Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Size and Stoichiometry Effects on the Reactivity of MoCy Nanoparticles Towards Ethylene

Abstract

Molybdenum carbides are promising catalysts alternative to Pt-group metals for the hydrogenation of unsaturated hydrocarbons. Nanostructuring has been shown to be an efficient way to boost the catalytic activity of these materials with MoCy nanoparticles (NPs) exhibiting a good performance when encapsulated inside zeolites or dispersed on inert supports such as carbon or gold. In this work, we focus on a systematic DFT study of the interaction of MoCy NPs with ethylene (C2H4), as a general and simple approach for examining binding and activation of C≡C bonds. Models for 14 NPs, with a Mo/C ratio in the 0.67 to 2.00 range, have been built following a cascade procedure. Several chemical descriptors, including the adsorption energy, structural NPs distortion, C≡C deformation, and C2H4 attachment energy have been analyzed along with a meticulous geometric and electronic characterization of bare NPs and C2H4 binding. The present results show that 1:1 stoichiometric Mo6C6, Mo12C12, and Mo24C24, and the non-stochiometric Mo4C6, Mo8C12 (MetCar), and Mo14C13 (Nanocube) are excellent systems for the binding and activation of ethylene, exhibiting a much bigger reactivity than a bulk δ-MoC(001) surface with a similar Mo:C ratio. In addition, C2H4 binding on the NPs with a Mo/C < 1.08 is advantageousmore » since, apart from a rather large adsorption energy, implies low energy values for NPs deformation (from 0.00 to 0.31 eV), C≡C distortion (from 0.30 to 0.52 eV), and C2H4 attachment (from -2.12 to -2.58 eV). These theoretical results point to the ideal MoCy size and composition for C2H4 binding, providing a background for further experimental studies aimed at the preparation of MoCy NPs as hydrogenation catalysts.« less

Authors:
 [1];  [2];  [1];  [2]; ORCiD logo [3];  [2]
+ Show Author Affiliations
  1. Univ. de Medellin (Colombia)
  2. Univ. de Barcelona (Spain)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Generalitat de Catalunya
OSTI Identifier:
1767414
Report Number(s):
BNL-221076-2021-JAAM
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
SC0012704; RTI2018-095460-B-I00; MDM-2017-0767; 2017SGR13
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 125; Journal Issue: 11; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ethylene; molybdenum carbide

Citation Formats

Jimenez-Orozco, Carlos, Figueras, Marc, Florez, Elizabeth, Vines, Francesc, Rodriguez, Jose A., and Illas, Francesc. Size and Stoichiometry Effects on the Reactivity of MoCy Nanoparticles Towards Ethylene. United States: N. p., 2021. Web. doi:10.1021/acs.jpcc.0c10689.
Copy to clipboard
Jimenez-Orozco, Carlos, Figueras, Marc, Florez, Elizabeth, Vines, Francesc, Rodriguez, Jose A., & Illas, Francesc. Size and Stoichiometry Effects on the Reactivity of MoCy Nanoparticles Towards Ethylene. United States. https://doi.org/10.1021/acs.jpcc.0c10689
Copy to clipboard
Jimenez-Orozco, Carlos, Figueras, Marc, Florez, Elizabeth, Vines, Francesc, Rodriguez, Jose A., and Illas, Francesc. Wed . "Size and Stoichiometry Effects on the Reactivity of MoCy Nanoparticles Towards Ethylene". United States. https://doi.org/10.1021/acs.jpcc.0c10689. https://www.osti.gov/servlets/purl/1767414.
Copy to clipboard
@article{osti_1767414,
title = {Size and Stoichiometry Effects on the Reactivity of MoCy Nanoparticles Towards Ethylene},
author = {Jimenez-Orozco, Carlos and Figueras, Marc and Florez, Elizabeth and Vines, Francesc and Rodriguez, Jose A. and Illas, Francesc},
abstractNote = {Molybdenum carbides are promising catalysts alternative to Pt-group metals for the hydrogenation of unsaturated hydrocarbons. Nanostructuring has been shown to be an efficient way to boost the catalytic activity of these materials with MoCy nanoparticles (NPs) exhibiting a good performance when encapsulated inside zeolites or dispersed on inert supports such as carbon or gold. In this work, we focus on a systematic DFT study of the interaction of MoCy NPs with ethylene (C2H4), as a general and simple approach for examining binding and activation of C≡C bonds. Models for 14 NPs, with a Mo/C ratio in the 0.67 to 2.00 range, have been built following a cascade procedure. Several chemical descriptors, including the adsorption energy, structural NPs distortion, C≡C deformation, and C2H4 attachment energy have been analyzed along with a meticulous geometric and electronic characterization of bare NPs and C2H4 binding. The present results show that 1:1 stoichiometric Mo6C6, Mo12C12, and Mo24C24, and the non-stochiometric Mo4C6, Mo8C12 (MetCar), and Mo14C13 (Nanocube) are excellent systems for the binding and activation of ethylene, exhibiting a much bigger reactivity than a bulk δ-MoC(001) surface with a similar Mo:C ratio. In addition, C2H4 binding on the NPs with a Mo/C < 1.08 is advantageous since, apart from a rather large adsorption energy, implies low energy values for NPs deformation (from 0.00 to 0.31 eV), C≡C distortion (from 0.30 to 0.52 eV), and C2H4 attachment (from -2.12 to -2.58 eV). These theoretical results point to the ideal MoCy size and composition for C2H4 binding, providing a background for further experimental studies aimed at the preparation of MoCy NPs as hydrogenation catalysts.},
doi = {10.1021/acs.jpcc.0c10689},
journal = {Journal of Physical Chemistry. C},
number = 11,
volume = 125,
place = {United States},
year = {Wed Mar 10 00:00:00 EST 2021},
month = {Wed Mar 10 00:00:00 EST 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.0c10689
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Coking-Resistant Sub-Nano Dehydrogenation Catalysts: Pt n Sn x /SiO 2 ( n = 4, 7)
journal, March 2020

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

Hydrogenation of benzene and toluene over Ir particles supported on γ-Al2O3
journal, September 2002

A systematic density functional theory study of the electronic structure of bulk and (001) surface of transition-metals carbides
journal, May 2005

  • Viñes, F.; Sousa, C.; Liu, P.
  • The Journal of Chemical Physics, Vol. 122, Issue 17
  • DOI: 10.1063/1.1888370

Microcalorimetric, Infrared Spectroscopic, and DFT Studies of Ethylene Adsorption on Pt/SiO 2 and Pt−Sn/SiO 2 Catalysts
journal, May 1999

  • Shen, Jianyi; Hill, Josephine M.; Watwe, Ramchandra M.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 19
  • DOI: 10.1021/jp9902452

Projector augmented-wave method
journal, December 1994

Critical Hydrogen Coverage Effect on the Hydrogenation of Ethylene Catalyzed by δ-MoC(001): An Ab Initio Thermodynamic and Kinetic Study
journal, May 2020

  • Jimenez-Orozco, Carlos; Flórez, Elizabeth; Viñes, Francesc
  • ACS Catalysis, Vol. 10, Issue 11
  • DOI: 10.1021/acscatal.0c00144

Hydrogenation of Olefins over Metals
journal, July 1953

  • Wilson, J. N.; Otvos, J. W.; Stevenson, D. P.
  • Industrial & Engineering Chemistry, Vol. 45, Issue 7
  • DOI: 10.1021/ie50523a035

An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO 2 Hydrogenation
journal, December 2019

  • Baddour, Frederick G.; Roberts, Emily J.; To, Anh T.
  • Journal of the American Chemical Society, Vol. 142, Issue 2
  • DOI: 10.1021/jacs.9b11238

Characterization of Molybdenum Carbide Nanoparticles Formed on Au(111) Using Reactive-Layer Assisted Deposition
journal, January 2005

  • Horn, Jillian M.; Song, Zhen; Potapenko, Denis V.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 1
  • DOI: 10.1021/jp044837i

Kinetics and mechanism of ethylene hydrogenation poisoned by CO on silica-supported monodisperse Pt nanoparticles
journal, February 2008

Bulk (in)stability as a possible source of surface reconstruction
journal, January 2020

  • Figueras, Marc; Jurado, Anabel; Morales-García, Ángel
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 34
  • DOI: 10.1039/D0CP03819A

Effective and Highly Selective CO Generation from CO 2 Using a Polycrystalline α-Mo 2 C Catalyst
journal, May 2017

  • Liu, Xianyun; Kunkel, Christian; Ramírez de la Piscina, Pilar
  • ACS Catalysis, Vol. 7, Issue 7
  • DOI: 10.1021/acscatal.7b00735

Supported Molybdenum Carbide Nanoparticles as Hot Hydrogen Reservoirs for Catalytic Applications
journal, September 2020

  • Figueras, Marc; Gutiérrez, Ramón A.; Viñes, Francesc
  • The Journal of Physical Chemistry Letters, Vol. 11, Issue 19
  • DOI: 10.1021/acs.jpclett.0c02608

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

Effects of carbon on the stability and chemical performance of transition metal carbides: A density functional study
journal, March 2004

  • Liu, Ping; Rodriguez, José A.
  • The Journal of Chemical Physics, Vol. 120, Issue 11
  • DOI: 10.1063/1.1647050

Hydrogenation and ring opening of naphthalene on bulk and supported Mo2C catalysts
journal, May 2007

Bulk and surface properties of metal carbides: implications for catalysis
journal, January 2018

  • Quesne, Matthew G.; Roldan, Alberto; de Leeuw, Nora H.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 10
  • DOI: 10.1039/C7CP06336A

Hydrogenation and Ring Opening of Aromatic and Naphthenic Hydrocarbons Over Noble Metal (Ir, Pt, Rh)/Al2O3 Catalysts
journal, March 2012

The bending machine: CO 2 activation and hydrogenation on δ-MoC(001) and β-Mo 2 C(001) surfaces
journal, January 2014

  • Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 28
  • DOI: 10.1039/C4CP01943A

Structure of Ethene Adsorption Sites on Supported Metal Catalysts from in Situ XANES Analysis
journal, July 2007

  • Bus, Eveline; Ramaker, David E.; van Bokhoven, Jeroen A.
  • Journal of the American Chemical Society, Vol. 129, Issue 26
  • DOI: 10.1021/ja0689233

Approaching nanoscale oxides: models and theoretical methods
journal, January 2009

  • Bromley, Stefan T.; Moreira, Ibério de P. R.; Neyman, Konstantin M.
  • Chemical Society Reviews, Vol. 38, Issue 9
  • DOI: 10.1039/b806400h

Beyond metallo-carbohedrenes: growth and decomposition of metal-carbon nanocrystals
journal, October 1993

  • Pilgrim, J. S.; Duncan, M. A.
  • Journal of the American Chemical Society, Vol. 115, Issue 21
  • DOI: 10.1021/ja00074a044

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation
journal, April 2009

  • Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu
  • Journal of the American Chemical Society, Vol. 131, Issue 16
  • DOI: 10.1021/ja809936n

Controlling Ethylene Hydrogenation Reactivity on Pt 13 Clusters by Varying the Stoichiometry of the Amorphous Silica Support
journal, June 2016

  • Crampton, Andrew S.; Rötzer, Marian D.; Schweinberger, Florian F.
  • Angewandte Chemie International Edition, Vol. 55, Issue 31
  • DOI: 10.1002/anie.201603332

Acetylene and Ethylene Adsorption on a β-Mo 2 C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions
journal, September 2017

  • Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres
  • The Journal of Physical Chemistry C, Vol. 121, Issue 36
  • DOI: 10.1021/acs.jpcc.7b05442

Simultaneous hydrodesulfurization, hydrodeoxygenation, and hydrogenation with molybdenum carbide
journal, March 1998

Low-energy nanoscale clusters of (TiC) n n = 6, 12: a structural and energetic comparison with MgO
journal, January 2013

  • Lamiel-Garcia, Oriol; Bromley, Stefan T.; Illas, Francesc
  • Theoretical Chemistry Accounts, Vol. 132, Issue 3
  • DOI: 10.1007/s00214-012-1312-x

Ti8C12+-Metallo-Carbohedrenes: A New Class of Molecular Clusters?
journal, March 1992

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

Understanding the reactivity of metallic nanoparticles: beyond the extended surface model for catalysis
journal, January 2014

  • Viñes, Francesc; Gomes, José R. B.; Illas, Francesc
  • Chem. Soc. Rev., Vol. 43, Issue 14
  • DOI: 10.1039/C3CS60421G

Atomic and electronic structure of molybdenum carbide phases: bulk and low Miller-index surfaces
journal, January 2013

  • Politi, José Roberto dos Santos; Viñes, Francesc; Rodriguez, Jose A.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 30
  • DOI: 10.1039/c3cp51389k

Recovery of Pt Surfaces for Ethylene Hydrogenation-Based Active Site Determination
journal, May 2014

Density Functional Theory (DFT) Studies of C1and C2Hydrocarbons Species on Pt Clusters
journal, December 1998

  • Watwe, R. M.; Spiewak, B. E.; Cortright, R. D.
  • Journal of Catalysis, Vol. 180, Issue 2
  • DOI: 10.1006/jcat.1998.2288

Kinetics and particle size effects in ethene hydrogenation over supported palladium catalysts at atmospheric pressure
journal, November 2009

The Ti 8 C 12 Metcar:  A New Model Catalyst for Hydrodesulfurization
journal, December 2004

  • Liu, Ping; Rodriguez, José A.; Muckerman, James T.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 49
  • DOI: 10.1021/jp045460j

Surface Chemistry of Transition Metal Carbides
journal, January 2005

  • Hwu, Henry H.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 105, Issue 1
  • DOI: 10.1021/cr0204606

Sn-modification of Pt 7 /alumina model catalysts: Suppression of carbon deposition and enhanced thermal stability
journal, January 2020

  • Li, Guangjing; Zandkarimi, Borna; Cass, Ashley C.
  • The Journal of Chemical Physics, Vol. 152, Issue 2
  • DOI: 10.1063/1.5129686

Transition metal carbides as novel materials for CO 2 capture, storage, and activation
journal, January 2016

  • Kunkel, Christian; Viñes, Francesc; Illas, Francesc
  • Energy & Environmental Science, Vol. 9, Issue 1
  • DOI: 10.1039/C5EE03649F

Hydroconversion of cyclohexene using catalysts containing Pt, Pd, Ir and Re supported on H-ZSM-5 zeolite
journal, April 2005

  • Aboul-Gheit, Ahmed K.; Aboul-Fotouh, Sameh M.; Aboul-Gheit, Noha A. K.
  • Applied Catalysis A: General, Vol. 283, Issue 1-2
  • DOI: 10.1016/j.apcata.2005.01.003

Boron Switch for Selectivity of Catalytic Dehydrogenation on Size-Selected Pt Clusters on Al 2 O 3
journal, August 2017

  • Ha, Mai-Anh; Baxter, Eric T.; Cass, Ashley C.
  • Journal of the American Chemical Society, Vol. 139, Issue 33
  • DOI: 10.1021/jacs.7b05894

Global Activity Search Uncovers Reaction Induced Concomitant Catalyst Restructuring for Alkane Dissociation on Model Pt Catalysts
journal, January 2021

Structure of Mo 2 C x and Mo 4 C x Molybdenum Carbide Nanoparticles and Their Anchoring Sites on ZSM-5 Zeolites
journal, February 2014

  • Gao, Jie; Zheng, Yiteng; Fitzgerald, George B.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 9
  • DOI: 10.1021/jp4106053

Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis
journal, August 1973

Benzene adsorption on Mo2C: A theoretical and experimental study
journal, May 2010

Energetics of H2 and O2 adsorption on Ir/γ-Al2O3 and Ir/SiO2 catalysts. Dependence on support and on metal particle size
journal, March 1998

Systematic Theoretical Study of Ethylene Adsorption on δ-MoC(001), TiC(001), and ZrC(001) Surfaces
journal, June 2016

  • Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres
  • The Journal of Physical Chemistry C, Vol. 120, Issue 25
  • DOI: 10.1021/acs.jpcc.6b03106

Platinum vs transition metal carbide surfaces as catalysts for olefin and alkyne conversion: binding and hydrogenation of ethylidyne
journal, June 2019

Fischer–Tropsch synthesis over alumina-supported molybdenum carbide catalyst
journal, May 2011

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: