Construction of S-scheme MnO2/BiOCl heterojunction boosting photocatalytic low-concentration peroxymonosulfate activation for contaminants removal

doi:10.1016/S1872-2067(26)65037-1

Abstract

Abstract:

Limited by secondary pollution of PMS and active species generation capacity, the development of photocatalytic PMS activation systems should focus on the improvement of PMS utilization efficiency. In this manuscript, S-scheme MnO₂/BiOCl heterojunction were constructed for various antibiotics and endocrine disruptors removal by photocatalytic peroxymonosulfate (PMS) activation. Under visible light and the low PMS concentration (0.08 mmol·L^-1), the doxycycline hydrochloride (DXC) and bisphenol A oxidation performance of MnO₂/BiOCl-2 composites have enhanced 16.3% and 67.2% compared with that of BiOCl materials. The photocatalytic PMS utilization efficiency of MOBC-2 composites reaches to 95.5%, wherein that of BiOCl materials is 36.1%. The PMS adsorption energy of MnO₂/BiOCl composites by the density functional thoery calculation possess exceptional PMS activation ability ascribed to the coupling with MnO₂. Furthermore, the calculation of electron spin-charge density and Gibbs free energy change demonstrates MnO₂/BiOCl composites can react with PMS for ¹O₂ formation. The liquid chromatography-tandem mass spectrometry measurement and Fukui function has been employed for inferring the intermediates of DXC in PMS oxidation process. This manuscript provides research insights and scientific references for construction of S-scheme heterojunction to employ in visible-light-driven low-concentration PMS activation process.

Key words: S-scheme heterojunction, Photocatalysis, MnO₂/BiOCl, Peroxymonosulfate, Pollutants removal

Jintao Dong, Rui Zhang, Zhishuai Wang, Shengqun Cao, Lina Li, Gaopeng Liu, Bin Wang, Yixuan Gao, Jiexiang Xia. Construction of S-scheme MnO₂/BiOCl heterojunction boosting photocatalytic low-concentration peroxymonosulfate activation for contaminants removal[J]. Chinese Journal of Catalysis, 2026, 85: 310-321.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65037-1

https://www.cjcatal.com/EN/Y2026/V85/I6/310

Figures/Tables 8

Fig. 1. (a) The schematic illustration for preparation process of MOBC-2 composites. The XPS spectra of MnO2, BiOCl and MOBC-2 composites: Bi 4f (b), Mn 2p (c), Cl 2p (d), and O 1s (e). (f) The electrostatic potential calculation of BiOCl materials and MnO2 materials.

Fig. 2. SEM images of BiOCl materials (a), MnO2 materials (d) and MOBC-2 composites (g). TEM images of BiOCl materials (b,c), MnO2 materials (e,f) and MOBC-2 composites (h,i). (j) TEM images and the corresponding elemental mapping images of MOBC-2 composites.

Fig. 3. The DXC degradation activity of MnO2, BiOCl and MOBC-x composites (a), and MOBC-2 composites with different PMS concentrations (b). The DXC degradation activity of MOBC-2/PMS/Vis system under cation interference (c) and anion interference condition (d). (e) The cycle stability of MOBC-2 composites for DXC removal. (f) The different pollutant degradation performance of MOBC-2 composites. (g) The BPA degradation activity of BiOCl and MOBC-2 composites. The UV-vis absorption spectra of iodometric PMS measure-ment systems of BiOCl (h) and MOBC-2 composites (i). Reaction conditions: [catalysts] = 0.2 g·L-1, [PMS] = 0.08 mmol·L-1, [pollutants] = 10 mg·L-1.

Fig. 4. (a) UV-vis DRS spectra of MnO2, BiOCl and MOBC-x composites. The transient photocurrents response (b), EIS spectra (c), PL spectra (d), and LSV curves (e,f) of BiOCl and MOBC-2 composites under different conditions.

Fig. 5. ESR spectra of DMPO-•O2− (a), DMPO-•OH and DMPO-SO4•-(b), and TEMPO-1O2 (c) in various systems. (d) The •O2−, 1O2, •OH and SO4•− species capture measurements of MOBC-2/PMS/Vis system.

Fig. 6. (a) The energy band diagram of MOBC composites before and after contact; charge transfer pathway of MOBC composites. (b) The possible photocatalytic PMS degradation mechanism in MOBC-2 composites.

Fig. 7. (a) The optimized molecule structure of DXC molecules. (b) HOMO and LUMO of DXC molecules. (c) The distribution of orbit weight Fukui function on the plane. (d) The orbital weights of f+, f−, f0. (e) The DXC possible degradation pathways for MOBC-2/PMS/Vis systems.

Fig. 8. Mechanism analysis of 1O2 generation of BiOCl, MnO2 and MnO2/BiOCl materials. (a) The schematic energy band diagrams showing charge transfer pathway for MnO2/BiOCl materials. (b) Gibbs free energy diagram of various intermediates at different adsorption sites in PMS. (c) pDOS diagram of oxygen, (d-f) the electron configuration in oxygen and 1O2. (g) The spin electron density of adsorbed oxygen and O-O (SO5). (h) The adsorption energy and rate-determining step energy changes.

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Construction of S-scheme MnO₂/BiOCl heterojunction boosting photocatalytic low-concentration peroxymonosulfate activation for contaminants removal

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