Preparation and Characterization of Graphene Oxide Aerogels: Exploring the Limits of Supercritical CO2 Fabrication Methods.

The supercritical carbon dioxide (scCO2 ) synthesis of non-reduced graphene oxide (GO) aerogels from dispersions of GO in ethanol is here reported as a low-cost, efficient, and environmentally friendly process. The preparation is carried out under the mild conditions of 333 K and 20 MPa. The high aspect ratio of the used GO sheets (ca. 30 µm lateral dimensions) allowed the preparation of aerogel monoliths by simultaneous scCO2 gelation and drying. Solid-state characterization results indicate that a thermally-stable mesoporous non-reduced GO aerogel was obtained by using the supercritical procedure, keeping most of the surface oxygenated groups on the GO sheets, thus, facilitating further functionalization. Moreover, the monoliths have a very low density, high specific surface area, and excellent mechanical integrity; characteristics which rival those of most light-weight reduced graphene aerogels reported in the literature.

Nanosecond Laser-Assisted Nitrogen Doping of Graphene Oxide Dispersions.

N-doped reduced graphene oxide (RGO) has been prepared in bulk form by laser irradiation of graphene oxide (GO) dispersed in an aqueous solution of ammonia. A pulsed Nd:YAG laser with emission wavelengths in the infrared (IR) 1064 nm, visible (Vis) 532 nm, and ultraviolet (UV) 266 nm spectral regions was employed for the preparation of the N-doped RGO samples. Regardless of the laser energy employed, the resulting material presents a higher fraction of pyrrolic nitrogen compared to nitrogen atoms in pyridinic and graphitic coordination. Noticeably, whereas increasing the laser fluence of UV and Vis wavelengths results in an increase in the total amount of nitrogen, up to 4.9 at. % (UV wavelength at 60 mJ cm-2 fluence), the opposite trend is observed when the GO is irradiated in ammonia solution through IR processing. The proposed laser-based methodology allows the bulk synthesis of N-doped reduced graphene oxide in a simple, fast, and cost efficient manner.

Enhanced thermal oxidation stability of reduced graphene oxide by nitrogen doping.

Nitrogen-doped reduced graphene oxide (N-doped RGO) samples with a high level of doping, up to 13 wt. %, have been prepared by annealing graphene oxide under a flow of pure ammonia. The presence of nitrogen within the structure of RGO induces a remarkable increase in the thermal stability against oxidation by air. The thermal stability is closely related with the temperature of synthesis and the nitrogen content. The combustion reaction of nitrogen in different coordination environments (pyridinic, pyrrolic, and graphitic) is analyzed against a graphene fragment (undoped) from a thermodynamic point of view. In agreement with the experimental observations, the combustion of undoped graphene turns out to be more spontaneous than when nitrogen atoms are present.

Cyclohexane Oxidative Dehydrogenation on Graphene-Oxide-Supported Cobalt Ferrite Nanohybrids: Effect of Dynamic Nature of Active Sites on Reaction Selectivity.

In this work, we investigated cyclohexane oxidative dehydrogenation (ODH) catalyzed by cobalt ferrite nanoparticles supported on reduced graphene oxide (RGO). We aim to identify the active sites that are specifically responsible for full and partial dehydrogenation using advanced spectroscopic techniques such as X-ray photoelectron emission microscopy (XPEEM) and X-ray photoelectron spectroscopy (XPS) along with kinetic analysis. Spectroscopically, we propose that Fe3+/Td sites could exclusively produce benzene through full cyclohexane dehydrogenation, while kinetic analysis shows that oxygen-derived species (O*) are responsible for partial dehydrogenation to form cyclohexene in a single catalytic sojourn. We unravel the dynamic cooperativity between octahedral and tetrahedral sites and the unique role of the support in masking undesired active (Fe3+/Td) sites. This phenomenon was strategically used to control the abundance of these species on the catalyst surface by varying the particle size and the wt % content of the nanoparticles on the RGO support in order to control the reaction selectivity without compromising reaction rates which are otherwise extremely challenging due to the much favorable thermodynamics for complete dehydrogenation and complete combustion under oxidative conditions.

Key Parameters for the Rational Design, Synthesis, and Functionalization of Biocompatible Mesoporous Silica Nanoparticles.

Over the last few years, research on silica nanoparticles has rapidly increased. Particularly on mesoporous silica nanoparticles (MSNs), as nanocarriers for the treatment of various diseases because of their physicochemical properties and biocompatibility. The use of MSNs combined with therapeutic agents can provide better encapsulation and effective delivery. MSNs as nanocarriers might also be a promising tool to lower the therapeutic dosage levels and thereby to reduce undesired side effects. Researchers have explored several routes to conjugate both imaging and therapeutic agents onto MSNs, thus expanding their potential as theranostic platforms, in order to allow for the early diagnosis and treatment of diseases. This review introduces a general overview of recent advances in the field of silica nanoparticles. In particular, the review tackles the fundamental aspects of silicate materials, including a historical presentation to new silicates and then focusing on the key parameters that govern the tailored synthesis of functional MSNs. Finally, the biomedical applications of MSNs are briefly revised, along with their biocompatibility, biodistribution and degradation. This review aims to provide the reader with the tools for a rational design of biocompatible MSNs for their application in the biomedical field. Particular attention is paid to the role that the synthesis conditions have on the physicochemical properties of the resulting MSNs, which, in turn, will determine their pharmacological behavior. Several recent examples are highlighted to stress the potential that MSNs hold as drug delivery systems, for biomedical imaging, as vaccine adjuvants and as theragnostic agents.

Encapsulation of Fullerenes: A Versatile Approach for the Confinement and Release of Materials Within Open-Ended Multiwalled Carbon Nanotubes.

We have employed fullerenes as versatile agents to "cork" the open tips of multiwalled carbon nanotubes (MWCNTs), and as promoting species for the release of the inorganic material filled within the nanotubes' cavities. High Z element compounds, namely, PbI2, ZnI2, and CeI3, were chosen to easily determine the presence of the filler inside the hosting nanotubes by transmission electron microscopy (TEM). Fullerenes can isolate inorganic nanostructures confined within the hollow cavities of MWCNTs, which allows the removal of the external material remnant after the filling. Otherwise, taking advantage of the affinity of fullerenes with selected solvents, we have confirmed the ability of the C60 molecules to promote the displacement of the inorganic guest from the host. We propose two different strategies to trigger the release, employing vapor and liquid phase treatments. The first protocol involves annealing filled MWCNTs in presence of fullerenes (to obtain C60PbI2@MWCNTs) and the subsequent washing of the sample in ethanol under mild conditions. On the other hand, the simultaneous introduction of the C60 molecules and the liberation of the guest are produced by a single step wet procedure; the latter being potentially useful when materials that are not stable at high temperatures are employed for filling.

Tuning the Nature of N-Based Groups From N-Containing Reduced Graphene Oxide: Enhanced Thermal Stability Using Post-Synthesis Treatments.

The synthesis of N-containing graphene derivatives by functionalization and doping of graphene oxide (GO) has been widely reported as an alternative to tune both their chemical and physical properties. These materials are of interest for a wide range of applications, including biomedicine, sensors, energy, and catalysis, to name some. Understanding the role of the nature, reactivity, concentration, and distribution of the N-based species, would pave the way towards the design of synthetic routes to obtain improved materials for specific applications. The N-groups can be present either as aliphatic fractions (amides and amines) or becoming part of the planar conjugated lattice (N-doping). Here, we have modified the distribution of N-based moieties present in N-containing RGO samples (prepared by ammonolysis of GO) and evaluated the role of the concentration and nature of the species in the thermal stability of the materials once thermally annealed (500 °C-1050 °C) under inert environments. After these post-synthesis treatments, samples underwent marked structural modifications that include the elimination and/or transformation of N-containing fractions, which might account for the observed enhanced thermal stability. It is remarkable the formation of pyridinic N-oxide species, which role in the properties of N-containing graphene derivatives has been barely reported. The presence of this fraction is found to confer an enhanced thermal stability to the material.

Particle size determination from magnetization curves in reduced graphene oxide decorated with monodispersed superparamagnetic iron oxide nanoparticles.

Reduced graphene oxide (RGO) decorated with superparamagnetic iron oxide nanoparticles (SPION) is a novel composite nanomaterial with a myriad of promising applications. However, processes such as the fast and simple synthesis of non-agglomerated monodispersed SPION on RGO and the accurate characterization of particle size distributions remain challenging. Here we present how to solve these two problems. Firstly, we introduce a new microwave-assisted synthesis of stabilized SPION on RGO which is fast, simple and up-scalable but at the same time renders well dispersed SPION with narrow size distributions. The coverage of the RGO flakes with SPION is extensively tuned and the results are compared with a non-stabilized microwave-assisted method. Secondly, we implement an accurate method for the determination of particle size distributions from magnetization curves in RGO-SPION composite nanomaterials. This method is applied to the prepared composites with different particle size distributions, degrees of particle agglomeration and coverage of the RGO flakes. The influence of sample characteristics in the size determination method is discussed and the results are compared with the values obtained from transmission electron microscopy (TEM) and X-ray diffraction (XRD), showing that the method is well suited for these and potentially other types of superparamagnetic composite nanomaterials.

Bacterial cellulose/graphene oxide aerogels with enhanced dimensional and thermal stability.

We present a novel method for processing bacterial cellulose/graphene oxide (BC/GO) aerogels with multifunctional properties. The addition of a small amount of dimethyl sulfoxide (DMSO) to the aqueous dispersion of the nanomaterials during the gelification process affected the water freezing temperature of the system and thereby affecting the porous structure of the aerogel obtained after liophilization. The possibility to obtain small and elongated pore with axial orientation allowed a significant improvement of the structural stability of the aerogels. Moreover, the aerogels reduction by thermal treatment with ammonia gas induced crosslinking between the different nanophases, thus given an incremental factor for the mechanical performance of the aerogels under harsh conditions. The resulting aerogels also showed significant improvements in terms of thermal stability and electrical conductivity. These multifunctional BC/GO aerogels present high potential as sustainable and ecological alternative materials for lightweight packaging, filters for atmosphere and water treatment, or energy applications.

Solvent-free functionalisation of graphene oxide with amide and amine groups at room temperature.

A new solvent free protocol is presented to introduce amide and amine functionalities (N-aliphatic groups) onto graphene oxide in an energy efficient manner. Nitrogen contents of 3.6 wt% are obtained in only 5 minutes at room temperature by using ammonia gas as the nitrogen source for the ammonolysis of graphene oxide.

Microwave-Assisted Synthesis of SPION-Reduced Graphene Oxide Hybrids for Magnetic Resonance Imaging (MRI).

Magnetic resonance imaging (MRI) is a useful tool for disease diagnosis and treatment monitoring. Superparamagnetic iron oxide nanoparticles (SPION) show good performance as transverse relaxation (T2) contrast agents, thus facilitating the interpretation of the acquired images. Attachment of SPION onto nanocarriers prevents their agglomeration, improving the circulation time and efficiency. Graphene derivatives, such as graphene oxide (GO) and reduced graphene oxide (RGO), are appealing nanocarriers since they have both high surface area and functional moieties that make them ideal substrates for the attachment of nanoparticles. We have employed a fast, simple and environmentally friendly microwave-assisted approach for the synthesis of SPION-RGO hybrids. Different iron precursor/GO ratios were used leading to SPION, with a median diameter of 7.1 nm, homogeneously distributed along the RGO surface. Good relaxivity (r2*) values were obtained in MRI studies and no significant toxicity was detected within in vitro tests following GL261 glioma and J774 macrophage-like cells for 24 h with SPION-RGO, demonstrating the applicability of the hybrids as T2-weighted MRI contrast agents.

Determination of the length of single-walled carbon nanotubes by scanning electron microscopy.

A methodology is presented to determine the length of well individualized single-walled carbon nanotubes (SWCNTs) by means of scanning electron microscopy (SEM). Accurate measurements on wide areas of the sample can be achieved in an easy, fast and trustworthy manner. We have tested several supports and solvents to optimize the dispersion of SWCNTs, as well as the SEM imaging conditions. The optimal methodology goes via dispersion of the sample in ortho-dichlorobenzene, deposition onto a continuous carbon film supported on a copper TEM grid, and SEM imaging at 2 kV in secondary electrons mode using a through-in-lens detector. •Individualization of SWCNTs is achieved by dispersion of SWCNTs in ortho-dichlorobenzene and deposition onto TEM grids•Individual SWCNTs are imaged by SEM•Length determination by SEM is as precise as AFM.

Epoxidation of Carbon Nanocapsules: Decoration of Single-Walled Carbon Nanotubes Filled with Metal Halides.

Methyl(trifluoromethyl)dioxirane (TFDO) can be used for the oxyfunctionalization of SWCNTs filled with NaI and LuCl3 under mild conditions. The chosen metal halides are of interest for theranostics, both for imaging and therapy when in their radioactive form. The applied functionalization methodology does not require metal catalyst, preserves the integrity of the nanotubes during treatment, avoiding the release of the filling material. In this way, epoxidation can be considered as an efficient methodology for the functionalization of carbon nanocapsules, where the traditional harsh oxidation conditions by acids are not applicable.

Selective Laser-Assisted Synthesis of Tubular van der Waals Heterostructures of Single-Layered PbI2 within Carbon Nanotubes Exhibiting Carrier Photogeneration.

The electronic and optical properties of two-dimensional layered materials allow the miniaturization of nanoelectronic and optoelectronic devices in a competitive manner. Even larger opportunities arise when two or more layers of different materials are combined. Here, we report on an ultrafast energy efficient strategy, using laser irradiation, which allows bulk synthesis of crystalline single-layered lead iodide in the cavities of carbon nanotubes by forming cylindrical van der Waals heterostructures. In contrast to the filling of van der Waals solids into carbon nanotubes by conventional thermal annealing, which favors the formation of inorganic nanowires, the present strategy is highly selective toward the growth of monolayers forming lead iodide nanotubes. The irradiated bulk material bearing the nanotubes reveals a decrease of the resistivity as well as a significant increase in the current flow upon illumination. Both effects are attributed to the presence of single-walled lead iodide nanotubes in the cavities of carbon nanotubes, which dominate the properties of the whole matrix. The present study brings in a simple, ultrafast and energy efficient strategy for the tailored synthesis of rolled-up single-layers of lead iodide (i.e., single-walled PbI2 nanotubes), which we believe could be expanded to other two-dimensional (2D) van der Waals solids. In fact, initial tests with ZnI2 already reveal the formation of single-walled ZnI2 nanotubes, thus proving the versatility of the approach.