Catalytic Activity of Multi-Boron-Doped Graphene from First Principles

Metal-free electrodes are essential to promote electrochemical reactions, the core of sustainable energy resources. In search of better carbon-based electrode materials, we have explored several spatial arrangements of boron (B) within proximity in the graphene lattice, as evident in recent experimental observations. Multi-boron substitution enriches sites by tuning electronic structure and strengthens binding of key intermediates of oxygen reduction, oxygen evolution, and hydrogen evolution reactions facilitating electrocatalytic performance. Our optimal B-doped site shows near thermo-neutral H adsorption (ΔGH*∼±0.4eV), consistent with experiments. The overpotentials are highly sensitive to the dopant motifs and the spread among configurations shows that experimentally accessible multi-B doping can serve as a practical active site engineering knob to achieve optimized multi-functional performance. In parallel, we find that specific multi-B configurations selectively capture and pre-activate NOx (NO/NO2) under ambient conditions while retaining weak affinity for NH3. These sites also interact with SO2 and related hazardous species, enabling selective air filtration and targeted NOx control within the electrocatalytic scope of this study.