Vasilios Georgakilas

Noncovalent Functionalization of Graphene and Graphene Oxide for Energy Materials, Biosensing, Catalytic, and Biomedical Applications

This Review focuses on noncovalent functionalization of graphene and graphene oxide with various species involving biomolecules, polymers, drugs, metals and metal oxide-based nanoparticles, quantum dots, magnetic nanostructures, other carbon allotropes (fullerenes, nanodiamonds, and carbon nanotubes), and graphene analogues (MoS2, WS2). A brief description of π-π interactions, van der Waals forces, ionic interactions, and hydrogen bonding allowing noncovalent modification of graphene and graphene oxide is first given. The main part of this Review is devoted to tailored functionalization for applications in drug delivery, energy materials, solar cells, water splitting, biosensing, bioimaging, environmental, catalytic, photocatalytic, and biomedical technologies. A significant part of this Review explores the possibilities of graphene/graphene oxide-based 3D superstructures and their use in lithium-ion batteries. This Review ends with a look at challenges and future prospects of noncovalently modified graphene and graphene oxide.

Cyanographene and Graphene Acid: Emerging Derivatives Enabling High-Yield and Selective Functionalization of Graphene

Efficient and selective methods for covalent derivatization of graphene are needed because they enable tuning of graphene’s surface and electronic properties, thus expanding its application potential. However, existing approaches based mainly on chemistry of graphene and graphene oxide achieve only limited level of functionalization due to chemical inertness of the surface and nonselective simultaneous attachment of different functional groups, respectively. Here we present a conceptually different route based on synthesis of cyanographene via the controllable substitution and defluorination of fluorographene. The highly conductive and hydrophilic cyanographene allows exploiting the complex chemistry of −CN groups toward a broad scale of graphene derivatives with very high functionalization degree. The consequent hydrolysis of cyanographene results in graphene acid, a 2D carboxylic acid with pKa of 5.2, showing excellent biocompatibility, conductivity and dispersibility in water and 3D supramolecular assemblies after drying. Further, the carboxyl groups enable simple, tailored and widely accessible 2D chemistry onto graphene, as demonstrated via the covalent conjugation with a diamine, an aminothiol and an aminoalcohol. The developed methodology represents the most controllable, universal and easy to use approach toward a broad set of 2D materials through consequent chemistries on cyanographene and on the prepared carboxy-, amino-, sulphydryl-, and hydroxy- graphenes.

Interfacial polymerization of conductive polymers: Generation of polymeric nanostructures in a 2-D space.

In the recent advances in the field of conductive polymers, the fibrillar or needle shaped nanostructures of polyaniline and polypyrrole have attracted significant attention due to the potential advantages of organic conductors that exhibit low-dimensionality, uniform size distribution, high crystallinity and improved physical properties compared to their bulk or spherically shaped counterparts. Carrying the polymerization reaction in a restricted two dimensional space, instead of the three dimensional space of the one phase solution is an efficient method for the synthesis of polymeric nanostructures with narrow size distribution and small diameter. Ultra-thin nanowires and nanofibers, single crystal nanoneedles, nanocomposites with noble metals or carbon nanotubes and layered materials can be efficiently synthesized with high yield and display superior performance in sensors and energy storage applications. In this critical review we will focus not only on the interfacial polymerization methods that leads to polymeric nanostructures and composites and their properties, but also on the mechanism and the physico-chemical processes that govern the diffusion and reactivity of molecules and nanomaterials at an interface. Recent advances for the synthesis of conductive polymer composites with an interfacial method for energy storage applications and future perspectives are presented.

A bottom-up approach for the synthesis of highly ordered fullerene-intercalated graphene hybrids

Much of the research effort on graphene focuses on its use as a building block for the development of new hybrid nanostructures with well-defined dimensions and properties suitable for applications such as gas storage, heterogeneous catalysis, gas/liquid separations, nanosensing and biomedicine. Towards this aim, here we describe a new bottom-up approach, which combines self-assembly with the Langmuir Schaefer deposition technique to synthesize graphene-based layered hybrid materials hosting fullerene molecules within the interlayer space. Our film preparation consists in a bottom-up layer-by-layer process that proceeds via the formation of a hybrid organo-graphene oxide Langmuir film. The structure and composition of these hybrid fullerene-containing thin multilayers deposited on hydrophobic substrates were characterized by a combination of X-ray diffraction, Raman and X-ray photoelectron spectroscopies, atomic force microscopy and conductivity measurements. The latter revealed that the presence of C60 within the interlayer spacing leads to an increase in electrical conductivity of the hybrid material as compared to the organo-graphene matrix alone.

Tuning the dispersibility of carbon nanostructures from organophilic to hydrophilic: towards the preparation of new multipurpose carbon-based hybrids.

The hydroxyphenyl derivatives of carbon nanostructures (graphene and carbon nanotubes) can be easily transformed into highly organophilic or hydrophilic derivatives by using the ionic interactions between the phenolic groups and oleylamine or tetramethylammonium hydroxide, respectively. The products were finely dispersed in homo-polymers or block co-polymers to create homogeneous carbon-based nanocomposites and were used as nanocarriers for the dispersion and protection of strongly hydrophobic compounds, such as large aromatic chromophores or anticancer drugs in aqueous solutions.

Encapsulation and protection of carbon dots within MCM-41 material

The effective encapsulation of Carbon Dots (CDs) within spherical-like MCM-41 nanoparticles is reported in this work, using a simple, low cost synthetic procedure, here focusing on blue luminescent CDs. CDs of 2 nm average size, with strong photoluminescence, are embedded into MCM-41 nanoparticles during the sol-gel procedure, using tetrathylorthosilicate as the precursor for the glass structure, whereas a cationic surfactant is used as the structure directing agent under basic conditions. The white powder of the final hybrid material showed long term, stable photoluminescence due to the presence of the CDs, indicating the protective character of the silica matrix. Most importantly, it is reported that the photoluminescence of the final hybrid material is not significantly affected by a thermal treatment at 550 °C. The transparent nature of the MCM-41, allows loading this type of mesoporous materials with CDs, thus, providing some new key composite photoluminescent materials for energy and other related applications.Graphical Abstract

Highly Conductive Water-Based Polymer/Graphene Nanocomposites for Printed Electronics

The preparation and characterization of highly conductive carbon inks is described based on nanocomposites that combine a polystyrene-acrylic resin or water-soluble polymers with a hydrophilic graphene/carbon nanotube hybrid. The water-based carbon inks showed high electrical conductivity and could be effectively used in advanced technologies such as gravure printing for printed electronics. Moreover, the conductivity was shown to be increased with a power law of the nanohybrid volume fraction, with an exponent close to that predicted from the percolation theory, indicating a limited impact of the polymer tunneling barrier on the electrical conductivity of such nanocomposites.

The Role of Diamines in the Formation of Graphene Aerogels

Aliphatic or aromatic diamines undergo nucleophilic attack on the epoxy groups of graphene oxide under hydrothermal conditions resulting in partial functionalization and partial reduction of the graphenic surface. The overall reaction decreases the solubility of graphene oxide and yields a hydrogel that can be dried to a 3D porous structure classified as an aerogel. This article compares the graphene aerogels derived from different aliphatic and aromatic diamines.

Self-assembly of one-side-functionalized graphene nanosheets in bilayered superstructures for drug delivery

In this article, we describe the one-side functionalization of graphene nanosheets with hydrophilic catechol-bearing pyrrolidine rings. For this purpose, we used, for the first time, a solvothermal alternative of 1,3 dipolar cycloaddition of azomethine ylide. To achieve asymmetrical reaction, graphene nanosheets were initially and during reaction deposited on glass substrate. The result of one-side functionalization of graphene was the formation of amphiphilic few-layered graphene nanosheets. The modified side becomes hydrophilic due to the attachment of catechols, while the nonmodified side remains hydrophobic. In the literature, there are limited examples of functionalized graphene with different sides, the so-called Janus-type graphenes. These amphiphilic graphene nanosheets dispersed in water were self-organized in bilayer superstructures, with hydrophilic outer surface and hydrophobic internal space. The later can host hydrophobic molecules such as anticancer drugs and could be used in drug delivery systems. As an example, camptothecin, a drug practically insoluble in water, was used here to show that it can be transferred to water phase using graphene as transporter.

Interfacial asymmetric post functionalization of graphene: amphiphilic graphene derivatives self-assembled to 3D superstructures.

The interfacial asymmetric post-functionalization of graphene nanosheets and their self-assembly into superstructures is presented. By performing two sequential functionalizations, graphene nanosheets lying in the interface of a biphasic aqueous-organic system become amphiphilic, thereby generating an organophilic side and a hydrophilic side. The as-prepared Janus type amphiphilic graphene nanosheets are then self-assembled to generate different interesting superstructures, depending on the nature of the solvent in which they are dispersed.