Structure evolution of graphitic surface upon oxidation: insights by scanning tunneling microscopy
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{
"revision": 5,
"id": "1609",
"created": "2023-01-11T15:44:02.734781+00:00",
"metadata": {
"doi": "10.24435/materialscloud:gx-se",
"status": "published",
"title": "Structure evolution of graphitic surface upon oxidation: insights by scanning tunneling microscopy",
"mcid": "2023.8",
"license_addendum": "Creative Commons Attribution Non Commercial No Derivatives 4.0 International (CC BY-NC-ND 4.0)",
"_files": [
{
"description": "Data set.",
"key": "2022, JACS Au, Shaoxian.rar",
"size": 19014323,
"checksum": "md5:3fcee78214c015a88ecfa83fcff567ef"
}
],
"owner": 920,
"_oai": {
"id": "oai:materialscloud.org:1609"
},
"keywords": [
"oxidation",
"functionalization",
"graphitic materials",
"vacancies",
"epoxy",
"ether",
"clusters",
"scanning tunneling microscopy",
"experimental",
"MARVEL"
],
"conceptrecid": "1608",
"is_last": true,
"references": [
{
"type": "Journal reference",
"doi": "10.1021/jacsau.1c00570",
"url": "https://pubs.acs.org/doi/full/10.1021/jacsau.1c00570",
"comment": "Paper in which the method is described",
"citation": "S. Li, M.T. Vahdat, S. Huang, K.J. Hsu, M. Rezaei, M. Mensi, N. Marzari, K.V. Agrawal, JACS Au 2, 723-730 (2022)."
}
],
"publication_date": "Jan 12, 2023, 14:06:45",
"license": "Creative Commons Attribution Non Commercial 4.0 International",
"id": "1609",
"description": "Oxidation of graphitic materials has been studied for more than a century to synthesize materials such as graphene oxide, nanoporous graphene, and to cut or unzip carbon nanotubes. However, the understanding of the early stages of oxidation is limited to theoretical studies, and experimental validation has been elusive. This is due to (i) challenging sample preparation for characterization because of the presence of highly mobile and reactive epoxy groups formed during oxidation, and (ii) gasification of the functional groups during imaging with atomic resolution, e.g., by transmission electron microscopy. Herein, we utilize a low-temperature scanning tunneling microscope (LT-STM) operating at 4 K to solve the structure of epoxy clusters form upon oxidation. Three distinct nanostructures corresponding to three stages of evolution of vacancy defects are found by quantitatively verifying the experimental data by the van der Waals density functional theory. The smallest cluster is a cyclic epoxy trimer. Their observation validates the theoretical prediction that epoxy trimers minimize the energy in the cyclic structure. The trimers grow into honeycomb superstructures to form larger clusters (1\u20133 nm). Vacancy defects evolve only in the larger clusters (2\u20133 nm) in the middle of the cluster, highlighting the role of lattice strain in the generation of vacancies. Semiquinone groups are also present and are assigned at the carbon edge in the vacancy defects. Upon heating to 800 \u00b0C, we observe cluster-free vacancy defects resulting from the loss of the entire epoxy population, indicating a reversible functionalization of epoxy groups.",
"version": 1,
"contributors": [
{
"email": "shaoxian.li@epfl.ch",
"affiliations": [
"Institut des Sciences et Ing\u00e9nierie Chimiques, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), CH-1951 Sion, Valais, Switzerland"
],
"familyname": "Li",
"givennames": "Shaoxian"
},
{
"email": "mohammad.vahdat@epfl.ch",
"affiliations": [
"Institut des Sciences et Ing\u00e9nierie Chimiques, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), CH-1951 Sion, Valais, Switzerland",
"Theory and Simulation of Materials (THEOS), National Centre for Computational Design and Discovery of Novel Materials (MARVEL), E\u0301cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), Lausanne 1015, Switzerland"
],
"familyname": "Tohidi Vahdat",
"givennames": "Mohammad"
},
{
"email": "shiqi.huang@epfl.ch",
"affiliations": [
"Institut des Sciences et Ing\u00e9nierie Chimiques, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), CH-1951 Sion, Valais, Switzerland"
],
"familyname": "Huang",
"givennames": "Shiqi"
},
{
"email": "kuang-jung.hsu@epfl.ch",
"affiliations": [
"Institut des Sciences et Ing\u00e9nierie Chimiques, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), CH-1951 Sion, Valais, Switzerland"
],
"familyname": "Hsu",
"givennames": "Kuang-Jung"
},
{
"email": "mojtaba.rezaei@epfl.ch",
"affiliations": [
"Institut des Sciences et Ing\u00e9nierie Chimiques, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), CH-1951 Sion, Valais, Switzerland"
],
"familyname": "Rezaei",
"givennames": "Mojtaba"
},
{
"email": "mounir.mensi@epfl.ch",
"affiliations": [
"Institut des Sciences et Ing\u00e9nierie Chimiques (ISIC), E\u0301cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), Sion 1950, Switzerland"
],
"familyname": "Mensi",
"givennames": "Mounir"
},
{
"email": "nicola.marzari@epfl.ch",
"affiliations": [
"Theory and Simulation of Materials (THEOS), National Centre for Computational Design and Discovery of Novel Materials (MARVEL), E\u0301cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), Lausanne 1015, Switzerland"
],
"familyname": "Marzari",
"givennames": "Nicola"
},
{
"email": "kumar.agrawal@epfl.ch",
"affiliations": [
"Institut des Sciences et Ing\u00e9nierie Chimiques, \u00c9cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), CH-1951 Sion, Valais, Switzerland"
],
"familyname": "Agrawal",
"givennames": "Kumar Varoon"
}
],
"edited_by": 576
},
"updated": "2023-01-12T13:06:45.169353+00:00"
}