AuNRs attached TiO2 NPs modified by cobalt-imidazolate frameworks as exceptional materials to improve the energy conversion efficiency of dye-sensitized solar cells.

This work reports a significant improvement in both the open-circuit voltage (VOC) and current density (J) of dye-sensitized solar cells (DSSCs) using gold nanorod-modified TiO2 nanoparticles (TiO2/AuNRs) together with a cobalt-imidazolate framework (ZIF-67) as an efficient photoanode. It was demonstrated that adding ZIF-67 (8 wt%) to TiO2 NPs increased the VOC by 160 mV and J by 2.5 times. This observation was described based on the significant increase in the amount of adsorbed dye in the presence of highly porous ZIF-67, which boosts the photoanode's light harvesting. Modifying TiO2 NPs with AuNRs also caused a remarkable enhancement in J (∼ 2.8 times), which can be explained via electron transfer between the TiO2 conduction band and AuNRs. It can result in a more efficient inhibiting effect on the interfacial charge recombination processes in TiO2/AuNRs/ZIF-67 because of the formation of a Schottky barrier at the interface between TiO2 and Au. These effects were confirmed by the reduction in the photoluminescence intensity of TiO2 in the presence of AuNRs. More reduction in the photoluminescence intensity was observed when ZIF-67 was added. The prepared photoanode showed an outstanding improvement in the overall efficiency of the DSSC (η) to 8.38% compared to the bare TiO2-based photoanode (1.83%). The notable improvement in the TiO2/AuNRs/ZIF-67 performance confirmed its practicality for high-efficiency DSSCs.

Non-Enzymatic Glucose Sensors Involving Copper: An Electrochemical Perspective.

Non-enzymatic glucose sensors based on the use of copper and its oxides have emerged as promising candidates to replace enzymatic glucose sensors owing to their stability, ease of fabrication, and superior sensitivity. This review explains the theories of the mechanism of glucose oxidation on copper transition metal electrodes. It also presents an overview on the development of among the best non-enzymatic copper-based glucose sensors in the past 10 years. A brief description of methods, interesting findings, and important performance parameters are provided to inspire the reader and researcher to create new improvements in sensor design. Finally, several important considerations that pertain to the nano-structuring of the electrode surface is provided.

Synthesis of new Zn-decorated metal-organic frameworks for enhanced removal of carcinogenic textile dye: equilibrium and kinetic modeling studies.

This paper describes the synthesis and characterization of Zn2+ decorated (adipic and terephthalic acid as linkers) piperazine-based metal-organic framework (P-MOFs) and their extraction behavior toward the Chicago sky blue (CSB) dye. The formation of Zn2+-decorated P-MOFs was confirmed by FT-IR spectroscopy, energy-dispersive spectroscopy, X-ray diffraction, BET surface area analysis and TGA. Adsorption behavior of the synthesized P-MOFs was explored through solid-phase adsorption (batch method) prior to UV-Vis spectrophotometric determination. Adsorption parameters, including adsorbent dosage, pH of solution, dye concentration, and time, were optimized. Excellent percentage removal of 94% and 95% for AP-Zn-MOF and TP-Zn-MOF, respectively, was achieved at pH 7.5. Kinetics studies indicated that the synthesized adsorbents AP-Zn-MOF and TP-Zn-MOF followed the pseudo-second-order rate model with R2 value 0.9989. The Freundlich isotherm with high R2 value as compared to Langmuir isotherm indicated that CSB adsorption for the synthesized MOFs follows multilayer adsorption.

Palm Fatty Acid Functionalized Fe3O4 Nanoparticles as Highly Selective Oil Adsorption Material.

The present work highlights the facile synthesis of hydrophobic palm fatty acid functionalized Fe3O4 nanoparticles (MNP-FA) for the efficient removal of oils from the surface of water. An intense hydrophobic layer was introduced on the surface of Fe3O4 nanoparticles functionalized by the palm fatty acid obtained from the hydrolysis of palm olein. Scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), Energy dispersive X-ray spectroscopy (EDX) and water contact angle analysis (WCA) measurements were used to characterize the newly fabricated palm fatty acid adorned magnetic Fe3O4 nanoparticles (MNP-FA). The obtained results confirmed the successful synthesis of palm fatty acid-functionalized magnetic nanoparticles. Oil removal tests performed with MNP-FA revealed that this newly prepared material could selectively adsorb lubricating oil up to 3.5 times of the particles' weight while completely repelling water. The main parameters affecting the adsorption of oil i.e., sorption time, mass of sorbent and pH of water were optimized.

Polyaniline-dicationic ionic liquid coated with magnetic nanoparticles composite for magnetic solid phase extraction of polycyclic aromatic hydrocarbons in environmental samples.

In this present study, magnetic nanoparticles (MNPs) nanocomposites modified with polyaniline (PANI) coated newly synthesised dicationic ionic liquid (DICAT) forming MNP-PANI-DICAT were successfully synthesised as new generation material for magnetic solid phase extraction (MSPE). MNP-PANI-DICAT was characterised by FT-IR NMR, CHN, BET, SEM, TEM, and VSM techniques and the results were compared with MNP-PANI and native MNP. This new material was applied as a magnetic adsorbent for the pre-concentration and separation of polycyclic aromatic hydrocarbons (PAHs) due to the π-π interaction between polyaniline shell and dicationic ionic liquid (DICAT) with PAHs compounds. Under the optimal conditions, the proposed method was evaluated and applied for the analysis of PAHs in environmental samples using gas chromatography-mass spectrometry (GC-MS). The validation method showed good linearity (0.005-500µgL-1) with the coefficient of determination (R2) > 0.999. The limits of detection (LOD) and quantification (LOQ) of the developed method (MNP-PANI-DICAT-MSPE) were in the range of 0.0008-0.2086µgL-1 and 0.0024-0.6320µgL-1, respectively. The enrichment factor (EF) of PAHs on MNP-PANI-DICAT-MSPE were in the range of 7.546-29.632. The extraction recoveries of natural water, sludge, and soil samples were ranged from 80.2% to 111.9% with relative standard deviation (RSD) less than 5.6%. The newly synthesised MNP-PANI-DICAT possess good sensitivity, reusability, and fast extraction of PAHs under the MSPE procedure in various environmental samples.

Novel Palm Fatty Acid Functionalized Magnetite Nanoparticles for Magnetic Solid-Phase Extraction of Trace Polycyclic Aromatic Hydrocarbons from Environmental Samples.

A novel adsorbent, palm fatty acid coated magnetic Fe3O4 nanoparticles (MNP-FA) was successfully synthesized with immobilization of the palm fatty acid onto the surface of MNPs. The successful synthesis of MNP-FA was further confirmed by X-Ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and Energy dispersive X-Ray spectroscopy (EDX) analyses and water contact angle (WCA) measurement. This newly synthesized MNP-FA was applied as magnetic solid phase extraction (MSPE) adsorbent for the enrichment of polycyclic aromatic hydrocarbons (PAHs), namely fluoranthene (FLT), pyrene (Pyr), chrysene (Cry) and benzo(a)pyrene (BaP) from environmental samples prior to High Performance Liquid Chromatography- Diode Array Detector (HPLC-DAD) analysis. The MSPE method was optimized by several parameters such as amount of sorbent, desorption solvent, volume of desorption solvent, extraction time, desorption time, pH and sample volume. Under the optimized conditions, MSPE method provided a low detection limit (LOD) for FLT, Pyr, Cry and BaP in the range of 0.01-0.05 ng mL-1. The PAHs recoveries of the spiked leachate samples ranged from 98.5% to 113.8% with the RSDs (n = 5) ranging from 3.5% to 12.2%, while for the spiked sludge samples, the recoveries ranged from 81.1% to 119.3% with the RSDs (n = 5) ranging from 3.1% to 13.6%. The recyclability study revealed that MNP-FA has excellent reusability up to five times. Chromatrographic analysis demonstrated the suitability of MNP-FA as MSPE adsorbent for the efficient extraction of PAHs from environmental samples.

The Effect of Temperature on Kinetics and Diffusion Coefficients of Metallocene Derivatives in Polyol-Based Deep Eutectic Solvents.

The temperature dependence of the density, dynamic viscosity and ionic conductivity of several deep eutectic solvents (DESs) containing ammonium-based salts and hydrogen bond donvnors (polyol type) are investigated. The temperature-dependent electrolyte viscosity as a function of molar conductivity is correlated by means of Walden's rule. The oxidation of ferrocene (Fc/Fc+) and reduction of cobaltocenium (Cc+/Cc) at different temperatures are studied by cyclic voltammetry and potential-step chronoamperometry in DESs. For most DESs, chronoamperometric transients are demonstrated to fit an Arrhenius-type relation to give activation energies for the diffusion of redox couples at different temperatures. The temperature dependence of the measured conductivities of DES1 and DES2 are better correlated with the Vogel-Tamman-Fulcher equation. The kinetics of the Fc/Fc+ and Cc+/Cc electrochemical systems have been investigated over a temperature range from 298 to 338 K. The heterogeneous electron transfer rate constant is then calculated at different temperatures by means of a logarithmic analysis. The glycerol-based DES (DES5) appears suitable for further testing in electrochemical energy storage devices.

G3 assisted rational design of chemical sensor array using carbonitrile neutral receptors.

Combined computational and experimental strategies for the systematic design of chemical sensor arrays using carbonitrile neutral receptors are presented. Binding energies of acetonitrile, n-pentylcarbonitrile and malononitrile with Ca(II), Mg(II), Be(II) and H⁺ have been investigated with the B3LYP, G3, CBS-QB3, G4 and MQZVP methods, showing a general trend H⁺ > Be(II) > Mg(II) > Ca(II). Hydrogen bonding, donor-acceptor and cation-lone pair electron simple models were employed in evaluating the performance of computational methods. Mg(II) is bound to acetonitrile in water by 12.5 kcal/mol, and in the gas phase the receptor is more strongly bound by 33.3 kcal/mol to Mg(II) compared to Ca(II). Interaction of bound cations with carbonitrile reduces the energies of the MOs involved in the proposed σ-p conjugated network. The planar malononitrile-Be(II) complex possibly involves a π-network with a cationic methylene carbon. Fabricated potentiometric chemical sensors show distinct signal patterns that can be exploited in sensor array applications.

The electrochemical behaviour of ferrocene in deep eutectic solvents based on quaternary ammonium and phosphonium salts.

The electrochemical behaviour of ferrocene (Fc) is investigated in six different deep eutectic solvents (DESs) formed by means of hydrogen bonding between selected ammonium and phosphonium salts with glycerol and ethylene glycol. Combinations of cyclic voltammetry and chronoamperometry are employed to characterise the DESs. The reductive and oxidative potential limits are reported versus the Fc/Fc(+) couple. The diffusion coefficient, D, of ferrocene in all studied DESs is found to lie between 8.49 × 10(-10) and 4.22 × 10(-8) cm(2) s(-1) (these do not change significantly with concentration). The standard rate constant for heterogeneous electron transfer across the electrode/DES interface is determined to be between 1.68 × 10(-4) and 5.44 × 10(-4) cm s(-1) using cyclic voltammetry. These results are of the same order of magnitude as those reported for other ionic liquids in the literature.