Sharif Digital Repository

Mononuclear nonheme iron containing systems are versatile and vital oxidants of substrate hydroxylation reactions in many biosystems, whereby the rate constant of hydroxylation correlates with the strength of the C-H bond that is broken in the process. The thermodynamic reason behind these correlations, however, has never been established. In this work results of a series of density functional theory calculations of substrate hydroxylation by a mononuclear nonheme iron(IV)-oxo oxidant with a 2 His/ 1Asp structural motif analogous to aketoglutarate dependent dioxygenases are presented. The calculations show that these oxidants are very efficient and able to hydroxylate strong C-H bonds,... 

In this work, cycling-induced aging occurring in 18650-type LiFePO4/graphite full cells at different C-rates is studied extensively. The mechanism of performance degradation is investigated using a combination of electrochemical and microstructural analyses. Half-cell studies are carried out after dismantling the full cells, using fresh and cycled LiFePO4 cathode and graphite anode to independently study them. The results show that the capacity of LiFePO4 electrodes is significantly recovered. The rate of capacity fading in the discharge state considered as irreversible capacity in the graphite is higher than LiFePO4 half cells, indicating a greater degradation in the performance of this... 

Gadolinium (Gd) and cobalt (Co) substituted Sr–Ba–Cu-based Y-type hexaferrites were synthesized with the help of the sol–gel auto-combustion route. XRD (X-ray diffraction) analysis was done to ratify the phase formation of hexaferrites. The impact of Gd3+ substitutions was measured on all the lattice parameters. Lattice constants “a” and “c” were found between 5.879–5.891 Å and 43.185–43.620 Å, respectively. It was observed from the XRD analysis that with an increase in Gd–Co contents, the enhancement in the average crystallite size is noted. The thermal decomposition process was studied using TGA (thermogravimetric analysis), revealing that the precursor may give the ending product when... 

In this work, cycling-induced aging occurring in 18650-type LiFePO4/graphite full cells at different C-rates is studied extensively. The mechanism of performance degradation is investigated using a combination of electrochemical and microstructural analyses. Half-cell studies are carried out after dismantling the full cells, using fresh and cycled LiFePO4 cathode and graphite anode to independently study them. The results show that the capacity of LiFePO4 electrodes is significantly recovered. The rate of capacity fading in the discharge state considered as irreversible capacity in the graphite is higher than LiFePO4 half cells, indicating a greater degradation in the performance of this... 

The equilibrium crystal structure and electronic structure of BaFe2-x Cox As2 (x = 0,1, 2) superconductor have been investigated by using the pseudopotential Quantum Espresso code based on the ab initio density functional theory in the generalized gradient approximation. The equilibrium crystal structure for x = 1.0 has been determined by considering five different Fe/Co configurations. This study shows that the spin calculation is essential to obtain the experimental values at x = 0.0. The total and partial density of states, band structure, and Fermi surfaces of the three compounds has been calculated. Density of states calculation indicates the important... 

Aluminum matrix in situ nanocomposite was produced by one to six passes friction stir processing (FSP) with pre-placed Fe3O4 nanoparticles (15-20 nm). Microstructure studies showed that solid-state reactions between the aluminum matrix and Fe3O4 particles during the process led to in situ formation of Al3Fe and Al5Fe2 in the stir zone. Initial Fe3O4 as well as Al-Fe intermetallic compounds (IMCs) particles were homogeneously dispersed in a fine grain matrix after six passes of FSP. Hardness and ultimate tensile strength of the composites were increased 64 and 27%, respectively, compared to the base metal. The reasons were studied in the light of reinforcing particles distribution, formation... 

Polyaniline/graphene oxide (PANI/GO) co-doped with Zn2+ and Fe3+ was synthesized via a simple and low cost one-step chronoamperometry method on stainless steel (SS) as the substrate. The Fe3+-Zn2+-PANI/GO nanocomposite is characterized using X-ray diffraction as well as Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and field emission scanning electron microscopy. Also, cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy are used to study the electrochemical performance of the as-prepared electrode materials. Significantly, the Fe3+-Zn2+-PANI/GO nanocomposite exhibits a specific... 

The reaction of Fe(acac)3 and 2-(2′-hydroxyphenyl)oxazoline (Hphox) as a bidentate O,N donor ligand afforded a six-coordinated iron(III) complex [Fe(phox)2(acac)] with distorted octahedral configuration. The complex was isolated as an air-stable crystalline solid and characterized by elemental analysis, FTIR, solution electrical conductivity, and by single-crystal X-ray structure analysis. The structure, electronic properties, and vibrational normal modes of the complex were investigated by DFT. The use of this complex as a catalyst for the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide as the primary oxidant was investigated. The catalyst shows very... 

Joining of Al-5083 alloy sheet to St-12 steel sheet was performed using a new friction stir spot welding (FSSW) technique in which the tool pin tip did not enter lower steel sheet. Effect of dwell time on the microstructure and mechanical properties of the joints was studied by various methods including microhardness measurements, shear test, stereo and light microscopy as well as scanning and transmission electron microscopy (SEM and TEM). Results indicated that compared to the conventional FSSW process, stronger joints can be achieved by this FSSW technique. Cross-sectional observation of the failed specimens indicated the occurrence of final fracture from the circumference of the tool pin... 

In recent years, thin silver nanowires (Ag NWs) with diameters smaller than 150 nm have been synthesized by implementation of NaCl or FeCl3 as reaction promoters and high molecular weight polyvinylpyrrolidone (PVP) as the capping agent. However, the yield of Ag NWs still remains low, mostly due to the insufficient aspect ratio (AR) of the synthesized nanostructures and the production of Ag nanoparticles, which is an undesirable by product. This study proposes a modified technique to alleviate the problem by using a mixture of FeCl3/CuCl2 as the reaction promoter and two different types of PVP with molecular weight of 360 k and 40 k as the capping agents. The appropriate mixtures of... 

Abstract: The loading of co-catalyst is an efficient way to increase the activity of synthesized carbon-based photocatalysts in the energy and environmental applications. Herein, Co and Ni decorated on g-C3N4 was synthesized as a visible light active photocatalyst and characterized with XRD, FT-IR, BET, DRS, TGA, FE-SEM, EDX, and EIS techniques. From the characterization results, it was demonstrated that cobalt and nickel which were present in the structure of the nanocatalyst, were in the metallic form. The decoration of Ni and Co reduced bandgap energy of g-C3N4 and made the synthesized nanocomposite active under visible light. The operating condition of O2 photocatalytic generation was... 

The influence of indium on the properties of Cu0.5Zn0.5Fe2O4 nano ferrites synthesized by sol–gel auto-combustion technique was studied. X-ray diffraction (XRD) analysis demonstrated that pure and substituted ferrites possessed cubic spinel structure. The lattice parameter increases with the inclusion of In3+ for x ≤ 0.16 and decreases subsequently. A linear decrease in crystallite size was found as concentration of indium increased. X-ray density, strain, and dislocation density were increased as indium content increases. Hopping lengths as well as radii of A and B sites revealed increasing behavior up to x = 0.16 and decreased thereafter. The spectral bands indicated the formation of... 

The influence of indium on the properties of Cu0.5Zn0.5Fe2O4 nano ferrites synthesized by sol–gel auto-combustion technique was studied. X-ray diffraction (XRD) analysis demonstrated that pure and substituted ferrites possessed cubic spinel structure. The lattice parameter increases with the inclusion of In3+ for x ≤ 0.16 and decreases subsequently. A linear decrease in crystallite size was found as concentration of indium increased. X-ray density, strain, and dislocation density were increased as indium content increases. Hopping lengths as well as radii of A and B sites revealed increasing behavior up to x = 0.16 and decreased thereafter. The spectral bands indicated the formation of... 

Effects of Fe particle volume percent (from 0 to 5%) and changing the tool rotation direction in each pass were studied on the microstructure evolution and mechanical properties of the in situ Al/intermetallic composites produced by three passes friction stir processing (FSP) with ∼10 µm Fe particles. Optical and scanning electron microscopes were used for the investigation of the composite homogeneity, formation of Al–Fe intermetallic compounds, and fracture surfaces. Tensile and microhardness tests were also carried out to evaluate the mechanical properties of the composites. Solid-state reactions between the aluminum matrix and Fe particles led to in situ formation of Al3Fe and Al5Fe2... 

Four derivatives of hyaluronic acid (HA) bearing thiol (HA-SH), hydrazide (HA-hy), 2-dithiopyridyl (HA-SSPy), and aldehyde groups (HA-al) respectively were synthesized. Thiol and 2-dithiopyridyl as well as hydrazide and aldehyde make up two chemically orthogonal pairs of chemo-selective functionalities that allow in situ formation of interpenetrating (IPN) disulfide and hydrazone networks simultaneously upon the mixing of the above derivatives at once. The formation of IPN was demonstrated by comparing it with the formulations of the same total HA concentration but lacking one of the reactive components. The hydrogel composed of all four components was characterized by a larger elastic... 

We substitute indium present in the CuInS2 ternary compound by iron and zinc using a facile one-pot synthesis method. The quaternary compound of CuIn1-xMxS2 (M = Fe and Zn) was synthesized by dissolving CuCl, InCl3, FeCl3, Zn(ac)2 and SC(NH2)2 as precursors in 1-octadecene, oleylamine and oleic acid as non-coordinating, coordinating and capping agent solvents, respectively. Oleic acid, oleylamine and thiourea were used respectively as a hard Lewis base, borderline Lewis base (in comparison with oleic acid) and soft Lewis base to form appropriate complexes. The complex formation, structure, and... 

A molybdenum complex, [MoO2Cl2(DMSO)2], was immobilized on amino propyl and Schiff base modified magnetic Fe3O4@SiO2 nanoparticles by covalent linkage. The resulting nanoparticles were used as efficient and recyclable catalysts for the selective oxidation of sulfides to sulfoxides using urea hydrogen peroxide as the oxidant. The complete characterization of catalysts was carried out by means of thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS), elemental analysis, FT-IR and Raman microprobe... 

A new, simple and rapid carbon dot (CD) based fluorescent probe for speciation of Fe2+ and Fe3+ ions was developed. The as-prepared CDs contain phenol groups on their surfaces and due to the special coordination interaction of phenol groups with Fe3+ ions, this sensing system exhibits excellent sensitivity and selectivity toward Fe3+. In order to detect Fe2+ ions as well, a specific amount of H2O2 was introduced to the detection system to transform Fe2+ to Fe3+ of which the latter is the determinable form of iron. Under the optimum experimental conditions, the fluorescence intensity of the sensor decreased as the Fe3+ ion concentration increased. The relationship plot between the... 

The present study dealt with the mechanism of competitive adsorption of Sb(III) and Fe(II) ions from a copper-containing aqueous solution on Purolite S957, a commercially available cationic ion-exchange adsorbent. Experiments were conducted using aqueous copper sulfate solutions containing either single or conjoint ions, using both sedentary and batch adsorption techniques to ascertain the sensitivity of the adsorption process to variation in pH, mass of resin, contact time, and temperature as well as establishing the optimal range of variables for maximum ion removal. The data from single ion adsorption tests were fitted by non-linear regression techniques to Henry, Langmuir, Freundlich,... 

An efficient protocol was developed for the nano CoCuFe2O4-catalyzed C-N and C-S bond formation. By this catalytic system, both amine and sulfide-based structural motifs were formed efficiently in aryl halide-free route. The amination reaction of phenyl boronic acid with various types of amines was conducted under ligand-free conditions, in ethanol as a green solvent at 60°C. Unsymmetrical diaryl/aryl alkyl sulfide synthesis via the coupling reaction of arylboronic acids with thiols was also conducted. The nano cobalt-copper ferrite was used as a heterogenous efficient, inexpensive, magnetically separable and recyclable catalyst that can be used for several cycles. © 2018 John Wiley & Sons,...