The role of oxygen during thermal reduction of graphene oxide studied by infrared absorption spectroscopy

Muge Acik, Geunsik Lee, Cecilia Mattevi, Adam Pirkle, Robert M. Wallace, Manish Chhowalla, Kyeongjae Cho, Yves Chabal

Research output: Contribution to journalArticle

424 Citations (Scopus)

Abstract

Understanding the thermal reduction of graphene oxide (GO) is important for graphene exfoliation, and chemical and morphological modifications. In this process, the role of trapped water and the evolution of oxygen during annealing are still not well-understood. To unravel the complex mechanisms leading to the removal of oxygen in reduced GO, we have performed in situ transmission infrared absorption spectroscopy measurements of GO films upon thermal annealing at 60-850°C in vacuum (10-3-10-4 Torr). Using cluster-based first-principles calculations, epoxides, ethers (pyrans and furans), hydroxyls, carboxyls, lactols, and various types of ketones and their possible derivatives have been identified from the spectroscopic data. Furthermore, the interactions between randomly arranged nearby oxygen species are found to affect the spectral response (red and blue shifts) and the overall chemistry during annealing. For instance, the initial composition of oxygen species (relative amounts and types of species, such as hydroxyls, carboxyls, and carbonyls) and reduction times determine the final oxygen concentration (% of initial concentrations), varying from ∼46-92% in multilayer GO to ∼3-5% in single-layer GO. In the multilayer case, there is no dependence on the layer thickness. An important indicator of the reduction efficiency is the relative concentration of carbonyls at intermediate annealing temperatures (∼200°C). These observations suggest that thermal annealing can foster the formation of free radicals containing oxygen in the presence of trapped water in GO, which further attack carboxyls, hydroxyls, and carbonyls, preferentially at edges rather than on basal plane defects. These findings impact the fabrication of electronics and energy storage devices.

Original languageEnglish
Pages (from-to)19761-19781
Number of pages21
JournalJournal of Physical Chemistry C
Volume115
Issue number40
DOIs
Publication statusPublished - Oct 13 2011

Fingerprint

Graphite
Infrared absorption
Absorption spectroscopy
Oxides
Graphene
infrared absorption
Infrared spectroscopy
graphene
absorption spectroscopy
infrared spectroscopy
Oxygen
oxides
oxygen
Annealing
annealing
Hydroxyl Radical
Multilayers
Furans
Pyrans
Ethers

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

The role of oxygen during thermal reduction of graphene oxide studied by infrared absorption spectroscopy. / Acik, Muge; Lee, Geunsik; Mattevi, Cecilia; Pirkle, Adam; Wallace, Robert M.; Chhowalla, Manish; Cho, Kyeongjae; Chabal, Yves.

In: Journal of Physical Chemistry C, Vol. 115, No. 40, 13.10.2011, p. 19761-19781.

Research output: Contribution to journalArticle

Acik, Muge ; Lee, Geunsik ; Mattevi, Cecilia ; Pirkle, Adam ; Wallace, Robert M. ; Chhowalla, Manish ; Cho, Kyeongjae ; Chabal, Yves. / The role of oxygen during thermal reduction of graphene oxide studied by infrared absorption spectroscopy. In: Journal of Physical Chemistry C. 2011 ; Vol. 115, No. 40. pp. 19761-19781.
@article{965812180eef47a9ba7b86d0a7dfdb04,
title = "The role of oxygen during thermal reduction of graphene oxide studied by infrared absorption spectroscopy",
abstract = "Understanding the thermal reduction of graphene oxide (GO) is important for graphene exfoliation, and chemical and morphological modifications. In this process, the role of trapped water and the evolution of oxygen during annealing are still not well-understood. To unravel the complex mechanisms leading to the removal of oxygen in reduced GO, we have performed in situ transmission infrared absorption spectroscopy measurements of GO films upon thermal annealing at 60-850°C in vacuum (10-3-10-4 Torr). Using cluster-based first-principles calculations, epoxides, ethers (pyrans and furans), hydroxyls, carboxyls, lactols, and various types of ketones and their possible derivatives have been identified from the spectroscopic data. Furthermore, the interactions between randomly arranged nearby oxygen species are found to affect the spectral response (red and blue shifts) and the overall chemistry during annealing. For instance, the initial composition of oxygen species (relative amounts and types of species, such as hydroxyls, carboxyls, and carbonyls) and reduction times determine the final oxygen concentration ({\%} of initial concentrations), varying from ∼46-92{\%} in multilayer GO to ∼3-5{\%} in single-layer GO. In the multilayer case, there is no dependence on the layer thickness. An important indicator of the reduction efficiency is the relative concentration of carbonyls at intermediate annealing temperatures (∼200°C). These observations suggest that thermal annealing can foster the formation of free radicals containing oxygen in the presence of trapped water in GO, which further attack carboxyls, hydroxyls, and carbonyls, preferentially at edges rather than on basal plane defects. These findings impact the fabrication of electronics and energy storage devices.",
author = "Muge Acik and Geunsik Lee and Cecilia Mattevi and Adam Pirkle and Wallace, {Robert M.} and Manish Chhowalla and Kyeongjae Cho and Yves Chabal",
year = "2011",
month = "10",
day = "13",
doi = "10.1021/jp2052618",
language = "English",
volume = "115",
pages = "19761--19781",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "40",

}

TY - JOUR

T1 - The role of oxygen during thermal reduction of graphene oxide studied by infrared absorption spectroscopy

AU - Acik, Muge

AU - Lee, Geunsik

AU - Mattevi, Cecilia

AU - Pirkle, Adam

AU - Wallace, Robert M.

AU - Chhowalla, Manish

AU - Cho, Kyeongjae

AU - Chabal, Yves

PY - 2011/10/13

Y1 - 2011/10/13

N2 - Understanding the thermal reduction of graphene oxide (GO) is important for graphene exfoliation, and chemical and morphological modifications. In this process, the role of trapped water and the evolution of oxygen during annealing are still not well-understood. To unravel the complex mechanisms leading to the removal of oxygen in reduced GO, we have performed in situ transmission infrared absorption spectroscopy measurements of GO films upon thermal annealing at 60-850°C in vacuum (10-3-10-4 Torr). Using cluster-based first-principles calculations, epoxides, ethers (pyrans and furans), hydroxyls, carboxyls, lactols, and various types of ketones and their possible derivatives have been identified from the spectroscopic data. Furthermore, the interactions between randomly arranged nearby oxygen species are found to affect the spectral response (red and blue shifts) and the overall chemistry during annealing. For instance, the initial composition of oxygen species (relative amounts and types of species, such as hydroxyls, carboxyls, and carbonyls) and reduction times determine the final oxygen concentration (% of initial concentrations), varying from ∼46-92% in multilayer GO to ∼3-5% in single-layer GO. In the multilayer case, there is no dependence on the layer thickness. An important indicator of the reduction efficiency is the relative concentration of carbonyls at intermediate annealing temperatures (∼200°C). These observations suggest that thermal annealing can foster the formation of free radicals containing oxygen in the presence of trapped water in GO, which further attack carboxyls, hydroxyls, and carbonyls, preferentially at edges rather than on basal plane defects. These findings impact the fabrication of electronics and energy storage devices.

AB - Understanding the thermal reduction of graphene oxide (GO) is important for graphene exfoliation, and chemical and morphological modifications. In this process, the role of trapped water and the evolution of oxygen during annealing are still not well-understood. To unravel the complex mechanisms leading to the removal of oxygen in reduced GO, we have performed in situ transmission infrared absorption spectroscopy measurements of GO films upon thermal annealing at 60-850°C in vacuum (10-3-10-4 Torr). Using cluster-based first-principles calculations, epoxides, ethers (pyrans and furans), hydroxyls, carboxyls, lactols, and various types of ketones and their possible derivatives have been identified from the spectroscopic data. Furthermore, the interactions between randomly arranged nearby oxygen species are found to affect the spectral response (red and blue shifts) and the overall chemistry during annealing. For instance, the initial composition of oxygen species (relative amounts and types of species, such as hydroxyls, carboxyls, and carbonyls) and reduction times determine the final oxygen concentration (% of initial concentrations), varying from ∼46-92% in multilayer GO to ∼3-5% in single-layer GO. In the multilayer case, there is no dependence on the layer thickness. An important indicator of the reduction efficiency is the relative concentration of carbonyls at intermediate annealing temperatures (∼200°C). These observations suggest that thermal annealing can foster the formation of free radicals containing oxygen in the presence of trapped water in GO, which further attack carboxyls, hydroxyls, and carbonyls, preferentially at edges rather than on basal plane defects. These findings impact the fabrication of electronics and energy storage devices.

UR - http://www.scopus.com/inward/record.url?scp=80053900341&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80053900341&partnerID=8YFLogxK

U2 - 10.1021/jp2052618

DO - 10.1021/jp2052618

M3 - Article

AN - SCOPUS:80053900341

VL - 115

SP - 19761

EP - 19781

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 40

ER -