journal article·2020-09Open access

Activation of two-dimensional MoS2 nanosheets by wet-chemical sulfur vacancy engineering for the catalytic reduction of nitroarenes and organic dyes

S. García-Dalí, J.I. Paredes, B. Caridad, S. Villar-Rodil, M. Díaz-González, C. Fernández-Sánchez, A. Adawy, A. Martínez-Alonso, J.M.D. Tascón

Abstract

Two-dimensional 2H-phase MoS2 nanosheets can be used as a non-noble metal-based catalyst for nitroarene and organic dye reduction, thus being of potential utility towards the treatment of industrial wastewater. However, their activity is severely limited by the inertness of their pristine basal surface. We report here a simple approach for the catalytic activation of solvent-dispersed MoS2 nanosheets based on the introduction of sulfur vacancies by hydrazine treatment. MoS2 nanosheets boasting markedly improved catalytic activities in the reduction of 4-nitrophenol, 4-nitroaniline, methyl orange and methylene blue by NaBH4 could be obtained, outperforming many prior non-noble metal-based catalysts developed for such reactions. Notably, the improvement in catalytic activity was not compromised by the use of a proper dispersant to colloidally stabilize the activated nanosheets in the aqueous reaction medium. Substrate-supported catalysts could be prepared by immobilizing the nanosheets on melamine foam, facilitating their handling and reutilization. The chemical processes taking place between the investigated reagents and the MoS2 catalyst were also discussed and rationalized, based on which a mechanism for nitroarene/dye reduction mediated by the sulfur vacancies was proposed.
Source: openaire · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: MXene and MAX Phase Materials · Nanomaterials for catalytic reactions · Advanced Photocatalysis Techniques

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (83)

Show source-provided references
1. Recent development of two-dimensional transition metal dichalcogenides and their applications10.1016/j.mattod.2016.10.002 ↗
2. Various structures of 2D transition-metal dichalcogenides and their applications10.1002/smtd.201800094 ↗
3. Catalysis with two-dimensional materials and their heterostructures10.1038/nnano.2015.340 ↗
4. Characteristics and performance of two-dimensional materials for electrocatalysis10.1038/s41929-018-0181-7 ↗
5. TMD-based highly efficient electrocatalysts developed by combined computational and experimental approaches10.1039/C7CS00705A ↗
6. The role of cobalt and molybdenum sulphides in hydrodesulphurisation catalysts: a review10.1016/0022-5088(74)90119-2 ↗
7. High resolution electron microscopy of hydrodesulfurization catalysts: a review10.1016/S0166-9834(00)84467-X ↗
8. Surface chemistry and catalysis confined under two-dimensional materials10.1039/C6CS00424E ↗
9. Understanding the high-electrocatalytic performance of two-dimensional MoS2 nanosheets and their composite materials10.1039/C7TA08327K ↗
10. CO2 methanation catalyzed by oriented MoS2 nanoplatelets supported on few layers graphene10.1016/j.apcatb.2018.12.034 ↗
11. Chemically exfoliated MoS2 nanosheets as an efficient catalyst for reduction reactions in the aqueous phase10.1021/am506922q ↗
12. Fe3O4@MoS2 core–shell composites: preparation, characterization and catalytic application10.1021/acs.jpcc.5b02516 ↗
13. Emerging parallel dual 2D composites: natural clay mineral hybridizing MoS2 and interfacial structure10.1002/adfm.201504942 ↗
14. Preparation of MoS2-reduced graphene oxide (rGO) hybrid paper for catalytic applications by simple exfoliation-costacking10.1016/j.carbon.2016.11.001 ↗
15. Hierarchical MoS2 intercalated clay hybrid nanosheets with enhanced catalytic activity10.1007/s12274-016-1315-3 ↗
16. Green synthesis of layered 1T-MoS2/reduced graphene oxide nanocomposite with excellent catalytic performances for 4-nitrophenol reduction10.1016/j.apsusc.2016.10.136 ↗
17. Magnetic Co-doped MoS2 nanosheets for efficient catalysis of nitroarene reduction10.1021/acsomega.7b00848 ↗
18. Effects of morphology and crystallinity of MoS2 nanocrystals on the catalytic reduction of p-nitrophenol10.1007/s11051-018-4432-y ↗
19. Bi2Te3-MoS2 layered nanoscale heterostructures for electron transfer catalysis10.1021/acsanm.9b00025 ↗
20. Catalysis by metallic nanoparticles in aqueous solution: model reactions10.1039/c2cs35029g ↗
21. Nitroarene reduction: a trusted model reaction to test nanoparticle catalysts10.1039/C5CC01131K ↗
22. Synthesis and stabilization of metal nanocatalysts for reduction reactions – a review10.1039/C5TA00753D ↗
23. Recent advances in the nanocatalyst-assisted NaBH4 reduction of nitroaromatics in water10.1021/acsomega.8b03051 ↗
24. Removal of nitrophenols and their derivatives by chemical redox: a review10.1016/j.cej.2018.11.111 ↗
25. Hybrid microgels for catalytic and photocatalytic removal of nitroarenes and organic dyes from aqueous medium: a review
26. Chemical reduction of methylene blue in the presence of nanocatalysts: a critical review
27. Au@TiO2 nanocomposites for the catalytic degradation of methyl orange and methylene blue: an electron relay effect10.1016/j.jiec.2013.08.002 ↗
28. Highly efficient degradation of organic dyes by palladium nanoparticles decorated on 2D magnetic reduced graphene oxide nanosheets10.1039/C5DT01036E ↗
29. Carboxymethylcellulose-based magnetic Au or Ag nanosystems: Eminent candidates in catalysis, sensing applications based on SERS, and electrochemistry10.1016/j.apmt.2018.12.001 ↗
30. Reduction of nitroarenes catalyzed by microgel-stabilized silver nanoparticles10.1016/j.jhazmat.2019.05.080 ↗
31. Hydrogenation of nitrophenols catalyzed by carbon black-supported nickel nanoparticles under mild conditions10.1016/j.apcatb.2015.06.043 ↗
32. Copper and cobalt nanoparticles doped nitrogen-containing carbon frameworks derived from CuO-encapsulated ZIF-67 as high-efficiency catalyst for hydrogenation of 4-nitrophenol10.1016/j.apcatb.2019.117792 ↗
33. Metallic MoS2 for high performance energy storage and energy conversion10.1002/smll.201800640 ↗
34. Synthesis, stabilization and applications of 2-dimensional 1T metallic MoS210.1039/C8TA08152B ↗
35. Oxidation suppression during hydrothermal phase reversion allows synthesis of monolayer semiconducting MoS2 in stable aqueous suspension10.1039/C7NR01193H ↗
36. Chemical stability and transformation of molybdenum disulfide nanosheets in environmental media10.1021/acs.est.9b00318 ↗
37. Impact of covalent functionalization on the aqueous processability, catalytic activity, and biocompatibility of chemically exfoliated MoS2 nanosheets10.1021/acsami.6b08444 ↗
38. Two-dimensional nanosheets produced by liquid exfoliation of layered materials10.1126/science.1194975 ↗
39. Large-scale exfoliation of inorganic layered compounds in aqueous surfactant solution10.1002/adma.201102584 ↗
40. Large-scale production of size-controlled MoS2 nanosheets by shear exfoliation10.1021/cm5044864 ↗
41. Aqueous exfoliation of transition metal dichalcogenides assisted by DNA/RNA nucleotides: catalytically active and biocompatible nanosheets stabilized by acid-base interactions10.1021/acsami.6b13619 ↗
42. Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies10.1038/nmat4465 ↗
43. Atomic structure of defects and dopants in 2D layered transition metal dichalcogenides10.1039/C8CS00236C ↗
44. Aqueous cathodic exfoliation strategy toward solution-processable and phase-preserved MoS2 nanosheets for energy storage and catalytic applications10.1021/acsami.9b13484 ↗
45. Edge and confinement effects allow in situ measurement of size and thickness in liquid-exfoliated nanosheets10.1038/ncomms5576 ↗
46. Strong photoluminescence enhancement of MoS2 through defect engineering and oxygen bonding10.1021/nn500532f ↗
47. Activating basal-plane catalytic activity of two-dimensional MoS2 monolayer with remote hydrogen plasma10.1016/j.nanoen.2016.09.010 ↗
48. Two-dimensional MoS2 under ion irradiation: from controlled defect production to electronic structure engineering10.1088/2053-1583/aa6b17 ↗
49. Defect engineering in single-layer MoS2 using heavy ion irradiation10.1021/acsami.8b17145 ↗
50. Tunable sulfur desorption in exfoliated MoS2 by means of thermal annealing in ultra-high vacuum10.1016/j.cplett.2013.10.034 ↗
51. Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution10.1038/ncomms15113 ↗
52. Reductive exfoliation of substoichiometric MoS2 bilayers using hydrazine salts10.1039/C6NR04327E ↗
53. Atomic plane-vacancy engineering of transition-metal dichalcogenides with enhanced hydrogen evolution capability10.1021/acsami.9b07856 ↗
54. Water-soluble defect-rich MoS2 ultrathin nanosheets for enhanced hydrogen evolution10.1021/acs.jpclett.9b01121 ↗
55. Atomically thin MoS2: a new direct-gap semiconductor10.1103/PhysRevLett.105.136805 ↗
56. Photoluminiscence from chemically exfoliated MoS210.1021/nl201874w ↗
57. Recent development of metallic (1T) phase of molybdenum disulfide for energy conversion and storage10.1002/aenm.201703482 ↗
58. Vacancy-induced ferromagnetism of MoS2 nanosheets10.1021/ja5120908 ↗
59. Role of sulfur vacancies and undercoordinated Mo regions in MoS2 nanosheets toward the evolution of hydrogen10.1021/acsnano.9b01583 ↗
60. Electrochemical interaction of few-layer molybdenum disulfide composites vs sodium: new insights on the reaction mechanism10.1021/acs.chemmater.7b01245 ↗
61. The ligand shell as an energy barrier in surface reactions on transition metal nanoparticles10.1021/jacs.6b00179 ↗
62. Direct exfoliation and dispersion of two-dimensional materials in pure water via temperature control10.1038/ncomms9294 ↗
63. Exfoliated MoS2 in water without additives10.1371/journal.pone.0154522 ↗
64. Colloidal 2D nanosheets of MoS2 and other transition metal dichalcogenides through liquid-phase exfoliation10.1016/j.cis.2017.04.014 ↗
65. Hopping transport through defect-induced localized states in molybdenum disulfide10.1038/ncomms3642 ↗
66. Theoretical studies of transition metal sulfide hydrodesulfurization catalysts
67. One-dimensional metallic edge states in MoS210.1103/PhysRevLett.87.196803 ↗
68. Direct imaging of band profile in single layer MoS2 on graphite: quasiparticle energy gap, metallic edge states, and edge band bending10.1021/nl501133c ↗
69. Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS210.1039/C9SC03337H ↗
70. Selective adsorption of thiol molecules at sulfur vacancies on MoS2(0001), followed by vacancy repair via S-C dissociation10.1021/jp307267h ↗
71. Towards intrinsic charge transport in monolayer molybdenum disulfide by defect and interface engineering10.1038/ncomms6290 ↗
72. Electrical and optical characterization of MoS2 with sulfur vacancy passivation by treatment with alkanethiol molecules10.1021/acsnano.5b04400 ↗
73. Towards a comprehensive understanding of the reaction mechanisms between defective MoS2 and thiol molecules10.1002/anie.201706038 ↗
74. Chemical and electronic repair mechanism of defects in MoS2 monolayers10.1021/acsnano.7b04162 ↗
75. Hydrogen generation from chemical hydrides10.1021/ie8016225 ↗
76. Spontaneous hydrolysis of sodium borohydride in harsh conditions10.1016/j.ijhydene.2010.10.055 ↗
77. Hydrogen physisorption based on the dissociative hydrogen chemisorption at the sulphur vacancy of MoS2 surface10.1038/s41598-017-07178-9 ↗
78. Probing the electronic properties of monolayer MoS2 via interaction with molecular hydrogen10.1002/aelm.201800591 ↗
79. In situ infrared (FTIR) study of the borohydride oxidation reaction10.1016/j.elecom.2008.11.018 ↗
80. Rotating disk electrode (RDE) investigation of BH4- and BH3OH- electro-oxidation at Pt and Au: implications for BH4- fuel cells10.1021/jp900933c ↗
81. Reduction of nitrophenols to aminophenols under concerted catalysis by Au/g-C3N4 contact system10.1016/j.apcatb.2016.09.051 ↗
82. Constructing metallic nanoroads on a MoS2 monolayer via hydrogenation10.1039/C3NR05218D ↗
83. Effect of NaBH4 on properties of nanoscale zero-valent iron and its catalytic activity for reduction of p-nitrophenol10.1016/j.apcatb.2015.10.006 ↗