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Title: Reduction of Graphene Oxide Thin Films by Cobaltocene and Decamethylcobaltocene

Abstract

Reduced graphene oxide (RGO) films have been prepared by immersion of graphene oxide (GO) films at room temperature in nonaqueous solutions containing simple, outer-sphere metallocene reductants. Specifically, solutions of cobaltocene, cobaltocene and trifluoroacetic acid (TFA), and decamethylcobaltocene each showed activity for the rapid reduction of GO films cast on a wide variety of substrates. Each reactant increased the conductivity of the films by several orders of magnitude, with RGO films prepared with either decamethylcobaltocene or cobaltocene and TFA possessing the highest conductivities (~104 S m–1). X-ray photoelectron spectroscopy suggested that while all three reagents lowered the content of carbon–oxygen functionalities, solutions of cobaltocene and TFA were the most effective at reducing the material to sp2 carbon. Separately, Raman spectra and atomic force micrographs indicated that RGO films prepared with decamethylcobaltocene consisted of the largest graphitic domains and lowest macroscopic roughness. Cumulatively, the data suggest that the outer-sphere reductants can affect the conversion to RGO but the reactivity and mechanism depend on the standard potential of the reductant and the availability of protons. This work both demonstrates a new way to prepare high-quality RGO films on a wide range of substrate materials without annealing and motivates future work to elucidate themore » chemistry of RGO synthesis through the tunability of outer-sphere reductants such as metallocenes.« less

Authors:
; ; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1415332
Alternate Identifier(s):
OSTI ID: 1508282
Grant/Contract Number:  
SC006628; SC0006628
Resource Type:
Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Name: ACS Applied Materials and Interfaces Journal Volume: 10 Journal Issue: 2; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electrochemical; graphene oxide; metallocene; outer-sphere reductant; reduced graphene oxide

Citation Formats

MacInnes, Molly M., Hlynchuk, Sofiya, Acharya, Saurabh, Lehnert, Nicolai, and Maldonado, Stephen. Reduction of Graphene Oxide Thin Films by Cobaltocene and Decamethylcobaltocene. United States: N. p., 2017. Web. https://doi.org/10.1021/acsami.7b15599.
MacInnes, Molly M., Hlynchuk, Sofiya, Acharya, Saurabh, Lehnert, Nicolai, & Maldonado, Stephen. Reduction of Graphene Oxide Thin Films by Cobaltocene and Decamethylcobaltocene. United States. https://doi.org/10.1021/acsami.7b15599
MacInnes, Molly M., Hlynchuk, Sofiya, Acharya, Saurabh, Lehnert, Nicolai, and Maldonado, Stephen. Thu . "Reduction of Graphene Oxide Thin Films by Cobaltocene and Decamethylcobaltocene". United States. https://doi.org/10.1021/acsami.7b15599.
@article{osti_1415332,
title = {Reduction of Graphene Oxide Thin Films by Cobaltocene and Decamethylcobaltocene},
author = {MacInnes, Molly M. and Hlynchuk, Sofiya and Acharya, Saurabh and Lehnert, Nicolai and Maldonado, Stephen},
abstractNote = {Reduced graphene oxide (RGO) films have been prepared by immersion of graphene oxide (GO) films at room temperature in nonaqueous solutions containing simple, outer-sphere metallocene reductants. Specifically, solutions of cobaltocene, cobaltocene and trifluoroacetic acid (TFA), and decamethylcobaltocene each showed activity for the rapid reduction of GO films cast on a wide variety of substrates. Each reactant increased the conductivity of the films by several orders of magnitude, with RGO films prepared with either decamethylcobaltocene or cobaltocene and TFA possessing the highest conductivities (~104 S m–1). X-ray photoelectron spectroscopy suggested that while all three reagents lowered the content of carbon–oxygen functionalities, solutions of cobaltocene and TFA were the most effective at reducing the material to sp2 carbon. Separately, Raman spectra and atomic force micrographs indicated that RGO films prepared with decamethylcobaltocene consisted of the largest graphitic domains and lowest macroscopic roughness. Cumulatively, the data suggest that the outer-sphere reductants can affect the conversion to RGO but the reactivity and mechanism depend on the standard potential of the reductant and the availability of protons. This work both demonstrates a new way to prepare high-quality RGO films on a wide range of substrate materials without annealing and motivates future work to elucidate the chemistry of RGO synthesis through the tunability of outer-sphere reductants such as metallocenes.},
doi = {10.1021/acsami.7b15599},
journal = {ACS Applied Materials and Interfaces},
number = 2,
volume = 10,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsami.7b15599

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Cited by: 3 works
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Figures / Tables:

Table 1 Table 1: Reported Methods for the Preparation of RGO and the Resulting Conductivity

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Works referenced in this record:

Preparation and properties of surface-active organocobalt complexes having long-chain alkyl groups
journal, January 1990

  • Sakai, Shizuyoshi; Takayanagi, Hitoshi; Sumimoto, Norifumi
  • Applied Organometallic Chemistry, Vol. 4, Issue 1
  • DOI: 10.1002/aoc.590040107

Controlled Synthesis of Large-Area and Patterned Electrochemically Reduced Graphene Oxide Films
journal, June 2009

  • Zhou, Ming; Wang, Yuling; Zhai, Yueming
  • Chemistry - A European Journal, Vol. 15, Issue 25
  • DOI: 10.1002/chem.200900596

Colloidal Suspensions of Highly Reduced Graphene Oxide in a Wide Variety of Organic Solvents
journal, April 2009

  • Park, Sungjin; An, Jinho; Jung, Inhwa
  • Nano Letters, Vol. 9, Issue 4, p. 1593-1597
  • DOI: 10.1021/nl803798y

In situ Raman spectroelectrochemistry of graphene oxide: In situ Raman spectroelectrochemistry of graphene oxide
journal, November 2013

  • Bouša, Milan; Frank, Otakar; Jirka, Ivan
  • physica status solidi (b), Vol. 250, Issue 12
  • DOI: 10.1002/pssb.201300105

Solvent and electrolyte effects on the kinetics of ferrocenium-ferrocene self-exchange. A reevaluation
journal, March 1989

  • Nielson, Roger M.; McManis, George E.; Safford, Lance K.
  • The Journal of Physical Chemistry, Vol. 93, Issue 5
  • DOI: 10.1021/j100342a086

Influence of the growth temperature on the first and second-order Raman band ratios and widths of carbon nanotubes and fibers
journal, August 2012


Statistical Raman Microscopy and Atomic Force Microscopy on Heterogeneous Graphene Obtained after Reduction of Graphene Oxide
journal, March 2014

  • Eigler, Siegfried; Hof, Ferdinand; Enzelberger-Heim, Michael
  • The Journal of Physical Chemistry C, Vol. 118, Issue 14
  • DOI: 10.1021/jp500580g

Characterisation of reduced graphene oxide: Effects of reduction variables on electrical conductivity
journal, March 2015

  • Mohan, Velram Balaji; Brown, Reuben; Jayaraman, Krishnan
  • Materials Science and Engineering: B, Vol. 193
  • DOI: 10.1016/j.mseb.2014.11.002

Raman spectra of Graphon carbon black
journal, January 1984


Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide
journal, June 2007


The reduction of graphene oxide
journal, August 2012


Generation of Ultra-High-Molecular-Weight Polyethylene from Metallocenes Immobilized onto N-Doped Graphene Nanoplatelets
journal, January 2013

  • Choi, Baekhap; Lee, Juno; Lee, Seungjun
  • Macromolecular Rapid Communications, Vol. 34, Issue 6
  • DOI: 10.1002/marc.201200768

Thiourea Dioxide as a Green Reductant for the Mass Production of Solution-Based Graphene
journal, December 2012

  • Wang, Yanqing; Sun, Ling; Fugetsu, Bunshi
  • Bulletin of the Chemical Society of Japan, Vol. 85, Issue 12
  • DOI: 10.1246/bcsj.20120174

The Importance of Interbands on the Interpretation of the Raman Spectrum of Graphene Oxide
journal, April 2015

  • Claramunt, Sergi; Varea, Aïda; López-Díaz, David
  • The Journal of Physical Chemistry C, Vol. 119, Issue 18
  • DOI: 10.1021/acs.jpcc.5b01590

Quantifying ion-induced defects and Raman relaxation length in graphene
journal, April 2010


Direct reduction of graphene oxide films into highly conductive and flexible graphene films by hydrohalic acids
journal, December 2010


Electrochemical reduction of substituted cobalticinium cations in aqueous media
journal, December 1981


Water-enhanced oxidation of graphite to graphene oxide with controlled species of oxygenated groups
journal, January 2016

  • Chen, Ji; Zhang, Yao; Zhang, Miao
  • Chemical Science, Vol. 7, Issue 3
  • DOI: 10.1039/c5sc03828f

Reactivity of Proton Sources with a Nickel Hydride Complex in Acetonitrile: Implications for the Study of Fuel-Forming Catalysts
journal, May 2016


Raman Spectrum of Graphite
journal, August 1970

  • Tuinstra, F.; Koenig, J. L.
  • The Journal of Chemical Physics, Vol. 53, Issue 3
  • DOI: 10.1063/1.1674108

Evaluation of Solution-Processed Reduced Graphene Oxide Films as Transparent Conductors
journal, February 2008

  • Becerril, Héctor A.; Mao, Jie; Liu, Zunfeng
  • ACS Nano, Vol. 2, Issue 3
  • DOI: 10.1021/nn700375n

Anodic chlorine/nitrogen co-doping of reduced graphene oxide films at room temperature
journal, August 2012


Raman spectroscopy for the study of reduction mechanisms and optimization of conductivity in graphene oxide thin films
journal, January 2013

  • Díez-Betriu, Xavier; Álvarez-García, Susana; Botas, Cristina
  • Journal of Materials Chemistry C, Vol. 1, Issue 41
  • DOI: 10.1039/c3tc31124d

Carbon nanomaterials for electronics, optoelectronics, photovoltaics, and sensing
journal, January 2013

  • Jariwala, Deep; Sangwan, Vinod K.; Lauhon, Lincoln J.
  • Chem. Soc. Rev., Vol. 42, Issue 7
  • DOI: 10.1039/c2cs35335k

Reduced Graphene Oxide Molecular Sensors
journal, October 2008

  • Robinson, Jeremy T.; Perkins, F. Keith; Snow, Eric S.
  • Nano Letters, Vol. 8, Issue 10
  • DOI: 10.1021/nl8013007

In situ FTIR and Raman spectroelectrochemical characterization of graphene oxide upon electrochemical reduction in organic solvents
journal, January 2015

  • Viinikanoja, Antti; Kauppila, Jussi; Damlin, Pia
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 18
  • DOI: 10.1039/c5cp00942a

Reduction of graphene oxide to highly conductive graphene by Lawesson's reagent and its electrical applications
journal, January 2013

  • Liu, Hongtao; Zhang, Lei; Guo, Yunlong
  • Journal of Materials Chemistry C, Vol. 1, Issue 18
  • DOI: 10.1039/c3tc00067b

The Role of Oxygen during Thermal Reduction of Graphene Oxide Studied by Infrared Absorption Spectroscopy
journal, September 2011

  • Acik, Muge; Lee, Geunsik; Mattevi, Cecilia
  • The Journal of Physical Chemistry C, Vol. 115, Issue 40
  • DOI: 10.1021/jp2052618

Raman spectroscopy as a versatile tool for studying the properties of graphene
journal, April 2013


Catalytic N 2 -to-NH 3 Conversion by Fe at Lower Driving Force: A Proposed Role for Metallocene-Mediated PCET
journal, February 2017

  • Chalkley, Matthew J.; Del Castillo, Trevor J.; Matson, Benjamin D.
  • ACS Central Science, Vol. 3, Issue 3
  • DOI: 10.1021/acscentsci.7b00014

Graphene for batteries, supercapacitors and beyond
journal, May 2016


Production of Ultrahigh-Molecular-Weight Polyethylene/Pristine MWCNT Composites by Half-Titanocene Catalysts
journal, February 2009


Electrochemical reduction of graphene oxide films in aqueous and organic solutions
journal, February 2013


Solvent dynamical effects in electron transfer: comparisons of self-exchange kinetics for cobaltocenium-cobaltocene and related redox couples with theoretical predictions
journal, June 1988

  • Nielson, Roger M.; McManis, George E.; Golovin, M. Neal
  • The Journal of Physical Chemistry, Vol. 92, Issue 12
  • DOI: 10.1021/j100323a026

A Chemical Route to Graphene for Device Applications
journal, November 2007

  • Gilje, Scott; Han, Song; Wang, Minsheng
  • Nano Letters, Vol. 7, Issue 11, p. 3394-3398
  • DOI: 10.1021/nl0717715

Vitamin C Is an Ideal Substitute for Hydrazine in the Reduction of Graphene Oxide Suspensions
journal, March 2010

  • Fernández-Merino, M. J.; Guardia, L.; Paredes, J. I.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 14
  • DOI: 10.1021/jp100603h

Transparent, Conductive Graphene Electrodes for Dye-Sensitized Solar Cells
journal, January 2008

  • Wang, Xuan; Zhi, Linjie; Müllen, Klaus
  • Nano Letters, Vol. 8, Issue 1, p. 323-327
  • DOI: 10.1021/nl072838r

Raman spectroscopy in graphene
journal, April 2009


Fundamentals, overtones, and combinations in the Raman spectrum of graphite
journal, October 1995


Dual Path Mechanism in the Thermal Reduction of Graphene Oxide
journal, November 2011

  • Larciprete, Rosanna; Fabris, Stefano; Sun, Tao
  • Journal of the American Chemical Society, Vol. 133, Issue 43
  • DOI: 10.1021/ja205168x

Enhancing the electrical conductivity of vacuum-ultraviolet-reduced graphene oxide by multilayered stacking
journal, May 2017

  • Tu, Yudi; Utsunomiya, Toru; Ichii, Takashi
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 35, Issue 3
  • DOI: 10.1116/1.4982722

An introduction to the chemistry of graphene
journal, January 2015

  • Wang, Xiluan; Shi, Gaoquan
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 43
  • DOI: 10.1039/c5cp05212b

A novel synthesis of ultra thin graphene sheets for energy storage applications using malonic acid as a reducing agent
journal, January 2014

  • Kumar, Anil; Khandelwal, Mahima
  • J. Mater. Chem. A, Vol. 2, Issue 47
  • DOI: 10.1039/c4ta04986a

Kinetics and mechanism of the reduction of protons to hydrogen by cobaltocene
journal, March 1988

  • Koelle, Ulrich; Infelta, Pierre P.; Graetzel, Michael
  • Inorganic Chemistry, Vol. 27, Issue 5
  • DOI: 10.1021/ic00278a026

One-pot reduction of graphene oxide at subzero temperatures
journal, January 2011

  • Cui, Peng; Lee, Junghyun; Hwang, Eunhee
  • Chemical Communications, Vol. 47, Issue 45
  • DOI: 10.1039/c1cc15569e

One-step synthesis of superior dispersion of chemically converted graphene in organic solvents
journal, January 2010

  • Pham, Viet Hung; Cuong, Tran Viet; Nguyen-Phan, Thuy-Duong
  • Chemical Communications, Vol. 46, Issue 24
  • DOI: 10.1039/c0cc00363h

Reducing Graphene Oxide via Hydroxylamine: A Simple and Efficient Route to Graphene
journal, May 2011

  • Zhou, Xuejiao; Zhang, Jiali; Wu, Haixia
  • The Journal of Physical Chemistry C, Vol. 115, Issue 24
  • DOI: 10.1021/jp202575j

Interpretation of Raman spectra of disordered and amorphous carbon
journal, May 2000


Atomic Structure of Reduced Graphene Oxide
journal, April 2010

  • Gómez-Navarro, Cristina; Meyer, Jannik C.; Sundaram, Ravi S.
  • Nano Letters, Vol. 10, Issue 4
  • DOI: 10.1021/nl9031617

Electron transfer between methyl viologen radicals and graphene oxide: Reduction, electron storage and discharge
journal, June 2011

  • Krishnamurthy, Sachidananda; Lightcap, Ian V.; Kamat, Prashant V.
  • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 221, Issue 2-3
  • DOI: 10.1016/j.jphotochem.2011.02.024

A simple and efficient method to prepare graphene by reduction of graphite oxide with sodium hydrosulfite
journal, December 2010


Chemical analysis of graphene oxide films after heat and chemical treatments by X-ray photoelectron and Micro-Raman spectroscopy
journal, January 2009


Reduction of graphite oxide using alcohols
journal, January 2011

  • Dreyer, Daniel R.; Murali, Shanthi; Zhu, Yanwu
  • J. Mater. Chem., Vol. 21, Issue 10
  • DOI: 10.1039/c0jm02704a

Lithium Aluminum Hydride as Reducing Agent for Chemically Reduced Graphene Oxides
journal, June 2012

  • Ambrosi, Adriano; Chua, Chun Kiang; Bonanni, Alessandra
  • Chemistry of Materials, Vol. 24, Issue 12
  • DOI: 10.1021/cm300382b

Probing the chemical nature of surface oxides during coal char oxidation by high-resolution XPS
journal, August 2015


Raman microprobe studies on carbon materials
journal, January 1994


The Anodic Oxidation of Triphenylmethane Dyes
journal, May 1964

  • Galus, Z.; Adams, Ralph N.
  • Journal of the American Chemical Society, Vol. 86, Issue 9
  • DOI: 10.1021/ja01063a003

Sels de cobalticinium
journal, June 1976


Chemical Reduction of Graphene Oxide to Graphene by Sulfur-Containing Compounds
journal, November 2010

  • Chen, Wufeng; Yan, Lifeng; Bangal, P. R.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 47
  • DOI: 10.1021/jp107131v

Graphene production via electrochemical reduction of graphene oxide: Synthesis and characterisation
journal, September 2014

  • Toh, Shaw Yong; Loh, Kee Shyuan; Kamarudin, Siti Kartom
  • Chemical Engineering Journal, Vol. 251
  • DOI: 10.1016/j.cej.2014.04.004

Transparent conductive graphene films prepared by hydroiodic acid and thermal reduction
journal, February 2014


Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information
journal, July 2005


General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy
journal, April 2006

  • Cançado, L. G.; Takai, K.; Enoki, T.
  • Applied Physics Letters, Vol. 88, Issue 16
  • DOI: 10.1063/1.2196057

Highly efficient reduction of graphene oxide using ammonia borane
journal, January 2013

  • Pham, Viet Hung; Hur, Seung Hyun; Kim, Eui Jung
  • Chemical Communications, Vol. 49, Issue 59
  • DOI: 10.1039/c3cc43503b

Efficient Reduction of Graphite Oxide by Sodium Borohydride and Its Effect on Electrical Conductance
journal, June 2009

  • Shin, Hyeon‐Jin; Kim, Ki Kang; Benayad, Anass
  • Advanced Functional Materials, Vol. 19, Issue 12
  • DOI: 10.1002/adfm.200900167

Transparent conductive thin film of ultra large reduced graphene oxide monolayers
journal, March 2014


Facile and controllable electrochemical reduction of graphene oxide and its applications
journal, January 2010

  • Shao, Yuyan; Wang, Jun; Engelhard, Mark
  • J. Mater. Chem., Vol. 20, Issue 4
  • DOI: 10.1039/b917975e

Preparation of graphene by the rapid and mild thermal reduction of graphene oxide induced by microwaves
journal, April 2010


Transparent and conducting electrodes for organic electronics from reduced graphene oxide
journal, June 2008

  • Eda, Goki; Lin, Yun-Yue; Miller, Steve
  • Applied Physics Letters, Vol. 92, Issue 23
  • DOI: 10.1063/1.2937846

A Green Approach to the Synthesis of Graphene Nanosheets
journal, August 2009

  • Guo, Hui-Lin; Wang, Xian-Fei; Qian, Qing-Yun
  • ACS Nano, Vol. 3, Issue 9
  • DOI: 10.1021/nn900227d

New insights into the structure and reduction of graphite oxide
journal, July 2009

  • Gao, Wei; Alemany, Lawrence B.; Ci, Lijie
  • Nature Chemistry, Vol. 1, Issue 5, p. 403-408
  • DOI: 10.1038/nchem.281

Reduction of graphene oxide via l -ascorbic acid
journal, January 2010

  • Zhang, Jiali; Yang, Haijun; Shen, Guangxia
  • Chem. Commun., Vol. 46, Issue 7
  • DOI: 10.1039/b917705a

Radical anions formed by reaction of cobaltocene with protic acids
journal, January 1972

  • Banthorpe, D. V.; Charlwood, B. V.; Wassermann, A.
  • Journal of the Chemical Society, Chemical Communications, Issue 5
  • DOI: 10.1039/c39720000294

Chemical reduction of graphene oxide: a synthetic chemistry viewpoint
journal, January 2014

  • Chua, Chun Kiang; Pumera, Martin
  • Chem. Soc. Rev., Vol. 43, Issue 1
  • DOI: 10.1039/c3cs60303b

Electrical and Spectroscopic Characterizations of Ultra-Large Reduced Graphene Oxide Monolayers
journal, November 2009

  • Su, Ching-Yuan; Xu, Yanping; Zhang, Wenjing
  • Chemistry of Materials, Vol. 21, Issue 23
  • DOI: 10.1021/cm902182y

Carbon Nanotubes as a Ligand in Cp2ZrCl2-Based Ethylene Polymerization
journal, January 2006

  • Park, Sungjin; Yoon, Seung Woong; Lee, Kyung-Bok
  • Macromolecular Rapid Communications, Vol. 27, Issue 1
  • DOI: 10.1002/marc.200500614

Facile heterogenization of a cobalt catalyst via graphene adsorption: robust and versatile dihydrogen production systems
journal, January 2014

  • Eady, Shawn C.; Peczonczyk, Sabrina L.; Maldonado, Stephen
  • Chem. Commun., Vol. 50, Issue 59
  • DOI: 10.1039/c4cc02920h

Reduced graphene oxide by chemical graphitization
journal, September 2010

  • Moon, In Kyu; Lee, Junghyun; Ruoff, Rodney S.
  • Nature Communications, Vol. 1, Issue 1
  • DOI: 10.1038/ncomms1067

Carbon black: a promising electrode material for sodium-ion batteries
journal, November 2001

  • Alcántara, Ricardo; Jiménez-Mateos, Juan M.; Lavela, Pedro
  • Electrochemistry Communications, Vol. 3, Issue 11, p. 639-642
  • DOI: 10.1016/s1388-2481(01)00244-2

Chemical Redox Agents for Organometallic Chemistry
journal, January 1996

  • Connelly, Neil G.; Geiger, William E.
  • Chemical Reviews, Vol. 96, Issue 2
  • DOI: 10.1021/cr940053x

Stable dispersions of graphene and highly conducting graphene films: a new approach to creating colloids of graphene monolayers
journal, January 2009

  • Chen, Yao; Zhang, Xiong; Yu, Peng
  • Chemical Communications, Issue 30
  • DOI: 10.1039/b907723e

Reduction with complex metal hydrides
journal, August 1957

  • Gaylord, Norman G.
  • Journal of Chemical Education, Vol. 34, Issue 8
  • DOI: 10.1021/ed034p367