Unraveling the Mechanisms of Visible Light Photocatalytic NO Purification on Earth-Abundant Insulator-Based Core-Shell Heterojunctions

Earth-abundant insulators are seldom exploited as photocatalysts. In this work, we constructed a novel family of insulator-based heterojunctions and demonstrated their promising applications in photocatalytic NO purification, even under visible light irradiation. The heterojunction formed between the insulator SrCO3 and the photosensitizer BiOI, via a special SrCO3-BiOI core-shell structure, exhibits an enhanced visible light absorbance between 400-600 nm, and an unprecedentedly high photocatalytic NO removal performance. Further density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) analysis revealed that the covalent interaction between the O 2p orbital of the insulator (SrCO3, n-type) and the Bi 6p orbital of photosensitizer (BiOI, p-type) can provide an electron transfer channel between SrCO3 and BiOI, allowing the transfer of the photoexcited electrons from the photosensitizer to the conduction band of insulator (confirmed by charge difference distribution analysis and time-resolved fluorescence spectroscopy). The center dot O-2(-) and center dot OH radicals are the main reactive species in photocatalytic NO oxidation. A reaction pathway study based on both in situ FT-IR and molecular-level simulation of NO adsorption and transformation indicates that this heterojunction can efficiently transform NO to harmless nitrate products via the NO -> NO+ and NO2+-> nitrate or nitrite routes. This work provides numerous opportunities to explore earth-abundant insulators as visible-light-driven photocatalysts, and also offers a new mechanistic understanding of the role of gas-phase photocatalysis in controlling air pollution.