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Highly effective visible-photocatalytic hydrogen evolution and simultaneous organic pollutant degradation over an urchin-like oxygen-doped MoS2/ZnIn2S4 composite

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Abstract

Achieving hydrogen production and simultaneous decomposition of organic pollutants through dual-functional photocatalytic reactions has received increasing attention due to the environmentally friendly and cost-effective characteristics of this approach. In this work, an urchin-like oxygen-doped MoS2/ZnIn2S4 (OMS/ZIS) composite was fabricated for the first time using a simple solvothermal method. The unique microstructure with abundant active sites and fast charge transfer channels further shortened the charge migration distance and compressed carrier recombination. The obtained composite exhibited an efficient H2 evolution reaction rate of 12.8 mmol/g/h under visible light, which was nearly times higher than pristine ZnIn2S4, and the apparent quantum efficiency was 14.9% (420 nm). The results of the simultaneous photocatalytic H2 evolution and organic pollutant decomposition test were satisfactory, resulting in decomposition efficiencies of resorcinol, tetracycline, and bisphenol A that reached 41.5%, 63.5%, and 53.0% after 4 h, respectively, and the highest H2 evolution rate was 672.7 µmol/g/h for bisphenol A. Furthermore, natural organic matter (NOM) abundantly found in actual water was adopted as an electron donor for H production under simulated sunlight irradiation, indicating the promising practicability of simultaneous hydrogen evolution and NOM decomposition. Moreover, the mechanisms of the dual-purpose photocatalytic reactions, as well as the synergistic effect between the molecular structures of the organic pollutants and the corresponding adsorption behavior on the photocatalyst surface were illustrated in detail. These obtained results may serve as an inspiration for the rational design of highly efficient, dual-functional photocatalysts in the future.

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References

  • Byskov L S, Nørskov J K, Clausen B S, Topsøe H (1999). DFT calculations of unpromoted and promoted MoS2-based hydrodesulfurization catalysts. Journal of Catalysis, 187(1): 109–122

    Article  CAS  Google Scholar 

  • Chai B, Liu C, Wang C, Yan J, Ren Z (2017). Photocatalytic hydrogen evolution activity over MoS2/ZnIn2S4 microspheres. Chinese Journal of Catalysis, 38(12): 2067–2075

    Article  CAS  Google Scholar 

  • Chandrasekaran S, Yao L, Deng L, Bowen C, Zhang Y, Chen S, Lin Z, Peng F, Zhang P (2019). Recent advances in metal sulfides: from controlled fabrication to electrocatalytic, photocatalytic and photoelectrochemical water splitting and beyond. Chemical Society Reviews, 48(15): 4178–4280

    Article  CAS  Google Scholar 

  • Chen G, Ding N, Li F, Fan Y, Luo Y, Li D, Meng Q (2014). Enhancement of photocatalytic H2 evolution on ZnIn2S4 loaded with in-situ photo-deposited MoS2 under visible light irradiation. Applied Catalysis B: Environmental, 160–161: 614–620

    Article  Google Scholar 

  • Chen S, Li S, Xiong L, Wang G (2018). In-situ growth of ZnIn2S4 decorated on electrospun TiO2 nanofibers with enhanced visible-light photocatalytic activity. Chemical Physics Letters, 706: 68–75

    Article  CAS  Google Scholar 

  • Cho Y J, Moon G H, Kanazawa T, Maeda K, Choi W (2016). Selective dual-purpose photocatalysis for simultaneous H2 evolution and mineralization of organic compounds enabled by a Cr2O3 barrier layer coated on Rh/SrTiO3. Chemical Communications, 52(62): 9636–9639

    Article  CAS  Google Scholar 

  • Daskalaki V M, Antoniadou M, Li Puma G, Kondarides D I, Lianos P (2010). Solar light-responsive Pt/CdS/TiO2 photocatalysts for hydrogen production and simultaneous degradation of inorganic or organic sacrificial agents in wastewater. Environmental Science & Technology, 44(19): 7200–7205

    Article  CAS  Google Scholar 

  • Ding N, Fan Y, Luo Y, Li D, Meng Q (2015). Enhancement of H2 evolution over new ZnIn2S4/RGO/MoS2 photocatalysts under visible light. APL Materials, 3(10): 104417

    Article  Google Scholar 

  • Du C, Zhang Q, Lin Z, Yan B, Xia C, Yang G (2019). Half-unit-cell ZnIn2S4 monolayer with sulfur vacancies for photocatalytic hydrogen evolution. Applied Catalysis B: Environmental, 248: 193–201

    Article  CAS  Google Scholar 

  • Eisenstein M (2015). Pesticides: Seeking answers amid a toxic debate. Nature, 521(7552): S52–S55

    Article  Google Scholar 

  • Gao B, Du X, Ma Y, Li Y, Li Y, Ding S, Song Z, Xiao C (2020). 3D flower-like defected MoS2 magnetron-sputtered on candle soot for enhanced hydrogen evolution reaction. Applied Catalysis B: Environmental, 263: 117750

    Article  CAS  Google Scholar 

  • Guan Z, Wang P, Li Q, Li G, Yang J (2018). Constructing a ZnIn2S4 nanoparticle/MoS2-RGO nanosheet 0D/2D heterojunction for significantly enhanced visible-light photocatalytic H2 production. Dalton Transactions (Cambridge, England), 47(19): 6800–6807

    Article  CAS  Google Scholar 

  • Hao M, Deng X, Xu L, Li Z (2019). Noble metal free MoS2/ZnIn2S4 nanocomposite for acceptorless photocatalytic semi-dehydrogenation of 1,2,3,4-tetrahydroisoquinoline to produce 3,4-dihydroisoquinoline. Applied Catalysis B: Environmental, 252: 18–23

    Article  CAS  Google Scholar 

  • Hou Y, Laursen A B, Zhang J, Zhang G, Zhu Y, Wang X, Dahl S, Chorkendorff I (2013). Layered nanojunctions for hydrogen-evolution catalysis. Angewandte Chemie International Edition, 52(13): 3621–3625

    Article  CAS  Google Scholar 

  • Hu P, Su H, Chen Z, Yu C, Li Q, Zhou B, Alvarez P J J, Long M (2017). Selective degradation of organic pollutants using an efficient metal-free catalyst derived from carbonized polypyrrole via peroxymonosulfate activation. Environmental Science & Technology, 51(19): 11288–11296

    Article  CAS  Google Scholar 

  • Huang T, Chen W, Liu T Y, Hao Q L, Liu X H (2017). ZnIn2S4 hybrid with MoS2: A non-noble metal photocatalyst with efficient photocatalytic activity for hydrogen evolution. Powder Technology, 315: 157–162

    Article  CAS  Google Scholar 

  • Jiang G, Wang K, Li J, Fu W, Zhang Z, Johnson G, Lv X, Zhang Y, Zhang S, Dong F (2018a). Electrocatalytic hydrodechlorination of 2,4-dichlorophenol over palladium nanoparticles and its pH-mediated tug-of-war with hydrogen evolution. Chemical Engineering Journal, 348: 26–34

    Article  CAS  Google Scholar 

  • Jiang X H, Wang L C, Yu F, Nie Y C, Xing Q J, Liu X, Pei Y, Zou J P, Dai W L (2018b). Photodegradation of organic pollutants coupled with simultaneous photocatalytic evolution of hydrogen using quantum-dot-modified g-C3N4 catalysts under visible-light irradiation. ACS Sustainable Chemistry & Engineering, 6(10): 12695–12705

    Article  CAS  Google Scholar 

  • Jo W K, Natarajan T S (2016). Fabrication and efficient visible light photocatalytic properties of novel zinc indium sulfide (ZnIn2S4) − graphitic carbon nitride (g-C3N4)/bismuth vanadate (BiVO4) nanorod-based ternary nanocomposites with enhanced charge separation via Z-scheme transfer. Journal of Colloid and Interface Science, 482: 58–72

    Article  CAS  Google Scholar 

  • Kampouri S, Nguyen T N, Spodaryk M, Palgrave R G, Züttel A, Smit B, Stylianou K C (2018). Concurrent photocatalytic hydrogen generation and dye degradation using MIL − 125 − NH2 under visible light irradiation. Advanced Functional Materials, 28(52): 1806368

    Article  Google Scholar 

  • Kampouri S, Stylianou K C (2019). Dual-functional photocatalysis for simultaneous hydrogen production and oxidation of organic substances. ACS Catalysis, 9(5): 4247–4270

    Article  CAS  Google Scholar 

  • Li T, Zhong W, Jing C, Li X, Zhang T, Jiang C, Chen W (2020). Enhanced hydrolysis of p-nitrophenyl phosphate by iron (hydr) oxide nanoparticles: Roles of exposed facets. Environmental Science & Technology, 54(14): 8658–8667

    Article  CAS  Google Scholar 

  • Li W, Lin Z, Yang G (2017). A 2D self-assembled MoS2/ZnIn2S4 heterostructure for efficient photocatalytic hydrogen evolution. Nanoscale, 9(46): 18290–18298

    Article  CAS  Google Scholar 

  • Li Y, Lu G, Li S (2001). Photocatalytic hydrogen generation and decomposition of oxalic acid over platinized TiO2. Applied Catalysis A, General, 214(2): 179–185

    Article  CAS  Google Scholar 

  • Lin Z, Li L, Yu L, Li W, Yang G (2017). Dual-functional photocatalysis for hydrogen evolution from industrial wastewaters. Physical Chemistry Chemical Physics, 19(12): 8356–8362

    Article  CAS  Google Scholar 

  • Liu C, Wang L, Tang Y, Luo S, Liu Y, Zhang S, Zeng Y, Xu Y (2015). Vertical single or few-layer MoS2 nanosheets rooting into TiO2 nanofibers for highly efficient photocatalytic hydrogen evolution. Applied Catalysis B: Environmental, 164: 1–9

    Article  CAS  Google Scholar 

  • Liu H, Zhang J, Ao D (2018a). Construction of heterostructured ZnIn2S4@NH2−MIL−125(Ti) nanocomposites for visible-light-driven H2 production. Applied Catalysis B: Environmental, 221: 433–442

    Article  CAS  Google Scholar 

  • Liu J, Fang W, Wei Z, Qin Z, Jiang Z, Shangguan W (2018b). Metallic 1T−LixMoS2 co-catalyst enhanced photocatalytic hydrogen evolution over ZnIn2S4 floriated microspheres under visible light irradiation. Catalysis Science & Technology, 8(5): 1375–1382

    Article  CAS  Google Scholar 

  • Liu K H, Zhong H X, Li S J, Duan Y X, Shi M M, Zhang X B, Yan J M, Jiang Q (2018c). Advanced catalysts for sustainable hydrogen generation and storage via hydrogen evolution and carbon dioxide/nitrogen reduction reactions. Progress in Materials Science, 92: 64–111

    Article  CAS  Google Scholar 

  • Ma J, Wang H, Liu X, Lu L, Nie L, Yang X, Chai Y, Yuan R (2017). Synthesis of tube shape MnO/Cp composite from 3,4,9,10-perylenetetracarboxylic dianhydride for lithium ion batteries. Chemical Engineering Journal, 309: 545–551

    Article  CAS  Google Scholar 

  • Maqbool T, Qin Y, Ly Q V, Zhang J, Li C, Asif M B, Zhang Z (2020). Exploring the relative changes in dissolved organic matter for assessing the water quality of full-scale drinking water treatment plants using a fluorescence ratio approach. Water Research, 183: 116125

    Article  CAS  Google Scholar 

  • Mo Z, Xu H, Chen Z, She X, Song Y, Wu J, Yan P, Xu L, Lei Y, Yuan S, Li H (2018). Self-assembled synthesis of defect-engineered graphitic carbon nitride nanotubes for efficient conversion of solar energy. Applied Catalysis B: Environmental, 225: 154–161

    Article  CAS  Google Scholar 

  • Nie Y C, Yu F, Wang L C, Xing Q J, Liu X, Pei Y, Zou J P, Dai W L, Li Y, Suib S L (2018). Photocatalytic degradation of organic pollutants coupled with simultaneous photocatalytic H2 evolution over graphene quantum dots/Mn−N−TiO2/g−C3N4 composite catalysts: performance and mechanism. Applied Catalysis B: Environmental, 227: 312–321

    Article  CAS  Google Scholar 

  • Patsoura A, Kondarides D I, Verykios X E (2006). Enhancement of photoinduced hydrogen production from irradiated Pt/TiO2 suspensions with simultaneous degradation of azo-dyes. Applied Catalysis B: Environmental, 64(3–4): 171–179

    Article  CAS  Google Scholar 

  • Sun N, Qu Y, Yang C, Yang Z, Yan R, E W, Zhang Z, Li Z, Li H, Khan I (2020). Efficiently photocatalytic degradation of monochlorophenol on in-situ fabricated BiPO4/β-Bi2O3 heterojunction microspheres and O2-free hole-induced selective dechloridation conversion with H2 evolution. Applied Catalysis B: Environmental, 263: 118313

    Article  CAS  Google Scholar 

  • Swain G, Sultana S, Parida K (2019). One-pot-architectured Au-nanodot-promoted MoS2/ZnIn2S4: A novel p−n heterojunction photocatalyst for enhanced hydrogen production and phenol degradation. Inorganic Chemistry, 58(15): 9941–9955

    Article  CAS  Google Scholar 

  • Tang Y J, Wang Y, Wang X L, Li S L, Huang W, Dong L Z, Liu C H, Li Y F, Lan Y Q (2016). Molybdenum disulfide/nitrogen-doped reduced graphene oxide nanocomposite with enlarged interlayer spacing for electrocatalytic hydrogen evolution. Advanced Energy Materials, 6(12): 1600116

    Article  Google Scholar 

  • Tian G, Chen Y, Ren Z, Tian C, Pan K, Zhou W, Wang J, Fu H (2014). Enhanced photocatalytic hydrogen evolution over hierarchical composites of ZnIn2S4 nanosheets grown on MoS2 slices. Chemistry, An Asian Journal, 9(5): 1291–1297

    Article  CAS  Google Scholar 

  • Wan S, Ou M, Zhong Q, Zhang S, Song F (2017). Construction of Z-scheme photocatalytic systems using ZnIn2S4, CoOx-loaded Bi2MoO6 and reduced graphene oxide electron mediator and its efficient nonsacrificial water splitting under visible light. Chemical Engineering Journal, 325: 690–699

    Article  CAS  Google Scholar 

  • Wang H, Wu Y, Feng M, Tu W, Xiao T, Xiong T, Ang H, Yuan X, Chew J W (2018a). Visible-light-driven removal of tetracycline antibiotics and reclamation of hydrogen energy from natural water matrices and wastewater by polymeric carbon nitride foam. Water Research, 144: 215–225

    Article  CAS  Google Scholar 

  • Wang Q, Huang J, Sun H, Ng Y H, Zhang K Q, Lai Y (2018b). MoS2 quantum dots@TiO2 nanotube arrays: An extended-spectrum-driven photocatalyst for solar hydrogen evolution. ChemSusChem, 11(10): 1708–1721

    Article  CAS  Google Scholar 

  • Wang S, Zhu B, Liu M, Zhang L, Yu J, Zhou M (2019). Direct Z-scheme ZnO/CdS hierarchical photocatalyst for enhanced photocatalytic H2-production activity. Applied Catalysis B: Environmental, 243: 19–26

    Article  CAS  Google Scholar 

  • Wei L, Chen Y, Lin Y, Wu H, Yuan R, Li Z (2014). MoS2 as non-noble-metal co-catalyst for photocatalytic hydrogen evolution over hexagonal ZnIn2S4 under visible light irradiations. Applied Catalysis B: Environmental, 144: 521–527

    Article  CAS  Google Scholar 

  • Wei Z, Liu J, Fang W, Xu M, Qin Z, Jiang Z, Shangguan W (2019). Photocatalytic hydrogen evolution with simultaneous antibiotic wastewater degradation via the visible-light-responsive bismuth spheres-g-C3N4 nanohybrid: Waste to energy insight. Chemical Engineering Journal, 358: 944–954

    Article  CAS  Google Scholar 

  • Wu Z, Liu X, Liu J, Liu S, Zha Z, Chen Z (2019). Molybdenum disulfide based composites and their photocatalytic degradation and hydrogen evolution properties. Progress in Chemistry, 31(8): 1086–1102 (in Chinese)

    CAS  Google Scholar 

  • Xiao X, Hao R, Liang M, Zuo X, Nan J, Li L, Zhang W (2012). One-pot solvothermal synthesis of three-dimensional (3D) BiOI/BiOCl composites with enhanced visible-light photocatalytic activities for the degradation of bisphenol-A. Journal of Hazardous Materials, 233–234: 122–130

    Article  Google Scholar 

  • Xu Y, Yan A, Jiang L, Huang F, Hu D, Duan G, Zheng F (2022). MoS2/HCSs/ZnIn2S4 nanocomposites with enhanced charge transport and photocatalytic hydrogen evolution performance. Journal of Alloys and Compounds, 895: 162504

    Article  CAS  Google Scholar 

  • Yang G, Ding H, Chen D, Feng J, Hao Q, Zhu Y (2018). Construction of urchin-like ZnIn2S4−Au−TiO2 heterostructure with enhanced activity for photocatalytic hydrogen evolution. Applied Catalysis B: Environmental, 234: 260–267

    Article  CAS  Google Scholar 

  • Yi H, Huang D, Qin L, Zeng G, Lai C, Cheng M, Ye S, Song B, Ren X, Guo X (2018). Selective prepared carbon nanomaterials for advanced photocatalytic application in environmental pollutant treatment and hydrogen production. Applied Catalysis B: Environmental, 239: 408–424

    Article  CAS  Google Scholar 

  • Yuan Y J, Chen D, Zhong J, Yang L X, Wang J, Liu M J, Tu W G, Yu Z T, Zou Z G (2017). Interface engineering of a noble-metal-free 2D−2D MoS2/Cu−ZnIn2S4 photocatalyst for enhanced photocatalytic H2 production. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 5(30): 15771–15779

    Article  CAS  Google Scholar 

  • Yuan Y J, Tu J R, Ye Z J, Chen D Q, Hu B, Huang Y W, Chen T T, Cao D P, Yu Z T, Zou Z G (2016). MoS2-graphene/ZnIn2S4 hierarchical microarchitectures with an electron transport bridge between light-harvesting semiconductor and cocatalyst: A highly efficient photocatalyst for solar hydrogen generation. Applied Catalysis B: Environmental, 188: 13–22

    Article  CAS  Google Scholar 

  • Zhang G, Chen D, Li N, Xu Q, Li H, He J, Lu J (2020). Construction of hierarchical hollow Co9S8/ZnIn2S4 tubular heterostructures for highly efficient solar energy conversion and environmental remediation. Angewandte Chemie, 132(21): 8332–8338

    Article  Google Scholar 

  • Zhang S, Gu P, Ma R, Luo C, Wen T, Zhao G, Cheng W, Wang X (2019). Recent developments in fabrication and structure regulation of visible-light-driven g-C3N4-based photocatalysts towards water purification: A critical review. Catalysis Today, 335: 65–77

    Article  CAS  Google Scholar 

  • Zhang S, Liu X, Liu C, Luo S, Wang L, Cai T, Zeng Y, Yuan J, Dong W, Pei Y, Liu Y (2018a). MoS2 quantum dot growth induced by S vacancies in a ZnIn2S4 monolayer: atomic-level heterostructure for photocatalytic hydrogen production. ACS Nano, 12(1): 751–758

    Article  CAS  Google Scholar 

  • Zhang S, Wang L, Liu C, Luo J, Crittenden J, Liu X, Cai T, Yuan J, Pei Y, Liu Y (2017). Photocatalytic wastewater purification with simultaneous hydrogen production using MoS2 QD-decorated hierarchical assembly of ZnIn2S4 on reduced graphene oxide photocatalyst. Water Research, 121: 11–19

    Article  CAS  Google Scholar 

  • Zhang X H, Li N, Wu J, Zheng Y Z, Tao X (2018b). Defect-rich O-incorporated 1T−MoS2 nanosheets for remarkably enhanced visible-light photocatalytic H2 evolution over CdS: The impact of enriched defects. Applied Catalysis B: Environmental, 229: 227–236

    Article  CAS  Google Scholar 

  • Zhang Z, Huang L, Zhang J, Wang F, Xie Y, Shang X, Gu Y, Zhao H, Wang X (2018c). In situ constructing interfacial contact MoS2/ZnIn2S4 heterostructure for enhancing solar photocatalytic hydrogen evolution. Applied Catalysis B: Environmental, 233: 112–119

    Article  CAS  Google Scholar 

  • Zhao T, Xing Z, Xiu Z, Li Z, Yang S, Zhou W (2019). Oxygen-doped MoS2 nanospheres/CdS quantum dots/g-C3N4 nanosheets superarchitectures for prolonged charge lifetime and enhanced visible-light-driven photocatalytic performance. ACS Applied Materials & Interfaces, 11(7): 7104–7111

    Article  CAS  Google Scholar 

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Acknowledgements

This study was supported by the National Key Scientific Instrument and Equipment Development Project of China (No. 21627809), the National Natural Science Foundation of China (No. 21777056), the Natural Science Foundation of Shandong Province (China) (Nos. ZR2020MB091 and ZR2020MB037), the Youth Innovative Talents Recruitment and Cultivation Program of Shandong Higher Education (China), and the Jinan Scientific Research Leader Workshop Project (China) (No. 2018GXRC021).

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Authors and Affiliations

  1. School of Water Conservancy and Environment, University of Jinan, Jinan, 250022, China

    Tao Yan, Qianqian Yang, Rui Feng, Yanxia Zhao, Meng Sun & Liangguo Yan

  2. Key Laboratory of Interfacial Reaction & Sensing Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan, 250022, China

    Xiang Ren & Qin Wei

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  1. Tao Yan
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  2. Qianqian Yang
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  3. Rui Feng
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  4. Xiang Ren
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  5. Yanxia Zhao
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  6. Meng Sun
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  7. Liangguo Yan
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  8. Qin Wei
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Correspondence to Tao Yan or Meng Sun.

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Highlights

• An urchin-like OMS/ZIS composite was fabricated by a facile solvothermal method.

• The OMS/ZIS exhibits superior photocatalytic H2 evolution for organics degradation.

• A probable mechanism of dual-functional photocatalysis was proposed in detail.

• This work provides an inspiration for rational design of dual-functional catalysts.

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11783_2022_1566_MOESM1_ESM.pdf

Highly effective visible-photocatalytic hydrogen evolution and simultaneous organic pollutant degradation over an urchin-like oxygen-doped MoS2/ZnIn2S4 composite

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Yan, T., Yang, Q., Feng, R. et al. Highly effective visible-photocatalytic hydrogen evolution and simultaneous organic pollutant degradation over an urchin-like oxygen-doped MoS2/ZnIn2S4 composite. Front. Environ. Sci. Eng. 16, 131 (2022). https://doi.org/10.1007/s11783-022-1566-z

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