Self-floating Bi4O5Br2/P-doped C3N4/carbon fiber cloth with S-scheme heterostructure for boosted photocatalytic removal of emerging organic contaminants

doi:10.1016/S1872-2067(25)64780-2

Chinese Journal of Catalysis ›› 2025, Vol. 76: 37-49.DOI: 10.1016/S1872-2067(25)64780-2

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Self-floating Bi₄O₅Br₂/P-doped C₃N₄/carbon fiber cloth with S-scheme heterostructure for boosted photocatalytic removal of emerging organic contaminants

Shijie Li^a^,^b^,^*(), Rui Li^a, Kexin Dong^a, Yanping Liu^a, Xin Yu^b, Wenyao Li^c, Tong Liu^d, Zaiwang Zhao^e, Mingyi Zhang^f^,^*(), Bin Zhang^a^,^*(), Xiaobo Chen^g

^aZhejiang Key Laboratory of Pollution Control for Port-Petrochemical Industry, National Engineering Research Center for Marine Aquaculture, Zhejiang Ocean University, Zhoushan 316022, Zhejiang, China
^bHenan Engineering Research Center of Resource & Energy Recovery from Waste, School of Energy Science and Technology, Henan University, Zhengzhou 450046, Henan, China
^cSchool of Materials Science and Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
^dKey Laboratory of Green Chemical Process, Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, Hubei, China
^eCollege of Energy Materials and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010070, Inner Mongolia, China
^fKey Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Physics and Electronic Engineering, Harbin Normal University, Harbin 150025, Heilongjiang, China
^gDivision of Energy, Matter, and Systems, School of Science and Engineering, University of Missouri-Kansas City, Kansas City, MO 64110, USA

Received:2025-04-04 Accepted:2025-07-02 Online:2025-09-18 Published:2025-09-10
Contact: Shijie Li, Mingyi Zhang, Bin Zhang
Supported by:
National Natural Science Foundation of China(U1809214);National Natural Science Foundation of China(U23A20263);National Natural Science Foundation of China(51708504);Natural Science Foundation of Zhejiang Province(LY20E080014);Natural Science Foundation of Zhejiang Province(LTGN23E080001);Science and Technology Project of Zhoushan(2022C41011);and the Open Cooperation Foundation of the Department of Chemical Science of Henan University

Abstract

Abstract:

The industrial implementation of Solar-driven photocatalysis is hampered by inefficient charge separation, poor reusability and hard retrieval of powdery catalysts. To conquer these drawbacks, a self- floating S-scheme Bi₄O₅Br₂/P-doped C₃N₄/carbon fiber cloth (BB/PN/CC) composed of carbon fibers (CC) as the core and Bi₄O₅Br₂/P-doped C₃N₄ (BB/PN) nanosheets as the shell was constructed as a competent, recyclable cloth-shaped photocatalyst for safe and efficient degradation of aquacultural antibiotics. The BB/PN/CC fabric achieves an exceptional tetracycline degradation rate constant of 0.0118 min^‒1, surpassing CN/CC (0.0015 min^‒1), BB/CC (0.0066 min^‒1) and PN/CC (0.0023 min^‒1) by 6.9, 0.8 and 4.1 folds, respectively. Beyond its catalytic prowess, the photocatalyst’s practical superiority is evident in its effortless recovery and environmental adaptability. The superior catalytic effectiveness stems from the S-scheme configuration, which retains the maximum redox capacities of the constituent BB and PN while enabling efficient spatial detachment of photo-carriers. X-ray photoelectron spectroscopy (XPS), in-situ XPS, and electron paramagnetic resonance analyses corroborate the S-scheme mechanism, revealing electron accumulation on PN and hole retention on BB under illumination. Density functional theory calculations further confirm S-scheme interfacial charge redistribution and internal electric field formation. This study advances the design of macroscopic S-scheme heterojunction photocatalysts for sustainable water purification.

Key words: Bi₄O₅Br₂/P-doped C₃N₄, Self-floating S-scheme heterojunction, Internal electric field, Photocatalysis, Antibiotic removal

Shijie Li, Rui Li, Kexin Dong, Yanping Liu, Xin Yu, Wenyao Li, Tong Liu, Zaiwang Zhao, Mingyi Zhang, Bin Zhang, Xiaobo Chen. Self-floating Bi₄O₅Br₂/P-doped C₃N₄/carbon fiber cloth with S-scheme heterostructure for boosted photocatalytic removal of emerging organic contaminants[J]. Chinese Journal of Catalysis, 2025, 76: 37-49.

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Figures/Tables 8

Fig. 1. Synthetic process of BB/PN/CC materials.

Fig. 2. Photos and SEM images of CC (a-d), PN/CC (e-h), and BB/PN/CC (i-l). (m) Mapping images of BB/PN/CC. (n-q) TEM and HRTEM images of BB/PN/CC.

Fig. 3. (a) XRD profiles. Bi 4f (b), Br 3d (c), O 1s (d), P 2p (e) and N 1s (f) XPS spectra.

Fig. 4. Temporal evolution of photocatalytic TC eradication (a) and reaction kinetics (b) over various fabric catalysts. (c) Time course of photocatalytic enrofloxacin, ciprofloxacin and oxytetracycline destruction activity over BB/PN/CC. (d) TC destruction efficiencies over BB/PN/CC with different sizes. Impacts of HA (e) and ions (f) on the catalytic effectiveness of BB/PN/CC. (g) TC annihilation performance of BB/PN/CC in real water matrices. (h) Cycle stabilities of BB/PN/CC. (i) TC elimination over BB/PN/CC in the presence of diverse scavengers.

Fig. 5. (a) TC destruction process over BB/PN/CC. (b-d) Eco-toxicity test results.

Fig. 6. Water contact angle photographs of CC (a), BB/CC (b), PN/CC (c), and BB/PN/CC (d). Transient photocurrent signals (e) and EIS curves (f) for BB/CC PN/CC and BB/PN/CC.

Fig. 7. (a) UV-vis absorption plots. Tauc profiles (b,c), Mott-Schottky curves (d,e), and UPS plots (f) of PN and BB. (g,h) In-situ XPS measurement on BB/PN/CC.

Fig. 8. EPR results of DMPO-•O2- (a) and DMPO-•OH (b). Computed Φ values of BB (c) and PN (d). 3D (e) and 2D (f) charge difference distribution for BB/PN/CC. (g) Schematic representation of the operation mechanism of BB/PN/CC for TC destruction.

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Self-floating Bi₄O₅Br₂/P-doped C₃N₄/carbon fiber cloth with S-scheme heterostructure for boosted photocatalytic removal of emerging organic contaminants

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