The rise of two-dimensional MoS₂ for catalysis

Abstract

Two-dimensional (2D) MoS₂ is used as a catalyst or support and has received increased research interest because of its superior structural and electronic properties compared with those of bulk structures. In this article, we illustrate the active sites of 2D MoS₂ and various strategies for enhancing its intrinsic catalytic activity. The recent advances in the use of 2D MoS₂-based materials for applications such as thermocatalysis, electrocatalysis, and photocatalysis are discussed. We also discuss the future opportunities and challenges for 2D MoS₂-based materials, in both fundamental research and industrial applications.

Keywords

catalysis / 2D materials / MoS₂ / non-precious metal / electronic properties

References

[1] J. K. Nørskov, T. Bligaard, J. Rossmeisl, and C. H. Christensen, Towards the computational design of solid catalysts, Nat. Chem. 1(1), 37 (2009)

[2] S. Bag, A. F. Gaudette, M. E. Bussell, and M. G. Kanatzidis, Spongy chalcogels of non-platinum metals act as effective hydrodesulfurization catalysts, Nat. Chem. 1(3), 217 (2009)

[3] S. Hu, M. R. Shaner, J. A. Beardslee, M. Lichterman, B. S. Brunschwig, and N. S. Lewis, Amorphous TiO₂ coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation, Science 344(6187), 1005 (2014)

[4] H. Zhang, Ultrathin two-dimensional nanomaterials, ACS Nano 9(10), 9451 (2015)

[5] A. J. Mannix, X. F. Zhou, B. Kiraly, J. D. Wood, D. Alducin, B. D. Myers, X. Liu, B. L. Fisher, U. Santiago, J. R. Guest, M. J. Yacaman, A. Ponce, A. R. Oganov, M. C. Hersam, and N. P. Guisinger, Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs, Science 350(6267), 1513 (2015)

[6] G. R. Bhimanapati, Z. Lin, V. Meunier, Y. Jung, J. J. Cha, et al., Recent advances in two-dimensional materials beyond graphene, ACS Nano 9(12), 11509 (2015)

[7] S. Z. Butler, S. M. Hollen, L. Cao, Y. Cui, J. A. Gupta, H. R. Gutierrez, T. F. Heinz, S. S. Hong, J. Huang, A. F. Ismach, E. Johnston-Halperin, M. Kuno, V. V. Plashnitsa, R. D. Robinson, R. S. Ruoff, S. Salahuddin, J. Shan, L. Shi, M. G. Spencer, M. Terrones, W. Windl, and J. E. Goldberger, Progress, challenges, and opportunities in two-dimensional materials beyond graphene, ACS Nano 7(4), 2898 (2013)

[8] P. Miró, M. Audiffred, and T. Heine, An atlas of twodimensional materials, Chem. Soc. Rev. 43(18), 6537 (2014)

[9] R. Zhao, B. Grisafe, R. K. Ghosh, S. Holoviak, B. Wang, K. Wang, and J. Robinson, Two-dimensional tantalum disulfide: Controlling structure and properties via synthesis, 2D Mater. 5(2), 025001 (2018)

[10] X. Guo, G. Yang, J. Zhang, and X. Xu, Structural, mechanical and electronic properties of in-plane 1T/2H phase interface of MoS₂ heterostructures, AIP Adv. 5(9), 097174 (2015)

[11] M. Xu, T. Liang, M. Shi, and H. Chen, Graphenelike two-dimensional materials, Chem. Rev. 113(5), 3766 (2013)

[12] Y. Yin, J. C. Han, Y. M. Zhang, X. H. Zhang, P. Xu, Q. Yuan, L. Samad, X. J. Wang, Y. Wang, Z. H. Zhang, P. Zhang, X. Z. Cao, B. Song, and S. Jin, Contributions of phase, sulfur vacancies, and edges to the hydrogen evolution reaction catalytic activity of porous molybdenum disulfide nanosheets, J. Am. Chem. Soc. 138(25), 7965 (2016)

[13] V. P. Santos, B. van der Linden, A. Chojecki, G. Budroni, S. Corthals, H. Shibata, G. R. Meima, F. Kapteijn, M. Makkee, and J. Gascon, Mechanistic insight into the synthesis of higher alcohols from syngas: the role of K promotion on MoS₂ catalysts, ACS Catal. 3(7), 1634 (2013)

[14] Y. Q. Yang, C. T. Tye, and K. J. Smith, Influence of MoS₂ catalyst morphology on the hydrodeoxygenation of phenols, Catal. Commun. 9(6), 1364 (2008)

[15] B. Yoosuk, D. Tumnantong, and P. Prasassarakich, Unsupported MoS₂ and CoMoS₂ catalysts for hydrodeoxygenation of phenol, Chem. Eng. Sci. 79, 1 (2012)

[16] J. Zhu, Y. Wei, W. Chen, Z. Zhao, and A. Thomas, Graphitic carbon nitride as a metal-free catalyst for NO decomposition, Chem. Commun. 46(37), 6965 (2010)

[17] Y. Romero, F. Richard, and S. Brunet, Hydrodeoxygenation of 2-ethylphenol as a model compound of biocrude over sulfided Mobased catalysts: Promoting effect and reaction mechanism, Appl. Catal. B 98(3–4), 213 (2010)

[18] D. H. Deng, K. S. Novoselov, Q. Fu, N. F. Zheng, Z. Q. Tian, and X. H. Bao, Catalysis with two-dimensional materials and their heterostructures, Nat. Nanotechnol. 11(3), 218 (2016)

[19] L. Yuwen, F. Xu, B. Xue, Z. Luo, Q. Zhang, B. Bao, S. Su, L. Weng, W. Huang, and L. Wang, General synthesis of noble metal (Au, Ag, Pd, Pt) nanocrystal modified MoS₂ nanosheets and the enhanced catalytic activity of Pd-MoS₂ for methanol oxidation, Nanoscale 6(11), 5762 (2014)

[20] H. Huang, X. Feng, C. C. Du, S. Y. Wu, and W. B. Song, Incorporated oxygen in MoS₂ ultrathin nanosheets for efficient ORR catalysis, J. Mater. Chem. A 3(31), 16050 (2015)

[21] M. Asadi, B. Kumar, C. Liu, P. Phillips, P. Yasaei, A. Behranginia, P. Zapol, R. F. Klie, L. A. Curtiss, and A. Salehi-Khojin, Cathode based on molybdenum disulfide nanoflakes for lithium-oxygen batteries, ACS Nano 10(2), 2167 (2016)

[22] H. Vrubel, D. Merki, and X. L. Hu, Hydrogen evolution catalyzed by MoS₃ and MoS₂ particles, Energy Environ. Sci. 5(3), 6136 (2012)

[23] J. Xie, H. Zhang, S. Li, R. Wang, X. Sun, M. Zhou, J. Zhou, X. W. Lou, and Y. Xie, Defect-rich MoS₂ ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution,Adv. Mater. 25(40), 5807 (2013)

[24] X. Zong, J. Han, G. Ma, H. Yan, G. Wu, and C. Li, Photocatalytic H2 evolution on CdS loaded with WS₂ as cocatalyst under visible light irradiation, J. Phys. Chem. C 115(24), 12202 (2011)

[25] Y. Liang, Y. Li, H. Wang, and H. Dai, Strongly coupled inorganic/nanocarbon hybrid materials for advanced electrocatalysis, J. Am. Chem. Soc. 135(6), 2013 (2013)

[26] L. Liao, J. Zhu, X. Bian, L. Zhu, M. D. Scanlon, H. H. Girault, and B. Liu, MoS₂ formed on mesoporous graphene as a highly active catalyst for hydrogen evolution, Adv. Funct. Mater. 23(42), 5326 (2013)

[27] P. F. Liu, L. Zhou, T. Frauenheim, and L. M. Wu, New quantum spin Hall insulator in two-dimensional MoS₂ with periodically distributed pores, Nanoscale 8(9), 4915 (2016)

[28] Q. H. Wang, K. Kalantar-Zadeh, A. Kis, J. N. Coleman, and M. S. Strano, Electronics and optoelectronics of two-dimensional transition metal dichalcogenides, Nat. Nanotechnol. 7(11), 699 (2012)

[29] Z. S. Wu, S. Yang, Y. Sun, K. Parvez, X. Feng, and K. Müllen, 3D nitrogen-doped graphene aerogel-supported Fe₃O₄ nanoparticles as efficient electrocatalysts for the oxygen reduction reaction, J. Am. Chem. Soc. 134(22), 9082 (2012)

[30] J. D. Benck, Z. Chen, L. Y. Kuritzky, A. J. Forman, and T. F. Jaramillo, Amorphous molybdenum sulfide catalysts for electrochemical hydrogen production: Insights into the origin of their catalytic activity, ACS Catal. 2(9), 1916 (2012)

[31] Y. H. Chang, C. T. Lin, T. Y. Chen, C. L. Hsu, Y. H. Lee, W. Zhang, K. H. Wei, and L. J. Li, Highly efficient electrocatalytic hydrogen production by MoS_x grown on graphene-protected 3D Ni foams, Adv. Mater. 25(5), 756 (2013)

[32] A. B. Laursen, P. C. K. Vesborg, and I. Chorkendorff, A high-porosity carbon molybdenum sulphide composite with enhanced electrochemical hydrogen evolution and stability, Chem. Commun. 49(43), 4965 (2013)

[33] R. J. H. Voorhoeve and J. C. M. Stuiver, The mechanism of the hydrogenation of cyclohexene and benzene on nickel-tungsten sulfide catalysts, J. Catal. 23(2), 243 (1971)

[34] G. Hagenbach, P. Courty, and B. Delmon, Physicochemical investigations and catalytic activity measurements on crystallized molydbenum sulfide-cobalt sulfide mixed catalysts, J. Catal. 31(2), 264 (1973)

[35] J. V. Lauritsen, M. Nyberg, J. K. Nørskov, B. S. Clausen, H. Topsøe, E. Lægsgaard, and F. Besenbacher, Hydrodesulfurization reaction pathways on MoS₂ nanoclusters revealed by scanning tunneling microscopy, J. Catal. 224(1), 94 (2004)

[36] M. Daage and R. R. Chianelli, Structure-function relations in molybdenum sulfide catalysts: The “rim-edge” model, J. Catal. 149(2), 414 (1994)

[37] Y. Iwata, Y. Araki, K. Honna, Y. Miki, K. Sato, and H. Shimada, Hydrogenation active sites of unsupported molybdenum sulfide catalysts for hydroprocessing heavy oils, Catal. Today 65(2–4), 335 (2001)

[38] H. Shimada, Morphology and orientation of MoS₂ clusters on Al₂O₃ and TiO₂ supports and their effect on catalytic performance, Catal. Today 86(1–4), 17 (2003)

[39] X. Zhang and Y. Xie, Recent advances in free-standing two-dimensional crystals with atomic thickness: Design, assembly and transfer strategies, Chem. Soc. Rev. 42(21), 8187 (2013)

[40] Q. Fu, L. Yang, W. Wang, A. Han, J. Huang, P. Du, Z. Fan, J. Zhang, and B. Xiang, Synthesis and enhanced electrochemical catalytic performance of monolayer WS_2(1−x)Se_2x with a tunable band gap, Adv. Mater. 27(32), 4732 (2015)

[41] J. Xie, X. Sun, N. Zhang, K. Xu, M. Zhou, and Y. Xie, Layer-by-layer b-Ni(OH)₂/graphene nanohybrids for ultraflexible all-solid-state thin-film supercapacitors with high electrochemical performance, Nano Energy 2(1), 65 (2013)

[42] B. Hinnemann, P. G. Moses, J. Bonde, K. P. Jørgensen, J. H. Nielsen, S. Horch, I. Chorkendorff, and J. K. Nørskov, Biomimetic hydrogen evolution: MoS₂ nanoparticles as catalyst for hydrogen evolution, J. Am. Chem. Soc. 127(15), 5308 (2005)

[43] T. F. Jaramillo, K. P. Jørgensen, J. Bonde, J. H. Nielsen, S. Horch, and I. Chorkendorff, Identification of active edge sites for electrochemical H₂ evolution from MoS₂ nanocatalysts, Science 317(5834), 100 (2007)

[44] J. Deng, H. B. Li, J. P. Xiao, Y. C. Tu, D. H. Deng, H. Yang, and X. H. Bao, Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS₂ surface via single-atom metal doping, Energy Environ. Sci. 8(5), 1594 (2015)

[45] H. Li, L. Wang, Y. Dai, Z. Pu, Z. Lao, Y. Chen, M. Wang, X. Zheng, J. Zhu, W. Zhang, R. Si, C. Ma, and J. Zeng, Synergetic interaction between neighbouring platinum monomers in CO₂ hydrogenation, Nat. Nanotechnol. 13(5), 411 (2018)

[46] H. Li, C. Tsai, A. L. Koh, L. Cai, A. W. Contryman, A. H. Fragapane, J. Zhao, H. S. Han, H. C. Manoharan, F. Abild-Pedersen, J. K. Norskov, and X. Zheng, Corrigendum: Activating and optimizing MoS₂ basal planes for hydrogen evolution through the formation of strained sulphur vacancies, Nat. Mater. 15(3), 364 (2016)

[47] C. Tsai, H. Li, S. Park, J. Park, H. S. Han, J. K. Norskov, X. Zheng, and F. Abild-Pedersen, Electrochemical generation of sulfur vacancies in the basal plane of MoS₂ for hydrogen evolution, Nat. Commun. 8, 15113 (2017)

[48] R. Prins, V. H. J. De Beer, and G. A. Somorjai, Structure and function of the catalyst and the promoter in Co-Mo hydrodesulfurization catalysts, Catal. Rev. 31(1–2), 1 (1989)

[49] G. L. Liu, A. W. Robertson, M. M. J. Li, W. C. Kuo, M. T. Darby, M. H. Muhieddine, Y. C. Lin, K. Suenaga, M. Stamatakis, J. H. Warner, and S. C. E. Tsang, MoS₂ monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction, Nat. Chem. 9(8), 810 (2017)

[50] C. F. Zhang, H. G. Li, J. M. Lu, X. C. Zhang, K. E. MacArthur, M. Heggen, and F. Wang, Promoting lignin depolymerization and restraining the condensation via an oxidation-hydrogenation strategy, ACS Catal. 7(5), 3419 (2017)

[51] V. S. Dorokhov, E. A. Permyakov, P. A. Nikulshin, V. V. Maximov, and V. M. Kogan, Experimental and computational study of syngas and ethanol conversion mechanisms over K-modified transition metal sulfide catalysts, J. Catal. 344, 841 (2016)

[52] H. Tao, Y. Gao, N. Talreja, F. Guo, J. Texter, C. Yan, and Z. Sun, Two-dimensional nanosheets for electrocatalysis in energy generation and conversion, J. Mater. Chem. A 5(16), 7257 (2017)

[53] J. Wang, W. Cui, Q. Liu, Z. Xing, A. M. Asiri, and X. Sun, Recent progress in cobalt-based heterogeneous catalysts for electrochemical water splitting, Adv. Mater. 28(2), 215 (2016)

[54] J. Deng, H. B. Li, S. H. Wang, D. Ding, M. S. Chen, C. Liu, Z. Q. Tian, K. S. Novoselov, C. Ma, D. H. Deng, and X. H. Bao, Multiscale structural and electronic control of molybdenum disulfide foam for highly efficient hydrogen production, Nat. Commun. 8, 14430 (2017)

[55] J. Zhang, Y. Liu, C. Sun, P. Xi, S. Peng, D. Gao, and D. Xue, Accelerated hydrogen evolution reaction in CoS₂ by transition-metal doping, ACS Energ. Lett 3(4), 779 (2018)

[56] J. Xie, J. Zhang, S. Li, F. Grote, X. Zhang, H. Zhang, R. Wang, Y. Lei, B. Pan, and Y. Xie, Controllable disorder engineering in oxygen-incorporated MoS₂ ultrathin nanosheets for efficient hydrogen evolution, J. Am. Chem. Soc. 135(47), 17881 (2013)

[57] Y. Li, H. Wang, L. Xie, Y. Liang, G. Hong, and H. Dai, MoS₂ nanoparticles grown on graphene: An advanced catalyst for the hydrogen evolution reaction, J. Am. Chem. Soc. 133(19), 7296 (2011)

[58] H. Zhang, Y. Tian, J. Zhao, Q. Cai, and Z. Chen, Small dopants make big differences: Enhanced electrocatalytic performance of MoS₂ monolayer for oxygen reduction reaction (ORR) by N- and P-doping, Electrochim. Acta 225, 543 (2017)

[59] K. Zhao, W. Gu, L. Zhao, C. Zhang, W. Peng, and Y. Xian, MoS₂/nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction, Electrochim. Acta 169, 142 (2015)

[60] M. Asadi, B. Kumar, A. Behranginia, B. A. Rosen, A. Baskin, N. Repnin, D. Pisasale, P. Phillips, W. Zhu, R. Haasch, R. F. Klie, P. Kral, J. Abiade, and A. Salehi-Khojin, Robust carbon dioxide reduction on molybdenum disulphide edges, Nat. Commun. 5(1), 4470 (2014)

[61] P. Abbasi, M. Asadi, C. Liu, S. Sharifi-Asl, B. Sayahpour, A. Behranginia, P. Zapol, R. Shahbazian-Yassar, L. A. Curtiss, and A. Salehi-Khojin, Tailoring the edge structure of molybdenum disulfide toward electrocatalytic reduction of carbon dioxide, ACS Nano 11(1), 453 (2017)

[62] M. Asadi, B. Sayahpour, P. Abbasi, A. T. Ngo, K. Karis, J. R. Jokisaari, C. Liu, B. Narayanan, M. Gerard, P. Yasaei, X. Hu, A. Mukherjee, K. C. Lau, R. S. Assary, F. Khalili-Araghi, R. F. Klie, L. A. Curtiss, and A. Salehi-Khojin, A lithium-oxygen battery with a long cycle life in an air-like atmosphere, Nature 555(7697), 502 (2018)

[63] J. Balach, T. Jaumann, and L. Giebeler, Nanosized Li₂S-based cathodes derived from MoS₂ for high-energy density Li-S cells and Si-Li₂S full cells in carbonatebased electrolyte, Energ. Storage Mater 8, 209 (2017)

[64] Z. Li, S. Deng, R. Xu, L. Wei, X. Su, and M. Wu, Combination of nitrogen-doped graphene with MoS₂ nanoclusters for improved Li-S battery cathode: Synthetic effect between 2D components, Electrochim. Acta 252, 200 (2017)

[65] S. R. Meyers and M. W. Grinstaff, Biocompatible and bioactive surface modifications for prolonged in vivo efficacy, Chem. Rev. 112(3), 1615 (2012)

[66] Y. Sun, H. Cheng, S. Gao, Z. Sun, Q. Liu, Q. Liu, F. Lei, T. Yao, J. He, S. Wei, and Y. Xie, Freestanding tin disulfide single-layers realizing efficient visible-light water splitting, Angew. Chem. Int. Ed. 51(35), 8727 (2012)

[67] A. J. Esswein and D. G. Nocera, Hydrogen production by molecular photocatalysis, Chem. Rev. 107(10), 4022 (2007)

[68] F. E. Osterloh, Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting, Chem. Soc. Rev. 42(6), 2294 (2013)

[69] F. A. Frame and F. E. Osterloh, CdSe-MoS₂: A quantum size-confined photocatalyst for hydrogen evolution from water under visible light, J. Phys. Chem. C 114(23), 10628 (2010)

[70] Y. Yan, B. Y. Xia, X. M. Ge, Z. L. Liu, J. Y. Wang, and X. Wang, Ultrathin MoS₂ nanoplates with rich active sites as highly efficient catalyst for hydrogen evolution, ACS Appl. Mater. Interfaces 5(24), 12794 (2013)

[71] T. Jia, A. Kolpin, C. Ma, R. C. T. Chan, W. M. Kwok, and S. C. E. Tsang, A graphene dispersed CdS-MoS₂ nanocrystal ensemble for cooperative photocatalytic hydrogen production from water, Chem. Commun. 50(10), 1185 (2014)

[72] K. Pramoda, U. Gupta, I. Ahmad, R. Kumar, and C. N. R. Rao, Assemblies of covalently cross-linked nanosheetsof MoS₂ and of MoS₂-RGO: Synthesis and novel properties, J. Mater. Chem. A 4(23), 8989 (2016)

[73] U. Maitra, U. Gupta, M. De, R. Datta, A. Govindaraj, and C. N. Rao, Highly effective visible-lightinduced H₍₂₎ generation by single-layer 1T-MoS₍₂₎ and a nanocomposite of few-layer 2H-MoS₍₂₎ with heavily nitrogenated graphene, Angew. Chem. Int. Ed. 52(49), 13057 (2013)

[74] S. Bai, L. Wang, X. Chen, J. Du, and Y. Xiong, Chemically exfoliated metallic MoS₂ nanosheets: A promising supporting co-catalyst for enhancing the photocatalytic performance of TiO₂ nanocrystals, Nano Res. 8(1), 175 (2015)

[75] M. Shen, Z. Yan, L. Yang, P. Du, J. Zhang, and B. Xiang, MoS₂ nanosheet/TiO₂ nanowire hybrid nanostructures for enhanced visible-light photocatalytic activities, Chem. Commun. 50(97), 15447 (2014)

[76] W. Zhou, Z. Yin, Y. Du, X. Huang, Z. Zeng, Z. Fan, H. Liu, J. Wang, and H. Zhang, Synthesis of few-layer MoS₂ nanosheet-coated TiO₂ nanobelt heterostructures for enhanced photocatalytic activities, Small 9(1), 140 (2013)

[77] Y. J. Yuan, F. Wang, B. Hu, H. W. Lu, Z. T. Yu, and Z. G. Zou, Significant enhancement in photocatalytic hydrogen evolution from water using a MoS₂ nanosheetcoated ZnO heterostructure photocatalyst, Dalton T. 44(24), 10997 (2015)

[78] S. Guo, X. Li, J. Zhu, T. Tong, and B. Wei, Au NPs@MoS₂ sub-micrometer sphere-ZnO nanorod hybrid structures for efficient photocatalytic hydrogen evolution with excellent stability, Small 12(41), 5692 (2016)

[79] B. Zhu, B. Lin, Y. Zhou, P. Sun, Q. Yao, Y. Chen, and B. Gao, Enhanced photocatalytic H₂ evolution on ZnS loaded with graphene and MoS₂ nanosheets as cocatalysts, J. Mater. Chem. A 2(11), 3819 (2014)

[80] X. Zong, G. Wu, H. Yan, G. Ma, J. Shi, F. Wen, L. Wang, and C. Li, Photocatalytic H₂ evolution on MoS₂/CdS catalysts under visible light irradiation, J. Phys. Chem. C 114(4), 1963 (2010)

[81] X. Zong, H. Yan, G. Wu, G. Ma, F. Wen, L. Wang, and C. Li, Enhancement of photocatalytic H₂ evolution on CdS by loading MoS₂ as cocatalyst under visible light irradiation, J. Am. Chem. Soc. 130(23), 7176 (2008)

[82] J. Zhang, Z. Zhu, and X. Feng, Construction of twodimensional MoS₂/CdS p-n nanohybrids for highly efficient photocatalytic hydrogen evolution, Chemistry 20(34), 10632 (2014)

[83] J. He, L. Chen, F. Wang, Y. Liu, P. Chen, C. T. Au, and S. F. Yin, CdS nanowires decorated with ultrathin MoS₂ nanosheets as an efficient photocatalyst for hydrogen evolution, ChemSusChem 9(6), 624 (2016)

[84] D. P. Kumar, S. Hong, D. A. Reddy, and T. K. Kim, Noble metal-free ultrathin MoS₂ nanosheet-decorated CdS nanorods as an efficient photocatalyst for spectacular hydrogen evolution under solar light irradiation, J. Mater. Chem. A 4(47), 18551 (2016)

[85] Y. Hou, A. B. Laursen, J. Zhang, G. Zhang, Y. Zhu, X. Wang, S. Dahl, and I. Chorkendorff, Layered nanojunctions for hydrogen-evolution catalysis, Angew. Chem. Int. Ed. 52(13), 3621 (2013)

[86] L. Ge, C. Han, X. Xiao, and L. Guo, Synthesis and characterization of composite visible light active photocatalysts MoS_2-g-C₃N₄ with enhanced hydrogen evolution activity, Int. J. Hydrogen Energy 38(17), 6960 (2013)

[87] X. Jin, X. Fan, J. Tian, R. Cheng, M. Li, and L. Zhang, MoS₂ quantum dot decorated g-C₃N₄ composite photocatalyst with enhanced hydrogen evolution performance, RSC Advances 6(58), 52611 (2016)

[88] L. Karimiech, Combination of mesoporous titanium dioxide with MoS₂ nanosheets for high photocatalytic activity, Pol. J. Chem. Technol. 19, 56 (2017)

[89] X. Hu, H. Zhao, J. Tian, J. Gao, Y. Li, and H. Cui, Synthesis of few-layer MoS₂ nanosheets-coated TiO₂ nanosheets on graphite fibers for enhanced photocatalytic properties, Sol. Energy Mater. Sol. Cells 172, 108 (2017)

[90] W. Dai, J. Yu, Y. Deng, X. Hu, T. Wang, and X. Luo, Facile synthesis of MoS₂/Bi₂WO₆ nanocomposites for enhanced CO₂ photoreduction activity under visible light irradiation, Appl. Surf. Sci. 403, 230 (2017)

[91] J. Di, J. Xia, M. Ji, L. Xu, S. Yin, Z. Chen, and H. Li, Bidirectional acceleration of carrier separation spatially via N-CQDs/atomically-thin BiOI nanosheets nanojunctions for manipulating active species in a photocatalytic process, J. Mater. Chem. A 4(14), 5051 (2016)

[92] L. Shi, W. Ding, S. Yang, Z. He, and S. Liu, Rationally designed MoS₂/protonated g-C₃N₄ nanosheet composites as photocatalysts with an excellent synergistic effect toward photocatalytic degradation of organic pollutants, J. Hazard. Mater. 347, 431 (2018)

[93] S. Sun, X. Li, W. Wang, L. Zhang, and X. Sun, Photocatalytic robust solar energy reduction of dinitrogen to ammonia on ultrathin MoS₂, Appl. Catal. B 200, 323 (2017)

[94] Y. Wu, B. Yuan, M. Li, W. H. Zhang, Y. Liu, and C. Li, Well-defined BiOCl colloidal ultrathin nanosheets: Synthesis, characterization, and application in photocatalytic aerobic oxidation of secondary amines, Chem. Sci. 6(3), 1873 (2015)

[95] L. S. Byskov, J. K. Nørskov, B. S. Clausen, and H. Topsøe, DFT calculations of unpromoted and promoted MoS₂-based hydrodesulfurization catalysts, J. Catal. 187(1), 109 (1999)

[96] H. Zhao, G. Yang, X. Gao, C. H. Pang, S. W. Kingman, and T. Wu, Hg⁰ capture over CoMoS/g-Al₂O₃ with MoS₂ nanosheets at low temperatures, Environ. Sci. Technol. 50(2), 1056 (2016)

[97] D. Wang, Z. Wang, L. Wang, L. Hu, and J. Jin, Ultrathin membranes of single-layered MoS₂ nanosheets for high-permeance hydrogen separation, Nanoscale 7(42), 17649 (2015)

[98] A. Midya, A. Ghorai, S. Mukherjee, R. Maiti, and S. K. Ray, Hydrothermal growth of few layer 2H-MoS₂ for heterojunction photodetector and visible light induced photocatalytic applications, J. Mater. Chem. A 4(12), 4534 (2016)

[99] C. Liu, D. Kong, P. C. Hsu, H. Yuan, H.W. Lee, Y. Liu, H. Wang, S. Wang, K. Yan, D. Lin, P. A. Maraccini, K. M. Parker, A. B. Boehm, and Y. Cui, Rapid water disinfection using vertically aligned MoS₂ nanofilms and visible light, Nat. Nanotechnol. 11(12), 1098 (2016)

[100] W. Li, Y. Yang, J. K. Weber, G. Zhang, and R. Zhou, Tunable, strain-controlled nanoporous MoS₂ filter for water desalination, ACS Nano 10(2), 1829 (2016)

[101] K. Ai, C. Ruan, M. Shen, and L. Lu, MoS₂ nanosheets with widened interlayer spacing for high-efficiency removal of mercury in aquatic systems, Adv. Funct. Mater. 26(30), 5542 (2016)

[102] S. Xie, Z. Shen, J. Deng, P. Guo, Q. Zhang, H. Zhang, C. Ma, Z. Jiang, J. Cheng, D. Deng, and Y. Wang, Visible light-driven C-H activation and C-C coupling of methanol into ethylene glycol, Nat. Commun. 9(1), 1181 (2018)

[103] Z. Li, D. Zhang, J. Ma, D. Wang, and C. Xie, Fabrication of MoS₂ microflowers for hydrogenation of nitrobenzene, Mater. Lett. 213, 350 (2018)

[104] X. L. Wang, Z. Zhao, Z. T. Chen, J. M. Li, A. J. Duan, C. M. Xu, and J. Y. Fan, Effect of synthesis temperature on structure-activity-relationship over NiMo/g-Al₂O₃ catalysts for the hydrodesulfurization of DBT and 4, 6-DMDBT, Fuel Process. Technol. 161, 52 (2017)

[105] P. Zheng, A. Duan, K. Chi, L. Zhao, C. Zhang, C. Xu, and J. Fan, Influence of sulfur vacancy on thiophene hydrodesulfurization mechanism at different MoS₂ edges: A DFT study, Chem. Eng. Sci. 164, 292 (2017)

[106] W. Wang, S. Tan, K. Wu, G. Zhu, Y. Liu, L. Tan, and Y. Yang, Hydrodeoxygenation of p-cresol as a model compound for bio-oil on MoS₂: Effects of water and benzothiophene on the activity and structure of catalyst, Fuel 214, 480 (2018)

[107] M. Grilc, G. Veryasov, B. Likozar, A. Jesih, and J. Levec, Hydrodeoxygenation of solvolysed lignocellulosic biomass by unsupported MoS₂, MoO₂, Mo₂C and WS₂ catalysts, Appl. Catal. B 163, 467 (2015)

[108] H. Wang, C. Tsai, D. Kong, K. Chan, F. Abild-Pedersen, J. K. Nørskov, and Y. Cui, Transition-metal doped edge sites in vertically aligned MoS₂ catalysts for enhanced hydrogen evolution, Nano Res. 8(2), 566 (2015)

[109] J. Bonde, P. G. Moses, T. F. Jaramillo, J. K. Nørskov, and I. Chorkendorff, Hydrogen evolution on nanoparticulate transition metal sulfides, Faraday Discuss. 140, 219 (2009)

[110] G. Ye, Y. Gong, J. Lin, B. Li, Y. He, S. T. Pantelides, W. Zhou, R. Vajtai, and P. M. Ajayan, Defects engineeredmonolayer MoS₂ for improved hydrogen evolution reaction, Nano Lett. 16(2), 1097 (2016)

[111] L. Tao, X. Duan, C. Wang, X. Duan, and S. Wang, Plasma-engineered MoS₂ thin-film as an efficient electrocatalyst for hydrogen evolution reaction, Chem. Commun. 51(35), 7470 (2015)

[112] S. Shin, Z. Jin, D. H. Kwon, R. Bose, and Y. S. Min, High turnover frequency of hydrogen evolution reaction on amorphous MoS₂ thin film directly grown by atomic layer deposition, Langmuir 31(3), 1196 (2015)

[113] D. Merki, S. Fierro, H. Vrubel, and X. Hu, Amorphous molybdenum sulfide films as catalysts for electrochemical hydrogen production in water, Chem. Sci. 2(7), 1262 (2011)

[114] J. Kibsgaard, Z. Chen, B. N. Reinecke, and T. F. Jaramillo, Engineering the surface structure of MoS₂ to preferentially expose active edge sites for electrocatalysis, Nat. Mater. 11(11), 963 (2012)

[115] D. Kong, H. Wang, J. J. Cha, M. Pasta, K. J. Koski, J. Yao, and Y. Cui, Synthesis of MoS₂ and MoSe₂ films with vertically aligned layers, Nano Lett. 13(3), 1341 (2013)

[116] J. P. Shi, D. L. Ma, G. F. Han, Y. Zhang, Q. Q. Ji, T. Gao, J. Y. Sun, X. J. Song, C. Li, Y. S. Zhang, X. Y. Lang, Y. F. Zhang, and Z. F. Liu, Controllable growth and transfer of monolayer MoS₂ on Au foils and its potential application in hydrogen evolution reaction, ACS Nano 8(10), 10196 (2014)

[117] L. Yang, H. Hong, Q. Fu, Y. Huang, J. Zhang, X. Cui, Z. Fan, K. Liu, and B. Xiang, Single-crystal atomiclayered molybdenum disulfide nanobelts with high surface activity, ACS Nano 9(6), 6478 (2015)

[118] X. Sun, J. Huo, Y. Yang, L. Xu, and S. Wang, The Co₃O₄ nanosheet array as support for MoS₂ as highly efficient electrocatalysts for hydrogen evolution reaction, J. Energ. Chem 26(6), 1136 (2017)

[119] M. A. Lukowski, A. S. Daniel, F. Meng, A. Forticaux, L. Li, and S. Jin, Enhanced hydrogen evolution catalysis from chemically exfoliated metallic MoS₂ nanosheets, J. Am. Chem. Soc. 135(28), 10274 (2013)

[120] A. Splendiani, L. Sun, Y. Zhang, T. Li, J. Kim, C. Y. Chim, and F. Wang, Emerging photoluminescence in monolayer MoS₂, Nano Lett. 10(4), 1271 (2010)

[121] L. Yang, W. Zhou, D. Hou, K. Zhou, G. Li, Z. Tang, L. Li, and S. Chen, Porous metallic MoO₂-supported MoS₂ nanosheets for enhanced electrocatalytic activity in the hydrogen evolution reaction, Nanoscale 7(12), 5203 (2015)

[122] Y. Yan, X. Ge, Z. Liu, J. Y. Wang, J. M. Leea, and X. Wang, Facile synthesis of low crystalline MoS₂ nanosheet-coated CNTs for enhanced hydrogen evolution reaction., Nanoscale 5(17), 7768 (2013)

[123] R. D. Nikam, A. Y. Lu, P. A. Sonawane, R. Kumar, K. Yadav, L. J. Li, and Y. T. Chen, Three-dimensional heterostructures of MoS₂ nanosheets on conducting MoO₂ as an efficient electrocatalyst to enhance hydrogen evolution reaction, ACS Appl. Mater. Interfaces 7(41), 23328 (2015)

[124] D. J. Li, U. N. Maiti, J. Lim, D. S. Choi, W. J. Lee, Y. Oh, G. Y. Lee, and S. O. Kim, Molybdenum sulfide/Ndoped CNT forest hybrid catalysts for high-performance hydrogen evolution reaction, Nano Lett. 14(3), 1228 (2014)

[125] Y. Huang, Y. E. Miao, L. Zhang, W. W. Tjiu, J. Panb, and T. Liu, Synthesis of few-layered MoS₂ nanosheetcoated electrospun SnO₂ nanotube heterostructures for enhanced hydrogen evolution reaction, Nanoscale 6(18), 10673 (2014)

[126] P. Ge, M. D. Scanlon, P. Peljo, X. Bian, H. Vubrel, A. O’Neill, J. N. Coleman, M. Cantoni, X. Hu, K. Kontturi, B. Liu, and H. H. Girault, Hydrogen evolution across nano-Schottky junctions at carbon supported MoS₂ catalysts in biphasic liquid systems, Chem. Commun. 48(52), 6484 (2012)

[127] M. R. Gao, J. X. Liang, Y. R. Zheng, Y. F. Xu, J. Jiang, Q. Gao, J. Li, and S. H. Yu, An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation, Nat. Commun. 6(1), 5982 (2015)

[128] Z. H. Deng, L. Li, W. Ding, K. Xiong, and Z. D. Wei, Synthesized ultrathin MoS₂ nanosheets perpendicular to graphene for catalysis of hydrogen evolution reaction, Chem. Commun. 51(10), 1893 (2015)

[129] Z. Chen, D. Cummins, B. N. Reinecke, E. Clark, M. K. Sunkara, and T. F. Jaramillo, Core-shell MoO₃-MoS₂ nanowires for hydrogen evolution: A functional design for electrocatalytic materials, Nano Lett. 11(10), 4168 (2011)

[130] Q. Gong, L. Cheng, C. Liu, M. Zhang, Q. Feng, H. Ye, M. Zeng, L. Xie, Z. Liu, and Y. Li, Ultrathin MoS_2(1−x)Se_2x alloy nanoflakes for electrocatalytic hydrogen evolution reaction, ACS Catal. 5(4), 2213 (2015)

[131] L. Yang, Q. Fu, W. Wang, J. Huang, J. Huang, J. Zhang, and B. Xiang, Large-area synthesis of monolayered MoS_2(1−x)Se_2x with a tunable band gap and its enhanced electrochemical catalytic activity, Nanoscale 7(23), 10490 (2015)

[132] L. Yang, W. Wang, Q. Fu, J. Zhang, and B. Xiang, MoS_2(1−x)Se_2x nanobelts for enhanced hydrogen evolution, Electrochim. Acta 185, 236 (2015)

[133] R. Ye, P. del Angel-Vicente, Y. Liu, M. J. Arellano-Jimenez, Z. Peng, T. Wang, Y. Li, B. I. Yakobson, S. H. Wei, M. J. Yacaman, and J. M. Tour, High-performance hydrogen evolution from MoS_2(1−x)P_x solid solution, Adv. Mater. 28(7), 1427 (2016)

[134] X. Y. Yu, Y. Feng, Y. Jeon, B. Guan, X. W. Lou, and U. Paik, Formation of Ni-Co-MoS₂ nanoboxes with enhanced electrocatalytic activity for hydrogen evolution, Adv. Mater. 28(40), 9006 (2016)

[135] C. Tang, L. Zhong, B. Zhang, H. F. Wang, and Q. Zhang, 3D mesoporous van der Waals heterostructures for trifunctional energy electrocatalysis, Adv. Mater. 30(5), 1705110 (2018)

[136] J. Zhao, J. Zhao, and Q. Cai, Single transition metal atom embedded into a MoS₂ nanosheet as a promising catalyst for electrochemical ammonia synthesis, Phys. Chem. Chem. Phys. 20(14), 9248 (2018)

[137] L. Yang, D. Zhong, J. Zhang, Z. Yan, S. Ge, P. Du, J. Jiang, D. Sun, X. Wu, Z. Fan, S. A. Dayeh, and B. Xiang, Optical properties of metal-molybdenum disulfide hybrid nanosheets and their application for enhanced photocatalytic hydrogen evolution, ACS Nano 8(7), 6979 (2014)

[138] U. Gupta and C. N. R. Rao, Hydrogen generation by water splitting using MoS₂ and other transition metal dichalcogenides, Nano Energy 41, 49 (2017)

[139] Q. Xiang, J. Yu, and M. Jaroniec, Synergetic effect of MoS₂ and graphene as cocatalysts for enhanced photocatalytic H₂ production activity of TiO₂ nanoparticles, J. Am. Chem. Soc. 134(15), 6575 (2012)

[140] D. Deng, L. Yu, X. Chen, G. Wang, L. Jin, X. Pan, J. Deng, G. Sun, and X. Bao, Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction, Angew. Chem. Int. Ed. 52(1), 371 (2013)

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