Applied Nanoscience

, Volume 9, Issue 1, pp 19–32 | Cite as

Heterojunction of TiO2 nanoparticle embedded into ZSM5 to 2D and 3D layered-structures of MoS2 nanosheets fabricated by pulsed laser ablation and microwave technique in deionized water: structurally enhanced photocatalytic performance

  • Ali Balati
  • Dipendra Wagle
  • Kelly L. Nash
  • Heather J. ShipleyEmail author
Original Article


In this paper, we report a one-step, fast and ecofriendly synthesis of layered-structured MoS2 nanosheets (NSs) by pulsed laser ablation in liquids (PLAL). The resultant MoS2 NS was used to construct TiO2–ZSM5–MoS2 nanocomposite. After impregnating ZSM5 structures with TiO2 nanoparticles (TiO2 NPs), heterojunctions of MoS2 NS were made on the fabricated TiO2–ZSM5 by microwave treatment at high temperature and pressure. Formation of 2D and 3D structures of MoS2 was shown. Crystal structure, size and shape of the synthesized nanostructures were studied by X-ray powder diffraction (XRD) and microscopy techniques. Results of the structural analysis showed that the PLAL constructed MoS2 NSs mainly had a layered morphology several micrometers in size with horizontally and vertically aligned layers. The hexagonal crystalline structure of MoS2 NS, anatase TiO2 NPs and microcrystalline ZSM5 structures were determined by XRD, high-resolution transmission electron microscopy (HRTEM) and fast Fourier transform (FFT) analysis. Formation of MoS2 NS was further shown with Raman peaks at approximately 385.30 and 407.50 cm−1 corresponding to the E1 2 g and A1g vibrational modes of MoS2 NS. The PLAL synthesized MoS2 NS demonstrated broad absorption in the visible region. Photocatalytic activity of TiO2–ZSM5–MoS2 nanocomposite was tested with arsenite. TiO2–ZSM5–MoS2 nanocomposite exhibited approximately 100% arsenite photo-conversion to arsenate.


PLAL MoS2 NSs Microwave treatment Heterostructure composite Arsenic photo-oxidation 



We acknowledge financial support from the National Science Foundation CBET 1650278. Author (KLN) would like to acknowledge financial support from Air Force Office of Scientific Research FA9550-15-1-0109.

Compliance with ethical standards

Conflict of interest

There are no conflicts to declare.

Supplementary material

13204_2018_902_MOESM1_ESM.docx (3.1 mb)
Supplementary material 1 (DOCX 3136 KB)
13204_2018_902_MOESM2_ESM.docx (1.5 mb)
Supplementary material 2 (DOCX 1566 KB)
13204_2018_902_MOESM3_ESM.docx (13 kb)
Supplementary material 3 (DOCX 13 KB)


  1. Bagnall A, Liang W, Marseglia E, Welber B (1980) Raman studies of MoS2 at high pressure. Phys B+ C 99:343–346Google Scholar
  2. Balati A, Shahbazi A, Amini MM, Hashemi SH, Jadidi K (2014) Comparison of the efficiency of mesoporous silicas as absorbents for removing naphthalene from contaminated water. Eur J Environ Sci 4:69–76Google Scholar
  3. Balati A, Shahbazi A, Amini MM, Hashemi SH (2015) Adsorption of polycyclic aromatic hydrocarbons from wastewater by using silica-based organic–inorganic nanohybrid material. J Water Reuse Desalination 5:50–63Google Scholar
  4. Balati A, Ghanbari M, Behzad SK, Amini MM (2017a) Functionalization of graphene oxide with 9-aminoanthracene for the adsorptive removal of persistent aromatic pollutants from aqueous solution. Acta Chim Slov 64:479–790Google Scholar
  5. Balati A, Shipley H, Nash K (2017b) Heterojunction of TiO2 nanoparticle embedded into ZSM-5 to layer-structured MoS2 fabricated by pulsed laser ablation and microwave technique in deionized water: application in drinking water purification. In: Abstracts of papers of the American Chemical SocietyGoogle Scholar
  6. Bertrand P (1991) Surface-phonon dispersion of MoS2. Phys Rev B 44:5745Google Scholar
  7. Bin F, Song C, Lv G, Song J, Wu S, Li X (2014) Selective catalytic reduction of nitric oxide with ammonia over zirconium-doped copper/ZSM-5 catalysts. Appl Catal B Environ 150:532–543Google Scholar
  8. Burdett JK, Hughbanks T, Miller GJ, Richardson JW Jr, Smith JV (1987) Structural-electronic relationships in inorganic solids: powder neutron diffraction studies of the rutile and anatase polymorphs of titanium dioxide at 15 and 295K. J Am Chem Soc 109:3639–3646Google Scholar
  9. Chen X, Cui Y (2017) Black TiO2 nanomaterials for energy applications. World Scientific, SingaporeGoogle Scholar
  10. Chen X et al (2013) Properties of disorder-engineered black titanium dioxide nanoparticles through hydrogenation. Sci Rep 3:1510Google Scholar
  11. Chen G et al (2016) Defect assisted coupling of a MoS2/TiO2 interface and tuning of its. Electron Struct Nanotechnol 27:355203Google Scholar
  12. Compagnini G, Sinatra MG, Messina GC, Patanè G, Scalese S, Puglisi O (2012) Monitoring the formation of inorganic fullerene-like MoS2 nanostructures by laser ablation in liquid environments. Appl Surf Sci 258:5672–5676Google Scholar
  13. Corma A, Garcia H (2004) Zeolite-based photocatalysts. Chem Commun 13:1443–1459Google Scholar
  14. Elsellami L, Dappozze F, Fessi N, Houas A, Guillard C (2018) Highly photocatalytic activity of nanocrystalline TiO2 (anatase, rutile) powders prepared from TiCl4 by sol–gel method in aqueous solutions. Process Saf Environ Prot 113:109–121Google Scholar
  15. Feldman Y, Wasserman E, Srolovitz D, Tenne R (1995) High-rate, gas-phase growth of MoS2 nested inorganic fullerenes and nanotubes. Science 267:222Google Scholar
  16. Ferguson MA, Hering JG (2006) TiO2-photocatalyzed As (III) oxidation in a fixed-bed flow-through reactor. Environ Sci Technol 40:4261–4267Google Scholar
  17. Ferguson MA, Hoffmann MR, Hering JG (2005) TiO2-photocatalyzed As(III) oxidation in aqueous suspensions: reaction kinetics and effects of adsorption. Environ Sci Technol 39:1880–1886Google Scholar
  18. Fukahori S, Ichiura H, Kitaoka T, Tanaka H (2003) Photocatalytic decomposition of bisphenol A in water using composite TiO2-zeolite sheets prepared by a. papermaking technique. Environ Sci Technol 37:1048–1051. Google Scholar
  19. Guo B et al (2015) Firework-shaped TiO2 microspheres embedded with few-layer MoS2 as an anode material for excellent performance lithium-ion batteries. J Mater Chem A 3:6392–6401Google Scholar
  20. Hajijafari Bidgoli S, Sadeghzadeh Attar A, Bafandeh MR (2017) Structural and optical properties of Sr-modified bismuth silicate nanostructured films synthesized by sol gel method. J Nanostruct 7:258–265Google Scholar
  21. He H et al (2016) MoS2/TiO2 edge-on heterostructure for efficient photocatalytic hydrogen evolution. Adv Energy Mater 6:1600464Google Scholar
  22. He D et al (2017) Enhanced activity and stability of Sm-doped HZSM-5 zeolite catalysts for catalytic methyl mercaptan (CH3SH) decomposition. Chem Eng J 317:60–69. Google Scholar
  23. Hu K, Hu X, Xu Y, Pan X (2010) The effect of morphology and size on the photocatalytic properties of MoS2 reaction kinetics. Mech Catal 100:153–163Google Scholar
  24. Hu X, Zhao H, Tian J, Gao J, Li Y, Cui H (2017) Synthesis of few-layer MoS2 nanosheets-coated TiO2 nanosheets on graphite fibers for enhanced photocatalytic properties. Sol Energy Mater Sol Cells 172:108–116Google Scholar
  25. Hunt ST, Román-Leshkov Y (2018) Principles and methods for the rational design of core–shell nanoparticle catalysts with ultralow noble metal loadings. Acc Chem Res 51:1054–1062Google Scholar
  26. Jiang Y et al (2018) Ta3N5 nanoparticles/TiO2 hollow sphere (0D/3D) heterojunction: facile synthesis, enhanced photocatalytic activities of levofloxacin degradation and H2 evolution. Dalton Trans 47:13113–13125Google Scholar
  27. Kanazawa T (2006) MFI zeolite as a support for automotive catalysts with reduced Pt sintering. Appl Catal B Environ 65:185–190. Google Scholar
  28. Kong D, Wang H, Cha JJ, Pasta M, Koski KJ, Yao J, Cui Y (2013) Synthesis of MoS2 and MoSe2 films with vertically aligned layers. Nano Lett 13:1341–1347Google Scholar
  29. Kusmierek E, Chrzescijanska E (2015) Application of TiO2–RuO2/Ti electrodes modified with WO3 in electro-and photoelectrochemical oxidation of Acid Orange 7 dye. J Photochem Photobiol A Chem 302:59–68Google Scholar
  30. Kuwahara Y, Yamashita H (2011) Efficient photocatalytic degradation of organics diluted in water and air using TiO2 designed with zeolites and mesoporous silica materials. J Mater Chem 21:2407–2416Google Scholar
  31. Li H, Zhang Q, Yap CCR, Tay BK, Edwin THT, Olivier A, Baillargeat D (2012a) From bulk to monolayer MoS2: evolution of Raman scattering. Adv Func Mater 22:1385–1390Google Scholar
  32. Li S-L, Miyazaki H, Song H, Kuramochi H, Nakaharai S, Tsukagoshi K (2012b) Quantitative Raman spectrum and reliable thickness identification for atomic layers on insulating substrates. ACS Nano 6:7381–7388Google Scholar
  33. Li H, Wu J, Yin Z, Zhang H (2014) Preparation and applications of mechanically exfoliated single-layer and multilayer MoS2 and WSe2 nanosheets. Acc Chem Res 47:1067–1075Google Scholar
  34. Li J et al (2017) Fast electron transfer and enhanced visible light photocatalytic activity using multi-dimensional components of carbon quantum dots@ 3D daisy-like In2S3/single-wall carbon nanotubes. Appl Catal B 204:224–238Google Scholar
  35. Lin H, Chen X, Li H, Yang M, Qi Y (2010) Hydrothermal synthesis and characterization of MoS2. Nanorods Mater Lett 64:1748–1750Google Scholar
  36. Liu F et al (2012) ZSM-5 zeolite single crystals with b-axis-aligned mesoporous channels as an efficient catalyst for conversion of bulky organic molecules. J Am Chem Soc 134:4557–4560Google Scholar
  37. Lu X, Utama MIB, Zhang J, Zhao Y, Xiong Q (2013) Layer-by-layer thinning of MoS2 by thermal annealing. Nanoscale 5:8904–8908Google Scholar
  38. Ma S, Song Y, Xu P, Fu X, Ye Z, Xue J (2018) Facile one-step synthesis of Cu1. 96S/g-C3N4 0D/2D pn heterojunctions with enhanced visible light photoactivity toward ciprofloxacin degradation. Mater Lett 213:370–373Google Scholar
  39. Monrad M et al (2017) Low-level arsenic in drinking water and risk of incident myocardial infarction: a cohort study. Environ Res 154:318–324. Google Scholar
  40. Neppolian B, Mine S, Horiuchi Y, Bianchi CL, Matsuoka M, Dionysiou DD, Anpo M (2016) Efficient photocatalytic degradation of organics present in gas and liquid phases using Pt-TiO2/Zeolite (H-ZSM). Chemosphere 153:237–243. Google Scholar
  41. Nguyen T, Vigneswaran S, Ngo H, Kandasamy J, Choi H (2008a) Arsenic removal by photo-catalysis hybrid system. Sep Purif Technol 61:44–50Google Scholar
  42. Nguyen TV, Vigneswaran S, Ngo HH, Kandasamy J, Choi HC (2008b) Arsenic removal by photo-catalysis hybrid system. Sep Purif Technol 61:44–50. Google Scholar
  43. Nithyaa N, Jaya NV (2018) Structural, optical, and magnetic properties of Gd-doped TiO2 nanoparticles. J Supercond Novel Magn. Google Scholar
  44. Oztas T, Sen HS, Durgun E, Ortaç B (2014) Synthesis of colloidal 2D/3D MoS2 nanostructures by pulsed laser ablation in an organic liquid environment. J Phys Chem C 118:30120–30126Google Scholar
  45. Popa M et al (2009) Synthesis, structural characterization, and photocatalytic properties of iron-doped TiO2 aerogels. J Mater Sci 44:358Google Scholar
  46. Qin S, Lei W, Liu D, Chen Y (2014) In situ and tunable nitrogen-doping of MoS2 nanosheets. Sci Rep 4:7582Google Scholar
  47. Quan LN, Jang YH, Jang YJ, Kim J, Lee W, Moon JH, Kim DH (2014) Mesoporous carbon-TiO2 beads with nanotextured surfaces as photoanodes in dye-sensitized. Solar Cells ChemSusChem 7:2590–2596Google Scholar
  48. Radisavljevic B, Radenovic A, Brivio J, Giacometti IV, Kis A (2011) Single-layer MoS2 transistors. Nat Nanotechnol 6:147–150Google Scholar
  49. Rahmanian E, Malekfar R, Pumera M (2018) Frontispiece: nanohybrids of two-dimensional transition-metal dichalcogenides and titanium dioxide for photocatalytic applications. Chem Eur J 24:18–31Google Scholar
  50. Ren X et al (2016) 2D co-catalytic MoS2 nanosheets embedded with 1D TiO2 nanoparticles for enhancing photocatalytic activity. J Phys D Appl Phys 49:315304Google Scholar
  51. Romanello MB, de Cortalezzi MMF (2013) An experimental study on the aggregation of TiO2 nanoparticles under environmentally relevant conditions. Water Res 47:3887–3898Google Scholar
  52. Ryu J, Choi W (2004) Effects of TiO2 surface modifications on photocatalytic oxidation of arsenite: the role of superoxides. Environ Sci Technol 38:2928–2933Google Scholar
  53. Ryu J, Choi W (2006) Photocatalytic oxidation of arsenite on TiO2: understanding the controversial oxidation mechanism involving superoxides and the effect of alternative electron acceptors. Environ Sci Technol 40:7034–7039Google Scholar
  54. Song R, Zhou W, Luo B, Jing D (2017) Highly efficient photocatalytic H2 evolution using TiO2 nanoparticles integrated with electrocatalytic metal phosphides as cocatalysts. Appl Surf Sci 416:957–964Google Scholar
  55. Tao L, Duan X, Wang C, Duan X, Wang S (2015) Plasma-engineered MoS2 thin-film as an efficient electrocatalyst for hydrogen evolution reaction. Chem Commun 51:7470–7473Google Scholar
  56. Vattikuti S, Byon C (2015) Synthesis and characterization of molybdenum disulfide nanoflowers and nanosheets: nanotribology. J Nanomater 2015:9Google Scholar
  57. Wang C, Liu P, Cui H, Yang G (2005) Nucleation and growth kinetics of nanocrystals formed upon pulsed-laser ablation in liquid. Appl Phys Lett 87:201913Google Scholar
  58. Wang F, Li W, Gu S, Li H, Wu X, Ren C, Liu X (2017) Facile fabrication of direct Z-scheme MoS2/Bi2WO6 heterojunction photocatalyst with superior photocatalytic performance under visible light irradiation. J Photochem Photobiol A 335:140–148Google Scholar
  59. Wu Y et al (2017) Electrocatalytic hydrogen gas generation by cobalt molybdenum disulfide (CoMoS2) synthesized using alkyl-containing thiomolybdate precursors. Int J Hydrogen Energy 42:20669–20676Google Scholar
  60. Wu M-h, Li L, Xue Y-c, Xu G, Tang L, Liu N, Huang W-y (2018) Fabrication of ternary GO/g-C3N4/MoS2 flower-like heterojunctions with enhanced photocatalytic activity for water remediation. Appl Catal B 228:103–112Google Scholar
  61. Xu H et al (2012) Synthesis, characterization and photocatalytic property of AgBr/BiPO4 heterojunction photocatalyst. Dalton Trans 41:3387–3394Google Scholar
  62. Xu J, Li J, Wu F, Zhang Y (2013) Rapid photooxidation of As (III) through surface complexation with nascent colloidal ferric hydroxide. Environ Sci Technol 48:272–278Google Scholar
  63. Xu J, Li J, Wu F, Zhang Y (2014) Rapid photooxidation of As(III) through surface complexation with nascent colloidal ferric hydroxide. Environ Sci Technol 48:272–278. Google Scholar
  64. Xu B, Su Y, Li L, Liu R, Lv Y (2017) Thiol-functionalized single-layered MoS2 nanosheet as a photoluminescence sensing platform via charge transfer for dopamine detection. Sens Actuators B 246:380–388Google Scholar
  65. Yan Z, Chrisey DB (2012) Pulsed laser ablation in liquid for micro-/nanostructure generation. J Photochem Photobiol C 13:204–223Google Scholar
  66. Yosefi L, Haghighi M (2018) Fabrication of nanostructured flowerlike p-BiOI/p-NiO heterostructure and its efficient photocatalytic performance in water treatment under visible-light irradiation. Appl Catal B 220:367–378Google Scholar
  67. Yu J, Qi L, Jaroniec M (2010) Hydrogen production by photocatalytic water splitting over Pt/TiO2 nanosheets with exposed (001) facets. J Phys Chem C 114:13118–13125Google Scholar
  68. Yu JH et al (2015) Vertical heterostructure of two-dimensional MoS2 and WSe2 with vertically aligned layers. Nano Lett 15:1031–1035Google Scholar
  69. Zhang F-S, Itoh H (2006) Photocatalytic oxidation and removal of arsenite from water using slag-iron oxide-TiO2 adsorbent. Chemosphere 65:125–131Google Scholar
  70. Zhang C et al (2017) Solvent-free and mesoporogen-free synthesis of mesoporous aluminosilicate ZSM-5 zeolites with superior catalytic properties in the methanol-to-olefins reaction. Ind Eng Chem Res 56:1450–1460Google Scholar
  71. Zhao W, Liu Y, Wei Z, Yang S, He H, Sun C (2016a) Fabrication of a novel p–n heterojunction photocatalyst n-BiVO4@ p-MoS2 with core–shell structure and its excellent visible-light photocatalytic reduction and oxidation activities. Appl Catal B 185:242–252Google Scholar
  72. Zhao W, Liu Y, Wei Z, Yang S, He H, Sun C (2016b) Fabrication of a novel p–n heterojunction photocatalyst n-BiVO4@p-MoS2 with core–shell structure and its excellent visible-light photocatalytic reduction and oxidation activities. Appl Catal B 185:242–252. Google Scholar
  73. Zhou W et al (2014) Ordered mesoporous black TiO2 as highly efficient hydrogen evolution photocatalyst. J Am Chem Soc 136:9280–9283. Google Scholar
  74. Zhou K et al (2016) Synthesized TiO2/ZSM-5 composites used for the photocatalytic degradation of azo dye: intermediates, reaction pathway, mechanism and bio-toxicity. Appl Surf Sci 383:300–309Google Scholar
  75. Zhu Y, Ling Q, Liu Y, Wang H, Zhu Y (2015) Photocatalytic H2 evolution on MoS2–TiO2 catalysts synthesized via mechanochemistry. Phys Chem Chem Phys 17:933–940Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Ali Balati
    • 1
  • Dipendra Wagle
    • 1
  • Kelly L. Nash
    • 2
  • Heather J. Shipley
    • 1
    Email author
  1. 1.Department of Civil and Environmental EngineeringUniversity of Texas at San AntonioSan AntonioUSA
  2. 2.Department of Physics and AstronomyThe University of Texas at San AntonioSan AntonioUSA

Personalised recommendations