Enhancing hydrogen evolution reaction activity through defects and strain engineering in monolayer MoS2.

Molybdenum disulfide (MoS2) has recently emerged as a promising electrocatalyst for the hydrogen evolution reaction (HER). However, the poor in-plane electrical conductivity and inert basal plane activity pose major challenges in realizing its practical application. Herein, we demonstrate a new approach to induce biaxial strain into CVD-grown MoS2 monolayers by draping it over an array of patterned gold nanopillar arrays (AuNAs) as an efficient strategy to enhance its HER activity. We vary the magnitude of applied strain by changing the inter-pillar spacing, and its effect on the HER activity is investigated. To capitalize on the synergistic effect of improved ΔG H via strain engineering and leverage basal plane activation by introduction of sulphur vacancies, we further exposed the strained MoS2 monolayers to oxygen plasma treatment to create S-vacancies. The strained MoS2 on AuNAs with optimal inter-pillar spacing is exposed to oxygen plasma treatment for different durations, and we study its electrocatalytic activity towards the HER using on-chip microcell devices. The strained and vacancy-rich monolayer MoS2 draped on AuNAs with a 0.5 µm inter-pillar spacing and exposed to plasma for 50 s (S0.5µmV50-MoS2) is shown to exhibit remarkable improvement in HER activity, with an overpotential of 53 mV in 0.5 M H2SO4. Thus, the synergistic creation of additional vacancy defects, along with strain-induced active sites, results in enhancement in HER performance of CVD-grown monolayer MoS2. The present study provides a highly promising route for engineering 2D electrocatalysts towards efficient hydrogen evolution.

Two-Dimensional Materials/Biopolymer-Based Antimicrobial Coatings to Thwart Biofilm Formation on Medical Implants.

Infections associated with medical implants due to bacterial adhesion and biofilm formation are a serious problem, leading to acute health risks to patients by compromising their immune system. Therefore, suppressing biofilm formation on biomedical implants is a challenging task, especially for overcoming the drug resistance of bacterial biofilms. Herein, a synergistic efficient surface coating method was developed to inhibit biofilm formation on a model medical implant by combining the antimicrobial property of trimethyl chitosan (TMC) with either 2D material graphene oxide (GO) or black phosphorus (BP) sheets using layer-by-layer (LbL) self-assembly. The multilayer coatings of TMC/GO and TMC/BP were optimized on the glass surface (a model implant) and characterized by using spectroscopic and microscopy techniques. Next, we investigated the antibiofilm formation properties of the TMC/GO and TMC/BP coatings on glass surfaces against both Gram-negative, Escherichia coli (E. coli), and Gram-positive, Bacillus subtilis (B. subtilis), bacteria. The antibiofilm formation was studied using crystal violet (CV) and live/dead assays. Both the live/dead and the CV assays confirmed that the TMC/2D material (2DM)-coated surfaces prevented biofilm formation much more effectively compared to the uncoated surfaces. Scanning electron microscopy analyses revealed that the bacteria were affected physically by incubating with TMC/2DM-coated surfaces due to membrane perturbation, thereby preventing cell attachment and biofilm formation. Further, BP composite coatings (TMC/BP) showed a much better ability to thwart biofilm formation than GO composite coatings (TMC/GO). Also, multilayer coatings showed superior cytocompatibility with human foreskin fibroblast (HFF). Our results demonstrate that the developed coatings TMC/2DMs could be potential candidates for thwarting biofilm formation on medical implants.

Polyimide-Based Aqueous Potassium Energy Storage Systems Using Concentrated WiSE Electrolyte.

Aqueous batteries are considered as promising alternative power sources due to their eco-friendly, cost-effective, and nonflammable attributes. Employing organic-based electrode materials offers further advantages toward building greener and sustainable systems, owing to their tunability and environmental friendliness. In order to enhance the energy and power densities, superconcentrated aqueous electrolytes, such as water-in-salt electrolytes (WiSE), have renewed the interest in aqueous batteries due to their enhanced stability and much wider electrochemical stability window (>1.23 V) compared with the traditional aqueous electrolytes. Here, we present a perylene diimide-based electrode material (PDI-Urea) as an appealing anode for aqueous potassium energy storage systems and investigate their electrochemical performance in three WiSE electrolytes, namely, 30 M potassium acetate, 40 M potassium formate and 30 M potassium bis(fluorosulfonyl)imide (KFSI). To explore the potential of PDI-Urea for potassium-based electrochemical energy systems, we fabricated full cell devices such as aqueous potassium dual-ion battery (APDIB) and aqueous K-ion battery (AKIB) and studied their electrochemical properties with 30 M KFSI electrolyte. The full cell K-ion battery, using a PBA cathode, exhibited excellent electrochemical performance with good rate capability and impressive capacity retention of 91% upon 1000 cycles. Further, the reaction mechanism of the electrodes is systematically analyzed using ex-situ studies.

Heterointerface engineering of cobalt molybdenum suboxide for overall water splitting.

Highly active and earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are of great significance for sustainable hydrogen generation through alkaline water electrolysis. Here, with an aim to enhance the bifunctional electrocatalytic activity of cobalt molybdate towards overall water splitting, we demonstrate a simple method involving the modulation of the cobalt to molybdenum ratio and creation of phase-modulated heterointerfaces. Samples with varying Co/Mo molar ratios are obtained via a microwave-assisted synthesis method using appropriate starting precursors. The synthesis conditions are modified to create a heterointerface involving multiple phases of cobalt molybdenum suboxides (CoO/CoMoO3/Co2Mo3O8) supported on Ni foam (NF). Detailed electrochemical studies reveal that modulating the composition and hence the interface can tweak the bifunctional electrocatalytic activity of the material for HER and OER and thus improve the overall water splitting efficiency with very high durability over 500 h. To further evaluate the practical applicability of the studied catalyst in water splitting, an alkaline electrolyser is fabricated with the optimized cobalt molybdenum suboxide material (CMO-1.25) as a bifunctional electrocatalyst. A current density of 220 mA cm-2 @1.6 V and 670 mA cm-2 @1.8 V was obtained, and the device showed very good long-term durability.

Mass Balancing of Hybrid Ion Capacitor Electrodes: A Simple and Generalized Semiempirical Approach.

Hybrid ion capacitors (HICs) are emerging as promising energy-storage devices exhibiting the advantages of both batteries and supercapacitors. However, the difference in the electrodes' specific capacities and rate capabilities makes it extremely challenging to achieve optimum mass balancing for a full-cell HIC device. Here, we demonstrate a method to predict well-performing mass ratios of electrodes for a Na-HIC by analyzing the capacities of anodes and cathodes as a function of the actual current densities experienced by the individual electrodes. We employ a simple design tool, a "Ragone Plot Simulator", to predict specific energy and specific power on Ragone plots and study the performance trend of devices with varying electrode mass ratios. The validation of the proposed method is done based on the experimental data obtained from several hybrid ion capacitor devices reported in the literature, which closely matches with the simulated Ragone plots. Further, we exemplify the validity of our calculations by comparing the simulated Ragone plot with that of a Na-HIC fabricated using in-house-made carbon. This unique approach presents a simple, generalized, yet never reported, method, which could be employed as a design tool to guide the selection of optimized HIC devices for the intended applications.

Engineering of Exciton-Plasmon Coupling Using 2D-WS2 Nanosheets for 1000-Fold Fluorescence Enhancement in Surface Plasmon-Coupled Emission Platforms.

Enhancement of fluorescence emission from single-photon quantum emitters on plasmonic nanomaterials using surface plasmon-coupled emission (SPCE) platforms has seen significant advancements. In parallel, there has also been an exponential rise in applications involving two-dimensional (2D) transition-metal dichalcogenides (TMDs) that exhibit unique exciton-plasmon interactions. Although both these Frontier research areas have impacted the development of sensor and sensing technologies, no study coalesces these two arenas for translational applications. In this work, we use thin WS2 nanosheets for realizing 1000-fold fluorescence enhancement on the SPCE platform. Structure-dependent fluorescence enhancement exhibited by WS2 provides new insight into the use of TMDs and exciton-plasmon coupling in SPCE substrates. Cellphone-based detection of the emitting dipole is another unique aspect of this work that presents a low-cost alternative in comparison with high-end detectors.

Anomalously polarised emission from a MoS2/WS2 heterostructure.

We report circularly polarised emission, with helicity opposite to the optical excitation, from a van der Waals heterostructure (HS) consisting of a monolayer MoS2 and three-layer WS2. Selective excitation of the MoS2 layer confirms that this cross-polarized emission is due to the charge transfer from the WS2 layers to the MoS2 layer. We propose that the high levels of n-doping in the constituent layers due to sulphur vacancies and defects give rise to an enhanced transition rate of electrons from the k valley of WS2 to the k' valley of MoS2, which leads to the emission, counter polarized to the excitation. Simulations based on the rate equation model support this conclusion.

Hierarchically Engineered Nanocarbon Florets as Bifunctional Electrode Materials for Adsorptive and Intercalative Energy Storage.

Three-dimensional dendritic nanostructured carbon florets (NCFs) with tailored porosity are demonstrated as electrochemically versatile electrodes for both adsorptive and intercalative energy storage pathways. Achieved through a single-step template-driven approach, the NCFs exhibit turbostratic graphitic lamellae in a floral assembly leading to high specific surface area and multi-modal pore distribution (920 m2/g). The synergism in structural and chemical frameworks, along with open-ended morphology, enables bifunctionality of hard carbon NCFs as symmetric adsorptive electrodes for supercapacitors (SCs) and intercalation anodes for hybrid potassium-ion capacitors (KICs). Flexible, all-solid-state SCs through facile integration of NCF with the ionic-liquid-imbibed porous polymeric matrix achieve high-energy density (20 W h/kg) and power density (32.7 kW/kg) without compromising on mechanical flexibility and cyclability (94% after 20k cycles). Furthermore, NCF as an anode in a full-cell hybrid KIC (activated carbon as cathode) delivers excellent electrochemical performance with maximum energy and power densities of 57 W h/kg and 12.5 kW/kg, respectively, when cycled in a potential window of 1.0-4.0 V. The exceptional bifunctional performance of NCF highlights the possibility of utilizing such engineered nanocarbons for high-performance energy storage devices.

Functionalized Phosphorene Quantum Dots as Efficient Electrocatalyst for Oxygen Evolution Reaction.

Phosphorene has attracted great interest in the rapidly emerging field of two-dimensional layered nanomaterials. Recent studies show promising electrocatalytic activity of few-layered phosphorene sheets toward the oxygen evolution reaction (OER). However, controllable synthesis of mono/few-layered phosphorene nanostructures with a large number of electrocatalytically active sites and exposed surface area is important to achieve significant enhancement in OER activity. Here, a novel strategy for controlled synthesis and in situ surface functionalization of phosphorene quantum dots (PQDs) using a single-step electrochemical exfoliation process is demonstrated. Phosphorene quantum dots functionalized with nitrogen-containing groups (FPQDs) exhibit efficient and stable electrocatalytic activity for OER with an overpotential of 1.66 V @ 10 mA cm-2, a low Tafel slope of 48 mV dec-1, and excellent stability. Further, we observe enhanced electron transfer kinetics for FPQDs toward the Fe2+/Fe3+ redox probe in comparison with pristine PQDs. The results demonstrate the promising potential of phosphorene as technologically viable OER electrodes for water-splitting devices.

Oxygen incorporated WS2 nanoclusters with superior electrocatalytic properties for hydrogen evolution reaction.

Transition metal dichalcogenides (TMDs) exhibit unique properties and show potential for promising applications in energy conversion. Mono/few-layered TMDs have been widely explored as active electrocatalysts for the hydrogen evolution reaction (HER). A controlled synthesis of TMD nanostructures with unique structural and electronic properties, leading to highly active sites or higher conductivity, is essential to achieve enhanced HER activity. Here, we demonstrate a new approach to controllably synthesize highly catalytically active oxygen-incorporated 1T and 2H WS2 nanoclusters from oxygen deficient WO3 nanorods, following chemical exfoliation and ultrasonication processes, respectively. The as-synthesized 1T nanoclusters, with unique properties of tailored edge sites, and enhanced conductivity resulting from the metallic 1T phase and oxygen incorporation, have been identified as highly active and promising electrocatalysts for the HER, with a very low Tafel slope of 47 mV per decade and a low onset overpotential of 88 mV, along with exceptionally high exchange current density and very good stability. The study could be extended to other TMD materials for potential applications in energy conversion and storage.

Exfoliation of Reduced Graphene Oxide with Self-Assembled π-Gelators for Improved Electrochemical Performance.

Among several methodologies to improve the solution processing of graphene-based materials, noncovalent functionalization has been considered as the simplest and nondestructive method. Herein, we show that molecular self-assembly process can be used as a useful tool to exfoliate reduced graphene oxide (RGO), resulting in hybrid materials with improved physical properties. Upon interacting with a π-gelator, the dispersing ability of the RGO increased significantly in most of nonpolar and polar aprotic solvents when compared to the bare one. The amount of RGO dispersed was 1.7-1.8 mg mL-1 in solvents such as toluene, o-dichlorobenzene (ODCB) and tetrahydrofuran (THF). Morphological studies revealed that aggregation of π-gelator over RGO helps to exfoliate graphene layers to remain as individual sheets with higher surface area. Experimental studies revealed enhanced surface area (250 m2 g-1) and better conductivity (3.7 S m-1) of the hybrid materials with 30% of RGO content resulting in excellent electrochemical performance (specific capacitance of 181 F g-1) as electrodes for supercapacitors.

Highly Ordered Vertical Arrays of TiO2/ZnO Hybrid Nanowires: Synthesis and Electrochemical Characterization.

We report the fabrication of vertically aligned hierarchical arrays of TiO2/ZnO hybrid nanowires, consisting of ZnO nanowires grown directly from within the pores of TiO2 nanotubes, through a combination of electrochemical anodization and hydrothermal techniques. These novel nano-architectured hybrid nanowires with its unique properties show promise as high performance supercapacitor electrodes. The electrochemical behaviour of these hybrid nanowires has been studied using Cyclic voltammetry, Galvanostatic charge-discharge and Electrochemical impedance spectroscopy (EIS) measurements using 1.5 M tetraethylammoniumtetrafluoroborate in acetonitrile as the electrolyte. Excellent electrochemical performances with a maximum specific capacitance of 2.6 mF cm-2 at a current density of 10 µA cm-2, along with exceptional cyclic stability, have been obtained for TiO2/ZnO-1 h hybrid material. The obtained results demonstrate the possibility of fabricating new geometrical architectures of inorganic hybrid nanowires with well adhered interfaces for the development of hybrid energy devices.

Electrochemical synthesis of luminescent MoS2 quantum dots.

Size-controlled synthesis of luminescent quantum dots of MoS2 (≤2 layers) with narrow size distribution, ranging from 2.5 to 6 nm, from their bulk material using a unique electrochemical etching of bulk MoS2 is demonstrated. Excitation-dependent photoluminescence emission is observed in the MoS2 QDs. "As-synthesized" MoS2 QDs also exhibit excellent electrocatalytic activity towards hydrogen evolution reactions.

MoS2 quantum dot-interspersed exfoliated MoS2 nanosheets.

We report the synthesis of heterodimensional nanostructures of MoS2 quantum dots interspersed in few-layered sheets of MoS2, using a liquid exfoliation technique in organic solvents. This unique hybrid morphology results from the optimized experimental conditions involving bath sonication followed by ultrasound probe sonication. We show that such heterodimensional hybrid materials could easily be extracted from the solvent as precipitates when post-treated with less polar volatile solvents such as chloroform. Such tailored MoS2 nanostructures, when directly used as electrodes for hydrogen evolution reaction, showed excellent electrocatalytic activity with low overpotential. Hence, we believe this could lead to large-scale synthesis of liquid-exfoliated layered nanostructures for their potential applications.

Towards a consensus on a hearing preservation classification system.

CONCLUSION: The comprehensive Hearing Preservation classification system presented in this paper is suitable for use for all cochlear implant users with measurable pre-operative residual hearing. If adopted as a universal reporting standard, as it was designed to be, it should prove highly beneficial by enabling future studies to quickly and easily compare the results of previous studies and meta-analyze their data. OBJECTIVES: To develop a comprehensive Hearing Preservation classification system suitable for use for all cochlear implant users with measurable pre-operative residual hearing. METHODS: The HEARRING group discussed and reviewed a number of different propositions of a HP classification systems and reviewed critical appraisals to develop a qualitative system in accordance with the prerequisites. RESULTS: The Hearing Preservation Classification System proposed herein fulfills the following necessary criteria: 1) classification is independent from users' initial hearing, 2) it is appropriate for all cochlear implant users with measurable pre-operative residual hearing, 3) it covers the whole range of pure tone average from 0 to 120 dB; 4) it is easy to use and easy to understand.

Covalently interconnected three-dimensional graphene oxide solids.

The creation of three-dimensionally engineered nanoporous architectures via covalently interconnected nanoscale building blocks remains one of the fundamental challenges in nanotechnology. Here we report the synthesis of ordered, stacked macroscopic three-dimensional (3D) solid scaffolds of graphene oxide (GO) fabricated via chemical cross-linking of two-dimensional GO building blocks. The resulting 3D GO network solids form highly porous interconnected structures, and the controlled reduction of these structures leads to formation of 3D conductive graphene scaffolds. These 3D architectures show promise for potential applications such as gas storage; CO2 gas adsorption measurements carried out under ambient conditions show high sorption capacity, demonstrating the possibility of creating new functional carbon solids starting with two-dimensional carbon layers.

Hybrid nanostructures for energy storage applications.

Materials engineering plays a key role in the field of energy storage. In particular, engineering materials at the nanoscale offers unique properties resulting in high performance electrodes and electrolytes in various energy storage devices. Consequently, considerable efforts have been made in recent years to fulfill the future requirements of electrochemical energy storage using these advanced materials. Various multi-functional hybrid nanostructured materials are currently being studied to improve energy and power densities of next generation storage devices. This review describes some of the recent progress in the synthesis of different types of hybrid nanostructures using template assisted and non-template based methods. The potential applications and recent research efforts to utilize these hybrid nanostructures to enhance the electrochemical energy storage properties of Li-ion battery and supercapacitor are discussed. This review also briefly outlines some of the recent progress and new approaches being explored in the techniques of fabrication of 3D battery structures using hybrid nanoarchitectures.

Conformal coating of thin polymer electrolyte layer on nanostructured electrode materials for three-dimensional battery applications.

Various three-dimensional (3D) battery architectures have been proposed to address effective power delivery in micro/nanoscale devices and for increasing the stored energy per electrode footprint area. One step toward obtaining 3D configurations in batteries is the formation of core-shell nanowires that combines electrode and electrolyte materials. One of the major challenges however in creating such architectures has been the coating of conformal thin nanolayers of polymer electrolytes around nanostructured electrodes. Here we show conformal coatings of 25-30 nm poly(methyl methacralate) electrolyte layers around individual Ni-Sn nanowires used as anodes for Li ion battery. This configuration shows high discharge capacity and excellent capacity retention even at high rates over extended cycling, allowing for scalable increase in areal capacity with electrode thickness. Our results demonstrate conformal nanoscale anode-electrolyte architectures for an efficient Li ion battery system.