Black Phosphorus Cytotoxicity Assessments Pitfalls: Advantages and Disadvantages of Metabolic and Morphological Assays.

Black phosphorus (BP) belongs to a group of 2D nanomaterials and nowadays attracts constantly increasing attention. Parallel to the growing utilization of BP nanomaterial increase also the requirements for the thorough comprehension of its potential impact on human and animal health. The aim of this study was to compare and discuss five assays commonly used for the cytotoxicity assessments of nanomaterials with a special focus on BP nanoparticles. A comprehensive survey of factors and pitfalls is provided that should be accounted for when assessing their toxicity and pointed to their inconsistency. BP might introduce various levels of interference during toxicity assessments depending on its concentration applied. More importantly, the BP toxicity evaluation was found to be influenced by the nature of assay chosen. These are based on different principles and do not have to assess all the cellular events equally. A commercial assay based on the measurement of protease activity was identified to be the most suitable for the BP toxicity assessment. Further, the benefit of time-lapse quantitative phase imaging for nanomaterial toxicity evaluation was highlighted. Unlike the conventional assessments it provides real-time analysis of the processes accompanying BP administration and enables to understand them deeper and in the context.

In Situ Doping of Black Phosphorus by High-Pressure Synthesis.

Black phosphorus is a two-dimensional semiconductor with promising properties for catalysis, energy storage, and conversion as well as electronic device applications, and control of its electronic structure is critical for such applications. Substitutional doping of phosphorus by electron donating (e.g., sulfur) or electron accepting elements (e.g., germanium) can significantly change its properties, especially charge carrier concentration. Here, we report the in situ doping of black phosphorus by its direct synthesis from a mixture of red phosphorus and a dopant by high pressure synthesis. In detail, we study the incorporation of germanium, sulfur, selenium, and tellurium within black phosphorus, showing significant differences in incorporation of individual elements and assess their suitability for potential electrochemical applications.

Fluorographene and Graphane as an Excellent Platform for Enzyme Biocatalysis.

The application of enzymes is a crucial issue for current biotechnological application in pharmaceutical, as well as food and cosmetic industry. Effective platforms for enzyme immobilization are necessary for their industrial use in various biosynthesis procedures. Such platforms must provide high yield of immobilization and retain high activity at various conditions for their large-scale applications. Graphene derivatives such as hydrogenated graphene (graphane) and fluorographene can be applied for enzyme immobilization with close to 100 % yield that can result to activities of the composites significantly exceeding activity of free enzymes. The hydrophobic properties of graphene stoichiometric derivatives allowed for excellent non-covalent bonding of enzymes and their use in various organic solvents. The immobilized enzymes retain their high activities even at elevated temperatures. These findings show excellent application potential of enzyme biocatalysts immobilized on graphene stoichiometric derivatives.

Hydrogenation of Fluorographite and Fluorographene: An Easy Way to Produce Highly Hydrogenated Graphene.

Fluorographene is an excellent precursor for the synthesis of graphene derivatives. Relative to pure graphene, fluorographene possesses higher reactivity and, in comparison with graphene oxide, is also homogenous in composition, which enables the preparation of well-defined materials. Recently, it has been shown that several graphene derivatives can be synthesized from fluorographene, thus yielding various products such as graphene acid or alkylated graphene. This study focuses on the hydrogenation of fluorographene by using various hydrogenation reactions, including the use complex hydrides and solvated electrons in different media. In addition, a comparison of these reactions shows that fluorinated graphite has significantly lower reactivity than fluorographene. The conversion rates of these reactions are higher when fluorographene is used relative to fluorographite. These reactions can be used to tune the hydrogen/fluorine composition on a graphene backbone.

Synergetic Metals on Carbocatalyst Shungite.

The naturally occurring Palaeoproterozoic carbon mineral shungite is a complex raw carbon microporous matrix, loaded with a wide range of elements. Shungite exhibits a disordered and amorphous structure with highly irregular building blocks. Shungite incorporates metals in its structure; typically catalytic elements such Fe and Ni are present, as well as the toxic elements Pb and As at mg g-1 levels. We show here that incorporation of the metals in the carbon matrix of shungite leads into synergistic catalytic effect. We investigate the application of shungite in energy related electrochemical catalytic reactions, such as the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). All elements have a synergetic effect, thus contributing for shungite's interesting catalytic performance towards a different range of electrochemical reactions, outperforming other tested carbon allotropes, such as carbon black, metal loaded carbon nanotubes, fullerene, and glassy carbon. These findings have profound impact on the application of the natural carbon materials for catalysis.

Planar Polyolefin Nanostripes: Perhydrogenated Graphene.

Graphene hydrogenation gives an opportunity to introduce a band gap into the graphene electronic structure. Complete hydrogenation may lead to the graphane, a fully hydrogenated counterpart of graphene. However, pure graphane has not been successfully prepared to this day. Here, we show that hydrogenation of single-walled carbon nanotubes by means of Birch reduction leads to graphene-based carbon nanostripes with uniform dimensions. Such a material exhibits interesting electrocatalytic and magnetic properties as well huge potential for hydrogen storage since the weight concentration of hydrogen is 8.78 wt.% corresponding to the composition of C1 H1.22 O0.05 and thus exceeding the theoretical concentration in pure graphane (7.74 wt.%). The obtained concentration of hydrogen is the highest value ever reported for any graphene-based material and significantly exceeds the ultimate goal of the U.S. Department of Energy for a hydrogen storage material of 7.5 wt.%.

Universal Method for Large-Scale Synthesis of Layered Transition Metal Dichalcogenides.

The layered transition metal dichalcogenides are currently amongst the most intensively investigated materials. These compounds constitute a broad family of materials, with characteristic layered structures, covering both semiconductors and metallic materials. The great attention arises from the possibility to exfoliate these materials down to single layers with many unique properties, such as thickness dependent band-gap energy, and the possibility of tuning transport properties by phase transitions. The research in the field of transition metal dichalcogenides is also motivated by their high electrocatalytic activity towards several industrially important reactions, such as the hydrogen evolution reaction, as well as many other applications in nano- and optoelectronics. Although these materials are studied intensively, their availability is extremely limited and only disulfides of molybdenum and tungsten are broadly commercially available. Here an optimized procedure for simple direct synthesis of transition metal dichalcogenides using powder metals and elemental chalcogens is reported. The optimized thermal treatment allowed the synthesis scaling of the sulfides, selenides and tellurides of 4th, 5th, 6th, and 7th group of layered-structure dichalcogenides. The synthesized transition metal dichalcogenides were single phase. The phase purity, structure, and morphology were investigated in detail by electron microscopy and EDS, X-ray diffraction, and Raman spectroscopy.

Fluorographene Modified by Grignard Reagents: A Broad Range of Functional Nanomaterials.

Fluorographene is the youngest stoichiometric derivative of graphene; hence, its reactivity is only poorly explored. Compared to graphene, the significantly higher reactivity of C-F bonds makes this material a suitable platform for a large number of chemical modifications. Fluorographene is also the only member of the halographene family that can be prepared in the stoichiometric composition (C1 F1 ). Herein, the chemical modification of fluorographene with Grignard reagents, which are well known in organic synthesis for the formation of new C-C bonds, is presented. The reaction with alkyl magnesium bromides led to successful modification of fluorographene with ethyl, vinyl, ethynyl and propargyl groups. Chemical characterisation showed the presence of covalently bonded functional groups in a high concentration exceeding one functional group per C6 motif. The reactivity of Grignard reagents with fluorographene decreased from ethyl to ethynyl. The terminal carbon-carbon triple bonds were used for click reactions with organic azides leading to the formation of triazole rings. These findings open up a broad spectrum of opportunities for simple and robust modification of graphene by chemical reactions proceeding at room temperature under mild conditions. These results have major application potential in sensing, biomedical and energy-related applications.

Thin, High-Flux, Self-Standing, Graphene Oxide Membranes for Efficient Hydrogen Separation from Gas Mixtures.

The preparation and gas-separation performance of self-standing, high-flux, graphene oxide (GO) membranes is reported. Defect-free, 15-20 µm thick, mechanically stable, unsupported GO membranes exhibited outstanding gas-separation performance towards H2 /CO2 that far exceeded the corresponding 2008 Robeson upper bound. Remarkable separation efficiency of GO membranes for H2 and bulky C3 or C4 hydrocarbons was achieved with high flux and good selectivity at the same time. On the contrary, N2 and CH4 molecules, with larger kinetic diameter and simultaneously lower molecular weight, relative to that of CO2 , remained far from the corresponding H2 /N2 or H2 /CH4 upper bounds. Pore size distribution analysis revealed that the most abundant pores in GO material were those with an effective pore diameter of 4 nm; therefore, gas transport is not exclusively governed by size sieving and/or Knudsen diffusion, but in the case of CO2 was supplemented by specific interactions through 1) hydrogen bonding with carboxyl or hydroxyl functional groups and 2) the quadrupole moment. The self-standing GO membranes presented herein demonstrate a promising route towards the large-scale fabrication of high-flux, hydrogen-selective gas membranes intended for the separation of H2 /CO2 or H2 /alkanes.

Graphene oxide layers modified by light energetic ions.

In this paper, the effect of light ion irradiation on graphene oxide foil structure and composition was studied. Due to the excellent properties of graphene based materials suitable for application in electronics, optoelectronics, micro-mechanics and space technologies, the interaction of energetic ions with graphene based structures is worth studying. From the fundamental point of view, it is also interesting to get information about graphene oxide structure modification and the possible functional properties after irradiation by energetic ions. The light ion irradiation of graphene oxide (GO) foil was performed using 2.5 MeV H+ and 5.1 MeV He2+ ions. The change in the elemental composition of the GO foils after ion irradiation was investigated using Rutherford Backscattering Spectrometry and Elastic Recoil Detection Analysis. The influence of ion irradiation was further studied by microscopy methods. The chemical composition and structural changes of the GO foil surface were characterized by spectroscopy techniques including XPS, FTIR and Raman spectroscopy. Although the results of ion beam analysis indicated no significant compositional changes in the bulk of GO foils connected to ion irradiation, XPS, ATR-FTIR and Raman spectroscopy revealed reduction and removal of oxygen functionalities on the surface of graphene oxide. This reduction leads to a surface resistivity decrease after ion irradiation dependent on the ion species, fluence and energy.

Pnictogen (As, Sb, Bi) Nanosheets for Electrochemical Applications Are Produced by Shear Exfoliation Using Kitchen Blenders.

Layered materials are of high importance because of their anisotropy and as a source of 2D materials. Whilst there is a plethora of multi-elemental 2D materials, the number mono-elemental 2D materials is rather limited. Herein, we demonstrate that aqueous shear exfoliation can be used to obtain As, Sb, and Bi exfoliated nanosheets. Morphological and chemical characterization of the exfoliated materials shows a decrease in thickness, sheet-to-nanosheet scale, and partial oxidation owing to a higher surface area. The electrochemical performance is tested in terms of inherent electrochemistry, electron transfer, and sensing applications as demonstrated with ascorbic acid. Potential energy-related applications are evaluated in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR), with shear-exfoliated Sb having the best electrochemical performance overall. These findings will have a profound impact on the preparation and application of 2D mono-elemental materials.

The Covalent Functionalization of Layered Black Phosphorus by Nucleophilic Reagents.

Layered black phosphorus has been attracting great attention due to its interesting material properties which lead to a plethora of proposed applications. Several approaches are demonstrated here for covalent chemical modifications of layered black phosphorus in order to form P-C and P-O-C bonds. Nucleophilic reagents are highly effective for chemical modification of black phosphorus. Further derivatization approaches investigated were based on radical reactions. These reagents are not as effective as nucleophilic reagents for the surface covalent modification of black phosphorus. The influence of covalent modification on the electronic structure of black phosphorus was investigated using ab initio calculations. Covalent modification exerts a strong effect on the electronic structure including the change of band-gap width and spin polarization.

Partially Hydrogenated Graphene Materials Exhibit High Electrocatalytic Activities Related to Unintentional Doping with Metallic Impurities.

Partially hydrogenated graphene materials, synthesized by the chemical reduction/hydrogenation of two different graphene oxides using zinc powder in acidic environment or aluminum powder in alkaline environment, exhibit high electrocatalytic activities, as well as electrochemical sensing properties. The starting graphene oxides and the resultant hydrogenated graphenes were characterized in detail. Their electrocatalytic activity was examined in the oxygen reduction reaction, whereas sensing properties towards explosives were tested by using picric acid as a redox probe. Findings indicate that the high electrocatalytic performance originates not only from the hydrogenation of graphene, but also from unintentional contamination of graphene with manganese and other metals during synthesis. A careful evaluation of the obtained data and a detailed chemical analysis are necessary to identify the origin of this anomalous electrocatalytic activity.

Impact Electrochemistry: Detection of Graphene Nanosheets Labeled with Metal Nanoparticles through Oxygen Reduction Mediation.

We have prepared Pt/Fe- and Fe-nanoparticle-labeled graphene sheets and demonstrate that these sheets can be detected by using impact electrochemistry through oxygen reduction mediation.

Layered Black Phosphorus: Strongly Anisotropic Magnetic, Electronic, and Electron-Transfer Properties.

Layered elemental materials, such as black phosphorus, exhibit unique properties originating from their highly anisotropic layered structure. The results presented herein demonstrate an anomalous anisotropy for the electrical, magnetic, and electrochemical properties of black phosphorus. It is shown that heterogeneous electron transfer from black phosphorus to outer- and inner-sphere molecular probes is highly anisotropic. The electron-transfer rates differ at the basal and edge planes. These unusual properties were interpreted by means of calculations, manifesting the metallic character of the edge planes as compared to the semiconducting properties of the basal plane. This indicates that black phosphorus belongs to a group of materials known as topological insulators. Consequently, these effects render the magnetic properties highly anisotropic, as both diamagnetic and paramagnetic behavior can be observed depending on the orientation in the magnetic field.

Graphane Nanostripes.

Graphane, the hydrogenated counterpart of graphene, was shown to exhibit properties such as tunable band gaps through varied degrees of hydrogenation, fluorescence, or ferromagnetism. Graphane nanostripe properties have also been theoretically predicted. Herein, we show that graphane nanostripes can be prepared by opening carbon nanotubes using Birch reduction in liquid ammonia utilizing potassium as a reducing agent and water as a proton donor. The prepared graphane nanostripes exhibit several exceptional properties when coupled with trace metal dopants. The interplay of metallic nanoparticles and defects lead to a spin polarization and induction of ferromagnetic moment, as well as to enhanced electrocatalytic properties in the hydrogen evolution reaction when compared to non-hydrogenated carbon nanotubes.

Mesomeric Effects of Graphene Modified with Diazonium Salts: Substituent Type and Position Influence its Properties.

In the last decade, graphene and graphene derivatives have become some of the most intensively studied materials. Tuning of the electronic and electrochemical properties of graphene is of paramount importance. In this study, six diazonium-modified graphenes containing different functional groups according to the diazonium salt precursor were investigated. These diazonium moieties have a strong mesomeric (resonance) effect and act as either electron-donating or -withdrawing species. Different graphene precursors, such as thermally and chemically reduced graphenes were studied. All the products were characterized in detail by elemental combustion analysis, FTIR spectroscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. Resistivity and zeta potential measurements were consistent with theoretical (DFT) calculations. The results show that chemical modification of graphene by diazotation strongly influences its properties, creating a huge application potential in microelectronics, energy storage and conversion devices, and electrocatalysis.

Hydrogenated Graphenes by Birch Reduction: Influence of Electron and Proton Sources on Hydrogenation Efficiency, Magnetism, and Electrochemistry.

Interest in chemical functionalisation of graphenes today is largely driven by associated changes to its physical and material properties. Functionalisation with hydrogen was employed to obtain hydrogenated graphenes (also termed graphane if fully hydrogenated), which exhibited properties including fluorescence, magnetism and a tuneable band gap. Although the classical Birch reduction has been employed for hydrogenation of graphite oxide, variation exists between the choice of alkali metals and alcohols/water as quenching agents. A systematic study of electron (Li, Na, K, Cs) and proton sources (tBuOH, iPrOH, MeOH, H2O) has been performed to identify optimal conditions. The proton source exerted a great influence on the resulting hydrogenation with water and out-performed alcohols, and the lowest carbon-to-hydrogen ratio was observed with sodium and water with composition of C1.4H1O0.3. Although ferromagnetism at room temperature correlates well with increasing hydrogen concentrations, small contributions from trace iron impurities cannot be completely eliminated. In contrast, hydrogenated graphenes exhibit a significant paramagnetic moment at low temperatures that has no correlation with impurities, and therefore, originates from the carbon system. This is in comparison to graphene, which is strongly diamagnetic, and concentrations of paramagnetic centres in hydrogenated graphenes are one order of magnitude larger than that in graphite. Nonetheless, hydrogenation over a particular level might also excessively disrupt intrinsic sp(2) conjugation, resulting in unintended reduction of electrochemical properties. This was observed with heterogeneous electron-transfer rates and it was postulated that hydrogenated graphenes should generally have high defect densities, but only moderately high hydrogenation, should they be employed as electrode materials.

Separation of thorium ions from wolframite and scandium concentrates using graphene oxide.

The separation of rare metals from the ores and commercially available compounds is an important issue due to the need of their high purity in advanced materials and devices. Important examples of two highly important elements that co-exist in the ores are scandium and thorium. Scandium containing ores and consequently also commercially available scandium compounds often contain traces of thorium which is very difficult to separate. We used graphene oxide for the selective sorption of thorium ions from scandium and thorium mixtures originating from the mined ores as well as from commercially available scandium salts. Our results showed that graphene oxide has an extreme affinity towards thorium ions. After the sorption process the graphene oxide contained over 20 wt% of thorium while the amount of scandium sorbed on GO was very low. This phenomenon of high sorption selectivity of graphene oxide can be applied in industry for the purification of various chemicals containing scandium and for separation of thorium containing mixtures. Alternatively, this methodology can be used for preconcentration of thorium from low-grade ores and its further use in the new generation of nuclear reactors.

Functionalized germanane/SWCNT hybrid films as flexible anodes for lithium-ion batteries.

Germanium, with a high theoretical capacity based on alloyed lithium and germanium (1384 mA h g-1 Li15Ge4), has stimulated tremendous research as a promising candidate anode material for lithium-ion batteries (LIBs). However, due to the alloying reaction of Li/Ge, the problems of inferior cycle life and massive volume expansion of germanium are equally obvious. Among all Ge-based materials, the unique layered 2D germanane (GeH and GeCH3) with a graphene-like structure, obtained by a chemical etching process from the Zintl phase CaGe2, could enable storage of large quantities of lithium between their interlayers. Besides, the layered structure has the merit of buffering the volume expansion due to the tunable interlayer spacing. In this work, the beyond theoretical capacities of 1637 mA h g-1 for GeH and 2048 mA h g-1 for GeCH3 were achieved in the initial lithiation reaction. Unfortunately, the dreadful capacity fading and electrode fracture happened during the subsequent electrochemical process. A solution, i.e. introducing single-wall carbon nanotubes (SWCNTs) into the structure of the electrodes, was found and further confirmed to improve their electrochemical performance. More noteworthy is the GeH/SWCNT flexible electrode, which exhibits a capacity of 1032.0 mA h g-1 at a high current density of 2000 mA g-1 and a remaining capacity of 653.6 mA h g-1 after 100 cycles at 500 mA g-1. After 100 cycles, the hybrid germanane/SWCNT electrodes maintained good integrity without visible fractures. These results indicate that introducing SWCNTs into germanane effectively improves the electrochemical performance and maintains the integrity of the electrodes for LIBs.