Preparation of Sb2S3/Sn3O4 S-scheme Heterostructures and Its Performance for Methyl Orange Photocatalytic Degradation

doi:10.11901/1005.3093.2025.339

Chinese Journal of Materials Research

2026, Vol. 40

Issue (5): 352-360 DOI: 10.11901/1005.3093.2025.339

Special Section on Photocatalysis

Current Issue | Archive | Adv Search

Preparation of Sb₂S₃/Sn₃O₄ S-scheme Heterostructures and Its Performance for Methyl Orange Photocatalytic Degradation

YIN Xiaotong¹, TIAN Yuxin¹, FENG Sheng¹, LI Wenying¹, WANG Lixing¹, ZHANG Lina¹^,²(

), ZHANG Wei¹^,²

^1.College of Physical Science and Technology, Bohai University, Jinzhou 121013, China
^2.Institute of Ocean Research, Bohai University, Jinzhou 121013, China

Cite this article:

YIN Xiaotong, TIAN Yuxin, FENG Sheng, LI Wenying, WANG Lixing, ZHANG Lina, ZHANG Wei. Preparation of Sb₂S₃/Sn₃O₄ S-scheme Heterostructures and Its Performance for Methyl Orange Photocatalytic Degradation. Chinese Journal of Materials Research, 2026, 40(5): 352-360.

Download:

HTML

PDF(7067KB)
Export: BibTeX | EndNote (RIS)

Abstract

A photocatalyst of Sb₂S₃/Sn₃O₄ S-scheme heterojunction was prepared via hydrothermal method by in-situ growing Sn₃O₄ nanosheets on the surface of Sb₂S₃ nanorods. The phase constituents, morphology, elemental distribution, light absorption properties, and charge separation efficiency of the acquired photocatalyst were characterized by using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV-Visible absorption spectroscopy, photocurrent, electrochemical impedance spectroscopy and photoluminescence spectroscopy. The performance of Sb₂S₃/Sn₃O₄ heterojunction catalysts with different deposited amount of Sb₂S₃ for degradation of methyl orange (MO, initial concentration: 20 mg/L) was investigated under visible light irradiation. The results indicate that these photocatalysts with heterogeneous structure all exhibit significantly high photocatalytic activity, the optimized photocatalyst with 0.1 g of Sb₂S₃ achieves a degradation rate of 91% for MO within 40 min. The results of XPS analysis, band gap structure and free radical trapping analysis revealed that the photogenerated charge carriers in this heterostructure follow a S-scheme transfer mechanism.

Key words: inorganic non-metallic materials S-scheme heterostructure photocatalysis Sb₂S₃ Sn₃O₄ methyl orange degradation

Received: 17 November 2025

ZTFLH:

X703.1

Fund: Institute of Ocean Research of Bohai University(BDHYYJY2022014);Institute of Ocean Research of Bohai University(2022009)

Corresponding Authors: ZHANG Lina, Tel: 18704208573, E-mail: zhanglina@bhu.edu.cn

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	YIN Xiaotong
	TIAN Yuxin
	FENG Sheng
	LI Wenying
	WANG Lixing
	ZHANG Lina
	ZHANG Wei

URL:

https://www.cjmr.org/EN/10.11901/1005.3093.2025.339 OR https://www.cjmr.org/EN/Y2026/V40/I5/352

Fig.1 SEM images of Sb₂S₃ (a), Sn₃O₄ (b), and SS(0.1) (c, d), TEM images of SS(0.1) (e, f, h), HRTEM images corresponding to the region marked in Fig. 1f (g) and Fig. 1h (i), and EDS elemental mapping showing the distribution of Sn, O, Sb, and S in SS(0.1) (j)

Fig.2 XRD patterns of Sb₂S₃, Sn₃O₄ and SS(0.1) (a), XPS spectra of Sn₃O₄, Sb₂S₃, and SS(0.1) (b), and high-resolution spectra of Sn 3d (c), O 1s (d), Sb 3d (e), and S 2p (f)

Fig.3 UV-Vis absorption spectra of Sn₃O₄, Sb₂S₃, and SS(0.1) (a), Tauc plots of (αhν)² versus photon energy (hν) for Sn₃O₄ and Sb₂S₃ (b)

Fig.4 Transient photocurrent responses (a), EIS spectra (inset is the equivalent circuit model) (b) and PL spectra (c) of Sb₂S₃, Sn₃O₄ and SS(0.1)

Fig.5 Degradation efficiency (a), pseudo-first-order kinetics (b), apparent rate constants (c) of the catalysts, and cycling stability of the SS(0.1) catalyst (d)

Fig.6 Mott-Schottky plots of Sb₂S₃ (a) and Sn₃O₄ (b)

Fig.7 Degradation efficiency of MO by SS(0.1) in the presence of different scavengers (a), ESR signal for $⋅$ O $2 -$ (b) and $⋅$ OH (c)

Fig.8 Schematic diagram of the charge transfer pathway in the photocatalytic degradation of MO by Sb₂S₃/Sn₃O₄ heterojunction

[1]	Bora L V, Mewada R K. Visible/solar light active photocatalysts for organic effluent treatment: fundamentals, mechanisms and parametric review [J]. Renew. Sustain. Energy Rev., 2017, 76: 1393 doi: 10.1016/j.rser.2017.01.130
[2]	Hanafi M F, Sapawe N. A review on the water problem associate with organic pollutants derived from phenol, methyl orange, and remazol brilliant blue dyes [J]. Mater. Today Proc., 2020, 31: A141
[3]	Ma X E, Hu M F, Song X L, et al. Photocatalytic degradation of methyl orange using palygorskite supported Zn-In LDO/ZnS/In₂S₃ composites [J]. Chin. J. Mater. Res., 2025, 39: 413
	马雪娥, 胡美凤, 宋雪丽等. 坡缕石负载Zn-In LDO/ZnS/In₂S₃复合材料对甲基橙的光催化降解 [J]. 材料研究学报, 2025, 39: 413 doi: 10.11901/1005.3093.2024.273
[4]	Chen Z S, Liang X P, Fan X W, et al. Fabrication and photocatalytic properties of Ce-La-Ag Co-doped TiO₂/basalt fiber composite photocatalyst [J]. Chin. J. Mater. Res., 2019, 33: 515
	陈子尚, 梁小平, 樊小伟等. Ce-La-Ag共掺杂TiO₂/玄武岩纤维复合光催化剂的制备和性能 [J]. 材料研究学报, 2019, 33: 515 doi: 10.11901/1005.3093.2018.588
[5]	Hashemi S H, Kaykhaii M. Chapter 15-Azo dyes: sources, occurrence, toxicity, sampling, analysis, and their removal methods [A]. DaluT, TavengwaNT. Emerging Freshwater Pollutants [M]. Amsterdam: Elsevier, 2022: 267
[6]	El Messaoudi N, Miyah Y, Abd Al Qadr Imad Wan-Mohtar W, et al. Advancements in adsorption and photocatalytic degradation technologies of brilliant green from water: current status, challenges, and future prospects [J]. Mater. Today Chem., 2024, 42: 102399
[7]	Navidpour A H, Xu B T, Ahmed M B, et al. Immobilization of TiO₂ and ZnO by facile surface engineering methods to improve semiconductor performance in photocatalytic wastewater treatment: a review [J]. Mater. Sci. Semicond. Process., 2024, 179: 108518 doi: 10.1016/j.mssp.2024.108518
[8]	Yu X, Li C C, Zhang J, et al. Recent progress on Sn₃O₄ nanomaterials for photocatalytic applications [J]. Int. J. Miner. Metall. Mater., 2024, 31: 231 doi: 10.1007/s12613-023-2761-z
[9]	He Y H, Li D Z, Chen J, et al. Sn₃O₄: a novel heterovalent-tin photocatalyst with hierarchical 3D nanostructures under visible light [J]. RSC Adv., 2014, 4: 1266 doi: 10.1039/C3RA45743E
[10]	Chen L, Hou C, Liu Z Q, et al. Inhibition of Sn(II) oxidation in Z-scheme BiVO₄-QD@Sn₃O₄ for overall water splitting [J]. Chem. Commun., 2020, 56(89): 13884 doi: 10.1039/D0CC05566B
[11]	Zeng D B, Yu C L, Fan Q Z, et al. Theoretical and experimental research of novel fluorine doped hierarchical Sn₃O₄ microspheres with excellent photocatalytic performance for removal of Cr(VI) and organic pollutants [J]. Chem. Eng. J., 2020, 391: 123607 doi: 10.1016/j.cej.2019.123607
[12]	Xie Q X, Zhu Y T, Zhao P, et al. A strategic co-assembly of carbon nanotubes and graphene on hierarchical flower-like Sn₃O₄ clusters aimed to enhance lithium storage capability [J]. J. Electroanal. Chem., 2021, 880: 114898 doi: 10.1016/j.jelechem.2020.114898
[13]	Li X D, Zhang L N, Tian Y X, et al. An S-scheme photocatalyst constructed by modifying SnIn₄S₈ nanosheets on AgVO₃ nanorods for enhanced photocatalytic performance [J]. J. Alloy. Compd., 2025, 1016: 178954 doi: 10.1016/j.jallcom.2025.178954
[14]	Chen Z Y, Zhang H, Wang J H, et al. Designing Bi₂O₃-Sn₃O₄ Z-scheme heterojunction on TiO₂ NTs for improving photocatalytic performance [J]. J. Mol. Liq., 2024, 412: 125844 doi: 10.1016/j.molliq.2024.125844
[15]	Li S G, Liu Z Y, Qu Z H, et al. An all-solid-state Z-scheme Na-NbO₃-Au-Sn₃O₄ photocatalyst for effective degradation of carbofuran under sunlight irradiation [J]. J. Photochem. Photobiol., 2020, 389A: 112246
[16]	Wang D D, Lin Z X, Miao C, et al. An S-scheme photocatalyst constructed by modifying Ni-doped Sn₃O₄ micro-flowers on g-C₃N₄ nanosheets for enhanced visible-light-driven hydrogen evolution [J]. J. Ind. Eng. Chem., 2022, 113: 380 doi: 10.1016/j.jiec.2022.06.013
[17]	Zhou S J, Wei Z, Xie H R, et al. Ultrafast photoreduction of Cr(VI) by enhanced adsorption and internal electric field induced via S-scheme In₂S₃/Sn₃O₄ heterostructures with robust interface [J]. Sep. Purif. Technol., 2025, 354: 128653 doi: 10.1016/j.seppur.2024.128653
[18]	Wallace A G, King R P, Zhelev N, et al. Anodic Sb₂S₃ electrodeposition from a single source precursor for resistive random-access memory devices [J]. Electrochim. Acta, 2022, 432: 141162 doi: 10.1016/j.electacta.2022.141162
[19]	Son N, Do J Y, Kang M. Characterization of core@shell-structured ZnO@Sb₂S₃ particles for effective hydrogen production from water photo spitting [J]. Ceram. Int., 2017, 43: 11250 doi: 10.1016/j.ceramint.2017.05.175
[20]	Ma Z, Yang Y H, Wei X L, et al. CdSe quantum dots supported on Sb₂S₃ nanorods as S-scheme heterojunction photoanode in photoelectrochemical cells [J]. ACS Appl. Nano Mater., 2024, 7: 24213 doi: 10.1021/acsanm.4c05053
[21]	Yang M J, Fan Z Y, Du J Y, et al. Tailoring the crystallographic orientation of a Sb₂S₃ thin film for efficient photoelectrochemical water reduction [J]. ACS Catal., 2022, 12: 8175 doi: 10.1021/acscatal.2c01384
[22]	Li W, Li J Y, Ma T H, et al. Construction of core-shell Sb₂S₃@CdS nanorod with enhanced heterointerface interaction for chromium-containing wastewater treatment [J]. Small, 2023, 19: 2302737 doi: 10.1002/smll.v19.42
[23]	Tian Y X, Zhang W, Li X D, et al. Enhanced photocatalytic activity of Sn₃O₄/TiO₂ heterostructures for Cr(VI) reduction and isoniazid degradation [J]. Mater. Sci. Semicond. Process., 2025, 192: 109441 doi: 10.1016/j.mssp.2025.109441
[24]	Li M, Li W F, Lyu J, et al. Constructed Co₃O₄-Sn₃O₄ hierarchical nanoflower-tree heterostructure with boosting photoelectrocatalytic efficiency for water decontamination [J]. Chem. Eng. J., 2021, 423: 130252 doi: 10.1016/j.cej.2021.130252
[25]	Wang Q Y, Zhao Y H, Zhang Z F, et al. Hydrothermal preparation of Sn₃O₄/TiO₂ nanotube arrays as effective photocatalysts for boo-sting photocatalytic dye degradation and hydrogen production [J]. Ceram. Int., 2023, 49: 5977 doi: 10.1016/j.ceramint.2022.11.113
[26]	Zhao J F, Cheng Y F, Chen Y Q, et al. Defects regulation of Sb₂S₃ by construction of Sb₂S₃/In₂S₃ direct Z-scheme heterojunction with enhanced photoelectrochemical performance [J]. Appl. Surf. Sci., 2021, 568: 150917 doi: 10.1016/j.apsusc.2021.150917
[27]	Kong D Z, Fan H H, Yin D, et al. AgFeO₂ nanoparticle/ZnIn₂S₄ microsphere p-n heterojunctions with hierarchical nanostructures for efficient visible-light-driven H₂ evolution [J]. ACS Sustain. Chem. Eng., 2021, 9: 2673 doi: 10.1021/acssuschemeng.0c07638
[28]	Zhang W, Tian Y X, Zhang L N, et al. Construction of a direct Z-scheme Sn₃O₄/In₂O₃ heterostructure: boosting photocatalytic degradation of contaminants [J]. Mater. Today Nano, 2025, 31: 100651
[29]	Jia W F, Xiong R Z, Sun Y T, et al. A well-designed hierarchical Bi₁₉S₂₇Br₃ nanorods@SnIn₄S₈ nanosheet core-shell S-scheme heterostructure for robust photothermal-assisted photocatalytic CO₂ reduction [J]. J. Mater. Chem., 2024, 12A: 4513
[30]	Cui X Q, Li H, Yang Z Y, et al. A novel CaIn₂S₄/TiO₂ NTAs heterojunction photoanode for highly efficient photocathodic protection performance of 316 SS under visible light [J]. Nanotechnology, 2021, 32: 395702 doi: 10.1088/1361-6528/ac0b1a
[31]	Zhang J, Zhang R, Cao J, et al. DFT-proved Z-type ZnO/SnIn₄S₈ heterojunction for detecting hexavalent chromium [J]. J. Alloy. Compd., 2022, 922: 166266 doi: 10.1016/j.jallcom.2022.166266
[32]	Zhao W, Wei Z B, He H, et al. Supporting 1-D AgVO₃ nanoribbons on single layer 2-D graphitic carbon nitride ultrathin nanosheets and their excellent photocatalytic activities [J]. Appl. Catal., 2015, 501A: 74
[33]	Miao Z R, Wang Q L, Zhang Y F, et al. In situ construction of S-scheme AgBr/BiOBr heterojunction with surface oxygen vacancy for boosting photocatalytic CO₂ reduction with H₂O [J]. Appl. Catal., 2022, 301B: 120802
[34]	Tan P F, Yang L, Liu H L, et al. CdS QDs decorated on 3D flower-like Sn₃O₄: a hierarchical photocatalyst with boosted charge separation for hydrogen production [J]. New J. Chem., 2024, 48: 300 doi: 10.1039/D3NJ03611A
[35]	Chen S F, Hu Y F, Ji L, et al. Preparation and characterization of direct Z-scheme photocatalyst Bi₂O₃/NaNbO₃ and its reaction mechanism [J]. Appl. Surf. Sci., 2014, 292: 357 doi: 10.1016/j.apsusc.2013.11.144
[36]	Liu C P, Wang H E, Ng T W, et al. Hybrid photovoltaic cells based on ZnO/Sb₂S₃/P3HT heterojunctions [J]. Phys. Status Solidi, 2012, 249b: 627
[37]	Zhang L Y, Zhang J J, Yu J G, et al. Charge-transfer dynamics in S-scheme photocatalyst [J]. Nat. Rev. Chem., 2025, 9: 328 doi: 10.1038/s41570-025-00698-3
[38]	Wu X H, Sayed M, Wang G H, et al. COF-based S-scheme heterojunction photocatalyst [J]. Adv. Mater., 2026, 38: e11322 doi: 10.1002/adma.v38.2
[39]	Ouyang C, Quan X Y, Zhang C L, et al. Direct Z-scheme ZnIn₂S₄@MoO₃ heterojunction for efficient photodegradation of tetracycline hydrochloride under visible light irradiation [J]. Chem. Eng. J., 2021, 424: 130510 doi: 10.1016/j.cej.2021.130510
[40]	Wang B L, Chai Y F, Tan S X, et al. Construction and photocatalytic performance study of g-C₃N₄/CdS S-scheme heterojunction [J]. Chin. J. Mater. Res., 2025, 39: 712
	王炳林, 柴一峰, 谭圣霞等. g-C₃N₄/CdS S型异质结复合光催化材料的制备及其性能 [J]. 材料研究学报, 2025, 39: 712 doi: 10.11901/1005.3093.2024.503

[1]	YU Hanbo, HU Yan, XU Tingting, ZHANG Yiwen, ZHANG Chi, TAN Jiewen, LI Yongxiang, WANG Han. Degradation Performance of Heterojunction Photocatalyst Bi₄O₅I₂/Bi₇O₉I₃ for Ciprofloxacin Solution[J]. 材料研究学报, 2026, 40(5): 321-332.
[2]	LIU Danyang, JING Miaomiao, ZHAO Qiang, WANG Junli, JIA Zhifang, LI Zuopeng, WANG Kewei, GUO Yong. Synthesis of Cu₂O/N,S-BiOBr Composite Photocatalysts and Their Performance for Tetracycline Degradation[J]. 材料研究学报, 2026, 40(5): 333-342.
[3]	ZHANG Zhikai, LEI Jiashuang, YAO Bingya, CHEN Siyu, LIU Shuo, SUN Yuwei, TANG Qian. Preparation and Piezoelectric-photocatalytic Performance for Tetracycline Degradation of Z-type Heterojunction Composite CuFe₂O₄/BaTiO₃[J]. 材料研究学报, 2026, 40(5): 361-371.
[4]	ZHAO Ruize, TIAN Li, SONG Peiyuan, FANG Yao, SUN Meng, FAN Sainan, OU Zhimin, ZHU Haibo, HUANG Rongjiao, YANG Li. Preperation and Electrochemical Performance of Rare Earth La³⁺-doped Vanadium Dioxide[J]. 材料研究学报, 2026, 40(4): 313-320.
[5]	ZOU Jun, ZHAO Run, DAI Chenmin. Photoelectric Properties of WSe₂/BiFeO₃/Q2DEG Hybrid Heterojunctions[J]. 材料研究学报, 2026, 40(3): 210-216.
[6]	HAN Yang, LI Mengchen, YU Hongyue, QIAO Liang, SHEN Yuge, GAO Shanbin, JIAO Yilai, CHI Kebin. Synthesis of Hierarchical ZSM-22 Zeolite and its Catalytic Performance for Hydrogenation Isomerization of n-Dodecane[J]. 材料研究学报, 2026, 40(1): 1-12.
[7]	ZHAN Jie, CHEN Xiaojiang, ZOU Zhili, SU Xingdong, XIE Shiyu, JIANG Liang, WANG Jinling, WANG Lielin. Preparation of Nano Ag⁰@ACF Material and Its Adsorption Performance for Gaseous Iodine[J]. 材料研究学报, 2025, 39(9): 673-682.
[8]	SHI Yuanji, CHENG Cheng, ZHANG Haitao, HU Daochun, CHEN Jingjing, LI Junwan. Nanoscale Analysis of Material Removal Behavior of β-SiC Semiconductor Devices during Sliding Wear[J]. 材料研究学报, 2025, 39(9): 701-711.
[9]	ZHOU Yingying, ZHANG Yingxian, DAN Zhuoya, DU Xu, DU Haonan, ZHEN Enyuan, LUO Fa. Influence of La Doping on Microwave Absorption Properties of YFeO₃ Ceramics[J]. 材料研究学报, 2025, 39(8): 561-568.
[10]	GENG Ruiwen, YANG Zhijiang, YANG Weihua, XIE Qiming, YOU Jinjing, LI Lijun, WU Haihua. Molecular Dynamics Simulation of Subsurface Damage of 6H-SiC Bulk Materials Induced by Grinding with Nano-sized Diamond Particles[J]. 材料研究学报, 2025, 39(8): 603-611.
[11]	LIU Zhihua, WANG Mingyue, LI Yijuan, QIU Yifan, LI Xiang, SU Weizhao. Preparation and Photocatalytic Performance of 1T/2H O-MoS₂@S-pCN Composite Catalyst in Degradation of Hexavalent Chromium and Ciprofloxacin[J]. 材料研究学报, 2025, 39(7): 551-560.
[12]	HAN Leilei, WANG Wentao, WU Yun, CHEN Jiajun, ZHAO Yong. High Temperature Growth Process of YBCO Superconducting Solder by Fluorine-free Chemical Solution Method[J]. 材料研究学报, 2025, 39(6): 474-480.
[13]	YUAN Xinyu, SHI Fei, LIU Jingxiao, ZHANG Haojie, YANG Dayi, WANG Meiyu, REN Ming. Effect of Er₂O₃ Addition on Crystallization Behavior and Properties of Lithium Disilicate Glass Ceramics[J]. 材料研究学报, 2025, 39(6): 455-462.
[14]	LI Ying, NIE Xuetong, QIAN Liguo, ZHU Yiren. Synthesis of Co₃O₄/ZnO@MG-C₃N_x Catalysts and Their Visible Light Degradation of Methylene Blue Performance[J]. 材料研究学报, 2025, 39(4): 241-250.
[15]	CHEN Shiyu, LI Wei, KUANG Haiyan, GAO Shaowei, PANG Dongfang. Dielectric-, Ferroelectric- and Piezoelectric-property of Lu³⁺ Doped 0.67BiFeO₃-0.33BaTiO₃ Lead-free Piezoelectric Ceramics[J]. 材料研究学报, 2025, 39(4): 272-280.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed