Microemulsion-mediated hydrothermal synthesis of flower-like MoS<sub>2</sub> nanomaterials with enhanced catalytic activities for anthracene hydrogenation

doi:10.1007/s11705-017-1677-4

Front. Chem. Sci. Eng.

2018, Vol. 12

Issue (1) : 32-42 https://doi.org/10.1007/s11705-017-1677-4

RESEARCH ARTICLE

Microemulsion-mediated hydrothermal synthesis of flower-like MoS₂ nanomaterials with enhanced catalytic activities for anthracene hydrogenation

Yuxia Jiang^1,², Donge Wang¹, Zhendong Pan¹, Huaijun Ma¹, Min Li^1,², Jiahe Li^1,², Anda Zheng^1,², Guang Lv^1,², Zhijian Tian^1,³(

)

¹. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
². University of Chinese Academy of Sciences, Beijing 100049, China
³. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Download: PDF(473 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Flower-like intercalated MoS₂ nanomaterials have been successfully synthesized via a microemulsion-mediated hydrothermal (MMH) method, and characterized by X-ray diffraction, Raman spectroscopy, element analysis, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy in detail. Their catalytic performance for anthracene hydrogenation was evaluated using a slurry-bed batch reactor with an initial hydrogen pressure of 80 bar at 350 °C for 4 h. The intercalated MoS₂ nanoflowers synthesized from Na₂MoO₄ (MoS₂-S) and H₂MoO₄ (MoS₂-A) as molybdenum precursors have diameters of about 150 and 50 nm, respectively. MoS₂ nanosheets on MoS₂-S and MoS₂-A possess stacking layer numbers of 5–10 and 2–5, and slab lengths of about 15 and 10 nm, respectively. The interlayer distances of MoS₂-S and MoS₂-A are both enlarged from 0.62 nm to about 0.95 nm due to the intercalation of NH₄⁺ and surfactant molecules. The MoS₂ nanoflowers have high catalytic activities for anthracene hydrogenation. The selectivity for octahydroanthracene, a deeply hydrogenated product, over MoS₂-A is 89.8%, which is 31.0 times higher than that over commercial bulk MoS₂. Fully hydrogenated product (perhydroanthracene) was also detected over MoS₂ nanoflowers with a selectivity of 3.7%. The enhanced hydrogenation activities of MoS₂ nanoflowers can be ascribed to the high exposure of catalytic active sites, resulting from the smaller particle size, fewer stacking layer, shorter slab length and enlarged interlayer distance of MoS₂ nanoflowers compared with commercial bulk MoS₂. In addition, a possible growth mechanism of MoS₂ nanoflowers synthesized via the MMH method was proposed.

Keywords microemulsion intercalated MoS₂ catalytic hydrogenation active sites

Corresponding Author(s): Zhijian Tian

Just Accepted Date: 17 August 2017 Online First Date: 31 October 2017 Issue Date: 26 February 2018

Cite this article:

Yuxia Jiang,Donge Wang,Zhendong Pan, et al. Microemulsion-mediated hydrothermal synthesis of flower-like MoS₂ nanomaterials with enhanced catalytic activities for anthracene hydrogenation[J]. Front. Chem. Sci. Eng., 2018, 12(1): 32-42.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1677-4
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I1/32

Fig.1 XRD patterns of MoS₂-A, MoS₂-S and MoS₂-C

Fig.2 SEM images of (a, b) MoS₂-C, (c, d) MoS₂-S, and (e, f) MoS₂-A

Fig.3 Raman spectra of MoS₂-C, MoS₂-S and MoS₂-A

Fig.4 HRTEM images of (a, b) MoS₂-C, (c, d) MoS₂-S, and (e, f) MoS₂-A

Tab.1 Element analysis of MoS₂-S and MoS₂-A

Fig.5 TG curves of MoS₂-C, MoS₂-S, and MoS₂-A

Fig.6 FT-IR spectra of MoS₂-C, MoS₂-S, and MoS₂-A

Fig.7 A possible growth mechanism of MoS₂ nanoflowers

Fig.8 Scheme1 Possible pathways of anthracene hydrogenation using MoS₂ as a catalyst

Fig.9 (a) The conversions and hydrogenation ratios; (b) the selectivities for the hydrogenation of anthracene over MoS₂-C, MoS₂-S and MoS₂-A catalysts

1	Hershfinkel M, Gheber L A, Volterra V, Hutchison J L, Margulis L, Tenne R. Nested polyhedra of MX2 (M= W, Mo; X= S, Se) probed by high-resolution electron microscopy and scanning tunneling microscopy. Journal of the American Chemical Society, 1994, 116(5): 1914–1917 https://doi.org/10.1021/ja00084a035
2	Chhowalla M, Shin H S, Eda G, Li L J, Loh K P, Zhang H. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nature Chemistry, 2013, 5(4): 263–275 https://doi.org/10.1038/nchem.1589
3	Bano S, Ahmad S, Woo S, Saleem F. Heavy oil hydroprocessing: Effect of nanostructured morphologies of MoS2 as catalyst. Reaction Kinetics, Mechanisms and Catalysis, 2015, 114(2): 473–487 https://doi.org/10.1007/s11144-014-0822-z
4	Deng D, Novoselov K S, Fu Q, Zheng N, Tian Z, Bao X. Catalysis with two-dimensional materials and their heterostructures. Nature Nanotechnology, 2016, 11(3): 218–230 https://doi.org/10.1038/nnano.2015.340
5	Daage M, Chianelli R R. Structure-function relations in molybdenum sulfide catalysts—the rim-edge model. Journal of Catalysis, 1994, 149(2): 414–427 https://doi.org/10.1006/jcat.1994.1308
6	Zhang N, Li H, Yu K, Zhu Z. Differently structured MoS2 for the hydrogen production application and a mechanism investigation. Journal of Alloys and Compounds, 2016, 685: 65–69 https://doi.org/10.1016/j.jallcom.2016.05.228
7	Iwata Y, Araki Y, Honna K, Miki Y, Sato K, Shimada H. Hydrogenation active sites of unsupported molybdenum sulfide catalysts for hydroprocessing heavy oils. Catalysis Today, 2001, 65(2): 335–341 https://doi.org/10.1016/S0920-5861(00)00554-X
8	Li Z, He J, Wang H, Wang B, Ma X. Enhanced methanation stability of nano-sized MoS2 catalysts by adding Al2O3. Frontiers of Chemical Science and Engineering, 2015, 9(1): 33–39 https://doi.org/10.1007/s11705-014-1446-6
9	Salvatore G A, Münzenrieder N, Barraud C, Petti L, Zysset C, Büthe L, Ensslin K, Tröster G. Fabrication and transfer of flexible few-layers MoS2 thin film transistors to any arbitrary substrate. ACS Nano, 2013, 7(10): 8809–8815 https://doi.org/10.1021/nn403248y
10	Zheng J, Zhang H, Dong S, Liu Y, Tai Nai C, Suk Shin H, Young Jeong H, Liu B, Ping Loh K. High yield exfoliation of two-dimensional chalcogenides using sodium naphthalenide. Nature Communications, 2014, 5: 2995 https://doi.org/10.1038/ncomms3995
11	Nath M, Govindaraj A, Rao C N R. Simple synthesis of MoS2 and WS2 nanotubes. Advanced Materials, 2001, 13(4): 283–286 https://doi.org/10.1002/1521-4095(200102)13:4<283::AID-ADMA283>3.0.CO;2-H
12	Lee Y H, Zhang X Q, Zhang W, Chang M T, Lin C T, Chang K D, Yu Y C, Wang J T W, Chang C S, Li L J, Lin T W. Synthesis of large-area MoS2 atomic layers with chemical vapor deposition. Advanced Materials, 2012, 24(17): 2320–2325 https://doi.org/10.1002/adma.201104798
13	Sheng B, Liu J, Li Z, Wang M, Zhu K, Qiu J, Wang J. Effects of excess sulfur source on the formation and photocatalytic properties of flower-like MoS2 spheres by hydrothermal synthesis. Materials Letters, 2015, 144: 153–156 https://doi.org/10.1016/j.matlet.2015.01.056
14	Liu M, Li X, Xu Z, Li B, Chen L, Shan N. Synthesis of chain-like MoS2 nanoparticles in W/O reverse microemulsion and application in photocatalysis. Chinese Science Bulletin, 2012, 57(30): 3862–3866 https://doi.org/10.1007/s11434-012-5339-0
15	Gong H, Zheng F, Li Z, Li Y, Hu P, Gong Y, Song S, Zhan F, Zhen Q. Hydrothermal preparation of MoS2 nanoflake arrays on Cu foil with enhanced supercapacitive property. Electrochimica Acta, 2017, 227: 101–109 https://doi.org/10.1016/j.electacta.2017.01.012
16	Ye L, Wu C, Guo W, Xie Y. MoS2 hierarchical hollow cubic cages assembled by bilayers: One-step synthesis and their electrochemical hydrogen storage properties. Chemical Communications, 2006, 45(45): 4738–4740 https://doi.org/10.1039/b610601c
17	Lu X, Lin Y, Dong H, Dai W, Chen X, Qu X, Zhang X. One-step hydrothermal fabrication of three-dimensional MoS2 nanoflower using polypyrrole as template for efficient hydrogen evolution reaction. Scientific Reports, 2017, 7: 42309 https://doi.org/10.1038/srep42309
18	Akram H, Mateos-Pedrero C, Gallegos-Suárez E, Guerrero-Ruíz A, Chafik T, Rodríguez-Ramos I. Effect of electrolytes nature and concentration on the morphology and structure of MoS2 nanomaterials prepared using one-pot solvothermal method. Applied Surface Science, 2014, 307(2): 319–326 https://doi.org/10.1016/j.apsusc.2014.04.034
19	Li M, Wang D, Li J, Pan Z, Ma H, Jiang Y, Tian Z, Lu A. Surfactant-assisted hydrothermally synthesized MoS2 samples with controllable morphologies and structures for anthracene hydrogenation. Chinese Journal of Catalysis, 2017, 38(3): 597–606 https://doi.org/10.1016/S1872-2067(17)62779-7
20	Yan Y, Xia B, Ge X, Liu Z, Wang J, Wang X. Ultrathin MoS2 nanoplates with rich active sites as highly efficient catalyst for hydrogen evolution. ACS Applied Materials & Interfaces, 2013, 5(24): 12794–12798 https://doi.org/10.1021/am404843b
21	Chikan V, Kelley D F. Size-dependent spectroscopy of MoS2 nanoclusters. Journal of Physical Chemistry B, 2002, 106(15): 3794–3804 https://doi.org/10.1021/jp011898x
22	Yu H, Liu Y, Brock S L. Synthesis of discrete and dispersible MoS2 nanocrystals. Inorganic Chemistry, 2008, 47(5): 1428–1434 https://doi.org/10.1021/ic701020s
23	Xiong Y, Xie Y, Li Z, Li X, Zhang R. Micelle-assisted fabrication of necklace-shaped assembly of inorganic fullerene-like molybdenum disulfide nanospheres. Chemical Physics Letters, 2003, 382(1-2): 180–185 https://doi.org/10.1016/j.cplett.2003.10.063
24	Marchand K, Tarret M, Lechaire J, Normand L, Kasztelan S, Cseri T. Investigation of AOT-based microemulsions for the controlled synthesis of MoSx nanoparticles: An electron microscopy study. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2003, 214(1): 239–248 https://doi.org/10.1016/S0927-7757(02)00412-0
25	Ganguli A K, Ganguly A, Vaidya S. Microemulsion-based synthesis of nanocrystalline materials. Chemical Society Reviews, 2010, 39(2): 474–485 https://doi.org/10.1039/B814613F
26	Wu M, Long J, Huang A, Luo Y, Feng S, Xu R. Microemulsion-mediated hydrothermal synthesis and characterization of nanosize rutile and anatase particles. Langmuir, 1999, 15(26): 8822–8825 https://doi.org/10.1021/la990514f
27	Yang L, Liu L, Xiao D, Zhu J. Preparation and characterization of ZnSe nanocrystals by a microemulsion-mediated method. Materials Letters, 2012, 72: 113–115 https://doi.org/10.1016/j.matlet.2011.12.064
28	Yin J, Lu X, Dong Q. The experiment and theory studies of silver substituting cadmium in CdS quantum dots. Journal of Alloys and Compounds, 2017, 695: 1301–1306 https://doi.org/10.1016/j.jallcom.2016.10.260
29	Gao M R, Chan M K Y, Sun Y. Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production. Nature Communications, 2015, 6: 7493 https://doi.org/10.1038/ncomms8493
30	Li J, Wang D, Ma H, Pan Z, Jiang Y, Li M, Tian Z. Ionic liquid assisted hydrothermal synthesis of hollow core/shell MoS2 microspheres. Materials Letters, 2015, 160: 550–554 https://doi.org/10.1016/j.matlet.2015.08.049
31	Li M, Wang D, Li J, Pan Z, Ma H, Jiang Y, Tian Z. Facile hydrothermal synthesis of MoS2 nano-sheets with controllable structures and enhanced catalytic performance for anthracene hydrogenation. RSC Advances, 2016, 6(75): 71534–71542 https://doi.org/10.1039/C6RA16084K
32	Wu Z, Tang C, Zhou P, Liu Z, Xu Y, Wang D, Fang B. Enhanced hydrogen evolution catalysis from osmotically swollen ammoniated MoS2. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2015, 3(24): 13050–13056 https://doi.org/10.1039/C5TA02010G
33	Anto Jeffery A, Nethravathi C, Rajamathi M. Two-dimensional nanosheets and layered hybrids of MoS2 and WS2 through exfoliation of ammoniated MS2 (M= Mo,W). Journal of Physical Chemistry C, 2014, 118(2): 1386–1396 https://doi.org/10.1021/jp410918c
34	Matusinovic Z, Shukla R, Manias E, Hogshead C G, Wilkie C A. Polystyrene/molybdenum disulfide and poly(methyl methacrylate)/molybdenum disulfide nanocomposites with enhanced thermal stability. Polymer Degradation & Stability, 2012, 97(12): 2481–2486 https://doi.org/10.1016/j.polymdegradstab.2012.07.004
35	Frey G L, Tenne R, Matthews M J, Dresselhaus M S, Dresselhaus G. Raman and resonance Raman investigation of MoS2 nanoparticles. Physical Review B: Condensed Matter and Materials Physics, 1999, 60(4): 2883–2892 https://doi.org/10.1103/PhysRevB.60.2883
36	Wang Z, Ma L, Chen W, Huang G, Chen D, Wang L, Lee J Y. Facile synthesis of MoS2/graphene composites: Effects of different cationic surfactants on microstructures and electrochemical properties of reversible lithium storage. RSC Advances, 2013, 3(44): 21675–21684 https://doi.org/10.1039/c3ra43699c
37	Ramakrishna Matte H S S, Gomathi A, Manna A K, Late D J, Datta R, Pati S K, Rao C N R. MoS2 and WS2 analogues of graphene. Angewandte Chemie International Edition, 2010, 49(24): 4059–4062 doi:10.1002/anie.201000009
38	Koroteev V O, Bulusheva L G, Asanov I P, Shlyakhova E V, Vyalikh D V, Okotrub A V. Charge transfer in the MoS2/Carbon nanotube composite. Journal of Physical Chemistry C, 2011, 115(43): 21199–21204 https://doi.org/10.1021/jp205939e
39	Lee C, Yan H, Brus L E, Heinz T F, Hone J, Ryu S. Anomalous lattice vibrations of single- and few-layer MoS2. ACS Nano, 2010, 4(5): 2695–2700 https://doi.org/10.1021/nn1003937
40	Nogueira A, Znaiguia R, Uzio D, Afanasiev P, Berhault G. Curved nanostructures of unsupported and Al2O3-supported MoS2 catalysts: Synthesis and HDS catalytic properties. Applied Catalysis A, General, 2012, 429–430: 92–105 https://doi.org/10.1016/j.apcata.2012.04.013
41	Iwata Y, Sato K, Yoneda T, Miki Y, Sugimoto Y, Nishijima A, Shimada H. Catalytic functionality of unsupported molybdenum sulfide catalysts prepared with different methods. Catalysis Today, 1998, 45(1-4): 353–359 https://doi.org/10.1016/S0920-5861(98)00262-4
42	Bellussi G, Rispoli G, Molinari D, Landoni A, Pollesel P, Panariti N, Millini R, Montanari E. The role of MoS2 nano-slabs in the protection of solid cracking catalysts for the total conversion of heavy oils to good quality distillates. Catalysis Science & Technology, 2013, 3(1): 176–182 https://doi.org/10.1039/C2CY20448G
43	Zhou K, Jiang S, Bao C, Song L, Wang B, Tang G, Hu Y, Gui Z. Preparation of poly(vinyl alcohol) nanocomposites with molybdenum disulfide (MoS2): Structural characteristics and markedly enhanced properties. RSC Advances, 2012, 2(31): 11695–11703 https://doi.org/10.1039/c2ra21719h
44	Zhou K, Liu J, Wang B, Zhang Q, Shi Y, Jiang S, Hu Y, Gui Z. Facile preparation of poly(methyl methacrylate)/MoS2 nanocomposites via in situ emulsion polymerization. Materials Letters, 2014, 126: 159–161 https://doi.org/10.1016/j.matlet.2014.04.040
45	Barzegar-Bafrooei H, Ebadzadeh T, Tazike M. A survey on dispersion mechanisms of multi-walled carbon nanotubes in an aqueous media by UV-Vis, raman spectroscopy, TGA, and FTIR. Journal of Dispersion Science and Technology, 2012, 33(7): 955–959 https://doi.org/10.1080/01932691.2011.590420
46	Boyjoo Y, Wang M, Pareek V K, Liu J, Jaroniec M. Synthesis and applications of porous non-silica metal oxide submicrospheres. Chemical Society Reviews, 2016, 45(21): 6013–6047 https://doi.org/10.1039/C6CS00060F
47	Yang T, Ling H, Lamonier J F, Jaroniec M, Huang J, Monteiro M J, Liu J. A synthetic strategy for carbon nanospheres impregnated with highly monodispersed metal nanoparticles. NPG Asia Materials, 2016, 8(2): e240 https://doi.org/10.1038/am.2015.145
48	Pinilla J L, Purón H, Torres D, Suelves I, Millan M. Ni-MoS2 supported on carbon nanofibers as hydrogenation catalysts: Effect of support functionalisation. Carbon, 2015, 81: 574–586 https://doi.org/10.1016/j.carbon.2014.09.092

[1]	Huanhuan Shang, Xiaoman Zhang, Jing Xu, Yifan Han. Effects of preparation methods on the activity of CuO/CeO₂ catalysts for CO oxidation[J]. Front. Chem. Sci. Eng., 2017, 11(4): 603-612.

Viewed

Full text

Abstract

Cited

Shared

Discussed