Enhanced Electrochemical Performance of Ca-Doped Na3V2(PO4)2F3/C Cathode Materials for Sodium-Ion Batteries.

Na3V2(PO4)2F3 (NVPF) with a NASICON structure has garnered attention as a cathode material owing to its stable 3D structure, rapid ion diffusion channels, high operating voltage, and impressive cycling stability. Nevertheless, the low intrinsic electronic conductivity of the material leading to a poor rate capability presents a significant challenge for practical application. Herein, we develop a series of Ca-doped NVPF/C cathode materials with various Ca2+ doping levels using a simple sol-gel and carbon thermal reduction approach. X-ray diffraction analysis confirmed that the inclusion of Ca2+ does not alter the crystal structure of the parent material but instead expands the lattice spacing. Density functional theory calculations depict that substituting Ca2+ ions at the V3+ site reduces the band gap, leading to increased electronic conductivity. This substitution also enhanced the structural stability, preventing lattice distortion during the charge/discharge cycles. Furthermore, the presence of the Ca2+ ion introduces two localized states within the band gap, resulting in enhanced electrochemical performance compared to that of Mg-doped NVPF/C. The optimal NVPF-Ca-0.05/C cathode exhibits superior specific capacities of 124 and 86 mAh g-1 at 0.1 and 10 C, respectively. Additionally, the NVPF-Ca-0.05/C demonstrates satisfactory capacity retention of 70% after 1000 charge/discharge cycles at 10 C. These remarkable results can be attributed to the optimized particle size, excellent structural stability, and enhanced ionic and electronic conductivity induced by the Ca doping. Our findings provide valuable insight into the development of cathode material with desirable electrochemical properties.

Tuning the Crystallinity and Coverage of SiO2-ZnIn2S4 Core-Shell Nanoparticles for Efficient Hydrogen Generation.

The coverage, thickness, and crystallinity of ZnIn2S4 (ZIS) shells on SiO2 core nanoparticles (SiO2@ZIS) were systematically investigated using microwave-assisted solvothermal methods aided by the addition of acid in ethanolic medium. The surface modification of the SiO2 cores with (3-mercaptopropyl)trimethoxysilane was found to be critical to generate a homogeneous coverage of ZnIn2S4. The SiO2@ZIS core-shell nanoparticles exhibited the best coverage but poor crystallinity when synthesized in pure ethanol, whereas best crystallinity but poor coverage was observed when synthesized in an aqueous solution. The addition of selected amounts of acid (HCl) led to improved crystallinity in the ethanolic medium. The thickness of the ZIS shell could be controlled in an ethanolic solution by judiciously varying the amounts of acid and the concentration of the ZIS precursor. Increasing the concentration of the ZIS precursor to twice the standard concentration in ethanolic solution with the addition of 100 µL of HCl afforded better crystallinity, homogeneous coverage, and optimal photocatalytic hydrogen production.

Hollow Gold-Silver Nanoshells Coated with Ultrathin SiO2 Shells for Plasmon-Enhanced Photocatalytic Applications.

This article details the preparation of hollow gold-silver nanoshells (GS-NSs) coated with tunably thin silica shells for use in plasmon-enhanced photocatalytic applications. Hollow GS-NSs were synthesized via the galvanic replacement of silver nanoparticles. The localized surface plasmon resonance (LSPR) peaks of the GS-NSs were tuned over the range of visible light to near-infrared (NIR) wavelengths by adjusting the ratio of silver nanoparticles to gold salt solution to obtain three distinct types of GS-NSs with LSPR peaks centered near 500, 700, and 900 nm. Varying concentrations of (3-aminopropyl)trimethoxysilane and sodium silicate solution afforded silica shell coatings of controllable thicknesses on the GS-NS cores. For each type of GS-NS, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images verified our ability to grow thin silica shells having three different thicknesses of silica shell (~2, ~10, and ~15 nm) on the GS-NS cores. Additionally, energy-dispersive X-ray (EDX) spectra confirmed the successful coating of the GS-NSs with SiO2 shells having controlled thicknesses. Extinction spectra of the as-prepared nanoparticles indicated that the silica shell has a minimal effect on the LSPR peak of the gold-silver nanoshells.

Optically Tunable Tin Oxide-Coated Hollow Gold-Silver Nanorattles for Use in Solar-Driven Applications.

Core@shell metal nanoparticles have emerged as promising photocatalysts because of their strong and tunable plasmonic properties; however, marked improvements in photocatalytic efficiency are needed if these materials are to be widely used in practical applications. Accordingly, the design of new and functional light-responsive nanostructures remains a central focus of nanomaterial research. To this end, we report the synthesis of nanorattles comprising hollow gold-silver nanoshells encapsulated within vacuous tin oxide shells of adjustable thicknesses (∼10 and ∼30 nm for the two examples prepared in this initial report). These composite nanorattles exhibited broad tunable optical extinctions ranging from ultraviolet to near-infrared spectral regions (i.e., 300-745 nm). Zeta potential measurements showed a large negative surface charge of approximately -35 mV, which afforded colloidal stability to the nanorattles in aqueous solution. We also characterized the nanorattles structurally and compositionally using scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Futhermore, finite-difference time-domain simulation and photoluminescence properties of the composited nanoparticles were investigated. Collectively, these studies indicate that our tin oxide-coated hollow gold-silver nanorattles are promising candidates for use in solar-driven applications.

Composition Modulation of Ionic Liquid Hybrid Electrolyte for 5 V Lithium-Ion Batteries.

Electrolyte is a key component in high-voltage lithium-ion batteries (LIBs). Bis(trifluoromethanesulfonyl)imide-based ionic liquid (IL)/organic carbonate hybrid electrolytes have been a research focus owing to their excellent balance of safety and ionic conductivity. Nevertheless, corrosion of Al current collectors at high potentials usually happens for this kind of electrolyte. In this study, this long-standing problem is solved via the modulation of the IL/carbonate ratio and LiPF6 concentration in the hybrid electrolyte. The proposed electrolyte suppresses Al dissolution and electrolyte oxidation at 5 V (vs Li+/Li) and thus allows for ideal lithiation/delithiation performance of a high-voltage LiNi0.5Mn1.5O4 (LNMO) cathode even at 55 °C. The underlying mechanism is examined in this work. Excellent cycling stability (97% capacity retention) for an LNMO cathode after 300 cycles is achieved. This electrolyte shows good wettability toward a polyethylene separator and low flammability. In addition, satisfactory compatibility with both graphite and Si-based anodes is confirmed. The proposed electrolyte design strategies have great potential for applications in high-voltage LIBs.

Temperature-Responsive Hydrogel-Coated Gold Nanoshells.

Gold nanoshells (~160 nm in diameter) were encapsulated within a shell of temperature-responsive poly(N-isopropylacrylamide-co-acrylic acid) (P(NIPAM-co-AA)) using a surface-bound rationally-designed free radical initiator in water for the development of a photothermally-induced drug-delivery system. The morphologies of the resultant hydrogel-coated nanoshells were analyzed by scanning electron microscopy (SEM), while the temperature-responsive behavior of the nanoparticles was characterized by dynamic light scattering (DLS). The diameter of the P(NIPAM-co-AA) encapsulated nanoshells decreased as the solution temperature was increased, indicating a collapse of the hydrogel layer with increasing temperatures. In addition, the optical properties of the composite nanoshells were studied by UV-visible spectroscopy. The surface plasmon resonance (SPR) peak of the hydrogel-coated nanoshells appeared at ~800 nm, which lies within the tissue-transparent range that is important for biomedical applications. Furthermore, the periphery of the particles was conjugated with the model protein avidin to modify the hydrogel-coated nanoshells with a fluorescent-tagged biotin, biotin-4-fluorescein (biotin-4-FITC), for colorimetric imaging/monitoring.

Broadening the photoresponsive activity of anatase titanium dioxide particles via decoration with partial gold shells.

Titanium dioxide (TiO2) has gained increasing interest in materials research due to its outstanding properties and promising applications in a wide range of fields. From this perspective, we report the synthesis of custom-designed anatase TiO2 submicrometer particles coated with partial Au shells (ATiO2-AuShl). The synthetic strategy used herein yields uniformly shaped monodisperse particles. Amorphous TiO2 core particles were synthesized using template-free oxidation and hydrolysis of titanium nitride (TiN); subsequent hydrothermal treatment generated anatase TiO2 (ATiO2) particles. Coating ATiO2 particles with partial Au shells was accomplished using a simple seeded-growth method. Evaluation of the optical properties of these ATiO2-AuShl particles showed that these submicrometer composites exhibited an intense absorption peak for TiO2 in the UV region (∼326 nm) and a broad extinction band in the visible range (∼650 nm) arising from the incomplete Au shell. These ATiO2-AuShl composite particles provide a unique and effective means for broadening the optical response of TiO2-based nano- and micron-scale materials. The simplicity of our synthetic method should broaden the application of ATiO2-AuShl particles in various visible light-driven technologies.

Electrolyte Engineering: Optimizing High-Rate Double-Layer Capacitances of Micropore- and Mesopore-Rich Activated Carbon.

Various types of electrolyte cations as well as binary cations are used to optimize the capacitive performance of activated carbon (AC) with different pore structures. The high-rate capability of micropore-rich AC, governed by the mobility of desolvated cations, can outperform that of mesopore-rich AC, which essentially depends on the electrolyte conductivity.

Eco-Efficient Synthesis of Highly Porous CoCO3 Anodes from Supercritical CO2 for Li+ and Na+ Storage.

An eco-efficient synthetic route for the preparation of high-performance carbonate anodes for Li+ and Na+ batteries is developed. With supercritical CO2 (scCO2 ) as the precursor, which has gas-like diffusivity, extremely low viscosity, and near-zero surface tension, CoCO3 particles are uniformly formed and tightly connected on graphene nanosheets (GNSs). This synthesis can be conducted at 50 °C, which is considerably lower than the temperature required for conventional preparation methods, minimizing energy consumption. The obtained CoCO3 particles (ca. 20 nm in diameter), which have a unique interpenetrating porous structure, can increase the number of electroactive sites, promote electrolyte accessibility, shorten ion diffusion length, and readily accommodate the strain generated upon charging/discharging. With a reversible capacity of 1105 mAh g-1 , the proposed CoCO3 /GNS anode shows an excellent rate capability, as it can deliver 745 mAh g-1 in 7.5 min. More than 98 % of the initial capacity is retained after 200 cycles. These properties are clearly superior to those of previously reported CoCO3 -based electrodes for Li+ storage, indicating the merit of our scCO2 -based synthesis, which is facile, green, and can be easily scaled up for mass production.

Plasmonically Enhanced Photocatalytic Hydrogen Production from Water: The Critical Role of Tunable Surface Plasmon Resonance from Gold-Silver Nanoshells.

Gold-silver nanoshells (GS-NSs) having a tunable surface plasmon resonance (SPR) were employed to facilitate charge separation of photoexcited carriers in the photocalytic production of hydrogen from water. Zinc indium sulfide (ZnIn2S4; ZIS), a visible-light-active photocatalyst, where the band gap varies with the [Zn]/[In] ratio, was used as a model ZIS system (E(g) = 2.25 eV) to investigate the mechanisms of plasmonic enhancement associated with the nanoshells. Three types of GS-NS cores with intense absorptions centered roughly at 500, 700, and 900 nm were used as seeds for preparing GS-NS@ZIS core-shell structures via a microwave-assisted hydrothermal reaction, yielding core-shell particles with composite diameters of ∼200 nm. Notably, an interlayer of dielectric silica (SiO2) between the GS-NSs and the ZIS photocatalyst provided another parameter to enhance the production of hydrogen and to distinguish the charge-transfer mechanisms. In particular, the direct transfer of hot electrons from the GS-NSs to the ZIS photocatalyst was blocked by this layer. Of the 10 particle samples examined in this study, the greatest hydrogen gas evolution rate was observed for GS-NSs having a SiO2 interlayer thickness of ∼17 nm and an SPR absorption centered at ∼700 nm, yielding a rate 2.6 times higher than that of the ZIS without GS-NSs. The apparent quantum efficiencies for these core-shell particles were recorded and compared to the absorption spectra. Analyses of the charge-transfer mechanisms were evaluated and are discussed based on the experimental findings.

Silver-Free Gold Nanocages with Near-Infrared Extinctions.

This article reports the preparation of silver-free Au nanocages from cubic palladium templates. Pd nanocubes were subjected to galvanic replacement with Au3+ to produce Pd@Au nanocages having tunable dimensions (i.e., edge length, gold layer thickness, and hollow pore size), which allowed selectable positioning of the optical extinction maxima from the visible to the near infrared. These new nanocages circumvent the problems associated with previous Ag-derived gold alloy nanocages, which suffer from the toxicity of residual silver and the possible fragmentation of such alloyed nanostructures, thereby limiting their potential applications. In contrast, the present materials represent stable, nontoxic, tunable, and hollow plasmonic nanostructures.

MoS2/graphene cathodes for reversibly storing Mg(2+) and Mg(2+)/Li(+) in rechargeable magnesium-anode batteries.

Commercial micron-scale low-cost MoS2 is subjected to an electrochemically derived 2H-to-1T phase transformation, which makes it capable of reversibly storing Mg(2+)/Li(+) and Mg(2+) in all-phenyl-complex (APC) electrolytes with and without Li(+), respectively. The MoS2/graphene composite shows a high capacity (225 mA h g(-1)) and great cyclic stability in the Li(+)-containing APC electrolyte.

In situ growth of hollow gold-silver nanoshells within porous silica offers tunable plasmonic extinctions and enhanced colloidal stability.

Porous silica-coated hollow gold-silver nanoshells were successfully synthesized utilizing a procedure where the porous silica shell was produced prior to the transformation of the metallic core, providing enhanced control over the structure/composition of the bimetallic hollow core. By varying the reaction time and the precise amount of gold salt solution added to a porous silica-coated silver-core template solution, composite nanoparticles were tailored to reveal a readily tunable surface plasmon resonance that could be centered across the visible and near-IR spectral regions (∼445-800 nm). Characterization by X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and transmission electron microscopy revealed that the synthetic methodology afforded particles having uniform composition, size, and shape. The optical properties were evaluated by absorption/extinction spectroscopy. The stability of colloidal solutions of our composite nanoparticles as a function of pH was also investigated, revealing that the nanoshells remain intact over a wide range of conditions (i.e., pH 2-10). The facile tunability, enhanced stability, and relatively small diameter of these composite particles (∼110 nm) makes them promising candidates for use in tumor ablation or as photothermal drug-delivery agents.

Surface-engineered growth of AgIn5S8 crystals.

The growth of semiconductor crystals and thin films plays an essential role in industry and academic research. Considering the environmental damage caused by energy consumption during their fabrication, a simpler and cheaper method is desired. In fact, preparing semiconductor materials at lower temperatures using solution chemistry has potential in this research field. We found that solution chemistry, the physical and chemical properties of the substrate surface, and the phase diagram of the multicomponent compound semiconductor have a decisive influence on the crystal structure of the material. In this study, we used self-assembled monolayers (SAMs) to modify the silicon/glass substrate surface and effectively control the density of the functional groups and surface energy of the substrates. We first employed various solutions to grow octadecyltrichlorosilane (OTS), 3-mercaptopropyl-trimethoxysilane (MPS), and mixed OTS-MPS SAMs. The surface energy can be adjusted between 24.9 and 50.8 erg/cm(2). Using metal sulfide precursors in appropriate concentrations, AgIn5S8 crystals can be grown on the modified substrates without any post-thermal treatment. We can easily adjust the nucleation in order to vary the density of AgIn5S8 crystals. Our current process can achieve AgIn5S8 crystals of a maximum of 1 µm in diameter and a minimum crystal density of approximately 0.038/µm(2). One proof-of-concept experiment demonstrated that the material prepared from this low temperature process showed positive photocatalytic activity. This method for growing crystals can be applied to the green fabrication of optoelectronic materials.

Reduced colloidal repulsion imparted by adsorbed polymer of particle dimensions.

This work investigated the detailed interparticle interactions in a concentrated polymer-coated colloidal system in which the bare colloidal particles and the adsorbed polymers are of comparable size and, hence, the polymer adsorption cannot be foreseen to induce repulsive or attractive interactions. Specifically, poly(ethylene oxide) (PEO) chains (R(g) approximately 10nm) adsorbed onto fine silica colloidal particles (SAXS-determined radius approximately 7.4nm; width of log-normal size distribution approximately 0.28) were considered as a model system, for which the impact of a small amount of polymer adsorption (0.18mg/m(2)) in controlling the interactions of the PEO-coated silica particles was systematically explored by analyzing the small-angle X-ray scattering (SAXS) data against three interaction potentials-the equivalent hard-sphere (EHS) potential, the Hayter-Penfold-Yukawa (HPY) potential, and the square-well (SW) potential. Moreover, the SAXS analysis was enforced by dynamic light scattering (DLS) for predetermining the adsorption behavior, as well as for evaluating the possibility of polymer bridging. Under a dilute condition, the DLS analysis showed no sign of forming colloidal multiplets. In concentrated dispersions, both the HPY and SW potentials clearly revealed a systematic decrease of colloidal repulsions with increased PEO coverage, ascribed to a partially "screened" electrostatic interaction and/or the formation of PEO-bridged silica doublets. The present findings have interesting implications for controlling the colloidal interactions and microstructures of fine polymer-coated particles in dense or condensed phases.

Patterned networks of mouse hippocampal neurons on peptide-coated gold surfaces.

Patterned networks of hippocampal neurons were generated on peptide-coated gold substrates prepared by microscope projection photolithography and microcontact printing. A 19 amino acid peptide fragment of laminin A (PA22-2) that includes the IKVAV cell adhesion domain was used to direct patterns of cell adhesion in primary culture. Microscale grid patterns of peptide were deposited on gold-coated glass cover slips by soft lithography using "stamps" fashioned from polydimethylsiloxane. Strong coordination bonding between gold atoms on the surface and the sulfur atoms of the N-terminal cysteine residues supported stable adhesion of the peptide, which was confirmed by immunofluorescence using anti-IKVAV antiserum. Dispersed hippocampal cells isolated from neonatal mouse pups were grown on peptide-patterned gold substrates for 7 days. Neurons preferentially adhered to peptide-coated regions of the gold surface and restricted their processes to the peptide patterns. Whole cell recordings of neurons grown in patterned arrays revealed an average membrane potential of -50 mV, as well as the presence of voltage-gated ion conductances. Peptide-modified gold surfaces serve as convenient and effective substrates for growing ordered neural networks that are compatible with existing multi-electrode array recording technology.