Surface Properties and Catalytic Activity of Ferrospinels Containing Cobalt, Nickel and Copper

The present study describes the surface properties and catalytic activities of ferrospinels containing Co, Ni and Cu prepared by the low temperature route. Various physico-chemical methods have been adopted to characterise the systems. The reactions carried out are the Friedel-Crafts benzoylation of aromatics and the cyclohexanol decomposition. We have attempted the sulphate modification of the ferrites and have studied the surface and catalytic properties of the sulphated analogues.The work is presented in six chapters, the last chapter giving the summary and conclusions of the results presented earlier. Our samples prove as potential catalysts for the benzoylation of aromatics , for which truly heterogeneous catalysts are rare. Again , the materials show remarkable dehydration/dehydrogenation activities during cyclohexanol decomposition. There is plenty of scope for research in this field, especially in the development of environmentally benign catalysts for acylation reactions.

Surface properties and catalytic activity of ferrospinels of nickel, cobalt and copper, prepared by soft chemical methods

Ferrospinels of nickel, cobalt and copper and their sulphated analogues were prepared by the room temperature coprecipitation route to yield samples with high surface areas. The intrinsic acidity among the ferrites was found to decrease in the order: cobalt> nickel> copper. Sulphation caused an increase in the number of weak and medium strong acid sites, whereas the strong acid sites were left unaffected. Electron donor studies revealed that copper ferrite has both the highest proportion of strong sites and the lowest proportion of weak basic sites. All the ferrite samples proved to be good catalysts for the benzoy lation of toluene with benzoyl chloride. copper and cobalt ferrites being much more active than nickel ferrite. The catalytic activity for benzoylation was not much influenced by sulphation, but it increased remarkably with calcination temperature of the catalyst. Surface Lewis acid sites, provided by the octahedral cations on the spinel surface, are suggested to be responsible for the catalytic activity for the benzoylation reaction.

Thermal diffusivity of some polymer supported halogeno benzimidazole complexes of cobalt(II) and copper(II) - a photoacoustic study

The thermal diffusivities of some polystyrene supported Schiff complexes of Co(II) and Cu(II) were determined by the laser induced photoacoustic technique. The effect of metal as well as the halogen part on thermal diffusivity of polymer supported complexes was studied. The thermal diffusivity of Co complexes increases while it decreases in Cu complexes with Cl, Br and I substitutions, respectively.

Spectral studies of naphthalocyanine (Nc) and rare earth phthalocyanine (RePc) molecules in an inorganic glassy borate matrix

Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

Optical studies of phthalocyanine molecules in PVA film

Optical absorption and emission spectral studies of various phthalocyanine (Pc) molecules in PVA matrix have been reported for the first time. The recorded spectra are analyzed to get the important spectral parameters, such as optical absorption cross-section (σa), emission cross-section (σe), oscillator strength (f), fluorescence bandwidth (Δλ), emission wavelength (λ), radiative decay time (τ) and optical gain (G). Analysis shows that the emission cross-section and optical gain are maximum in the NdHPc2-doped PVA matrix. However, a comparison of the calculated emission parameters with that of borate glass matrix show that they are many times smaller in the present matrix.

Optical absorption studies of free (H2Pc) and rare earth (RePc) phthalocyanine doped borate glasses

Optical absorption studies of free base and rare earth incorporated phthalocyanine doped borate glass matrix are reported for the first lime. The absorption spectra recorded in the UV- VIS region show two well defined absorption bands of phthalocyanine (Pc) molecule, namely the Soret band (B) and the Q band. The Q band always shows its characteristic splitting in all the doped glass matrices and the intensities of these components are found to vary from one Pc to another. Some of the important optical parameters, namely optical absorption coefficient (a), molar extinction coefficient (ε), absorption cross section (σa), oscillator strength (f), electric dipole strength (q2), absorption half bandwidth (Δλ) of the principal optical transitions have also been evaluated. Moreover, the spectral dependence of refractive index (n) and thereby the optical dielectric constant (ε) on wavelength yielded values of carrier concentration to effective mass ratio (N/m*) of the phthalocyanine molecule in the present glassy systems. Optical band gap (Eg) and width of the band tail (Et) are computed and their variations among the prepared samples are also discussed.

Optical properties of phthalocyanine molecules in cyano acrylate polymer matrix

Optical absorption and emission spectral studies of various phthalocyanine molecules, viz., LaPc, NdPc, SmPc, EuPc, CuPc and ZnPc in a polymer matrix of cyano acrylate are reported for the first time. All the absorption spectra show an intense B band (Soret) in the UV region followed by a weaker Q band in the visible region. The positions of the Q and B bands are found to have dependence on the metallic substitution. Values of the important spectral parameters, viz., molar extinction coefficient (ϵ), oscillator strength (f), radiative transition rate and decay time of the excited singlet state are also presented and compared with other solid matrices. The recorded fluorescence spectrum shows two broad emission bands in the case of NdPc, whereas for ZnPc only a very weak band is observed. The absence of emission bands for the other metallated phthalocyanines is attributed to increased spin orbit interaction and intersystem crossing.

Photoacoustic spectrum of samarium phthalocyanine powder

Photoacoustic spectrum of samarium phthalocyanine powder is recorded and compared with previously reported UV–vis absorption spectra of the same dissolved in different liquid and solid host media. The Davidov splitting of Q band is observed in the PA spectrum but the two bands are overlapped considerably and the shorter wavelength band is more intense and dominating one in the powder spectrum.

Template assisted fabrication of I-D nanostructures of Nickel,Cobalt, Iron Oxide and Carbon nanotubes and a study on their structural, magnetic and nonlinear optical properties for applications

Department of Physics, Cochin University of Science & Technology

Spectral dependence of third order nonlinear optical susceptibility of zinc phthalocyanine

Wavelength dependence of saturable absorption (SA) and reverse saturable absorption (RSA) of zinc phthalocyanine was studied using 10 Hz, 8 ns pulses from a tunable laser, in the wavelength range of 520–686 nm, which includes the rising edge of the Q band in the electronic absorption spectrum. The nonlinear response is wavelength dependent and switching from RSA to SA has been observed as the excitation wavelength changes from the low absorption window region to higher absorption regime near the Q band. The SA again changes back to RSA when we further move over to the infrared region. Values of the imaginary part of third order susceptibility are calculated for various wavelengths in this range. This study is important in identifying the spectral range over which the nonlinear material acts as RSA based optical limiter.

Spectral dependence of third order nonlinear optical susceptibility of zinc phthalocyanine

Wavelength dependence of saturable absorption (SA) and reverse saturable absorption (RSA) of zinc phthalocyanine was studied using 10 Hz, 8 ns pulses from a tunable laser, in the wavelength range of 520–686 nm, which includes the rising edge of the Q band in the electronic absorption spectrum. The nonlinear response is wavelength dependent and switching from RSA to SA has been observed as the excitation wavelength changes from the low absorption window region to higher absorption regime near the Q band. The SA again changes back to RSA when we further move over to the infrared region. Values of the imaginary part of third order susceptibility are calculated for various wavelengths in this range. This study is important in identifying the spectral range over which the nonlinear material acts as RSA based optical limiter.

Optical-limiting response of rare-earth metallo-phthalocyanine-doped copolymer matrix

The nanosecond optical-limiting characteristics (at 532 nm) of some rare-earth metallo-phthalocyanines (Sm(Pc)2, Eu(Pc)2, and LaPc) doped in a copolymer matrix of poly(methyl methacrylate) and methyl-2-cyanoacrylate have been studied for the first time to our knowledge. The optical-limiting response is attributed to reverse saturable absorption due to excited-state absorption. The performance of LaPc in a copolymer host is studied at different linear transmissions. The laser damage thresholds of all the samples are also reported.

Measurement of thermal diffusivity of some halogeno benzimidazole complexes of cobalt(II), copper (II) and copper(I) using laser induced photoacoustic effect

Cochin University of Science and Technology

Synthesis of High Coercivity Cobalt Nanotubes with Acetate Precursors and Elucidation of the Mechanism of Growth

Cobalt nanotubes (CoNTs) with very high longitudinal coercivity were prepared by electrodeposition of cobalt acetate for the first time by using anodized alumina (AAO) template. They were then characterized with X-ray diffraction (XRD), a field emission scanning electron microscope (FESEM), and a transmission electron microscope (TEM). Formation of a highly ordered hexagonal cobalt phase is observed. Room temperature SQUID (superconducting quantum interference device) magnetometer measurements indicate that the easy axis of magnetization is parallel to the nanotube axis. These CoNTs exhibit very high longitudinal coercivity of ∼820 Oe. A very high intertubular interaction resulting from magnetostatic dipolar interaction between nanotubes is observed. Thick-walled nanotubes were also fabricated by using cobalt acetate tetrahydrate precursors. A plausible mechanism for the formation of CoNTs based on mobility assisted growth is proposed. The role of the hydration layer and the mobility of metal ions are elucidated in the case of the growth mechanism of one-dimensional geometry

Inverse magnetocaloric effect in sol–gel derived nanosized cobalt ferrite

The magnetocaloric properties of cobalt ferrite nanoparticles were investigated to evaluate the potential of these materials as magnetic refrigerants. Nanosized cobalt ferrites were synthesized by the method of sol–gel combustion. The nanoparticles were found to be spherical with an average crystallite size of 14 nm. The magnetic entropy change ( Sm) calculated indirectly from magnetization isotherms in the temperature region 170–320 K was found to be negative, signifying an inverse magnetocaloric effect in the nanoparticles. The magnitudes of the Sm values were found to be larger when compared to the reported values in the literature for the corresponding ferrite materials in the nanoregime.