Powering the Future: Unleashing the Potential of MXene-Based Dual-Functional Photoactive Cathodes in Photo-Rechargeable Zinc-Ion Capacitor.

Dual-functional photo-rechargeable (photo-R) energy storage devices, which acquire stored energy from solar energy harvesting, are being developed to battle the current energy crisis. In this study, these findings on the photo-driven characteristics of MXene-based photocathodes in photo-R zinc-ion capacitors (ZICs) are presented. Along with the pristine Ti3 C2 Tx MXene, tellurium/Ti3 C2 Tx (Te/Ti3 C2 Tx ) hybrid nanostructure is synthesized via facile chemical vapor transport technique to examine them for photocathodes in ZICs. Interestingly, the evaluated self-powered photodetector devices using MXene-based samples revealed a pyro-phototronic behavior introduced into the samples, with higher desirability observed in Te/Ti3 C2 Tx . The photo-R ZICs results exhibited a capacitance enhancement of 50.86% for Te/Ti3 C2 Tx at two scan rates of 5 and 10 mV s-1 under illumination, compared to dark conditions. In contrast, a capacitance enhancement of 30.20% is obtained for the pristine Ti3 C2 Tx at only a 5 mV s-1 scan rate. Furthermore, both samples achieved photo-charging voltage responses of ≈960 mV, and photoconversion efficiencies of 0.01% (for Te/ Ti3 C2 Tx ) and 0.07% (for Ti3 C2 Tx ). These characteristics in MXene-based single photo-R ZICs are significant and considerable with the distinguished integrated photo-R supercapacitors with solar cells, or coupled energy-harvesting and energy-storing devices reported recently in the literature.

Carbonaceous Oxygen Evolution Reaction Catalysts: From Defect and Doping-Induced Activity over Hybrid Compounds to Ordered Framework Structures.

Oxygen evolution reaction (OER) is expected to be of great importance for the future energy conversion and storage in form of hydrogen by water electrolysis. Besides the traditional noble-metal or transition metal oxide-based catalysts, carbonaceous electrocatalysts are of great interest due to their huge structural and compositional variety and unrestricted abundance. This review provides a summary of recent advances in the field of carbon-based OER catalysts ranging from "pure" or unintentionally doped carbon allotropes over heteroatom-doped carbonaceous materials and carbon/transition metal compounds to metal oxide composites where the role of carbon is mainly assigned to be a conductive support. Furthermore, the review discusses the recent developments in the field of ordered carbon framework structures (metal organic framework and covalent organic framework structures) that potentially allow a rational design of heteroatom-doped 3D porous structures with defined composition and spatial arrangement of doping atoms to deepen the understanding on the OER mechanism on carbonaceous structures in the future. Besides introducing the structural and compositional origin of electrochemical activity, the review discusses the mechanism of the catalytic activity of carbonaceous materials, their stability under OER conditions, and potential synergistic effects in combination with metal (or metal oxide) co-catalysts.

Microwave-Induced Structural Engineering and Pt Trapping in 6R-TaS2 for the Hydrogen Evolution Reaction.

The nanoengineering of the structure of transition metal dichalcogenides (TMDs) is widely pursued to develop viable catalysts for the hydrogen evolution reaction (HER) alternative to the precious metallic ones. Metallic group-5 TMDs have been demonstrated to be effective catalysts for the HER in acidic media, making affordable real proton exchange membrane water electrolysers. Their key-plus relies on the fact that both their basal planes and edges are catalytically active for the HER. In this work, the 6R phase of TaS2 is "rediscovered" and engineered. A liquid-phase microwave treatment is used to modify the structural properties of the 6R-TaS2 nanoflakes produced by liquid-phase exfoliation. The fragmentation of the nanoflakes and their evolution from monocrystalline to partly polycrystalline structures improve the HER-activity, lowering the overpotential at cathodic current of 10 mA cm-2 from 0.377 to 0.119 V. Furthermore, 6R-TaS2 nanoflakes act as ideal support to firmly trap Pt species, which achieve a mass activity (MA) up 10 000 A gPt -1 at overpotential of 50 mV (20 000 A gPt -1 at overpotentials of 72 mV), representing a 20-fold increase of the MA of Pt measured for the Pt/C reference, and approaching the state-of-the-art of the Pt mass activity.

Free-Standing Black Phosphorus Foils for Energy Storage and Catalysis.

Few-layered black phosphorus (BP) is a two-dimensional material that has attracted intensive attention for applications in energy storage and catalysis due to its large surface area and good electrical and thermal conductivity. Herein, a comparable study of BP electrochemical exfoliation in various solutions of tetrabutylammonium salts (TBAX; X is PF6 - , BF4 - , and ClO4 - ) in DMSO is reported. Based on morphological and structural analyses, it is shown that TBAPF6 /DMSO medium was specifically appropriate for the production of high-quality BP nanosheets with micrometer lateral size and a thickness of about 2.4 nm. TBAPF6 /DMSO-processed, few-layered BP exhibits enhanced hydrogen evolution reaction (HER) catalytic activity compared with that of samples exfoliated with the assistance of BF4 - and ClO4 - ions. Finally, the fabrication of flexible, free-standing BP films and their performance in an all-solid-state supercapacitor device are demonstrated.

"Top-down" Arsenene Production by Low-Potential Electrochemical Exfoliation.

Arsenene, as an exotic representative of two-dimensional (2D) materials, has received great interest, yet the interest is mainly based on theoretical study. The reason for this is a restricted ability to operate the material from its synthesis to implementation. Beginning with the production, electrochemical exfoliation has been found as an extremely effective method for the preparation of 2D materials from bulk materials. Here, for the first time, we demonstrate the electrochemical exfoliation of bulk black arsenic in the anhydrous electrolyte medium. Spectro- and microscopic analyses evidence micrometer lateral size few-layer arsenene in a netlike porous shape formed of 2D flakes. We demonstrate that the surfactant-free exfoliation successfully resulted in a stable dispersion for which only washing with the corresponding solvent was sufficient. This electrochemistry route for the black arsenic exfoliation toward few-layer arsenene will broaden the materials' scope applications in new-generation devices.

Chemistry of Graphene Derivatives: Synthesis, Applications, and Perspectives.

The chemistry of graphene and its derivatives is one of the hottest topics of current material science research. The derivatisation of graphene is based on various approaches, and to date functionalization with halogens, hydrogen, various functional groups containing oxygen, sulfur, nitrogen, phosphorus, boron, and several other elements have been reported. Most of these functionalizations are based on sp3 hybridization of carbon atoms in the graphene skeleton, which means the formation of out-of-plane covalent bonds. Several elements were also reported for substitutional modification of graphene, where the carbon atoms are substituted with atoms like nitrogen, boron, and several others. From tens of functional groups, for only two of them were reported full functionalization of graphene skeleton and formation of its stoichiometric counterparts, fluorographene and hydrogenated graphene. The functionalization of graphene is crucial for most of its applications including energy storage and conversion devices, electronic and optic applications, composites, and many others.

Morphological Effects and Stabilization of the Metallic 1T Phase in Layered V-, Nb-, and Ta-Doped WSe2 for Electrocatalysis.

Layered transition-metal dichalcogenides (TMDs) are valued for their electrocatalytic properties toward the hydrogen-evolution reaction (HER) and oxygen-reduction reaction (ORR). One effective strategy to activate the electrocatalytic properties of TMDs is through doping. The optimistic outlook of doped-MoS2 as an electrocatalyst witnessed in previous reports spurred us to examine the effect of doping WSe2 with Group 5 transition-metal species, namely V, Nb, and Ta, in aspects of inherent electroactivities and catalysis. Apart from the mild reduction signal unique to the Group 5 transition-metal dopants, the Group 5 transition-metal-doped WSe2 materials are found to possess largely identical inherent electrochemistry to the undoped WSe2 with a characteristic anodic peak. Living up to expectations, the Group 5 transition-metal-doped WSe2 materials exhibit improved electrocatalytic HER efficiency, as evident by the lower HER overpotentials and Tafel slopes relative to undoped WSe2 . After doping with V, Nb, or Ta species, an increased number of active sites is observed given the distinct changes in morphology from thick bulky pieces in undoped WSe2 to thinner fragments in doped WSe2 . Although undoped WSe2 exists in the semiconducting 2H phase, the Group 5 transition-metal-doped WSe2 materials are dominated by the metallic 1T phase. Doping WSe2 with V, Nb, or Ta stabilizes the catalytic 1T phase and appears to induce the transition from the 2H to 1T phase. In contrast to the enhanced HER performance of WSe2 upon doping, Group 5 transition-metal dopants proved futile in activating the ORR electrocatalytic behavior of WSe2 , for which the ORR efficiency is unchanged. Therefore, these findings facilitate the understanding of the role of Group 5 transition-metal dopants in the electrochemical and catalytic properties of WSe2 relative to their morphological features and provide an evaluation of the efficacy of doping TMDs in electrocatalytic applications.

Unconventionally Layered CoTe2 and NiTe2 as Electrocatalysts for Hydrogen Evolution.

Two members of the transition metal ditelluride family, CoTe2 and NiTe2 , exist in multiple structures encompassing marcasite-, pyrite- and CdI2 related structures. The allotrope modification is influenced by weak changes in stoichiometry and synthesis. It is crucial to emphasize that the CdI2 structure type is manifested by NiTe2 while the CoTe2 adopts a related structure for a non-stoichiometric composition with ratio below 1:1.8. The obtained structure is based on LiTiS2 which is derived from CdI2 structure, however contains a polymeric cobalt network. Despite the atypical nature of their layered structure, layered phases of CoTe1.8 and NiTe2 are rarely cast into the spotlight. Here, layered CoTe1.8 and NiTe2 are investigated for their electrochemical and electrocatalytic properties. In electrocatalytic aspects, layered CoTe1.8 and NiTe2 demonstrate low overpotentials and small Tafel slopes that are quintessential features of hydrogen evolution electrocatalysts. These findings impart fundamental insights to the transition metal ditelluride family and affirm the prospective use of layered CoTe1.8 and NiTe2 in electrochemical applications.

Graphene/Group 5 Transition Metal Dichalcogenide Composites for Electrochemical Applications.

In comparison to the extensive research and great success attained by Group 6 transition metal dichalcogenides (TMDs) as hydrogen evolution reaction (HER) electrocatalysts, there is limited research focused on metallic Group 5 TMDs for use as electrocatalysts for hydrogen evolution. Density functional theory calculations have pointed out that Group 5 TMDs are highly favorable for HER, especially vanadium disulfide. In this work, nanocomposites of graphene and Group 5 TMDs were synthesized by thermal exfoliation of graphene oxide/TMD precursors in an H2 S atmosphere or in a H2 atmosphere as a control. Graphene oxide was prepared by the Hummers method while vanadium tetrachloride, niobium pentachloride, and tantalum pentachloride were utilized as TMD precursors. Then the potential of these nanocomposites as electrocatalysts towards HER was explored. Although these nanocomposites do not have comparable HER performance to Group 6 TMDs, they exhibit higher electrocatalytic activity in comparison with thermally reduced graphene oxide (TRGO) in the absence of TMD modification. In addition, the capacitive performance of these materials was also investigated in consideration of the high capacitance of graphene. It was indicated that the presence of TMDs on graphene actually suppress the capacitance performance of graphene itself.

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.

The Origin of MoS2 Significantly Influences Its Performance for the Hydrogen Evolution Reaction due to Differences in Phase Purity.

Molybdenum disulfide (MoS2 ) is at the forefront of materials research. It shows great promise for electrochemical applications, especially for hydrogen evolution reaction (HER) catalysis. There is a significant discrepancy in the literature on the reported catalytic activity for HER catalysis on MoS2 . Here we test the electrochemical performance of MoS2 obtained from seven sources and we show that these sources provide MoS2 of various phase purity (2H and 3R, and their mixtures) and composition, which is responsible for their different electrochemical properties. The overpotentials for HER at -10 mA cm-2 for MoS2 from seven different sources range from -0.59 V to -0.78 V vs. reversible hydrogen electrode (RHE). This is of very high importance as with much interest in 2D-MoS2 , the use of the top-down approach would usually involve the application of commercially available MoS2 . These commercially available MoS2 are rarely characterized for composition and phase purity. These key parameters are responsible for large variance of reported catalytic properties of MoS2 .

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.

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.

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.

A study of the effect of sonication time on the catalytic performance of layered WS2 from various sources.

WS2 is a transition metal dichalcogenide (TMD) with many potential applications from catalysis to sensing, and is of interest both in its bulk and monolayer forms. There is discrepancy in the literature on the reported electrocatalytic effect of layered WS2. In this study, we examine two issues: the influence of the WS2 source and the effect of a common agitation technique via ultrasonication on the observed electrocatalysis. Bulk WS2 from five different chemical providers demonstrated different HER electrocatalytic performances. Changes to the duration of sonication result in different HER electrocatalytic performances across all WS2 materials. This may affect the efficiency of subsequent modifications from which these TMD materials serve as precursor materials. On the other hand, while WS2 materials from different suppliers showed varying HET performances, changes in sonication time have no significant effect on their HET performances. Both the WS2 source and the duration of sonication have different implications for the electrochemical performance of bulk WS2 and thus represent important variables to consider in research involving WS2.

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.

Layered Post-Transition-Metal Dichalcogenides (X-M-M-X) and Their Properties.

AIII BVI chalcogenides are an interesting group of layered semiconductors with several attractive properties, such as tunable band gaps and the formation of solid solutions. Unlike the typically sandwiched structure of transition-metal dichalcogenides, AIII BVI layered chalcogenides with hexagonal symmetry are stacked through the X-M-M-X motif, in which M is gallium and indium, and X is sulfur, selenium, and tellurium. In view of the inadequate study of the electrochemical properties and great interest in layered materials towards energy-related research, herein the inherent electrochemistry of GaS, GaSe, GaTe, and InSe has been studied, as well as the exploration of their potential as hydrogen evolution reaction (HER) electrocatalysts. All four materials show redox peaks during cyclic voltammetry measurements. Furthermore, insights into catalysis of the HER are provided; these indicate the conductivity and number of active sites of the materials. All of these findings have important implications on their possible applications.

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.