Interlayer Charge Transfer Over Graphitized Carbon Nitride Enabling Highly‐Efficient Photocatalytic Nitrogen Fixation

Abstract Exploiting cost‐effective, high‐efficiency, and contamination‐free semiconductors for photocatalytic nitrogen reduction reaction (N 2 RR) is still a great challenge, especially in sacrificial‐free system. On basis of the electron “acceptance–donation” concept, a boron‐doped and carbon‐deficient g ‐C 3 N 4 (B x CvN) is herein developed through precise dopant and defect engineering. The optimized B 15 CvN exhibisted an NH 3 production rate of 135.3 µmol h −1 g −1 in pure water with nine‐fold enhancement to the pristine graphitic carbon nitride ( g ‐C 3 N 4 ), on account of the markedly elevated visible‐light harvesting, N 2 activation, and multi‐directional photoinduced carriers transfer. The decorated B atoms with coexistent occupied and empty sp 3 hybridized orbitals are theoretically proved to be in charge of the increase of N 2 adsorption energy from –0.08 to –0.26 eV and the change in N 2 adsorption model from one‐way to two‐way end‐on pattern. Noticeably, the elaborate coordination of doped B atoms and carbon vacancies greatly facilitated the interlayer interaction and vertical charge migration of B x CvN, which is distinctly revealed through the charge density difference calculations. The current study provides an alternative groundbreaking perspective for advancing photocatalytic N 2 RR through the targeted configuration of the defect and dopant sites.