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For the initial instance, oxygen deficiency-enriched vanadium pentoxide (O─V2O5@500) thin film electrodes are tuned by the Pulsed Laser Ablation technique. The O─V2O5@500 thin film electrode shows remarkable electrochemical performances confirming the greater potential window of -0.4 to 0.9 V versus Hg/HgO in an alkaline electrolyte; also, the O─V2O5@ 500 thin film electrode exhibits a noteworthy volumetric capacity of 167.7 mAh cm-3 (areal capacity of 73.3 µAh cm-2). Additionally, Density Functional Theory (DFT) theory calculations are carried out for oxygen-deficient V2O5. From the partial density of states (pDOS) and partial charge density analysis, it is clear that oxygen vacancy improves the electrical conductivity due to the higher degree of electron delocalization of V─O─V near the vacancy and enhances the redox properties due to the formation of in-gap states. Further, it is reported that a O─V2O5@ 500 ||PVA-KOH|| Bi2O3 A-650 thin film supercapbattery (TFSCB) device attains an exceptional discharge volumetric capacitance of 182.85 F cm-3 (equal volumetric capacity of 124.5 mAh cm-3). Furthermore, the TFSCB device exhibits an extraordinary maximum volumetric energy (power) density of 14.28 mWh cm-3 (1.66 W cm-3); TFSCB succeeds in supreme capacity retention of 86% with outstanding coulombic efficiency of 94.4% after 21 000 cycles.

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This present study describes the synthesis of ultrafine Bi-Sn nanoparticles decorated on carbon aerogels (Bi-Sn NP/CAG) as a nanocomposite for the electrochemical simultaneous determination of dopamine (DA) and clozapine (CLZ). The typical characterization techniques, such as XRD, Raman, BET, FT-IR, TGA, XPS, and FE-SEM/TEM, showed useful insights into the crystal phase and morphology of Bi-Sn NP/CAG. Integrated Bi-Sn NP/CAG built into a cost-effective screen printed carbon electrode (SPCE) offers a high electrochemical surface area (ECSA) compared to unmodified, Bi-Sn, and CAG/SPCEs, such that it favourably allowed the binding of DA and CLZ molecules onto the surface at the Bi-Sn/CAG, which was demonstrated by cyclic and differential pulse voltammetry techniques. As a result, the DA and CLZ sensing exhibited low detection limits (DL, 4.6 and 97.6 nM (S/N = 3)), and sensitivity (3.402 and 0.4 µA µM-1 cm-2) over a wide linear range (0.02-97.59 and 0.5-2092 µM), respectively. To go a step further, the Bi-Sn NP/CAG/SPCE was applied for the simultaneous determination of DA and CLZ which featured lower DL (23.1 and 31.3 nM (S/N = 3)), and sensitivity (0.4979 and 0.04 µA µM-1 cm-2) over a wide linear range (2-182 and 10-910 µM), respectively. The selectivity for DA and CLZ in the presence of a 10-fold concentration of their potentially interfering active species was demonstrated. Finally, this sensing methodology enables the rapid electrochemical determination of the amount of DA and CLZ in a rat brain region serum sample with successful recovery outcomes.

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The electrochemical determination of 4-nitrophenol using a nanohybrid consisting of glassy carbon (GC) and zinc oxide/graphitic carbon nitride (ZnO/g-CN nanosheet), is described. The ZnO/g-CN nanohybrid was in situ synthesized by chemical method and well characterized using absorption spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopic analysis. It was observed that the nanosized ZnO particles were present inside the sheet-like g-CN nanostructure. The nanohybrid-modified electrode showed an enhanced electrocatalytic response for 4-nitrophenol reduction compared with the bare GC electrode. The assay exhibited linear ranges of 13.4-100 µM and 100-1000 µM for 4-NP determination. The limit of detection and limit of quantification were 4.0 and 13.4 µM, respectively, at the working potential of - 0.85 V. An appreciable precision was found towards the stability of the assay in the determination. It provides selectivity against inorganic and organic substances such as calcium chloride, potassium chloride, nitrobenzene, uric acid, 1-chloro,2,4-dinitrobenzene, 1-bromo,2-nitrobenzene and 1-iodo,2-nitrobenzene. The practical applicability of the assay was also checked in the analysis of real water samples and satisfactory recovery of 4-NP was found. Schematic representation of the synthesis of zinc oxide (ZnO) nanostructures incorporated graphitic carbon nitride nanosheets (g-C3N4 NSs) and its application in the voltammetric determination of 4-nitrophenol (4-NP) is presented. The nanohybrid assay showed selectivity among coexisting compounds and good recovery in real sample analysis.

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A sensitive and novel electrochemical sensor was developed for the detection of hydrogen peroxide (H2O2) using a reduced graphene oxide-nafion@silver6 (rGO-Nf@Ag6) nanohybrid modified glassy carbon electrode (GC/rGO-Nf@Ag6). The GC/rGO-Nf@Ag6 electrode exhibited an excellent electrochemical sensing ability for determining H2O2 with high sensitivity and selectivity. The detection limit of the electrochemical sensor using the GC/rGO-Nf@Ag6 electrode for H2O2 determination was calculated to be 5.35×10-7M with sensitivity of 0.4508µAµM-1. The coupling between rGO-Nf with silver nanoparticles (AgNPs) significantly boosted the electroanalytical performance by providing more active area for analyte interaction, thereby allowing more rapid interfacial electron transfer process. The interfering effect on the current response of H2O2 was studied and the results revealed that the sensor electrode exhibited an excellent immunity from most common interferents. The proposed non-enzymatic electrochemical sensor was used for determining H2O2 in apple juice, and the sensor electrode provided satisfactory results with reliable recovery values. These studies revealed that the novel GC/rGO-Nf@Ag6 sensor electrode could be a potential candidate for the detection of H2O2.

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In the present investigation, gold-silver@titania (Au-Ag@TiO2) plasmonic nanocomposite materials with different Au and Ag compositions were prepared using a simple one-step chemical reduction method and used as photoanodes in high-efficiency dye-sensitized solar cells (DSSCs). The Au-Ag incorporated TiO2 photoanode demonstrated an enhanced solar-to-electrical energy conversion efficiency of 7.33%, which is ∼230% higher than the unmodified TiO2 photoanode (2.22%) under full sunlight illumination (100 mW cm-2, AM 1.5G). This superior solar energy conversion efficiency was mainly due to the synergistic effect between the Au and Ag, and their surface plasmon resonance effect, which improved the optical absorption and interfacial charge transfer by minimizing the charge recombination process. The influence of the Au-Ag composition on the overall energy conversion efficiency was also explored, and the optimized composition with TiO2 was found to be Au75-Ag25. This was reflected in the femtosecond transient absorption dynamics in which the electron-phonon interaction in the Au nanoparticles was measured to be 6.14 ps in TiO2/Au75:Ag25, compared to 2.38 ps for free Au and 4.02 ps for TiO2/Au100:Ag0. The slower dynamics indicates a more efficient electron-hole separation in TiO2/Au75:Ag25 that is attributed to the formation of a Schottky barrier at the interface between TiO2 and the noble metal(s) that acts as an electron sink. The significant boost in the solar energy conversion efficiency with the Au-Ag@TiO2 plasmonic nanocomposite showed its potential as a photoanode for high-efficiency DSSCs.

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Nitrogen-doped graphene quantum dots (N-GQDs) were decorated on a three-dimensional (3D) MoS2-reduced graphene oxide (rGO) framework via a facile hydrothermal method. The distribution of N-GQDs on the 3D MoS2-rGO framework was confirmed using X-ray photoelectron spectroscopy, energy dispersive X-ray elemental mapping, and high-resolution transmission electron microscopy techniques. The resultant 3D nanohybrid was successfully demonstrated as an efficient electrocatalyst toward the oxygen reduction reaction (ORR) under alkaline conditions. The chemical interaction between the electroactive N-GQDs and MoS2-rGO and the increased surface area and pore size of the N-GQDs/MoS2-rGO nanohybrid synergistically improved the ORR onset potential to +0.81 V vs reversible hydrogen electrode (RHE). Moreover, the N-GQDs/MoS2-rGO nanohybrid showed better ORR stability for up to 3000 cycles with negligible deviation in the half-wave potential (E 1/2). Most importantly, the N-GQDs/MoS2-rGO nanohybrid exhibited a superior methanol tolerance ability even under a high concentration of methanol (3.0 M) in alkaline medium. Hence, the development of a low-cost metal-free graphene quantum dot-based 3D nanohybrid with high methanol tolerance may open up a novel strategy to design selective cathode electrocatalysts for direct methanol fuel cell applications.

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Amine functionalized silicate sol-gel stabilized titania (P25)-polyoxometalate (PTA)-gold (Au) nanocomposite materials (APS/(P25-PTA-Au)(NCM)) were prepared by a simple chemical reduction method and were used to fabricate modified photoelectrode for the photoelectrocatalytic oxidation of formic acid. The APS/(P25-PTA-Au)(NCM) photoelectrode showed synergistic photoelectrocatalytic behavior towards the oxidation of formic acid. The photoresponse of the APS/(P25-PTA-Au)(NCM) modified photoelectrode was found to be higher when compared to the controlled photoelectrodes. The present study shows that the loading of Au(nps) on APS/P25-PTA is more beneficial to enhance the photoinduced interfacial charge transfer process, which leads to increased photocurrent generation. The present study concludes that the photoelectrocatalytic oxidation of formic acid at the APS/(P25-PTA-Au)(NCM) photoelectrode will boost the formic acid fuel cell performance.

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In this report, silver nanoparticles (Ag NPs) were successfully deposited on graphene oxide (GO) sheets to form GO-Ag nanocomposite using garlic extract and sunlight and the nanocomposite modified glassy carbon (GC) electrode was applied as an electrochemical sensor for the detection of nitrite ions. The formation of GO-Ag nanocomposite was confirmed by using UV-visible absorption spectroscopy, TEM, XRD and FTIR spectroscopy analyses. Further, TEM pictures showed a uniform distribution Ag on GO sheets with an average size of 19 nm. The nanocomposite modified electrode produced synergistic catalytic current in nitrite oxidation with a negative shift in overpotential. The limit of detection (LOD) values were found as 2.1 µM and 37 nM, respectively using linear sweep voltammetry (LSV) and amperometric i-t curve techniques. The proposed sensor was stable, reproducible, sensitive and selective toward the detection nitrite and could be applied for the detection of nitrite in real water sample.

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A silver nanoparticle-decorated N,S-co-doped TiO2 nanocomposite was successfully prepared and used as an efficient photoanode in high-performance dye-sensitized solar cells (DSSCs) with N719 dye. The DSSCs assembled with the N,S-TiO2@Ag-modified photoanode demonstrated an enhanced solar-to-electrical energy conversion efficiency of 8.22%, which was better than that of a DSSC photoanode composed of unmodified TiO2 (2.57%) under full sunlight illumination (100 mWcm(-2), AM 1.5 G). This enhanced efficiency was mainly attributed to the reduced band gap energy, improved interfacial charge transfer, and retarded charge recombination process. The influence of the Ag content on the overall efficiency was also investigated, and the optimum Ag content with N,S-TiO2 was found to be 20 wt%. Because of the enhanced solar energy conversion efficiency of the N,S-TiO2@Ag nanocomposite, it should be considered as a potential photoanode for high-performance DSSCs.

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Gold nanorods (Au NRs) are elongated nanoparticles with unique optical properties which depend on their shape anisometry. The Au NR-based longitudinal localized surface plasmon resonance (longitudinal LSPR) band is very sensitive to the surrounding local environment and upon the addition of target analytes, the interaction between the analytes and the surface of the Au NRs leads to a change in the longitudinal LSPR band. This makes it possible to devise Au NR probes with application potential to the detection of toxic metal ions with an improved limit of detection, response time, and selectivity for the fabrication of sensing devices. The effective surface modification of Au NRs helps in improving their selectivity and sensitivity toward the detection of toxic metal ions. In this review, we discuss different methods for the preparation of surface modified Au NRs for the detection of toxic metal ions based on the LSPR band of the Au NRs and the types of interactions between the surface of Au NRs and metal ions. We summarize the work that has been done on Au NR-based longitudinal LSPR detection of environmentally toxic metal ions, sensing mechanisms, and the current progress in various modified Au NR-based longitudinal LSPR sensors for toxic metal ions. Finally, we discuss the applications of Au NR-based longitudinal LSPR sensors to real sample analysis and some of the future challenges facing longitudinal LSPR-based sensors for the detection of toxic metal ions toward commercial devices.

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The fabrication of an electrochemical sensor based on an iron oxide/graphene modified glassy carbon electrode (Fe3O4/rGO/GCE) and its simultaneous detection of dopamine (DA) and ascorbic acid (AA) is described here. The Fe3O4/rGO nanocomposite was synthesized via a simple, one step in-situ wet chemical method and characterized by different techniques. The presence of Fe3O4 nanoparticles on the surface of rGO sheets was confirmed by FESEM and TEM images. The electrochemical behavior of Fe3O4/rGO/GCE towards electrocatalytic oxidation of DA was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) analysis. The electrochemical studies revealed that the Fe3O4/rGO/GCE dramatically increased the current response against the DA, due to the synergistic effect emerged between Fe3O4 and rGO. This implies that Fe3O4/rGO/GCE could exhibit excellent electrocatalytic activity and remarkable electron transfer kinetics towards the oxidation of DA. Moreover, the modified sensor electrode portrayed sensitivity and selectivity for simultaneous determination of AA and DA. The observed DPVs response linearly depends on AA and DA concentration in the range of 1-9 mM and 0.5-100 µM, with correlation coefficients of 0.995 and 0.996, respectively. The detection limit of (S/N = 3) was found to be 0.42 and 0.12 µM for AA and DA, respectively.

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In this work, lipase from Candida rugosa was immobilized onto chitosan/graphene oxide beads. This was to provide an enzyme-immobilizing carrier with excellent enzyme immobilization activity for an enzyme group requiring hydrophilicity on the immobilizing carrier. In addition, this work involved a process for the preparation of an enzymatically active product insoluble in a reaction medium consisting of lauric acid and oleyl alcohol as reactants and hexane as a solvent. This product enabled the stability of the enzyme under the working conditions and allowed the enzyme to be readily isolated from the support. In particular, this meant that an enzymatic reaction could be stopped by the simple mechanical separation of the "insoluble" enzyme from the reaction medium. Chitosan was incorporated with graphene oxide because the latter was able to enhance the physical strength of the chitosan beads by its superior mechanical integrity and low thermal conductivity. The X-ray diffraction pattern showed that the graphene oxide was successfully embedded within the structure of the chitosan. Further, the lipase incorporation on the beads was confirmed by a thermo-gravimetric analysis. The lipase immobilization on the beads involved the functionalization with coupling agents, N-hydroxysulfosuccinimide sodium (NHS) and 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC), and it possessed a high enzyme activity of 64 U. The overall esterification conversion of the prepared product was 78% at 60 °C, and it attained conversions of 98% and 88% with commercially available lipozyme and novozyme, respectively, under similar experimental conditions.

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This paper reports a rapid and in-situ electrochemical polymerization method for the fabrication of polypyrrole nanoparticles incorporated reduced graphene oxide (rGO@PPy) nanocomposites on a ITO conducting glass and its application as a counter electrode for platinum-free dye-sensitized solar cell (DSSC). The scanning electron microscopic images show the uniform distribution of PPy nanoparticles with diameter ranges between 20 and 30 nm on the rGO sheets. The electrochemical studies reveal that the rGO@PPy has smaller charge transfer resistance and similar electrocatalytic activity as that of the standard Pt counter electrode for the I3(-)/I(-) redox reaction. The overall solar to electrical energy conversion efficiency of the DSSC with the rGO@PPy counter electrode is 2.21%, which is merely equal to the efficiency of DSSC with sputtered Pt counter electrode (2.19%). The excellent photovoltaic performance, rapid and simple fabrication method and low-cost of the rGO@PPy can be potentially exploited as a alternative counter electrode to the expensive Pt in DSSCs.

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Titanium dioxide (TiO2) with highly exposed {001} facets was synthesized through a facile solvo-thermal method and its surface was decorated by using reduced graphene oxide (rGO) sheets. The morphology and chemical composition of the prepared rGO/TiO2 {001} nanocomposite were examined by using suitable characterization techniques. The rGO/TiO2 {001} nanocomposite was used to modify glassy carbon electrode (GCE), which showed higher electrocatalytic activity towards the oxidation of dopamine (DA) and ascorbic acid (AA), when compared to unmodified GCE. The differential pulse voltammetric studies revealed good sensitivity and selectivity nature of the rGO/TiO2 {001} nanocomposite modified GCE for the detection of DA in the presence of AA. The modified GCE exhibited a low electrochemical detection limit of 6 µM over the linear range of 2-60 µM. Overall, this work provides a simple platform for the development of GCE modified with rGO/TiO2 {001} nanocomposite with highly exposed {001} facets for potential electrochemical sensing applications.

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Aminosilicate sol-gel supported titania-keggin type polyoxometalate-gold nanocomposite materials (APS/(P25-PTA-Au)NCM) (APS, (3-aminopropyl)triethoxysilane; P25, Degussa-TiO2; PTA, Na3PW12O40·xH2O) were prepared by a simple chemical reduction method and characterized by diffuse reflectance spectroscopy, photoluminescence, x-ray diffraction, transmission electron microscopy and energy-dispersive x-ray analysis. The as-prepared APS/(P25-PTA-Au)NCM was used to fabricate the photoelectrode for a photoelectrochemical cell. The photoelectrocatalytic activity of the APS/(P25-PTA-Au)NCM modified photoelectrode in methanol oxidation was investigated. The APS/(P25-PTA-Au)NCM modified photoelectrode showed a higher photocurrent for methanol oxidation than control photoelectrodes. The modification of titania using PTA and Au nanoparticles significantly boosted the photoelectrocatalytic performance by a synergistic effect and thus improved the interfacial charge transfer processes. The presence of Au nanoparticles enhances the interfacial electron transfer process. The APS silicate sol-gel matrix acts as a very good support material for the preparation of the nanocomposite material and for preparation of the chemically modified electrode. This newly fabricated APS/(P25-PTA-Au)NCM modified photoelectrode could be a promising candidate for photoelectrochemical cells.

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Aminosilicate sol-gel supported titanium dioxide-gold (EDAS/(TiO(2)-Au)(nps)) nanocomposite materials were synthesized by simple deposition-precipitation method and characterized. The photocatalytic oxidation and reduction activity of the EDAS/(TiO(2)-Au)(nps) film was evaluated using hexavalent chromium (Cr(VI)) and methylene blue (MB) dye under irradiation. The photocatalytic reduction of Cr(VI) to Cr(III) was studied in the presence of hole scavengers such as oxalic acid (OA) and methylene blue (MB). The photocatalytic degradation of MB was investigated in the presence and absence of Cr(VI). Presence of Au(nps) on the (TiO(2))(nps) surface and its dispersion in the silicate sol-gel film (EDAS/(TiO(2)-Au)(nps)) improved the photocatalytic reduction of Cr(VI) and oxidation of MB due to the effective interfacial electron transfer from the conduction band of the TiO(2) to Au(nps) by minimizing the charge recombination process when compared to the TiO(2) and (TiO(2)-Au)(nps) in the absence of EDAS. The EDAS/(TiO(2)-Au)(nps) nanocomposite materials provided beneficial role in the environmental remediation and purification process through synergistic photocatalytic activity by an advanced oxidation-reduction processes.

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The N-[3-(trimethoxysilyl)propyl]ethylenediamine (EDAS) derived silicate matrix supported core-shell TiO(2)-Au nanoparticles (EDAS/(TiO(2)-Au)(nps)) were prepared by NaBH(4) reduction of HAuCl(4) precursor on preformed TiO(2) nanoparticles in the presence of EDAS monomer. The core-shell (TiO(2)-Au)(nps) nanoparticles were stabilized by the amine functional group of the EDAS silicate sol-gel network. The potential application of this EDAS/(TiO(2)-Au)(nps) modified electrode toward the photoelectrochemical oxidation of methanol was explored. The EDAS/(TiO(2)-Au)(nps) modified electrode showed a 12-fold enhancement in the catalytic activity toward photoelectrooxidation of methanol when compared to TiO(2) dispersed in EDAS silicate sol-gel matrix. This improved photoelectrochemical performance is explained on the basis of beneficial promotion of interfacial charge transfer processes of the EDAS/(TiO(2)-Au)(nps) nanocomposite. A methanol oxidation peak current density of 12.3 mA cm(-2) was achieved at an optimum loading of Au(nps) on TiO(2) particles. This novel amine functionalized EDAS silicate sol-gel stabilized core-shell (TiO(2)-Au)(nps) nanomaterial could be an excellent candidate for the photocatalytic and photoelectrochemical applications.

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