Construction of Fe(III) Active Sites on Phenanthroline-Grafted g-C3N4: Reduced Work Function and Enhanced Intramolecular Charge Transfer for Efficient N2 Photofixation.

Abstract

Photocatalytic nitrogen fixation is one of the important pathways for green and sustainable ammonia synthesis, but the extremely high bonding energy of the N≡N triple bond makes it difficult for conventional nitrogen fixation photocatalysts to directly activate and hydrogenate. Given this, we covalently grafted the phenanthroline unit onto graphitic carbon nitride nanosheets (CN) by the simple thermal oxidation method and complexed it with transition metal Fe3+ ions to obtain stable dispersed Fe active sites, which can significantly improve the photocatalytic activity. The Fe(III)-4-P-CN photocatalyst morphology consists of porous lamellar structures internally connected by nanowires. The special morphology of the catalysts gives them excellent nitrogen fixation performance, with an average NH3 yield of 492.9 μmol g-1 h-1, which is 6.5 times higher than that of the pristine CN, as well as better photocatalytic cycling stability. Comprehensive experiments and density-functional theory results show that Fe(III)-4-P-CN is more favorable than pristine CN for *N2 activation, effectively lowering the reaction energy barrier. Moreover, other byproducts (such as nitrate and H2O2) are also produced during the photocatalytic nitrogen fixation process, which also provides a new way for nitrogen-fixing photocatalysts to achieve multifunctional applications.