DFT Studies on a Metal Oxide@Graphene-Decorated D-π1-π2-A Novel Multi-Junction Light-Harvesting System for Efficient Dye-Sensitized Solar Cell Applications.

Graphene nanocomposites have emerged as potential photoanode materials for increased performance of the dye-sensitized solar cells (DSSCs) via charge transfer. Various metal-oxide-decorated graphene nanocomposites have widespread applications in energy devices, such as solar cells, fuel cells, batteries, sensors, electrocatalysis, and photocatalysis. However, the possible role of these composites in DSSC applications has largely remained unexplored. Herein, we studied a Sb2O3-decorated graphene-D-π1-π2-A sensitized TiO2 nanocomposite (dye-(TiO2)9/Sb2O3@GO) as a model multi-junction light-harvesting system and examined the impact of various π-bridges on the optical and photovoltaic properties of the push-pull dye system employed in this light-harvesting system. We have shown that by changing the spacer unit, the light sensitivity of nanocomposites can be varied from visible to near-infrared wavelengths. Furthermore, with the integration of metal-oxide-decorated graphene nanocomposites on D-π1-π2-A systems and D-π-A systems, composite photoelectrodes displayed better optical and photovoltaic characteristics with an enhanced absorption spectrum in the wavelength range of 800-1000 nm. The performance of the D-π1-π2-A system has been evaluated in terms of various photovoltaic parameters such as the highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps, excited-state oxidation potential (E dye *), free energy of electron injection (G inject), total reorganization energy (λtotal), and open-circuit voltage (V oc). This work throws light on the current trends and the future opportunities in graphene-metal oxide nanocomposite-based DSSCs for better harvesting of the solar spectrum and better performance of solar devices.

Electrochemical analysis of glyphosate using porous biochar surface corrosive nZVI nanoparticles.

Glyphosate [N-(phosphonomethyl)glycine] is a widely used phosphonate herbicide for different agricultural purposes. Due to its widespread use, suspected toxicity, and ubiquitous bioaccumulation, it is one of the most harmful contaminants found in drinking water. This demands efficient sensing and removal of glyphosate from contaminated water. Here, we report the decoration of novel and highly porous biochar with nanozero-valent iron (nZVI) nanoparticles to develop an efficient electrochemical sensor for the trace detection of glyphosate. The as-synthesized composite was thoroughly characterized by various state-of-the-art instrumental techniques. The electron micrographs of the composite materials revealed the cavity-like structure and the abundant loading of nZVI nanoparticles. FTIR and XPS analyses confirmed the presence of oxygen-rich functionalities and Fe(0) in the composite nanostructure. Electrochemical analysis through CV, LSV, and DPV techniques suggested efficient sensing activity with a limit of detection as low as 0.13 ppm. Furthermore, the chronopotentiometric response suggested excellent and superior stability for long-term applications. To gain more insight into the interaction between glyphosate and the composite material, DFT calculations were carried out. The Frontier Molecular Orbital study (FMO), Molecular Electrostatic Potentials (MEPs), and Density of States (DOS) suggest an increase in the electron density, an increase in the DOS, and a decrease in the HOMO-LUMO band gap by combining nZVI nanoparticles and biochar. The results suggest more facile electron transfer from the composite for trace detection of glyphosate. As a proof of concept, we have demonstrated that real-time analysis of milk, apple juice, and the as-synthesized composite shows promising results for glyphosate detection with an excellent recovery rate.

Biomass-derived carbon quantum dots: a novel and sustainable fluorescent "ON-OFF-ON" sensor for ferric ions.

Fluorescent carbon dot sensing probes have attracted much attention in recent times due to their amazing properties regarding chemical inertness, solubility, non-toxicity, optoelectronic behavior, and charge transport functionality. Herein, we report the green synthesis of lotus stem-derived carbon dots (LS-CQDs) from the naturally available lotus stem by a simple and economical hydrothermal method without the use of an oxidizing agent. HR-TEM and DLS measurements confirm the quasi-spherical shaped LS-CQDs, with a 2.5 nm average diameter. The LS-CQDs possess better aqueous dispersibility and stability due to the presence of hydrophilic hydroxyl, carboxyl, and amine surface functional groups, as manifested by FT-IR analysis. The LS-CQDs demonstrate excellent fluorescence properties that are sensitive to conditions of pH, time, and temperature. Furthermore, the prepared LS-CQDs display an interesting fluorescence "ON-OFF-ON" property. The LS-CQDs depict a selective and sensitive fluorescence quenching response in the presence of ferric ions. Moreover, the prepared LS-CQDs exhibit a quantum yield of about 0.44%. The LS-CQDs show an excellent sensing response with the limit of detection (LOD) equal to 0.212 ppm. The promising sensitivity and selectivity of LS-CQDs were utilized for the detection of ferric ions in the water samples collected from three polluted sources viz. lake water (Dal lake), underground water (tube well), and stream water. For all the collected water samples the results were reasonably good with the achievement of recovery factor above 1. Therefore, we strongly believe that the present study will serve as a good guiding star for the selective and sensitive detection of ferric ions from various polluted water bodies.

Studies on a glutathione coated hollow ZnO modified glassy carbon electrode; a novel Pb(ii) selective electrochemical sensor.

Herein, we report the electrochemical detection of heavy metal ions such as Pb(ii), Cd(ii) and Hg(ii) ions while using glutathione coated hollow ZnO modified glassy carbon electrode (Glu-h-ZnO/GCE). An excellent voltammetric response of the modified electrode towards these metal ions was observed by different voltammetric techniques. Among the different target metal ions, a selective electrochemical response (sensitivity = 4.57 µA µM-1) for the detection of Pb(ii) ions was obtained with differential pulse voltammetric (DPV) measurements. Besides, under optimal experimental conditions and in the linear concentration range of 2-18 µM, a very low detection limit of 0.42 µM was obtained for Pb(ii) ion. The observed electrochemical behaviour of Glu-h-ZnO/GCE towards these metal ions is in conformity with the band gap of the composite in the presence of various test metal ions. The band gap studies of the composite and various "Composite-Metal Ion" systems were obtained by reflectance as well as by computational methods where results are in close agreement, justifying the observed electrochemical behaviour of the systems. The lowest band gap value of the "Composite-Pb" system may be the reason for the excellent electrochemical response of the Glu-h-ZnO modified GCE towards the detection of Pb(ii) ion.

Enhanced and Selective Adsorption of Zn(II), Pb(II), Cd(II), and Hg(II) Ions by a Dumbbell- and Flower-Shaped Potato Starch Phosphate Polymer: A Combined Experimental and DFT Calculation Study.

Microwave-ultrasound-assisted facile synthesis of a dumbbell- and flower-shaped potato starch phosphate (PSP) polymer, hereafter PSP, was carried out by cross-linking the hydroxyl groups of native potato starch (NPS) using phosphoryl chloride as a cross-linking agent. Structural and morphological analysis manifested the successful formation of the dumbbell- and flower-shaped PSP biosorbent with enhanced specific surface area and thermal stability. Viscoelastic behavior of NPS and PSP suggested increased rigidity in PSP, which helped the material to store more deformation energy in an elastic manner. The synthesized PSP biosorbent material was successfully tested for efficient and quick uptake of Zn(II), Pb(II), Cd(II), and Hg(II) ions from aqueous medium under competitive and noncompetitive batch conditions with q m values of 130.54, 106.25, 91.84, and 51.38 mg g-1, respectively. The adsorption selectivity was in consonance with Pearson's hard and soft acids and bases (HSAB) theory in addition to their order of hydrated radius. Adsorption of Zn(II), Pb(II), Cd(II), and Hg(II) followed a second-order kinetics and the adsorption data fitted well with the Langmuir isotherm model. Quantum computations using density functional theory (DFT) further supported the experimental adsorption selectivity, Zn(II) > Pb(II) > Cd(II) > Hg(II), in terms of metal-oxygen binding energy measurements. What was more intriguing about PSP was its reusability over multiple adsorption cycles by treating the metal(II)-complexed PSP with 0.1 M HCl without any appreciable loss of its adsorption capacity.

Enhancing the photoresponse by CdSe-Dye-TiO2 -based multijunction systems for efficient dye-sensitized solar cells: A theoretical outlook.

This work presents theoretical modeling of some systems, using density functional theory (DFT), for enhancing the photoresponse of a dye-sensitized solar cell. The optimization of the dye (NKX 2587) as well as the dye derivatives was carried out using B3LYP and 6-311g (d,p) level of theory, using DFT as incorporated in Gaussian 03 level of programming. The HOMO-LUMO energy gaps are lower for (CdSe)13 -Dye-(TiO2 )6 multijunction systems in comparison with both the isolated dyes as well as dye-TiO2 systems. The absorption peaks were found to be mostly red-shifted for (CdSe)13 -Dye-(TiO2 )6 multijunction systems with respect to the Dye-TiO2 systems, indicating the enhancement of the absorption behavior of the dye sensitizer by its interaction with the CdSe framework. The results thus indicate some sort of co-sensitization of the TiO2 by the dye sensitizer as well as the CdSe quantum dot and are hence expected to increase the efficiency of the solar device. © 2019 Wiley Periodicals, Inc.

Microwave-assisted synthesis of glutathione-coated hollow zinc oxide for the removal of heavy metal ions from aqueous systems.

Glutathione has tremendous binding potential with metal ions present in water. However, the solubility of glutathione in water limits its productivity in the removal of these toxic ions from aqueous systems. The removability of heavy ions with glutathione and the associated adsorption capability are enhanced; for this purpose, glutathione is coated over hollow zinc oxide particles. Glutathione-coated hollow zinc oxide (Glu@h-ZnO) was successfully synthesized under microwave (MW) conditions using polystyrene (PS) as the template. The as-synthesized material was characterized by Fourier transform infrared (FTIR) spectroscopy, and the results were supported by X-ray diffraction crystallography (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), differential thermal analysis (DTA), dynamic light scattering (DLS), Brunauer-Emmett-Teller (BET) studies and zeta potential (ζ) analysis. The sorption performance of Glu@h-ZnO towards the uptake of Hg2+, Cd2+ and Pb2+ ions from an aqueous medium under non-competitive batch conditions was investigated and the material was found to have the maximum affinity for Hg2+ ions with a maximum adsorption (q m) capacity of 233 mg g-1. The adsorption kinetics for Hg2+ ions and the effects of pH and ζ on the adsorption properties were also studied in detail. Finally, the experimental data were correlated with theoretical data obtained from density functional theory (DFT) studies and good agreement between the two was obtained.

Optoelectronic and nonlinear optical properties of triarylamine helicenes: a DFT study.

This work involved the design of a new series of triarylaminehelicenes (TAH) with significant hole transport capacity and enhanced nonlinear optical response. The geometries, electronic properties and nonlinear response of TAH derivatives were studied using density functional theory at the B3PW91/6-311++G (2d, 2p) level. Charge transfer and nonlinear optical response were analyzed and correlated with modifications in geometry and energy levels. Calculations indicated that trivial changes in the torsional angle occur in TAH derivatives with electron-donating substituents as compared to those with electron-withdrawing substituents, resulting in lower reorganization energies for TAH derivatives 2-6. TAH derivatives with an -N(CH3)2 group have the greatest highest occupied molecular orbital (HOMO) level, and thus the least ionization potential, indicating significant hole transfer efficiency as compared to unsubstituted TAH. A decrease in the HOMO-LUMO gap occurs upon substitution with electron-releasing groups, whereas there is an increase in the case of -NO2, -COOH, and -CN TAH derivatives. Topological analysis of the HOMOs of the neutral molecules revealed that these orbitals are concentrated mainly in the helicene backbone, with an important contribution from fused phenyl rings, nitrogen atoms and carbonyl groups. However, the lowest unoccupied molecular orbitals (LUMO) are invariably constituted by fused phenyl rings without any contribution from the central nitrogen atom. Studying the effect of substitution on the nonlinear optical response of TAH derivatives, the calculated polarizability and hyperpolarizability at B3PW91/6-311++G (2d,2p) level of theory exhibited a prominent improvement as compared to unsubstituted TAH. Both electron-donating groups and electron-withdrawing groups result in a red shift in the electronic absorption bands of the substitution derivatives, in particular those with -N(CH3)2 and -NH2 groups.

Electron transport and nonlinear optical properties of substituted aryldimesityl boranes: a DFT study.

A comprehensive theoretical study was carried out on a series of aryldimesityl borane (DMB) derivatives using Density Functional theory. Optimized geometries and electronic parameters like electron affinity, reorganization energy, frontiers molecular contours, polarizability and hyperpolarizability have been calculated by employing B3PW91/6-311++G (d, p) level of theory. Our results show that the Hammett function and geometrical parameters correlates well with the reorganization energies and hyperpolarizability for the series of DMB derivatives studied in this work. The orbital energy study reveals that the electron releasing substituents increase the LUMO energies and electron withdrawing substituents decrease the LUMO energies, reflecting the electron transport character of aryldimesityl borane derivatives. From frontier molecular orbitals diagram it is evident that mesityl rings act as the donor, while the phenylene and Boron atom appear as acceptors in these systems. The calculated hyperpolarizability of secondary amine derivative of DMB is 40 times higher than DMB (1). The electronic excitation contributions to the hyperpolarizability studied by using TDDFT calculation shows that hyperpolarizability correlates well with dipole moment in ground and excited state and excitation energy in terms of the two-level model. Thus the results of these calculations can be helpful in designing the DMB derivatives for efficient electron transport and nonlinear optical material by appropriate substitution with electron releasing or withdrawing substituents on phenyl ring of DMB system.

Theoretical investigations into spectral and non-linear optical properties of brucine and strychnine using density functional theory.

The density functional theoretical (DFT) computations were performed at the B3LYP/6-311G++(d, p) level to calculate the equilibrium geometry, vibrational wave numbers, intensities, and various other molecular properties of brucine and strychnine, which were found in satisfactory agreement with the experimental data. The out-of-phase stretching modes of aromatic rings and carbonyl stretching modes in combination with CH stretching modes at stereogenic centers generate VCD signals, which are remarkably efficient configuration markers for these chiral molecular systems. NBOs analysis reveals that the large values of second order perturbation energy (47.24kcal/mol for brucine and 46.93kcal/mol for strychnine) confirms strong hyperconjugative interaction between the orbital containing the lone pair of electron of nitrogen and the neighboring CO antibonding orbital. The molecular electrostatic potential map of strychnine molecule, with no polar groups other than the lone keto group, shows less polarization, which accounts for its lower susceptibility towards electrophilic attack as compared to brucine.

Preparation and characterization of 5-sulphosalicylic acid doped tetraethoxysilane composite ion-exchange material by sol-gel method.

In this manuscript, we report the preparation and characterization of sulphosalicylic doped tetraethoxysilane (SATEOS), composite material by sol-gel method as a new ion exchanger for the removal of Ni(II) from aqueous solution. The fine granular material was prepared by acid catalyzed condensation polymerization through sol-gel mechanism in the presence of cationic surfactant. The material has an ion exchange capacity of 0.64 mequiv./g(dry) for sodium ions, 0.60 mequiv./g(dry) for potassium ions, 1.84 mequiv./g(dry) for magnesium ions, 1.08 mequiv./g(dry) for calcium ions and 1.36 mequiv./g(dry) for strontium ions. Its X-ray diffraction studies suggest that it is crystalline in nature. The material has been characterized by SEM, IR, TGA and DTG so as to identify the various functional groups and ion exchange sites present in this material. Quantum chemical computations at DFT/B3LYP/6-311G (d,p) level on model systems were performed to substantiate the structural conclusions based ion instrumental techniques. Investigations into the elution behaviour, ion exchange reversibility and distribution capacities of this material towards certain environmentally hazardous metal ions are also performed. The material shows good chemical stability towards acidic conditions and exhibits fast elution of exchangeable H(+) ions under neutral conditions. This material shows remarkable selectivity for Ni(II) and on the basis of its Kd value (4×10(2) in 0.01M HClO4) some binary separations of Ni(II) from other metal ions are performed.

Conformational analysis and vibrational circular dichroism of tris(ethylenediamine)ruthenium(II) complex: a theoretical study.

The conformational preferences and vibrational circular dichroism of tris(ethylenediamine)ruthenium complex in two main configurations (Lambda) and (Delta), have been performed using density functional theory. We find that for the free [Ru(en)(3)](2+) ion in the Delta-configuration, the conformational stability order is Delta(deltadeltadelta) > Delta(lambdadeltadelta) > Delta(lambdalambdadelta) > Delta(lambdalambdalambda) and that for the Lambda-configuration it is Lambda(deltadeltadelta) < Lambda(lambdadeltadelta) < Lambda(lambdalambdadelta) < Lambda(lambdalambdalambda). The energy differences between the four conformers for both the configurations Delta and Lambda are relatively small, but the activation barriers for ring inversion from one conformation to another are significant, as compared to other such systems. We trace the origin of these results to the lower oxidation state of Ru and relatively larger Ru-N bond length. We have also studied the effect of counterions on the conformational stability for Ru(en)(3)Cl(2.) Our results indicate a reverse stability order for the associated complex, Ru(en)(3) Cl(2) and higher activation barriers for ring inversion as compared to the free complex ion Ru(en)(3)(2+). It is because of larger hydrogen bonding interactions between the three N-H bonds and the chloride ion in these two conformers as compared to other conformations, which is also evident from the VCD spectra of N-H stretching modes. We also investigate IR spectra for all conformations in Delta- and Lambda-configurations and together with energetics and VCD spectra elucidate the spectroscopic characteristics of Ru(en)(3)(2+) complexes with and without the associated counterions.