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Title: Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

Abstract

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate for the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of New Mexico, Albuquerque, NM (United States). Chemical and Biological Engineering Dept. Center for Micro-Engineered Materials; Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. of New Mexico, Albuquerque, NM (United States). Chemical and Biological Engineering Dept. Center for Micro-Engineered Materials; Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1440453
Alternate Identifier(s):
OSTI ID: 1437516
Report Number(s):
LA-UR-18-21724
Journal ID: ISSN 1463-9076
Grant/Contract Number:  
AC52-06NA25396; AR 1261-4005; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 21; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Material Science

Citation Formats

Matanovic, Ivana, and Garzon, Fernando H. Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study. United States: N. p., 2018. Web. doi:10.1039/C8CP01643G.
Matanovic, Ivana, & Garzon, Fernando H. Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study. United States. doi:10.1039/C8CP01643G.
Matanovic, Ivana, and Garzon, Fernando H. Thu . "Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study". United States. doi:10.1039/C8CP01643G. https://www.osti.gov/servlets/purl/1440453.
@article{osti_1440453,
title = {Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study},
author = {Matanovic, Ivana and Garzon, Fernando H.},
abstractNote = {We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate for the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.},
doi = {10.1039/C8CP01643G},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 21,
volume = 20,
place = {United States},
year = {2018},
month = {4}
}

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Works referenced in this record:

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

Ammonia Synthesis at Atmospheric Pressure
journal, October 1998


The nature of the active site in heterogeneous metal catalysis
journal, January 2008

  • Nørskov, Jens K.; Bligaard, Thomas; Hvolbæk, Britt
  • Chemical Society Reviews, Vol. 37, Issue 10
  • DOI: 10.1039/b800260f

Computational high-throughput screening of electrocatalytic materials for hydrogen evolution
journal, October 2006

  • Greeley, Jeff; Jaramillo, Thomas F.; Bonde, Jacob
  • Nature Materials, Vol. 5, Issue 11, p. 909-913
  • DOI: 10.1038/nmat1752

Projector augmented-wave method
journal, December 1994


Direct Catalytic Conversion of Cellulose into Ethylene Glycol Using Nickel-Promoted Tungsten Carbide Catalysts
journal, October 2008

  • Ji, Na; Zhang, Tao; Zheng, Mingyuan
  • Angewandte Chemie International Edition, Vol. 47, Issue 44
  • DOI: 10.1002/anie.200803233

Progress in the Electrochemical Synthesis of Ammonia
journal, May 2017


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


Highly active Au/δ-MoC and Au/β-Mo 2 C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance
journal, January 2017

  • Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun
  • Catalysis Science & Technology, Vol. 7, Issue 22
  • DOI: 10.1039/C7CY00639J

Experimental and Theoretical Investigation of Molybdenum Carbide and Nitride as Catalysts for Ammonia Decomposition
journal, February 2013

  • Zheng, Weiqing; Cotter, Thomas P.; Kaghazchi, Payam
  • Journal of the American Chemical Society, Vol. 135, Issue 9
  • DOI: 10.1021/ja309734u

Ammonia synthesis at low temperatures
journal, March 2000

  • Rod, T. H.; Logadottir, A.; Nørskov, J. K.
  • The Journal of Chemical Physics, Vol. 112, Issue 12
  • DOI: 10.1063/1.481103

Surface structure and composition of high-surface-area molybdenum nitrides
journal, May 1994


Molybdenum nitride catalysts I. Influence of the synthesis factors on structural properties
journal, March 1994


Catalyst Design by Interpolation in the Periodic Table:  Bimetallic Ammonia Synthesis Catalysts
journal, August 2001

  • Jacobsen, Claus J. H.; Dahl, Søren; Clausen, Bjerne S.
  • Journal of the American Chemical Society, Vol. 123, Issue 34
  • DOI: 10.1021/ja010963d

Electro-reduction of nitrogen on molybdenum nitride: structure, energetics, and vibrational spectra from DFT
journal, January 2014

  • Matanović, Ivana; Garzon, Fernando H.; Henson, Neil J.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 7
  • DOI: 10.1039/c3cp54559h

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Trends in the Exchange Current for Hydrogen Evolution
journal, January 2005

  • Nørskov, J. K.; Bligaard, T.; Logadottir, A.
  • Journal of The Electrochemical Society, Vol. 152, Issue 3
  • DOI: 10.1149/1.1856988

Electroreduction of N 2 to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments
journal, December 2015


Molybdenum nitride and carbide catalysts for ammonia synthesis
journal, October 2001


High-precision sampling for Brillouin-zone integration in metals
journal, August 1989


Electrochemical Synthesis of Ammonia Based on Co3Mo3N Catalyst and LiAlO2–(Li,Na,K)2CO3 Composite Electrolyte
journal, December 2014


Molybdenum carbide catalysts II. Topotactic synthesis of unsupported powders
journal, July 1988


Review of electrochemical ammonia production technologies and materials
journal, November 2013


Water-Gas-Shift Reaction on Molybdenum Carbide Surfaces:  Essential Role of the Oxycarbide
journal, October 2006

  • Liu, Ping; Rodriguez, José A.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 39
  • DOI: 10.1021/jp0621629

Temperature stability range of the binary MoC phase
journal, December 1992

  • Kouvetdkis}, J.; Brewer, L.
  • Journal of Phase Equilibria, Vol. 13, Issue 6
  • DOI: 10.1007/BF02667207

A theory of overpotential
journal, January 1927


Nitrogen electrochemically reduced to ammonia with hematite: density-functional insights
journal, January 2015

  • Nguyen, Manh-Thuong; Seriani, Nicola; Gebauer, Ralph
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 22
  • DOI: 10.1039/C4CP04308A

Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO 2 : The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability
journal, June 2016

  • Posada-Pérez, Sergio; Ramírez, Pedro J.; Evans, Jaime
  • Journal of the American Chemical Society, Vol. 138, Issue 26
  • DOI: 10.1021/jacs.6b04529

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


The role of oxygen and water on molybdenum nanoclusters for electro catalytic ammonia production
journal, January 2014

  • Howalt, Jakob G.; Vegge, Tejs
  • Beilstein Journal of Nanotechnology, Vol. 5
  • DOI: 10.3762/bjnano.5.11

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

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


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

Analysis of the electrocatalytic activity of α-molybdenum carbide thin porous electrodes toward the hydrogen evolution reaction
journal, December 2016


Hydrogen evolution by a metal-free electrocatalyst
journal, April 2014

  • Zheng, Yao; Jiao, Yan; Zhu, Yihan
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4783

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Catalyst size matters: Tuning the molecular mechanism of the water–gas shift reaction on titanium carbide based compounds
journal, November 2008


Phonon and elastic instabilities in MoC and MoN
journal, February 2000


The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations
journal, June 2015

  • Montoya, Joseph H.; Tsai, Charlie; Vojvodic, Aleksandra
  • ChemSusChem, Vol. 8, Issue 13
  • DOI: 10.1002/cssc.201500322

Electrochemically Synthesized Nanoporous Molybdenum Carbide as a Durable Electrocatalyst for Hydrogen Evolution Reaction
journal, December 2017


DFT based study of transition metal nano-clusters for electrochemical NH3 production
journal, January 2013

  • Howalt, J. G.; Bligaard, T.; Rossmeisl, J.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 20
  • DOI: 10.1039/c3cp44641g

Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis
journal, September 2012


Electrochemical ammonia production on molybdenum nitride nanoclusters
journal, January 2013

  • Howalt, J. G.; Vegge, T.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 48
  • DOI: 10.1039/c3cp53160k

Challenges in reduction of dinitrogen by proton and electron transfer
journal, January 2014

  • van der Ham, Cornelis J. M.; Koper, Marc T. M.; Hetterscheid, Dennis G. H.
  • Chem. Soc. Rev., Vol. 43, Issue 15
  • DOI: 10.1039/C4CS00085D

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

Calculated Phase Diagrams for the Electrochemical Oxidation and Reduction of Water over Pt(111)
journal, November 2006

  • Rossmeisl, Jan; Nørskov, Jens K.; Taylor, Christopher D.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 43
  • DOI: 10.1021/jp0631735

Preparation and catalytic properties of transition metal carbides and nitrides
journal, June 1992