Breaking CO₂ reduction scaling relations via heterogeneous B/N coordination environments in single-atom catalysts

Electrochemical CO₂ reduction (CO₂RR) powered by renewable energy offers a promising approach to mitigate greenhouse gas emissions while producing valuable chemical feedstocks. However, catalytic efficiency is often constrained by scaling relationships between reaction intermediates, limiting performance for high-value product formation. Here, we systematically investigate how heterogeneous coordination environments affect these scaling relationships in single-atom catalysts (SACs) supported on boron and nitrogen co-doped graphene. Through comprehensive density functional theory calculations of 182 potential catalytic structures, we demonstrate that asymmetric B/N coordination environments effectively disrupt the linear scaling between C-bound and O-bound intermediates that typically limits catalytic performance. Our analysis reveals promising candidates with notable activity and selectivity: Ag-B₂N₂-hex for CO, Pt-B₂N₂-hex for HCOOH, Ni-B₂N₂-hex for CH₃OH, and Au-B₃N₁ for CH₄ production. The heterogeneous B/N coordination enables independent tuning of intermediate binding energies, resulting in significantly reduced limiting potentials compared to conventional homogeneous coordination environments. This work establishes coordination environment engineering as a powerful strategy for rational design of efficient CO₂RR catalysts beyond traditional scaling limitations.