Carbonization and oxidation of metal–organic frameworks based on 1,4-naphthalene dicarboxylates

Abstract

Three new isostructural metal–organic frameworks (MOFs), [V(OH)(NDC)] (1), [Cr(OH)(NDC)] (2), and [Ga(OH)(NDC)] (3) have been synthesized hydrothermally using 1,4-naphthalene dicarboxylate (NDC) as the linker. These MOFs (1, 2 and 3) have been used as a template for the synthesis of metal-oxide-inserted nanoporous carbon materials. The newly synthesized MOFs and the resulting porous carbon hybrid functional materials have been characterized using powder x-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy dispersive x-ray spectroscopic analysis. Results show that compounds 2 and 3 form their respective metal oxide nanoparticles on the surface of the carbon materials during carbonization at 800 °C. The gas sorption properties of the new MOFs and their corresponding carbon frameworks have been reported.     

Spectroscopic investigations of Cu2+ in Li2O-Na2O-B2O3-Bi2O3 glasses

Pure and copper doped glasses with composition,x Li ₂ O-(40-x)Na ₂ O-50B ₂ O ₃-10Bi ₂ O ₃,have been prepared over the range 0 ≤ x ≤ 40. The electron paramagnetic resonance (EPR) spectra of Cu²⁺ ions of these glasses have been recorded in the X-band at room temperature. Spin Hamiltonian parameters have been calculated. The molecular bonding coefficients, α² and β², have been calculated by recording the optical absorption spectra in the wavelength range 200–1200 nm. It has been observed that the site symmetry around Cu²⁺ ions is tetragonally distorted octahedral. The density and glass transition temperature variation with alkali content shows non-linear behaviour. The IR studies show that the glassy system contains BO₃ and BO₄ units in the disordered manner.     

Preparation and characterization of Ag-added Bi1.84Pb0.4Sr2Ca2.2Cu3O10+x bulk tube conductors for cryogen free superconducting magnet

Bulk tube conductors of Bi _1.84 Pb _0.4 Sr ₂ Ca _2.2 Cu ₃ O _10+x with addition of silver varying from 0 to 25 wt% (not reported earlier) were systematically studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical transport and a.c. susceptibility techniques. The tube conductors formed by cold isostatic pressing (CIP) of the powders obtained from spray drying method have been made successfully. It was found that Ag addition has not only affected the formation of the desired Bi-2223 phase and the microstructure of these large bulk tube samples thereby influencing on the critical current ( I _c ),it also reduces the contact resistance to minimize the cryogen losses. These variations have been found to be Ag content dependent. An optimized value of 10 wt% Ag has been found to produce the best quality tubes showing reproducible I _c value > 120 Amp at 77 K which is in general a requirement to energies of the cryogen free conventional/HTSC superconducting magnets below 20 K.     

Optical properties of samarium doped zinc-tellurite glasses

Glasses with the composition, (Sm₂ O ₃) _x (ZnO)_(40-x)(TeO ₂)₍₆₀₎, were prepared by conventional melt quenching method. The density, molar volume, and optical energy band gap of these glasses have been measured. The refractive index, molar refraction and polarizability of oxide ion have been calculated by using Lorentz-Lorentz relations. Optical absorption spectra of these glasses were recorded in the range 300–700 nm at room temperature. The oxide ion polarizabilities deduced from two different quantities, viz. refractive index and optical energy band gap, agree well compared with other glasses. The nonlinear variation of the above optical parameters with respect to samarium dopant has been explained.     

Synthesis and properties of polycyclic quinones condensed with 1,6-methano[10]annulene

Two types of polycyclic quinones condensed with 1,6-methano[10]annulenes as type A: 1,6-methanonaphtho[2,3-c][10]annulene-7,12-dione 5a, and type B: 1,6-methanonaphtho[2,3-c][10]annulene-5,14-dione 18, bis(1,6-methano[10]annuleno[3,4-b; 3,4-g])anthracene-10,21-dione 20, 1,6-methanoanthraceno[2,3-c][10]annulene-5,16-dione 22, 1,6-methanotetraceno[2,3-c][10]annulene-6,17-dione 23, and 1,6-methano phenanthreno[2,3-c][10]annulene-5,6-dione 24 have been synthesized. The acene derivative 6 corresponding to that of 5a was synthesized by the reduction of quinone 5a. The physical, spectral, and chemical properties of these new compounds have been investigated.     

Multiple strengthening mechanisms in nanoparticle-reinforced copper matrix composites

The multiple hardening mechanisms of a copper matrix have been presented and discussed. The pre-alloyed ball milled Cu–3 wt.%Al and the atomized Cu–0·6 wt.%Ti–2·5 wt.%TiB ₂ powders have been used as starting materials. Dispersoid particles Al ₂ O ₃ and TiB _2\thinspace _{{\bf 2}\thinspace }were formed in situ. The powders have been hot consolidated. Optical microscopy, SEM, TEM, and X-ray diffraction analysis were performed for microstructural characterization. Increase in microhardness of Cu–3 wt.%Al compacts is a consequence of the crystallite size refinement and the presence of Al ₂ O ₃ particles. High hardening of Cu–0·6 wt.%Ti–2·5 wt.%TiB ₂ is a consequence of the presence of modular structure, Cu ₄ Ti_(m), and TiB ₂ particles.     

Observation of curious spiral growth features in Tl doped Hg bearing high temperature superconducting tapes

Synthesis of Hg(Tl)Ba ₂ Ca ₂ Cu ₃ O _8+δ superconducting tapes have been accomplished by annealing the precursor tape, Ba ₂ Ca ₂ Cu ₃ O _y (fabricated by doctor blade tape casting technique) in an environment of Hg(Tl) vapour. Characterization of superconducting HTSC tape sample was carried out through XRD, TEM, SEM and R-T measurements. Surface morphological investigations of the as-synthesized Hg(Tl)Ba ₂ Ca ₂ Cu ₃ O _8+δ HTSC tapes by scanning electron microscope have shown the occurrence of curious growth characteristics resembling spiral like features. These growth spirals encompass nearly the whole grain suggesting that spiral growth led to the formation of small crystal like grains of superconducting material Hg(Tl)Ba ₂ Ca ₂ Cu ₂ O _8+δ .The likely mechanism for the generation of these screw dislocations has been elucidated in terms of incoherent coalescence of growth fronts formed from Hg(Tl):1223 and Hg(Tl):1234 nuclei.     

Dielectric properties of Be(IO<Subscript>3</Subscript>)<Subscript>2</Subscript>⋅4H<Subscript>2</Subscript>O crystals

The article studies the dielectric properties, dc conductivity and ac conductivity of Be(IO₃)₂⋅4H₂O single crystals. The dielectric constant ε has been defined for the three directions of the vectors a, b and c in the crystals in the temperature interval 280–340 K and frequency range 100 Hz–10⁶ Hz. The crystals show strongly expressed anisotropy, at 20 ^∘C and frequency 100 Hz ε_a = 235, ε_b = 30 and ε_c = 85. The frequency dependence of ε is evidence of the presence of low-frequency relaxation polarization in the crystals. The activation energies of the three directions in the crystals have been derived from the temperature dependence of dc conductivity, and they are 1.03 eV, 0.836 eV and 1.2 eV respectively.     

Optical properties of lead-bismuth cuprous glasses

The optical transmission and absorption spectra in UV- VIS were recorded in the wavelength range 350–800 nm for different glass compositions in the system (CuO) _x (PbO) ₅₀−x(Bi₂O₃)₅₀ (x = 2.5, 5.0, 7.5, 10.0, 12.5, 15.0, 20.0). Absorption coefficient (α), optical energy gap (E_opt), refractive index (n_D), optical dielectric constant (ε′_∞), measure of extent of band tailing (ΔE), constant (β) and ratio of carrier concentration to the effective mass (N/m*) have been reported. The effects of compositions of glasses on these parameters have been discussed. It has been indicated that a small compositional modification of the glasses lead to an important change in all the optical properties including non-linear behaviour. The optical parameters were found to be almost the same for different glasses in the same family.     

Synthesis,Spectral Investigations,and Thermal Stability of [60]Fullerene Complexes with TMTSF: 2(C60) · 2(TMTSF) · (C6H6), C60 · TMTSF · 2(CS2), and 2(C60) · 2(TMTSF) · (C6H5Cl)

Abstract

Molecular complexes of [60]fullerene with tetramethyltetraselenafulvalene (TMTSF): C₆₀ · (TMTSF) · 2(CS₂) (1), 2(C₆₀) · (2(TMTSF) · (C₆H₆) (2), and 2(C₆₀) · (2(TMTSF) · (C₆H₅Cl) (3) have been synthesized and their thermal stability and IR spectra vs. light polarization and temperature have been performed.     

(BETS)2[RuX5NO] (X = Cl, Br): An Explanation of Different Conductive Properties Through Structural and Spectroscopic Studies

For the development of new crystal and electronic structures in molecular conductors, dimeric tetrathiafulvalene (TTF) and tetraselenafulvalenes (TSFs)1–3 linked by single or double methyl antimony bridge(s) have been prepared and their neutral crystal structures have been investigated. The donor2 (cis-2) forms a metallic cation radical salt with tetracyanoquinodimethane (TCNQ) containing one-dimensional array interactions.     

Potentiometric study of polyaniline film synthesized with various dopants and composite-dopant: A comparative study

The potentiometric study of polyaniline (PANI) film synthesized with dopants viz. polyvinyl sulfonic acid (PVS),p-toluene sulfonic acid (p TS), dodecyl benzene sulfonic acid (DBS) and composite-dopants viz. PVS-p TS and PVS-DBS, has been carried out. The synthesized PANI films were characterized by electrochemical technique, UV-visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and conductivity measurement. It was found that the PANI doped with PVS gives good electrochemical properties, conductivity as well as surface morphology as compared to p TS and DBS, whereas in composite dopants the PANI doped with PVS-pTS gives good polymer matrix as compared to PVS-DBS.     

Environmentally benign novel green pigments: Pr1-xCaxPO4 (x = 0-0.4)

Rare earth based materials have recently attracted considerable attention as potential ecofriendly colourants for low temperature as well as high temperature applications. In the present study, we have synthesized a series of Ca-doped PrPO₄ compounds with the general formula, Pr_1-xCa_xPO₄ (x = 0-0.4 in steps of 0.1) and characterized the compounds by powder X-ray diffraction. All the compositions show a monoclinic monazite structure. The optical properties of the brilliantly coloured pigments [ L (brightness),a* (+ red- green),b* (+ yellow - blue) have been examined. These materials can find application as potential green colourants.     

Temperature dependence of the electromagnetic response function for strong-coupling amorphous Bi films

The temperature dependence of the electromagnetic response functionI(0, 0,T) has been inferred from the temperature dependence of the kinetic inductance of thin, amorphous Bi films. For normalization purposesI(0, 0, 0) has been calculated from tunneling data with the microscopic strong-coupling theory. The results are not consistent with scaled weak-coupling theory, but instead exhibit strong-coupling effects. The calculated value ofI(0, 0, 0) is approximately 40% below the BCS value for a weak-coupling superconductor, qualtiatively in agreement with determinations ofI(0, 0, 0) for Pb by Kerchner and Ginsberg. The temperature dependence ofI(0, 0,T) differs in the opposite direction from the BCS dependence as that observed for Pb.Research supported by the Robert A. Welch Foundation, Houston, Texas.     

Two novel propylenedioxythiophene-based copolymers with donor–acceptor structures for organic solar cell materials

Two novel conjugated copolymers consisting of alternating electron-rich propylenedioxythiophene and electron-deficient 2,3-diphenyltheno[3,4-b]pyrazine or 6,7-diphenyl[1,2,5]thiadiazole units have been synthesized through palladium catalyzed Sonogashira triple-bond coupling reaction. The structures and properties of the two copolymers, P ₁ , P ₂ , were characterized by FT-IR, NMR, UV–Vis absorbance (Abs), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and cyclic voltammetry (CV). UV–Vis absorption spectra of the polymers show two absorption bands both in CHCl₃ solution and films. The absorption peak maxima of P ₁ , P ₂ are 600 nm, 766 nm in solution and 627 nm, 823 nm in films, respectively. Thermal gravimetric analysis demonstrates that the two polymers are stable below 300 °C. Cyclic voltammetry studies reveal that the band gaps of P ₁ , P ₂ are 1.62 eV and 1.50 eV, suggesting their potential for applications as organic solar cell materials.     

Combustion synthesis and photoluminescence study of silicate biomaterials

Silicate based bioceramics are promising candidates as biomaterials for tissue engineering. The combustion synthesis method provides control on the morphology and particle size of the synthesised material. This paper discusses the combustion synthesis of akermanite (Ca ₂ MgSi ₂ O ₇ and Sr ₂ MgSi ₂ O ₇ ), which has been shown to have good in vitro and in vivo bioactivities by earlier studies. Both Ca ₂ MgSi ₂ O ₇ and Sr ₂ MgSi ₂ O ₇ have akermanite structure. Ca ₂ MgSi ₂ O ₇ and Sr ₂ MgSi ₂ O ₇ were prepared using urea and ammonium nitrate. The combustion synthesis using urea and ammonium nitrate was found to be cost effective and efficient method of synthesis. The photoluminescence study of Ca ₂ MgSi ₂ O ₇ : Eu²⁺^{\boldsymbol{2+}} and Sr ₂ MgSi ₂ O ₇ : Eu²⁺^{\boldsymbol{2+}} shows host specific intense emission of Eu²⁺^{\boldsymbol{2+}}.     

Effect of zirconium addition on the recrystallization behaviour of a commercial Al-Cu-Mg alloy

It is well known that the second phase particles have an effect on recrystallization and grain growth behaviour of an alloy. Particularly the bimodal distribution of second phase particles has an effect which is opposite in sense where coarse second phase particles (> 1 μm) stimulate nucleation while fine particles exhibit Zener drag. In the literature, the effect of zirconium addition to aluminium alloys has been well documented in order to produce superplasticity by giving ultra fine grain size to the alloy. Addition of zirconium produces Al ₃ Zr particles which pin the grain boundaries during recrystallization and grain growth. In the present work, zirconium was added to a commercial Al-Cu-Mg alloy and by heat treatment Al ₃ Zr particles were precipitated and after forging, the grain size was an order of magnitude lower than the alloy without zirconium. Transmission electron microscopy was employed to characterize the second phase particles, i.e. Al ₃ Zr particles and found to be rod shaped and identified to be cubic ordered L 1 ₂ phase with a lattice parameter of 0.408 nm. Further, it was observed that fine (100 nm) Al ₃ Zr particles promote only continuous recrystallization which is polygonization of subgrains and subgrain growth. It was found that the fine dispersion of Al ₃ Zr particles inhibits both recrystallization and grain growth in the commercial Al-Cu-Mg alloy.     

Synthesis and characterization of chiral liquid crystal polymers containing donor–acceptor group

A series of new chiral side-chain liquid crystalline polymers with electron donor–acceptor action were prepared containing chiral monomer with donor group and nematic LC monomer with acceptor group. All polymers were synthesized by graft polymerization using polymethylhydrosiloxane as backbone. The mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analyses (TGA), and X-ray diffraction measurements (XRD). The chemical structures of monomers and polymers were confirmed by Fourier transform infrared (FTIR), proton nuclear magnetic resonance spectra (¹H NMR and ¹³CNMR). M ₁ did not show liquid crystalline phase and M ₂ turned out nematic phase on heating and cooling cycle. Polymers P ₂ –P ₇ were cholesteric phase. Cholesteric phase and low glass temperature liquid crystalline polymers have been obtained, which offered the possibility of application. Experimental results demonstrated that the glass-transition temperatures rose and isotropization temperatures decreased and the ranges of the mesophase temperature reduced with increasing the content of chiral agent. All of the obtained polymers showed high thermal stability.     

First Order-Like Out-of-Plane Resistive Transition in YBa2Cu3O7−δ for B Exactly Parallel to ab-Planes

Melting transition of a flux line lattice// ab -planes has been studied in twinned YBa ₂ Cu ₃ O _7– single crystals using transport measurements along the c -axis. In contrast to previously studied geometry with field and current in planes (W.K. Kwok et al., Phys. Rev. Lett. 72 , 1088 (1994)), a step-like c -axis resistive transition has been found for exact field alignment along ab -planes. The angular dependence of _c with rotation of the crystal around the c -axis was studied. The results show that below the resistive step, the pinning force is anomalously increased when the field is aligned along ac ( bc )-crystal facets.     

Homogenization of zinc distribution in vertical Bridgman grown Cd0.96Zn0.04Te crystals

One of the most pressing issues in the growth of high quality single crystal Cd _0.96 Zn _0.04 Te material, is to achieve homogenization of the high axial variation of Zn concentration, caused by the larger than unity segregation coefficient of Zn in CdTe. This is achieved in our crystals (i) by thermal annealing of the CdZnTe crystal, which redistributes the as grown Zn distribution by solid state diffusion of Zn (this solid state diffusion of Zn occurs at three stages (a) during the growth when the solidified crystal is near to the melting point temperature, (b) during the post growth annealing of the crystal at a high temperature and (c) during the cooldown to room temperature) and (ii) by the reduction of Zn segregation during the growth stage by enhanced convective mixing of the melt, through a proper choice of ampoule and furnace dimensions. By adopting suitable growth parameters and sufficient post growth annealing it has been possible to grow Cd _0.96 Zn _0.04 Te crystals, which have nearly 75% of their fraction within 1% Zn concentration variation.