G-C3N4@CPP/BiOClBr-OV biomimetic fractal heterojunction synergistically enhance carrier dynamics for boosted CO2 photoreduction activity

Abstract

In recent years, there has been significant interest in generating high-value solar fuels via the photocatalytic reduction of CO2. Nonetheless, its large-scale application is impeded by low energy utilization efficiency and limited photocatalytic activity. This study employed carbonized pomelo peel (CPP), a waste biomass material, to successfully craft a CN@CPP/BOCB-OV ternary heterojunction abundant in N/O vacancy defects through secondary calcination and in-situ growth. The construction of the heterojunction and the emergence of defect-induced donor energy levels create a built-in interface electric field (IEF) and an interfacial electron transmission channel respectively, fortifying the separation and transport of photogenerated electrons. Crucially, following the incorporation of CPP, its distinctive 3D porous and heterojunction bionic flower structures expand the spectral absorption range. Acting as a superior electron acceptor, CPP reinforces the IEF, notably boosting carrier transport efficiency. Simultaneously, it operates as a hub for photothermal synergy and CO2 adsorption activation, achieving multi-site synergistic enhancement of photoreduction CO2 activity. Hence, the CN@CPP/BOCB-OV heterojunction demonstrates a substantial quantitative enhancement in CO2 photoreduction activity. Remarkably, it exhibits the capability to catalyze CO2 reduction even under infrared light excitation, which is of great significance for the cascade utilization of solar energy. Furthermore, employing DFT calculations, we elucidate the electron transfer mechanism at the heterojunction interface and outline potential pathways for photocatalytic CO2 reduction. The combination of waste biomass utilization, heterostructure construction and defect engineering provides a promising strategy for developing efficient heterostructure photocatalysts.