High-Entropy NASICON Phosphates (Na3M2(PO4)3 and NaMPO4Ox, M = Ti, V, Mn, Cr, and Zr) for Sodium Electrochemistry.

High-entropy materials, with complex compositions and unique cocktail characteristics, have recently drawn significant attention. Additionally, a family of sodium super ion conductors (NASICONs)-structured phosphates in energy storage areas shows a comprehensive application for traditional alkaline ion batteries and, in particular, solid-state electrolytes. However, there is no precedent in fabricating this kind of NASICON-type high-entropy phase. Here, we report the successful fabrication of two well-crystallized high-entropy phosphates, namely, Na3(Ti0.2V0.2Mn0.2Cr0.2Zr0.2)2(PO4)3 (HE-N3M2P3) and Na(Ti0.2V0.2Mn0.2Cr0.2Zr0.2)2PO4Ox (HE-NMP). The prepared materials in which the transition metals (TMs) of Ti, V, Mn, Cr, and Zr occupy the same 12c Wykoff position can form a structure analogous to R3̅c Na3V2(PO4)3 that is carefully determined by X-ray diffraction, neutron diffraction, and transmission electron microscopy. Further, their performance for sodium ion batteries and sodium-based solid-state electrolytes was evaluated. The HE-N3M2P3 might exhibit a promising electrochemical performance for sodium storage in terms of its structure resembling that of Na3V2(PO4)3. Meanwhile, the HE-NMP shows considerable electrochemical activity with numerous broad redox ranges during extraction and insertion of Na+, related to the coexistence of several TM elements. The evaluated temperature-dependent ionic conductivity for HE-NMP solid electrolyte varies from 10-6 to 10-5 S cm-1 from room temperature to 398.15 K, offering high potential for energy storage applications as a new high-entropy system.

Direct Observation of Magnon-Phonon Strong Coupling in Two-Dimensional Antiferromagnet at High Magnetic Fields.

We report the direct observation of strong coupling between magnons and phonons in a two-dimensional antiferromagnetic semiconductor FePS_{3}, via magneto-Raman spectroscopy at magnetic fields up to 30 Tesla. A Raman-active magnon at 121 cm^{-1} is identified through Zeeman splitting in an applied magnetic field. At a field-driven resonance with a nearby phonon mode, a hybridized magnon-phonon quasiparticle is formed due to strong coupling between the two modes. We develop a microscopic model of the strong coupling in the two-dimensional magnetic lattice, which enables us to elucidate the nature of the emergent quasiparticle. Our polarized Raman results directly show that the magnons transfer their spin angular momentum to the phonons and generate phonon spin through the strong coupling.

A Metal-Doped Fungi-Based Biomaterial for Advanced Electrocatalysis.

Nature and its highly sophisticated biomaterials are an endless source of inspiration for engineers and scientists across a wide range of disciplines. During the last decade, concepts of bioinspired synthesis of hierarchically structured nano- and micromaterials have been attracting increasing attention. In this article, we have utilized the natural ability of fungi to absorb metal ions for a bioinspired synthesis of carbonaceous material doped by selected transition metals. As an all-around metal accumulator, Hebeloma mesophaeum was selected, and it was cultivated in the presence of three transition-metal ions: NiII , FeII , and MnII . The metal-doped carbonized biomaterial possessed enhanced catalytic activity toward hydrazine oxidation, oxygen reduction, and cumene hydroperoxide reduction. Thus, we have shown possible transformation of a waste product (fungi grown on a contaminated soil) into a value-added carbonaceous material with tailored catalytic properties. This bioinspired synthesis can outline an attractive route for the fabrication of catalysts for important industrial applications on a large scale.

One-Step Synthesis of B/N Co-doped Graphene as Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction: Synergistic Effect of Impurities.

In the last decade, numerous studies of graphene doping by various metal and nonmetal elements have been done in order to obtain tailored properties, such as non-zero band gap, electrocatalytic activity, or controlled optical properties. From nonmetal elements, boron and nitrogen were the most studied dopants. Recently, it has been shown that in some cases the enhanced electrocatalytic activity of graphene and its derivatives can be attributed to metal impurities rather than to nonmetal elements. In this paper, we investigated the electrocatalytical properties of B/N co-doped graphene with respect to the content of metallic impurities introduced by the synthesis procedures. For this purpose, a permanganate (Hummers) and a chlorate (Hofmann) route were used for the preparation of the starting graphene oxides (GO). The GO used for the synthesis of B/N co-doped graphene had significantly difference compositions of oxygen functionalities as well as metallic impurities introduced by the different synthetic procedures. We performed a detailed structural and chemical analysis of the doped graphene samples to correlate their electrocatalytic activity with the concentration of incorporated boron and nitrogen as well as metallic impurities.

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.

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.%.

Concentration of Nitric Acid Strongly Influences Chemical Composition of Graphite Oxide.

Graphite oxide is the most widely used precursor for the synthesis of graphene through top-down methods. We demonstrate a significant influence of nitric acid concentration on the structure and composition of the graphite oxide prepared by graphite oxidation. In general, two main chlorate-based oxidation methods are currently used for graphite oxide synthesis: the Staudenmaier method using 98 wt % nitric acid, and the Hofmann method with 68 wt % nitric acid. However, a gradual change in nitric acid concentration allows a continuous change in the graphite oxide composition. The prepared samples are thoroughly characterised by microscopic techniques as well as various spectroscopic and analytical methods. Lowering the nitric acid concentration leads to an increase in oxidation degree, and in particular, to the concentration of epoxy and hydroxyl groups. This knowledge is not only useful for the large-scale synthesis of graphite oxide with tuneable size and chemical composition, but the use of nitric acid in lower concentrations can also reduce the overall cost of the synthesis significantly.

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.

Selective Bromination of Graphene Oxide by the Hunsdiecker Reaction.

Halogenated graphenes have been attracting great attention in the recent years. The currently used methods are usually non-specific, and halogen groups are randomly distributed over the graphene. Here we demonstrate a selective graphene functionalization based on a well known reaction mechanism-Hunsdiecker reaction-applied on selective bromination of graphene oxide. The chemical analysis using various spectroscopic methods proved a high efficiency of this functionalization method. Bromination can be carried out under mild conditions without any high temperature or high pressure treatment. The chemical modification led to introduction of up to 20 wt.% of bromine covalently bonded to the graphene skeleton. The modified graphene was characterized in detail using a broad range of microscopic and spectroscopic methods and no significant contamination by reaction by-products was detected.

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.

2H→1T Phase Engineering of Layered Tantalum Disulfides in Electrocatalysis: Oxygen Reduction Reaction.

Tremendous attention is currently being paid to renewable sources of energy. Transition-metal dichalcogenides (TMDs) have been intensively studied for their promising catalytic activities in the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR). In this fundamental work, we explored the catalytic properties of TMD family members 2H TaS2 and 1T TaS2 . Our findings reveal that both polytypes exhibit poor HER performance, which is even more pronounced after electrochemical reduction/oxidation. Our experimental data show that 1T TaS2 has a lower overpotential at a current density of -10 mA cm-1 , despite theoretical DFT calculations that indicated that the more favorable free energy of hydrogen adsorption should make "perfect" 2H TaS2 a better HER catalyst. Thorough characterization showed that the higher conductivity of 1T TaS2 and a slightly higher surface oxidation of 2H TaS2 explains this discrepancy. Moreover, changes in the catalytic activity after electrochemical treatment are addressed here. For the ORR in an alkaline environment, the electrochemical treatment led to an improvement in catalytic properties. With onset potentials similar to that of Pt/C catalysts, TaS2 was found to be an efficient catalyst for the ORR, rather than for proton reduction, in contrast to the behavior of Group 6 layered TMDs.

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.

Erbium ion implantation into diamond - measurement and modelling of the crystal structure.

Diamond is proposed as an extraordinary material usable in interdisciplinary fields, especially in optics and photonics. In this contribution we focus on the doping of diamond with erbium as an optically active centre. In the theoretical part of the study based on DFT simulations we have developed two Er-doped diamond structural models with 0 to 4 carbon vacancies in the vicinity of the Er atom and performed geometry optimizations by the calculation of cohesive energies and defect formation energies. The theoretical results showed an excellent agreement between the calculated and experimental cohesive energies for the parent diamond. The highest values of cohesive energies and the lowest values of defect formation energies were obtained for models with erbium in the substitutional carbon position with 1 or 3 vacancies in the vicinity of the erbium atom. From the geometry optimization the structural model with 1 vacancy had an octahedral symmetry whereas the model with 3 vacancies had a coordination of 10 forming a trigonal structure with a hexagonal ring. In the experimental part, erbium doped diamond crystal samples were prepared by ion implantation of Er+ ions using ion implantation fluences ranging from 1 × 1014 ions per cm2 to 5 × 1015 ions per cm2. The experimental results revealed a high degree of diamond structural damage after the ion implantation process reaching up to 69% of disordered atoms in the samples. The prepared Er-doped diamond samples annealed at the temperatures of 400, 600 and 800 °C in a vacuum revealed clear luminescence, where the 〈110〉 cut sample has approximately 6-7 times higher luminescence intensity than the 〈001〉 cut sample with the same ion implantation fluence. The reported results are the first demonstration of the Er luminescence in the single crystal diamond structure for the near-infrared spectral region.

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.

A New Member of the Graphene Family: Graphene Acid.

A new member of the family of graphene derivatives, namely, graphene acid with a composition close to C1 (COOH)1 , was prepared by oxidation of graphene oxide. The synthetic procedure is based on repeated oxidation of graphite with potassium permanganate in an acidic environment. The oxidation process was studied in detail after each step. The multiple oxidations led to oxidative removal of other oxygen functional groups formed in the first oxidation step. Detailed chemical analysis showed only a minor amount of other oxygen-containing functional groups such as hydroxyl and the dominant presence of carboxyl groups in a concentration of about 30 wt %. Further oxidation led to complete decomposition of graphene acid. The obtained material exhibits unique sorption capacity towards metal ions and carbon dioxide. The highly hydrophilic nature of graphene acid allowed the assembly of ultrathin free-standing membranes with high transparency.

Simple Synthesis of Fluorinated Graphene: Thermal Exfoliation of Fluorographite.

Fluorinated graphene can be prepared directly by thermal exfoliation of fluorographite. The exfoliation was performed in a dynamic nitrogen atmosphere at various temperatures and the exfoliation products were analysed in detail by GC-MS. The structure and properties of all prepared fluorinated graphenes with various contents of fluorine were characterized by a number of analytical techniques. The results show both the dependence of fluorine concentration on exfoliation temperature and the suitability of this method for the synthesis of graphene with controlled concentration of fluorine. The high-temperature exfoliated fluorographite exhibits a high heterogeneous electron transfer rate and excellent catalytic properties towards the oxygen reduction reaction. These synthetic procedures can open a simple way for the synthesis of fluorinated graphene-based devices with tailored properties.

Electrochemistry of layered GaSe and GeS: applications to ORR, OER and HER.

Though many studies examined the properties of the class of IIIA-VIA and IVA-VIA layered materials, few have delved into the electrochemical aspect of such materials. In light of the burgeoning interest in layered structures towards various electrocatalytic applications, we endeavored to study the inherent electrochemical properties of representative layered materials of this class, GaSe and GeS, and their impact towards electrochemical sensing of redox probes as well as catalysis of oxygen reduction, oxygen evolution and hydrogen evolution reactions. In contrast to the typical sandwich structure of MoS2 layered materials, GeS is isoelectronic to black phosphorus with the same structure; GaSe is a layered material consisting of GaSe sheets bonded in the sequence Se-Ga-Ga-Se. We characterized GaSe and GeS by employing scanning electron microscopy, X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy complemented by electronic structure calculations. It was found that the encompassing surface oxide layers on GaSe and GeS greatly influenced their electrochemical properties, especially their electrocatalytic capabilities towards hydrogen evolution reaction. These findings provide fresh insight into the electrochemical properties of these IIIA-VIA and IVA-VIA layered structures which enables development for future applications.

Synthesis of Graphene Oxide by Oxidation of Graphite with Ferrate(VI) Compounds: Myth or Reality?

It is well established that graphene oxide can be prepared by the oxidation of graphite using permanganate or chlorate in an acidic environment. Recently, however, the synthesis of graphene oxide using potassium ferrate(VI) ions has been reported. Herein, we critically replicate and evaluate this new ferrate(VI) oxidation method. In addition, we test the use of potassium ferrate(VI) for the synthesis of graphene oxide under various experimental routes. The synthesized materials are analyzed by a number of analytical methods in order to confirm or disprove the possibility of synthesizing graphene oxide by the ferrate(VI) oxidation route. Our results confirm the unsuitability of using ferrate(VI) for the oxidation of graphite on graphene oxide because of its high instability in an acidic environment and low oxidation power in neutral and alkaline environments.