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A highly active electrochemical amphiphilic POM–CNT nanohybrid using non-covalent interactions for highly efficient detection of H2O2 is reported. The synergy between POMs and CNTs results in 10 times higher current response than pristine POM.

Eco-friendly inhibitors have attracted considerable interest due to the increasing environmental issues caused by the extensive use of hazardous corrosion inhibitors. In this paper, environmentally friendly PDG-g-PANI/Al2O3 composites were prepared by a low-cost inverse emulsion polymerization for corrosion inhibition of mild steel (MS) and stainless steel (SS). The PDG-g-PANI/Al2O3 composites were characterized by different techniques such as X-ray diffraction (XRD), UV/Vis, and FTIR spectroscopy. XRD measurements show that the PDG-g-PANI/Al2O3 composite is mostly amorphous and scanning electron micrographs (SEM) reveal a uniform distribution of Al2O3 on the surface of the PDG-g-PANI matrix. The composite was applied as a corrosion inhibitor on mild steel (MS) and stainless steel (SS), and its efficiency was investigated by potentiodynamic polarization measurement in a 3.5% NaCl and 1 M H2SO4 solution. Corrosion kinetic parameters obtained from Tafel evaluation show that the PDG-g-PANI/Al2O3 composites protect the surface of MS and SS with inhibition efficiencies of 92.3% and 51.9% in 3.5% NaCl solution, which is notably higher than those obtained with untreated epoxy resin (89.3% and 99.5%). In particular, the mixture of epoxy/PDG-g-PANI/Al2O3 shows the best performance with an inhibition efficiency up to 99.9% on MS and SS. An equivalent good inhibition efficiency was obtained for the composite for 1M H2SO4. Analysis of activation energy, formation enthalpy, and entropy values suggest that the epoxy/PDG-g-PANI/Al2O3 coating is thermodynamically favorable for corrosion protection of MS and exhibits long-lasting stability.

Structure engineering of boron dipyrromethene (BODIPY) organic dye, to increase its light-harvesting efficiency in dye-sensitized solar cells, has been the subject of rigorous research recently. Herein, we report on the rational designing of BODIPY-carbazole (D-π-A-A) dyads using density functional theory (DFT). The structure of BODIPY-carbazole was first modified by substituting an electron-donating −N(CH3)2 group at the electron-rich carbazole moiety, and two electron-accepting −COOH groups at the BODIPY core. The DFT calculations showed a significant lowering of the band gap from 2.9 eV (pristine BODIPY-carbazole dyad) to 1.87 eV (modified BODIPY-carbazole dyad). Further modification was demonstrated by the incorporation of heterocyclic rings such as thiophene (denoted as D1T), furan (D1F), and phosphole (D1P) into BODIPY-carbazole moiety, which red-shifted the light absorption spectra and consequently improved the light-harvesting efficiency of the dyes. The interactions at the dye/semiconductor interface were studied by employing their bridged-bidentate adsorption models over the titanium dioxide (TiO2)38 nanocluster. Results suggested that the electrons can be efficiently injected from the lowest unoccupied molecular orbital (LUMO) of dyes into the conduction band of TiO2. Among the three dyads, D1P exhibited superior photovoltaic performance with a maximum power conversion efficiency of 13.50%, a short-circuit current density (Jsc) of 27.2 mA·cm–2, and an open-circuit voltage (Voc) of 731 mV. The structurally configured new D1P dye can be used as a potential alternative photosensitizer for high-performance dye-sensitized solar cells.

Oxide thermoelectric materials are considered promising for high-temperature thermoelectric applications in terms of low cost, temperature stability, reversible reaction, and so on. Oxide materials have been intensively studied to suppress the defects and electronic charge carriers for many electronic device applications, but the studies with a high concentration of defects are limited. It desires to improve thermoelectric performance by enhancing its charge transport and lowering its lattice thermal conductivity. For this purpose, here, we modified the stoichiometry of cation and anion vacancies in two different systems to regulate the carrier concentration and explored their thermoelectric properties. Both cation and anion vacancies act as a donor of charge carriers and act as phonon scattering centers, decoupling the electrical conductivity and thermal conductivity.

Transition-metal sulfides with nanostructured features grown on a conductive substrate have been suggested as a promising alternative to precious metal-based electrocatalysts for energy conversion ...

The preparation of a stable, efficient, inexpensive and high capacitance electrode material for supercapacitors is posing great challenges for researchers.

Made available in DSpace on 2022-04-29T08:46:46Z (GMT). No. of bitstreams: 0 Previous issue date: 2022-09-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Magnetic Molecularly imprinted polymers (MMIPs) have been recently recognized as an exceptional tool for monitoring and decontamination of environmental and biological samples of diverse nature. Based on the potential applications as sorbents and biomimetic sensors, herein, a core-shell magnetic-molecularly imprinted polymer (MMIP) was developed as a selective material for separation and sensing of sunset yellow (SY) dye in an aqueous environment and real samples. The MMIP was synthesized via precipitation polymerization using SY as a template, MAA as a functional monomer (chosen based on simulation studies), EGDMA as a cross-linking agent, and AIBN as an initiator. To elaborate the specificity of MMIP, a comparative agent, magnetic non-imprinted polymer (MNIP) was also synthesized. The XRD results showed that the MMIP showed both crystalline and amorphous structure attributed to the presence and polymeric and non-polymeric groups. The FTIR spectra confirmed synthesis of intermediate and final MMIP product. The SEM results showed spherical morphology and porous structure of the MMIP with an average particle size of 0.636 μm in diameter. The MMIP was first employed as a sorbent for the removal of SY from the aqueous environment. The binding experiments performed at optimized operating conditions (pH 2; time 30 min; sorbent dosage 3 mg; sorbate concentration 80 ppm) showed more selectivity when compared with MNIP. The data fitted best to Langmuir's sorption isotherm (Qo 359.8 mg/g) and followed the pseudo-second-order kinetic model. The synthesized MMIP was also used as an electrochemical sensor for detection of SY dye in the aqueous environment, which exhibited a linear range of detection as (1.51 × 10−6 – 1.5 × 10−3 M). The limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.00413 M and 0.0137 M, respectively. While the R2 value was found to be 0.997 at optimized analytical conditions. These results suggested that the synthesized MMIP can be applied for the selective separation and quantification of SY dye in sample of diverse nature. Institute of Chemical Sciences University of Peshawar, Khyber Pakhtunkhwa Department of Chemistry Islamia College University, KP Laboratory of Physical Chemistry Research Faculty of Sciences National University of Engineering, Av. Tupac Amaru 210, Rimac Institute of Chemistry São Paulo State University (UNESP) and National Institute of Alternative Technologies for Detection Toxicological Evaluation and Removal of Micropollutants and Radioactives (INCT-DATREM), SP Institute of Chemistry São Paulo State University (UNESP) and National Institute of Alternative Technologies for Detection Toxicological Evaluation and Removal of Micropollutants and Radioactives (INCT-DATREM), SP FAPESP: 2019/00677-7

The C and N atomic doping and co-doping at all possible lattice sites in (STO) perovskite crystal structure have been investigated using density functional theory (DFT) calculations. Calculated formation energies indicate that C and N doping at O site in STO is more stable than at Sr site and Ti site. C incorporation at anion site significantly affects the electronic bandgap of STO by inducing spin-polarized defect states in bandgap region. Consequently transforming the non-magnetic STO to a magnetic with a magnetic moment of 2.0 per C atom and reduced the direct (indirect) bandgap 0.86 eV (0.18 eV) for spin-up (spin-down) channel, respectively. Further, with an increase of C atom concentration the magnetic moment of 2.0 per C atom remains constant, and also, half-metallicity is observed due to spin-down channel. Similarly, N atom substitution at anion site in STO crystal structure induces magnetism of 1.0 . N causes defect states due to which the bandgap of the spin-up channel decreased to 1.68 eV and shows half-metallicity due to the spin-down channel. We found that further increasing the N atom concentration enhanced the half-metallicity by increasing the number of states of the spin-down channel at Fermi energy. Finally, we studied the FM and AFM alignment of the magnetic moments at the dopants C, N and their co-doping in STO with different distances. We found that the C atom prefers AFM states, while the N atom prefers FM states. The calculated Curie temperature for two N atoms at near and far dopants is 722.16 K and 860.91 K, respectively. The results of tailored electronic and magnetic properties above room temperature are interesting from a theoretical perspective and may open opportunities for STO in electronic and spintronic devices.

Using first-principles calculations based on density functional theory (DFT) with generalized gradient approximation (GGA), the electronic and thermoelectric properties of KCaF3 are calculated. The electronic structure calculated with GGA shows that KCaF3 is an insulator. The thermoelectric properties of KCaF3 are computed as a function of chemical potential μ and charge carrier concentrations (1018–1022 cm−3). Both hole and electron doping decrease the absolute value of Seebeck coefficient. The calculated power factor shows that p-type KCaF3 has a larger power factor at the optimized charge carriers. The maximum figure of merit (ZT) occurs around 1021 cm−3 hole carrier concentrations and the largest value of ZT ∼0.7 is achieved at 800 K. When KCaF3 is doped with electron, the maximum ZT occurs around 1020 cm−3 and the largest value of ZT at 800 K is about 0.4. Hence, high ZT in KCaF3 is possible at high hole carrier concentrations as compared with electron carrier concentrations. Compared with n-type KCaF3, p-type KCaF3 has good thermoelectric properties, which are attributed to larger effective mass and low thermal conductivity of holes.

Elemental doping is considered to be an effective strategy to improve the photoelectrochemical (PEC) activity of hematite (α-Fe2O3) as a photoanode for water splitting, but the precise function (s) of the dopant remains unclear. In this study, we report on the structural and charge separation properties of titanium-doped hematite (Ti doped Fe2O3) films prepared by a simple electrospray technique for PEC water oxidation. The effect of Ti doping on the structure, morphology, light absorption, and electrical and photoelectrochemical properties was investigated on α-Fe2O3 films. SEM images revealed a reduction in particle sizes for 2% Ti doped α-Fe2O3, while an increase in particle size was observed for higher Ti content. XRD confirmed the presence of α-Fe2O3 without any impurity or other phases. From XPS spectra, the incorporation of Ti was confirmed in the form of Ti4+ as predominant species while no impurities from the substrate were detected. When the Ti doped Fe2O3 (2% Ti) film was used as a photoanode in a PEC cell, it delivered the best performance with a maximum photocurrent density of 1.09 mA cm−2 (at 1.8 V vs. RHE and under standard 1 sun illumination conditions (AM 1.5 G, 100 mW cm−2)), which is 2 times higher than that of the un-doped α-Fe2O3 (0.51 mA cm−2). The photoelectrode also showed a superior incident photon to current efficiency (IPCE) as compared to an un-doped α-Fe2O3. This enhancement in performance was attributed to the better charge separation and transport properties of α-Fe2O3 due to Ti doping, as revealed by an electrochemical impedance spectroscopy (EIS) analysis.

Controlling oxygen vacancy in undoped SrTiO3 was used to realize the phonon-glass electron-crystal (PGEC) concept. The undoped SrTiO3 samples were synthesized through solid-state-reaction method in air and then reduced through annealing under low oxygen partial pressure conditions. We show that decreasing the oxygen partial pressure (Po2) results in increase of the electrical conductivity, and the oxygen vacancies act as phonon scattering centers, which lead to decrease in the lattice thermal conductivity. Both the enhanced electrical conductivity (σ) and reduced thermal conductivity (κ) were achieved simultaneously through oxygen vacancy in undoped SrTiO3. This significantly increases the ratio of σ/κ that results in an enormously enhanced ZT value of about 13 times larger as compared with the samples reduced under relatively high Po2. Density-functional theory calculations also reveal that oxygen vacancies in SrTiO3 reduce the band-gap, and consequently increase the electrical conductivity.

The development of biocompatible, cost effective and more efficient materials to control or inhibit the growth of microorganisms in necessary to fight against resistant microbes. Here, we demonstrate the synthesis of nickel oxide-incorporated polyaniline/polyvinyl alcohol (PANI/PVA/NiOx) composite material by single-step polymerization and its application as antibacterial agent. The composite films were characterized using UV-visible spectroscopy (UV-Vis), Thermogravimetric analysis (TGA), Fourier Transform Infrared spectroscopy (FTIR), X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). UV-Vis spectra revealed the enhancement in absorption properties of PANI/PVA/NiOx with optimum 5% incorporation of NiOx. TGA results indicated slightly enhanced thermal stability of the PANI/PVA/NiOx composite film as compared to PANI/PVA. FTIR spectra for composites revealed the existence of NiOx in polymers. However the crystallinity of PANI/PVA was not much affected. The antibacterial activity of the prepared composites was examined against four different gram negative bacteria, Salmonella, Shigella, Pseudomonas and Escherichia coli (E. coli). The composite exhibited excellent antibacterial activity against E. coli, Salmonella and Shigella while pseudomonas showed some resistance. Based on the results, PANI/PVA/ NiOx (5%) composite showed the highest activity against the tested bacterial strains, thus showing its potential to be used as an effective antibacterial agent.

\textit{Ab-initio} calculations based on density functional theory with local spin density approximation are used to study defects-driven magnetism in bulk $\alpha$-Li$ _{3}$N. Our calculations show that bulk Li$ _{3} $N is a non-magnetic semiconductor. Two types of Li vacancies (Li-I and Li-II) are considered, and Li-vacancies (either Li-I or Li-II type) can induce magnetism in Li$ _{3}$N with a total magnetic moment of 1.0 $\mu_{\rm B}$ which arises mainly due to partially occupied N-$p$-orbitals around the Li vacancies. The defect formation energies dictate that Li-II vacancy, which is in the Li$ _{2}$N plane, is thermodynamically more stable as compared with Li-I vacancy. The electronic structures of Li-vacancies show half-metallic behavior. On the other hand N-vacancy does not induce magnetism and has a larger formation energy than Li-vacancies. N vacancy derived bands at the Fermi energy are mainly contributed by the Li atoms. Carbon is also doped at Li-I and Li-II sites, and it is expected that doping C at Li-I site is thermodynamically more stable as compared with Li-II site. Carbon can induce metallicity with zero magnetic moment when doped at Li-I site, whereas magnetism is observed when Li-II site is occupied by the C impurity atom and C-driven magnetism is spread over the N atoms as well. Carbon can also induce half-metallic magnetism when doped at N site in Li$ _{3}$N, and has a smaller defect formation energy as compared with Li-II site doping. The ferromagnetic (FM) and antiferromagnetic (AFM) coupling between the C atoms is also investigated, and we conclude that FM state is more stable than the AFM state., Comment: Accepted; J. Mag. Mag. Mat. (2018)

Made available in DSpace on 2021-06-25T11:08:37Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-02-01 This research study reports the formation of flexible and multifunctional organic-inorganic hybrid membranes (BC-SiO2-TiO2/Ag) based on bacterial cellulose (BC) that contain photoactive (TiO2) and antibacterial (Ag) components, rendering them photocatalytic, self-cleaning and UV-shielding properties (due to TiO2) as well as antibacterial activity. Coating of BC with sol-gel derived silica and titania particles was achieved through hydrolysis-polycondensation of tetraethyl orthosilicate and titanium (IV) isopropoxide, respectively, and a soft hydrothermal treatment (140 °C, 20 h) was used to obtain well-crystalline TiO2. The prepared BC-SiO2-TiO2/Ag photoactive membranes were characterized by an array of analytical techniques including XRD, XRF, SEM-EDS, electronic absorption spectroscopy and vibrational spectroscopy. The morphology of TiO2 coatings changes from a homogenous film-like smooth one to a rougher one consisting of randomly oriented titania particles (170 ± 35 nm) upon increasing the TiO2 loading of the membranes. These prepared photoactive BC-SiO2-TiO2 membranes exhibited excellent TiO2-loading dependent photocatalytic/self-cleaning activity towards crystal violet dye deposited as an over-layer on the surface of the membranes, degrading 97 % of the dye within 50 min of UV illumination. In addition to good photoactivity, the BC-SiO2-TiO2/Ag membranes demonstrated reasonable antibacterial activity against five different bacterial strains under dark conditions. These flexible BC-based hybrid membranes with photocatalytic, self-cleaning, antibacterial properties have the potential to be used in the design of self-cleaning and antibacterial surfaces, filters and facemasks that could be easily disinfected under UV irradiation from a lamp or natural sunlight and safely discarded and even recycled. Institute of Chemical Sciences University of Peshawar Institute of Chemistry São Paulo State University - UNESP, CP 355 Government Girls Degree College Institute of Research and Development Duy Tan University Institute of Physics Federal University of Mato Grosso do Sul Institute of Chemistry São Paulo State University - UNESP, CP 355

congestion in road networks and intersections is a ubiquitous problem which occurs due to several causes. Kabul city the capital of Afghanistan has felt this propagating problem from the establishment of its new administration in 2001. The rapid population growth urbanization, low capacity of roads, and lack of a comprehensive strategy to manage traffic systems and tackle traffic congestions are the leading contributors to the traffic congestion problem. Therefore, it is vital to utilize advanced software tools to explore possible solutions to the traffic congestion problem. This study was aimed to evaluate and analyze Baraki Intersection in Kabul city Afghanistan using SIDRA INTERSECTION 5 software. It assessed traffic performance in one of the most important junctions in Kabul based on parameters such as Level of service, delays, Queue, Fuel consumption and production of CO2, CO, (CH2O)n, NO x. The results showed that there was a notable time delay, dangerous amount of emissions and low level of service (LOS F). After a comprehensive investigation of the results it was concluded that building an underpass from north to south direction will significantly reduce delays and emissions and increase the level of service until 2030.

Hematite (Fe2O3) is one of the best candidates for photoelectrochemical water splitting due to its abundance and suitable bandgap. However, its efficiency is mostly impeded due to the intrinsically low conductivity and poor light absorption. In this study, we targeted this intrinsic behavior to investigate the thermodynamic stability, photoconductivity and optical properties of rhodium doped hematite using density functional theory. The calculated formation energy of pristine and rhodium doped hematite was − 4.47 eV and − 5.34 eV respectively, suggesting that the doped material is thermodynamically more stable. The DFT results established that the bandgap of doped hematite narrowed down to the lower edge (1.61 eV) in the visible region which enhanced the optical absorption and photoconductivity of the material. Moreover, doped hematite has the ability to absorb a broad spectrum (250–800) nm. The enhanced optical absorption boosted the photocurrent and incident photon to current efficiency. The calculated results also showed that the incorporation of rhodium in hematite induced a redshift in optical properties.

Reduced graphene oxide/poly(pyrrol-co-thiophene) (RGO/COP), prepared by facile in-situ oxidative copolymerization, is reported as a new hybrid composite material with improved supercapacitance performance as compared to the respective homopolymers and their composites with RGO. The as-prepared hybrid materials were characterized with ultraviolet&ndash, visible (UV&ndash, Vis) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) analysis. The electrochemical behavior and energy storage properties of the materials were tested by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrostatic impedance spectroscopy (EIS) techniques in 0.5 M H2SO4. The specific capacitance (Csp) for RGO/COP calculated from the CV curve was 467 F/g at a scan rate of 10 mV/s. While the Csp calculated from the GCD was 417 F/g at a current density of 0.81 A/g. The energy density calculated was 86.4 Wh/kg with a power density of 630 W/kg. The hybrid composite exhibits good cyclic stability with 65% capacitance retention after 1000 cycles at a scan rate of 100 mV/s. The present work brings a significance development of RGO/COP composites to the electrode materials for pseudocapacitive application.

Reduced graphene oxide/poly(pyrrol-co-thiophene) (RGO/COP), prepared by facile in-situ oxidative copolymerization, is reported as a new hybrid composite material with improved supercapacitance performance as compared to the respective homopolymers and their composites with RGO. The as-prepared hybrid materials were characterized with ultraviolet–visible (UV–Vis) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray (EDX) analysis. The electrochemical behavior and energy storage properties of the materials were tested by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD), and electrostatic impedance spectroscopy (EIS) techniques in 0.5 M H2SO4. The specific capacitance (Csp) for RGO/COP calculated from the CV curve was 467 F/g at a scan rate of 10 mV/s. While the Csp calculated from the GCD was 417 F/g at a current density of 0.81 A/g. The energy density calculated was 86.4 Wh/kg with a power density of 630 W/kg. The hybrid composite exhibits good cyclic stability with 65% capacitance retention after 1000 cycles at a scan rate of 100 mV/s. The present work brings a significance development of RGO/COP composites to the electrode materials for pseudocapacitive application.

Structural and electronic properties of pristine two-dimensional group IV Xenes (X=C, Si, Ge, Sn, Pb) and hydrogenated Xenes are studied, using density functional theory (DFT) calculations with and without spin-orbit coupling (SOC). The pristine hexagonal monolayer Xenes show buckled structure upon relaxation except graphene. The buckling $\delta$ increases linearly from graphene to plumbene. The bond angle $\theta$ between the X atoms is correlated with the degree of hybridization.% $D The band structures without SOC of group-IV Xenes are semi-metallic. However, inclusion of SOC mainly opens the bandgap at the Dirac point. The degree of hybridization and bandgap opening due to SOC are mainly explained in terms of the contribution of $p_{\mathrm{x}}/p_{\mathrm{y}}$ and $p_{z}$ electronic states at Fermi level. Semi hydrogenation (SH) leads to enhanced buckling in all Xenes which indicate a tendency towards more $sp^3$ like structures. The electronic structures of SH Xenes do not show Dirac cones. Incorporating SOC in the non-spin polarized band structure calculations results into splitting of the states. On the other hand, spin polarized band structures show magnetism with magnetic moment of 1.0~$\mu_{\rm{B}}$ and all SH Xenes are magnetic semiconductor except SH plumbene. Full hydrogenation vanishes buckling upon relaxation and the structure becomes planar implying $sp^2$-like hybridization. The band structures for FH Xenes turns out to be semiconducting and the Dirac cones also disappear. The bandgap changes from indirect to direct at FH stanene, while FH plumbene turns out to be semi-metallic. No spin polarized states are observed. The effect of SOC does not instigate any noteworthy changes in the bandgap for FH graphene to FH stanene. On the other hand, the SOC gives rise to bandgap of 0.47 eV in FH plumbene, which is otherwise a semi-metal.

The production of hydrogen, the future fuel, on stable, efficient, and robust electrocatalysts represents an attractive approach for the conversion and storage of carbon-free energy resources. In this study, earth-abundant nickel sulfide (NiS) electrocatalyst were grown on fluorine-doped tin oxide (FTO) substrate by a simple and cost-effective chemical bath deposition for hydrogen evolution reaction (HER). Energy dispersive X-ray analysis and X-ray photoelectron spectra indicated the presence of highly pure NiS. The HER performance of the catalyst was examined in alkaline solution (1.0 M NaOH; pH = 13.5). Notably, NiS film prepared at 100 °C demonstrated superior HER activity with an overpotential of 290 mV to afford a current density of 10 mA/cm2 and a Tafel slope of 143.4 mV/dec which are among the promising results obtained for sulfide-based HER electrocatalysts. The catalyst exhibited 100% faradaic efficiency and electrochemical stability which indicate its potential as noble-metal-free HER electrocatalyst.