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Optoelectronics and sensing devices are of enormous importance in our modern lives, which has propelled the scientific community to explore new two-dimensional (2D) nanomaterials to meet the requirements of future devices. Herein, we present the exfoliation of palladium thiophosphate (Pd3(PS4)2) by mechanical shear force exfoliation. The Pd3(PS4)2-based photoelectrochemical (PEC) device demonstrated self-powered broadband photodetection in the range of 385-940 nm with an unprecedented responsivity of 2 A W-1 and a specific detectivity of about 8.67 × 1011 cm Hz1/2 W-1 under the illumination of 420 nm LED light. The crucial parameters such as photoresponsivity, response, and recovery time of the device can be controlled by an externally applied voltage and the analyte concentration. Moreover, Pd3(PS4)2-based vapor-sensing devices exhibited frequency-dependent selective acetone sensing in the presence of other organic vapors with an ultrafast response and a recovery time of less than 1 s. Finally, the photocatalytic activity of Pd3(PS4)2 was revealed, which can be attributed to the presence of an appropriate band alignment with the catalytic activity of Pd. This novel material with the aforementioned fascinating phenomenon will pave the way toward practical future applications in optoelectronics and sensing.

Two-dimensional transitional metal halides have recently attracted significant attention due to their thickness-dependent and electrostatically tunable magnetic properties. However, this class of materials is highly reactive chemically, which leads to irreversible degradation and catastrophic dissolution within seconds in ambient conditions, severely limiting subsequent characterization, processing, and applications. Here, we impart long-term ambient stability to the prototypical transition metal halide CrI3 by assembling a noncovalent organic buffer layer, perylenetetracarboxylic dianhydride (PTCDA), which templates subsequent atomic layer deposition (ALD) of alumina. X-ray photoelectron spectroscopy demonstrates the necessity of the noncovalent organic buffer layer since the CrI3 undergoes deleterious surface reactions with the ALD precursors in the absence of PTCDA. This organic-inorganic encapsulation scheme preserves the long-range magnetic ordering in CrI3 down to the monolayer limit as confirmed by magneto-optical Kerr effect measurements. Furthermore, we demonstrate field-effect transistors, photodetectors, and optothermal measurements of CrI3 thermal conductivity in ambient conditions.

MAX phases are layered ternary carbides or nitrides that are attractive for catalysis applications due to their unusual set of properties. They show high thermal stability like ceramics, but they are also tough, ductile, and good conductors of heat and electricity like metals. Here, we study the potential of the Ti3AlC2 MAX phase as a support for molybdenum oxide for the reverse water–gas shift (RWGS) reaction, comparing this new catalyst to more traditional materials. The catalyst showed higher turnover frequency values than MoO3/TiO2 and MoO3/Al2O3 catalysts, due to the outstanding electronic properties of the Ti3AlC2 support. We observed a charge transfer effect from the electronically rich Ti3AlC2 MAX phase to the catalyst surface, which in turn enhances the reducibility of MoO3 species during reaction. The redox properties of the MoO3/Ti3AlC2 catalyst improve its RWGS intrinsic activity compared to TiO2- and Al2O3-based catalysts. We thank the Netherlands Organisation for Scientific Research (NWO) for the grant “Developing novel catalytic materials for converting CO2, methane and ethane to high-value chemicals in a hybrid plasma-catalytic reactor” (China.15.119). We also acknowledge financial support by MINECO (Spain) through projects MAT2017-86992-R and MAT2016-80285-P. Z.S. was supported by the project LTAUSA19034, from the Ministry of Education Youth and Sports (MEYS). M.H. and M.T. gratefully acknowledge NWO under LIFT, Launchpad for Innovative Future Technology, PreCiOuS, 731.015.407. We also thank the staff of the Swiss Light Source (SLS) synchrotron (SuperXAS beamline and proposal number 20190956), Maarten Nachtegaal and Adam Clark, for support during synchrotron measurements.

The ever decreasing sources of fossil fuels have launched extensive research of alternative materials that might play a key role in their replacement. Therefore, the scientific community continuously investigates the possibilities of maximizing the working capacity of such materials in order to fulfill energy challenges in the near future. In this context, doping of the semiconducting materials is a versatile strategy to trigger their physicochemical properties as well their electrochemical performance. Herein, the impact of rhenium doping toward photoelectrochemical activity of MoSe2 and WSe2 was studied. Our results indicate that rhenium as a dopant contributes to better overall electrochemical performance, that is, an easier electron transfer of these materials compared to pristine compounds. Additionally, the photoelectrochemical measurements revealed that the doping with rhenium generated an enhancement of the photocurrent response of MoSe2 as well as WSe2 under UV light illumination.

Na2Ti3O7 (NTO) is considered a promising anode material for Na‐ion batteries due to its layered structure with an open framework and low and safe average operating voltage of 0.3 V vs. Na+/Na. However, its poor electronic conductivity needs to be addressed to make this material attractive for practical applications among other anode choices. Here, we report a safe, controllable and affordable method using urea that significantly improves the rate performance of NTO by producing surface defects such as oxygen vacancies and hydroxyl groups, and the secondary phase Na2Ti6O13. The enhanced electrochemical performance agrees with the higher Na+ ion diffusion coefficient, higher charge carrier density and reduced bandgap observed in these samples, without the need of nanosizing and/or complex synthetic strategies. A comprehensive study using a combination of diffraction, microscopic, spectroscopic and electrochemical techniques supported by computational studies based on DFT calculations, was carried out to understand the effects of this treatment on the surface, chemistry and electronic and charge storage properties of NTO. This study underscores the benefits of using urea as a strategy for enhancing the charge storage properties of NTO and thus, unfolding the potential of this material in practical energy storage applications., A safe, controllable and affordable method using urea at mild temperatures to synthesise a series of sodium titanate samples with different levels of oxygen vacancies is reported. The formation of oxygen vacancies leads to the reduction of Ti4+ to Ti3+ ions in NTO, together with the formation of hydroxyl groups and a secondary phase, Na2Ti6O13.The urea‐treated samples showed superior electrochemical performance at high rates with respect to pristine NTO.

We report on the fabrication of the defect-free mixed-matrix membrane (MMM) based on the polyethylenimine (PEI) matrix with uniformly dispersed metal-organic framework (MOF) filler UiO-66-NH2, covalently bonded by polyvinylpyrrolidone (PVP). The key feature of the molecular level-controlled filler deposition in prepared UiO-66-NH2-PVP-PEI membranes was bridging the MOF particles to the PEI polymer matrix via PVP polymer chains. Such an approach improved the polymer-filler interface interactions and boosted the MOF dispersion into the polymer matrix for higher MOF loadings up to 23 wt %. The overall membrane structure and properties were characterized using FTIR, XRD, TG, DSC, SEM and 3D optical profiler techniques. Obtained results revealed the uniform dispersion of UiO-66-NH2, the strong polymer-filler interface interactions and entanglement of PEI with UiO-66-NH2-PVP. Furthermore, the outstanding CO2/H2 separation performance was determined for the UiO-66-NH2-PVP-PEI membrane with 18 wt % of MOF loading; the average CO2 permeability of 394 Barrer and the separation factor of 12 for circa 100 h of the membrane testing overcome the 2008 Robeson reverse upper bound limit. Such improved CO2/H2 separation performance was achieved due to the combination of the diffusion-solution mechanism with the preferential adsorption of the CO2 via the reversible bicarbonate reaction with amino groups of the UiO-66-NH2 and PEI which acts as fixed CO2 carrier sites in MMM structure.

Black phosphorus (BP) has extraordinary properties, but its ambient instability remains a critical challenge. Functionalization has been employed to overcome the sensitivity of BP to ambient conditions while preserving its properties. Herein, a simultaneous exfoliation–functionalization process is reported that functionalizes BP flakes during exfoliation and thus provides increased protection, which can be attributed to minimal exposure of the flakes to ambient oxygen and water. A tetrabutylammonium salt was employed for intercalation of BP, resulting in the formation of flakes with large lateral dimensions. The addition of an aryl iodide or an aryl iodonium salt to the exfoliation solvent creates a scalable strategy for the production of functionalized few‐layer BP flakes. The ambient stability of functionalized BP was prolonged to a period of one week, as revealed by STEM, AFM, and X‐ray photoelectron spectroscopy.

Emerging layered semiconductors present multiple advantages for optoelectronic technologies including high carrier mobilities, strong light-matter interactions, and tunable optical absorption and emission. Here, metal-semiconductor-metal avalanche photodiodes (APDs) are fabricated from Bi2O2Se crystals, which consist of electrostatically bound [Bi2O2]2+ and [Se]2− layers. The resulting APDs possess an intrinsic carrier multiplication factor up to 400 at 7 K with a responsivity gain exceeding 3,000 A/W and bandwidth of ~ 400 kHz at a visible wavelength of 515.6 nm, ultimately resulting in a gain bandwidth product exceeding 1 GHz. Due to exceptionally low dark currents, Bi2O2Se APDs also yield high detectivities up to 4.6 × 1014 Jones. A systematic analysis of the photocurrent temperature and bias dependence reveals that the carrier multiplication process in Bi2O2Se APDs is consistent with a reverse biased Schottky diode model with a barrier height of ~ 44 meV, in contrast to the charge trapping extrinsic gain mechanism that dominates most layered semiconductor phototransistors. In this manner, layered Bi2O2Se APDs provide a unique platform that can be exploited in a diverse range of high-performance photodetector applications.

Layered black phosphorus (BP) is a member of a layered material family with anisotropic properties and layer-dependent band gaps that can be exfoliated down to single-layered phosphorene. Compared with graphene, few-layered BP and its single-layer phosphorene are significantly more reactive, and this reactivity can be applied for the autogenous reduction of gold ions to metallic gold nanoparticles supported by few-layered BP (Au/BP). Few-layered BP and gold are well-known oxidation catalysts important in organic synthesis and also in the catalytic treatment and purification of industrial wastewater. The treatment of organic contamination present in industrial wastewater presents serious problems and is an important issue for current catalysis. Here, we show the high catalytic activity of the gold supported on few-layered black phosphorus (Au/BP) for wet oxidation of acrylic acid, including samples of industrial wastewater with complex composition. The catalyst Au/BP exhibits high stability, which allows utilization of its easily accessible 2D surface for the preparation of 2D material-supported metal catalysts.

Two-dimensional transition-metal dichalcogenides (TMDs) are lately in the scope within the scientific community owing to their exploitation as affordable catalysts for next-generation energy devices. Undoubtedly, only precise tailoring and control over the catalytic properties can ensure high efficiency and successful implementation of such devices in day-to-day practical utilization. However, contrary to theoretical predictions, systematic experimental work dealing with the doped materials and their impact to electrocatalysis are relatively underrated despite the considerable effect that it could bring into this field. Herein, we investigate the effect of four different dopants (i.e., Ti, V, Mn, and Fe) incorporated to both layered MoS2 and WS2 as solid-state solution toward their electrocatalytic performance through their evaluation as catalysts for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Our results pointed out that doping by Mn and Fe can enhance the electrocatalytic performance toward ORR, whereas doping by Ti and V revealed poor electrocatalytic effects (inhibition) compared to both undoped MoS2 and WS2. Surprisingly, none of the dopants contributed to the improvement of either MoS2 or WS2 toward HER activity. Therefore, in addition to the experimental data, density functional theory calculations were performed to further investigate the role of the dopants in the performance of MoS2 toward HER. According to these calculations, all dopants preferably occupied the edges of the crystal structure and thus could affect the electrocatalytic properties of the initial material. However, the observed ΔG values for hydrogen adsorption revealed that MoS2 is the best catalyst with a subsequent trend for doped materials following the less negative binding energies V < Ti < Mn < Fe, which was in good agreement with experimentally obtained overpotentials of the respective samples. This study thus elucidates the reasons for negative effects of doping in TMDs. This study brings an insight that not all dopants are beneficial and not all reactions are affected in the same way by dopants in TMDs.

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.

Metallic two-dimensional transition-metal dichalcogenides (TMDs) of the group 5 metals are emerging as catalysts for an efficient hydrogen evolution reaction (HER). The HER activity of the group 5 TMDs originates from the unsaturated chalcogen edges and the highly active surface basal planes, whereas the HER activity of the widely studied group 6 TMDs originates solely from the chalcogen- or metal-unsaturated edges. However, the batch production of such nanomaterials and their scalable processing into high-performance electrocatalysts is still challenging. Herein, we report the liquid-phase exfoliation of the 2H-TaS2 crystals by using 2-propanol to produce single/few-layer (1H/2H) flakes, which are afterward deposited as catalytic films. A thermal treatment-aided texturization of the catalytic films is used to increase their porosity, promoting the ion access to the basal planes of the flakes, as well as the number of catalytic edges of the flakes. The hybridization of the H-TaS2 flakes and H-TaSe2 flakes tunes the Gibbs free energy of the adsorbed atomic hydrogen onto the H-TaS2 basal planes to the optimal thermo-neutral value. In 0.5 M H2SO4, the heterogeneous catalysts exhibit a low overpotential (versus RHE, reversible hydrogen electrode) at the cathodic current of 10 mA cm-2 (η10) of 120 mV and high mass activity of 314 A g-1 at an overpotential of 200 mV. In 1 M KOH, they show a η10 of 230 mV and a mass activity of 220 A g-1 at an overpotential of 300 mV. Our results provide new insight into the usage of the metallic group 5 TMDs for the HER through scalable material preparation and electrode processing.

Two-dimensional (2D) layered antimony (Sb) and antimony telluride (Sb2 Te3 ) are two valuable materials for optoelectronic devices and thermoelectric applications. Preparing high-quality sheets of these materials is the initial phase to promote their expected issues. Herein, micrometer-sized few-to-multilayered sheets of Sb and Sb2 Te3 have been obtained by electrochemical exfoliation. The layered rhombohedral Sb was exfoliated in Na2 SO4 and Li2 SO4 electrolytes by anodic-cationic intercalation, and Sb2 Te3 was exfoliated in Na2 SO4 . These findings are important contributions for the solution-based room-temperature electrochemical exfoliation, which is stable under glove-box-free conditions, to further improve the production of high-quality exfoliated sheets.

Efficient exfoliation and downsizing of Sb2 S3 and Bi2 S3 layered compounds by using scalable bipolar electrochemistry on their suspensions in aqueous media are here demonstrated. The resulting samples were characterized in detail by transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy; their electrochemistry toward hydrogen evolution was also investigated. Hydrogen evolution ability of exfoliated Sb2 S3 and Bi2 S3 was investigated and compared to the bulk counterparts.

Black phosphorus is currently among the most explored two-dimensional (2D) materials. Currently, the synthesis methods are dominantly based on vapor-phase growth of black phosphorus. In this manuscript, we demonstrate large-scale synthesis of black phosphorus by rapid high-pressure transition of red phosphorus. The high-pressure conversion of red phosphorus led to high-density nanocrystalline black phosphorus ceramics. The resulting material was explored in detail including structural and morphological characterization in addition to thermal and electrical transport and basic thermophysical properties. The nanocrystalline black phosphorus can be employed for large-scale production of stable few/single-layer black phosphorus colloidal solutions in various solvents.

Self-propelled micromachines have recently attracted attention for environmental remediation, yet their use for radioactive waste management has not been addressed. Engineered micromotors that are able to combine highly adsorptive capabilities together with fast autonomous motion in liquid media are promising tools for the removal of nuclear waste, which is one of the most difficult types to manage. Herein, we fabricate self-propelled micromotors based on metal-organic frameworks (MOFs) via template-based interfacial synthesis and show their potential for efficient removal of radioactive uranium. A crucial challenge of the MOF-based motors is their stability in the presence of fuel (hydrogen peroxide) and acidic media. We have ensured their structural stability by Fe doping of zeolitic imidazolate framework-8 (ZIF-8). The implementation of magnetic ferroferric oxide nanoparticles (Fe3O4 NPs) and catalytic platinum nanoparticles (Pt NPs) results in the magnetically responsive and bubble-propelled micromotors. In the presence of 5 wt % H2O2, these micromotors are propelled at a high speed of ca. 860 ± 230 μm·s-1 (i.e., >60 body lengths per second), which is significantly faster than that of other microrod-based motors in the literature. These micromotors demonstrate a highly efficient removal of uranium (96%) from aqueous solution within 1 h, with the subsequent recovery under magnetic control, as well as stable recycling ability and high selectivity. Such self-propelled magnetically recoverable micromotors could find a role in the management and remediation of radioactive waste.

An electroadsorption technique similar to the ultrafast charging mechanism in supercapacitors is utilized to remove metals with different sizes and hydrophilicities from contaminated water using self-propelled microswimmers. The swimmers carry graphite fibre or bismuth with a layered crystal structure providing high electrostatic double-layer capacitances. Unlike previous methods, this electrochemical technique does not only utilize the surface of the swimmers, but due to the interlayer spacing of the graphite and bismuth, it is able to store metals in ≈400 layers, allowing removal and recovery of >50 ppm lithium in only 5 min. A larger interlayer distance between bismuth sheets allows the removal of bigger cations (sodium and calcium), expanding the application of this method to a large variety of natural elements. Finally, magnetic navigation of charged swimmers to an oxygen-saturated media causes oxidation and thus immediate release of the metal ions from the swimmers.

Among van der Waals nanomaterials, topological insulators such as antimony chalcogenides (Sb2X3, X = S, Se, Te) have interesting thermoelectric and optical properties. Expressly, Sb2S3 is regarded ...

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.

Nano/micromotors based on biodegradable and biocompatible polymers represent a progressively developing group of self-propelled artificial devices capable of delivering biologically active compounds to target sites. The majority of these machines are micron sized, and biologically active compounds are simply attached to their surface. Micron-sized devices cannot enter cells, but they provide rapid velocity, which scales down with the size of the device; nanosized devices can enter cells, but their velocity is negligible. An advanced hierarchical design of the micro/nanodevices is an important tool in the development of functional biocompatible transport systems and their implementation in real in vivo applications. In this work, we demonstrate a "mothership" concept, whereby self-propelled microrobots transport smaller cargo-carrying nanorobots that are released by enzymatic degradation.

The construction of flexible electrochemical devices for energy storage and generation is of utmost importance in modern society. In this article, we report on the synthesis of flexible MoS2-based composite paper by high-energy shear force milling and simple vacuum filtration. This composite material combines high flexibility, mechanical strength and good chemical stability. Chronopotentiometric charge–discharge measurements were used to determine the capacitance of our paper material. The highest capacitance achieved was 33 mF·cm−2 at a current density of 1 mA·cm−2, demonstrating potential application in supercapacitors. We further used the material as a cathode for the hydrogen evolution reaction (HER) with an onset potential of approximately −0.2 V vs RHE. The onset potential was even lower (approximately −0.1 V vs RHE) after treatment with n-butyllithium, suggesting the introduction of new active sites. Finally, a potential use in lithium ion batteries (LIB) was examined. Our material can be used directly without any binder, additive carbon or copper current collector and delivers specific capacity of 740 mA·h·g−1 at a current density of 0.1 A·g−1. After 40 cycles at this current density the material still reached a capacity retention of 91%. Our findings show that this composite material could find application in electrochemical energy storage and generation devices where high flexibility and mechanical strength are desired.Keywords: flexible composites; hydrogen evolution reaction (HER); lithium ion batteries (LIBs); molybdenum disulfide; nanoarchitectonics; supercapacitors

A significant amount of research is currently being undertaken to decrease the overall cost which governs the running of electrolyzer technologies. If the cost associated with electrolyzers was significantly reduced, it would pave a path to the efficient and economical generation of clean molecular hydrogen that could be used as a feedstock to create energy. As of now, only a handful of materials can challenge the performance of the current state-of-the-art cathodic catalyst, platnium, utilized in porous exchange-membrane electrolyzer devices. Herein, we show that 6.6 wt % of Pt on a homemade graphene film can achieve comparable hydrogen evolution activity to bulk platinum metal and surpass that of non-noble metal materials on carbon films previously reported.

We demonstrate challenging material properties of flat free-standing chemically modified single wall carbon nanotube (SWCNT) sheets potentially usable as new support materials for gas separation composite membranes. Carbon nanotube samples in bare and oxidized forms were assembled into buckypaper by a vacuum filtration from SWCNT colloidal suspension. The fundamental structure, composition and mechanical properties were examined via SEM, EDS, AFM, XPS, Raman spectroscopy and dynamical mechanical analysis. Gas permeability was determined by the fixed-volume pressure-increase permeation method at 25 °C and 1 bar feed overpressure. The mild SWCNT oxidation caused substantial structural rearrangement of buckypaper with significant impact on its properties. Determined partial opening of nanotubes and the introduction of oxygen-containing species decreased the initial extremely-high H2 permeability from circa 20 million (bare) to almost 5 million barrers while the ideal H2/CO2 selectivity α increased from almost non-selective 1.1 (bare) to 3.5 for the oxidized sample. Furthermore, oxidized form exhibited 2 times lower tensile strength but 2.5 times higher ductility. Such behavior indicates improved mechanical properties of oxidized samples that can undergo significant plastic deformation before the rupture. Determined features make mildly oxidized SWCNT buckypapers potentially attractive as new robust and tunable membrane support material for highly effective hydrogen separation.

MoS2 is one of the most explored and promising material for electrocatalytic water splitting by hydrogen evolution reaction (HER). However, in its bulk form, MoS2 possesses only poor activity towards HER. Therefore, appropriate treatment has to be employed to tune its catalytic properties. In this study, we report the influence of ion bombardment (S, Se and Te ions) with medium ion energy (400 keV) and various ion fluences (1 × 1014–1 × 1016 ions/cm2) on the electrocatalytic properties of bulk MoS2 crystals. Our results showed that upon irradiation, sulfur vacancies were created. Upon exposure to ambient atmosphere, sulfur vacancies were partially replaced by oxygen, which led to surface oxidation. Nevertheless, samples irradiated using the higher range of ion fluences have generally showed enhanced catalytic HER performance in comparison with untreated MoS2 crystals. Furthermore, we have also demonstrated that ion irradiation/implantation can serve as a tool for doping of MoS2 crystals with Se and Te which can also influence the HER performance. The reported results demonstrate that ion beam irradiation can be used for doping as well as creation of sulfur vacancies in bulk MoS2 crystals which is fundamental for the HER performance.

Monochalcogenides of heavier Group 13 (AIII) elements represent a unique family of compounds which, unlike the corresponding sesquichalcogenides, do not follow the classical valence concept. Their low-dimensional structures and semiconducting transport characteristics make them prospective candidates for various applications such as nanoelectronics, photonics and thermoelectric conversion. On the other hand, the variety of the respective phase diagrams involving several coexisting phases in narrow compositional ranges and high volatility of the components represent a challenge for their reproducible synthesis. In this study we explore the thermodynamic properties of In and Ga monochalcogenides by ab-initio density functional theory calculations of enthalpies of formation, low temperature heat capacity measurement to assess the standard entropies and differentials scanning calorimetry to obtain the temperature dependence of heat capacity above the reference temperature.

A facile one-step MoS2 spray-coating method was applied to a range of rigid, flexible, porous and 3D printed carbon-based surfaces, yielding high loadings in MoS2 flakes. The characterization of MoS2 flakes from a commercial lubricant spray reveals up to micron-scale bulk sheets of the layered material, constituted in its majority by the semiconducting 2H polymorph, in the presence of the metallic 1T phase. Consequently, the process generates MoS2 spray-coated surfaces with improved hydrogen evolution reaction (HER) catalytic performance. In the case of carbon-based screen printed electrodes (SPE), a short-term thermal post-treatment of the MoS2 spray-coated SPE had a further beneficial effect in the HER overpotential. The MoS2 spray-coated 3D metallic meshes held the lowest HER overpotential of the series. Finally, MoS2 spray-coated 3D printed electrodes yielded improved heterogeneous charge transfer and a 500 mV shift in the required overpotential at a current density of -10 mA cm-2. The MoS2 spray-coated 3D printed electrode displayed an abundant coverage at the inner, external and planar zones of electrodes by the MoS2 sheets, even after long-term operation conditions. These outcomes can be beneficial for future tailoring of MoS2 spray-coated surfaces and their implementation in energy conversion technologies.

The oxygen evolution and reduction reactions are two extremely important reactions in terms of energy applications. Currently, the Oxygen Evolution Reaction (OER) hinders the efficient running of electrolyzer devices which convert water into molecular H2. This H2 can subsequently be used in a H2/O2 fuel cell for the renewable generation of electricity with only H2O as a by-product. However, this fuel cell process is not economy feasible due to the sluggish kinetics of the Oxygen Reduction Reaction (ORR) at the device cathode, even with expensive state-of-the-art electrocatalytic materials. As of late, the amount of interest in the OER and ORR, from research laboratories from all over the globe, has risen rapidly in order to find cheap and efficient catalysts to replace the expensive platinum based catalysts currently used in the two aforementioned energy conversion/generation technologies. Layered transition metal oxides, based on the cheap transition metal oxides Mn, Co, Ni and Fe have been reported as viable catalysts for the OER and ORR. Layered structures have an added advantage over non-layered materials as the surface area can be increase by means of exfoliation, with potential for tailoring electrocatalytic activity. It has been shown that the fabrication process and post-synthetic treatments, e.g. anion exchange or exfoliation, of these materials can alter the catalytic activity of these materials. Here we summarise various fabrication methods and modifications utilised in literature to tailor the performance of layered transition metal and hydroxide based catalysts for the ORR and OER toward that of the state-of-the-art materials for these technologies.

The hydrogen evolution reaction (HER) is one of the most promising ways to produce clean energy. However, its wide-spread use is hindered by the price of the state-of-the-art catalysts based on precious metals. Transition metal dichalcogenide (TMD) nanomaterials are a cheap alternative, but a relatively large portion of them remains unexplored in terms of the HER. Here we report the HER performance of rhenium disulfide and diselenide in an acidic environment. We used sodium naphthalenide as an exfoliation agent. In comparison with other TMDs, the degree of exfoliation was relatively low. On the other hand, rhenium disulfide and diselenide both exhibit high chemical stability towards oxidation even after the exfoliation. The reported HER performance of the exfoliated rhenium dichalcogenides was strongly dependent on electrochemical treatment and to further enhance the performance, we used a series of electrochemical pretreatments at potentials as high as -2 V in sulfuric acid. While the morphology of the samples remained unchanged, the surface was found out to be chalcogen deficient, pointing out the formation of chalcogen vacancies. Consequentially, the HER performance was substantially enhanced. These results were corroborated by theoretical calculations showing improved bonding of hydrogen by chalcogenide vacancies at the surface. Our results show that a very simple electrochemical procedure can be used to improve the electrocatalytic performance of rhenium dichalcogenides and, possibly, also other TMDs.

It has been more than a decade since nano/micromachines (NMMs) have received the particular attention of scientists in different research fields. They are able to convert chemical energy into mechanical motion in their surrounding environment. Herein, a powerful, efficient and fast strategy of using nanosized reduced graphene oxide flake (n-rGO)-based self-propelled tubular micromachines for the removal of nitroaromatic compounds (NACs) is described. This method relies on the integration of the rGO as a well-known adsorbent of aromatic compounds with chemically powered engines for the removal of explosive compounds such as 2,4,6-trinitrotoluene (TNT), 2,4,6-trinitrophenol (TNP) and 2,4-dinitrotoluene (DNT). Nanographene oxide reduced electrochemically inside the pores of the polycarbonate membrane to form an outer layer (n-rGO, adsorbent layer) of the micromachines. Subsequent electrodeposition of nickel (Ni, magnetic layer) and platinum (Pt, catalytic layer) resulted in the formation of n-rGO/Ni/Pt micromachines. Notably, the bubble-propelled micromachines were able to remove nitroaromatic compounds with high efficiency (∼90-92%) compared to the efficiency of magnetic-guided (22-42%) and static (2.5-7%) micromachines. Most importantly, the micromachines were regenerated and reused several times. The regeneration is based on an electrochemical method in which electron injection into the machine causes the expulsion of contaminants from the outer layer of the micromachines within a few seconds. The integration of the powerful self-propulsion, high adsorbent capacity of rGO and the introduced ultrafast regeneration procedure are beneficial for the realization of an active platform for water remediation.

The irradiation with 1.2 MeV He+ ions to various fluences was successfully used for modification of graphene oxide (GO). The elemental composition of the GO foils before and after He+ ion irradiation was investigated using Rutherford Backscattering Spectrometry and Elastic Recoil Detection Analysis. The chemical composition and structural changes of the GO foil surface were characterized by X-Ray Photoelectron and Raman spectroscopy and changes in the electrical properties was studied by standard two point method. The obtained data indicate the removal of oxygen functionalities and growth of the graphene domains on the GO surface that leads to the improvement of surface conductivity which is a growing function of the ion fluence.

In this paper, a unique nano-coating consisting of a mixture of graphene oxide and multi-walled carbon nanotubes was applied on carbon-bonded alumina substrates. Graphene oxide (GO) was prepared according to the modified Tour's method. GO in combination with carbon nanotubes (CNTs) and modified coal tar pitch was spray-coated on conventional carbon-bonded alumina material for investigations in contact with steel. Temperature and time-dependent experiments were performed in a hot stage microscope to analyze the wetting behavior. The microstructures of the substrates before and after heating were compared by scanning electron microscopy. The results showed that the coating containing both GO and CNTs delivered a fast stabilization of the wetting angle with low wettability towards the metal melt. Similar coatings may offer an innovative approach to improve purification of steel melts by filtration in the steel industry.

Two-dimensional (2D) layered materials are currently one of the most explored materials for developing efficient and stable electrocatalysts in energy conversion applications. Some of the 2D metal phosphorous trichalcogenides (M2P2X6 or MPX3 in its simplified form) have been reported to be useful catalysts for water splitting, although results have been less promising for the sluggish oxygen evolution reaction (OER) due to insufficient activity or compromised stability. Herein, we report the OER catalysis of a series of M2P2X6 (M2+ = Mn, Fe, Co, Zn, Cd; X = S, Se). From the series of MPX3, CoPS3 yields the best results with an overpotential within the range of values usually obtained for IrO2 or RuO2 catalysts. The liquid-phase exfoliation of CoPS3 even improves the OER activity due to abundant active edges of the downsized sheets, accompanied by the presence of surface oxides. The influence of the OER medium and underlying substrate electrode is studied, with the exfoliated CoPS3 reaching the lowest overpotential at 234 mV at a current density of 10 mA/cm2, also able to sustain high current densities, with an overpotential of 388 mV at a current density of 100 mA/cm2, and excellent stability after multiple cycles or long-term operation. Quantum chemical models reveal that these observations are likely tied to moieties on CoPS3 edges, which are responsible for low overpotentials through a two-site mechanism. The OER performance of exfoliated CoPS3 reported herein yields competitive values compared to those reported for other Co-based and MPX3 in the literature, thus holding substantial promise for use as an efficient material for the anodic water-splitting reaction.

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.

Zinc indium sulfide belongs to the family of layered ternary chalcogenides. Although ZnIn2S4 has a suitable bandgap in the visible range, its optoelectronic properties are not fully investigated. Most photodetectors based on layered semiconductors suffer from large dark currents, which hamper their performance and energy efficiency. In this work, high quality ZnIn2S4 single crystals are synthesized via chemical vapor transport. The free-standing crystals are ≈20 μm thick and up to 2 cm2 in area and produce large photocurrents upon UV–vis illumination, while also maintaining extremely low currents in the dark. This allows to fabricate a simple photodetector with ohmic contacts, exhibiting extremely small dark currents down to 10–12 A. The ON/OFF (light/dark) switching ratio reaches value of 106, the highest reported for a layered semiconductor. Furthermore, the photodetector exhibits remarkable responsivity of 173 A W–1 and excellent detectivity of 1.7 × 1012 Jones. To demonstrate sensitivity and flexibility of the ZnIn2S4 crystals, a wearable device is also fabricated. The wearable is able to record human heart rate and compare it with signal measured by a commercial smartwatch. The results suggest a substantial research potential in further explorations of ZnIn2S4 and other ternary chalcogenides for optoelectronic applications., This work was supported by project LTAUSA19034 from Ministry of Education, Youth and Sports (MEYS) and by the specific university research IGA grant -A2_FCHT_2021_006. The TEM measurements were performed in the Laboratorio de Microscopias Avanzadas (LMA) at the Universidad de Zaragoza (Spain). R.A. acknowledges funding from the Spanish MICINN (project grant PID2019-104739GB-100/AEI/10.13039/501100011033), Government of Aragon (project DGA E13-20R), and European Union H2020 programs “ESTEEM3” (823717) and Graphene Flagship (881603).

Perovskite solar cells (PSCs) have proved their potential for delivering high power conversion efficiencies (PCE) alongside low fabrication cost and high versatility. The stability and the PCE of PSCs can readily be improved by implementing engineering approaches that entail the incorporation of two-dimensional (2D) materials across the device's layered configuration. In this work, two-dimensional (2D) 6R-TaS2 flakes were exfoliated and incorporated as a buffer layer in inverted PSCs, enhancing the device's PCE, lifetime and thermal stability. A thin buffer layer of 6R-TaS2 flakes was formed on top of the electron transport layer to facilitate electron extraction, thus improving the overall device performance. The optimized devices reach a PCE of 18.45%, representing a 12% improvement compared to the reference cell. The lifetime stability measurements of the devices under ISOS-L2, ISOS-D1, ISOS-D1I and ISOS-D2I protocols revealed that the TaS2 buffer layer retards the intrinsic, thermally activated degradation processes of the PSCs. Notably, the devices retain more than the 80% of their initial PCE over 330 h under continuous 1 Sun illumination at 65 °C.

Two-dimensional (2D) transition-metal monochalcogenides have been recently predicted to be potential photo(electro)catalysts for water splitting and photoelectrochemical (PEC) reactions. Differently from the most established InSe, GaSe, GeSe, and many other monochalcogenides, bulk GaS has a large band gap of ∼2.5 eV, which increases up to more than 3.0 eV with decreasing its thickness due to quantum confinement effects. Therefore, 2D GaS fills the void between 2D small-band-gap semiconductors and insulators, resulting of interest for the realization of van der Waals type-I heterojunctions in photocatalysis, as well as the development of UV light-emitting diodes, quantum wells, and other optoelectronic devices. Based on theoretical calculations of the electronic structure of GaS as a function of layer number reported in the literature, we experimentally demonstrate, for the first time, the PEC properties of liquid-phase exfoliated GaS nanoflakes. Our results indicate that solution-processed 2D GaS-based PEC-type photodetectors outperform the corresponding solid-state photodetectors. In fact, the 2D morphology of the GaS flakes intrinsically minimizes the distance between the photogenerated charges and the surface area at which the redox reactions occur, limiting electron–hole recombination losses. The latter are instead deleterious for standard solid-state configurations. Consequently, PEC-type 2D GaS photodetectors display a relevant UV-selective photoresponse. In particular, they attain responsivities of 1.8 mA W–1in 1 M H2SO4[at 0.8 V vs reversible hydrogen electrode (RHE)], 4.6 mA W–1in 1 M Na2SO4(at 0.9 V vs RHE), and 6.8 mA W–1in 1 M KOH (at 1.1. V vs RHE) under 275 nm illumination wavelength with an intensity of 1.3 mW cm–2. Beyond the photodetector application, 2D GaS-based PEC-type devices may find application in tandem solar PEC cells in combination with other visible-sensitive low-band-gap materials, including transition-metal monochalcogenides recently established for PEC solar energy conversion applications.

Developing resource-abundant and sustainable metal-free bifunctional oxygen electrocatalysts is essential for the practical application of zinc-air batteries (ZABs). 2D black phosphorus (BP) with fully exposed atoms and active lone pair electrons can be promising for oxygen electrocatalysts, which, however, suffers from low catalytic activity and poor electrochemical stability. Herein, guided by density functional theory (DFT) calculations, an efficient metal-free electrocatalyst is demonstrated via covalently bonding BP nanosheets with graphitic carbon nitride (denoted BP-CN-c). The polarized PN covalent bonds in BP-CN-c can efficiently regulate the electron transfer from BP to graphitic carbon nitride and significantly promote the OOH* adsorption on phosphorus atoms. Impressively, the oxygen evolution reaction performance of BP-CN-c (overpotential of 350 mV at 10 mA cm−2, 90% retention after 10 h operation) represents the state-of-the-art among the reported BP-based metal-free catalysts. Additionally, BP-CN-c exhibits a small half-wave overpotential of 390 mV for oxygen reduction reaction, representing the first bifunctional BP-based metal-free oxygen catalyst. Moreover, ZABs are assembled incorporating BP-CN-c cathodes, delivering a substantially higher peak power density (168.3 mW cm−2) than the Pt/C+RuO2-based ZABs (101.3 mW cm−2). The acquired insights into interfacial covalent bonds pave the way for the rational design of new and affordable metal-free catalysts

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.

Two-dimensional materials attract enormous attention across several scientific fields. The current demands in nano- and optoelectronics, semiconductors, or in catalysis have been accelerating the research process in the field of 2D materials. Among the 14th group 2D materials besides graphene and silicene, layered germanium represents a promising candidate for another class of materials, and its functionalization represents a way to tune either its electronic or optical properties. Here, the exfoliation and functionalization of germanane surface is achieved via abstraction of hydrogen from Ge-H bond and its subsequent alkylation utilizing n-alkyl halides or trifluoromethyl (CF3) group containing benzyl halides. Composition of materials is confirmed by several methods including FT-IR, Raman, X-ray photoelectron, and energy-dispersive X-ray spectroscopy as well as X-ray powder diffraction. Scanning and transmission electron spectroscopy is used to reveal the layered morphology of functionalized germananes.

Gallium selenide (GaSe) is a layered compound, which has been exploited in nonlinear optical applications and photodetectors due to its anisotropic structure and pseudo-direct optical gap. Theoretical studies predicted that its two-dimensional (2D) form is a potential photocatalyst for water splitting reactions. Herein, we first report the photoelectrochemical (PEC) characterization of GaSe nanoflakes (single-/few-layer flakes), produced via liquid phase exfoliation, for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in both acidic and alkaline media. In 0.5 M H2SO4, the GaSe photoelectrodes display the best PEC performance, i.e. a ratiometric power-saved metric for HER ({\Phi}saved,HER) of 0.09% and a ratiometric power-saved metric for OER ({\Phi}saved,OER) of 0.25%. When used as PEC-type photodetectors, GaSe photoelectrodes show a responsivity of ~0.16 A W-1 upon 455 nm illumination at light intensity of 63.5 uW cm-2 and applied potential of -0.3 V vs. reversible hydrogen electrode (RHE). The stability analysis of the GaSe photodetectors evidences a durable operation over tens of cathodic linear sweep voltammetry scans in 0.5 M H2SO4 for HER. Viceversa, degradation effects have been observed in both alkaline and anodic operation due to highly oxidizing environment and O2-induced (photo-)oxidation effects. Our results provide new insight into PEC properties of GaSe nanoflakes for their exploitation in photoelectrocatalysis, PEC-type photodetectors and (bio)sensors.

Layered indium selenide (InSe) is an emerging two-dimensional semiconductor that has shown significant promise for high-performance transistors and photodetectors. The range of optoelectronic applications for InSe can potentially be broadened by forming mixed-dimensional van der Waals heterostructures with zero-dimensional molecular systems that are widely employed in organic electronics and photovoltaics. Here, we report the spatially resolved investigation of photoinduced charge separation between InSe and two molecules (C

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 g(Pt)(-1) at overpotential of 50 mV (20 000 A g(Pt)(-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.

Freestanding electrodes for lithium ion batteries are considered as a promising option to increase the total gravimetric energy density of the cells due to a decreased weight of electrochemically inactive materials. We report a simple procedure for the fabrication of freestanding LiFe0.2Mn0.8PO4 (LFMP)/rGO electrodes with a very high loading of active material of 83 wt%, high total loading of up to 8 mg cm−2, high energy density, excellent cycling stability and at the same time very fast charging rate, with a total performance significantly exceeding the values reported in the literature. The keys to the improved electrode performance are optimization of LFMP nanoparticles via nanoscaling and doping; the use of graphene oxide (GO) with its high concentration of surface functional groups favoring the adhesion of high amounts of LFMP nanoparticles, and freeze-casting of the GO-based nanocomposites to prevent the morphology collapse and provide a unique fluffy open microstructure of the freestanding electrodes. The rate and the cycling performance of the obtained freestanding electrodes are superior compared to their Al-foil coated equivalents, especially when calculated for the entire weight of the electrode, due to the extremely reduced content of electrochemically inactive material (17 wt% of electrochemically inactive material in case of the freestanding compared to 90 wt% for the Al-foil based electrode), resulting in 120 mAh g−1electrode in contrast to 10 mAh g−1electrode at 0.2 C. The electrochemical performance of the freestanding LFMP/rGO electrodes is also considerably better than the values reported in literature for freestanding LFMP and LMP composites, and can even keep up with those of LFP-based analogues. The freestanding LFMP/rGO reported in this work is additionally attractive due to its high gravimetric energy density (604 Wh kg−1LFMP at 0.2C). The obtained results demonstrate the advantage of freestanding LiFe0.2Mn0.8PO4/rGO electrodes and their great potential for applications in lithium ion batteries.

Transition metal carbides, known as MXenes, are generated via the selective etching of "A" layers from their layered, ternary parent compounds, MAX phases, where M corresponds to early d-transition metal, A being a main group sp-element from either Group 13 or 14 and carbon or nitrogen being denoted by X. MXenes are being recognized as a new and uprising class of 2D materials with extraordinary physical and electrochemical properties. The huge specific surface area and outstanding electrical conductivity of MXenes, make them ideal candidates for sensing and energy applications. Herein, we demonstrated the successful incorporation of pristine MXene, Ti₃C₂ produced via HF etching and subsequent delamination with TBAOH, as a transducer platform toward the development of a second generation electrochemical glucose biosensor. Chronoamperometric studies demonstrate that the proposed biosensing system exhibits high selectivity and excellent electrocatalytic activity toward the detection of glucose, spanning over wide linear ranges of 50-27 750 μM and possess a low limit of detection of 23.0 μM. The findings reported in this study conceptually proves the probable applications of pristine MXenes toward the field of biosensors and pave ways for the future developments of highly selective and sensitive electrochemical biosensors for biomedical and food sampling applications. M.P. acknowledges the financial support of Grant Agency of the Czech Republic (EXPRO: 19-26896X). Z.S. was supported by the Neuron Foundation for scientific support.

Self-motile mesoporous ZnO/Pt-based Janus micromotors accelerated by bubble propulsion that provide efficient removal of explosives and dye pollutants via photodegradation under visible light are presented. Decomposition of H2O2 (the fuel) is triggered by a platinum catalytic layer asymmetrically deposited on the nanosheets of the hierarchical and mesoporous ZnO microparticles. The size-dependent motion behavior of the mesoporous micromotors is studied; the micromotors with average size ∼1.5 μm exhibit enhanced self-diffusiophoretic motion, whereas the fast bubble propulsion is detected for micromotors larger than 5 μm. The bubble-propelled mesoporous ZnO/Pt Janus micromotors show remarkable speeds of over 350 μm s-1 at H2O2 concentrations lower than 5 wt %, which is unusual for Janus micromotors based on dense materials such as ZnO. This high speed is related to efficient bubble nucleation, pinning, and growth due to the highly active and rough surface area of these micromotors, whereas the ZnO/Pt particles with a smooth surface and low surface area are motionless. We discovered new atomic interfaces of ZnO2 introduced into the ZnO/Pt micromotor system, as revealed by X-ray diffraction (XRD), which contribute to enhance their photocatalytic activity under visible light. Such coupling of the rapid movement with the high catalytic performance of ZnO/Pt Janus micromotors provides efficient removal of nitroaromatic explosives and dye pollutants from contaminated water under visible light without the need for UV irradiation. This paves the way for real-world environmental remediation efforts using microrobots.

Photoactivated micromachines are at the forefront of the micro- and nanomotors field, as light is the main power source of many biological systems. Currently, this rapidly developing field is based on metal-containing segments, typically TiO2 and precious metals. Herein, we present metal-free tubular micromotors solely based on graphitic carbon nitride, as highly scalable and low-cost micromachines that can be actuated by turning on/off the light source. These micromotors are able to move by a photocatalytic-induced bubble-propelled mechanism under visible light irradiation, without any metal-containing part or biochemical molecule on their structure. Furthermore, they exhibit interesting properties, such as a translucent tubular structure that allows the optical visualization of the O2 bubble formation and migration inside the microtubes, as well as inherent fluorescence and adsorptive capability. Such properties were exploited for the removal of a heavy metal from contaminated water with the concomitant...

Metal phosphorus chalcogenides is a new class of 2D materials that have shown interesting semiconducting, electronic, anisotropic, magnetic, dielectric, structural and optical properties. Recently, NiPS3, FePS3 and CoPS3 in particular have been highlighted for promising potential in important energy applications such as electrocatalysts for water splitting and hydrogen storage. However, little is known about the toxicological hazards that they may pose on humans. Here, we investigated the cytotoxicity of NiPS3, FePS3 and CoPS3 on human lung carcinoma cells (A549) and normal human bronchial cells (BEAS-2B) to address this concern. Upon treatment of these cells with different MPXY materials, we determined the remaining cell viability using water soluble tetrazolium salt (WST-8) assay. We found that CoPS3 was most toxic followed by FePS3 with intermediate toxicity while NiPS3 showed the lowest toxicity among the three materials tested for both cell lines. When viewed with other layered materials, these MPXY samples present comparable toxicities with transition metal dichalcogenides and black phosphorus at low concentrations. NRF (Natl Research Foundation, S’pore) Accepted version

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.

Graphitic carbon nitride has attracted extensive interests recently because of its potential in biosensing, photocatalytic, and biomedical applications. Similar to graphene, it is a two-dimensional carbon and nitrogen-based nanomaterial with weak van der Waals forces between each layer. Carbon nitrides can have various structural moieties such as triazine and heptazine. Unlike graphene-substituted nanosheets, the toxicity of graphitic carbon nitrite is largely unknown. In respond to that, toxicological study was carried out to determine its toxicity toward human lung carcinoma epithelial cells (A549). Two formazan-based cell viability assays (water-soluble tetrazolium salt (WST-8) assay and methylthiazolyldiphenyltetrazolium bromide (MTT) assay) were utilized on the A549 cell line to derive the cytotoxicity profile. Both materials demonstrated a dose-dependent toxicological effect with triazine-based carbon nitrides being more cytotoxic than heptazine-based carbon nitrides. These findings are of great imp...

Deterioration of the surface of black phosphorus (BP) caused by ambient atmosphere is an undesired process, limiting broader use of BP in many areas. The mechanism of BP degradation was explained theoretically, and the oxidized materials were thoroughly characterized experimentally. However, the surface analysis techniques introduce only a limited insight into the real state of the material. Here, we report a thorough analysis of the composition of mixtures obtained after a prolonged exposure of suspensions of BP to atmospheric oxygen with the aim to further disclosure the processes involved in the decomposition process. The results are compared with the predicted structures of the oxidized material and confirm the results of the theoretical calculations. The comparison of reactivity of BP with reactivity of white phosphorus under similar conditions concludes a similar distribution of the products in both cases.