The role of ozone in the formation and structural evolution of graphene oxide obtained from nanographite

Groveman, Sam; Peng, Jing; Itin, Boris; Diallo, Ibrahim; Pratt, Lawrence M.; Greer, Alexander; Biddinger, Elizabeth J.; Greenbaum, Steve G.; Drain, Charles Michael; Francesconi, Lynn; Vittadello, Michele

doi:10.1016/j.carbon.2017.06.092

Title: The role of ozone in the formation and structural evolution of graphene oxide obtained from nanographite

Journal Article · Wed Jun 28 00:00:00 EDT 2017 · Carbon

DOI:https://doi.org/10.1016/j.carbon.2017.06.092· OSTI ID:1462685

Groveman, Sam ^[1]; Peng, Jing ^[1]; Itin, Boris ^[2]; Diallo, Ibrahim ^[1]; Pratt, Lawrence M. ^[1]; Greer, Alexander ^[3]; Biddinger, Elizabeth J. ^[1]; Greenbaum, Steve G. ^[1]; Drain, Charles Michael ^[1]; Francesconi, Lynn ^[1];

^[1]

City University of New York (CUNY), NY (United States)
New York Structural Biology Center, New York, NY (United States)
Brooklyn College of CUNY, Brooklyn, NY (United States)

Chemical exfoliation of graphite under strong oxidizing conditions yields graphene oxide nanosheets with oxy functional groups on the carbon basal plane. The importance of ozone in the chemical oxidation mechanism of graphite by the widely-used Hummers' method has been largely overlooked. Herein we demonstrate that the ozonolysis of graphite leads to the formation of secondary epoxy and perox-ymonosulfate ester functional groups arising from a rotationally hindered Criegee intermediate and sulfuric acid, in a strongly favored thermodynamic process. This mechanistic step is followed by formation of adjacent epoxy and hydroxy groups as major functionalities on graphene oxides via a radical process, and leaves a significant amount of unreacted peroxides well above levels previously recognized. The thermal decomposition of graphene releases sulfur oxygen species (SO₂ and SO), but does not appear to release ozone even if this reaction pathway is moderately favored thermodynamically. Here we propose anew structural model for graphene oxide based on detailed chemical and spectroscopic data that provides insight into observed chemical reactivity and physical properties, including the antimicrobial activity and protein deactivation.

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Research Organization:: Lawrence Berkeley National Laboratory, Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); City Univ. of New York (CUNY), NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); National Science Foundation (NSF); US Air Force Office of Scientific Research (AFOSR); National Institute on Minority Health and Health Disparities; City University of New York (CUNY)

Grant/Contract Number:: AC02-05CH11231; IGERT 0965983; CHE-1610755; FA9550-16-1-0279; 8G12 MD007599; CHE1464975; 68125-0046

OSTI ID:: 1462685

Alternate ID(s):: OSTI ID: 1576043

Journal Information:: Carbon, Vol. 122, Issue C; ISSN 0008-6223

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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References (51)

Reversible Oxidation of Graphene Through Ultraviolet/Ozone Treatment and Its Nonthermal Reduction through Ultraviolet Irradiation Mulyana, Yana; Uenuma, Mutsunori; Ishikawa, Yasuaki The Journal of Physical Chemistry C, Vol. 118, Issue 47 https://doi.org/10.1021/jp508026g	journal	November 2014
Evolution of Surface Functional Groups in a Series of Progressively Oxidized Graphite Oxides Szabó, Tamás; Berkesi, Ottó; Forgó, Péter Chemistry of Materials, Vol. 18, Issue 11 https://doi.org/10.1021/cm060258+	journal	May 2006
Ozonated Graphene Oxide Film as a Proton-Exchange Membrane Gao, Wei; Wu, Gang; Janicke, Michael T. Angewandte Chemie International Edition, Vol. 53, Issue 14 https://doi.org/10.1002/anie.201310908	journal	February 2014
A new structural model for graphite oxide He, Heyong; Klinowski, Jacek; Forster, Michael Chemical Physics Letters, Vol. 287, Issue 1-2 https://doi.org/10.1016/S0009-2614(98)00144-4	journal	April 1998
Microwave Enabled One-Pot, One-Step Fabrication and Nitrogen Doping of Holey Graphene Oxide for Catalytic Applications Patel, Mehulkumar; Feng, Wenchun; Savaram, Keerthi Small, Vol. 11, Issue 27 https://doi.org/10.1002/smll.201403402	journal	February 2015
The chemistry of graphene oxide Dreyer, Daniel R.; Park, Sungjin; Bielawski, Christopher W. Chem. Soc. Rev., Vol. 39, Issue 1 https://doi.org/10.1039/B917103G	journal	January 2010
Synthesis of Water Soluble Graphene Si, Yongchao; Samulski, Edward T. Nano Letters, Vol. 8, Issue 6 https://doi.org/10.1021/nl080604h	journal	June 2008
Encapsulation and convex-face thiozonolysis of triatomic sulfur (S3) with carbon nanotubes Castillo, Álvaro; Lee, Leda; Greer, Alexander Journal of Physical Organic Chemistry, Vol. 25, Issue 1 https://doi.org/10.1002/poc.1866	journal	June 2011
DRIFT study of deuterium-exchanged graphite oxide Szabó, Tamás; Berkesi, Ottó; Dékány, Imre Carbon, Vol. 43, Issue 15 https://doi.org/10.1016/j.carbon.2005.07.013	journal	December 2005
XPS and SIMS studies of biodegradable suture materials Brinen, J. S.; Greenhouse, S.; Jarrett, P. K. Surface and Interface Analysis, Vol. 17, Issue 5 https://doi.org/10.1002/sia.740170507	journal	May 1991
XPS O 1s binding energies for polymers containing hydroxyl, ether, ketone and ester groups López, Gabriel P.; Castner, David G.; Ratner, Buddy D. Surface and Interface Analysis, Vol. 17, Issue 5 https://doi.org/10.1002/sia.740170508	journal	May 1991
Comparative study of serum protein binding to three different carbon-based nanomaterials Sopotnik, Maja; Leonardi, Adrijana; Križaj, Igor Carbon, Vol. 95 https://doi.org/10.1016/j.carbon.2015.08.018	journal	December 2015
Chemical shift referencing in MAS solid state NMR Morcombe, Corey R.; Zilm, Kurt W. Journal of Magnetic Resonance, Vol. 162, Issue 2 https://doi.org/10.1016/S1090-7807(03)00082-X	journal	June 2003
Reversible Formation of Ammonium Persulfate/Sulfuric Acid Graphite Intercalation Compounds and Their Peculiar Raman Spectra Dimiev, Ayrat M.; Bachilo, Sergei M.; Saito, Riichiro ACS Nano, Vol. 6, Issue 9 https://doi.org/10.1021/nn3020147	journal	August 2012
Biological relevance of oxidative debris present in as-prepared graphene oxide Pattammattel, Ajith; Williams, Christina L.; Pande, Paritosh RSC Advances, Vol. 5, Issue 73 https://doi.org/10.1039/C5RA10306A	journal	January 2015
Water-enhanced oxidation of graphite to graphene oxide with controlled species of oxygenated groups Chen, Ji; Zhang, Yao; Zhang, Miao Chemical Science, Vol. 7, Issue 3 https://doi.org/10.1039/C5SC03828F	journal	January 2016
The Role of Oxygen during Thermal Reduction of Graphene Oxide Studied by Infrared Absorption Spectroscopy Acik, Muge; Lee, Geunsik; Mattevi, Cecilia The Journal of Physical Chemistry C, Vol. 115, Issue 40 https://doi.org/10.1021/jp2052618	journal	September 2011
Mechanism of Graphene Oxide Formation Dimiev, Ayrat M.; Tour, James M. ACS Nano, Vol. 8, Issue 3 https://doi.org/10.1021/nn500606a	journal	March 2014
Auger parameters for sulfur-containing compounds using a mixed aluminum-silver excitation source Yu, Xiang-Rong; Liu, Fen; Wang, Zhong-Yan Journal of Electron Spectroscopy and Related Phenomena, Vol. 50, Issue 2 https://doi.org/10.1016/0368-2048(90)87059-W	journal	January 1990
Advances in charge neutralization for XPS measurements of nonconducting materials Barth, G.; Linder, R.; Bryson, C. Surface and Interface Analysis, Vol. 11, Issue 6-7 https://doi.org/10.1002/sia.740110607	journal	April 1988
13C and 1H MAS NMR studies of graphite oxide and its chemically modified derivatives Lerf, A. Solid State Ionics, Vol. 101-103 https://doi.org/10.1016/S0167-2738(97)00319-6	journal	November 1997
Mechanism of Graphene Oxide as an Enzyme Inhibitor from Molecular Dynamics Simulations Sun, Xiaotian; Feng, Zhiwei; Hou, Tingjun ACS Applied Materials & Interfaces, Vol. 6, Issue 10 https://doi.org/10.1021/am500167c	journal	May 2014
Heteronuclear decoupling in rotating solids Bennett, Andrew E.; Rienstra, Chad M.; Auger, Michèle The Journal of Chemical Physics, Vol. 103, Issue 16 https://doi.org/10.1063/1.470372	journal	October 1995
Pristine Graphite Oxide Dimiev, Ayrat; Kosynkin, Dmitry V.; Alemany, Lawrence B. Journal of the American Chemical Society, Vol. 134, Issue 5 https://doi.org/10.1021/ja211531y	journal	January 2012
High-temperature IR-spectroscopic investigation of the structural and kinetic characteristics of sulfate formation by thermal decomposition of potassium persulfate Lapshin, A. I.; Tleulieva, K. A. Journal of Applied Spectroscopy, Vol. 24, Issue 4 https://doi.org/10.1007/BF00938660	journal	April 1976
Tuning the Electrical and Optical Properties of Graphene by Ozone Treatment for Patterning Monolithic Transparent Electrodes Yuan, Jiangtan; Ma, Lai-Peng; Pei, Songfeng ACS Nano, Vol. 7, Issue 5 https://doi.org/10.1021/nn400682u	journal	April 2013
Synthesis and Solid-State NMR Structural Characterization of 13C-Labeled Graphite Oxide Cai, W.; Piner, R. D.; Stadermann, F. J. Science, Vol. 321, Issue 5897 https://doi.org/10.1126/science.1162369	journal	September 2008
Response of MicroRNAs to In Vitro Treatment with Graphene Oxide Li, Yiping; Wu, Qiuli; Zhao, Yunli ACS Nano, Vol. 8, Issue 3 https://doi.org/10.1021/nn4065378	journal	February 2014
Sulfur Species in Graphene Oxide Eigler, Siegfried; Dotzer, Christoph; Hof, Ferdinand Chemistry - A European Journal, Vol. 19, Issue 29 https://doi.org/10.1002/chem.201300387	journal	June 2013
A theoretical study of the ozonolysis of C₆₀: primary ozonide formation, dissociation, and multiple ozone additions Chapleski, Robert C.; Morris, John R.; Troya, Diego Phys. Chem. Chem. Phys., Vol. 16, Issue 13 https://doi.org/10.1039/C3CP55212H	journal	January 2014
Oxidation Debris in Graphene Oxide Is Responsible for Its Inherent Electroactivity Bonanni, Alessandra; Ambrosi, Adriano; Chua, Chun Kiang ACS Nano, Vol. 8, Issue 5 https://doi.org/10.1021/nn404255q	journal	April 2014
Peroxymonosulfate Rapidly Inactivates the Disease-Associated Prion Protein Chesney, Alexandra R.; Booth, Clarissa J.; Lietz, Christopher B. Environmental Science & Technology, Vol. 50, Issue 13 https://doi.org/10.1021/acs.est.5b06294	journal	June 2016
Ozone Oxidation of Surface-Adsorbed Polycyclic Aromatic Hydrocarbons: Role of PAH−Surface Interaction Chu, Sophie N.; Sands, Sophia; Tomasik, Michelle R. Journal of the American Chemical Society, Vol. 132, Issue 45 https://doi.org/10.1021/ja1014772	journal	October 2010
Availability of the Basal Planes of Graphene Oxide Determines Whether It Is Antibacterial Hui, Liwei; Piao, Ji-Gang; Auletta, Jeffrey ACS Applied Materials & Interfaces, Vol. 6, Issue 15 https://doi.org/10.1021/am503070z	journal	July 2014
Molecular vibrational spectra of potassium peroxymonosulfate, KHSO5 and KHSO5 · H2O, and of the aqueous peroxymonosulfate ion Appelman, Evan H.; Basile, Louis J.; Kim, Hyunyong Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 41, Issue 11 https://doi.org/10.1016/0584-8539(85)80237-3	journal	January 1985
Evolution of Electrical, Chemical, and Structural Properties of Transparent and Conducting Chemically Derived Graphene Thin Films Mattevi, Cecilia; Eda, Goki; Agnoli, Stefano Advanced Functional Materials, Vol. 19, Issue 16 https://doi.org/10.1002/adfm.200900166	journal	August 2009
Effect of Crystallinity on the XPS Spectrum of Poly(Ethylene Terephthalate) Beamson, G.; Clark, D. T.; Hayes, N. W. Surface Science Spectra, Vol. 3, Issue 4 https://doi.org/10.1116/1.1247788	journal	October 1994
Molecular Spectroscopy by Means of ESCA III. Carbon compounds Gelius, U.; Hedén, P. F.; Hedman, J. Physica Scripta, Vol. 2, Issue 1-2 https://doi.org/10.1088/0031-8949/2/1-2/014	journal	July 1970
Adsorption of some substituted ethylene molecules on Pt(111) at 95 K Part 1: NEXAFS, XPS and UPS studies Bournel, F.; Laffon, C.; Parent, Ph. Surface Science, Vol. 350, Issue 1-3 https://doi.org/10.1016/0039-6028(95)01254-0	journal	April 1996
Ramped-Amplitude Cross Polarization in Magic-Angle-Spinning NMR Metz, G.; Wu, X. L.; Smith, S. O. Journal of Magnetic Resonance, Series A, Vol. 110, Issue 2 https://doi.org/10.1006/jmra.1994.1208	journal	October 1994
Hidden Second Oxidation Step of Hummers Method Kang, Jong Hun; Kim, Taehoon; Choi, Jaeyoo Chemistry of Materials, Vol. 28, Issue 3 https://doi.org/10.1021/acs.chemmater.5b03700	journal	January 2016
Direct Observation, Molecular Structure, and Location of Oxidation Debris on Graphene Oxide Nanosheets Chen, Xiaoxiao; Chen, Baoliang Environmental Science & Technology, Vol. 50, Issue 16 https://doi.org/10.1021/acs.est.6b01020	journal	August 2016
New insights into the structure and reduction of graphite oxide Gao, Wei; Alemany, Lawrence B.; Ci, Lijie Nature Chemistry, Vol. 1, Issue 5, p. 403-408 https://doi.org/10.1038/nchem.281	journal	July 2009
Preparation of Graphitic Oxide Hummers, William S.; Offeman, Richard E. Journal of the American Chemical Society, Vol. 80, Issue 6, p. 1339-1339 https://doi.org/10.1021/ja01539a017	journal	March 1958
Synthesis of Graphene Peroxide and Its Application in Fabricating Super Extensible and Highly Resilient Nanocomposite Hydrogels Liu, Jiaqi; Chen, Caifeng; He, Changcheng ACS Nano, Vol. 6, Issue 9 https://doi.org/10.1021/nn302874v	journal	August 2012
Unusual infrared-absorption mechanism in thermally reduced graphene oxide Acik, M.; Lee, G.; Mattevi, C. Nature Materials, Vol. 9, Issue 10 https://doi.org/10.1038/nmat2858	journal	September 2010
Journey Describing Applications of Oxone in Synthetic Chemistry Hussain, Hidayat; Green, Ivan R.; Ahmed, Ishtiaq Chemical Reviews, Vol. 113, Issue 5 https://doi.org/10.1021/cr3004373	journal	March 2013
The identification of peroxy-features at polymer surfaces by ESCA Dilks, A. Journal of Polymer Science: Polymer Chemistry Edition, Vol. 19, Issue 6 https://doi.org/10.1002/pol.1981.170190604	journal	June 1981
Carbon Nanostructure Reactivity: Reactions of Graphite Powders with Ozone Razumovskii, S. D.; Gorshenev, V. N.; Kovarskii, A. L. Fullerenes, Nanotubes and Carbon Nanostructures, Vol. 15, Issue 1 https://doi.org/10.1080/15363830600812423	journal	March 2007
Solution-Processable Graphene Oxide as an Efficient Hole Transport Layer in Polymer Solar Cells Li, Shao-Sian; Tu, Kun-Hua; Lin, Chih-Cheng ACS Nano, Vol. 4, Issue 6, p. 3169-3174 https://doi.org/10.1021/nn100551j	journal	June 2010
Fluorine End-Capped Optical Fibers for Photosensitizer Release and Singlet Oxygen Production Bartusik, Dorota; Aebisher, David; Ghosh, Goutam The Journal of Organic Chemistry, Vol. 77, Issue 10 https://doi.org/10.1021/jo3006107	journal	May 2012

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