Jan Luxa

Catalytic and Charge Transfer Properties of Transition Metal Dichalcogenides Arising from Electrochemical Pretreatment

Layered transition metal dichalcogenides (TMDs) have been the center of attention in the scientific community due to their properties that can be tapped on for applications in electrochemistry and hydrogen evolution reaction (HER) catalysis. We report on the effect of electrochemical treatment of exfoliated MoS2, WS2, MoSe2 and WSe2 nanosheets toward the goal of activating the electrochemical and HER catalytic properties of the TMDs. In particular, electrochemical activation of the heterogeneous electron transfer (HET) abilities of MoS2, MoSe2 and WSe2 is achieved via reductive treatments at identified reductive potentials based on their respective inherent electrochemistry. Comparing all TMDs, the charge transfer activation is most accentuated in MoSe2 and can be concluded that Mo metal and Se chalcogen type are more susceptible to electrochemical activation than W metal and S chalcogen type. With regards to the HER, we show that while MoS2 displayed enhanced performance when subjected to electrochemical reduction, WS2 fared worse upon oxidation. On the other hand, the HER performance of MoSe2 and WSe2 is independent of electrochemical redox treatment. We can conclude therefore that for the HER, S-containing TMDs are more responsive to redox treatment than compounds with the Se chalcogen. Our findings are beneficial toward understanding the electrochemistry of TMDs and the extent to which activation by electrochemical means is effective. In turn, when such knowledge is administered aptly, it will be promising for electrochemical uses.

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.

Nitrogen doped graphene: influence of precursors and conditions of the synthesis

Heteroatoms doped graphenes, especially nitrogen doped graphenes, have attracted much attention due to their remarkable performance as parts of lithium-ion batteries, advanced catalyst supports, super capacitors and fuel cells. The performance of doped materials strongly depends on the level of doping. While the nitrogen doped graphenes are synthesized by various methods, the parameters influencing the level of doping are seldom studied. Here we prepare nitrogen doped graphenes by exfoliation of different graphite oxides (i.e. Staudenmaier, Hofmann and Hummers) in an ammonia atmosphere at various exfoliation temperatures (i.e. 600 °C, 800 °C and 1000 °C). We study the efficiency of nitrogen doping using characterization methods such as scanning electron microscopy, Raman spectroscopy, combustible elemental analysis and X-ray photoelectron spectroscopy. We show that the level of doping strongly depends on the type of the starting graphite oxide. This has very important implication on the fabrication of doped graphenes and we suggest that the graphite oxide preparation route must be always considered when one performs heteroatom doping of graphenes via a thermal exfoliation route. In addition, we present an optimized, scalable technique for fabrication of large quantities of highly nitrogen doped (>7 at.%) graphenes.

Tuning of graphene oxide composition by multiple oxidations for carbon dioxide storage and capture of toxic metals

Graphene oxide (GO) is a material used as a precursor for the synthesis of graphene and its derivatives. Chemical properties of graphene are strongly influenced by the chemical composition of the original GO. In this paper we would like to show that the amount as well as the type of functional groups can be significantly increased and controlled by multiple oxidations of GO. For this purpose we performed multiple oxidations using two chlorate methods (Staudenmaier and Hofmann) and a permanganate method (Hummers). The results show a possibility of tuning the composition of GO functionalities by multiple oxidations. The obtained results also show that the second and third subsequent reoxidation reactions significantly increase the amount of oxygen containing groups in GO, mainly carboxylic groups. The multiple oxidation of graphene oxide led to a significant increase of carbon storage capacity. The high concentration of oxygen functionalities led to an increase of sorption capacity by more than one order of magnitude.

Exfoliation of Layered Topological Insulators Bi2Se3 and Bi2Te3 via Electrochemistry

Among layered materials, topological insulators such as Bi2Se3 and Bi2Te3 are lately attracting much attention due to particular electronic properties and, especially with Bi2Te3, excellent thermoelectric properties. Methods of preparation of few-layered nanosheets of Bi2Se3 and Bi2Te3 range from the bottom-up chemical vapor deposition or hydrothermal synthesis from oxide precursors to the top-down mechanical exfoliation and liquid-based exfoliation supported by sonication from the natural bulk crystals. Here, we propose a simple and rapid electrochemical approach to exfoliate natural Bi2Se3 and Bi2Te3 crystals in aqueous media to single/few-layer sheets. The exfoliated materials have been characterized by scanning transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, high-resolution transmission electron microscopy, and Raman spectroscopy in addition to evaluation of their electrochemical properties. This electrochemical procedure represents a simple, reagent-free, and scalable method for the fabrication of single/few-layer sheets of these 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.

Nanosized graphane (C1H1.14)n by hydrogenation of carbon nanofibers by Birch reduction method

Graphane, fully hydrogenated graphene with the composition (C1H1)n, has been theoretically predicted but never experimentally realized. Graphane stands out of the variety of heteroatom modified graphene for its well defined structure. Here we show that by employing Birch reduction on graphite nanofibers, one can reach hydrogenation levels close to 100%. We name this material graphane or graphane-like since its composition is relatively close to ideal theoretical stoichiometry C1H1. We systematically study the effect of the size and structure of the starting material and conditions of the synthesis. The morphology and properties of the synthesized graphane-like material are strongly dependent on the structure of the starting material. The extremely highly hydrogenated nanographanes should find applications ranging from nanoelectronics to electrochemistry such as in supercapacitors or electrocatalysts.

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.

Toward graphene chloride: chlorination of graphene and graphene oxide

Halogenated graphene derivatives are interesting due to their outstanding physical and chemical properties. In this paper, we present various methods for the synthesis of chlorinated graphene derivatives from graphene oxide and thermally reduced graphene. We performed exfoliation of graphene oxide in a chlorine atmosphere, plasma assisted exfoliation of graphite oxide using microwave radiation and finally direct chlorination of thermally reduced graphene by liquid chlorine under deep UV irradiation. The influence of the chlorination method on the resulting chlorinated graphenes was investigated by characterization of the graphenes, which was carried out using various techniques, including SEM, SEM-EDS, high-resolution XPS, FTIR, STA and Raman spectroscopy. Electrochemical properties were investigated by cyclic voltammetry. Although the graphenes were structurally similar, they involved remarkably different chlorine concentrations. The most highly chlorinated graphene exhibits a chlorine concentration of 11.7 at%. Chlorinated graphenes with such properties could be used for reversible chlorine storage or as a starting material for further chemical modifications.

Iridium- and Osmium-decorated Reduced Graphenes as Promising Catalysts for Hydrogen Evolution

Renewable energy sources are highly sought after as a result of numerous worldwide problems concerning the environment and the shortage of energy. Currently, the focus in the field is on the development of catalysts that are able to provide water splitting catalysis and energy storage for the hydrogen evolution reaction (HER). While platinum is an excellent material for HER catalysis, it is costly and rare. In this work, we investigated the electrocatalytic abilities of various graphene-metal hybrids to replace platinum for the HER. The graphene materials were doped with 4f metals, namely, iridium, osmium, platinum and rhenium, as well as 3d metals, namely, cobalt, iron and manganese. We discovered that a few hybrids, in particular iridium- and osmium-doped graphenes, have the potential to become competent electrocatalysts owing to their low costs and-more importantly-to their promising electrochemical performances towards the HER. One of the more noteworthy observations of this work is the superiority of these two hybrids over MoS2 , a well-known electrocatalyst for the HER.