ZIF-8/Graphene Oxide Hybrid Membranes as Breathable and Protective Barriers against Chemical Warfare Agents.

Personal protective equipment against chemical warfare agents and other toxic chemicals must be protective, be breathable, and have a low thermal burden. Selectively permeable membranes are promising candidates for such equipment. In this study, a hybrid membrane consisting of a continuous and thin zeolitic imidazolate framework (ZIF)-8 layer on an oxygen-rich small-flake graphene oxide layer was produced using a simple and scalable synthesis method. The small intrinsic pores of ZIF-8 allow it to selectively separate chemicals via size exclusion while permitting water vapor to permeate out. The ZIF-8/graphene oxide membrane had high selectivity for the penetration of water vapor over nerve agent simulants (ratio of dimethyl methylphosphonate to water vapor transmittance rates of ∼312) with a high water vapor transmittance rate of 3000 g m-2 day-1. This protective barrier layer is a promising material for next-generation protective clothing with enhanced comfort and operability.

Ultralight and Ultrathin Electrospun Membranes with Enhanced Air Permeability for Chemical and Biological Protection.

With the growing interest in chemical and biological warfare agents (CWAs/BWAs), the focus has shifted toward aerosol protection using protective clothing. However, compared to air-permeable membranes, those with water vapor permeability have been investigated more extensively. Filtering membranes without air permeability have limited practical usage in personal protective suits and masks. In this study, polyacrylonitrile membranes with tightly attached activated carbon and doped copper(II) oxide were prepared via electrospinning. The nanofibers with uniformly controlled diameters and smooth morphologies enable water/air breathability and protection against aerosol (100 nm polystyrene nanobeads similar to SARS-CoV-2) penetration. The uniformly distributed and tightly attached activated carbon and doped copper(II) oxide particles enhance the sorptive performance of the membranes by blocking gaseous CWAs, including soman, nerve chemical agents, and BWAs. Such dual-purpose membranes can be implemented in protective equipment owing to their high performance and easy processing.

Short-chain fluorocarbon-based polymeric coating with excellent nonwetting ability against chemical warfare agents.

The ongoing concerns and regulations on long-chain fluorinated compounds (C8 or higher) for nonwetting coatings have driven the market to search for sustainable alternative chemistries. In this study, a copolymeric coating containing short-chain fluorinated groups was synthesized to achieve excellent nonwetting ability against hazardous chemical warfare agents (CWAs). A copolymer of 1H,1H,2H,2H-perfluorooctyl methacrylate (PFOMA) and ethylene glycol dimethacrylate (EGDMA, crosslinker) was directly coated onto a textile fabric via initiated chemical vapor deposition. The p(PFOMA-co-EGDMA) coating shows a rough-textured morphology with a bumpy, raspberry-like structure leading to high contact angles (θ water > 150° and θ dodecane = 113.8°) and a small water shedding angle (<5°). Moreover, the p(PFOMA-co-EGDMA) coating was further analysed for application in military fabrics: air permeability, tensile strength, and safety against toxic perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Outstanding nonwetting was noticeably achieved against different CWAs, including bis(2-chloroethyl)sulfide (HD), pinacolyl methylfluorophosphonate (GD), and O-ethyl S-(2-diisopropylaminoethyl)methylphosphonothioate (VX) (θ HD = 119.1°, θ GD = 117.0°, and θ VX = 104.1°). The coating retained its nano-structuration and nonwetting ability for water and n-dodecane despite being subjected to 250 cycles of Martindale abrasion and harsh chemicals (NaOH and HCl). The robustness and scalable straightforward preparation route of the coating make it an ideal approach for designing durable next-generation CWA nonwetting coatings for fabrics with favorable health and environmental properties.

Generation of high-density nanoparticles in the carbothermal shock method.

The carbothermal shock (CTS) method has attracted considerable attention in recent years because it enables the generation of finely controlled polyelemental alloy nanoparticles (NPs). However, fabricating high surface coverage of NPs with minimized exposure of the carbon substrate is essential for various electrochemical applications and has been a critical limitation in CTS method. Here, we developed a methodology for creating NPs with high surface coverage on a carbon substrate by maximizing defect sites of cellulose during CTS. Cu NPs with high surface coverage of ~85%, various single NPs and polyelemental alloy NPs were densely fabricated with high uniformity and dispersity. The synthesized Cu NPs on cellulose/carbon paper substrate were used in electrocatalytic CO2 reduction reaction showing selectivity to ethylene of ~49% and high stability for over 30 hours of reaction. Our cellulose-derived CTS method enables the greater availability of polyelemental NPs for a wide range of catalytic and electrochemical applications.

Understanding Reaction Pathways in High Dielectric Electrolytes Using ß-Mo2C as a Catalyst for Li-CO2 Batteries.

The rechargeable Li-CO2 battery has attracted considerable attention in recent years because of its carbon dioxide (CO2) utilization and because it represents a practical Li-air battery. As with other battery systems such as the Li-ion, Li-O2, and Li-S battery systems, understanding the reaction pathway is the first step to achieving high battery performance because the performance is strongly affected by reaction intermediates. Despite intensive efforts in this area, the effect of material parameters (e.g., the electrolyte, the cathode, and the catalyst) on the reaction pathway in Li-CO2 batteries is not yet fully understood. Here, we show for the first time that the discharge reaction pathway of a Li-CO2 battery composed of graphene nanoplatelets/beta phase of molybdenum carbide (GNPs/ß-Mo2C) is strongly influenced by the dielectric constant of its electrolyte. Calculations using the continuum solvents model show that the energy of adsorption of oxalate (C2O42-) onto Mo2C under the low-dielectric electrolyte tetraethylene glycol dimethyl ether is lower than that under the high-dielectric electrolyte N,N-dimethylacetamide (DMA), indicating that the electrolyte plays a critical role in determining the reaction pathway. The experimental results show that under the high-dielectric DMA electrolyte, the formation of lithium carbonate (Li2CO3) as a discharge product is favorable because of the instability of the oxalate species, confirming that the dielectric properties of the electrolyte play an important role in the formation of the discharge product. The resulting Li-CO2 battery exhibits improved battery performance, including a reduced overpotential and a remarkable discharge capacity as high as 14,000 mA h g-1 because of its lower internal resistance. We believe that this work provides insights for the design of Li-CO2 batteries with enhanced performance for practical Li-air battery applications.

Ultrafast-Selective Nanofiltration of an Hybrid Membrane Comprising Laminated Reduced Graphene Oxide/Graphene Oxide Nanoribbons.

In this study, reduced graphene oxide (rGO) and graphene oxide nanoribbons (GONRs) are used to fabricate a composite membrane that exhibits ultrafast water permeance (312.8 L m-2 h-1 bar-1) and precise molecular separation (molecular weight cutoff: 269 Da), which surpass the upper bound of previously reported polymer and graphene-based nanofiltration membranes. As two-dimensional GONR exhibits a width on the scale of nanometers, its nanochannels can be enlarged without hindering the stacking of rGO. Moreover, abundant oxygen-containing groups on the edge and surface of GONR enhance the electrostatic interactions between the filtered molecules and the membrane nanochannel. By the synergistic effect, rejection and water flux are considerably increased. Owing to the chemically stable nature of rGO, the composite membrane is highly stable in aqueous media (from acidic to alkaline) and is recyclable during repeated filtration tests.

Formation of toroidal Li2O2 in non-aqueous Li-O2 batteries with Mo2CT x MXene/CNT composite.

Due to the growing demand for high energy density devices, Li-O2 batteries are considered as a next generation energy storage system. The battery performance is highly dependent on the Li2O2 morphology, which arises from formation pathways such as the surface growth and the solution growth models. Thus, controlling the formation pathway is important in designing cathode materials. Herein for the first time, we controlled the Li2O2 formation pathway by using Mo2CT x MXene on a catalyst support. The cathode was fabricated by mixing the positively charged CNT/CTAB solution with the negatively charged Mo2CT x solution. After introducing Mo2CT x , important battery performance metrics were considerably enhanced. More importantly, the discharge product analysis showed that the functional groups on the surface of Mo2CT x inhibit the adsorption of O2 on the cathode surface, resulting in the formation of toroidal Li2O2 via the solution growth model. It was supported by density functional theory (DFT) calculations that adsorption of O2 on the Mo2CT x surface is implausible due to the large energy penalty for the O2 adsorption. Therefore, the introduction of MXene with abundant functional groups to the cathode surface can provide a cathode design strategy and can be considered as a universal method in generating toroidal Li2O2 morphology.

Edge-Functionalized Graphene Nanoribbon Chemical Sensor: Comparison with Carbon Nanotube and Graphene.

With growing focus on the use of carbon nanomaterials in chemical sensors, one-dimensional graphene nanoribbon (GNR) has become one of the most attractive channel materials, owing to its enhanced conductance fluctuation by quantum confinement effects and dense, abundant edge sites. Due to the narrow width of a basal plane with one-dimensional morphology, chemical modification of edge sites would greatly affect the electrical channel properties of a GNR. Here, we demonstrate for the first time that chemically functionalizing the edge sites with aminopropylsilane (APS) molecules can significantly enhance the sensing performance of the GNR sensor. The resulting APS-functionalized GNR has a sensitivity ((Δ R/ Rb)max) of ∼30% at 0.125 ppm nitrogen dioxide (NO2) and an ultrafast response time (∼6 s), which are, respectively, 7- and 15-fold enhancements compared to a pristine GNR sensor. This is the fastest and most sensitive gas-sensing performance of all GNR sensors reported. To demonstrate the superiority of the GNR-APS sensor, we compare its sensing performance with that of APS-functionalized carbon nanotube (CNT) and reduced graphene oxide (rGO) sensors prepared in identical synthesis conditions. Very interestingly, the GNR-APS sensor exhibited 30- and 93-fold enhanced sensitivity compared to the CNT-APS and rGO-APS sensors. This might be attributed to highly active edge sites with superior chemical reactivity, which are not present in CNT and rGO materials. Density functional theory clearly shows that the greatly enhanced gas response of GNR with edge functionalization can be attributed to the higher electron densities in the highest occupied molecular orbital levels of GNR-APS and incorporation of additional adsorption sites. This finding is the first demonstration of the importance of edge functionalization of GNR for chemical sensors.

Correction: A three-dimensional metal grid mesh as a practical alternative to ITO.

Correction for 'A three-dimensional metal grid mesh as a practical alternative to ITO' by Sungwoo Jang et al., Nanoscale, 2016, 8, 14257-14263.

Rational Design of Aminopolymer for Selective Discrimination of Acidic Air Pollutants.

Strong acidic gases such as CO2, SO2, and NO2 are harsh air pollutants with major human health threatening factors, and as such, developing new tools to monitor and to quickly sense these gases is critically required. However, it is difficult to selectively detect the acidic air pollutants with single channel material due to the similar chemistry shared by acidic molecules. In this work, three acidic gases (i.e., CO2, SO2, and NO2) are selectively discriminated using single channel material with precise moiety design. By changing the composition ratio of primary (1°), secondary (2°), and tertiary (3°) amines of polyethylenimine (PEI) on CNT channels, unprecedented high selectivity between CO2 and SO2 is achieved. Using in situ FT-IR characterizations, the distinct adsorption phenomenon of acidic gases on each amine moiety is precisely demonstrated. Our approach is the first attempt at controlling gas adsorption selectivity of solid-state sensor via modulating chemical moiety level within the single channel material. In addition, discrimination of CO2, SO2, and NO2 with the single channel material solid-state sensor is first reported. We believe that this approach can greatly enhance air pollution tracking systems for strong acidic pollutants and thus aid future studies on selective solid-state gas sensors.

Ultrathin graphene oxide membranes on freestanding carbon nanotube supports for enhanced selective permeation in organic solvents.

Among the various factors required for membranes in organic solvent separations, the stability of membrane supports is critical in the preparation of membranes with universal chemical stability, mechanical flexibility, and high flux. In this study, nanoporous freestanding carbon nanotube (CNT) films were fabricated and utilized as supports for enhanced permeation in organic solvents. The excellent chemical stability of the CNT support allowed it to withstand various organic solvents such as toluene, acetone, and dimethylformamide. In addition, the structural stability and high pore density of CNT supports allowed the deposition of an ultrathin selective layer for an enhanced-flux membrane. Membrane performance was demonstrated by depositing a thin graphene oxide (GO) layer on the CNT support; GO was selected because of its high chemical stability. CNT-supported GO membranes effectively blocked molecules with molecular weight larger than ~800 g mol-1 while allowing the fast permeation of small molecules such as naphthalene (permeation was 50 times faster than that through thick GO membranes) and maintaining selective permeation in harsh solvents even after 72 hours of operation. We believe that the developed CNT support can provide fundamental insights in utilizing selective materials toward organic solvent membranes.

Universal Method for Creating Hierarchical Wrinkles on Thin-Film Surfaces.

One of the most interesting topics in physical science and materials science is the creation of complex wrinkled structures on thin-film surfaces because of their several advantages of high surface area, localized strain, and stress tolerance. In this study, a significant step was taken toward solving limitations imposed by the fabrication of previous artificial wrinkles. A universal method for preparing hierarchical three-dimensional wrinkle structures of thin films on a multiple scale (e.g., nanometers to micrometers) by sequential wrinkling with different skin layers was developed. Notably, this method was not limited to specific materials, and it was applicable to fabricating hierarchical wrinkles on all of the thin-film surfaces tested thus far, including those of metals, two-dimensional and one-dimensional materials, and polymers. The hierarchical wrinkles with multiscale structures were prepared by sequential wrinkling, in which a sacrificial layer was used as the additional skin layer between sequences. For example, a hierarchical MoS2 wrinkle exhibited highly enhanced catalytic behavior because of the superaerophobicity and effective surface area, which are related to topological effects. As the developed method can be adopted to a majority of thin films, it is thought to be a universal method for enhancing the physical properties of various materials.

Selective Molecular Separation on Ti3C2Tx-Graphene Oxide Membranes during Pressure-Driven Filtration: Comparison with Graphene Oxide and MXenes.

In this work, we prepared 90 nm thick Ti3C2Tx-graphene oxide (GO) membranes laminated on a porous support by mixing GO with Ti3C2Tx. This process was chosen to prevent the penetration of target molecules through inter-edge defects or voids with poor packing. The lattice period of the prepared membrane was 14.28 Å, as being swelled with water, resulting in an effective interlayer spacing of around 5 Å, which corresponds to two layers of water molecules. The composite membranes effectively rejected dye molecules with hydrated radii above 5 Å, as well as positively charged dye molecules, during pressure-driven filtration at 5 bar. Rejection rates were 68% for methyl red, 99.5% for methylene blue, 93.5% for rose Bengal, and 100% for brilliant blue (hydrated radii of 4.87, 5.04, 5.88, and 7.98 Å, respectively). Additionally, the rejections of composite membrane were compared with GO membrane and Ti3C2Tx membrane.

Facile Synthesis of Composition-Controlled Graphene-Supported PtPd Alloy Nanocatalysts and Their Applications in Methanol Electro-Oxidation and Lithium-Oxygen Batteries.

A new and simple approach is reported for the synthesis of uniformly dispersed PtPd alloy nanocatalysts supported on graphene nanoplatelets (GNPs) (PtPd-GNPs) through the introduction of bifunctional materials, which can modify the GNP surface and simultaneously reduce metal ions. With the use of poly(4-styrenesulfonic acid), poly(vinyl pyrrolidone), poly(diallyldimethylammonium chloride), and poly(vinyl alcohol) as bifunctional materials, PtPd-GNPs can be produced through a procedure that is far simpler than previously reported methods. The as-prepared nanocrystals on GNPs clearly exhibit uniform PtPd alloy structures of around 2 nm in size, which are strongly anchored and well distributed on the GNP sheets. The Pt/Pd atomic ratio and loading density of the nanocrystals on the GNPs are controlled easily by changing the metal precursor feed ratio and the mass ratio of GNP to the metal precursor, respectively. As a result of the synergism between Pt and Pd, the as-prepared PtPd-GNPs exhibit markedly enhanced electrocatalytic performance during methanol electro-oxidation compared with monometallic Pt-GNP or commercially available Pt/C. Furthermore, the PtPd-GNP nanocatalysts also show greatly enhanced catalytic activity toward the oxygen reduction/evolution reaction in a lithium-oxygen (Li-O2 ) process, resulting in greatly improved cycling stability of a Li-O2 battery.

Role of Alumina Basicity in CO2 Uptake in 3-Aminopropylsilyl-Grafted Alumina Adsorbents.

Oxide-supported amine materials are widely known to be effective CO2 sorbents under simulated flue-gas and direct-air-capture conditions. Most work has focused on amine species loaded onto porous silica supports, though potential stability advantages may be offered through the use of porous alumina supports. Unlike silica materials, which are comparably inert, porous alumina materials can be tuned to have substantial acidity and/or basicity. Owing to their amphoteric nature, alumina supports play a more active role in CO2 sorption than silica supports, potentially directly participating in the adsorption process. In this work, primary amines associated with 3-aminopropyltriethoxysilane are grafted onto two different mesoporous alumina materials having different levels of basicity. Adsorbent materials with different amine loadings are prepared, and the CO2 -adsorption behavior of similar amines on the two alumina supports is demonstrated to be different. At low amine loadings, the inherent properties of the support surface play a significant role, whereas at high amine loadings, when the alumina surface is effectively blocked, the sorbents prepared on the two supports behave similarly. At high amine loadings, amine-CO2 -amine interactions are shown to dominate, leading to adsorbed species that appear similar to the species formed over silica-supported amine materials. The sorbent properties are comprehensively characterized using N2 physisorption analysis, in situ FTIR spectroscopy, and adsorption microcalorimetry.

A three-dimensional metal grid mesh as a practical alternative to ITO.

The development of a practical alternative to indium tin oxide (ITO) is one of the most important issues in flexible optoelectronics. In spite of recent progress in this field, existing approaches to prepare transparent electrodes do not satisfy all of their essential requirements. Here, we present a new substrate-embedded tall (∼350 nm) and thin (∼30 nm) three-dimensional (3D) metal grid mesh structure with a large area, which is prepared via secondary sputtering. This structure satisfies most of the essential requirements of transparent electrodes for practical applications in future opto-electronics: excellent optoelectronic performance (a sheet resistance of 9.8 Ω□(-1) with a transmittance of 85.2%), high stretchability (no significant change in resistance for applied strains <15%), a sub-micrometer mesh period, a flat surface (a root mean square roughness of approximately 5 nm), no haze (approximately 0.5%), and strong adhesion to polymer substrates (it survives attempted detachment with 3M Scotch tape). Such outstanding properties are attributed to the unique substrate-embedded 3D structure of the electrode, which can be obtained with a high aspect ratio and in high resolution over large areas with a simple process. As a demonstration of its suitability for practical applications, our transparent electrode was successfully tested in a flexible touch screen panel. We believe that our approach opens up new practical applications in wearable electronics.

The Role of Layer-Controlled Graphene for Tunable Microwave Heating and Its Applications to the Synthesis of Inorganic Thin Films.

In this paper, we present the first method for precisely controlling the heat generated by microwave heating by tuning the number of graphene layers grown by chemical vapor deposition. The conductivity of the graphene increases linearly with the number of graphene layers, indicating that Joule heating plays a primary role in the temperature control of the graphene layer. In this method, we successfully synthesize TiO2 and MoS2 thin films, which do not interact well with microwaves, on a layer-controlled graphene substrate for a very short time (3 min) through microwave heating.

Highly Enhanced Fluorescence Signals of Quantum Dot-Polymer Composite Arrays Formed by Hybridization of Ultrathin Plasmonic Au Nanowalls.

Enhancement of the fluorescence intensity of quantum dot (QD)-polymer nanocomposite arrays is an important issue in QD studies because of the significant reduction of fluorescence signals of such arrays due to nonradiative processes in densely packed polymer chains in solid films. In this study, we enhance the fluorescence intensity of such arrays without significantly reducing their optical transparency. Enhanced fluorescence is achieved by hybridizing ultrathin plasmonic Au nanowalls onto the sidewalls of the arrays via single-step patterning and hybridization. The plasmonic Au nanowall induces metal-enhanced fluorescence, resulting in a maximum 7-fold enhancement of the fluorescence signals. We also prepare QD nanostructures of various shapes and sizes by controlling the dry etching time. In the near future, this facile approach can be used for fluorescence enhancement of colloidal QDs with plasmonic hybrid structures. Such structures can be used as optical substrates for imaging applications and for fabrication of QD-LED devices.

Complete magnesiothermic reduction reaction of vertically aligned mesoporous silica channels to form pure silicon nanoparticles.

Owing to its simplicity and low temperature conditions, magnesiothermic reduction of silica is one of the most powerful methods for producing silicon nanostructures. However, incomplete reduction takes place in this process leaving unconverted silica under the silicon layer. This phenomenon limits the use of this method for the rational design of silicon structures. In this effort, a technique that enables complete magnesiothermic reduction of silica to form silicon has been developed. The procedure involves magnesium promoted reduction of vertically oriented mesoporous silica channels on reduced graphene oxides (rGO) sheets. The mesopores play a significant role in effectively enabling magnesium gas to interact with silica through a large number of reaction sites. Utilizing this approach, highly uniform, ca. 10 nm sized silicon nanoparticles are generated without contamination by unreacted silica. The new method for complete magnesiothermic reduction of mesoporous silica approach provides a foundation for the rational design of silicon structures.

High quality reduced graphene oxide through repairing with multi-layered graphene ball nanostructures.

We present a simple and up-scalable method to produce highly repaired graphene oxide with a large surface area, by introducing spherical multi-layered graphene balls with empty interiors. These graphene balls are prepared via chemical vapor deposition (CVD) of Ni particles on the surface of the graphene oxides (GO). Transmission electron microscopy and Raman spectroscopy results reveal that defects in the GO surfaces are well repaired during the CVD process, with the help of nickel nanoparticles attached to the functional groups of the GO surface, further resulting in a high electrical conductivity of 18,620 S/m. In addition, the graphene balls on the GO surface effectively prevent restacking of the GO layers, thus providing a large surface area of 527 m(2)/g. Two electrode supercapacitor cells using this highly conductive graphene material demonstrate ideal electrical double layer capacitive behavior, due to the effective use of the outstanding electric conductivity and the large surface area.