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Solar-powered volatile organic compound oxidation attracts interest, but its efficiency suffers from poor utilization of photogenerated electrons. Oxygen can capture the electrons and convert them into superoxide radicals upon being activated. As a unique oxygen-deficiency oxide, WO2 chemisorbs and activates oxygen and functions as a potential cocatalyst for improving the utilization of charge carriers. Here, we report a WO2/SnS2 composite photocatalyst with SnS2 nanosheets vertically growing out of WO2 nanofibers. In situ X-ray photoelectron spectroscopy and density functional theory calculations suggest the electron transfer from WO2 to SnS2, creating an internal electric field (IEF) at the interfaces with a direction pointing from WO2 to SnS2. The IEF promotes spatial charge separation by driving photogenerated electrons in SnS2 to move to WO2, while photogenerated holes remain immobile. WO2 shows a strong affinity for oxygen-containing species and chemisorbs O2 and H2O molecules in a dissociative way, significantly reducing the kinetic barriers for the production of reactive oxygen species (•OH and •O2–). Under visible light irradiation, the WS30 nanofibers exhibit enhanced photocatalytic degradation of HCHO and CH3COCH3, 4.8 and 7.2 times greater than that of pristine SnS2, respectively. The enhanced performance is attributed to the one-dimensional fibrous nanostructures, robust chemisorption of reactants, and IEF-driven charge separation. This work may inspire efforts to develop higher oxygen-affinity photocatalysts for photodegradation. [ABSTRACT FROM AUTHOR]

Photocatalytic oxidation technology can mineralize hazardous volatile organic compounds (VOCs), but the poor photocatalytic oxidation activity limits its practical application. Here we develop Cu‐doped WO3 electrospun nanofibers through a non‐equivalent doping strategy. The Cu dopant prefers substituting five‐coordinated W atoms atop the WO3 matrix, inducing strong dopant/matrix interaction (SDMI) effect and prominent charge rearrangement. A localized electric field (LEF) forms pointing from positively charged WO3 matrix to negatively charged Cu dopant, which triggers efficient photoexcited charge separation. Further, the Cu dopant promoted the production of ⋅OH radicals and thereby enhanced VOCs photodegradation. The 0.7 % Cu‐doped WO3 nanofibers show optimal photocatalytic oxidation performance towards formaldehyde and acetone, 5.5 and 4.8 times higher than pristine WO3 nanofibers, respectively. This work highlights the role of dopant‐induced LEF on the charge carriers separation and might shed light on developing more efficient photocatalysts with non‐equivalent dopants. [ABSTRACT FROM AUTHOR]

[Display omitted] • Electron rearrangement occurs around Co dopant owing to the strong dopant/matrix interaction. • Localized electric field is present with direction pointing from Co dopant to WO 3 matrix. • Efficient charge separation and transfer are achieved owing to the LEF. • Co dopants activate oxygen with favorable production of O 2 – radicals for VOCs oxidation. Exploring efficient photocatalysts for degrading hazardous volatile organic compounds (VOCs) is gaining increasing popularity. Herein, we developed Co-doped WO 3 nanofibrous photocatalysts by incorporating Co dopant into the WO 3 lattice, where hexavalent W(VI) is replaced with divalent Co(II). This heterovalent substitution causes significant charge rearrangement around the Co dopant, resulting in a localized electric field (LEF) that enhances oxygen adsorption and activation. Such an electric field drives photoexcited electrons to gather at the Co dopant, thereby achieving spatial charge separation. Both the efficient oxygen activation and LEF forming contribute to the production of superoxide radicals. The Co0.8-WO 3 nanofibers demonstrated improved photocatalytic oxidation of gaseous HCHO and CH 3 COCH 3 compared to WO 3. This study highlights the significant promotion of dopant-induced oxygen adsorption and LEF-induced efficient carrier separation. These findings offer a new direction for developing more efficient photocatalysts using unique doping approaches. [ABSTRACT FROM AUTHOR]