Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons.

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Graphene Oxide: Fundamentals and Applications

Due to its unique properties, graphene oxide has become one of the most studied materials of the last decade and a great variety of applications have been reported in areas such as sensors, catalysis and biomedical applications. This comprehensive volume systematically describes the fundamental aspects and applications of graphene oxide. The book is designed as an introduction to the topic, so each chapter begins with a discussion on fundamental concepts, then proceeds to review and summarize recent advances in the field. Divided into two parts, the first part covers fundamental aspects of graphene oxide and includes chapters on formation and chemical structure, characterization methods, reduction methods, rheology and optical properties of graphene oxide solutions. Part Two covers numerous graphene oxide applications including field effect transistors, transparent conductive films, sensors, energy harvesting and storage, membranes, composite materials, catalysis and biomedical applications. In each case the differences and advantages of graphene oxide over its non-oxidised counterpart are discussed. The book concludes with a chapter on the challenges of industrial-scale graphene oxide production. Graphene Oxide: Fundamentals and Applications is a valuable reference for academic researchers, and industry scientists interested in graphene oxide, graphene and other carbon materials. \ua9 2017 John Wiley & Sons, Ltd. All rights reserved

Mechanism of Graphene Oxide Formation

Despite intensive research, the mechanism of graphene oxide (GO) formation remains unclear. The role of interfacial interactions between solid graphite and the liquid reaction medium, and transport of the oxidizing agent into the graphite, has not been well-addressed. In this work, we show that formation of GO from graphite constitutes three distinct independent steps. The reaction can be stopped at each step, and the corresponding intermediate products can be isolated, characterized, and stored under appropriate conditions. The first step is conversion of graphite into a stage-1 graphite intercalation compound (GIC). The second step is conversion of the stage-1 GIC into oxidized graphite, which we define as pristine graphite oxide (PGO). This step involves diffusion of the oxidizing agent into the preoccupied graphite galleries. This rate-determining step makes the entire process diffusive-controlled. The third step is conversion of PGO into conventional GO after exposure to water, which involves hydrolysis of covalent sulfates and loss of all interlayer registry

Layer-by-layer removal of graphene

The present invention provides methods of selectively removing one or more graphene layers from a graphene material by: (1) applying a metal to a surface of the graphene material; and (2) applying a hydrogen containing solution to the surface of the graphene material that is associated with the metal. The hydrogen containing solution dissolves the metal along with one or more layers of graphene associated with the metal, thereby removing the layer(s) of graphene from the graphene material. In some embodiments, the hydrogen containing solution is an acidic solution, such as hydrochloric acid. In some embodiments, the metal is zinc. In some embodiments, the methods of the present invention are utilized to selectively remove one or more layers of graphene from one or more targeted sites on the surface of a graphene material

Nickel on Oxidatively Modified Carbon as a Promising Cost-Efficient Catalyst for Reduction of P-Nitrophenol

The reduction of p-nitrophenol to p-aminophenol has become a benchmark reaction for testing the efficiency of new catalytic systems. In this study, we use oxidatively modified carbon (OMC) as a structural support to develop a new cost-efficient nickel-based catalytic system. The newly developed material comprises single nickel ions, chemically bound to the oxygen functional groups on the OMC surface. The highly oxidized character of OMC ensures the high lateral density of nickel ions on its surface at relatively low nickel content. We demonstrate excellent catalytic properties of the new material by using it as a stationary phase in a prototype of a continuous flow reactor: the reagent fed into the reactor is p-nitrophenol, and the product, exiting the reactor, is the fully converted p-aminophenol. The catalytic properties of the new catalyst are associated with its specific morphology, and with high lateral density of active sites on the surface. The reaction can be considered as an example of single-atom catalysis. The resulting material can be used as an inexpensive but efficient catalyst for industrial wastewater treatment. The study opens the doors for the synthesis of a new series of catalytic systems comprising transition metal atoms on the OMC structural support

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

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

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

High Permittivity Polymer Composites on the Basis of Long Single-Walled Carbon Nanotubes: The Role of the Nanotube Length

Controlling the permittivity of dielectric composites is critical for numerous applications dealing with matter/electromagnetic radiation interaction. In this study, we have prepared polymer composites, based on a silicone elastomer matrix and Tuball carbon nanotubes (CNT) via a simple preparation procedure. The as-prepared composites demonstrated record-high dielectric permittivity both in the low-frequency range (102–107 Hz) and in the X-band (8.2–12.4 GHz), significantly exceeding the literature data for such types of composite materials at similar CNT content. Thus, with the 2 wt% filler loading, the permittivity values reach 360 at 106 Hz and >26 in the entire X-band. In similar literature, even the use of conductive polymer hosts and various highly conductive additives had not resulted in such high permittivity values. We attribute this phenomenon to specific structural features of the used Tuball nanotubes, namely their length and ability to form in the polymer matrix percolating network in the form of neuron-shaped clusters. The low cost and large production volumes of Tuball nanotubes, as well as the ease of the composite preparation procedure open the doors for production of cost-efficient, low weight and flexible composites with superior high permittivity