Understanding the Behavior of Supercapacitor Materials via Electrochemical Impedance Spectroscopy: A Review.

Energy harvesting and energy storage are two critical aspects of supporting the energy transition and sustainability. Many studies have been conducted to achieve excellent performance devices for these two purposes. As energy-storing devices, supercapacitors (SCs) have tremendous potential to be applied in several sectors. Some electrochemical characterizations define the performance of SCs. Electrochemical impedance spectroscopy (EIS) is one of the most powerful analyses to determine the performance of SCs. Some parameters obtained from this analysis include bulk resistance, charge-transfer resistance, total resistance, specific capacitance, response frequency, and response time. This work provides a holistic and comprehensive review of utilizing EIS for SC characterization. Overall, researchers can benefit from this review by gaining a comprehensive understanding of the utilization of electrochemical impedance spectroscopy (EIS) for characterizing supercapacitors (SCs), enabling them to enhance SC performance and contribute to the advancement of energy harvesting and storage technologies.

Carbonized Polymer Dots for Controlling Construction of MoS2 Flower-Like Nanospheres to Achieve High-Performance Li/Na Storage Devices.

Despite being one of the most promising materials in anode materials, molybdenum sulfide (MoS2 ) encounters certain obstacles, such as inadequate cycle stability, low conductivity, and unsatisfactory charge-discharge (CD) rate performance. In this study, a novel approach is employed to address the drawbacks of MoS2 . Carbon polymer dots (CPDs) are incorporated to prepare three-dimensional (3D) nanoflower-like spheres of MoS2 @CPDs through the self-assembly of MoS2 2D nanosheets, followed by annealing at 700 °C. The CPDs play a main role in the creation of the nanoflower-like spheres and also mitigate the MoS2 nanosheet limitations. The nanoflower-like spheres minimize volume changes during cycling and improve the rate performance, leading to exceptional rate performance and cycling stability in both Lithium-ion and Sodium-ion batteries (LIBs and SIBs). The optimized MoS2 @CPDs-2 electrode achieves a superb capacity of 583.4 mA h g-1 at high current density (5 A g-1 ) after 1000 cycles in LIBs, and the capacity remaining of 302.8 mA h g-1 after 500 cycles at 5 A g-1 in SIBs. Additionally, the full cell of LIBs/SIBs exhibits high capacity and good cycling stability, demonstrating its potential for practical application in fast-charging and high-energy storage.

Silver nanoparticles, nanoneedles and nanorings: impact of electromagnetic near-field on surface-enhanced Raman scattering.

The dimension of plasmonic nanostructures does matter in localizing electromagnetic (EM) field and improving surface-enhanced Raman scattering (SERS) activity. Zero-dimensional (0D), one-dimensional (1D) and two-dimensional (2D) plasmonic nanostructures are promising candidates to validate SERS enhancement and the mechanisms thereof. In this work, silver (Ag) nanoparticles (NPs), nanoneedles (NNs) and nanorings (NRs) have been considered to demonstrate the impact of EM near-field distributions on SERS of the corresponding 0D (i.e. Ag-NPs), 1D (i.e. Ag-NNs) and 2D (i.e. Ag-NRs) nanostructures. Ag-NPs, Ag-NNs and Ag-NRs fabricated on zinc oxide (ZnO) ultrathin layer through sputtering technique have been characterized thoroughly by high-resolution field emission scanning electron microscopy (FESEM). FESEM micrographs confirmed a relatively narrow size distribution, 48.88 ± 8.32 nm, of Ag-NPs along with an estimated coverage density of ∼4 × 1010 cm-2. In the case of 1D nanostructures, Ag-NNs were estimated to have a relatively broadened length distribution, 534.36 ± 85.61 nm, and relatively narrow base distribution, 77.39 ± 25.25 nm, along with an estimated coverage density of ∼5 × 108 cm-2. However, as for 2D nanostructures, the FESEM micrographs revealed that Ag-NRs consisted of Ag clusters of various shapes and sizes, instead of a perfect ring structure along with much lower coverage density, ∼8.05 × 103 cm-2. The same specimens were used in microscopic SERS measurements and SERS activities were evaluated for individual nanostructures using Rhodamine 6G as Raman-active dye. The SERS activity of Ag-NRs was found to be the highest with reference to those of Ag-NPs and Ag-NNs. The scenario was supported as well by EM near-field distributions extracted from finite difference time domain (FDTD) analysis. Three models were developed according to the FESEM micrographs of Ag-NPs, Ag-NNs and Ag-NRs nanostructures and FDTD analysis was carried out to understand EM near-field distributions for individual nanostructures. EM near-field distributions at different planes for individual models were extracted for s-, p- and 45° incident polarizations. Such a correlated investigation facilitated an understanding and correlation of the impact of EM near-field distributions on SERS of the corresponding 0D (i.e. Ag-NPs), 1D (i.e. Ag-NNs) and 2D (i.e. Ag-NRs) nanostructures.

2D/1D MoS2 /TiO2 Heterostructure Photocatalyst with a Switchable CO2 Reduction Product.

Regulating the transfer pathway of charge carriers in heterostructure photocatalysts is of great importance for selective CO2 photoreduction. Herein, the charge transfer pathway and in turn the redox potential succeeded to regulate in 2D MoS2 /1D TiO2 heterostructure by varying the light wavelength range. Several in situ measurements and experiments confirm that charge transfer follows either an S-scheme mechanism under simulated solar irradiation or a heterojunction approach under visible light illumination, elucidating the switchable property of the MoS2 /TiO2 heterostructure. Replacing the simulated sunlight irradiation with the visible light illumination switches the photocatalytic CO2 reduction product from CO to CH4. 13 CO2 isotope labeling confirms that CO2 is the source of carbon for CH4 and CO products. The photoelectrochemical H2 generation further supports the switching property of MoS2 /TiO2 . Unlike previous studies, density functional theory calculations are used to investigate the band structure of Van der Waals MoS2 /TiO2 S scheme after contact, allowing to propose accurate charge transfer pathways, in which the theoretical results are well matched with the experimental results. This work opens the opportunity to develop photocatalysts with switchable charge transport and tunable redox potential for selective artificial photosynthesis.

One-Step Hydrothermal Synthesis of Anatase TiO2 Nanotubes for Efficient Photocatalytic CO2 Reduction.

The hydrothermal dissolution-recrystallization process is a key step in the crystal structure of titania-based nanotubes and their composition. This work systematically studies the hydrothermal conditions for directly synthesizing anatase TiO2 nanotubes (ATNTs), which have not been deeply discussed elsewhere. It has been well-known that ATNTs can be synthesized by the calcination of titanate nanotubes. Herein, we found the ATNTs can be directly synthesized by optimizing the reaction temperature and time rather than calcination of titanate nanotubes, where at each temperature, there is a range of reaction times in which ATNTs can be prepared. The effect of NaOH/TiO2 ratio and starting materials was explored, and it was found that ATNTs can be prepared only if the precursor is anatase TiO2, using rutile TiO2 leads to forming titanate nanotubes. As a result, ATNTs produced directly without calcination have excellent photocatalytic CO2 reduction than titanate nanotubes and ATNTs prepared by titanate calcination.

Clusters-based silver nanorings: An active substrate for surface-enhanced Raman scattering.

Plasmonic nanostructures, particularly irregular surfaces of ring-like silver (Ag) nanostructures are promising candidates in surface-enhanced Raman scattering (SERS) spectroscopy. In this work, clusters-based Ag nanorings have been fabricated and characterized as SERS-active substrates. The rim of the as-fabricated Ag nanorings was found neither discontinuous nor linear aggregation of nanoparticles. High-resolution field emission scanning electron microscopy (FESEM) revealed that the individual constituent clusters were different from each other, particularly in terms of size and shape in addition to the cases how such clusters were emerged as the edge of the nanoring. Considering the dimensions of the clusters and the arrangement of such clusters as nanorings, it was speculated that the local electromagnetic (EM) near-field distributions would excel and thus enhanced SERS signals would be achieved. Indeed, the inherent features of the nanorings facilitated to achieve SERS enhancement factors as high as 2.1 × 104. SERS-activity of as-fabricated Ag nanorings was confirmed using Rhodamine 6G (R6G) as Raman-active dyes and the enhancement was compared to those obtained from R6G adsorbed on Ag-ZnO/Glass and ZnO/Glass. To the best of our knowledge, this is the first attempt to explore the impact of localized EM near-field within the segments of nanorings through SERS spectroscopy. A model was designed resembling the nanorings under this investigation to simulate EM near-field distributions by finite difference time domain (FDTD) analysis. The dimensions of the model geometry were chosen according to the observations achieved by FESEM. To simplify the simulations, nanoobjects were considered spherical and organized in a periodic fashion, although the constituent clusters of Ag nanorings were found irregular in shape and arrangement. Since EM near-field distribution highly depends on interparticle gaps, three scenarios were implemented, such as, small gap in between two adjacent nanoobjects and adjacent nanoobjects in touch and overlapped. Each configuration was simulated and EM near-field distribution was extracted for s-, p- and 450 of incident polarizations followed by a plausible correlation to SERS enhancements. Such correlated investigations as well as clusters-based Ag nanorings not only inspire the ones to look for cost-effective SERS-active substrate, but also understand the underlying EM mechanism in SERS enhancements.

Polymer-Templated Durable and Hydrophobic Nanostructures for Hydrogen Gas Sensing Applications.

A simple and hands-on one-step process has been implemented to fabricate polymer-templated hydrophobic nanostructures as hydrogen gas sensing platforms. Topographic measurements have confirmed irregular hills and dips of various dimensions that are responsible for creating air bubble pockets that satisfy the Cassie-Baxter state of hydrophobicity. High-resolution field-emission scanning electron microscopy (FESEM) has revealed double-layer structures consisting of fine microscopic flower-like structures of nanoscale petals on the top of base nanostructures. Wetting contact angle (WCA) measurements further revealed the contact angle to be ~142.0° ± 10.0°. Such hydrophobic nanostructures were expected to provide a platform for gas-sensing materials of a higher surface area. From this direction, a very thin layer of palladium, ca. 100 nm of thickness, was sputtered. Thereafter, further topographic and WCA measurements were carried out. FESEM micrographs revealed that microscopic flower-like structures of nanoscale petals remained intact. A sessile drop test reconfirmed a WCA of as high as ~130.0° ± 10.0°. Due to the inherent features of hydrophobic nanostructures, a wider surface area was expected that can be useful for higher target gas adsorption sites. In this context, a customized sensing facility was set up, and H2 gas sensing performance was carried out. The surface nanostructures were found to be very stable and durable over the course of a year and beyond. A polymer-based hydrophobic gas-sensing platform as investigated in this study will play a dual role in hydrophobicity as well as superior gas-sensing characteristics.

Plasmonic Pollen Grain Nanostructures: A Three-Dimensional Surface-Enhanced Raman Scattering (SERS)-Active Substrate.

A new route has been developed to design plasmonic pollen grain-like nanostructures (PGNSs) as surface-enhanced Raman scattering (SERS)-active substrate. The nanostructures consisting of silver (Ag) and gold (Au) nanoparticles along with zinc oxide (ZnO) nanoclusters as spacers were found highly SERS-active. The morphology of PGNSs and those obtained in the intermediate stage along with each elemental evolution has been investigated by a high-resolution field emission scanning electron microscopy. The optical band gaps and crystal structure have been identified by UV-vis absorption and X-ray powder diffraction (XRD) measurements, respectively. For PGNSs specimen, three distinct absorption bands related to constituent elements Ag, Au, and ZnO were observed, whereas XRD peaks confirmed the existence of Ag, Au, and ZnO within the composition of PGNSs. SERS-activity of PGNSs was confirmed using Rhodamine 6G (R6G) as Raman-active dyes. Air-cooled solid-state laser kits of 532 nm were used as excitation sources in SERS measurements. SERS enhancement factor was estimated for PGNSs specimen and was found as high as 3.5×106 . Finite difference time domain analysis was carried out to correlate the electromagnetic (EM) near-field distributions with the experiment results achieved under this investigation. EM near-field distributions at different planes were extracted for s-, p- and 45° of incident polarizations. EM near-field distributions for such nanostructures as well as current density distributions under different circumstances were demonstrated and plausible scenarios were elucidated given SERS enhancements. Such generic fabrication route as well as correlated investigation is not only indispensable to realize the potential of SERS applications but also unveil the underneath plasmonic characteristics of complex SERS-active nanostructures.

Microstructure Evaluation and Impurities in La Containing Silicon Oxynitrides.

Oxynitride glasses are not yet commercialised primarily due to the impurities present in the network of these glasses. In this work, we investigated the microstructure and instinctive defects in nitrogen rich La-Si-O-N glasses. Glasses were prepared by heating a powder mixture of pure La metal, Si3N4, and SiO2 in a nitrogen atmosphere at 1650-1800 °C. The microstructure and impurities in the glasses were examined by optical microscopy, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy in conjunction with electron energy-loss spectroscopy. Analyses showed that the glasses contain a small amount of spherical metal silicide particles, mostly amorphous or poorly crystalline, and having sizes typically ranging from 1 µm and less. The amount of silicide was estimated to be less than 2 vol. %. There was no systematic relation between silicide formation and glass composition or preparation temperature. The microstructure examination revealed that the opacity of these nitrogen rich glasses is due to the elemental Si arise from the decomposition reaction of silicon nitride and silicon oxide, at a high temperature above ~1600 °C and from the metallic silicide particles formed by the reduction of silicon oxide and silicon nitride at an early stage of reaction to form a silicide intermetallic with the La metal.

Fabrication and Characterization of Transparent and Scratch-Proof Yttrium/Sialon Thin Films.

Transparent and amorphous yttrium (Y)/Sialon thin films were successfully fabricated using pulsed laser deposition (PLD). The thin films were fabricated in three steps. First, Y/Sialon target was synthesized using spark plasma sintering technique at 1500 °C in an inert atmosphere. Second, the surface of the fabricated target was cleaned by grinding and polishing to remove any contamination, such as graphite and characterized. Finally, thin films were grown using PLD in an inert atmosphere at various substrate temperatures (RT to 500 °C). While the X-ray diffractometer (XRD) analysis revealed that the Y/Sialon target has ß phase, the XRD of the fabricated films showed no diffraction peaks and thus confirming the amorphous nature of fabricated thin films. XRD analysis displayed that the fabricated thin films were amorphous while the transparency, measured by UV-vis spectroscopy, of the films, decreased with increasing substrate temperature, which was attributed to a change in film thickness with deposition temperature. X-ray photoelectron spectroscopy (XPS) results suggested that the synthesized Y/Sialon thin films are nearly homogenous and contained all target's elements. A scratch test revealed that both 300 and 500 °C coatings possess the tough and robust nature of the film, which can resist much harsh loads and shocks. These results pave the way to fabricate different Sialon doped materials for numerous applications.

Novel Green Biomimetic Approach for Synthesis of ZnO-Ag Nanocomposite; Antimicrobial Activity against Food-borne Pathogen, Biocompatibility and Solar Photocatalysis.

A simple, eco-friendly, and biomimetic approach using Thymus vulgaris (T. vulgaris) leaf extract was developed for the formation of ZnO-Ag nanocomposites (NCs) without employing any stabilizer and a chemical surfactant. T. vulgaris leaf extract was used for the first time, in a novel approach, for green fabrication of ZnO-Ag NCs as a size based reducing agent via the hydrothermal method in a single step. Presence of phenols in T. vulgaris leaf extract has served as both reducing and capping agents that play a critical role in the production of ZnO-Ag NCs. The effect of silver nitrate concentration in the formation of ZnO-Ag NCs was studied. The in-vitro Antimicrobial activity of NCs displayed high antimicrobial potency on selective gram negative and positive foodborne pathogens. Antioxidant activity of ZnO-Ag NCs was evaluated via (2,2-diphenyl-1-picrylhydrazyl) DPPH method. Photocatalytic performance of ZnO-Ag NCs was appraised by degradation of phenol under natural sunlight, which exhibited efficient photocatalytic activity on phenol. Cytotoxicity of the NCs was evaluated using the haemolysis assay. Results of this study reveal that T. vulgaris leaf extract, containing phytochemicals, possess reducing property for ZnO-Ag NCs fabrication and the obtained ZnO-Ag NCs could be employed effectively for biological applications in food science. Therefore, the present study offers a promising way to achieve high-efficiency photocatalysis based on the hybrid structure of semiconductor/metal.