Synthetic routes contaminate graphene materials with a whole spectrum of unanticipated metallic elements

Significance Graphene is well-poised to revolutionize many industries because of its multitude of exceptional properties. Current bulk synthesis of graphene materials typically starts with the oxidation of graphite to graphite oxide followed by a reduction step. Many different methods exist for both the oxidation and reduction steps, leading to highly variable types and amounts of metallic contaminations that originate from the reagents themselves. These impurities are able to alter the graphene materials’ properties significantly, which impacts the range of potential applications for which these graphene materials are suitable. Thus, proper characterization of metallic contamination is highly important to ensure the suitability of a chosen set of synthetic procedures to the final application of the graphene material. The synthesis of graphene materials is typically carried out by oxidizing graphite to graphite oxide followed by a reduction process. Numerous methods exist for both the oxidation and reduction steps, which causes unpredictable contamination from metallic impurities into the final material. These impurities are known to have considerable impact on the properties of graphene materials. We synthesized several reduced graphene oxides from extremely pure graphite using several popular oxidation and reduction methods and tracked the concentrations of metallic impurities at each stage of synthesis. We show that different combinations of oxidation and reduction introduce varying types as well as amounts of metallic elements into the graphene materials, and their origin can be traced to impurities within the chemical reagents used during synthesis. These metallic impurities are able to alter the graphene materials’ electrochemical properties significantly and have wide-reaching implications on the potential applications of graphene materials.

[1]  Martin Pumera,et al.  Regulatory peptides are susceptible to oxidation by metallic impurities within carbon nanotubes. , 2010, Chemistry.

[2]  A. Krasheninnikov,et al.  Attractive interaction between transition-metal atom impurities and vacancies in graphene: a first-principles study , 2011 .

[3]  Bhavna S. Paratala,et al.  Physicochemical Characterization, and Relaxometry Studies of Micro-Graphite Oxide, Graphene Nanoplatelets, and Nanoribbons , 2012, PloS one.

[4]  Mianqi Xue,et al.  Superconductivity in potassium-doped few-layer graphene. , 2012, Journal of the American Chemical Society.

[5]  M. Pumera Graphene-based nanomaterials and their electrochemistry. , 2010, Chemical Society reviews.

[6]  Jae-Young Choi,et al.  Efficient Reduction of Graphite Oxide by Sodium Borohydride and Its Effect on Electrical Conductance , 2009 .

[7]  Robert H. Hurt,et al.  Iron Bioavailability and Redox Activity in Diverse Carbon Nanotube Samples , 2007 .

[8]  Ming Zhou,et al.  Controlled synthesis of large-area and patterned electrochemically reduced graphene oxide films. , 2009, Chemistry.

[9]  Chongwu Zhou,et al.  Continuous, highly flexible, and transparent graphene films by chemical vapor deposition for organic photovoltaics. , 2010, ACS nano.

[10]  V. M. Suresh,et al.  Porous graphene frameworks pillared by organic linkers with tunable surface area and gas storage properties. , 2014, Chemical communications.

[11]  S. Stankovich,et al.  Graphene-based composite materials , 2006, Nature.

[12]  Richard G Compton,et al.  Carbon nanotubes contain metal impurities which are responsible for the "electrocatalysis" seen at some nanotube-modified electrodes. , 2006, Angewandte Chemie.

[13]  Martin Pumera,et al.  Chemically reduced graphene contains inherent metallic impurities present in parent natural and synthetic graphite , 2012, Proceedings of the National Academy of Sciences.

[14]  R. Ruoff,et al.  Graphene-based ultracapacitors. , 2008, Nano letters.

[15]  M. Pumera,et al.  Impurities in graphenes and carbon nanotubes and their influence on the redox properties , 2012 .

[16]  W. S. Hummers,et al.  Preparation of Graphitic Oxide , 1958 .

[17]  Meijuan Yu,et al.  Metal impurities dominate the sorption of a commercially available carbon nanotube for Pb(II) from water. , 2010, Environmental science & technology.

[18]  Martin Pumera,et al.  Graphene-based nanomaterials for energy storage , 2011 .

[19]  M. Pumera,et al.  Lithium Aluminum Hydride as Reducing Agent for Chemically Reduced Graphene Oxides , 2012 .

[20]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[21]  S. Hur,et al.  Large-scale production of high-quality reduced graphene oxide , 2013 .

[22]  Jie Yin,et al.  Facile synthesis of soluble graphene via a green reduction of graphene oxide in tea solution and its biocomposites. , 2011, ACS applied materials & interfaces.

[23]  M. Pumera,et al.  “Metal-free” catalytic oxygen reduction reaction on heteroatom- doped graphene is caused by trace metal impurities. , 2013, Angewandte Chemie.

[24]  L. Staudenmaier,et al.  Verfahren zur Darstellung der Graphitsäure , 1898 .

[25]  Robert H. Hurt,et al.  Bioavailability of Nickel in Single‐Wall Carbon Nanotubes , 2007 .

[26]  R. Compton,et al.  Apparent 'electrocatalytic' activity of multiwalled carbon nanotubes in the detection of the anaesthetic halothane: occluded copper nanoparticles. , 2006, The Analyst.

[27]  Q. Jiang,et al.  Enhancement of CO detection in Al doped graphene , 2008, 0806.3172.

[28]  K. Ozoemena,et al.  Insights into the electro-oxidation of hydrazine at single-walled carbon-nanotube-modified edge-plane pyrolytic graphite electrodes electro-decorated with metal and metal oxide films , 2008 .

[29]  R. Ruoff,et al.  Hydrazine-reduction of graphite- and graphene oxide , 2011 .

[30]  Richard G Compton,et al.  Iron oxide particles are the active sites for hydrogen peroxide sensing at multiwalled carbon nanotube modified electrodes. , 2006, Nano letters.

[31]  R. Webster,et al.  Graphene oxide nanoribbons from the oxidative opening of carbon nanotubes retain electrochemically active metallic impurities. , 2013, Angewandte Chemie.

[32]  Liangzhu Feng,et al.  Graphene in biomedicine: opportunities and challenges. , 2011, Nanomedicine.

[33]  Martin Pumera,et al.  Carbon nanotubes contain residual metal catalyst nanoparticles even after washing with nitric acid at elevated temperature because these metal nanoparticles are sheathed by several graphene sheets. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[34]  M. Pumera,et al.  Chemical reduction of graphene oxide: a synthetic chemistry viewpoint. , 2014, Chemical Society reviews.

[35]  J. G. Terrill,et al.  Neutron activation analysis. , 1957, Public health reports.

[36]  A. Panich,et al.  Paramagnetic Impurities in Graphene Oxide , 2013 .

[37]  Jian‐guo Wang,et al.  Enhanced role of Al or Ga-doped graphene on the adsorption and dissociation of N2O under electric field. , 2011, Physical chemistry chemical physics : PCCP.

[38]  J. Grossman,et al.  Water desalination across nanoporous graphene. , 2012, Nano letters.

[39]  U. Hofmann,et al.  Untersuchungen über Graphitoxyd , 1937 .

[40]  Zhuang Liu,et al.  PEGylated nanographene oxide for delivery of water-insoluble cancer drugs. , 2008, Journal of the American Chemical Society.

[41]  Benjamin Collins Brodie,et al.  On the Atomic Weight of Graphite , 1859 .

[42]  J. Kučera,et al.  Verification of k0-NAA results at the LVR-15 reactor in Řež with the use of Au+Mo+Rb(+Zn) monitor set , 2014, Journal of Radioanalytical and Nuclear Chemistry.

[43]  L. Boulton The Oxygen Flask Method. , 1973 .

[44]  Hui-Ming Cheng,et al.  Purification of carbon nanotubes , 2008 .

[45]  U. Hofmann,et al.  Über die Säurenatur und die Methylierung von Graphitoxyd , 1939 .

[46]  J. Rogers Electronic materials: making graphene for macroelectronics. , 2008, Nature nanotechnology.

[47]  A. Panich,et al.  Magnetic resonance evidence of manganese-graphene complexes in reduced graphene oxide , 2012 .

[48]  C. Rao,et al.  Graphene Produced by Radiation-Induced Reduction of Graphene Oxide , 2010, 1009.1028.

[49]  J. Kučera,et al.  A new monitor set for the determination of neutron flux parameters in short-time k0-NAA , 2011 .

[50]  R. Webster,et al.  Metallic impurities in graphenes prepared from graphite can dramatically influence their properties. , 2012, Angewandte Chemie.

[51]  Malcolm L. H. Green,et al.  Copper oxide nanoparticle impurities are responsible for the electroanalytical detection of glucose seen using multiwalled carbon nanotubes , 2008 .

[52]  S. Stankovich,et al.  Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide , 2007 .

[53]  Shaojun Dong,et al.  Reducing sugar: new functional molecules for the green synthesis of graphene nanosheets. , 2010, ACS nano.

[54]  S. Umapathy,et al.  Is Chemically Synthesized Graphene ‘Really’ a Unique Substrate for SERS and Fluorescence Quenching? , 2013, Scientific Reports.

[55]  A. Macdonald The oxygen flask method. A review , 1961 .

[56]  T. Ohta,et al.  Controlling the Electronic Structure of Bilayer Graphene , 2006, Science.

[57]  A. Abbaspour,et al.  Electrocatalytic oxidation and determination of hydrazine on nickel hexacyanoferrate nanoparticles-modified carbon ceramic electrode , 2009 .

[58]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.