[en] Molybdenum disulfide (MoS2) has a theoretical catalytic activity comparable to Pt but in practice is a poor catalyst in bulk form due to the scarcity of metal edge sites and low electrical conductivity. Recent developments on MoS2 monolayers (MLs) are more encouraging in developing cheap and efficient catalysts, but the majority metal atoms are on the basal plane and catalytically inactive. The rapid recombination of the electron-hole pairs and electronic band structure of the most stable 2H-MoS2 MLs are also unsuitable for efficient photocatalysis, especially for solar-driven water splitting. Here, we show that reducing the lateral size and creating sulphur (S) vacancies of MoS2 MLs not only increases dramatically the density of catalytically active sites, but also adjusts the band structure to become highly suitable for solar-driven catalysis. In addition, this preparation efficiently avoids fast charge recombination associated with MoS2, improves light harvesting, and gives a newly formed metallic state to transfer electrons for photocatalytic reactions. By way of example, we have demonstrated remarkable photocatalytic degradation of methylene blue (MB) and methylene orange (MO) dyes using the Sdepleted Mo-S nanocrystals (NCs, 2–25 nm). The NCs are also promising to efficiently generate hydrogen (H2) from water with sacrificial reagents and solar light irradiation. Our study shows how careful design and modification of materials can result in highly efficient photocatalysts, which give considerable opportunities of the transition metal dichalcogenides (TMDs) beyond just MoS2 to develop highly efficient and economic catalysts.
Disciplines :
Physics
Author, co-author :
Lin, Liangxu
Miao, Naihua
Huang, Juntong
Zhang, Shaowei
Zhu, Yanqiu
Horsell, David D.
Ghosez, Philippe ; Université de Liège > Département de physique > Physique théorique des matériaux
Sun, Zhimei
Allwood, Dan A.
Language :
English
Title :
A photocatalyst of sulphur depleted monolayered molybdenum sulfide nanocrystals for dye degradation and hydrogen evolution reaction
Hinnemann, B., Moses, P.G., Bonde, J., Jøergensen, K.P., Nielsen, J.H., Horch, S., Chorkendorff, I., Nørskov, J.K., Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution. J. Am. Chem. Soc. 127 (2005), 5308–5309.
Jaramillo, T.F., Jøergensen, K.P., Bonde, J., Nielsen, J.H., Horch, S., Chorkendorff, I., Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317 (2007), 100–102.
Xie, J., Zhang, H., Li, S., Wang, R., Sun, X., Zhou, M., Zhou, J., Lou, X.W.D., Xie, Y., Defect-rich MoS2 ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv. Mater. 25 (2013), 5807–5813.
Le, D., Rawal, T.B., Rahman, T.S., Single-layer MoS2 with sulfur vacancies: structure and catalytic application. J. Phys. Chem. C 118 (2014), 5346–5351.
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. Nat. Chem. 5 (2013), 263–275.
Karunadasa, H.I., Montalvo, E., Sun, Y., Majda, M., Long, J.R., Chang, C.J., A Molecular MoS2 edge site mimic for catalytic hydrogen generation. Science 335 (2012), 698–702.
Kibsgaard, J., Chen, Z., Reinecke, B.N., Jaramillo, T.F., Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis. Nat. Mater. 11 (2012), 963–969.
Wang, H., Lu, Z., Xu, S., Kong, D., Cha, J.J., Zheng, G., Hsu, P.-C., Yan, K., Bradshaw, D., Prinz, F.B., Cui, Y., Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction. Proc. Natl. Acad. Sci. USA 110 (2013), 19701–19706.
Voiry, D., Yang, J., Chhowalla, M., Recent strategies for improving the catalytic activity of 2D TMD nanosheets toward the hydrogen evolution reaction. Adv. Mater. 28 (2016), 6197–6206.
Li, H., Tsai, C., Koh, A.L., Cai, L., Contryman, A.W., Fragapane, A.H., Zhao, J., Han, H.S., Manoharan, H.C., Abild-Pedersen, F., Nørskov, J.K., Zheng, X., Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies. Nat. Mater. 15 (2016), 48–53.
Voiry, D., Salehi, M., Silva, R., Fujita, T., Chen, M., Asefa, T., Shenoy, V.B., Eda, G., Chhowalla, M., Conducting MoS2 nanosheets as catalysts for hydrogen evolution reaction. Nano Lett. 13 (2013), 6222–6227.
Yu, Y., Huang, S.-Y., Li, Y., Steinmann, S.N., Yang, W., Cao, L., Layer-dependent electrocatalysis of MoS2 for hydrogen evolution. Nano Lett. 14 (2014), 553–558.
Voiry, D., Fullon, R., Yang, J., de Carvalho Castro e Silva, C., Kappera, R., Bozkurt, I., Kaplan, D., Lagos, M.J., Batson, P.E., Gupta, G., Mohite, A.D., Dong, L., Er, D., Shenoy, V.B., Asefa, W., Chhowalla, M., The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen. Nat. Commun. 15 (2016), 1003–1009.
Eda, G., Yamaguchi, H., Voiry, D., Fujita, T., Chen, M., Chhowalla, M., Photoluminescence from chemically exfoliated MoS2. Nano Lett. 11 (2011), 5111–5116.
Baker, M.A., Gilmore, R., Lenardi, C., Gissler, W., XPS investigation of preferential sputtering of S from MoS2 and determination of MoSx stoichiometry from Mo and S peak positions. Appl. Surf. Sci. 150 (1999), 255–262.
Wilcoxon, J.P., Newcomer, P.P., Samara, G.A., Synthesis and optical properties of MoS2 and isomorphous nanoclusters in the quantum confinement regime. J. Appl. Phys. 81 (1997), 7934–7944.
Lin, L., Huang, J., Li, X., Abass, M.A., Zhang, S., Effective surface disorder engineering of metal oxide nanocrystals for improved photocatalysis. Appl. Catal. B-Environ. 203 (2017), 615–624.
He, Z., Que, W., Chen, J., Yin, X., He, Y., Ren, J., Photocatalytic degradation of methyl orange over nitrogen-fluorine codoped TiO2 nanobelts prepared by solvothermal synthesis. ACS Appl. Mater. Interfaces 4 (2012), 6816–6826.
Bühler, N., Meier, K., Rober, J., Photochemical hydrogen production with cadmium sulfide suspensions. J. Phys. Chem. 88 (1984), 3261–3268.
Liu, H., Shanguan, W., Photochemical reduction and oxidation of water including sacrificial reagents and Pt/TiO2 catalyst. Energy Fuel 20 (2006), 2289–2292.
Gu, Q., Zhuang, H., Long, J., An, X., Lin, H., Lin, H., Enhanced hydrogen production over C-Doped CdO photocatalyst in Na2S/Na2SO3 solution under visible light irradiation. Int. J. Photoenergy, 22, 2012, 857345.
Chen, H., Sun, Z., Ye, S., Lu, D., Du, P., Molecular cobalt-salen complexes as novel cocatalysts for highly efficient photocatalytic hydrogen production over a CdS nanorod photosensitizer under visible light. J. Mater. Chem. A 3 (2015), 15729–15737.
Gomathisankar, P., Hachisuka, K., Katsumata, H., Suzuki, T., Funasaka, K., Kaneco, S., Photocatalytic hydrogen production from aqueous Na2S + Na2SO3 solution with B-doped ZnO. ACS Sustain. Chem. Eng. 1 (2013), 982–988.
Zhu, B., Lin, B., Zhou, Y., Sun, P., Yao, Q., Chen, Y., Gao, B., Enhanced photocatalytic H2 evolution on ZnS loaded with graphene and MoS2 nanosheets as cocatalysts. J. Mater. Chem. A 2 (2014), 3819–3827.
Zhou, W., Yin, Z., Du, Y., Huang, X., Zeng, Z., Liu, H., Wang, J., Zhang, H., Synthesis of few-layer MoS2 nanosheet-coated TiO2 nanobelt heterostructures for enhanced photocatalytic activities. Small 9 (2013), 140–147.
Hafner, J., Ab-Initio simulations of materials using VASP: density-functional theory and beyond. J. Comput. Chem., 29, 2008, 2044.
Shi, H., Pan, H., Zhang, Y., Yakobson, B.I., Quasiparticle band structures and optical properties of strained monolayer MoS2 and WS2. Phys. Rev. B, 87, 2013, 155304.
Conley, H.J., Wang, B., Ziegler, J.I., Haglund, R.F. Jr., Pantelides, S.T., Bolotin, K.L., Bandgap engineering of strained monolayer and bilayer MoS2. Nano Lett. 13 (2013), 3626–3630.
Komsa, H., Krasheninnikov, A., Effects of confinement and environment on the electronic structure and exciton binding energy of MoS2 from first principles. Phys. Rev. B, 86, 2012, 241201.
Pearson, R.G., Absolute electronegativity and hardness: application to inorganic chemistry. Inorg. Chem. 27 (1988), 734–740.
Xu, Y., Schoonen, M.A.A., The absolute energy positions of conduction and valence bands of selected semiconducting minerals. Am. Mineral. 85 (2000), 543–556.
Bott, A.W., Electrochemistry of semiconductors. Curr. Sep. 17 (1998), 87–91.
Ran, J., Zhang, J., Yu, J., Jaroniec, M., Qiao, S.Z., Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting. Chem. Soc. Rev. 43 (2014), 7787–7812.
