Fluorination fine-tunes the electronic structure and hydrophobic microenvironment of metal-free nitrogen-doped carbon for efficient electrocatalytic CO2 reduction

Abstract

We exploit fluorine's electronegativity and hydrophobicity to tune the electronic structure and microenvironment of nitrogen-doped carbon. Fluorine selectively modulates the p-orbital of pyridinic nitrogen, shifting its p-band centre to lower the *COOH formation barrier, while its hydrophobicity enriches CO2 and excludes H2O/H+, together achieving efficient CO2-to-CO conversion with high selectivity and current density.