Formation of Supported Graphene Oxide: Evidence for Enolate Species

Zbynek Novotny; Manh Thuong Nguyen; Falko P. Netzer; Vassiliki Alexandra Glezakou; Roger Rousseau; Zdenek Dohnálek

doi:10.1021/jacs.7b12791

Formation of Supported Graphene Oxide: Evidence for Enolate Species

Zbynek Novotny, Manh Thuong Nguyen, Falko P. Netzer, Vassiliki Alexandra Glezakou, Roger Rousseau, Zdenek Dohnálek

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Graphene oxides are promising materials for novel electronic devices or anchoring of the active sites for catalytic applications. Here we focus on understanding the atomic oxygen (AO) binding and mobility on different regions of graphene (Gr) on Ru(0001). Differences in the Gr/Ru lattices result in the superstructure, which offers an array of distinct adsorption sites. We employ scanning tunneling microscopy and density functional theory to map out the chemical identity and stability of prepared AO functionalities in different Gr regions. The AO diffusion is utilized to establish that in the regions that are close to the metal substrate the terminally bonded enolate groups are strongly preferred over bridge-bonded epoxy groups. No oxygen species are observed on the graphene regions that are far from the underlying Ru, indicating their low relative stability. This study provides a clear fundamental basis for understanding the local structural, electronic factors and C-Ru bond strengthening/weakening processes that affect the stability of enolate and epoxy species.

Original language	English
Pages (from-to)	5102-5109
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	140
Issue number	15
DOIs	https://doi.org/10.1021/jacs.7b12791
State	Published - Apr 18 2018
Externally published	Yes

Funding

We thank Michael Schmid for development of a custom ImageJ macros, Ryan T. Frederick for assistance during the acquisition of small portion of the experimental data, Rentao Mu for numerous discussions in the early stages of this project, and Marcella Iannuzzi for sharing DFT graphene/Ru(0001) structures. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences and performed in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational Resources were provided by a user proposal at the NERSC user facility located at Lawrence Berkley National Laboratory, FPN acknowledges the award of an Alternate Sponsored Fellowship at PNNL and financial support of the University of Graz. The cover image was created by Cortland Johnson and Vassiliki-Alexandra Glezakou, PNNL.

Funders	Funder number
Office of Basic Energy Sciences
Office of Biological and Environmental Research
US Department of Energy
U.S. Department of Energy
Pacific Northwest National Laboratory
Chemical Sciences, Geosciences, and Biosciences Division
Karl-Franzens-Universität Graz

Access to Document

10.1021/jacs.7b12791

Cite this

@article{cba7d82c98d144068c183034a0da3582,

title = "Formation of Supported Graphene Oxide: Evidence for Enolate Species",

abstract = "Graphene oxides are promising materials for novel electronic devices or anchoring of the active sites for catalytic applications. Here we focus on understanding the atomic oxygen (AO) binding and mobility on different regions of graphene (Gr) on Ru(0001). Differences in the Gr/Ru lattices result in the superstructure, which offers an array of distinct adsorption sites. We employ scanning tunneling microscopy and density functional theory to map out the chemical identity and stability of prepared AO functionalities in different Gr regions. The AO diffusion is utilized to establish that in the regions that are close to the metal substrate the terminally bonded enolate groups are strongly preferred over bridge-bonded epoxy groups. No oxygen species are observed on the graphene regions that are far from the underlying Ru, indicating their low relative stability. This study provides a clear fundamental basis for understanding the local structural, electronic factors and C-Ru bond strengthening/weakening processes that affect the stability of enolate and epoxy species.",

author = "Zbynek Novotny and Nguyen, {Manh Thuong} and Netzer, {Falko P.} and Glezakou, {Vassiliki Alexandra} and Roger Rousseau and Zdenek Dohn{\'a}lek",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = apr,

day = "18",

doi = "10.1021/jacs.7b12791",

language = "English",

volume = "140",

pages = "5102--5109",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Formation of Supported Graphene Oxide

T2 - Evidence for Enolate Species

AU - Novotny, Zbynek

AU - Nguyen, Manh Thuong

AU - Netzer, Falko P.

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

AU - Dohnálek, Zdenek

PY - 2018/4/18

Y1 - 2018/4/18

N2 - Graphene oxides are promising materials for novel electronic devices or anchoring of the active sites for catalytic applications. Here we focus on understanding the atomic oxygen (AO) binding and mobility on different regions of graphene (Gr) on Ru(0001). Differences in the Gr/Ru lattices result in the superstructure, which offers an array of distinct adsorption sites. We employ scanning tunneling microscopy and density functional theory to map out the chemical identity and stability of prepared AO functionalities in different Gr regions. The AO diffusion is utilized to establish that in the regions that are close to the metal substrate the terminally bonded enolate groups are strongly preferred over bridge-bonded epoxy groups. No oxygen species are observed on the graphene regions that are far from the underlying Ru, indicating their low relative stability. This study provides a clear fundamental basis for understanding the local structural, electronic factors and C-Ru bond strengthening/weakening processes that affect the stability of enolate and epoxy species.

AB - Graphene oxides are promising materials for novel electronic devices or anchoring of the active sites for catalytic applications. Here we focus on understanding the atomic oxygen (AO) binding and mobility on different regions of graphene (Gr) on Ru(0001). Differences in the Gr/Ru lattices result in the superstructure, which offers an array of distinct adsorption sites. We employ scanning tunneling microscopy and density functional theory to map out the chemical identity and stability of prepared AO functionalities in different Gr regions. The AO diffusion is utilized to establish that in the regions that are close to the metal substrate the terminally bonded enolate groups are strongly preferred over bridge-bonded epoxy groups. No oxygen species are observed on the graphene regions that are far from the underlying Ru, indicating their low relative stability. This study provides a clear fundamental basis for understanding the local structural, electronic factors and C-Ru bond strengthening/weakening processes that affect the stability of enolate and epoxy species.

UR - http://www.scopus.com/inward/record.url?scp=85045565641&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b12791

DO - 10.1021/jacs.7b12791

M3 - Article

C2 - 29401394

AN - SCOPUS:85045565641

SN - 0002-7863

VL - 140

SP - 5102

EP - 5109

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 15

ER -

Formation of Supported Graphene Oxide: Evidence for Enolate Species

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this