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Title: Ultrafast molecular transport on carbon surfaces: The diffusion of ammonia on graphite

Abstract

We present a combined experimental and theoretical study of the self-diffusion of ammonia on exfoliated graphite. Using neutron time-of-flight spectroscopy we are able to resolve the ultrafast diffusion process of adsorbed ammonia, NH3, on graphite. Together with van der Waals corrected density functional theory calculations we show that the diffusion of NH3 follows a hopping motion on a weakly corrugated potential energy surface with an activation energy of about 4 meV which is particularly low for this type of diffusive motion. The hopping motion includes further a significant number of long jumps and the diffusion constant of ammonia adsorbed on graphite is determined with D = 3.9•10-8 m2/s at 94 K.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [4];  [1];  [4]
  1. Graz Univ. of Technology (Austria)
  2. Univ. of Surrey, Guildford (United Kingdom)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Cambridge (United Kingdom). Cavendish Lab.
  4. Inst. Laue-Langevin (ILL), Grenoble (France)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Engineering and Physical Sciences Research Council (EPSRC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1476645
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Carbon
Additional Journal Information:
Journal Volume: 126; Journal Issue: C; Journal ID: ISSN 0008-6223
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Adsorption; Ammonia; DFT; Diffusion; Graphite; Neutron scattering

Citation Formats

Tamtögl, Anton, Sacchi, M., Calvo-Almazán, I., Zbiri, M., Koza, M. M., Ernst, W. E., and Fouquet, P. Ultrafast molecular transport on carbon surfaces: The diffusion of ammonia on graphite. United States: N. p., 2018. Web. doi:10.1016/j.carbon.2017.09.104.
Tamtögl, Anton, Sacchi, M., Calvo-Almazán, I., Zbiri, M., Koza, M. M., Ernst, W. E., & Fouquet, P. Ultrafast molecular transport on carbon surfaces: The diffusion of ammonia on graphite. United States. https://doi.org/10.1016/j.carbon.2017.09.104
Tamtögl, Anton, Sacchi, M., Calvo-Almazán, I., Zbiri, M., Koza, M. M., Ernst, W. E., and Fouquet, P. Sun . "Ultrafast molecular transport on carbon surfaces: The diffusion of ammonia on graphite". United States. https://doi.org/10.1016/j.carbon.2017.09.104. https://www.osti.gov/servlets/purl/1476645.
@article{osti_1476645,
title = {Ultrafast molecular transport on carbon surfaces: The diffusion of ammonia on graphite},
author = {Tamtögl, Anton and Sacchi, M. and Calvo-Almazán, I. and Zbiri, M. and Koza, M. M. and Ernst, W. E. and Fouquet, P.},
abstractNote = {We present a combined experimental and theoretical study of the self-diffusion of ammonia on exfoliated graphite. Using neutron time-of-flight spectroscopy we are able to resolve the ultrafast diffusion process of adsorbed ammonia, NH3, on graphite. Together with van der Waals corrected density functional theory calculations we show that the diffusion of NH3 follows a hopping motion on a weakly corrugated potential energy surface with an activation energy of about 4 meV which is particularly low for this type of diffusive motion. The hopping motion includes further a significant number of long jumps and the diffusion constant of ammonia adsorbed on graphite is determined with D = 3.9•10-8 m2/s at 94 K.},
doi = {10.1016/j.carbon.2017.09.104},
journal = {Carbon},
number = C,
volume = 126,
place = {United States},
year = {2018},
month = {9}
}

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Works referenced in this record:

Chemical doping of graphene
journal, January 2011

  • Liu, Hongtao; Liu, Yunqi; Zhu, Daoben
  • J. Mater. Chem., Vol. 21, Issue 10
  • DOI: 10.1039/C0JM02922J

N-Doping of Graphene Through Electrothermal Reactions with Ammonia
journal, May 2009


Adsorption of ammonia on graphene
journal, May 2009


Graphene Nanomesh As Highly Sensitive Chemiresistor Gas Sensor
journal, September 2012

  • Paul, Rajat Kanti; Badhulika, Sushmee; Saucedo, Nuvia M.
  • Analytical Chemistry, Vol. 84, Issue 19
  • DOI: 10.1021/ac3012895

Graphene-based gas sensors
journal, January 2013

  • Yuan, Wenjing; Shi, Gaoquan
  • Journal of Materials Chemistry A, Vol. 1, Issue 35
  • DOI: 10.1039/c3ta11774j

Graphene/mica based ammonia gas sensors
journal, December 2014

  • Ben Aziza, Zeineb; Zhang, Qing; Baillargeat, Dominique
  • Applied Physics Letters, Vol. 105, Issue 25
  • DOI: 10.1063/1.4905039

Study on adsorption and desorption of ammonia on graphene
journal, September 2015


Detection of individual gas molecules adsorbed on graphene
journal, July 2007

  • Schedin, F.; Geim, A. K.; Morozov, S. V.
  • Nature Materials, Vol. 6, Issue 9, p. 652-655
  • DOI: 10.1038/nmat1967

Graphene on ferromagnetic surfaces and its functionalization with water and ammonia
journal, January 2011

  • Böttcher, Stefan; Weser, Martin; Dedkov, Yuriy S.
  • Nanoscale Research Letters, Vol. 6, Issue 1
  • DOI: 10.1186/1556-276X-6-214

Gas diffusion on graphene surfaces
journal, January 2017

  • Sun, Chengzhen; Bai, Bofeng
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 5
  • DOI: 10.1039/C6CP06267A

Isotopic ordering in adsorbed hydrogen monolayers
journal, October 1999


Neutron scattering from adsorbed systems
journal, January 1982


Neutron diffraction and incoherent neutron scattering from adsorbed layers
journal, May 2001


Progress in the measurement and modeling of physisorbed layers
journal, November 2007


Diffraction from physisorbed layers
journal, February 2012


Ballistic Diffusion in Polyaromatic Hydrocarbons on Graphite
journal, November 2016

  • Calvo-Almazán, Irene; Sacchi, Marco; Tamtögl, Anton
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 24
  • DOI: 10.1021/acs.jpclett.6b02305

Benzene diffusion on graphite described by a rough hard disk model
journal, November 2014


Measurement of single-molecule frictional dissipation in a prototypical nanoscale system
journal, July 2009

  • Hedgeland, H.; Fouquet, P.; Jardine, A. P.
  • Nature Physics, Vol. 5, Issue 8
  • DOI: 10.1038/nphys1335

Experimental Observation of Fast Diffusion of Large Antimony Clusters on Graphite Surfaces
journal, June 1995


C 60 Molecular Bearings
journal, February 2003


Ballistic nanofriction
journal, July 2010

  • Guerra, Roberto; Tartaglino, Ugo; Vanossi, Andrea
  • Nature Materials, Vol. 9, Issue 8
  • DOI: 10.1038/nmat2798

Superlubricity of graphene nanoribbons on gold surfaces
journal, February 2016


Internal degrees of freedom and transport of benzene on graphite
journal, July 2011


Single-molecule manipulation experiments to explore friction and adhesion
journal, February 2017

  • Pawlak, R.; Kawai, S.; Meier, T.
  • Journal of Physics D: Applied Physics, Vol. 50, Issue 11
  • DOI: 10.1088/1361-6463/aa599d

Making molecular machines work
journal, October 2006


Nuclear magnetic resonance studies of molecules physisorbed on homogeneous surfaces
journal, January 1980


Thermal desorption of gases and solvents from graphite and carbon nanotube surfaces
journal, November 2006


Adsorption of H 2 O , N H 3 , CO, N O 2 , and NO on graphene: A first-principles study
journal, March 2008


Adsorption capacity of H 2 O, NH 3 , CO, and NO 2 on the pristine graphene
journal, January 2013

  • Lin, Xianqing; Ni, Jun; Fang, Chao
  • Journal of Applied Physics, Vol. 113, Issue 3
  • DOI: 10.1063/1.4776239

Diffusion of molecular hydrogen in carbon aerogel
journal, March 2016


Structure and dynamics investigations of a partially hydrogenated graphene/Ni(111) surface
journal, April 2017


Characterisation of a basal-plane-oriented graphite
journal, January 1998

  • Gilbert, Elliot P.; Reynolds, Philip A.; White, John W.
  • Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 13
  • DOI: 10.1039/a801303i

Study of the Papyex structure using neutron Compton scattering
journal, August 2000


The structure of ammonia overlayers physisorbed onto the surface of single crystal graphite, determined by means of atomic beam diffraction
journal, March 1990

  • Rowntree, P.; Scoles, G.; Xu, J.
  • The Journal of Chemical Physics, Vol. 92, Issue 6
  • DOI: 10.1063/1.457842

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

Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009


Neutron Scattering from a Liquid on a Jump Diffusion Model
journal, February 1961


Effects of low-dimensionality in solid-state protonic conductors
journal, April 1995


Structure and dynamics of ammonia absorbed on graphitized carbon black. Part 3.—Neutron quasielastic and inelastic spectra
journal, January 1979

  • Gamlen, Philip H.; Thomas, Robert K.; Trewern, Timothy D.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 75, Issue 0
  • DOI: 10.1039/f19797501553

Adsorption and diffusion of water on graphene from first principles
journal, July 2011


Adsorption of nitrogen oxides on graphene and graphene oxides: Insights from density functional calculations
journal, January 2011

  • Tang, Shaobin; Cao, Zexing
  • The Journal of Chemical Physics, Vol. 134, Issue 4
  • DOI: 10.1063/1.3541249

Surface Self-Diffusion and Mean Displacement of Hydrogen on Graphite and a PEM Fuel Cell Catalyst Support
journal, October 2009

  • Haas, Ole-Erich; Simon, Jean Marc; Kjelstrup, Signe
  • The Journal of Physical Chemistry C, Vol. 113, Issue 47
  • DOI: 10.1021/jp902491s

Vibration and diffusion of Cs atoms on Cu(001)
journal, July 2007


Dynamics of adatoms on solid surfaces
journal, May 1994


Generalized Chudley-Elliott vibration-jump model in activated atom surface diffusion
journal, May 2007

  • Martínez-Casado, R.; Vega, J. L.; Sanz, A. S.
  • The Journal of Chemical Physics, Vol. 126, Issue 19
  • DOI: 10.1063/1.2735586

Effects of resolution and friction in the interpretation of QHAS measurements
journal, May 2004

  • Jardine, A. P.; Ellis, J.; Allison, W.
  • The Journal of Chemical Physics, Vol. 120, Issue 18
  • DOI: 10.1063/1.1695320

Atomic scale friction of molecular adsorbates during diffusion
journal, May 2013

  • Lechner, B. A. J.; de Wijn, A. S.; Hedgeland, H.
  • The Journal of Chemical Physics, Vol. 138, Issue 19
  • DOI: 10.1063/1.4804269

Linear response theory of activated surface diffusion with interacting adsorbates
journal, May 2010


Self-diffusion on low-index metallic surfaces: Ag and Au (100) and (111)
journal, July 1996


Multiple hops in multidimensional activated surface diffusion
journal, February 1999


Surface Diffusion of Pt on Pt(110): Arrhenius Behavior of Long Jumps
journal, June 1997


Atomic jumps during surface diffusion
journal, June 2009


The dynamics of activated surface diffusion
journal, November 2005


Diffusion, adsorption, and desorption of molecular hydrogen on graphene and in graphite
journal, July 2013

  • Petucci, Justin; LeBlond, Carl; Karimi, Majid
  • The Journal of Chemical Physics, Vol. 139, Issue 4
  • DOI: 10.1063/1.4813919

Repulsion-Induced Surface-Migration by Ballistics and Bounce
journal, September 2015

  • Guo, Si Yue; Jenkins, Stephen J.; Ji, Wei
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 20
  • DOI: 10.1021/acs.jpclett.5b01829

Nonstochastic Behavior of Atomic Surface Diffusion on Cu(111) down to Low Temperatures
journal, October 2004


Adsorption of Water and Ammonia on Graphene: Evidence for Chemisorption from X-ray Absorption Spectra
journal, July 2017

  • Böttcher, Stefan; Vita, Hendrik; Weser, Martin
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 15
  • DOI: 10.1021/acs.jpclett.7b01085

Electron energy loss spectroscopy of ammonia on Ru(001)
journal, April 1988

  • Parmeter, J. E.; Wang, Y.; Mullins, C. B.
  • The Journal of Chemical Physics, Vol. 88, Issue 8
  • DOI: 10.1063/1.454597

Selectivity in vibrationally mediated single-molecule chemistry
journal, May 2003


Studies of physisorbed ammonia overlayers adsorbed on graphite
journal, December 2005


Works referencing / citing this record:

Nanoscopic diffusion of water on a topological insulator
journal, January 2020


Activated quantum diffusion in a periodic potential above the crossover temperature
journal, July 2019

  • Ianconescu, Reuven; Pollak, Eli
  • The Journal of Chemical Physics, Vol. 151, Issue 2
  • DOI: 10.1063/1.5100010

Polarisation in spin-echo experiments: Multi-point and lock-in measurements
journal, February 2018

  • Tamtögl, Anton; Davey, Benjamin; Ward, David J.
  • Review of Scientific Instruments, Vol. 89, Issue 2
  • DOI: 10.1063/1.5017276

Nanoscopic diffusion of water on a topological insulator.
text, January 2020

  • Tamtögl, Anton; Sacchi, Marco; Avidor, Nadav
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.48374