Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c9sc03337h· OSTI ID:1624980
 [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2]
  1. Pennsylvania State Univ., University Park, PA (United States); DOE/OSTI
  2. Pennsylvania State Univ., University Park, PA (United States)
+ Show Author Affiliations
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.
Research Organization:
Univ. of Arkansas, Fayetteville, AR (United States)
Sponsoring Organization:
ACS Petroleum Research Fund; National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0016529
OSTI ID:
1624980
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 44 Vol. 10; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (54)

Defect-Rich MoS 2 Ultrathin Nanosheets with Additional Active Edge Sites for Enhanced Electrocatalytic Hydrogen Evolution journal August 2013
Differentiating Polymorphs in Molybdenum Disulfide via Electron Microscopy journal August 2018
In Situ Generated Iron Oxide Nanocrystals as Efficient and Selective Catalysts for the Reduction of Nitroarenes using a Continuous Flow Method journal September 2012
Low‐Temperature Solution Synthesis of Few‐Layer 1T ′‐MoTe 2 Nanostructures Exhibiting Lattice Compression journal January 2016
In Situ Generated Iron Oxide Nanocrystals as Efficient and Selective Catalysts for the Reduction of Nitroarenes using a Continuous Flow Method journal September 2012
Low-Temperature Solution Synthesis of Few-Layer 1T ′-MoTe 2 Nanostructures Exhibiting Lattice Compression journal January 2016
Selective Catalytic Hydrogenation of Functionalized Nitroarenes: An Update journal October 2009
Biomimetic Hydrogen Evolution: MoS2 Nanoparticles as Catalyst for Hydrogen Evolution journal June 2005
Selective Reduction of Nitroarenes with Molybdenum Disulfide journal July 2013
The Relation between Morphology and Hydrotreating Activity for Supported MoS2 Particles journal April 2001
Electron spin resonance study of active centers in nickel-tungsten sulfide hydrogenation catalysts journal November 1971
Hydrodesulfurization catalysis by transition metal sulfides journal February 1981
Crystal structures of tungsten disulfide and diselenide journal October 1987
Solid-state molybdenum sulfide clusters with an octahedral metal framework as hydrogenation, dehydrogenation, and hydrogenolysis catalysts similar to the platinum group metals journal September 2015
Review on selective hydrogenation of nitroarene by catalytic, photocatalytic and electrocatalytic reactions journal July 2018
Insight into chemoselectivity of nitroarene hydrogenation: A DFT-D3 study of nitroarene adsorption on metal surfaces under the realistic reaction conditions journal January 2017
Formation and Interlayer Decoupling of Colloidal MoSe 2 Nanoflowers journal April 2015
Colloidal Nanocrystals as Building Blocks for Well-Defined Heterogeneous Catalysts journal January 2019
Comprehensive Phase Diagrams of MoS 2 Edge Sites Using Dispersion-Corrected DFT Free Energy Calculations journal June 2018
Impact of Covalent Functionalization on the Aqueous Processability, Catalytic Activity, and Biocompatibility of Chemically Exfoliated MoS 2 Nanosheets journal October 2016
Transforming Nano Metal Nonselective Particulates into Chemoselective Catalysts for Hydrogenation of Substituted Nitrobenzenes journal November 2015
Nanolayered Co–Mo–S Catalysts for the Chemoselective Hydrogenation of Nitroarenes journal March 2017
Transition Metal Dichalcogenides and Beyond: Synthesis, Properties, and Applications of Single- and Few-Layer Nanosheets journal December 2014
Hydrogen Activation on Mo-Based Sulfide Catalysts, a Periodic DFT Study journal June 2002
Adsorption of Gases in Multimolecular Layers journal February 1938
Biomimetic Hydrogen Evolution:  MoS 2 Nanoparticles as Catalyst for Hydrogen Evolution journal April 2005
Colloidal Synthesis of 1T-WS 2 and 2H-WS 2 Nanosheets: Applications for Photocatalytic Hydrogen Evolution journal August 2014
Low-Temperature Solution Synthesis of Transition Metal Dichalcogenide Alloys with Tunable Optical Properties journal August 2017
Energy Level Engineering of MoS 2 by Transition-Metal Doping for Accelerating Hydrogen Evolution Reaction journal October 2017
Activation of the Basal Plane in Two Dimensional Transition Metal Chalcogenide Nanostructures journal September 2018
Room-Temperature Chemoselective Reduction of 3-Nitrostyrene to 3-Vinylaniline by Ammonia Borane over Cu Nanoparticles journal November 2018
Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes journal May 2013
MoS2 monolayer catalyst doped with isolated Co atoms for the hydrodeoxygenation reaction journal March 2017
Electrochemical generation of sulfur vacancies in the basal plane of MoS2 for hydrogen evolution journal April 2017
Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies journal November 2015
Hydrogenation using iron oxide–based nanocatalysts for the synthesis of amines journal March 2015
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
Synergetic interaction between neighbouring platinum monomers in CO2 hydrogenation journal March 2018
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Insights into the hydrogenation mechanism of nitrobenzene to aniline on Pd 3 /Pt(111): a density functional theory study journal January 2015
Well-structured bimetallic surface capable of molecular recognition for chemoselective nitroarene hydrogenation journal January 2016
Bulk iron pyrite as a catalyst for the selective hydrogenation of nitroarenes journal January 2017
Solution synthesis of few-layer WTe 2 and Mo x W 1−x Te 2 nanostructures journal January 2017
A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal December 2000
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
Defect engineering of two-dimensional transition metal dichalcogenides journal April 2016
Raman and photoluminescence spectra of two-dimensional nanocrystallites of monolayer WS 2 and WSe 2 journal April 2016
Projector augmented-wave method journal December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Generalized Gradient Approximation Made Simple journal October 1996
Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts journal July 2006
Nanoscale Fe2O3-Based Catalysts for Selective Hydrogenation of Nitroarenes to Anilines journal November 2013
Nanostructured transition metal dichalcogenide electrocatalysts for CO 2 reduction in ionic liquid journal July 2016

Figures / Tables (7)

Fig. 1(p. 2)figure Fig. 1
Fig. 2(p. 2)figure Fig. 2
Table 1(p. 3)table Table 1
Fig. 3(p. 4)figure Fig. 3
Fig. 4(p. 4)figure Fig. 4
Fig. 5(p. 4)figure Fig. 5
Fig. 6(p. 5)figure Fig. 6

Similar Records

Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation
Journal Article · Mon Apr 09 20:00:00 EDT 2018 · Nature Communications · OSTI ID:1511705

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry