B) doping on the catalytic performance of graphene nanoclusters (GNCs) for CORR using density functional theory (DFT). Pristine GNC (C₅₄H₁₈) and B-doped GNC (C₅₃H₁₈B) were examined through the computational hydrogen electrode (CHE) model. The results demonstrate that B doping slightly enhances adsorption energy, with C₅₃H₁₈B exhibiting higher adsorption energy (−2.40 × 10⁻² eV) than C₅₄H₁₈ (−0.79 × 10⁻² eV), indicating a modest improvement in interaction strength, which is attributed to the electron-deficient sites introduced by the B atom, which strengthen CO-surface interactions, as evidenced by a shorter distance of 3.62 Å in C₅₃H₁₈B compared to 3.92 Å in C₅₄H₁₈. Free energy diagrams for both models reveal that methanol formation follows the same pathway: *CO → *CHO → *CH₂O→ *OCH₃ →CH₃OH. Notably, the overpotential required for spontaneous reaction is significantly lower for B-GNC (0.89 V) than for the pristine GNC (1.50 V), indicating that B doping effectively enhances the electrocatalytic activity of GNCs for CORR. These findings highlight that B-GNC is a promising candidate for metal-free electrocatalysts with improved performance for sustainable COR applications.