Graphene Oxide. Origin of Acidity, Its Instability in Water, and a New Dynamic Structural Model

The existing structural models of graphene oxide (GO) contradict each other and cannot adequately explain the acidity of its aqueous solutions. Inadequate understanding of chemical structure can lead to a misinterpretation of observed experimental phenomena. Understanding the chemistry and structure of GO should enable new functionalization protocols while explaining GO’s limitations due to its water instability. Here we propose an unconventional view of GO chemistry and develop the corresponding “dynamic structural model” (DSM). In contrast to previously proposed models, the DSM considers GO as a system, constantly changing its chemical structure due to interaction with water. Using potentiometric titration, ¹³C NMR, FTIR, UV–vis, X-ray photoelectron microscopy, thermogravimetric analysis, and scanning electron microscopy we show that GO does not contain any significant quantity of preexisting acidic functional groups, but gradually generates them through interaction with water. The reaction with water results in C–C bond cleavage, formation of vinylogous carboxylic acids, and the generation of protons. An electrical double layer formed at the GO interface in aqueous solutions plays an important role in the observed GO chemistry. Prolonged exposure to water gradually degrades GO flakes converting them into humic acid-like structures. The proposed DSM provides an explanation for the acidity of GO aqueous solutions and accounts for most of the known spectroscopic and experimental data

New Details to Relaxation Dynamics of Dielectric Composite Materials Comprising Longitudinally Opened Carbon Nanotubes

The difference between intact and longitudinally opened multiwalled carbon nanotubes (referred to as CNT and OCNT) has been studied in their application as conductive filler in polymer composite materials. The dielectric properties have been studied in a broad frequency range at the temperatures varying from 293 K through 373 K. Introduction of as little as 0.5% and 1.0% of the conductive filler dramatically increased both parts of the complex permittivity. The percolation threshold is registered at ∼1.5% filling fraction. The main frequency dispersion of the dielectric permittivity lies in the low frequency end of the tested spectrum: from 10² Hz through 10⁴ Hz. At equal filling fractions, the permittivity of the OCNT-based samples exceeds that of the intact CNT-based samples. The relaxation dynamics is largely affected by the nanoscale geometry of the filler: the temperature dependence of such parameters as dielectric strength, activation energy, and relaxation time demonstrated significant difference between the charge transfer mechanism in the CNT-based and OCNT-based samples. The obtained activation energy is 150 and 85 kJ/mol for materials comprising CNTs and OCNTs, respectively. The relaxation mechanism is complex, and the exact factors behind the macroscopic dielectric properties of the tested materials cannot be singled out with certainty. Several experimental data points suggest that the individual nanotubes, not their aggregates, play the major role in the observed electrical properties of the composites. At the low loading fractions, we attained the highest dielectric strength values among all the data reported by the present day for the CNT/polymer host systems

Reversible Formation of Ammonium Persulfate/Sulfuric Acid Graphite Intercalation Compounds and Their Peculiar Raman Spectra

Graphite intercalation compounds (GICs) can be considered stacks of individual doped graphene layers. Here we demonstrate a reversible formation of sulfuric acid-based GICs using ammonium persulfate as the chemical oxidizing agent. No covalent chemical oxidation leading to the formation of graphite oxide occurs, which inevitably happens when other compounds such as potassium permanganate are used to charge carbon layers. The resulting acid/persulfate-induced stage-1 and stage-2 GICs are characterized by suppression of the 2D band in the Raman spectra and by unusually strong enhancement of the G band. The G band is selectively enhanced at different doping levels with different excitations. These observations are in line with recent reports for chemically doped and gate-modulated graphene and support newly proposed theories of Raman processes. At the same time GICs have some advantageous differences over graphene, which are demonstrated in this report. Our experimental observations, along with earlier reported data, suggest that at high doping levels the G band cannot be used as the reference peak for normalizing Raman spectra, which is a commonly used practice today. A Fermi energy shift of 1.20–1.25 eV and ∼1.0 eV was estimated for the stage-1 and stage-2 GICs, respectively, from the Raman and optical spectroscopy data

Homogeneous Liquid Phase Transfer of Graphene Oxide into Epoxy Resins

The quality of polymer composite materials depends on the distribution of the filler in the polymer matrix. Due to the presence of the oxygen functional groups, graphene oxide (GO) has a strong affinity to epoxy resins, providing potential opportunity for the uniform distribution of GO sheets in the matrix. Another advantage of GO over its nonoxidized counterpart is its ability to exfoliate to single-atomic-layer sheets in water and in some organic solvents. However, these advantages of GO have not yet been fully realized due to the lack of the methods efficiently introducing GO into the epoxy resin. Here we develop a novel homogeneous liquid phase transfer method that affords uniform distribution, and fully exfoliated condition of GO in the polymer matrix. The most pronounced alteration of properties of the cured composites is registered at the 0.10%–0.15% GO content. Addition of as little as 0.10% GO leads to the increase of the Young’s modulus by 48%. Moreover, we demonstrate successful introduction of GO into the epoxy matrix containing an active diluent-modifier; this opens new venues for fabrication of improved GO-epoxy-modifier composites with a broad range of predesigned properties. The experiments done on reproducing the two literature methods, using alternative GO introduction techniques, lead to either decrease or insignificant increase of the Young’s modulus of the resulting GO–epoxy composites

Revisiting the Mechanism of Oxidative Unzipping of Multiwall Carbon Nanotubes to Graphene Nanoribbons

Unzipping multiwall carbon nanotubes (MWCNTs) attracted great interest as a method for producing graphene nanoribbons (GNRs). However, depending on the production method, the GNRs have been proposed to form by different mechanisms. Here, we demonstrate that the oxidative unzipping of MWCNTs is intercalation-driven, not oxidative chemical-bond cleavage as was formerly proposed. The unzipping mechanism involves three consecutive steps: intercalation-unzipping, oxidation, and exfoliation. The reaction can be terminated at any of these three steps. We demonstrate that even in highly oxidative media one can obtain nonoxidized GNR products. The understanding of the actual unzipping mechanism lets us produce GNRs with hybrid properties varying from nonoxidized through heavily oxidized materials. We answer several questions such as the reason for the innermost walls of the nanotubes remaining zipped. The intercalation-driven reaction mechanism provides a rationale for the difficulty in unzipping single-wall and few-wall CNTs and aids in a reevaluation of the data from the oxidative unzipping process

Direct Real-Time Monitoring of Stage Transitions in Graphite Intercalation Compounds

Graphite intercalation compounds (GIC) possess a broad range of unique properties that are not specific to the parent materials. While the stage transition, changing the number of graphene layers sandwiched between the two layers of intercalant, is fundamentally important and has been theoretically addressed, experimental studies revealed only macroscopic parameters. On the microscale, the phenomenon remains elusive up to the present day. Here we monitor directly in real time the stage transitions using a combination of optical microscopy and Raman spectroscopy. These direct observations yield several mechanistic conclusions. While we obtained strong experimental evidence in support of the Daumas–Herold theory, we find that the conventional interpretation of stage transitions as sliding of the existing intercalant domains does not sufficiently capture the actual phenomena. The entire GIC structure transforms considerably during the stage transition. Among other observations, massive wavefront-like perturbations occur on the graphite surface, which we term the tidal wave effect

Direct Real-Time Monitoring of Stage Transitions in Graphite Intercalation Compounds

Graphite intercalation compounds (GIC) possess a broad range of unique properties that are not specific to the parent materials. While the stage transition, changing the number of graphene layers sandwiched between the two layers of intercalant, is fundamentally important and has been theoretically addressed, experimental studies revealed only macroscopic parameters. On the microscale, the phenomenon remains elusive up to the present day. Here we monitor directly in real time the stage transitions using a combination of optical microscopy and Raman spectroscopy. These direct observations yield several mechanistic conclusions. While we obtained strong experimental evidence in support of the Daumas–Herold theory, we find that the conventional interpretation of stage transitions as sliding of the existing intercalant domains does not sufficiently capture the actual phenomena. The entire GIC structure transforms considerably during the stage transition. Among other observations, massive wavefront-like perturbations occur on the graphite surface, which we term the tidal wave effect

<i>In Situ</i> Intercalation Replacement and Selective Functionalization of Graphene Nanoribbon Stacks

A cost-effective and potentially industrially scalable, <i>in situ</i> functionalization procedure for preparation of soluble graphene nanoribbon (GNRs) from commercially available carbon nanotubes is presented. The physical characteristics of the functionalized product were determined using SEM, evolved gas analysis, X-ray diffraction, solid-state ¹³C NMR, Raman spectroscopy, and GC–MS analytical techniques. A relatively high preservation of electrical properties in the bulk material was observed. Moreover, replacement of intercalated potassium with haloalkanes was obtained. While carbon nanotubes can be covalently functionalized, the conversion of the sp²-hybridized carbon atoms to sp³-hybridized atoms dramatically lowers their conductivity, but edge functionalized GNRs permit their heavy functionalization while leaving the basal planes intact

γ‑Iron Phase Stabilized at Room Temperature by Thermally Processed Graphene Oxide

Stabilizing nanoparticles on surfaces, such as graphene, is a growing field of research. Thereby, iron particle stabilization on carbon materials is attractive and finds applications in charge-storage devices, catalysis, and others. In this work, we describe the discovery of iron nanoparticles with the face-centered cubic structure that was postulated not to exist at ambient conditions. In bulk, the γ-iron phase is formed only above 917 °C, and transforms back to the thermodynamically favored α-phase upon cooling. Here, with X-ray diffraction and Mössbauer spectroscopy we unambiguously demonstrate the unexpected room-temperature stability of the γ-phase of iron in the form of the austenitic nanoparticles with low carbon content from 0.60% through 0.93%. The nanoparticles have controllable diameter range from 30 nm through 200 nm. They are stabilized by a layer of Fe/C solid solution on the surface, serving as the buffer controlling carbon content in the core, and by a few-layer graphene as an outermost shell