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Title: Exciting H2 Molecules for Graphene Functionalization

Abstract

Hydrogen functionalization of graphene by exposure to vibrationally excited H2 molecules is investigated by combined scanning tunneling microscopy, high-resolution electron energy loss spectroscopy, X-ray photoelectron spectroscopy measurements, and density functional theory calculations. The measurements reveal that vibrationally excited H2 molecules dissociatively adsorb on graphene on Ir(111) resulting in nanopatterned hydrogen functionalization structures. Calculations demonstrate that the presence of the Ir surface below the graphene lowers the H2 dissociative adsorption barrier and allows for the adsorption reaction at energies well below the dissociation threshold of the H–H bond. The first reacting H2 molecule must contain considerable vibrational energy to overcome the dissociative adsorption barrier. However, this initial adsorption further activates the surface resulting in reduced barriers for dissociative adsorption of subsequent H2 molecules. This enables functionalization by H2 molecules with lower vibrational energy, yielding an avalanche effect for the hydrogenation reaction. These results provide an example of a catalytically active graphene-coated surface and additionally set the stage for a re-interpretation of previous experimental work involving elevated H2 background gas pressures in the presence of hot filaments.

Authors:
 [1];  [2];  [1];  [1];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [2];  [1];  [3];  [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [5];  [3]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Aarhus Univ. (Denmark)
  2. Aix-Marseille Univ., Marseille (France)
  3. Lund Univ. (Sweden)
  4. Elettra-Sincrotrone, Trieste (Italy)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS) and Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Danish Council for Independent Research; Innovation Fund Denmark; European Research Council (ERC); Villum Foundation
OSTI Identifier:
1638185
Grant/Contract Number:  
AC02-05CH11231; 0602-02566B; 0602-02265B; 11744
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 1; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; graphene; vibrational excitation; nanostructured functionalization; band gap engineering; molecular hydrogen; catalysis

Citation Formats

Kyhl, Line, Bisson, Régis, Balog, Richard, Groves, Michael N., Kolsbjerg, Esben Leonhard, Cassidy, Andrew Martin, Jørgensen, Jakob Holm, Halkjær, Susanne, Miwa, Jill A., Grubišić Čabo, Antonija, Angot, Thierry, Hofmann, Philip, Arman, Mohammad Alif, Urpelainen, Samuli, Lacovig, Paolo, Bignardi, Luca, Bluhm, Hendrik, Knudsen, Jan, Hammer, Bjørk, and Hornekaer, Liv. Exciting H2 Molecules for Graphene Functionalization. United States: N. p., 2017. Web. doi:10.1021/acsnano.7b07079.
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Kyhl, Line, Bisson, Régis, Balog, Richard, Groves, Michael N., Kolsbjerg, Esben Leonhard, Cassidy, Andrew Martin, Jørgensen, Jakob Holm, Halkjær, Susanne, Miwa, Jill A., Grubišić Čabo, Antonija, Angot, Thierry, Hofmann, Philip, Arman, Mohammad Alif, Urpelainen, Samuli, Lacovig, Paolo, Bignardi, Luca, Bluhm, Hendrik, Knudsen, Jan, Hammer, Bjørk, & Hornekaer, Liv. Exciting H2 Molecules for Graphene Functionalization. United States. https://doi.org/10.1021/acsnano.7b07079
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Kyhl, Line, Bisson, Régis, Balog, Richard, Groves, Michael N., Kolsbjerg, Esben Leonhard, Cassidy, Andrew Martin, Jørgensen, Jakob Holm, Halkjær, Susanne, Miwa, Jill A., Grubišić Čabo, Antonija, Angot, Thierry, Hofmann, Philip, Arman, Mohammad Alif, Urpelainen, Samuli, Lacovig, Paolo, Bignardi, Luca, Bluhm, Hendrik, Knudsen, Jan, Hammer, Bjørk, and Hornekaer, Liv. Mon . "Exciting H2 Molecules for Graphene Functionalization". United States. https://doi.org/10.1021/acsnano.7b07079. https://www.osti.gov/servlets/purl/1638185.
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@article{osti_1638185,
title = {Exciting H2 Molecules for Graphene Functionalization},
author = {Kyhl, Line and Bisson, Régis and Balog, Richard and Groves, Michael N. and Kolsbjerg, Esben Leonhard and Cassidy, Andrew Martin and Jørgensen, Jakob Holm and Halkjær, Susanne and Miwa, Jill A. and Grubišić Čabo, Antonija and Angot, Thierry and Hofmann, Philip and Arman, Mohammad Alif and Urpelainen, Samuli and Lacovig, Paolo and Bignardi, Luca and Bluhm, Hendrik and Knudsen, Jan and Hammer, Bjørk and Hornekaer, Liv},
abstractNote = {Hydrogen functionalization of graphene by exposure to vibrationally excited H2 molecules is investigated by combined scanning tunneling microscopy, high-resolution electron energy loss spectroscopy, X-ray photoelectron spectroscopy measurements, and density functional theory calculations. The measurements reveal that vibrationally excited H2 molecules dissociatively adsorb on graphene on Ir(111) resulting in nanopatterned hydrogen functionalization structures. Calculations demonstrate that the presence of the Ir surface below the graphene lowers the H2 dissociative adsorption barrier and allows for the adsorption reaction at energies well below the dissociation threshold of the H–H bond. The first reacting H2 molecule must contain considerable vibrational energy to overcome the dissociative adsorption barrier. However, this initial adsorption further activates the surface resulting in reduced barriers for dissociative adsorption of subsequent H2 molecules. This enables functionalization by H2 molecules with lower vibrational energy, yielding an avalanche effect for the hydrogenation reaction. These results provide an example of a catalytically active graphene-coated surface and additionally set the stage for a re-interpretation of previous experimental work involving elevated H2 background gas pressures in the presence of hot filaments.},
doi = {10.1021/acsnano.7b07079},
journal = {ACS Nano},
number = 1,
volume = 12,
place = {United States},
year = {Mon Dec 18 00:00:00 EST 2017},
month = {Mon Dec 18 00:00:00 EST 2017}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acsnano.7b07079
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Cited by: 22 works
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Figures / Tables:

Figure 1 Figure 1: (a−d) STM images of gr/Ir(111) exposed to vibrationally excited H2 or D2: (a) H2 with method (i) at P = 2 x 10−5 mbar for 32 min. (b) D2 with method (ii) at P = 5 x 10−7 mbar for 20 min, TW > 2000 K. Features ofmore » types I and II are indicated with circles. The rhombus outlines a moiré unit cell, the “*” and the “+” denote the FCC and HCP areas, respectively, and the corners of the rhombus mark the atop regions. (c) D2 with method (ii) at P = 5 x 10−7 mbar for 60 min, TW > 2000 K. A type III feature is outlined. (d) D2 with method (ii) at P = 5 x 10−7 mbar for 60 min, TW > 2000 K. (e) Time evolution of hydrogenation structures during exposure to vibrationally excited H2, using method (i), at P = 1 x 10−5 mbar. Red dots: Total number of nucleation sites, normalized to the imaged area, plotted against time. Error bars represent the intrinsic error assuming a Poisson distribution. Blue triangles: Apparent hydrogenated area, in % of total image area, plotted against time. (f) A line profile through the Fourier transform shown in the inset, along the line indicated. The Fourier transform is performed on a larger scale STM image (see Supporting Information, S2) in the same area as shown in the STM image in (d). The Fourier transform illustrates a high degree of order on the surface after the exposure to vibrationally excited H2. The separation of the peaks indicated by arrows in the line profile corresponds to a real space separation of ∼21.5 Å which equals ∼25 Å x cos(30°), confirming a global hydrogen-induced patterning with moiré superlattice periodicity. Imaging parameters for (a−d): (a) Vt = 478.2 mV, It = 0.790 nA. (b) Vt = 67.1 mV, It = 1.090 nA. (c) Vt= −351.9 mV, It = −0.310 nA. (d) Vt = −351.9 mV, It = −0.320 nA.« less
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    Works referencing / citing this record:

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    Characterization of Pt- or Pd-doped graphene based on density functional theory for H 2 gas sensor
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    Hydrogen interaction with graphene on Ir(1 1 1): a combined intercalation and functionalization study
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    • Journal of Physics: Condensed Matter, Vol. 31, Issue 8
    • DOI: 10.1088/1361-648x/aaf76b
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