Exciting H2 Molecules for Graphene Functionalization

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

doi:10.1021/acsnano.7b07079

Title: Exciting H₂ Molecules for Graphene Functionalization

Journal Article · Mon Dec 18 00:00:00 EST 2017 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.7b07079· OSTI ID:1638185

Kyhl, Line ^[1]; Bisson, Régis ^[2]; Balog, Richard ^[1]; Groves, Michael N. ^[1]; Kolsbjerg, Esben Leonhard ^[1];

^[1]; Jørgensen, Jakob Holm ^[1]; Halkjær, Susanne ^[1]; Miwa, Jill A. ^[1]; Grubišić Čabo, Antonija ^[1]; Angot, Thierry ^[2]; Hofmann, Philip ^[1]; Arman, Mohammad Alif ^[3]; Urpelainen, Samuli ^[3];

^[4];

^[5]; Knudsen, Jan ^[3];

^[1];

^[1]

Aarhus Univ. (Denmark)
Aix-Marseille Univ., Marseille (France)
Lund Univ. (Sweden)
Elettra-Sincrotrone, Trieste (Italy)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS) and Chemical Sciences Division

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.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: 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

Grant/Contract Number:: AC02-05CH11231; 0602-02566B; 0602-02265B; 11744

OSTI ID:: 1638185

Journal Information:: ACS Nano, Vol. 12, Issue 1; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 22 works

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Hydrogen interaction with graphene on Ir(1 1 1): a combined intercalation and functionalization study Balog, Richard; Cassidy, Andrew; Jørgensen, Jakob Journal of Physics: Condensed Matter, Vol. 31, Issue 8 https://doi.org/10.1088/1361-648x/aaf76b	journal	January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
graphene
vibrational excitation
nanostructured functionalization
band gap engineering
molecular hydrogen
catalysis

Title: Exciting H2 Molecules for Graphene Functionalization

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