A key parametric study of ultrasonic exfoliation of 2D TiB2 using DI water as a unique medium.

Liquid Phase Exfoliation (LPE) is a very effective technique for the synthesis of few layered two dimensional (2D) nanosheets. There is a surge to find environment friendly solvents for efficient exfoliation of layered materials to produce 2D nanosheets. TiB2 is an important layered material with very little reported work on its 2D nanosheets. The present work is about successful LPE of TiB2 using deionized (DI) water as a clean, green and low cost dispersion medium to make TiB2 nanosheets. The impact of ultrasonication conditions i.e. input power and treatment duration for efficient synthesis of few layered 2D nanosheets in DI water is studied by Atomic Force Microscopy (AFM), X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). It is found that by increasing input power, the layer thickness is reduced from bulk to 34 nm with lateral dimensions as huge as up to 5 µm. The increased treatment duration has further reduced the layer thickness to 21 nm associated with a decrease in lateral dimensions to about 1 µm. The mechanism of variation in the aspect ratio of the 2D nanosheets with ultrasonication power and treatment duration is explained. The optimum conditions for the fabrication of high aspect ratio 2D nanosheets of TiB2 owe to a greater acoustic cavitation intensity, an optimum treatment duration and a homogenous distribution of the cavitation events while using an appropriate size of the sonotrode in the sonicated volume during ultrasonication.

Solvent-Assisted Crystallization of an α-Fe2O3 Electron Transport Layer for Efficient and Stable Perovskite Solar Cells Featuring Negligible Hysteresis.

Inorganic-organic metal halide perovskite solar cells (PSCs) show power conversion efficiency values approaching those of state-of-the-art silicon solar cells. In a quest to find suitable charge transport materials in PSCs, hematite (α-Fe2O3) has emerged as a potential electron transport layer (ETL) in n-i-p planar PSCs due to its low cost, UV light stability, and nontoxicity. Yet, the performance of α-Fe2O3-based PSCs is far lower than that of state-of-the-art PSCs owing to the poor quality of the α-Fe2O3 ETL. In this work, solvent-assisted crystallization of α-Fe2O3 ETLs was carried out to examine the impact of solvents on the optoelectronic properties of α-Fe2O3 thin films. Among the various solvents used in this study (deionized water, ethanol, iso-propanol, and iso-butanol), optimized ethanol-based α-Fe2O3 ETLs lead to champion device performance with a power conversion efficiency of 13% with a reduced hysteresis index of 0.04 in an n-i-p-configured PSC. The PSC also exhibited superior long-term inert and ambient stabilities compared to a reference device made using a SnO2 ETL. Through a series of experiments spanning structural, morphological, and optoelectronic properties of the various α-Fe2O3 thin films and their devices, we provide insights into the reasons for the improved photovoltaic performance. It is noted that the formation of a pinhole-free compact morphology of ETLs facilitates crack-free surface coverage of the perovskite film atop an α-Fe2O3 ETL, reduces interfacial recombination, and enhances charge transfer efficiency. This work opens up the route toward novel ETLs for the development of efficient and photo-stable PSCs.

Fabrication of cellulose paper-based counter electrodes for flexible dye-sensitized solar cells.

Here, we introduce the synthesis and deposition of organic/inorganic composite ink on cellulose paper using a rapid ultrasonic spray deposition approach that can be incorporated as a counter electrode (CE) in flexible dye-sensitized solar cells (FDSSCs). The composite ink comprised a copper indium sulfide (CuInS2) nanostructure ink and dispersion of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) in water. Fabricated counter electrodes are biodegradable, environment-friendly, flexible, and economical and meet the requirements for sustainable green energy. To evaluate the catalytic activities and power conversion efficiencies of DSSCs, the produced CuInS2/PEDOT:PSS composite ink-based CEs were compared with PEDOT:PSS counter electrodes. Cyclic voltammetry studies found that CuInS2/PEDOT:PSS had a greater cathodic charge transfer current density (Jc) (-1.23 mA cm-2). Moreover, it was found that the potential separation values are small, which indicate a stronger catalytic activity than PEDOT:PSS counter electrodes. The observed exchange current density (J0) was 3.98 mA cm-2, while the limiting current density (Jlim) increased to 45.7 mA cm-2, indicating a fast redox diffusion rate of the CuInS2/PEDOT:PSS CE. The photovoltaic performances of CuInS2/PEDOT:PSS and PEDOT: PSS-based DSSC's were measured and determined to be 5.66% and 4.41%, respectively, while the performance of CuInS2/PEDOT:PSS FDSSC composed of cellulose paper was 1.06%.

Design of Multilayered 2D Nanomaterial Composite Structures for EMI Shielding Analysis.

It is still very challenging to effectively design nanocomposite microstructures with significantly improved electromagnetic interference shielding effectiveness (EMI SE). Herein, we developed a facile method for fabrication of molybdenum disulfide/graphene nanoplatelets (MoS2/GNPs) nanocomposites, in which GNPs are utilized as highly effective electrical transport materials, while MoS2 resolves the agglomeration problem of GNPs. GNPs also serve as an efficient cluster of electrical transport systems and dampen the incoming electromagnetic wave. Two types of samples are synthesized and compared in context of EMI SE values: physically mixed composite and layered samples. The sandwiched MoS2 between GNP layers showed an EMI SE of ∼24 dB, which was an almost 14% improvement relative to MoS2/GNPs nanocomposites exhibiting an EMI SE value of ∼21 dB, both containing 0.5 wt % GNPs. This work provides a new strategy for the design of multifunctional nanocomposites using the simple low-cost vacuum filtration method for EMI shielding for future applications.

MOF-Derived AlCuSe2 Embedded in a Carbon Matrix for an Economical Anode of Lithium-Ion Battery.

Binary metal chalcogenides (TMCs) have emerged as a potential candidate for lithium-ion batteries due to their availability, abundance, chemical properties, and high theoretical capacities. Despite these characteristics, they suffer from significant volume change, limited life cycle, and inferior rate capabilities which hinder their practical applications. These issues can be addressed by selecting low-cost nanostructure metal combinations coupled with a carbon matrix, which tackles significant volume change to give prolonged cycle life and high-rate capabilities. Herein, novel MOF-derived aluminum copper selenide (ACSe@C) nanospheres embedded in a carbon matrix are synthesized via a facile solvothermal route. Owing to their uniform porous structure, ACSe@C nanospheres exhibit excellent electrochemical performance as an anode material for Li-ion batteries. ACSe@C delivers a high specific capacity of 633.6 mAh g-1 at 0.1 A g-1 and a good rate capability of 532 mAh g-1 at 0.1 A g-1 and 400 mAh g-1 at 8 A g-1. This study demonstrates that ACSe@C is a good candidate for next-generation energy-storage devices.

Challenges and issues with the performance of boron nitride rooted membrane for gas separation.

Various fillers such as zeolites, metal-organic framework, carbon, metal framework, graphene, and covalent organic framework have been incorporated into the polymers. However, these materials are facing issues such as incompatibility with the polymer matrix, which leads to the formation of non-selective voids and thus, reduces the gas separation properties. Recent studies show that hexagonal boron nitride (h-BN) possesses attractive characteristics such as high aspect ratio, good compatibility with polymer materials, enhanced gas barrier performance, and improved mechanical properties, which could make h-BN the potential candidate to replace conventional fillers. The synthesis of materials and membranes is the subject of this review, which focuses on recent developments and ongoing problems. Additionally, a summary of the mathematical models that were utilised to forecast how well polymer composites would perform in gas separation is provided. It was found in the previous studies that tortuosity is the governing factor for the determination of the effectiveness of a nanofiller as a gas barrier enhancer in polymer matrices. The shape of the nanofiller particles and sheets, disorientation and distribution of the nanofillers within the polymer matrix, state of aggregation and rate of reaggregation of the nanofiller particles, as well as the compatibility of the nanofiller with the polymer matrix all played a significant role in determining how well a particular nanofiller will perform in enhancing the gas barrier properties of the nanocomposites. For this purpose, this review has been focused not only on the experimentation work but also on the effect of tortuosity, exfoliation quality, compatibility, disorientation, and reaggregation of nanofillers.

Systematic Investigation of Structural, Morphological, Thermal, Optoelectronic, and Magnetic Properties of High-Purity Hematite/Magnetite Nanoparticles for Optoelectronics.

Iron oxide nanoparticles, especially hematite (α-Fe2O3) and magnetite (Fe3O4) have attained substantial research interest in various applications of green and sustainable energy harnessing owing to their exceptional opto-magneto-electrical characteristics and non-toxicity. In this study, we synthesized high-purity hematite and magnetite nanoparticles from a facile top-down approach by employing a high-energy ball mill followed by ultrasonication. A systematic investigation was then carried out to explore the structural, morphological, thermal, optoelectrical, and magnetic properties of the synthesized samples. The experimental results from scanning electron microscopy and X-ray diffraction corroborated the formation of highly crystalline hematite and magnetite nanoparticles with average sizes of ~80 nm and ~50 nm, respectively. Thermogravimetric analysis revealed remarkable results on the thermal stability of the newly synthesized samples. The optical studies confirmed the formation of a single-phase compound with the bandgaps dependent on the size of the nanoparticles. The electrochemical studies that utilized cyclic voltammetry and electrochemical impedance spectroscopy techniques verified these iron oxide nanoparticles as electroactive species which can enhance the charge transfer process with high mobility. The hysteresis curves of the samples revealed the paramagnetic behavior of the samples with high values of coercivity. Thus, these optimized materials can be recommended for use in future optoelectronic devices and can prove to be potential candidates in the advanced research of new optoelectronic materials for improved energy devices.

Controlling the Wettability of ZnO Thin Films by Spray Pyrolysis for Photocatalytic Applications.

Herein, we synthesized the zinc oxide (ZnO) thin films (TFs) deposited on glass substrates via spray pyrolysis (SP) to prepare self-cleaning glass. Various process parameters were used to optimize photocatalytic performance. Substrates were coated at room temperature (RT) and 250 °C with a 1 mL or 2 mL ZnO solution while maintaining a distance from the spray gun to the substrate of 20 cm or 30 cm. Several characterization techniques, i.e., XRD, SEM, AFM, and UV-Vis were used to determine the structural, morphological, and optical characteristics of the prepared samples. The wettability of the samples was evaluated using contact angle measurements. As ZnO is hydrophilic in nature, the RT deposited samples showed a hydrophilic character, whereas the ZnO TFs deposited at 250 °C demonstrated a hydrophobic character. The XRD results showed a higher degree of crystallinity for samples deposited on heated substrates. Because of this higher crystallinity, the surface energy decreased, and the contact angle increased. Moreover, by using 2 mL solution, better surface coverage and roughness were obtained for the ZnO TFs. However, by exploiting the distance of the spray to the samples size distribution and surface coverage can be controlled, the samples deposited at 30 mL showed a uniform particle size distribution from 30-40 nm. In addition, the photoactivity of the samples was tested by the degradation of rhodamine B dye. Substrates prepared with a 2 mL solution sprayed at 20 cm showed higher dye degradation than other samples, which can play a vital role in self-cleaning. Hence, by changing the said parameters, the ZnO thin film properties on glass substrates were optimized for self-cleaning diversity.

Nanoengineering of NiO/MnO2/GO Ternary Composite for Use in High-Energy Storage Asymmetric Supercapacitor and Oxygen Evolution Reaction (OER).

Designing multifunctional nanomaterials for high performing electrochemical energy conversion and storage devices has been very challenging. A number of strategies have been reported to introduce multifunctionality in electrode/catalyst materials including alloying, doping, nanostructuring, compositing, etc. Here, we report the fabrication of a reduced graphene oxide (rGO)-based ternary composite NiO/MnO2/rGO (NMGO) having a range of active sites for enhanced electrochemical activity. The resultant sandwich structure consisted of a mesoporous backbone with NiO and MnO2 nanoparticles encapsulated between successive rGO layers, having different active sites in the form of Ni-, Mn-, and C-based species. The modified structure exhibited high conductivity owing to the presence of rGO, excellent charge storage capacity of 402 F·g-1 at a current density of 1 A·g-1, and stability with a capacitance retention of ~93% after 14,000 cycles. Moreover, the NMGO//MWCNT asymmetric device, assembled with NMGO and multi-wall carbon nanotubes (MWCNTs) as positive and negative electrodes, respectively, exhibited good energy density (28 Wh·kg-1), excellent power density (750 W·kg-1), and capacitance retention (88%) after 6000 cycles. To evaluate the multifunctionality of the modified nanostructure, the NMGO was also tested for its oxygen evolution reaction (OER) activity. The NMGO delivered a current density of 10 mA·cm-2 at the potential of 1.59 V versus RHE. These results clearly demonstrate high activity of the modified electrode with strong future potential.

In Situ Synthesis of a Polyaniline/ Fe-Ni Codoped Co3O4 Composite for the Electrode Material of Supercapacitors with Improved Cyclic Stability.

Conductive polymers have become a remarkable candidate for electrode materials of supercapacitors. Polyaniline (PANI) is the most promising contender for supercapacitors because of its easy method of synthesis, low cost, and higher choice in the improvement of energy storage applications. The main issue in the use of PANI in supercapacitors is its lower stability. In this work, PANI@Fe-Ni codoped Co3O4 (PANI@FNCO) nanocomposite has been prepared by in situ addition of 10 wt % FNCO as fillers in the PANI matrix. The nanocomposites were then characterized via scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry to observe the morphology, crystal structure, functional groups, and thermal stability of samples, respectively. SEM results showed that FNCO was fairly dispersed in the PANI matrix, while XRD results showed a broad peak for nanocomposites because of the semicrystalline nature of polymers. The electrochemical properties of the samples were analyzed via cyclic voltammetry, galvanostatic charge and discharge, and electrochemical impedance spectroscopy. PANI@FNCO nanowires are found to overcome the shortcomings in electrochemical energy storage devices by exhibiting a higher value of specific capacitance of 1171 F g-1 and energy density of 144 W h kg-1 at a current density of 1 A g-1. Moreover, the FNCO nanowires also showed a cyclic charge/discharge stability of 84% for 2000 cycles.

Aluminum Doping Effects on Interface Depletion Width of Low Temperature Processed ZnO Electron Transport Layer-Based Perovskite Solar Cells.

Rapid improvement in efficiency and stabilities of perovskite solar cells (PSCs) is an indication of its prime role for future energy demands. Various research has been carried out to improve efficiency including reducing the exciton recombination and enhancement of electron mobilities within cells by using electron transport material (ETM). In the present research, electrical, optical, and depletion width reduction properties of low temperature processed ZnO electron transport layer-based perovskite solar cells are studied. The ZnO thin films vary with the concentration of Al doping, and improvement of optical transmission percentage up to 80% for doped samples is confirmed by optical analysis. Reduction in electrical resistance for 1% Al concentration and maximum conductivity 11,697.41 (1/Ω-cm) among the prepared samples and carrier concentration 1.06×1022 cm-3 were corroborated by Hall effect measurements. Systematic impedance spectroscopy of perovskite devices with synthesized ETM is presented in the study, while the depletion width reduction is observed by Mott Schottky curves. IV measurements of the device and the interfacial charge transfer between the absorber layer of methylammonium lead iodide and ETM have also been elaborated on interface electronic characteristics.

2D nanosheets and composites for EMI shielding analysis.

Liquid exfoliated, 2-dimensional (2D), few layered graphene and molybdenum disulfide nanosheets (GNS and MNS) are size selected for EMI shielding application. Scanning electron microscopy (SEM) has confirmed the lateral dimensions increase (1-2 µm for GNS and MNS) with lowering centrifugation speed (1000 to 500 rpm). The micron size (~ 15 µm) restacked structures of GNS and MNS (L ~ 2 µm) over a nylon membrane have shown ~ 16 dB and ~ 6 dB EMI shielding effectiveness (1-8 GHz frequency), respectively. The enhanced EMI shielding effectiveness for GNS-500 may be credited to its high carrier mobility as well as high aspect ratio of nanosheets. The GNS-500 are further dispersed (0.3 wt.%) in thermoplastic polyurethane for their applicability as flexible EMI shielding material. The dielectric characteristics predicted an enhancement for the attenuation (200 MHz-1 GHz). The experimental results (1-8 GHz) suggested the maximum attenuation ~ 18 dB showing the composite applicability as a broadband EMI shielding material.

3D Hierarchically Mesoporous Zinc-Nickel-Cobalt Ternary Oxide (Zn0.6Ni0.8Co1.6O4) Nanowires for High-Performance Asymmetric Supercapacitors.

Increased efforts have been devoted recently to develop high-energy-density supercapacitors (SC) without renouncing their power efficiency. Herein, a hierarchically mesoporous nanostructure of zinc-nickel-cobalt oxide (ZNCO) nanowires (NWs) is constructed by hierarchical aggregation of ZNCO nanoparticles. It is worth noting that cobalt and nickel rich lattice imparts higher charge storage capability by enhanced reversible Faradaic reaction while zinc provides structural stability and higher conductivity. Moreover, particulate nature of ZNCO NWs allows deep diffusion of electrolyte thus enabling reversible charge storage under higher current densities. The as-prepared ZNCO NWs exhibited excellent specific capacitance of 2082.21 F g-1 at the current density of 1 A g-1 with high stability up to 5,000 charge-discharge cycles. Further, the asymmetric SC device was assembled using ZNCO NWs (ZNCO NWs//MWCNTs) which exhibited high energy density of 37.89 Wh kg-1 and excellent capacitance retention up to 88.5% over 1,000 cycles. This work presents ways to construct multi-component high-energy-density materials for next-generation energy storage devices.

Metal/Carbon Hybrid Nanostructures Produced from Plasma-Enhanced Chemical Vapor Deposition over Nafion-Supported Electrochemically Deposited Cobalt Nanoparticles.

In this work, we report development of hybrid nanostructures of metal nanoparticles (NP) and carbon nanostructures with strong potential for catalysis, sensing, and energy applications. First, the etched silicon wafer substrates were passivated for subsequent electrochemical (EC) processing through grafting of nitro phenyl groups using para-nitrobenzene diazonium (PNBT). The X-ray photoelectron spectroscope (XPS) and atomic force microscope (AFM) studies confirmed presence of few layers. Cobalt-based nanoparticles were produced over dip or spin coated Nafion films under different EC reduction conditions, namely CoSO4 salt concentration (0.1 M, 1 mM), reduction time (5, 20 s), and indirect or direct EC reduction route. Extensive AFM examination revealed NP formation with different attributes (size, distribution) depending on electrochemistry conditions. While relatively large NP with >100 nm size and bimodal distribution were obtained after 20 s EC reduction in H3BO3 following Co2+ ion uptake, ultrafine NP (<10 nm) could be produced from EC reduction in CoSO4 and H3BO3 mixed solution with some tendency to form oxides. Different carbon nanostructures including few-walled or multiwalled carbon nanotubes (CNT) and carbon nanosheets were grown in a C2H2/NH3 plasma using the plasma-enhanced chemical vapor deposition technique. The devised processing routes enable size controlled synthesis of cobalt nanoparticles and metal/carbon hybrid nanostructures with unique microstructural features.