Optimizing the crystallization process of conjugated polymer photocatalysts to promote electron transfer and molecular oxygen activation

Photocatalytic reactive oxygen species (ROS)-induced reactions provide an appealing method to solve the environmental and energy issues, whereas the current oxidation reaction generally suffered from low efficiency and poor selectivity due to uncontrollable O₂ activation process. In view of the existence of competitive electron and energy transfer pathway, we propose that highly efficient superoxide radical anion (·O₂⁻) generation can be achieved by optimizing the order degree of the photocatalyst. Herein, by taking carbon nitride polymer as an example, we optimized the crystallization process of carbon nitride polymer by selecting precursors of different polymerization degrees with a molten salt method. Benefiting from the high crystallinity, extended π-conjugated system and strong van der-Waals interactions between interlayers, the modified carbon nitride polymer exhibited accelerated charge transport and enhancement in electron induced molecular oxygen activation reactions under visible light. Consequently, the CCN-P exhibits about 1.5 times higher conversion rate in hydroxylation of phenylboronic acid and over 6-fold faster degradation rate in Rh B organic pollutants photodegradation with respect to pristine carbon nitride. This study provides an in-depth understanding on the optimization of the O₂ activation process and the design of advanced photocatalysts.