Hostname: page-component-586b7cd67f-rcrh6 Total loading time: 0 Render date: 2024-11-22T18:27:29.250Z Has data issue: false hasContentIssue false
  • English
  • Français

A combined computational and experimental study of the adsorption of sulfur containing molecules on molybdenum disulfide nanoparticles

Published online by Cambridge University Press:  20 September 2018

Tao Yang ,
Junpeng Feng ,
Xingchen Liu Open the ORCID record for Xingchen Liu [Opens in a new window] ,
Yandan Wang ,
Hui Ge ,
Dongbo Cao ,
Hao Li ,
Qing Peng ,
Manuel Ramos  and
Xiao-Dong Wen
...Show all authors
Tao Yang
Affiliation:
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
Junpeng Feng
Affiliation:
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China
Xingchen Liu*
Affiliation:
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China; and Synfuels China Co. Ltd., Huairou, Beijing 100195, China
Yandan Wang
Affiliation:
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
Hui Ge
Affiliation:
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China
Dongbo Cao
Affiliation:
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China
Hao Li*
Affiliation:
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
Qing Peng
Affiliation:
Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor, Michigan 48109, USA
Manuel Ramos
Affiliation:
Department of Physics and Mathematics, Universidad Autónoma de Cd. Juárez, Juárez 32310, México
Xiao-Dong Wen
Affiliation:
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China; and Synfuels China Co. Ltd., Huairou, Beijing 100195, China
Baojian Shen*
Affiliation:
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
*
a)Address all correspondence to these authors. e-mail: [email protected]
b)e-mail: [email protected]
Get access

Abstract

Combining density functional theory calculations and temperature programmed desorption (TPD) experiments, the adsorption behavior of various sulfur containing compounds, including C2H5SH, CH3SCH3, tetrahydrothiophene, thiophene, benzothiophene, dibenzothiophene, and their derivatives on the coordinately unsaturated sites of Mo27Sx model nanoparticles, are studied systematically. Sulfur molecules with aromaticity prefer flat adsorption than perpendicular adsorption. The adsorption of nonaromatic molecules is stronger than the perpendicular adsorption of aromatic molecules, but weaker than the flat adsorption of them. With gradual hydrogenation (HYD), the binding affinity in the perpendicular adsorption modes increases, while in flat adsorption modes it increases first, then decreases. Significant steric effects on the adsorption of dimethyldibenzothiophene were revealed in perpendicular adsorption modes. The steric effect, besides weakening adsorption, could also activate the S–C bonds through a compensation effect. Finally, by comparing the theoretical adsorption energies with the TPD results, we suggest that HYD and direct-desulfurization path may happen simultaneously, but on different active sites.

Keywords

adsorptionhydrogenationcatalytic
Type
Article
Information
Journal of Materials Research , Volume 33 , Issue 21: Focus Issue: Catalytic Engineered Materials for Commercial and Industrial Energy Applications , 14 November 2018 , pp. 3589 - 3603
Copyright
Copyright © Materials Research Society 2018 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

c)

This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs.org/editor-manuscripts/.

References

REFERENCES

Delmon, B. and Froment, G.F.: Remote control of catalytic sites by spillover species: A chemical reaction engineering approach. Cat. Rev. 38, 69 (1996).CrossRefGoogle Scholar
Topsøe, H., Clausen, B., and Massoth, F.: Hydrotreating catalysis. In Catalysis, Anderson, J. and Boudart, M., eds. (Springer Berlin Heidelberg, New York, USA, 1996); p. 1.Google Scholar
European Parliament and of the Council, European Directive 98/70/CE of the European Parliament and of the Council, Official Journal of the European Communities, 350, 58 (1998).Google Scholar
Mills, P., Korlann, S., Bussell, M.E., Reynolds, M.A., Ovchinnikov, M.V., Angelici, R.J., Stinner, C., Weber, T., and Prins, R.: Vibrational study of organometallic complexes with thiophene ligands: Models for adsorbed thiophene on hydrodesulfurization catalysts. J. Phys. Chem. A 105, 4418 (2001).CrossRefGoogle Scholar
Mitchell, P.C.H., Green, D.A., Payen, E., Tomkinson, J., and Parker, S.F.: Interaction of thiophene with a molybdenum disulfide catalyst-an inelastic neutron scattering study. Phys. Chem. Chem. Phys. 1, 3357 (1999).CrossRefGoogle Scholar
Harris, S. and Chianelli, R.R.: Catalysis by transition metal sulfides: A theoretical and experimental study of the relation between the synergic systems and the binary transition metal sulfides. J. Catal. 98, 17 (1986).CrossRefGoogle Scholar
Sullivan, D.L. and Ekerdt, J.G.: Mechanisms of thiophene hydrodesulfurization on model molybdenum catalysts. J. Catal. 178, 226 (1998).CrossRefGoogle Scholar
Komarneni, M., Sand, A., and Burghaus, U.: Adsorption of thiophene on inorganic MoS2 fullerene-like nanoparticles. Catal. Lett. 129, 66 (2009).CrossRefGoogle Scholar
Atter, G.D., Chapman, D.M., Hester, R.E., Green, D.A., Mitchell, P.C.H., and Tomkinson, J.: Refined ab initio inelastic neutron scattering spectrum of thiophene. J. Chem. Soc., Faraday Trans. 93, 2977 (1997).CrossRefGoogle Scholar
Rodriguez, J.A.: Interaction of hydrogen and thiophene with Ni/MoS2 and Zn/MoS2 surfaces: A molecular orbital study. J. Phys. Chem. B 101, 7524 (1997).CrossRefGoogle Scholar
Toulhoat, H., Raybaud, P., Kasztelan, S., Kresse, G., and Hafner, J.: Transition metals to sulfur binding energies relationship to catalytic activities in HDS: Back to sabatier with first principle calculations1. Catal. Today 50, 629 (1999).CrossRefGoogle Scholar
Ma, X. and Schobert, H.H.: Molecular simulation on hydrodesulfurization of thiophenic compounds over MoS2 using ZINDO. J. Mol. Catal. A: Chem. 160, 409 (2000).CrossRefGoogle Scholar
Raybaud, P., Hafner, J., Kresse, G., and Toulhoat, H.: Adsorption of thiophene on the catalytically active surface of MoS2: An ab initio local-density-functional study. Phys. Rev. Lett. 80, 1481 (1998).CrossRefGoogle Scholar
Cristol, S., Paul, J-F., Schovsbo, C., Veilly, E., and Payen, E.: DFT study of thiophene adsorption on molybdenum sulfide. J. Catal. 239, 145 (2006).CrossRefGoogle Scholar
Mijoin, J., Pérot, G., Bataille, F., Lemberton, J.L., Breysse, M., and Kasztelan, S.: Mechanistic considerations on the involvement of dihydrointermediates in the hydrodesulfurization of dibenzothiophene-type compounds over molybdenum sulfide catalysts. Catal. Lett. 71, 139 (2001).CrossRefGoogle Scholar
Vanrysselberghe, V., Le Gall, R., and Froment, G.F.: Hydrodesulfurization of 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene on a CoMo/Al2O3 catalyst: Reaction network and kinetics. Ind. Eng. Chem. Res. 37, 1235 (1998).CrossRefGoogle Scholar
Duayne Whitehurst, D., Isoda, T., and Mochida, I.: Present state of the art and future challenges in the hydrodesulfurization of polyaromatic sulfur compounds. In Advances in Catalysis, Eley, D.D., Haag, W.O., Gates, B., and Knözinger, H., eds. (Academic Press, 1998); p. 345.Google Scholar
Raybaud, P., Hafner, J., Kresse, G., and Toulhoat, H.: Ab initio energy profiles for thiophene HDS on the MoS2 (1010) edge-surface. In Studies in Surface Science and Catalysis, Delmon, G.F.F.B. and Grange, P., eds. (Elsevier, Amsterdam, the Netherlands, 1999); p. 309.Google Scholar
Cristol, S., Paul, J.F., Payen, E., Bougeard, D., Hafner, J., and Hutschka, F.: Theoretical study of benzothiophene hydrodesulfurization on MoS2. In Studies in Surface Science and Catalysis, Delmon, G.F.F.B. and Grange, P., eds. (Elsevier, Amsterdam, the Netherlands, 1999); p. 327.Google Scholar
Todorova, T., Prins, R., and Weber, T.: A density functional theory study of the hydrogenolysis reaction of CH3SH to CH4 on the catalytically active (100) edge of 2H-MoS2. J. Catal. 236, 190 (2005).CrossRefGoogle Scholar
Todorova, T., Prins, R., and Weber, T.: A density functional theory study of the hydrogenolysis and elimination reactions of C2H5SH on the catalytically active (100) edge of 2H-MoS2. J. Catal. 246, 109 (2007).CrossRefGoogle Scholar
Joshi, Y.V., Ghosh, P., Venkataraman, P.S., Delgass, W.N., and Thomson, K.T.: Electronic descriptors for the adsorption energies of sulfur-containing molecules on Co/MoS2, using DFT calculations. J. Phys. Chem. C 113, 9698 (2009).CrossRefGoogle Scholar
Šarić, M., Rossmeisl, J., and Moses, P.G.: Modeling the adsorption of sulfur containing molecules and their hydrodesulfurization intermediates on the Co-promoted MoS2 catalyst by DFT. J. Catal. 358, 131 (2018).CrossRefGoogle Scholar
Moses, P.G., Mortensen, J.J., Lundqvist, B.I., and Nørskov, J.K.: Density functional study of the adsorption and van der Waals binding of aromatic and conjugated compounds on the basal plane of MoS2. J. Chem. Phys. 130, 104709 (2009).CrossRefGoogle Scholar
Orita, H., Uchida, K., and Itoh, N.: Adsorption of thiophene on an MoS2 cluster model catalyst: Ab initio density functional study. J. Mol. Catal. A: Chem. 193, 197 (2003).CrossRefGoogle Scholar
Orita, H., Uchida, K., and Itoh, N.: A volcano-type relationship between the adsorption energy of thiophene on promoted MoS2 cluster-model catalysts and the experimental HDS activity: Ab initio density functional study. Appl. Catal., A 258, 115 (2004).CrossRefGoogle Scholar
Yao, X-Q., Li, Y-W., and Jiao, H.: Mechanism of thiophene hydrodesulfurization on a Mo3S9 model catalyst. A computational study. J. Mol. Struct.: THEOCHEM 726, 81 (2005).CrossRefGoogle Scholar
McCarty, K.F. and Schrader, G.L.: Deuterodesulfurization of thiophene: An investigation of the reaction mechanism. J. Catal. 103, 261 (1987).CrossRefGoogle Scholar
Salnikov, O.G., Burueva, D.B., Barskiy, D.A., Bukhtiyarova, G.A., Kovtunov, K.V., and Koptyug, I.V.: A mechanistic study of thiophene hydrodesulfurization by the parahydrogen-induced polarization technique. ChemCatChem 7, 3508 (2015).CrossRefGoogle Scholar
Hensen, E.J.M., Vissenberg, M.J., de Beer, V.H.J., van Veen, J.A.R., and van Santen, R.A.: Kinetics and mechanism of thiophene hydrodesulfurization over carbon-supported transition metal sulfides. J. Catal. 163, 429 (1996).CrossRefGoogle Scholar
Roberts, J.T. and Friend, C.M.: Model hydrodesulfurization reactions: Saturated tetrahydrothiophene and 1-butanethiol on molybdenum(110). J. Am. Chem. Soc. 108, 7204 (1986).CrossRefGoogle Scholar
Liu, A.C. and Friend, C.M.: Evidence for facile and selective desulfurization: The reactions of 2,5-dihydrothiophene on molybdenum(110). J. Am. Chem. Soc. 113, 820 (1991).CrossRefGoogle Scholar
Markel, E.J., Schrader, G.L., Sauer, N.N., and Angelici, R.J.: Thiophene, 2,3- and 2,5-dihydrothiophene, and tetrahydrothiophene hydrodesulfurization on Mo and Reγ-Al2O3 catalysts. J. Catal. 116, 11 (1989).CrossRefGoogle Scholar
Hargreaves, A.E. and Ross, J.R.H.: An investigation of the mechanism of the hydrodesulfurization of thiophene over sulfided Co–MoAl2O3 catalysts. J. Catal. 56, 363 (1979).CrossRefGoogle Scholar
Devanneaux, J. and Maurin, J.: Hydrogenolysis and hydrogenation of thiophenic compounds on a Co–MoAl2O3 catalyst. J. Catal. 69, 202 (1981).CrossRefGoogle Scholar
Yang, H., Fairbridge, C., and Ring, Z.: Adsorption of dibenzothiophene derivatives over a MoS2 nanocluster: A density functional theory study of structure–reactivity relations. Energy Fuels 17, 387 (2003).CrossRefGoogle Scholar
Yang, H., Fairbridge, C., Chen, J., and Ring, Z.: Structure-HDS reactivity relationship of dibenzothiophenes based on density functional theory. Catal. Lett. 97, 217 (2004).CrossRefGoogle Scholar
Cristol, S., Paul, J-F., Payen, E., Bougeard, D., Hutschka, F., and Clémendot, S.: DBT derivatives adsorption over molybdenum sulfide catalysts: A theoretical study. J. Catal. 224, 138 (2004).CrossRefGoogle Scholar
de Beer, V.H.J., Dahlmans, J.G.J., and Smeets, J.G.M.: Hydrodesulfurization and hydrogenation properties of promoted MoS2 and WS2 catalysts under medium pressure conditions. J. Catal. 42, 467 (1976).CrossRefGoogle Scholar
Geneste, P., Amblard, P., Bonnet, M., and Graffin, P.: Hydrodesulfurization of oxidized sulfur compounds in benzothiophene, methylbenzothiophene, and dibenzothiophene series over CoO–MoO3–Al2O3 catalyst. J. Catal. 61, 115 (1980).CrossRefGoogle Scholar
Van Parijs, I.A., Hosten, L.H., and Froment, G.F.: Kinetics of the hydrodesulfurization on a cobalt–molybdenum/.gamma.–alumina catalyst. 2. Kinetics of the hydrogenolysis of benzothiophene. Ind. Eng. Chem. Prod. Res. Dev. 25, 437 (1986).CrossRefGoogle Scholar
Ho, T.C. and Sobel, J.E.: Kinetics of dibenzothiophene hydrodesulfurization. J. Catal. 128, 581 (1991).CrossRefGoogle Scholar
Kim, J.H., Ma, X., Song, C., Lee, Y-K., and Oyama, S.T.: Kinetics of two pathways for 4,6-dimethyldibenzothiophene hydrodesulfurization over NiMo, CoMo sulfide, and nickel phosphide catalysts. Energy Fuels 19, 353 (2005).CrossRefGoogle Scholar
Tuxen, A., Kibsgaard, J., Gøbel, H., Lægsgaard, E., Topsøe, H., Lauritsen, J.V., and Besenbacher, F.: Size threshold in the dibenzothiophene adsorption on MoS2 nanoclusters. ACS Nano 4, 4677 (2010).CrossRefGoogle ScholarPubMed
Tuxen, A.K., Füchtbauer, H.G., Temel, B., Hinnemann, B., Topsøe, H., Knudsen, K.G., Besenbacher, F., and Lauritsen, J.V.: Atomic-scale insight into adsorption of sterically hindered dibenzothiophenes on MoS2 and Co–Mo–S hydrotreating catalysts. J. Catal. 295, 146 (2012).CrossRefGoogle Scholar
Zheng, P., Duan, A., Chi, K., Zhao, L., Zhang, C., Xu, C., Zhao, Z., Song, W., Wang, X., and Fan, J.: Influence of sulfur vacancy on thiophene hydrodesulfurization mechanism at different MoS2 edges: A DFT study. Chem. Eng. Sci. 164, 292 (2017).CrossRefGoogle Scholar
Helveg, S., Lauritsen, J.V., Lægsgaard, E., Stensgaard, I., Nørskov, J.K., Clausen, B.S., Topsøe, H., and Besenbacher, F.: Atomic-scale structure of single-layer MoS2 nanoclusters. Phys. Rev. Lett. 84, 951 (2000).CrossRefGoogle ScholarPubMed
Silva, A.M. and Borges, I.: How to find an optimum cluster size through topological site properties: MoSx model clusters. J. Comput. Chem. 32, 2186 (2011).CrossRefGoogle ScholarPubMed
Li, Y-W., Pang, X-Y., and Delmon, B.: Ab initio study of the structural and electronic properties of a real size MoS2 slab: Mo27S54. J. Phys. Chem. A 104, 11375 (2000).CrossRefGoogle Scholar
Orita, H., Uchida, K., and Itoh, N.: Ab initio density functional study of the structural and electronic properties of an MoS2 catalyst model: A real size Mo27S54 cluster. J. Mol. Catal. A: Chem. 195, 173 (2003).CrossRefGoogle Scholar
Wen, X-D., Zeng, T., Li, Y-W., Wang, J., and Jiao, H.: Surface structure and stability of MoSx model clusters. J. Phys. Chem. B 109, 18491 (2005).CrossRefGoogle ScholarPubMed
Delley, B.: An all-electron numerical method for solving the local density functional for polyatomic molecules. J. Chem. Phys. 92, 508 (1990).CrossRefGoogle Scholar
Delley, B.: Fast calculation of electrostatics in crystals and large molecules. J. Phys. Chem. 100, 6107 (1996).CrossRefGoogle Scholar
Delley, B.: From molecules to solids with the DMol3 approach. J. Chem. Phys. 113, 7756 (2000).CrossRefGoogle Scholar
Bergner, A., Dolg, M., Küchle, W., Stoll, H., and Preuß, H.: Ab initio energy-adjusted pseudopotentials for elements of groups 13–17. Mol. Phys. 80, 1431 (1993).CrossRefGoogle Scholar
Andrae, D., Häußermann, U., Dolg, M., Stoll, H., and Preuß, H.: Energy-adjusted ab initio pseudopotentials for the second and third row transition elements. Theor. Chim. Acta 77, 123 (1990).CrossRefGoogle Scholar
Inada, Y. and Orita, H.: Efficiency of numerical basis sets for predicting the binding energies of hydrogen bonded complexes: Evidence of small basis set superposition error compared to Gaussian basis sets. J. Comput. Chem. 29, 225 (2008).CrossRefGoogle ScholarPubMed
Perdew, J.P. and Wang, Y.: Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 45, 13244 (1992).CrossRefGoogle ScholarPubMed
Wen, X-D., Zeng, T., Teng, B-T., Zhang, F-Q., Li, Y-W., Wang, J., and Jiao, H.: Hydrogen adsorption on a Mo27S54 cluster: A density functional theory study. J. Mol. Catal. A: Chem. 249, 191 (2006).CrossRefGoogle Scholar
Delmon, B.: Advances in hydropurification catalysts and catalysis. In Studies in Surface Science and Catalysis, Trimm, D.L., Akashah, S., Absi-Halabi, M., and Bishara, A., eds. (Elsevier, Amsterdam, the Netherlands, 1989); p. 1.Google Scholar
Li, S.Y., Rodriguez, J.A., Hrbek, J., Huang, H.H., and Xu, G.Q.: Reaction of hydrogen with SMo(110) and MoSx films: Formation of hydrogen sulfide. Surf. Sci. 366, 29 (1996).CrossRefGoogle Scholar
Liu, X., Tkalych, A., Zhou, B., Köster, A.M., and Salahub, D.R.: Adsorption of hexacyclic C6H6, C6H8, C6H10, and C6H12 on a Mo-terminated α-Mo2C (0001) surface. J. Phys. Chem. C 117, 7069 (2013).CrossRefGoogle Scholar
Houalla, M., Broderick, D.H., Sapre, A.V., Nag, N.K., de Beer, V.H.J., Gates, B.C., and Kwart, H.: Hydrodesulfurization of methyl-substituted dibenzothiophenes catalyzed by sulfided Co–Mo-γ-Al2O3. J. Catal. 61, 523 (1980).CrossRefGoogle Scholar
Bataille, F., Lemberton, J-L., Michaud, P., Pérot, G., Vrinat, M., Lemaire, M., Schulz, E., Breysse, M., and Kasztelan, S.: Alkyldibenzothiophenes hydrodesulfurization-promoter effect, reactivity, and reaction mechanism. J. Catal. 191, 409 (2000).CrossRefGoogle Scholar
Meille, V., Schulz, E., Lemaire, M., and Vrinat, M.: Hydrodesulfurization of alkyldibenzothiophenes over a NiMo/Al2O3 catalyst: Kinetics and mechanism. J. Catal. 170, 29 (1997).CrossRefGoogle Scholar
Michaud, P., Lemberton, J.L., and Pérot, G.: Hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene: Effect of an acid component on the activity of a sulfided NiMo on alumina catalyst. Appl. Catal., A 169, 343 (1998).CrossRefGoogle Scholar
Romero-Rivera, R., Camacho, A.G., Del Valle, M., Alonso, G., Fuentes, S., and Cruz-Reyes, J.: HDS of DBT with molybdenum disulfide catalysts prepared by in situ decomposition of alkyltrimethylammonium thiomolybdates. Top. Catal. 54, 561 (2011).CrossRefGoogle Scholar
Trakarnpruk, W. and Seentrakoon, B.: Hydrodesulfurization activity of MoS2 and bimetallic catalysts prepared by in situ decomposition of thiosalt. Ind. Eng. Chem. Res. 46, 1874 (2007).CrossRefGoogle Scholar
Moses, P.G., Hinnemann, B., Topsøe, H., and Nørskov, J.K.: The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS2 catalysts at realistic conditions: A density functional study. J. Catal. 248, 188 (2007).CrossRefGoogle Scholar
Supplementary material: File

Yang et al. supplementary material

Yang et al. supplementary material 1

Download Yang et al. supplementary material(File)
File 1.6 MB