Shear Stress Triggers Ultrathin-Nanosheet Carbon Nitride Assembly for Photocatalytic H₂O₂ Production Coupled with Selective Alcohol Oxidation

Coupled photocatalysis without cocatalysts can maximize the utilization of photons and atoms, which puts forward higher demands on photocatalysts. Polymeric carbon nitride (CN) has become the most promising photocatalyst, but still suffers from major drawbacks of insufficient catalytic sites and low quantum efficiency. Herein, we report a fluid shear stress-assisted molecular assembly to prepare ultrathin-nanosheet-assembled acanthosphere-like CN (ASCN) with nitrogen vacancy (Nv) and carbonyl modification. Shear stress breaks the stacking interactions between layers and cuts the stacked structure into ultrathin layers, which are further reassembled into acanthosphere bundles driven by “centrifugal force”. Benefitted greatly from the ultrathin nature that provides more exposed active sites and improves charge carrier separation, ASCN-3 exhibits a 20-fold higher activity than the bulk counterpart toward oxygen reduction to H₂O₂ coupled with 4-methoxybenzyl alcohol (4-MBA) oxidation to anisaldehyde (AA), with significantly increased turnover frequency (TOF) values (TOF: 1.69 h^-1 for H₂O₂ and 1.02 h^-1 for AA). Significantly, ASCN-3 exhibits 95.8% conversion for 4-MBA oxidation with nearly 100% selectivity. High apparent quantum yields of 11.7% and 9.3% at 420 nm are achieved for H₂O₂ photosynthesis and 4-MBA oxidation. Mechanism studies suggest that carbonyl induces holes concentrated at the neighboring melem unit to directly oxidize the C_α-H bond of 4-MBA to produce carbon radicals, and Nv as oxygen adsorption active site traps electrons to form a superoxide radical that further combines with the shed protons into H₂O₂. This work presents a simple physical method to break the layered stack of CN for creating hierarchical assembly for coupled photocatalysis. © 2023 American Chemical Society