Orientational dipole interaction mediated by crystallites and defects in biomass derived carbon materials of heterogeneous catalytic ozonation process

Abstract

Biomass-derived carbon (BC) are sustainable and low-cost materials for environmental catalysis, while the challenge in applications lies in the structural complexity of BC for on-demand catalyst design in advanced oxidation processes. Herein, we revealed the intrinsic role of hybridized defect state Enteromorpha prolifera BC (EBC) to regulate orientational dipole interactions in heterogeneous catalytic ozonation (HCO). The mechanisms were elucidated through experimental verifications, machine learning and density functional theory computations, successfully correlating HCO activity with the orientational dipole. Specifically, EBC with different hybrid states crystallites (sp²-C, sp³-C), intrinsic vacancy (C-v) and extrinsic functionality (N and O) defects collaboratively affect the distribution of orientational dipoles, consequently manipulating the surface potential and charge flow. As natural orientational dipole donors, crystallites exhibit stronger O₃ adsorption, while the defects are more conducive to O₃ activation. The regulation and prediction of adsorption and activation processes are both significantly correlated with orientational dipole descriptors, especially the orientational dipole in y directions (Dy). The orientational dipole interaction promoted the generation of •OH and O₂^•–, and generated the non-radical species such as singlet oxygen (¹O₂) and adsorbed oxygen atom (*O). This proposed orientational dipole interaction offers a new perspective on the HCO process involving both radical and non-radical pathways.