Solar-energy-enabled photocatalysis is a sustainable process to destruct persistent environmental pollutants via the attack of photogenerated reactive species (e.g., holes, reactive oxygen species such as OH, O2−/HO2, H2O2, and 1O2). Graphitic carbon nitride (g-C3N4) has emerged as a promising polymeric photocatalyst, and its highly tunable properties allow the material with an enhanced photocatalytic activity for environmental remediation. In this study, by taking advantage of simulation and experimental tools, we systematically evaluated the production of reactive species of undoped and carbon (C)-doped g-C3N4 samples, and identify the role of these species in contaminant oxidation under simulated visible sunlight irradiation (xenon lamp, λ > 400 nm). Both g-C3N4 samples produced negligible OH or triplet-excited states (3g-C3N4*), but the C-doped g-C3N4 sample generated more 1O2, O2−, and H2O2 compared to the undoped counterpart. Surprisingly, all these oxidative species did not contribute substantially for the degradation kinetics of contaminant phenol and atrazine, at least for the initial oxidation of the parent compounds; and the results otherwise highlighted the important role of the holes for contaminant transformation. The surface-mediated hole oxidation of the contaminants, including the adsorption of the contaminants on the photocatalyst surface (quantified by the binding free energy) and electron transfer kinetics from the contaminants to the excited photocatalysts (quantified by the concerted proton-coupled electron transfer (CPCET) rate) were investigated by molecular dynamics (MD) and density functional theory (DFT) simulations. The simulation results indicated that C-doping could favor the binding of atrazine but not of phenol on g-C3N4. The C-doping also significantly decreased the CPCET rate of phenol on g-C3N4 but could have little to no adverse impact for the CPCET rate of atrazine. These simulation and experimental results could explain the selective oxidation of phenol and atrazine on undoped and C-doped g-C3N4 in our previous study, and the results also highlight the dominant role of the holes for contaminant transformation that was largely overlooked before. This study generates mechanistic insights of photocatalytic oxidation, and will provide guidelines for the rational design of g-C3N4 as an effective visible-light-responsive photocatalyst for many applications, including contaminant degradation, chemical synthesis, and beyond.
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