Mesoporous Co3O4@CdS nanorods as anode for high-performance lithium ion batteries with improved lithium storage capacity and cycle life.

Transition metal oxides based anodes are facing crucial problems of capacity fading at long cycles and high rates due to electrode degradations. In this prospective, an effective strategy is employed to develop advanced electrode materials for lithium-ion batteries (LIBs). In the present work, a mesoporous Co3O4@CdS hybrid sructure is developed and investigated as anode for LiBs. The hybrid structure owning porous nature and large specific surface area, provides an opportunity to boost the lithium storage capabilities of Co3O4 nanorods. The Co3O4@CdS electrode delivers an initial discharge capacity of 1292 mA h g-1 at 0.1C and a very stable reversible capacity of 760 mA h g-1 over 200 cycles with a capacity retention rate of 92.7%. In addition, the electrode exhibits excellent cyclic stability even after 800 cycles and good rate performance as compared to previously reported electrodes. Moreover, density functional theory (DFT) and electrochemical impedance spectroscopy (EIS) confirm the enhanced kinetics of the Co3O4@CdS electrode. The efficient performance of the electrode may be due to the increased surface reactivity, abundant active sites/interfaces for rapid Li+ ion diffusion and the synergy between Co3O4 and CdS NPs. This work demonstrates that Co3O4@CdS hybrid structures have great potential for high performance batteries.

NiCo2O4@SnS2nanosheets on carbon cloth as efficient bi-functional material for high performance supercapacitor and sensor applications.

Bi-functional materials provide an opportunity for the development of high-performance devices. Up till now, bi-functional performance of NiCo2O4@SnS2nanosheets is rarely investigated. In this work, NiCo2O4@SnS2nanosheets were synthesized on carbon cloth by utilizing a simple hydrothermal technique. The developed electrode (NiCo2O4@SnS2/CC) was investigated for the detection of L-Cysteine and supercapacitors applications. As a non-enzymatic sensor, the electrode proved to be highly sensitive for the detection of L-cysteine. The electrode exhibits a reproducible sensitivity of 4645.82µA mM-1cm-2in a wide linear range from 0.5 to 5 mM with a low limit of detection (0.005µM). Moreover, the electrode shows an excellent selectivity and long-time stability. The high specific surface area, enhanced kinetics, good synergy and distinct architecture of NiCo2O4@SnS2nanosheets produce a large number of active sites with substantial energy storage potential. As a supercapacitor, the electrode exhibits improve capacitance of 655.7 F g-1at a current density of 2 A g-1as compare to NiCo2O4/CC (560 F g-1). Moreover, the electrode achieves 95.3% of its preliminary capacitance after 10 000 cycles at 2 A g-1. Our results show that NiCo2O4@SnS2/CC nanosheets possess binary features could be attractive electrode material for the development of non-enzymatic biosensors as well as supercapacitors.

Emerging Trends in Non-Enzymatic Cholesterol Biosensors: Challenges and Advancements.

The development of a highly sensitive and selective non-enzymatic electrochemical biosensor for precise and accurate determination of multiple disease biomarkers has always been challenging and demanding. The synthesis of novel materials has provided opportunities to fabricate dependable biosensors. In this perspective, we have presented and discussed recent challenges and technological advancements in the development of non-enzymatic cholesterol electrochemical biosensors and recent research trends in the utilization of functional nanomaterials. This review gives an insight into the electrochemically active nanomaterials having potential applications in cholesterol biosensing, including metal/metal oxide, mesoporous metal sulfide, conductive polymers, and carbon materials. Moreover, we have discussed the current strategies for the design of electrode material and key challenges for the construction of an efficient cholesterol biosensor. In addition, we have also described the current issues related to sensitivity and selectivity in cholesterol biosensing.

Mesoporous NiCo2S4nanoflakes as an efficient and durable electrocatalyst for non-enzymatic detection of cholesterol.

The detection of cholesterol is very crucial in clinical diagnosis for rapid and accurate monitoring of multiple disease-biomarkers. There is a great need for construction of a highly reliable and stable electrocatalyst for the efficient detection of cholesterol. In this work, mesoporous NiCo2S4nanoflakes of enhanced electrochemical properties are prepared through a facile hydrothermal approach. The developed nanoflakes modified nickel foam electrode exhibits outstanding electrocatalytic properties for the detection of cholesterol with high selectivity. The electrode displays excellent sensitivity of 8623.6µA mM-1cm-2, in the wide linear range from 0.01 to 0.25 mM with a low detection limit of 0.01µM. In addition, NiCo2S4structure reveals good thermal stability and reproducibility over a period of 8 weeks. Moreover, the nanoflakes show good response for detection of cholesterol in real samples. Our results demonstrate the potential use of NiCo2S4as a catalyst for the development of cost-effective electrochemical sensors for medical and industrial applications.

Oxygen vacancies boosted vanadium doped ZnO nanostructures-based voltage-switchable binary biosensor.

The development of a reliable non-enzymatic multi-analyte biosensor is remained a great challenge for biomedical and industrial applications. In this prospective, rationally designed electrode materials having voltage switchable electrocatalytic properties are highly promising. Here, we report vanadium doped ZnO engineered nanostructures (Zn1-xVxO where 0 ≤ x ≤ 0.1) which exhibit voltage switchable electrocatalytic properties for accurate measurements of glucose and hydrogen peroxide. Microstructures and chemical analysis show that the oxygen vacancies in the material can be tuned by controlling the stoichiometric ratios which play key role for voltage dependent measurements of different analytes. The developed Zn1-xVxO nanostructures exhibit outstanding sensing ability for binary analytes with a high selectivity, low detection limit, thermal stability and long-term stability. The Zn0.9V0.1O/glassy carbon (GC) electrode shows 3-fold increase in reproducible sensitivity for both glucose (655.24µA mM-1cm-2) and H2O2(13309.37µA mM-1cm-2) as compared to the pristine ZnO/GC electrode. Moreover, the electrode also shows good response for human blood serum and commercially available samples. The results demonstrate that defect engineering is a promising route for the development of cost-effective non-enzymatic multi-analyte sensors for practical applications.

Frequency stable dielectric constant with reduced dielectric loss of one-dimensional ZnO-ZnS heterostructures.

The synthesis of one-dimensional heterostructures having high dielectric constant and low dielectric loss has remained a great challenge. Until now, the dielectric performance of ZnO-ZnS heterostructures was scarcely investigated. In this work, large-scale ZnO-ZnS heterostructures were synthesized by employing the chemical vapor deposition method. High resolution transmission electron microscopy (HRTEM) confirms the formation of heterostructures. X-ray photoelectron spectroscopy (XPS) shows that S atoms fill up the oxygen vacancy (VO) in ZnO, leading to the suppression of charge carrier's movement from ZnO to ZnS; instead there is charge transfer from ZnS to ZnO. Conductivity mismatch between adjacent ZnO and ZnS materials leads to the accumulation of free charges at the interface of the heterostructure and can be considered as a capacitor-like structure. The electrical behaviors of the potential phases of ZnO, ZnS and the ZnO-ZnS heterostructure are well interpreted by a best fitted equivalent circuit model. Each heterostructure acts as a polarization node with a specific flip-flop frequency and all such nodes form continuous transmission of polarization, which jointly increase the dielectric energy-storage performance. The orientational polarization of the polarons and Zn2+-VO dipoles present at the heterostructure interface contributes to the frequency stable dielectric constant at ≥103 Hz. Our findings provide a systematic approach to tailor the electronic transport and dielectric properties at the interface of the heterostructure. We suggest that this approach can be extended for improving the energy harvesting, transformation and storage capabilities of the nanostructures for the development of high-performance energy-storage devices.

Ni and Co synergy in bimetallic nanowires for the electrochemical detection of hydrogen peroxide.

The development of a highly sensitive and selective non-enzymatic electrode catalyst for the detection of a target molecule was remained a great challenge. In this regard, bimetallic nanowires (BMNWs) are considered as promising electrode material for their fascinating physical/chemical properties superior to a single system. In this article, nickel cobalt (Ni x -Co) BMNWs with tunable stoichiometry were prepared by a template assisted electrodeposition method and their catalytic performance was investigated for the detection of hydrogen peroxide (H2O2). It has been found that Ni-Co (0.5:1) BMNWs/PC electrode exhibits superior non-enzymatic sensing ability toward H2O2 detection with a high selectivity. The electrode shows fast response within ∼3 s and an excellent reproducible sensitivity of 2211.4 µAmM-1 cm-2, which is the best compared to the individual Ni, Co, Ni-Co (0.3:1) BMNWs and previously reported electrodes. In addition, the electrode shows a linear response in the wide concentration range from 0.005 mM to 9 mM, low detection limit of 0.5 µM (S/N = 3.2) and a relatively long-term storage (50 d). Moreover, the sensor reveals excellent results for H2O2 detection in the real samples. The enhanced sensitivity of the Ni-Co (0.5:1) BMNWs based electrode may be due to the stable structure and synergy of Ni and Co. The results demonstrate that the catalytic activity of the electrode binary catalyst towards H2O2 detection can be improved by adjusting the Ni/Co ratio in BMNWs. The excellent performance of the electrode suggests that Ni-Co BMNWs are promising candidate for the construction of cost-effective electrochemical sensors for medical and industrial applications.

Voltage-Switchable Biosensor with Gold Nanoparticles on TiO2 Nanotubes Decorated with CdS Quantum Dots for the Detection of Cholesterol and H2O2.

A thin layer of gold nanoparticles (Au NPs) sputtered on cadmium sulfide quantum dots (CdS QDs) decorated anodic titanium dioxide nanotubes (TNTs) (Au/CdS QDs/TNTs) was fabricated and explored for the nonenzymatic detection of cholesterol and hydrogen peroxide (H2O2). Morphological studies of the sensor revealed the formation of uniform nanotubes decorated with a homogeneously dispersed CdS QDs and Au NPs layer. The electrochemical measurements showed an enhanced electrocatalytic performance with a fast electron transfer (∼2 s) between the redox centers of each analyte and electrode surface. The hybrid nanostructure (Au/CdS QDs/TNTs) electrode exhibited about a 6-fold increase in sensitivity for both cholesterol (10,790 µA mM-1 cm-2) and H2O2 (78,833 µA mM-1 cm-2) in analyses compared to the pristine samples. The hybrid electrode utilized different operational potentials for both analytes, which may lead to a voltage-switchable dual-analyte biosensor with a higher selectivity. The biosensor also demonstrated a good reproducibility, thermal stability, and increased shelf life. In addition, the clinical significance of the biosensor was tested for cholesterol and H2O2 in real blood samples, which showed maximum relative standard deviations of 1.8 and 2.3%, respectively. These results indicate that a Au/CdS QDs/TNTs-based hybrid nanostructure is a promising choice for an enzyme-free biosensor due to its suitable band gap alignment and higher electrocatalytic activities.

TiO2 nanotube array-modified electrodes for L-cysteine biosensing: experimental and density-functional theory study.

We report a non-enzymatic facile method for the detection of L-cysteine (L-Cyst) using free-standing TiO2 nanotube (TNT) array-modified glassy carbon electrodes (GCEs). Self-organized, highly ordered, and vertically oriented TNT arrays were fabricated by anodization of titanium sheets in ethylene glycol-based electrolyte. Detailed electrochemical measurements were performed and it was found that modified GCE exhibited high current compared to the pristine counterpart. The high current of the modified electrode was attributed to the high surface area and enhanced electrocatalytic activities of the TNTs toward the L-Cyst oxidation. Under the optimum conditions, the modified electrode exhibited a high sensitivity of ∼1.68 µA mM-1 cm-2 with a low detection limit of ∼0.1 mM. The fabricated electrode was found to be sensitive to pH and electrolyte temperature. The real sample analysis of the proposed method showed a decent recovery toward L-Cyst addition in human blood serum. Furthermore, the density-funcational theory (DFT) analysis revealed that TNTs have greater affinity toward L-Cyst, having stronger binding distance after its adsorption. The higher negative E ads values suggested a stable and chemisorption nature. The density of states results show that the E gap of TNTs is significantly reduced after L-Cyst adsorption. The modified GCE showed excellent selectivity, enhanced stability, and fast response, which make TNTs a promising candidate for the enzyme-free detection of other biological analytes.

Surfactant-encapsulated polyoxometalate building blocks: controlled assembly and their catalytic properties.

Polyoxometalates (POMs) are discrete anionic metal-oxide nanoclusters which exhibit unrivalled structural diversity, exceptional physical properties, and have many potential applications. Nonetheless, possessing high crystalline energy and hydrophilic nature, the assembly of POM clusters into rationally design architectures has been a long-standing bottleneck for their ultimate use in advanced materials and devices. To confront this challenge, both covalent and non-covalent modifications of POM nanoclusters are increasingly considered. This perspective reviews recent progress in the assembly of non-covalently modified surfactant-encapsulated POM nanoclusters with particular emphasis on our research work. The described solution-based assembly approach provides an excellent control on size, shape, and stability of the assembly structures. By effective exploitation of non-covalent interactions between the POM hybrid nanobuilding blocks, several unprecedented assembly structures including disks, cones, tubes, fullerene-like spheres, multiple shape flowers, wires, and thin films can be achieved. The assembly structures are highly robust and tunable in terms of size and shape and can act as hosts for guest nanomaterials to develop composite materials of combinatorial properties. In the last section of this manuscript, we present the catalytic properties of the assembly structures and their remote controlled manipulation in the reaction system.

Size effects in the oriented-attachment growth process: the case of Cu nanoseeds.

Size effects in the oriented-attachment (OA) growth process of Cu nanoseeds were found. Monodispersed Cu nanoseeds with average diameters of 2.2, 3.4, and 5.2 nm were controllably synthesized by the reduction of copper acetate in a boiling solvent and using dodecanethiol (DT) as a stabilizer and sulfur source of sulfide. These Cu nanoseeds were then treated under solvothermal conditions. When the diameters of Cu nanoseeds were smaller than 5 nm, Cu(2)S nanorods with lengths of approximately 30-100 nm and diameters of approximately 2-4 nm were obtained at lower temperatures, and Cu(2)S nanodisks with diameters of approximately 6-13 nm and thicknesses of approximately 2-4 nm were obtained at higher temperatures. Once the diameter of Cu nanoseeds was larger than 5 nm, only irregular particles were obtained, regardless of other conditions. The uniformity, which related to the density of DT on the surface of Cu nanoseeds, was the key for success of self-assembly of the final nanocrystals. High-resolution transmission electron microscopy images demonstrated that these nanorods, nanodisks, and particles were formed by an OA process of Cu nanoseeds into 1D, 2D, and 3D aggregates, which recrystallized into single crystals.