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Heterojunction combining with two kinds of different band structures semiconductors was constructed, and its photocatalytic performance could be greatly improved with the wider optical response range. The BiO2-x/ZnWO4 composite was prepared by a simple two-step hydrothermal method. The structure, morphology and optical properties of BiO2-x/ZnWO4 were characterized by XRD, SEM and UV-vis diffuse reflectometry. The photocatalytic performance and cyclic stability of BiO2-x/ZnWO4 were studied by degrading tetracycline under visible light. The results showed that with the synergistic action between BiO2-x and ZnWO4, the photo-generated carriers of BiO2-x/ZnWO4 could be effectively separated and the light absorption capacity of BiO2-x/ZnWO4 could be significantly enhanced. After 90 min of visible light illumination, the photodegradation efficiency of the composite towards tetracycline reached 86.04%, and the light response range and photocatalytic activity of the composite were better than the monomer BiO2-x and ZnWO4. In addition, the composite displayed good light stability. The capture experiments and ESR showed that h+, O2·- and ·OH were produced by the composites under light, in which h+ and O2·- were the main active substances in the process of photocatalysis, and ·OH was the minor active species, following the order of h+>O2·->·OH. It was inferred that the electron transfer mechanism of BiO2-x/ZnWO4 was Z-scheme heterojunction.

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