skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2

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.more » 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.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Univ. of Arkansas, Fayetteville, AR (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); ACS Petroleum Research Fund; US Air Force Office of Scientific Research (AFOSR)
OSTI Identifier:
1624980
Grant/Contract Number:  
SC0016529; DMR-1607135; 58373ND5; ACI-1053575; 1433311; 17RT0244
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 10; Journal Issue: 44; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Sun, Yifan, Darling, Albert J., Li, Yawei, Fujisawa, Kazunori, Holder, Cameron F., Liu, He, Janik, Michael J., Terrones, Mauricio, and Schaak, Raymond E. Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2. United States: N. p., 2019. Web. 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. United States. 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, and Schaak, Raymond E. Thu . "Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2". United States. https://doi.org/10.1039/c9sc03337h. https://www.osti.gov/servlets/purl/1624980.
@article{osti_1624980,
title = {Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2},
author = {Sun, Yifan and Darling, Albert J. and Li, Yawei and Fujisawa, Kazunori and Holder, Cameron F. and Liu, He and Janik, Michael J. and Terrones, Mauricio and Schaak, Raymond E.},
abstractNote = {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.},
doi = {10.1039/c9sc03337h},
journal = {Chemical Science},
number = 44,
volume = 10,
place = {United States},
year = {2019},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: (a) TEM and (b) HAADF-STEM images of 2H-WS2 nanoflowers. (c) Top (basal plane) and (d) side (edge) views of the hexagonal structure for 2H-WS2. (e) Raman spectrum and (f) powder XRD data for the as-prepared 2H-WS2 nanostructures.

Save / Share:

Works referenced in this record:

Transition Metal Dichalcogenides and Beyond: Synthesis, Properties, and Applications of Single- and Few-Layer Nanosheets
journal, December 2014

  • Lv, Ruitao; Robinson, Joshua A.; Schaak, Raymond E.
  • Accounts of Chemical Research, Vol. 48, Issue 1
  • DOI: 10.1021/ar5002846

Nanostructured transition metal dichalcogenide electrocatalysts for CO 2 reduction in ionic liquid
journal, July 2016


The Relation between Morphology and Hydrotreating Activity for Supported MoS2 Particles
journal, April 2001

  • Hensen, E. J. M.; Kooyman, P. J.; van der Meer, Y.
  • Journal of Catalysis, Vol. 199, Issue 2
  • DOI: 10.1006/jcat.2000.3158

Hydrodesulfurization catalysis by transition metal sulfides
journal, February 1981


Biomimetic Hydrogen Evolution:  MoS 2 Nanoparticles as Catalyst for Hydrogen Evolution
journal, April 2005

  • Hinnemann, Berit; Moses, Poul Georg; Bonde, Jacob
  • Journal of the American Chemical Society, Vol. 127, Issue 15
  • DOI: 10.1021/ja0504690

Selective Catalytic Hydrogenation of Functionalized Nitroarenes: An Update
journal, October 2009

  • Blaser, Hans-Ulrich; Steiner, Heinz; Studer, Martin
  • ChemCatChem, Vol. 1, Issue 2
  • DOI: 10.1002/cctc.200900129

Impact of Covalent Functionalization on the Aqueous Processability, Catalytic Activity, and Biocompatibility of Chemically Exfoliated MoS 2 Nanosheets
journal, October 2016

  • Paredes, Juan I.; Munuera, José M.; Villar-Rodil, Silvia
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 41
  • DOI: 10.1021/acsami.6b08444

Nanolayered Co–Mo–S Catalysts for the Chemoselective Hydrogenation of Nitroarenes
journal, March 2017


Selective Reduction of Nitroarenes with Molybdenum Disulfide
journal, July 2013

  • Huang, Lei; Luo, Pingfei; Xiong, Man
  • Chinese Journal of Chemistry, Vol. 31, Issue 8
  • DOI: 10.1002/cjoc.201300310

Well-structured bimetallic surface capable of molecular recognition for chemoselective nitroarene hydrogenation
journal, January 2016

  • Furukawa, Shinya; Takahashi, Katsuya; Komatsu, Takayuki
  • Chemical Science, Vol. 7, Issue 7
  • DOI: 10.1039/C6SC00817H

Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts
journal, July 2006


Bulk iron pyrite as a catalyst for the selective hydrogenation of nitroarenes
journal, January 2017

  • Morse, James R.; Callejas, Juan F.; Darling, Albert J.
  • Chemical Communications, Vol. 53, Issue 35
  • DOI: 10.1039/C7CC00120G

Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes
journal, May 2013

  • Westerhaus, Felix A.; Jagadeesh, Rajenahally V.; Wienhöfer, Gerrit
  • Nature Chemistry, Vol. 5, Issue 6
  • DOI: 10.1038/nchem.1645

Nanoscale Fe2O3-Based Catalysts for Selective Hydrogenation of Nitroarenes to Anilines
journal, November 2013


Room-Temperature Chemoselective Reduction of 3-Nitrostyrene to 3-Vinylaniline by Ammonia Borane over Cu Nanoparticles
journal, November 2018

  • Shen, Mengqi; Liu, Hu; Yu, Chao
  • Journal of the American Chemical Society, Vol. 140, Issue 48
  • DOI: 10.1021/jacs.8b11303

In Situ Generated Iron Oxide Nanocrystals as Efficient and Selective Catalysts for the Reduction of Nitroarenes using a Continuous Flow Method
journal, September 2012

  • Cantillo, David; Baghbanzadeh, Mostafa; Kappe, C. Oliver
  • Angewandte Chemie International Edition, Vol. 51, Issue 40
  • DOI: 10.1002/anie.201205792

Electron spin resonance study of active centers in nickel-tungsten sulfide hydrogenation catalysts
journal, November 1971


Colloidal Nanocrystals as Building Blocks for Well-Defined Heterogeneous Catalysts
journal, January 2019


Colloidal Synthesis of 1T-WS 2 and 2H-WS 2 Nanosheets: Applications for Photocatalytic Hydrogen Evolution
journal, August 2014

  • Mahler, Benoit; Hoepfner, Veronika; Liao, Kristine
  • Journal of the American Chemical Society, Vol. 136, Issue 40
  • DOI: 10.1021/ja506261t

Low-Temperature Solution Synthesis of Few-Layer 1T ′-MoTe 2 Nanostructures Exhibiting Lattice Compression
journal, January 2016

  • Sun, Yifan; Wang, Yuanxi; Sun, Du
  • Angewandte Chemie International Edition, Vol. 55, Issue 8
  • DOI: 10.1002/anie.201510029

Defect engineering of two-dimensional transition metal dichalcogenides
journal, April 2016


Formation and Interlayer Decoupling of Colloidal MoSe 2 Nanoflowers
journal, April 2015


Raman and photoluminescence spectra of two-dimensional nanocrystallites of monolayer WS 2 and WSe 2
journal, April 2016


Solution synthesis of few-layer WTe 2 and Mo x W 1−x Te 2 nanostructures
journal, January 2017

  • Sun, Yifan; Fujisawa, Kazunori; Terrones, Mauricio
  • Journal of Materials Chemistry C, Vol. 5, Issue 43
  • DOI: 10.1039/C7TC02860A

Crystal structures of tungsten disulfide and diselenide
journal, October 1987


Low-Temperature Solution Synthesis of Transition Metal Dichalcogenide Alloys with Tunable Optical Properties
journal, August 2017

  • Sun, Yifan; Fujisawa, Kazunori; Lin, Zhong
  • Journal of the American Chemical Society, Vol. 139, Issue 32
  • DOI: 10.1021/jacs.7b04443

Hydrogenation using iron oxide–based nanocatalysts for the synthesis of amines
journal, March 2015

  • Jagadeesh, Rajenahally V.; Stemmler, Tobias; Surkus, Annette-Enrica
  • Nature Protocols, Vol. 10, Issue 4
  • DOI: 10.1038/nprot.2015.025

Review on selective hydrogenation of nitroarene by catalytic, photocatalytic and electrocatalytic reactions
journal, July 2018


Differentiating Polymorphs in Molybdenum Disulfide via Electron Microscopy
journal, August 2018


Defect-Rich MoS 2 Ultrathin Nanosheets with Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen Evolution
journal, August 2013


Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution
journal, April 2017

  • Tsai, Charlie; Li, Hong; Park, Sangwook
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15113

Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies
journal, November 2015

  • Li, Hong; Tsai, Charlie; Koh, Ai Leen
  • Nature Materials, Vol. 15, Issue 1
  • DOI: 10.1038/nmat4465

Hydrogen Activation on Mo-Based Sulfide Catalysts, a Periodic DFT Study
journal, June 2002

  • Travert, Arnaud; Nakamura, Hiroyuki; van Santen, Rutger A.
  • Journal of the American Chemical Society, Vol. 124, Issue 24
  • DOI: 10.1021/ja011634o

Insights into the hydrogenation mechanism of nitrobenzene to aniline on Pd 3 /Pt(111): a density functional theory study
journal, January 2015

  • Zhang, Lianyang; Jiang, Junhui; Shi, Wei
  • RSC Advances, Vol. 5, Issue 43
  • DOI: 10.1039/C5RA02389K

Comprehensive Phase Diagrams of MoS 2 Edge Sites Using Dispersion-Corrected DFT Free Energy Calculations
journal, June 2018

  • Rosen, Andrew S.; Notestein, Justin M.; Snurr, Randall Q.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 27
  • DOI: 10.1021/acs.jpcc.8b02524

Activation of the Basal Plane in Two Dimensional Transition Metal Chalcogenide Nanostructures
journal, September 2018

  • Han, Jae Hyo; Kim, Hong Ki; Baek, Bongkwan
  • Journal of the American Chemical Society, Vol. 140, Issue 42
  • DOI: 10.1021/jacs.8b05477

MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction
journal, March 2017

  • Liu, Guoliang; Robertson, Alex W.; Li, Molly Meng-Jung
  • Nature Chemistry, Vol. 9, Issue 8
  • DOI: 10.1038/nchem.2740

Energy Level Engineering of MoS 2 by Transition-Metal Doping for Accelerating Hydrogen Evolution Reaction
journal, October 2017

  • Shi, Yi; Zhou, Yue; Yang, Dong-Rui
  • Journal of the American Chemical Society, Vol. 139, Issue 43
  • DOI: 10.1021/jacs.7b08881

Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation
journal, March 2018


Adsorption of Gases in Multimolecular Layers
journal, February 1938

  • Brunauer, Stephen; Emmett, P. H.; Teller, Edward
  • Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319
  • DOI: 10.1021/ja01269a023

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Projector augmented-wave method
journal, December 1994


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 111, Issue 15
  • DOI: 10.1063/1.480097

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.