Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2

Yifan Sun, Albert J. Darling, Yawei Li, Kazunori Fujisawa, Cameron F. Holder, He Liu, Michael J. Janik, Mauricio Terrones, Raymond E. Schaak

Research output: Contribution to journalArticle

Abstract

Transition metal dichalcogenides (TMDs) are well known catalysts as both bulk and nanoscale materials. Two-dimensional (2-D) TMDs, which contain single- and few-layer nanosheets, are increasingly studied as catalytic materials because of their unique thickness-dependent properties and high surface areas. Here, colloidal 2H-WS2 nanostructures are used as a model 2-D TMD system to understand how high catalytic activity and selectivity can be achieved for useful organic transformations. Free-standing, colloidal 2H-WS2 nanostructures containing few-layer nanosheets are shown to catalyze the selective hydrogenation of a broad scope of substituted nitroarenes to their corresponding aniline derivatives in the presence of other reducible functional groups. Microscopic and computational studies reveal the important roles of sulfur vacancy-rich basal planes and tungsten-terminated edges, which are more abundant in nanostructured 2-D materials than in their bulk counterparts, in enabling the functional group selectivity. At tungsten-terminated edges and on regions of the basal planes having high concentrations of sulfur vacancies, vertical adsorption of the nitroarene is favored, thus facilitating hydrogen transfer exclusively to the nitro group due to geometric effects. At lower sulfur vacancy concentrations on the basal planes, parallel adsorption of the nitroarene is favored, and the nitro group is selectively hydrogenated due to a lower kinetic barrier. These mechanistic insights reveal how the various defect structures and configurations on 2-D TMD nanostructures facilitate functional group selectivity through distinct mechanisms that depend upon the adsorption geometry, which may have important implications for the design of new and enhanced 2-D catalytic materials across a potentially broad scope of reactions.

Original languageEnglish (US)
Pages (from-to)10310-10317
Number of pages8
JournalChemical Science
Volume10
Issue number44
DOIs
StatePublished - Jan 1 2019

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Hydrogenation
Transition metals
Sulfur
Functional groups
Vacancies
Nanostructures
Defects
Tungsten
Nanosheets
Adsorption
Catalyst selectivity
Defect structures
Hydrogen
Catalyst activity
Derivatives
Catalysts
Kinetics
Geometry

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Sun, Y., Darling, A. J., Li, Y., Fujisawa, K., Holder, C. F., Liu, H., ... Schaak, R. E. (2019). Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2. Chemical Science, 10(44), 10310-10317. https://doi.org/10.1039/c9sc03337h
Sun, Yifan ; Darling, Albert J. ; Li, Yawei ; Fujisawa, Kazunori ; Holder, Cameron F. ; Liu, He ; Janik, Michael J. ; Terrones, Mauricio ; Schaak, Raymond E. / Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2. In: Chemical Science. 2019 ; Vol. 10, No. 44. pp. 10310-10317.
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Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2. / Sun, Yifan; Darling, Albert J.; Li, Yawei; Fujisawa, Kazunori; Holder, Cameron F.; Liu, He; Janik, Michael J.; Terrones, Mauricio; Schaak, Raymond E.

In: Chemical Science, Vol. 10, No. 44, 01.01.2019, p. 10310-10317.

Research output: Contribution to journalArticle

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AU - Sun, Yifan

AU - Darling, Albert J.

AU - Li, Yawei

AU - Fujisawa, Kazunori

AU - Holder, Cameron F.

AU - Liu, He

AU - Janik, Michael J.

AU - Terrones, Mauricio

AU - Schaak, Raymond E.

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N2 - Transition metal dichalcogenides (TMDs) are well known catalysts as both bulk and nanoscale materials. Two-dimensional (2-D) TMDs, which contain single- and few-layer nanosheets, are increasingly studied as catalytic materials because of their unique thickness-dependent properties and high surface areas. Here, colloidal 2H-WS2 nanostructures are used as a model 2-D TMD system to understand how high catalytic activity and selectivity can be achieved for useful organic transformations. Free-standing, colloidal 2H-WS2 nanostructures containing few-layer nanosheets are shown to catalyze the selective hydrogenation of a broad scope of substituted nitroarenes to their corresponding aniline derivatives in the presence of other reducible functional groups. Microscopic and computational studies reveal the important roles of sulfur vacancy-rich basal planes and tungsten-terminated edges, which are more abundant in nanostructured 2-D materials than in their bulk counterparts, in enabling the functional group selectivity. At tungsten-terminated edges and on regions of the basal planes having high concentrations of sulfur vacancies, vertical adsorption of the nitroarene is favored, thus facilitating hydrogen transfer exclusively to the nitro group due to geometric effects. At lower sulfur vacancy concentrations on the basal planes, parallel adsorption of the nitroarene is favored, and the nitro group is selectively hydrogenated due to a lower kinetic barrier. These mechanistic insights reveal how the various defect structures and configurations on 2-D TMD nanostructures facilitate functional group selectivity through distinct mechanisms that depend upon the adsorption geometry, which may have important implications for the design of new and enhanced 2-D catalytic materials across a potentially broad scope of reactions.

AB - Transition metal dichalcogenides (TMDs) are well known catalysts as both bulk and nanoscale materials. Two-dimensional (2-D) TMDs, which contain single- and few-layer nanosheets, are increasingly studied as catalytic materials because of their unique thickness-dependent properties and high surface areas. Here, colloidal 2H-WS2 nanostructures are used as a model 2-D TMD system to understand how high catalytic activity and selectivity can be achieved for useful organic transformations. Free-standing, colloidal 2H-WS2 nanostructures containing few-layer nanosheets are shown to catalyze the selective hydrogenation of a broad scope of substituted nitroarenes to their corresponding aniline derivatives in the presence of other reducible functional groups. Microscopic and computational studies reveal the important roles of sulfur vacancy-rich basal planes and tungsten-terminated edges, which are more abundant in nanostructured 2-D materials than in their bulk counterparts, in enabling the functional group selectivity. At tungsten-terminated edges and on regions of the basal planes having high concentrations of sulfur vacancies, vertical adsorption of the nitroarene is favored, thus facilitating hydrogen transfer exclusively to the nitro group due to geometric effects. At lower sulfur vacancy concentrations on the basal planes, parallel adsorption of the nitroarene is favored, and the nitro group is selectively hydrogenated due to a lower kinetic barrier. These mechanistic insights reveal how the various defect structures and configurations on 2-D TMD nanostructures facilitate functional group selectivity through distinct mechanisms that depend upon the adsorption geometry, which may have important implications for the design of new and enhanced 2-D catalytic materials across a potentially broad scope of reactions.

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Sun Y, Darling AJ, Li Y, Fujisawa K, Holder CF, Liu H et al. Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2. Chemical Science. 2019 Jan 1;10(44):10310-10317. https://doi.org/10.1039/c9sc03337h