Highly sensitive detection of environmental toxic fenitrothion in fruits and water using a porous graphene oxide nanosheets based disposable sensor.

Monitoring fenitrothion (FNT) residues in food and the environment is crucial due to its high environmental toxicity. In this study, we developed a sensitive, reliable electrochemical method for detecting FNT by using screen-printed carbon electrodes (SPCE) modified with porous graphene oxide (PGO) nanosheets. PGO surface properties have been meticulously characterized using advanced spectroscopic techniques. Electrochemical impedance spectroscopy and cyclic voltammetry were used to test the electrochemical properties of the PGO-modified sensor. The PGO-modified sensor exhibited remarkable sensitivity, achieving a detection limit as low as 0.061 µM and a broad linear range of 0.02-250 µM. Enhanced performance is due to PGO's high surface area and excellent electrocatalytic properties, which greatly improved electron transfer. Square wave voltammetry was used to demonstrate the sensor's efficacy as a real-time, on-site monitoring tool for FNT residues in fruit and water. The outstanding performance of the PGO/SPCE sensor underscores its applicability in ensuring food safety and environmental protection.

Simultaneous voltammetric determination of acetaminophen, naproxen, and theophylline using an in-situ polymerized poly(acrylic acid) nanogel covalently grafted onto a carbon black/La2O3 composite.

Lanthanum oxide nanomaterials were decorated with carbon black (CB) and grafted with a poly(acrylic acid) nanogel to obtain a composite material (CB-g-PAA/La2O3) for simultaneous determination of acetaminophen (AMP), naproxen (NPX), and theophylline (TPH). The nanogel was synthesized by in-situ free radical polymerization. The composite was dropped onto a glassy carbon electrode (GCE), and the modified GCE displays robust electrocatalytic activity towards AMP, NPX, and TPH, with voltammetric signals that are enhanced compared to a bare GCE. Features of merit for AMP, NPX, and TPH, respectively, include (a) peak potentials of 0.42, 0.85 and 0.12 V (vs. Ag/AgCl), (b) linear ranges from 0.05-887, 0.05-884, and 0.02-888 µM, and (c) detection limits of 20, 35, and 15 nM. The practical applicability of the CB-g-PAA/La2O3/GCE was illustrated by analyzing serum and urine samples. Graphical abstract Schematic presentation of simultaneous electrochemical sensing of acetaminophen (AMP), naproxen (NPX), and theophylline (TPH) in real sample analysis using poly(acrylic acid) nanogel covalently grafted onto a carbon black/La2O3 composite (CB-g-PAA/La2O3/GCE).

Enzyme-free electrochemical detection of nanomolar levels of the organophosphorus pesticide paraoxon-ethyl by using a poly(N-isopropyl acrylamide)-chitosan microgel decorated with palladium nanoparticles.

A rapid voltammetric method is described for the determination of the organophosphorus pesticide paraoxon-ethyl (PEL). A glassy carbon electrode (GCE) was modified with a composite consisting of a poly(N-isopropylacrylamide)-chitosan microgel with incorporated palladium nanoparticles. The microgel was characterized by FE-SEM, EDX, XPS, FTIR, XRD, and EIS. The modified GCE is shown to enable direct electro-reductive determination of PEL by using differential pulse voltammetry. The method works in pH 7 solution and in the 0.01 µM to 1.3 mM PEL concentration range. At a typical working potential of -0.66 V (vs. Ag/AgCl) (at 50 mV/s), the detection limit is as low as 0.7 nM, and the electrochemical sensitivity is 1.60 µA µM-1 cm-2. Intriguingly, the modified GCE displays good recovery when applied to bok choy and water samples. Graphical abstract Schematic of an electrochemical method for determination of paraoxon ethyl (PEL) in bok choy extract and water by using poly(N-isopropyl acrylamide)-chitosan microgel decorated with palladium nanoparticle-modified glassy carbon electrodes (PdNPs/PNIPAM-CT microgel/GCE).

Three-Dimensional Fibrous Network of Na0.21 MnO2 for Aqueous Sodium-Ion Hybrid Supercapacitors.

Sodium-ion hybrid supercapacitors are potential energy-storage devices and have recently received enormous interest. However, the development of cathode materials and the use of nonaqueous electrolyte remain a great challenge. Hence, aqueous Na-ion hybrid supercapacitors based on a three-dimensional network of NaMnO2 were developed. The cathode material was synthesized by the electro-oxidation of potassium manganese hexacyanoferrate nanocubes. The oxidized compound was confirmed to be Na0.21 MnO2 by various physical characterization methods. Manganese dioxide is a well-characterized material for aqueous asymmetric pseudocapacitors, but its usage at high operating voltages is limited due to the electrochemical stability of water. Nevertheless, high-potential and high-performance aqueous supercapacitors exhibiting a cell potential of 2.7 V were developed. Further, the practical applicability of an asymmetric supercapacitor based on NaMnO2 (cathode) and reduced graphene oxide (anode) was demonstrated by powering a 2.1 V red LED.

Synthesis, characterization, molecular modeling, binding energies of ß-cyclodextrin-inclusion complexes of quercetin: Modification of photo physical behavior upon ß-CD complexation.

We prepared a naturally occurring flavanoid namely quercetin from tea leaves and analyzed by Absorption, Emission, FT-IR, 1H, 13C nmr spectra and ESI-MS analysis. The inclusion behavior of quercetin in cyclodextrins like α-, ß-, γ-, per-6-ABCD and mono-6-ABCD cavities were supported such as UV-vis., Emission, FT-IR and ICD spectra and energy minimization studies. From the absorption and emission results, the type of complexes formed were found to depend on stoichiometry of Host:Guest. FT-IR data of CD complexes of quercetin supported inclusion complex formation of the substrate with α-, ß- and γ-CDs. The inclusion of host-guest complexation of quercetin with α-, ß-, γ-CDs, per-6-ABCD and mono-6-ABCDs provides very valuable information about the CD:quercetin complexes, the study also shows that ß-CD complexation improves water solubility, chemical stability and bioavailability of quercetin. Besides, phase solubility studies also supported the formation of 1:1 drug-CD soluble complexes. All these spectral results provide insight into the binding behavior of substrate into CD cavity in the order per-6-ABCD > Mono-6-ABCD > γ-CD > ß-CD > α-CD. The proposed model also finds strong support from the fact with excess CD this exciton coupling disappears indicates the formation of only 1:1 complex.

Unveiling high-power and high-safety lithium-ion battery separator based on interlayer of ZIF-67/cellulose nanofiber with electrospun poly(vinyl alcohol)/melamine nonwoven membranes.

Due to the poor thermal stability of conventional separators, lithium-ion batteries require a suitable separator to maintain system safety for long-term cycling performance. It must have high porosity, superior electrolyte uptake ability, and good ion-conducting properties even at high temperatures. In this work, we demonstrate a novel composite membrane based on sandwiching of zeolitic imidazole frameworks-67 decorated cellulose acetate nanofibers (ZIF-67@CA) with electrospun poly(vinyl alcohol)/melamine (denoted as PVAM) nonwoven membranes. The as-prepared sandwich-type membranes are called PVAM/x%ZIF-67@CA/PVAM. The middle layer of composite membranes is primarily filled with different weight percentages of ZIF-67 nanoparticles (x = 5, 15, and 25 wt%), which both reduces the non-uniform porous structure of CA and increases its thermal stability. Therefore, our sandwich-type PVAM/x%ZIF-67@CA/PVAM membrane exhibits a higher thermal shrinkage effect at 200 °C than the commercial polyethylene (PE) separator. Due to its high electrolyte uptake (646.8%) and porosity (85.2%), PVAM/15%ZIF-67@CA/PVAM membrane achieved high ionic conductivity of 1.46 × 10-3 S cm-1 at 70 °C, as compared to the commercial PE separator (ca. 6.01 × 10-4 S cm-1 at 70 °C). Besides, the cell with PVAM/15%ZIF-67@CA/PVAM membrane shows an excellent discharge capacity of about 167.5 mAh g-1after 100 cycles at a 1C rate with a capacity retention of 90.3%. The ZIF-67 fillers in our sandwich-type composite membrane strongly attract anions (PF6-) through Lewis' acid-base interaction, allowing uniform Li+ ion transport and suppressing Li dendrites. As a result, we found that the PVAM/15%ZIF-67@CA/PVAM composite nonwoven membrane is applicable to high-power, high-safety lithium-ion battery systems that can be used in electric vehicles (EVs).

'On and Off' intercalative binding behaviour of double chain surfactant cobalt(III) complex containing 2, 2'-bipyridyl ligand in ß-Cyclodextrin: A detail approach on Host-guest inclusion of surfactant cobalt(III) complex and CT-DNA binding in micro-heterogeneous medium.

The binding interaction of surfactant cobalt(III) complex, cis-[Co(bpy)2(HA)2](ClO4)3, in which bpy is 2,2-bipyridine and HA is hexadecylamine or cetylamnine with DNA was through intercalative mode via the long aliphatic chains present in the ligands. The binding was investigated by various techniques, electronic absorption, fluorescence spectroscopy, circular dichroism (CD), cyclic voltametry (CV) and viscosimetry measurements. The spectroscopic studies together with cyclic voltammetry and viscosity experiments support that the surfactant cobalt(III) complex binds to calf thymus DNA by intercalation through the aliphatic chain present in the complex into the base pairs of DNA. The presence of bipyridine ligand with larger π-frame work may also enhance intercalation. UV-vis., spectrum showed 4 nm bathochromic shift of the absorption band at 352 nm along with significant hypochromicity for the absorption band of the complex. The intrinsic binding constants(at below and above CMC are Kb = 2.41 × 105M-1, Kb = 3.12 × 106M-1 respectively) is more in keeping with intercalators and suggests this binding mode. The viscosity measurements showed that the surfactant cobalt(III) complex-DNA interaction can be hydrophobic and confirm intercalation. Moreover, the complex induced detectable changes in the CD spectrum of CT-DNA. Competitive binding study with ethidium bromide (EB) shows that the surfactant complex exhibits the ability to displace the DNA-bound EB indicating that the complex binds to DNA in strong competition with EB for the intercalative binding site. Also, CV results confirm this mode because, with increasing the CT-DNA concentration, shift to higher potential was observed. Besides the effect of binding of surfactant cobalt(III) complex to DNA in presence of ß-cyclodextrin has also studied. This binding of the surfactant cobalt(III) complex in presence of ß-cyclodextrin medium has been prevented (at below and above CMC are Kb = 5.45 × 104M-1, Kb = 6.92 × 105M-1 respectively) due to the incorporation of the aliphatic chains into the cavity of ß-cyclodextrin. In presence of ß-cyclodextrin the binding occur through surface and (or) groove binding can be attributed to the inclusion of the long aliphatic chain that is present in one of the ligands into cyclodextrin.

Effect of hydrophobicity and size of the ligands on the intercalative binding interactions of some metallo-surfactants containing π-conjugated systems with yeast tRNA.

The intercalative yeast t-RNA binding behavior of some metallo-surfactant complexes, Co(ip)2(TA)2](ClO4)3 (1) and [Co(dpq)2(TA)2](ClO4)3 (2) where TA = Tetradecylamine (Myristylamine), ip = imidazo[4,5-f][1,10]phenanthroline and dpq = dipyrido[3,2-d:2'-3'-f]quinoxaline containing π-conjugated systems (both below and above critical micelle concentration) have been investigated by means of absorption spectral titration, competitive binding, circular dichroism, cyclic voltammetry, and viscometry measurements. Absorption spectral titration results implicate yeast tRNA has significant effects on the binding behaviors of two surfactant complexes via intercalative mode showed a significant absorption band of hypochromicity with red shift. The intrinsic binding constant values below and above CMC were determined as Kb = 6.12 × 105 M-1, 2.31 × 106 M-1, for complex (1) and 7.23 × 105 M-1, 3.57 × 106 M-1, for complex (2). In both sets of complexes (1) and (2), the complexes bind more strongly to yeast tRNA in the above critical micelle concentration can be hydrophobic and confirm intercalation. Competitive displacement studies confirmed that complexes bind to yeast tRNA via intercalative mode. Cyclic voltammetry studies suggest the increasing amounts of yeast tRNA, the cathodic potential Epc for the two complexes shows a positive shift in peak potential indicated the process of binding via intercalation. These observations were further validated by CD, and hydrodynamic measurements. All these studies suggesting that a surfactant complex binds to yeast tRNA appear to be mainly intercalative because of hydrophobicity due to extending aromaticity of the π system of the ligand and planarity of the complex has a significant effect on tRNA binding affinity increasing in the order of complexes containing ligands ip < dpq.Communicated by Ramaswamy H. Sarma.

Impact of gadolinium oxide with functionalized carbon nanosphere: A portable advanced electrocatalyst for pesticide detection in aqueous environmental samples.

In this study, we developed a portable electrochemical sensor for realizing the pesticide residue in biological, environmental, and vegetable samples. A lower concentration of carbendazim pesticide (CBZ) was electrochemically exposed by newly developed gadolinium oxide/functionalized carbon nanosphere modified glassy carbon electrode (Gd2O3/f-CNS/GCE). The Gd2O3/f-CNS composite was prepared by two-pot ultrasonic-assisted co-precipitation method and characterized by various physicochemical analytical techniques. In addition, the electrocatalytic activity of the composite was investigated by cyclic voltammetry (CV) towards the detection of CBZ. Besides, the Gd2O3/f-CNS/GCE exhibited excellent electrocatalytic capability and sensitivity towards the oxidation of CBZ due to its high electrochemical active surface area, good conductivity, and fast electron transfer ability. A wide linear range of CBZ (0.5-552 µM) was attained with a low level of detection (LOD) of 0.009 µM L-1 and exceptional stability of 93.41%. The proposed sensor exemplifies practical feasibility in blood serum, water, and vegetable samples with an remarkable recovery range of 96.27-99.44% and primary current response of ∼91% after 15 days.

States of Aggregation and Phase Transformation Behavior of Metallosurfactant Complexes by Hexacyanoferrate(II): Thermodynamic and Kinetic Investigation of ETR in Ionic Liquids and Liposome Vesicles.

Electronic absorption spectroscopy was used to study the ETR of surfactant-cobalt(III) complexes containing imidazo[4,5-f][1,10]phenanthroline, dipyrido[3,2-d:2'-3'-f]quinoxaline and dipyrido[3,2-a:2',4'-c](6,7,8,9-tetrahydro)phenazine ligands by using ferrocyanide ions in unilamellar vesicles of dipalmitoylphosphotidylcholine (DPPC) and 1-butyl-3-methylimidazolium bromide ((BMIM)Br), at different temperatures under pseudo-first-order conditions using an excess of the reductant. The reactions were found to be second-order and the electron transfer is postulated as occurring in the outer sphere. The rate constant for the electron transfer reactions was found to increase with increasing concentrations of ionic liquids. Besides these, the effects of surfactant complex ions on liposome vesicles in these same reactions have also been studied on the basis of hydrophobicity. We observed that, below the phase transition temperature, there is an increasing amount of surfactant-cobalt(III) complexes expelled from the interior of the vesicle membrane through hydrophobic effects, while above the phase transition temperature, the surfactant-cobalt(III) complexes are expelled from the interior to the exterior surface of the vesicle. Kinetic data and activation parameters are interpreted in respect of an outer-sphere electron transfer mechanism. By assuming the existence of an outer-sphere mechanism, the results have been clarified based on the presence of hydrophobicity, and the size of the ligand increases from an ip to dpqc ligand and the reactants become oppositely charged. In all these media, the ΔS# values are recognized as negative in their direction in all the concentrations of complexes employed, indicative of a more ordered structure of the transition state. This is compatible with a model in which these complexes and [Fe(CN)6]4- ions bind to the DPPC in the transition state. Thus, the results have been interpreted based on the self-aggregation, hydrophobicity, charge densities of the co-ligand and the reactants with opposite charges.

MoO3 Nanoparticle Coatings on High-Voltage 5 V LiNi0.5Mn1.5O4 Cathode Materials for Improving Lithium-Ion Battery Performance.

To reduce surface contamination and increase battery life, MoO3 nanoparticles were coated with a high-voltage (5 V) LiNi0.5Mn1.5O4 cathode material by in-situ method during the high-temperature annealing process. To avoid charging by more than 5 V, we also developed a system based on anode-limited full-cell with a negative/positive electrode (N/P) ratio of 0.9. The pristine LiNi0.5Mn1.5O4 was initially prepared by high-energy ball-mill with a solid-state reaction, followed by a precipitation reaction with a molybdenum precursor for the MoO3 coating. The typical structural and electrochemical behaviors of the materials were clearly investigated and reported. The results revealed that a sample of 2 wt.% MoO3-coated LiNi0.5Mn1.5O4 electrode exhibited an optimal electrochemical activity, indicating that the MoO3 nanoparticle coating layers considerably enhanced the high-rate charge-discharge profiles and cycle life performance of LiNi0.5Mn1.5O4 with a negligible capacity decay. The 2 wt.% MoO3-coated LiNi0.5Mn1.5O4 electrode could achieve high specific discharge capacities of 131 and 124 mAh g-1 at the rates of 1 and 10 C, respectively. In particular, the 2 wt.% MoO3-coated LiNi0.5Mn1.5O4 electrode retained its specific capacity (87 mAh g-1) of 80.1% after 500 cycles at a rate of 10 C. The Li4Ti5O12/LiNi0.5Mn1.5O4 full cell based on the electrochemical-cell (EL-cell) configuration was successfully assembled and tested, exhibiting excellent cycling retention of 93.4% at a 1 C rate for 100 cycles. The results suggest that the MoO3 nano-coating layer could effectively reduce side reactions at the interface of the LiNi0.5Mn1.5O4 cathode and the electrolyte, thus improving the electrochemical performance of the battery system.

Imidazolatic-Framework Bimetal Electrocatalysts with a Mixed-Valence Surface Anchored on an rGO Matrix for Oxygen Reduction, Water Splitting, and Dye Degradation.

This paper presents a simple strategy for manufacturing bifunctional electrocatalysts-graphene nanosheets (GNS) coated with an ultrafine NiCo-MOF as nanocomposites (denoted NiCo-MOF@GNS) having a N-doped defect-rich and abundant cavity structure through one-pool treatment of metal-organic frameworks (MOFs). The precursors included N-doped dodecahedron-like graphene nanosheets (GNS), in which the NiCo-MOF was encompassed within the inner cavities of the GNS (NiCo-MOF@GNS) at the end or middle portion of the tubular furnace with several graphene layers. Volatile imidazolate N x species were trapped by the NiCo-MOF nanosheets during the pyrolysis process, simultaneously inserting N atoms into the carbon matrix to achieve the defect-rich porous nanosheets and the abundantly porous cavity structure. With high durability, the as-prepared nanomaterials displayed simultaneously improved performance in the oxygen reduction reaction (ORR), the oxygen evolution reaction (OER), and photocatalysis. In particular, our material NiCo-MOF@GNS-700 exhibited excellent electrocatalytic activity, including a half-wave potential of 0.83 V (E ORR, 1/2), a low operating voltage of 1.53 V (E OER, 10) at 10 mA cm-2, a potential difference (ΔE) of 1.02 V between E OER, 10 and E ORR, 1/2 in 0.1 M KOH, and a low band gap of 2.61 eV. This remarkable behavior was due to the structure of the defect-rich porous carbon nanosheets and the synergistic impact of the NPs in the NiCo-MOF, the N-doped carbon, and NiCo-N x . Furthermore, the hollow structure enhanced the conductivity and stability. This useful archetypal template allows the construction of effective and stable bifunctional electrocatalysts, with potential for practical viability for energy conversion and storage.

Nanomolar level detection of non-steroidal antiandrogen drug flutamide based on ZnMn2O4 nanoparticles decorated porous reduced graphene oxide nanocomposite electrode.

Flutamide is a non-steroidal antiandrogen drug and widely used in the treatment of prostatic carcinoma. Nevertheless, the excessive intake and improper disposal could affect the living organisms. In this work, we have synthesized a new nanocomposite based on ZnMn2O4 nanoparticles and porous reduced graphene oxide nanosheets (ZnMn2O4-PGO) for the electrocatalytic detection of flutamide (FLU) drug. The crystallinity and morphological properties of ZnMn2O4-PGO composite examined by different characterization techniques such as X-ray diffraction, Raman spectroscopy and so on. The fabricated ZnMn2O4-PGO nanocomposite modified electrode exhibited superior electrocatalytic performance to FLU drug in an optimized pH electrolyte. Fascinatingly, the electrode received a wide linear range (0.05-3.5 µM) with limit of detection of 8 nM. Besides, the developed ZnMn2O4-PGO nanocomposite electrode showed good sensitivity 1.05 µAµM-1 cm-2 and excellent selectivity for FLU detection in presence of various interfering species. A developed disposable electrode was scrutinized to determine FLU level in human urine samples by spiking method and the results achieved good recoveries in real sample analysis.

A novel hybrid construction of MnMoO4 nanorods anchored graphene nanosheets; an efficient electrocatalyst for the picomolar detection of ecological pollutant ornidazole in water and urine samples.

Nitroimidazole compounds are widely used antibiotics to encounter anaerobic bacterial and parasitic infections. The wide usage of antibiotic drugs became an ecological contaminant which in turn into potential monitoring. In this regards, we have designed and developed a new electrochemical sensing probe to monitor an antiprotozoal drug, ornidazole (ODZ), with the aid of a glassy carbon electrode (GCE) integrated with manganese molybdate nanorods (MnMoO4) decorated graphene nanosheets (GNS) hybrid materials that prepared by feasible probe sonochemical method (parameters: 2-4 W, 5 mV amp, 20 kHz). The electrochemical investigations of the developed probe were performed by using rapid scan electrochemical workstations namely cyclic voltammetry (CV) and amperometric (i-t) techniques. The as-prepared MnMoO4/GNS nanocomposite was characterized and its purity of nanocomposite formation was confirmed by various analytical techniques like X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and Raman spectroscopy. In addition to that, the textural morphology of the MnMoO4/GNS nanocomposite was examined with the aid of field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM). The MnMoO4/GNS nanocomposite rotating disk glassy carbon electrode (RDGCE) plays a crucial role in electrochemical detection of ODZ, which results in excellent anti-interference ability, a lower detection limit of 845 pM, massive linear ranges from 10 to 770 nM, and good sensitivity of about 104.62 µA µM-1 cm-2. From the acquired electrochemical studies, we have developed a disposable electrochemical sensor probe using a low-cost screen-printed carbon electrode (SPCE) with MnMoO4/GNS nanocomposite. The MnMoO4/GNS/SPCE are capably employed in real-time sensing of ODZ in water and urine samples. These electrochemical studies revealed the integral new vision on the electrocatalytic performance of the modified SPCE and also shown excellent amplification results in ultra-trace levels.

Graphene Nanosheet-Wrapped Mesoporous La0.8Ce0.2Fe0.5Mn0.5O3 Perovskite Oxide Composite for Improved Oxygen Reaction Electro-Kinetics and Li-O2 Battery Application.

A novel design and synthesis methodology is the most important consideration in the development of a superior electrocatalyst for improving the kinetics of oxygen electrode reactions, such as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in Li-O2 battery application. Herein, we demonstrate a glycine-assisted hydrothermal and probe sonication method for the synthesis of a mesoporous spherical La0.8Ce0.2Fe0.5Mn0.5O3 perovskite particle and embedded graphene nanosheet (LCFM(8255)-gly/GNS) composite and evaluate its bifunctional ORR/OER kinetics in Li-O2 battery application. The physicochemical characterization confirms that the as-formed LCFM(8255)-gly perovskite catalyst has a highly crystalline structure and mesoporous morphology with a large specific surface area. The LCFM(8255)-gly/GNS composite hybrid structure exhibits an improved onset potential and high current density toward ORR/OER in both aqueous and non-aqueous electrolytes. The LCFM(8255)-gly/GNS composite cathode (ca. 8475 mAh g-1) delivers a higher discharge capacity than the La0.5Ce0.5Fe0.5Mn0.5O3-gly/GNS cathode (ca. 5796 mAh g-1) in a Li-O2 battery at a current density of 100 mA g-1. Our results revealed that the composite's high electrochemical activity comes from the synergism of highly abundant oxygen vacancies and redox-active sites due to the Ce and Fe dopant in LaMnO3 and the excellent charge transfer characteristics of the graphene materials. The as-developed cathode catalyst performed appreciable cycle stability up to 55 cycles at a limited capacity of 1000 mAh g-1 based on conventional glass fiber separators.

Ultra-stable Mn1-xNixCO3 nano/sub-microspheres positive electrodes for high-performance solid-state asymmetric supercapacitors.

Long-term cycling performance of electrodes for application in supercapcitor has received large research interest in recent years. Ultra-stable Mn1-xNixCO3 (x-0, 0.20, 0.25 and 0.30) nano/sub-microspheres were synthesized via simple co-precipitation method and the Mn1-xNixCO3 was confirmed by XRD, FT-IR, XPS and their morphology was studied by SEM and TEM analysis. Among the various Mn1-xNixCO3 electrodes, the Mn0.75Ni0.25CO3 electrode exhibited the higher specific capacitance (364 F g-1 at 1 A g-1) with capacity retention of 96% after 7500 cycles at 5 A g-1. Moreover, the assembled solid-state asymmetric supercapacitor based on Mn0.75Ni0.25CO3//graphene nanosheets performed a high specific capacity of 46 F g-1 and energy density of 25 Wh kg-1 at a power density of 499 W kg-1 along with high capacity retention of 87.7% after 7500 cycles. The improved electrochemical performances are mainly owing to the intrinsic conductivity and electrochemical activity of MnCO3 after Mn1-xNixCO3 (x-0.20, 0.25 and 0.30) with appropriate Ni concentration. This study highlights the potentiality of the Mn0.75Ni0.25CO3//GNS asymmetric supercapacitor device for promising energy storage applications.

Direct pyrolysis and ultrasound assisted preparation of N, S co-doped graphene/Fe3C nanocomposite as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions.

Bifunctional electrocatalysts to enable efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for fabricating high performance metal-air batteries and fuel cells. Here, a defect rich nitrogen and sulfur co-doped graphene/iron carbide (NS-GR/Fe3C) nanocomposite as an electrocatalyst for ORR and OER is demonstrated. An ink of NS-GR/Fe3C is developed by homogeneously dispersing the catalyst in a Nafion containing solvent mixture using an ultrasonication bath (Model-DC150H; power - 150 W; frequency - 40 kHz). The ultrasonically prepared ink is used for preparing the electrode for electrochemical studies. In the case of ORR, the positive half-wave potential displayed by NS-GR/Fe3C is 0.859 V (vs. RHE) and for the OER, onset potential is 1.489 V (vs. RHE) with enhanced current density. The optimized NS-GR/Fe3C electrode exhibited excellent ORR/OER bifunctional activities, high methanol tolerance and excellent long-term cycling stability in an alkaline medium. The observed onset potential for NS-GR/Fe3C electrocatalyst is comparable with the commercial noble metal catalyst, thereby revealing one of the best low-cost alternative air-cathode catalysts for the energy conversion and storage application.

Facile fabrication of thin metal oxide films on porous carbon for high density charge storage.

In an effort to minimize the usage of non-renewable materials and to enhance the functionality of the renewable materials, we have developed thin metal oxide coated porous carbon derived from a highly abundant non-edible bio resource, i.e., palm kernel shell, using a one-step activation-coating procedure and demonstrated their superiority as a supercapacitive energy storage electrode. In a typical experiment, an optimized composition contained ~10 wt% of Mn2O3 on activated carbon (AC); a supercapacitor electrode fabricated using this electrode showed higher rate capability and more than twice specific capacitance than pure carbon electrode and could be cycled over 5000 cycles without any appreciable capacity loss in 1 M Na2SO4 electrolyte. A symmetric supercapacitor prototype developed using the optimum electrode showed nearly four times higher energy density than the pure carbon owing to the enhancements in voltage window and capacitance. A lithium ion capacitor fabricated in half-cell configuration using 1 M LiPF6 electrolyte showed larger voltage window, superior capacitance and rate capability in the ~10 wt% Mn2O3 @AC than the pure analogue. These results demonstrate that the current protocol allows fabrication of superior charge storing electrodes using renewable materials functionalized by minimum quantity of earthborn materials.

Temperature-Controlled Synthesis of Li- and Mn-Rich Li1.2Mn0.54Ni0.13Co0.13O2 Hollow Nano/Sub-Microsphere Electrodes for High-Performance Lithium-Ion Battery.

The calcination temperature plays a significant role in the structural, textural, and energy-storage performance of metal oxide nanomaterials in Li-ion battery application. Here, we report the formation of well-crystallized homogeneously dispersed Li1.2Mn0.54Ni0.13Co0.13O2 hollow nano/sub-microsphere architectures through a simple cost-effective coprecipitation and chemical mixing route without surface modification for improving the efficiency of energy storage devices. The synthesized Li1.2Mn0.54Ni0.13Co0.13O2 hollow nano/sub-microsphere cathode materials are calcined at 800, 900, 950, and 1000 °C. Among them, Li1.2Mn0.54Ni0.13Co0.13O2 calcined at 950 °C exhibits a high discharge capacity (277 mAh g-1 at 0.1C rate) and excellent capacity retention (88%) after 50 cycles and also delivers an excellent discharge capacity of >172 mAh g-1 at 5C rate. Good electrochemical performance of Li1.2Mn0.54Ni0.13Co0.13O2-950 is directly related to the optimized size of its primary particles (85 nm) (which constitute the spherical secondary particle, ∼720 nm) and homogeneous cation mixing. Higher calcination temperature (≥950 °C) leads to an increase of the primary particle size, poor cycling stability, and inferior rate capacity of Li1.2Mn0.54Ni0.13Co0.13O2 due to smashing of quasi-hollow spheres upon repeated lithium ion intercalations/deintercalations. Therefore, Li1.2Mn0.54Ni0.13Co0.13O2-950 is a promising electrode for the next-generation high-voltage and high-capacity Li-ion battery application.

Electrochemical co-preparation of cobalt sulfide/reduced graphene oxide composite for electrocatalytic activity and determination of H2O2 in biological samples.

In this work, we describe a simple approach for the preparation of cobalt sulfide/reduced graphene oxide (CoS/RGO) nanohybrids via single step electrochemical method. The electrocatalytic activity of the CoS/RGO nanohybrids was evaluated towards the detection hydrogen peroxide (H2O2). The physiochemical properties of the prepared composite was characterized by means of field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and X-ray powder diffraction patterns. The CoS/RGO modified electrode showed superior electrocatalytic activity towards the detection of H2O2. The amperometric (i-t) studies revealed that the CoS/RGO performed well by attaining a wide linear response range of H2O2 from 0.1 to 2542.4µM with a lower detection limit 42nM and the sensitivity of 2.519µAµM-1cm-2. Meanwhile, the CoS/RGO nanohybrids exhibited good selectivity, rapid and stable response towards H2O2. The practical applicability of the sensor was successfully evaluated in human serum and urine samples with satisfactory recoveries.