To improve the efficiency of photocatalytic oxidative degradation of antibiotic pollutants, it is essential to develop an efficient and stable photocatalyst. In this study, a polymer-assisted facile synthesis strategy is proposed for the polymorph-controlled α-Bi2O3/Bi2O2CO3 heterojunction retained at elevated calcination temperatures. The p-n heterojunction can effectively separate and migrate electron-hole pairs, which improves visible-light-driven photocatalytic degradation from tetracycline (TC). The BO-400@PAN-140 photocatalyst achieves the highest pollutant removal efficiency of 98.21% for photocatalytic tetracycline degradation in 1 h (λ > 420 nm), and the degradation efficiency was maintained above 95% after 5 cycles. The morphology, crystal structure, and chemical state of the composites were analysed by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Ultraviolet-visible diffuse reflection, transient photocurrent response, and electrochemical impedance spectroscopy were adopted to identify the charge transfer and separation efficiency of photogenerated electron-hole pairs. The EPR results verified h+ and ˙OH radicals as the primary active species in the photocatalytic oxidation reactions. This observation was also consistent with the results of radical trapping experiments. In addition, the key intermediate products of the photocatalytic degradation of TC over BO-400@PAN-140 were identified via high-performance liquid chromatography-mass spectrometry, which is compatible with two possible photocatalytic reaction pathways. This work provides instructive guidelines for designing heterojunction photocatalysts via a polymer-assisted semiconductor crystallographic transition pathway for TC degradation into cleaner production.

College of Chemical and Biological Engineering Zhejiang University Hangzhou 310058 China

School of Materials Science and Chemical Engineering Ningbo University Ningbo 315211 China

School of Petrochemical Engineering and Environment Zhejiang Ocean University Zhoushan 316022 China

Sustainable Process Integration Laboratory SPIL NETME Centre Faculty of Mechanical Engineering Brno University of Technology VUT Brno Technická 2896 2 616 69 Brno Czech Republic

United National Local Engineering Laboratory of Oil and Gas Storage and Transportation Technology Zhoushan Zhejiang 316022 China

Zhejiang Provincial Key Laboratory of Petrochemical Environmental Pollution Control Zhoushan Zhejiang 316022 China

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