Methyl contributes to the directed phosphorus doping of g-C3N4: pH-dependent selective reactive oxygen species enable customized degradation of organic pollutants

•The introduction of a methyl group successfully facilitated targeted phosphorus doping in g-C3N4.•The composite oxidation system facilitates the degradation of diverse pollutants.•The precise modulation of reactive oxygen species enables tailored degradation of pollutants.•The atomic reactivity of pollutants towards various reactive oxygen species was unveiled. In the photocatalytic degradation process, constructing a controllable composite oxidation system with radicals and nonradicals to meet the requirement for efficient and selective degradation of diverse pollutants is significant. Herein, a methylated and phosphorus-doped g-C3N4 (NPEA) can exhibit selective radical and nonradical species formation depending on the pH values. The NPEA can spontaneously switch the production of active species according to the pH value of the reaction system, exhibiting steady-state concentrations of ·O2− for 11.83 × 10−2 µmol L−1 s−1 (with 92.7 % selectivity) under alkaline conditions (pH = 11), and steady-state concentrations of 1O2 for 5.18 × 10−2 µmol L−1 s−1 (with 88.7 % selectivity) under acidic conditions (pH = 3). The NPEA exhibits stability and universality in the degradation of pollutants with rate constant for sulfamethazine (k = 0.261 min−1) and atrazine (k = 0.222 min−1). Moreover, the LC-MS and Fukui function demonstrated that the NPEA can tailor degradation pathways for pollutants, achieving selective degradation. This study offers a comprehensive insight into the mechanism of the photocatalytic oxidation system, elucidating the intricate interplay between pollutants and reactive oxygen species. [Display omitted]