Interfacial Mo-S bond modulated S-scheme Mn0.5Cd0.5S/Bi2MoO6 heterojunction for boosted photocatalytic removal of emerging organic contaminants

doi:10.1016/S1872-2067(24)60181-6

Abstract

Abstract:

Inefficient photo-carrier separation and sluggish photoreaction dynamics appreciably undermine the photocatalytic decontamination efficacy of photocatalysts. Herein, an S-scheme Mn_0.5Cd_0.5S/Bi₂MoO₆ heterojunction with interfacial Mo-S chemical bond is designed as an efficient photocatalyst. In this integrated photosystem, Bi₂MoO₆ and Mn_0.5Cd_0.5S function as oxidation and reduction centers of Mn_0.5Cd_0.5S/Bi₂MoO₆ microspheres, respectively. Importantly, the unique charge transfer mechanism in the chemically bonded S-scheme heterojunction with Mo-S bond as atom-scale charge transport highway effectively inhibits the photocorrosion of Mn_0.5Cd_0.5S and the recombination of photo-generated electron-hole pairs, endowing Mn_0.5Cd_0.5S/Bi₂MoO₆ photocatalyst with excellent photocatalytic decontamination performance and stability. Besides, integration of Mn_0.5Cd_0.5S nanocrystals into Bi₂MoO₆ improves hydrophilicity, conducive to the photoreactions. Strikingly, compared with Mn_0.5Cd_0.5S and Bi₂MoO₆, the Mn_0.5Cd_0.5S/Bi₂MoO₆ unveils much augmented photoactivity in tetracycline eradication, among which Mn_0.5Cd_0.5S/Bi₂MoO₆-2 possesses the highest activity with the rate constant up to 0.0323 min^‒1, prominently outperforming other counterparts. This research offers a chemical bonding engineering combining with S-scheme heterojunction strategy for constructing extraordinary photocatalysts for environmental purification.

Key words: Mn_0.5Cd_0.5S/Bi₂MoO₆, Interfacial chemical bond, S-scheme heterojunction, Emerging organic contaminants, Internal electric field, Photocatalysis

Shijie Li, Changjun You, Fang Yang, Guijie Liang, Chunqiang Zhuang, Xin Li. Interfacial Mo-S bond modulated S-scheme Mn_0.5Cd_0.5S/Bi₂MoO₆ heterojunction for boosted photocatalytic removal of emerging organic contaminants[J]. Chinese Journal of Catalysis, 2025, 68: 259-271.

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Figures/Tables 8

Fig. 1. (a) Preparation process of MSBO materials. SEM images of BMO (b), MCS (c), and MSBO-2 (d,e). (f,g) TEM images of MSBO-2. HRTEM image (h), EDX spectrum and mapping images (i) of MSBO-2.

Fig. 2. (a) XRD profiles. XPS profiles of Bi 4f and S 2p (b), Mo 3d (c), O 1s (d), Mn 2p (e) and Cd 3d (f) of MCS, BMO, and MSBO-2.

Fig. 3. (a) TC abatement curves over BMO, MCS, and MSBO heterojunctions. (b) Comparison of the catalytic performances of Bi2MoO6-based photocatalysts. (c) Photocatalytic elimination performance of norfloxacin, enrofloxacin and oxytetracycline by MSBO-2. (d?g) Photocatalytic effectiveness of MSBO-2 under diverse experimental conditions. (h) Cyclic runs for photocatalytic destruction of TC over MSBO-2. (i) TC abatement activity of MSBO-2 loaded with diverse scavengers.

Fig. 4. (a) Decomposition course of TC over MSBO-2. (b-d) Eco-toxicity estimation.

Fig. 5. EIS plots (a), Photocurrent intensities (b), and Photoluminescence plots (c) of BMO, MCS and MSBO materials. WCA tests on BMO (d), MCS (e) and MSBO-2 (f).

Fig. 6. (a) UV-vis DRS diagrams of BMO, MCS, and MSBO materials. Tauc curves (b,c) and Mott Schottky profiles (d,e) of BMO and MSC. (f) Diagram of the electronic band structure.

Fig. 7. (a) UPS measurement of BMO and MCS. Calculated work functions of BMO (b) and MCS (c). (d) The PDOS of MSBO. Computed 3D (e) and 2D (f) charge difference distribution of MSBO. XPS (in situ and ex situ) profiles of Bi 4f and S 2p (g), Cd 3d (h), and Mn 2p (i) of MSBO-2 under dark and light conditions.

Fig. 8. (a,b) EPR measurements of reactive radicals. (c) The operation mechanism of MSBO for TC eradication under visible light.

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Interfacial Mo-S bond modulated S-scheme Mn_0.5Cd_0.5S/Bi₂MoO₆ heterojunction for boosted photocatalytic removal of emerging organic contaminants

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