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Title: A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis

Abstract

We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH+), is a viable substitute for hydronium in the electrochemical process at a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH+ can selectively stabilize the *NNH intermediate relative to *NH or *NH2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.

Authors:
 [1];  [2];  [3];  [3];  [4];  [4];  [5]
  1. University of Science and Technology Beijing (China). Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE); SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering; Univ. of Southern California, Los Angeles, CA (United States). Mork Family Department of Chemical Engineering and Materials Science
  3. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering
  4. University of Science and Technology Beijing (China). Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1423520
Grant/Contract Number:  
AC02-76SF00515; 9455; DGE-1656518
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: 7; 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

Citation Formats

Zhang, Linan, Mallikarjun Sharada, Shaama, Singh, Aayush R., Rohr, Brian A., Su, Yanjing, Qiao, Lijie, and Nørskov, Jens K. A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis. United States: N. p., 2018. Web. doi:10.1039/c7cp05484j.
Zhang, Linan, Mallikarjun Sharada, Shaama, Singh, Aayush R., Rohr, Brian A., Su, Yanjing, Qiao, Lijie, & Nørskov, Jens K. A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis. United States. doi:10.1039/c7cp05484j.
Zhang, Linan, Mallikarjun Sharada, Shaama, Singh, Aayush R., Rohr, Brian A., Su, Yanjing, Qiao, Lijie, and Nørskov, Jens K. Wed . "A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis". United States. doi:10.1039/c7cp05484j. https://www.osti.gov/servlets/purl/1423520.
@article{osti_1423520,
title = {A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis},
author = {Zhang, Linan and Mallikarjun Sharada, Shaama and Singh, Aayush R. and Rohr, Brian A. and Su, Yanjing and Qiao, Lijie and Nørskov, Jens K.},
abstractNote = {We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH+), is a viable substitute for hydronium in the electrochemical process at a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH+ can selectively stabilize the *NNH intermediate relative to *NH or *NH2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.},
doi = {10.1039/c7cp05484j},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 7,
volume = 20,
place = {United States},
year = {2018},
month = {1}
}

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Cited by: 8 works
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Figures / Tables:

Fig. 1 Fig. 1: 2,6-Lutidinium adsorption configurations on Pt(111) – (a) parallel to the surface and (b) perpendicular to the surface. (1) indicates side view and (2) is the top view. The solid line represents the size of one unit cell.

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Works referenced in this record:

Nitrogen Adsorption and Hydrogenation on a MoFe 6 S 9 Complex
journal, May 1999


Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center
journal, December 2005

  • Schrock, Richard R.
  • Accounts of Chemical Research, Vol. 38, Issue 12
  • DOI: 10.1021/ar0501121

Electrolytic ammonia synthesis from water and nitrogen gas in molten salt under atmospheric pressure
journal, September 2005


Reduction of Dinitrogen to Ammonia at a Well-Protected Reaction Site in a Molybdenum Triamidoamine Complex
journal, June 2002

  • Yandulov, Dmitry V.; Schrock, Richard R.
  • Journal of the American Chemical Society, Vol. 124, Issue 22
  • DOI: 10.1021/ja020186x

Calculated details of a mechanism for conversion of N2 to NH3 at the FeMo cluster of nitrogenase
journal, January 1997


Ammonia synthesis over a Ru(0001) surface studied by density functional calculations
journal, December 2003


A first-principles study of molecular oxygen dissociation at an electrode surface: a comparison of potential variation and coadsorption effects
journal, January 2008

  • Wasileski, Sally A.; Janik, Michael J.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 25
  • DOI: 10.1039/b803157f

Modeling the electrified solid–liquid interface
journal, November 2008


A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals
journal, October 2015


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

A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


Studies Relevant to Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum Triamidoamine Complexes
journal, February 2005

  • Yandulov, Dmitry V.; Schrock, Richard R.
  • Inorganic Chemistry, Vol. 44, Issue 4
  • DOI: 10.1021/ic040095w

Enabling electrochemical reduction of nitrogen to ammonia at ambient conditions through rational catalyst design
journal, January 2015

  • Abghoui, Younes; Garden, Anna L.; Hlynsson, Valtýr Freyr
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 7
  • DOI: 10.1039/C4CP04838E

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


Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012


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

Nitrogen Activation in a Mars–van Krevelen Mechanism for Ammonia Synthesis on Co 3 Mo 3 N
journal, October 2015

  • Zeinalipour-Yazdi, Constantinos D.; Hargreaves, Justin S. J.; Catlow, C. Richard A.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 51
  • DOI: 10.1021/acs.jpcc.5b06811

An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002

  • Bahn, S. R.; Jacobsen, K. W.
  • Computing in Science & Engineering, Vol. 4, Issue 3
  • DOI: 10.1109/5992.998641

Global Population and the Nitrogen Cycle
journal, July 1997


Oxidations carried out by means of vanadium oxide catalysts
journal, January 1954


The Yandulov/Schrock Cycle and the Nitrogenase Reaction: Pathways of Nitrogen Fixation Studied by Density Functional Theory
journal, January 2006


A theory of overpotential
journal, January 1927


Ammonia for hydrogen storage: challenges and opportunities
journal, January 2008

  • Klerke, Asbjørn; Christensen, Claus Hviid; Nørskov, Jens K.
  • Journal of Materials Chemistry, Vol. 18, Issue 20
  • DOI: 10.1039/b720020j

Modeling the Nitrogenase FeMo Cofactor
journal, December 2000

  • Rod, Thomas H.; Nørskov, Jens K.
  • Journal of the American Chemical Society, Vol. 122, Issue 51
  • DOI: 10.1021/ja001163q

Ammonia synthesis over iron single-crystal catalysts: the effects of alumina and potassium
journal, September 1986

  • Bare, Simon R.; Strongin, D. R.; Somorjai, G. A.
  • The Journal of Physical Chemistry, Vol. 90, Issue 20
  • DOI: 10.1021/j100411a003

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

Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations
journal, October 2010

  • Skúlason, Egill; Tripkovic, Vladimir; Björketun, Mårten E.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 42
  • DOI: 10.1021/jp1048887

Adsorption of nitrogen on potassium promoted Fe(111) and (100) surfaces
journal, February 1982


Electric Field Effects in Electrochemical CO 2 Reduction
journal, September 2016


Electrochemical synthesis of ammonia at atmospheric pressure and low temperature in a solid polymer electrolyte cell
journal, January 2000

  • Kordali, V.; Kyriacou, G.; Lambrou, Ch.
  • Chemical Communications, Issue 17
  • DOI: 10.1039/b004885m

Predicting Catalysis:  Understanding Ammonia Synthesis from First-Principles Calculations
journal, September 2006

  • Hellman, A.; Baerends, E. J.; Biczysko, M.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 36
  • DOI: 10.1021/jp056982h

The Synthesis of Ammonia over a Ruthenium Single Crystal
journal, September 1998


Hydrogen Evolution Reaction Catalyzed by Transition-Metal Nitrides
journal, October 2017

  • Abghoui, Younes; Skúlason, Egill
  • The Journal of Physical Chemistry C, Vol. 121, Issue 43
  • DOI: 10.1021/acs.jpcc.7b06811

Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces
journal, July 2007


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

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

Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center
journal, July 2003


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

Catalytic Synthesis of Ammonia—A “Never-Ending Story”?
journal, May 2003


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

Mechanism of Molybdenum Nitrogenase
journal, January 1996

  • Burgess, Barbara K.; Lowe, David J.
  • Chemical Reviews, Vol. 96, Issue 7
  • DOI: 10.1021/cr950055x

Electrochemical Ammonia Synthesis—The Selectivity Challenge
journal, December 2016


Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
journal, January 2007

  • Skúlason, Egill; Karlberg, Gustav S.; Rossmeisl, Jan
  • Phys. Chem. Chem. Phys., Vol. 9, Issue 25
  • DOI: 10.1039/B700099E

Understanding trends in electrochemical carbon dioxide reduction rates
journal, May 2017

  • Liu, Xinyan; Xiao, Jianping; Peng, Hongjie
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15438

Synthesis of ammonia directly from air and water at ambient temperature and pressure
journal, January 2013

  • Lan, Rong; Irvine, John T. S.; Tao, Shanwen
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep01145

The Brønsted–Evans–Polanyi Relation and the Volcano Plot for Ammonia Synthesis over Transition Metal Catalysts
journal, January 2001

  • Logadottir, A.; Rod, T. H.; Nørskov, J. K.
  • Journal of Catalysis, Vol. 197, Issue 2
  • DOI: 10.1006/jcat.2000.3087

Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum: Theory versus Experiment
journal, June 2008

  • Schrock, Richard R.
  • Angewandte Chemie International Edition, Vol. 47, Issue 30
  • DOI: 10.1002/anie.200705246

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