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 (C 54 H 18 ) and B‐doped GNC (C 53 H 18 B) were examined through the computational hydrogen electrode (CHE) model. The results demonstrate that B doping slightly enhances adsorption energy, with C 53 H 18 B exhibiting higher adsorption energy (−2.40 × 10 −2 eV) than C 54 H 18 (−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 C 53 H 18 B compared to 3.92 Å in C 54 H 18 . Free energy diagrams for both models reveal that methanol formation follows the same pathway: *CO → *CHO → *CH 2 O→ *OCH 3 →CH 3 OH. 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.