Molybdenum Oxide Supported on Ti3AlC2 is an Active Reverse Water-Gas Shift Catalyst.

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.

Effect of surface chemistry on bio-conjugation and bio-recognition abilities of 2D germanene materials.

The interest of the scientific community for 2D graphene analogues has been recently focused on 2D-Xene materials from Group 14. Among them, germanene and its derivatives have shown great potential because of their large bandgap and easily tuneable electronic and optical properties. With the latter having been already explored, the use of chemically modified germanenes for optical bio-recognition is yet to be investigated. Herein, we have synthesized two germanene materials with different surface ligands namely hydrogenated germanene (Ge-H) and methylated germanene (Ge-Me) and used them as an optical platform for the label-free biorecognition of Ochratoxin A (OTA), a highly carcinogenic food contaminant. It was discovered that firstly the surface ligands on chemically modified germanenes have strong influence on the intrinsic fluorescence of the material; secondly they also highly affect both the bio-conjugation ability and the bio-recognition efficiency of the material towards the detection of the analyte. An improved calibration sensitivity, together with superior reproducibility and linearity of response, was obtained with a methylated germanene (Ge-Me) material, indicating also the better suitability of the latter for real sample analysis. Such research is highly beneficial for the development and optimization of 2D material based optical platforms for fast and cost-effective bioassays.

Single-Step Synthesis of Platinoid-Decorated Phosphorene: Perspectives for Catalysis, Gas Sensing, and Energy Storage.

The originality of phosphorene is suppressed by its structural defects, irreproducibility, and sensitivity to the ambient environment. To preserve phosphorene's essential characteristics, for example, influencing the charge redistribution and generating the formation of active centers, noble-metal decoration is found to be an efficient approach. Herein, we demonstrate a single-step electrochemical synthesis of platinoid-decorated few-layer phosphorene (FP). The material's structure and effects of metal (Ru, Rh, and Pd) deposition on the FP nanosheets were first explored by numerous analytical techniques and theoretical calculations. Platinoid-decorated FPs demonstrate high quality and consist of one to five layers modified with round- and heptagon-shaped metal nanoparticles with the most intense distribution of Pd. The high-rate Rh deposition provides the enhanced electrocatalytic efficiency for hydrogen evolution (79 mV·dec-1-Tafel slope) and almost 20 times increased capacity for the Li-ion batteries in comparison to bare and Ru-decorated FP. The chemosensing of platinoid-decorated FP indicates a response to methanol plus ethanol and shows inertness to acetone. The incorporation of Ru and Rh nanoparticles increases FP's selectivity toward methanol. This research provides a new approach for the in situ FP functionalization during top-down synthesis and thus broadens the material's feasibility for advanced nanotechnology.

Cloisite Microrobots as Self-Propelling Cleaners for Fast and Efficient Removal of Improvised Organophosphate Nerve Agents.

Naturally available microclays are well-known materials with great adsorption capabilities that are available in nature in megatons quantities. On the contrary, artificial nanostructures are often available at high cost via precision manufacturing. Such precision nanomanufacturing is also typically used for fabrication of self-propelled micromotors and nanomachines. Herein, we utilized naturally available Cloisite microclays to fabricate autonomous self-propelled microrobots and demonstrated their excellent performances in pesticide removal due to their excellent adsorption capability. Six different modified Cloisite microrobots were investigated by sputtering their microclays with platinum (Pt) for the fabrication of platinum-Cloisite (Pt-C) microrobots. The obtained microrobots displayed fast velocities (v > 110 µm/s) with fast and efficient enhanced removal of the pesticide fenitrothion, which is also considered as improvised nerve agent. The fabricated Pt-C microrobots exhibited low cytotoxicity even at high concentrations when incubated with human lung carcinoma epithelial cells, which make them safe for human handling.

Recoverable Bismuth-Based Microrobots: Capture, Transport, and On-Demand Release of Heavy Metals and an Anticancer Drug in Confined Spaces.

Self-propelled microrobots are seen as the next step of micro- and nanotechnology. The biomedical and environmental applications of these robots in the real world need their motion in the confined environments, such as in veins or spaces between the grains of soil. Here, self-propelled trilayer microrobots have been prepared using electrodeposition techniques, coupling unique properties of green bismuth (Bi) with a layered crystal structure, magnetic nickel (Ni), and a catalytic platinum (Pt) layer. These Bi-based microrobots are investigated as active self-propelled platforms that can load, transfer, and release both doxorubicin (DOX), as a widely used anticancer drug, and arsenic (As) and chromium (Cr), as hazardous heavy metals. The significantly high loading capability for such variable cargoes is due to the high surface area provided by the rhombohedral layered crystal structure of bismuth, as well as the defects introduced through the oxide layer formed on the surface of bismuth. The drug release is based on an ultrafast electroreductive mechanism in which the electron injection into microrobots and consequently into the loaded objects causes an electrostatic repulsion between them and thus an ultrafast release of the loaded cargos. Remarkably, we have presented magnetic control of the Bi-based microrobots inside a microfluidic system equipped with an electrochemical setup as a proof-of-concept to demonstrate (i) heavy metals/DOX loading, (ii) a targeted transport system, (iii) the on-demand release mechanism, and (iv) the recovery of the robots for further usage.

Shear-force exfoliation of indium and gallium chalcogenides for selective gas sensing applications.

Layered chalcogenides AIIIBVI of gallium and indium form a group of semiconducting nanomaterials with huge potential in electronic, sensor and energy storage applications. However, the preparation method predetermines the usage of the prepared nanomaterial. In this paper, we investigated shear-force milling exfoliation in a surfactant free water/ethanol mixture on indium and gallium chalcogenides and their utilization in the gas sensing of volatile organic compounds (VOCs). The exfoliation of bulk materials in a surfactant-free environment helped to avoid any surface contamination and allowed the preparation of materials without non-covalently bonded large organic molecules. Furthermore, the gas-sensing properties were evaluated by electrical impedance spectroscopy on VOCs. Our results showed high sensitivity and selectivity towards methanol. This suggests that shear-force milling is an effective method for the exfoliation of indium and gallium chalcogenides which can find application in the selective gas sensing of VOCs.

Cytotoxicity of Shear Exfoliated Pnictogen (As, Sb, Bi) Nanosheets.

The experimental achievement of phosphorene, which exhibits superior electronic, physical, and optical properties has spurred recent interest in other Group 15 elemental 2D nanomaterials such as arsenene, antimonene, and bismuthene. These unique and superior properties of the pnictogen nanosheets have spurred intensive research efforts and led to the discovery of their diversified potential applications; for instance, optical Kerr material, photonic devices, pnictogen-decorated microfibers, high-speed transistors, and flexible 2D electronics. Previous studies have mainly been dedicated to study the synthesis, properties, and applications of the heavy pnictogens nanosheets; however, the toxicological behaviour of these nanosheets has yet to be established. Herein, the cytotoxicity study of pnictogen nanosheets (As, Sb, and Bi) was conducted over 24 h of incubation with various concentrations of test materials and adenocarcinoma human lung epithelial A549 cells. After the treatment period, the remaining cell viabilities were obtained through absorbance measurements with WST-8 and MTT assays. These findings demonstrate that the toxicity of pnictogen nanosheets decreases down Group 15, whereby arsenic nanosheets are considered to be the most toxic, whereas bismuth nanosheets induce low cytotoxicity. The findings of this study constitute an important initial step towards enhancing our understanding of the toxicological effects of pnictogen nanosheets in light of their prospective commercial applications.

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

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

Cytotoxicity of Group 5 Transition Metal Ditellurides (MTe2 ; M=V, Nb, Ta).

Much research effort has been put in to study layered compounds with transition metal dichalcogenides (TMDs) being one of the most studied compounds. Due to their extraordinary properties such as excellent electrochemical properties, tuneable band gaps, and low shear resistance due to weak van der Waals interactions between layers, TMDs have been found to have wide applications such as electrocatalysts for hydrogen evolution reactions, supercapacitors, biosensors, field-effect transistors (FETs), photovoltaics, and lubricant additives. In very recent years, Group 5 transition metal ditellurides have received an immense amount of research attention. However to date, little has been known of the potential toxicities posed by these materials. As such, we conducted the cytotoxicity study by incubating various concentrations of the Group 5 transition metal ditellurides (MTe2 ; M=V, Nb, Ta) with human lung carcinoma epithelial A549 cells for 24 hours and the remaining cell viabilities after treatment was measured. Our findings indicate that VTe2 is highly toxic whereas NbTe2 and TaTe2 are deemed to exhibit mild toxicities. This study constitutes an exemplary first step towards the understanding of the Group 5 transition metal ditellurides' toxicity effects in preparation for their possible future commercialisation.

Surface properties of MoS2 probed by inverse gas chromatography and their impact on electrocatalytic properties.

Layered transition metal dichalcogenides (TMDs) are at the forefront of materials research. One of the most important applications of these materials is their electrocatalytic activity towards hydrogen evolution, and these materials are suggested to replace scarce platinum. Whilst there are significant efforts towards this goal, there are various reports of electrocatalysis of MoS2 (which is the most commonly tested TMD) with large variations of the reported electrocatalytic effect of the material, with overpotential varying by several hundreds of millivolts. Here, we analyzed surface properties of various bulk as well as single layer MoS2 samples using inverse gas chromatography. All samples displayed significant variations in surface energies and their heterogeneities. The surface energy ranged from 50 to 120 mJ m-2 depending on the sample and surface coverage. We correlated the surface properties and previously reported structural features of MoS2 with their electrochemical activities. We concluded that the observed differences in electrochemistry are caused by the surface properties. This is an important finding with an enormous impact on the whole field of electrocatalysis of layered materials.

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.

Investigation on the ability of heteroatom-doped graphene for biorecognition.

Doped graphene platforms have been attracting considerable attention due to their improved electrochemical performances. Recent studies have shown the advantage of using either p-type or n-type doped graphene materials as transducers for the detection of various electroactive probes. Here we wanted to take a step forward and extend the study to investigate the ability of heteroatom doped graphene as an electrochemical platform for biorecognition. To this aim, a boron-doped graphene, a nitrogen-doped graphene and an undoped graphene material prepared under similar conditions were employed for the detection of fumonisin B1, a highly carcinogenic mycotoxin found in food commodities. We found that the material structural features, such as the amount of oxygen functionalities, had a stronger influence on the sensitivity of biorecognition rather than the kind and amount of dopant. Our findings may be essential for the choice of a proper platform for the assessment of food safety.

Cytotoxicity of Exfoliated Layered Vanadium Dichalcogenides.

Transition-metal Group 5 vanadium dichalcogenides have shown promising properties for many applications, such as batteries, capacitors, electrocatalysts for hydrogen production and many more. However, their toxicological effects have not yet been well understood. Here, we studied the cytotoxicity of exfoliated VS2 , VSe2 and VTe2 by incubating various concentrations of the materials with human lung carcinoma (A549) cells for 24 h and measuring the remaining cell viabilities after the treatment. We found that these vanadium dichalcogenides are relatively more toxic compared to Group 6 transition-metal dichalcogenides (TMDs), namely MoS2 , WS2 and WSe2 . This study is important for a better understanding of the toxicity of TMDs in preparation for their actual commercialisation in the future.

Doped and undoped graphene platforms: the influence of structural properties on the detection of polyphenols.

There is a huge interest in doped graphene and how doping can tune the material properties for the specific application. It was recently demonstrated that the effect of doping can have different influence on the electrochemical detection of electroactive probes, depending on the analysed probe, on the structural characteristics of the graphene materials and on the type and amount of heteroatom used for the doping. In this work we wanted to investigate the effect of doping on graphene materials used as platform for the detection of catechin, a standard probe which is commonly used for the measurement of polyphenols in food and beverages. To this aim we compared undoped graphene with boron-doped graphene and nitrogen doped graphene platforms for the electrochemical detection of standard catechin oxidation. Finally, the material providing the best electrochemical performance was employed for the analysis of real samples. We found that the undoped graphene, possessing lower amount of oxygen functionalities, higher density of defects and larger electroactive surface area provided the best electroanalytical performance for the determination of catechin in commercial beer samples. Our findings are important for the development of novel graphene platforms for the electrochemical assessment of food quality.

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

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

The Cytotoxicity of Layered Black Phosphorus.

Black phosphorus (BP), the latest addition to the family of 2D layered materials, has attracted much interest owing to potential optoelectronics, nanoelectronics, and biomedicine applications. Little is known about its toxicity, such as whether it could be as toxic as white phosphorus. In response to the possibility of BP employment into commercial products and biomedical devices, its cytotoxicity to human lung carcinoma epithelial cells (A549) was investigated. Following a 24 h exposure of the cells with different BP concentrations, cell viability assessments were conducted using water-soluble tetrazolium salt (WST-8) and methylthiazolyldiphenyltetrazolium bromide (MTT) assays. The toxicological effects were found to be dose-dependent, with BP reducing cell viabilities to 48% (WST-8) and 34% (MTT) at 50 µg mL(-1) exposure. This toxicity was observed to be generally intermediate between that of graphene oxides and exfoliated transition-metal dichalcogenides (MoS2, WS2, WSe2). The relatively low toxicity paves the way to utilization of black phosphorus.

Insight into the mechanism of the thermal reduction of graphite oxide: deuterium-labeled graphite oxide is the key.

For the past decade, researchers have been trying to understand the mechanism of the thermal reduction of graphite oxide. Because deuterium is widely used as a marker in various organic reactions, we wondered if deuterium-labeled graphite oxide could be the key to fully understand this mechanism. Graphite oxides were prepared by the Hofmann, Hummers, Staudenmaier, and Brodie methods, and a deuterium-labeled analogue was synthesized by the Hofmann method. All graphite oxides were analyzed not only using the traditional techniques but also by gas chromatography-mass spectrometry (GC-MS) during exfoliation in hydrogen and nitrogen atmospheres. GC-MS enabled us to compare differences between the chemical compositions of the organic exfoliation products formed during the thermal reduction of these graphite oxides. Nuclear analytical methods (Rutherford backscattering spectroscopy, elastic recoil detection analysis) were used to calculate the concentrations of light elements, including the ratio of hydrogen to deuterium. Combining all of these results we were able to determine graphite oxide's thermal reduction mechanism. Carbon dioxide, carbon monoxide, and water are formed from the thermal reduction of graphite oxide. This process is also accompanied by various radical reactions that lead to the formation of a large amount of carcinogenic volatile organic compounds, and this will have major safety implications for the mass production of graphene.

The dopant type and amount governs the electrochemical performance of graphene platforms for the antioxidant activity quantification.

Graphene doped with heteroatoms can show new or improved properties as compared to the original undoped material. It has been reported that the type of heteroatoms and the doping conditions can have a strong influence on the electronic and electrochemical properties of the resulting material. Here, we wish to compare the electrochemical behavior of two n-type and two p-type doped graphenes, namely boron-doped graphenes and nitrogen-doped graphenes containing different amounts of heteroatoms. We show that the boron-doped graphene containing a higher amount of dopants provides the best electroanalytical performance in terms of calibration sensitivity, selectivity and linearity of response for the detection of gallic acid normally used as the standard probe for the quantification of antioxidant activity of food and beverages. Our findings demonstrate that the type and amount of heteroatoms used for the doping have a profound influence on the electrochemical detection of gallic acid rather than the structural properties of the materials such as amounts of defects, oxygen functionalities and surface area. This finding has a profound influence on the application of doped graphenes in the field of analytical chemistry.

Enhanced colloidal stability of nanoscale zero valent iron particles in the presence of sodium silicate water glass.

A method for the stabilization of nanoscale zero valent iron (nZVI) particles using silica was developed. Stabilization can significantly improve the performance characteristics of currently available nZVI products containing agglomerated particles. In the first step of the method, the agglomerates were broken using a sonication. A subsequent stabilizing effect was brought about by the deposition of silica onto the surface of the nZVI particles. The method was tested on three commercially available nZVI suspensions which formed agglomerates with mean sizes ranging from 1000 to 5000 nm. The application of the method resulted in a significant reduction of the mean size of the agglomerates to the values from 100 to 200 nm. The stabilizing effect of silica was also evidenced using scanning electron microscopy, zeta potential measurements and sedimentation analysis. The introduction of typical groundwater ions did not significantly affect the colloidal stability of the treated nZVI suspensions. The results of this study indicate that the silica coating have the potential to protect nZVI against agglomeration.

MoS2 exhibits stronger toxicity with increased exfoliation.

MoS2 belong to a class of inorganic 2D nanomaterials known as transition metal dichalcogenides (TMDs) which have recently attracted a renewed and growing interest due to their interesting electronic and catalytic properties when scaled down to single or few layer sheets. Although exfoliated MoS2 nanosheets have been proposed for numerous energy-related and biosensing applications, little is known about the toxicological impacts of using MoS2 nanosheets. Here, we report about the in vitro toxicity of MoS2 nanosheets that have been chemically exfoliated with different lithium intercalating agents and compared their respective cytotoxic influence. Methyllithium (Me-Li), n-butyllithium (n-Bu-Li) and tert-butyllithium (t-Bu-Li) were used for the exfoliation of bulk MoS2 and we found the t-Bu-Li and n-Bu-Li exfoliated MoS2 nanosheets to be more cytotoxic than MoS2 exfoliated by Me-Li. t-Bu-Li and n-Bu-Li provide more efficient exfoliation over Me-Li, and we establish that the extent of exfoliation that MoS2 undergo is a factor influencing their toxicity. Specifically, the more exfoliated the MoS2 nanosheets, the stronger its cytotoxic influence, which may be due to an increase in surface area and active edge sites. The potential toxicity of these MoS2 nanosheets should be taken into account before their employment in real world applications and we have shown the effect the amount of exfoliation can have on the toxicity of MoS2 nanosheets, representing the first step towards a better understanding of their toxicological properties.