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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
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
Corresponding
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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.

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Copyright © Materials Research Society 2018 

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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/.

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