Asymmetric P-N3 bonds in polymeric carbon nitride: Polarizing localized charge for efficient photocatalytic hydrogen evolution and selective alcohol oxidation.

The simultaneous generation of hydrogen (H₂) and the oxidative transformation of organic molecules through photocatalytic processes represents a highly promising dual-purpose strategy. This approach obviates the necessity for sacrificial agents while augmenting catalytic efficiency, thereby facilitating the integrated production of high-value chemicals and renewable energy carriers. Polymeric carbon nitride (PCN) has emerged as a leading candidate among coupled photocatalysts. Nevertheless, PCN's efficacy is constrained by the inefficient separation of charges and the functional limitations of its active sites. Herein, the incorporation of P-N₃ groups into PCN introduces active sites with pronounced charge asymmetry, resulting in strong local charge polarization. This asymmetric charge distribution, mediated by the P-N₃ groups, significantly enhances exciton dissociation. Remarkably, the P-N₃-modified narrow-dimensional fragmented carbon nitride (P-CNNS) achieves an 85 % conversion rate for 4-MBA with nearly 100 % selectivity, and a hydrogen evolution rate of 27.9 mmol g^-1 (with Pt as a co-catalyst), representing 6.2 times higher than that of bulk carbon nitride (BCN). The charge-polarized sites facilitate the transfer of electrons, which is a pivotal process in the activation of 4-methoxybenzyl alcohol (4-MBA). Additionally, these sites serve as adsorption sites, facilitating the oxidation of 4-MBA into anisaldehyde (AA). This work underscores the potential of non-metallic site catalysts for a wide range of coupled photocatalytic applications.