Metal-Organic Framework for Aluminum based Energy Storage Devices: Utilizing Redox Additives for Significant Performance Enhancement.

There are various methods being tried to address the sluggish kinetics observed in Al-ion batteries (AIBs). They mostly deal with morphology tuning, but have led to limited improvement. A new approach is proposed to overcome this limitation. It focuses on the use of a redox additive modified electrolyte in combination with framework like materials, which have wider channels. The ordered microporous and interconnected framework of ZIF 67, with large surface area, effectively facilitates the diffusion of aluminum ions. Therefore, AIBs are able to exhibit a superior discharge capacity of 288 mAh g-1 at 0.2 A g-1 current density with robust cycling stability. The addition of potassium ferricyanide as a redox-active species in an aqueous solution of aluminum chloride (supporting electrolyte) leads to significant enhancement in the specific capacity with much higher cycling stability. Al-ion based BatCap devices can be assembled by using ZIF 67 as the cathode, ZIF 67 derived porous carbon as the anode, and a redox additive modified electrolyte. The BatCap device exhibits excellent energy density of 86 Wh kg-1 at a power density of 2 KW kg-1, which is higher than reported aqueous AIBs. The ex situ characterization clearly explains the unexplored mechanism of redox additives in AIBs.

Utilization of DNA and 2D metal oxide interaction for an optical biosensor.

The efficient monitoring and early detection of viruses may provide essential information about diseases. In this work, we have highlighted the interaction between DNA and a two-dimensional (2D) metal oxide for developing biosensors for further detection of viral infections. Spectroscopic measurements have been used to probe the efficient interactions between single-stranded DNA (ssDNA) and the 2D metal oxide and make them ideal candidates for detecting viral infections. We have also used fully atomistic molecular dynamics (MD) simulation to give a microscopic understanding of the experimentally observed ssDNA-metal oxide interaction. The adsorption of ssDNA on the inorganic surface was found to be driven by favourable enthalpy change, and 5'-guanine was identified as the interacting nucleotide base. Additionally, the in silico assessment of the conformational changes of the ssDNA chain during the adsorption process was also performed in a quantitative manner. Finally, we comment on the practical implications of these developments for sensing that could help design advanced systems for preventing virus-related pandemics.

Dimensionality effects of g-C3N4 from wettability to solar light assisted self-cleaning and electrocatalytic oxygen evolution reaction.

Unique interfacial properties of 2D materials make them more functional than their bulk counterparts in a catalytic application. In the present study, bulk and 2D graphitic carbon nitride nanosheet (bulk g-C3N4 and 2D-g-C3N4 NS) coated cotton fabrics and nickel foam electrode interfaces have been applied for solar light-driven self-cleaning of methyl orange (MO) dye and electrocatalytic oxygen evolution reaction (OER), respectively. Compared to bulk, 2D-g-C3N4 coated interfaces show higher surface roughness (1.094 > 0.803) and enhanced hydrophilicity (θ âˆ¼ 32° < 62° for cotton fabric and θ âˆ¼ 25° < 54° for Ni foam substrate) due to oxygen defect induction as confirmed from morphological (HR-TEM and AFM) and interfacial (XPS) characterizations. The self-remediation efficiencies for blank and bulk/2D-g-C3N4 coated cotton fabrics are estimated through colorimetric absorbance and average intensity changes. The self-cleaning efficiency for 2D-g-C3N4 NS coated cotton fabric is 87%, whereas the blank and bulk-coated fabric show 31% and 52% efficiency. Liquid Chromatography-Mass Spectrometry (LC-MS) analysis determines the reaction intermediates for MO cleaning. 2D-g-C3N4 shows lower overpotential (108 mV) and onset potential (1.30 V) vs. RHE for 10 mA cm-2 OER current density in 0.1 M KOH. Also, the decreased charge transfer resistance (RCT = 12 Ω) and lower Tafel's slope (24 mV dec-1) of 2D-g-C3N4 make it the most efficient OER catalyst over bulk-g-C3N4 and state-of-the-art material RuO2. The pseudocapacitance behavior of OER governs the kinetics of electrode-electrolyte interaction through the electrical double layer (EDL) mechanism. The 2D electrocatalyst demonstrates long-term stability (retention ∼94%) and efficacy compared to commercial electrocatalysts.

Time-dependent exfoliation study of MoS2 for its use as a cathode material in high-performance hybrid supercapacitors.

Quick and precise exfoliation of bulk molybdenum sulphide into few layers can bring a quantum leap in the electrochemical performance of this material. Such a cost-effective exfoliation route to obtain few layers of MoS2 nanosheets with a high mass yield of ∼75% is presented in this study. The electrochemical behaviours of three types of samples, namely pristine MoS2 and MoS2 exfoliated for 3 h and 5 h, were compared and the reasons leading to their performance modulation are explained. The performance could be tuned by changing the nature of the electrolytes, as shown using three different electrolytes, i.e. H2SO4, Na2SO4, and KOH. The electrochemical performance of a supercapacitor device fabricated using the 5 h-exfoliated sample showed many fold improvement. The strategy of combining with a 2D material-based anode is an interesting way forward for such devices. In addition, the anode material has to be carefully chosen so that high performance can be ensured. The usefulness of 2D flake-like WO3 as an anode was investigated first before establishing its worthiness in a hybrid device. The hybrid device was able to deliver an excellent energy density of 33.74 W h kg-1 with long-term cycling stability and coulombic efficiency, thus proving its applicability for high-performance energy-storage devices.

Carbon material produced by hydrothermal carbonisation of food waste as an electrode material for supercapacitor application: A circular economy approach.

This study aims to use landfill leachate (LL) as an aqueous medium during hydrothermal carbonisation (HTC) of food waste to produce hydrochar (FWH-LL-C), which could be used as an electrode material in energy storage devices. The structural properties and electrochemical performance of the hydrochar were compared to that obtained using distilled water as a reaction medium (FWH-DW-C). The results showed that there is a difference in Brunauer-Emmett-Teller (BET) surface area of FWH-LL-C (220 m2 gm-1) and FWH-DW-C (319 m2 gm-1). The electrochemical properties were comparable, with FWH-LL-C having 227 F g-1 specific capacitance at 1 A g-1 current density and FWH-DW-C having 235 F g-1 specific capacitance at 1 A g-1 current density. Furthermore, at a power density of 634 W kg-1, FWH-DW-C achieved the highest energy density of 14.4 Wh kg-1. The energy retention capacity of the electrode was 98% which indicate that the material has an excellent energy storage capacity. The findings suggested that LL could be used as an alternative source of aqueous media during the HTC of food waste to produce hydrochar which could be used as an effective electrode material in supercapacitors.

High-Performance, Nitrogen-Doped, Carbon-Nanotube-Based Electrochemical Sensor For Vitamin D3 Detection.

With the fast changing lifestyle, vitamin D deficiency is becoming extremely common. Therefore, development of economical, efficient, and fast sensors for vitamin D is the need of the hour. Carbon-based nanomaterials are extensively explored in sensing of variety of biomolecules. In the present study, an antibody-free, highly sensitive, carbon-nanotube-based, highly responsive vitamin D3 sensor is reported. Nitrogen-doped carbon nanotubes are utilized to overcome the limiting factor of hydrophobic character of pure carbon. The synthesized N-doped CNTs showed a specific surface area of 24 m2/g. The surface charges of vitamin D3 and the vitamin D3/NCNT complex are found to be -20 and -6.4 mV, respectively, by zeta potential measurements. The sensor is able to deliver high performance in the concentration range of 0-10 nM, with a limit of detection of 16 pM. The response study indicated the sensitivity value as 0.000495 mA/cm2 nM. The sensor is also able to show a higher selectivity toward vitamin D3 in comparison to other biomolecules. The long-term stability, reproducibility, good linear range, and ultralow detection capability of the sensor are also reported.

Anomalous structural behavior and antiferroelectricity in BiGdO3: detailed temperature and high-pressure study.

A comprehensive temperature and high-pressure investigation on BiGdO3is carried out by means of dielectric constant, piezoelectric current, polarization-electric field loop, Raman scattering and x-ray diffraction measurements. Temperature dependent dielectric constant and dielectric loss show two anomalies at about 290 K (Tr) and 720 K (TC). The latter anomaly is most likely due to antiferroelectric to paraelectric transition as hinted by piezoelectric current and polarization-electric field loop measurements at room temperature, while the former anomaly suggests reorientation of polarization. A small deviation from linear behaviour of both the Raman modes due to structural modification in the vicinity ofTC; and sharp decrease in integrated intensities of these two modes aboveTCprovide further proof for the above antiferroelectric to paraelectric transition. Cubic to monoclinic structural transition is observed at about 10 GPa in high-pressure x-ray diffraction studies accompanied by anisotropic lattice parameter changes and large unit cell volume collapse during the transition. This structural transition is corroborated by anomalous softening and large increase in full width half maximum of M2(640 cm-1) Raman mode above 10 GPa. We speculate that enhancement of large structural distortion and large reduction inc/aratio above 10 GPa might be associated with antiferroelectric to ferroelectric transition in the system.

Hierarchical NaFePO4 nanostructures in combination with an optimized carbon-based electrode to achieve advanced aqueous Na-ion supercapacitors.

Recent trends in sodium-ion-based energy storage devices have shown the potential use of hollow structures as an electrode material to improve the performance of these storage systems. It is shown that, in addition to the use of hierarchical structures, the choice of the complementary carbon electrode determines the final performance of Na-ion-based devices. Here, we present simple synthesis strategies to prepare different structured carbonaceous materials that can be upscaled to an industrial level. Individual carbon materials deliver specific capacitance ranges from 120 to 220 F g-1 at a current density of 1 A g-1 (with excellent capacity retention). These structures, when combined with hollow NaFePO4 microspheres to fabricate an aqueous supercapacitor, show as high as a 1.7 V working potential window and can deliver a maximum energy density of 25.29 W h kg-1 capacity retention. These values are much higher than those reported by NaFePO4 solid particles and randomly chosen carbon structure-based supercapacitors.

Hierarchical cage-frame type nanostructure of CeO2 for bio sensing applications: from glucose to protein detection.

Self-assembled hierarchical nanostructures are slowly superseding their conventional counterparts for use in biosensors. These morphologies show high surface area with tunable porosity and packing density. Modulating the interfacial interactions and subsequent particle assembly occurring at the water-and-oil interface in inverse miniemulsions, are amongst the best strategies to stabilize various type of hollow nanostructures. The paper presents a successful protocol to obtain CeO2 hollow structures based biosensors that are useful for glucose to protein sensing. The fabricated glucose sensor is able to deliver high sensitivity (0.495 µA cm-2 nM-1), low detection limit (6.46 nM) and wide linear range (0 nM to 600 nM). CeO2 based bioelectrode can also be considered as a suitable candidate for protein sensors. It can detect protein concentrations varying from 0 to 30 µM, which is similar or higher than most reports in the literature. The limit of detection (LOD) for protein was ∼0.04 µM. Therefore, the hollow CeO2 electrodes, with excellent reproducibility, stability and repeatability, open a new area of application for cage-frame type particles.

A study of microbially fabricated bio-conjugated quantum dots for pico-molar sensing of H2O2 and glucose.

Quantum dots (QDs) as bio-detectors have been intensively explored owing to their size dependent optical properties and are still envisioned to be used in a plethora of biomedical and healthcare areas. However, the medical application of the biosensors demands the ultrasensitive detection of the analytes, which is usually limited for the conventional methods of colorimetric and fluorescence detection. The Fluorescence Resonance Energy Transfer (FRET) process, exploited by QDs, translates the close association between the analyte and the detector into optical properties and thus promises the effective detection of biomolecules. FRET based detection systems for biomolecules utilize surface-functionalized QDs which are usually modified post production using different organic groups. In this work, a novel protocol was formulated to produce bio-functionalized QDs with controlled chemical and optical characteristics. Here, we demonstrate the first-ever biological green synthesis of MoS2 QDs using Pseudomonas aeruginosa. The bio-functionalized QDs show green luminescence with a quantum yield of 42%, supporting their application as an optical sensor. These QDs are utilized to detect the pico-molar concentration of glucose, which makes them ideal for early diabetes detection and many biomedical applications. Also, the ability to sense pico-molar levels of H2O2 opens the path for its utilization in apprehending the plant signaling pathways under stress conditions.

Curcumin Complexed with Graphene Derivative for Breast Cancer Therapy.

In recent years, graphene-based materials complexed with drugs have been developed for application in cancer therapy, aimed at gaining synergistic effect. Here, we have prepared graphene oxide (GO) and graphene quantum dots (GQDs) with curcumin (Cur) in three different ratios (1:1, 1:3, and 1:5 w/v). We showed a successful complexation of GO and GQDs with Cur through various spectroscopy and microscopy techniques. The optical density of the complex through UV-vis spectroscopy showed less than 10% (for GQDs-Cur) and less than 20% (for GO-Cur) aggregation in 48 h, which confirms the stability of the complex. The UV-vis result estimates the loading efficiency of Cur to be 80 ± 1 and 83 ± 1% for GO-Cur and GQDs-Cur respectively. We tested the complexes GO-Cur and GQDs-Cur in different ratios as an anticancer drug against human breast cancer cell lines MCF-7 and MDA-MB-468 through the MTT assay. Following 48 h of incubation with the cell lines, a cell viability of more than 75% was observed in the case of GQDs & GO, while it was 40% in the case of Cur at a concentration of 100 µg/mL. The 1:1, 1:3, and 1:5 ratios of complexes enforced cell death ∼60, ∼80, and ∼95% at 100 µg/mL after 48 h of treatment, respectively. The optical images of cancerous cells treated with GO, GQDs, Cur, GO-Cur, and GQDs-Cur, at three different time intervals (0, 24, and 48 h), corroborated well with the results from the MTT assay in terms of the percentage of dead cells. The fluorescence images show a successful delivery of Cur drug inside the cancerous cell. The possible mechanism of killing of the cancerous cell with the complexes GO-Cur and GQDs-Cur is discussed. Moreover, this study opens a window to determine the mechanism of killing the cancerous cell.

Quantification of protein aggregation rates and quenching effects of amylin-inhibitor complexes.

The formation of amyloid aggregates is the hallmark of many protein misfolding diseases, including Type-II diabetes mellitus, which is caused by the fibrillation of amylin protein. It is established that nano-sized ligands such as curcumin, resveratrol and graphene quantum dots can modify protein aggregation rates. In this article, we report a comparative study of these ligands to estimate their protein aggregation rates and fluorescence quenching using various experimental techniques. Through light scattering experiments, the RH of bare amylin was found to increase at a rate of 43% per day, whereas in the presence of the ligands in different molar ratios (A1C10, A1R10 and A1GQDs20), the sizes of the complexes were found to grow at rates of 7%, 8% and 13% per day, respectively. We observed fluorescence quenching using photoluminescence experiments for all three protein-ligand complexes. The protein aggregation rate and fluorescence quenching exhibited a concentration-dependent competitive role in the inhibition process. Interestingly, for graphene quantum dots, the protein aggregation rate is more affected at lower concentrations, while fluorescence quenching dominates at higher concentrations; this is in contrast to curcumin and resveratrol, where fluorescence quenching dominates at all concentrations of the ligands in the complex. The FTIR data showed appreciable conversion of ß-sheets into less aggregation-prone secondary structures for all three amylin-ligand ratios; however, the inhibition performance of curcumin overshadowed those of the other two inhibitors. The inhibition behavior of these three ligands was corroborated by analysis of analytical and high-resolution TEM images of the fibrils.

DNA supported graphene quantum dots for Ag ion sensing.

The use of graphene quantum dots can be extended for bio-sensing and metal ion detection. Synergistic combination of graphene quantum dots (GQDs) with DNA leads to high performance Ag-ion detection system. The thoroughly characterized GQDs were found to have spherical morphology, with dimensions in the range of 5-10 nm. The atomic force microscopy studies proved that the synthesized GQDs were mostly comprised of two to four graphene layers. To make the system biocompatible, GQDs/NGQDs were combined with DNA. Two properties of DNA were exploited, capacity to provide nitrogen to GQDs; and to synergistically contribute to Ag+ detection. In addition to Ag+, the strong green photoluminescence (PL) of GQDs showed significant quenching, owing to the appearance of associated Förster resonance energy transfer processes. This led to high sensing efficiencies.

Pressure induced anomalous magnetic behaviour in nanocrystalline YCrO3 at room temperature.

High pressure behaviour of nanocrystalline YCrO3 is investigated up to 10 GPa using electrical, magnetic, synchrotron x-ray diffraction and Raman spectroscopy measurements. High pressure dielectric constant measurements show a sharp peak at 4.5 GPa, though the sample is found to be in ferroelectric phase up to the highest pressure of our study from piezoelectric current measurements. X-ray diffraction measurements show absence of any structural phase transition, however anomalies are observed in the unit cell structural parameters at about 4.3 GPa and the Y-atom position shows a maximum shift at the same pressure. In the absence of any structural transition, anomalous behaviour of relevant Raman modes with minimum in the Raman band width at about same pressure indicate towards a spin-phonon interaction. AC magnetic measurements in the toroid anvil cell show an anomalous enhancement of magnetic moment above 4 GPa indicating a collective magnetic response of nanoparticles.

Hollow nanostructures of metal oxides as next generation electrode materials for supercapacitors.

Hollow nanostructures of copper oxides help to stabilize appreciably higher electrochemical characteristics than their solid counter parts of various morphologies. The specific capacitance values, calculated using cyclic voltammetry (CV) and charge-discharge (CD) studies, are found to be much higher than the values reported in literature for copper oxide particles showing  intriguing morphologies or even composites with trendy systems like CNTs, rGO, graphene, etc. The proposed cost-effective synthesis route makes these materials industrially viable for application in alternative energy storage devices. The improved electrochemical response can be attributed to effective access to the higher number of redox sites that become available on the surface, as well as in the cavity of the hollow particles. The ion transport channels also facilitate efficient de-intercalation, which results in the enhancement of cyclability and Coulombic efficiency. The charge storage mechanism in copper oxide structures is also proposed in the paper.

Cerium-Doped Copper(II) Oxide Hollow Nanostructures as Efficient and Tunable Sensors for Volatile Organic Compounds.

Tuning sensing capabilities of simple to complex oxides for achieving enhanced sensitivity and selectivity toward the detection of toxic volatile organic compounds (VOCs) is extremely important and remains a challenge. In the present work, we report the synthesis of pristine and Ce-doped CuO hollow nanostructures, which have much higher VOC sensing and response characteristics than their solid analogues. Undoped CuO hollow nanostructures exhibit high response for sensing of acetone as compared to commercial CuO nanoparticles. As a result of doping with cerium, the material starts showing selectivity. CuO hollow structures doped with 5 at. % of Ce return highest response toward methanol sensing, whereas increasing the Ce doping concentration to 10%, the material shows high response for both-acetone and methanol. The observed tunability in selectivity is directly linked to the varying concentration of the oxygen defects on the surface of the nanostructures. The work also shows that the use of hollow nanostructures could be the way forward for obtaining high-performance sensors even by using conventional and simple metal or semiconductor oxides.

Evolution of hollow nanostructures in hybrid Ce1-x Cu x O2 under droplet confinement leading to synergetic effects on the physical properties.

The paper discusses a successful strategy for tuning the hollow, porous or even solid morphologies of pure and Cu2+-doped CeO2 nanostructures. The reaction of nanodroplets at the interface in miniemulsions is significantly affected by the concentration of dopants. The growth mechanism is both reaction- as well as diffusion-controlled, which finally determines the particular morphology. With a varying degree of dopant concentration and quantum confinement, the concentration of Ce3+ available on the surface of the nano-droplets and -particles is found to change quite appreciably. This immediately leads to modulation in the physical properties, such as ferromagnetism or absorption. The significant red shift in the absorption spectra and associated broadband visible photoluminescence opens newer applications for the present material in visible optoelectronic devices.

Enhancing Specific Energy and Power in Asymmetric Supercapacitors - A Synergetic Strategy based on the Use of Redox Additive Electrolytes.

The strategy of using redox additive electrolyte in combination with multiwall carbon nanotubes/metal oxide composites leads to a substantial improvements in the specific energy and power of asymmetric supercapacitors (ASCs). When the pure electrolyte is optimally modified with a redox additive viz., KI, ~105% increase in the specific energy is obtained with good cyclic stability over 3,000 charge-discharge cycles and ~14.7% capacitance fade. This increase is a direct consequence of the iodine/iodide redox pairs that strongly modifies the faradaic and non-faradaic type reactions occurring on the surface of the electrodes. Contrary to what is shown in few earlier reports, it is established that indiscriminate increase in the concentration of redox additives will leads to performance loss. Suitable explanations are given based on theoretical laws. The specific energy or power values being reported in the fabricated ASCs are comparable or higher than those reported in ASCs based on toxic acetonitrile or expensive ionic liquids. The paper shows that the use of redox additive is economically favorable strategy for obtaining cost effective and environmentally friendly ASCs.

A new approach for crystallization of copper(II) oxide hollow nanostructures with superior catalytic and magnetic response.

We report the synthesis of copper(II) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism.

Significant Performance Enhancement in Asymmetric Supercapacitors based on Metal Oxides, Carbon nanotubes and Neutral Aqueous Electrolyte.

Amongst the materials being investigated for supercapacitor electrodes, carbon based materials are most investigated. However, pure carbon materials suffer from inherent physical processes which limit the maximum specific energy and power that can be achieved in an energy storage device. Therefore, use of carbon-based composites with suitable nano-materials is attaining prominence. The synergistic effect between the pseudocapacitive nanomaterials (high specific energy) and carbon (high specific power) is expected to deliver the desired improvements. We report the fabrication of high capacitance asymmetric supercapacitor based on electrodes of composites of SnO2 and V2O5 with multiwall carbon nanotubes and neutral 0.5 M Li2SO4 aqueous electrolyte. The advantages of the fabricated asymmetric supercapacitors are compared with the results published in the literature. The widened operating voltage window is due to the higher over-potential of electrolyte decomposition and a large difference in the work functions of the used metal oxides. The charge balanced device returns the specific capacitance of ~198 F g(-1) with corresponding specific energy of ~89 Wh kg(-1) at 1 A g(-1). The proposed composite systems have shown great potential in fabricating high performance supercapacitors.