Koodlur Sannegowda Lokesh

Dendrimer-rhodium nanoparticle modified glassy carbon electrode for amperometric detection of hydrogen peroxide

Metallic nanoparticles of rhodium were prepared by using the newly synthesized N,N-bis-succinamide-based dendrimer as stabilizers. The Rh nanoparticles were spherical shaped with a particle size of approximately 2 nm. The dendrimer Rh-encapsulated nanoparticles (Rh-DENs) were immobilized on glassy carbon electrode (GCE) and their electrocatalytic activity towards hydrogen peroxide reduction was investigated using cyclic voltammetry and chronoamperometry. The Rh-DENs modified GCE showed excellent electrocatalytic activity for hydrogen peroxide reduction reactions. The steady-state cathodic current response of the modified electrode at -0.3 V (vs SCE) in phosphate buffer (pH 7.0) showed a linear response to hydrogen peroxide concentration ranging from 8 to 30 microM with a detection limit and sensitivity of 5 microM and 0.03103x10(-6) A microM(-1), respectively.

Self-Assembled Supramolecular Array of Polymeric Phthalocyanine on Gold for the Determination of Hydrogen Peroxide

This Article describes for the first time the formation of a supramolecular self-assembled monolayer of polymeric phthalocyanine (poly(CuPc)) onto a gold substrate. The latter is established through the interaction of the cyano group, belonging to the poly(CuPc), with the metal substrate. The functionalized gold substrate was characterized using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrochemical methods. Results clearly demonstrated the interaction between gold and the nitrogen atom of cyano group and showed at the same time the formation of a completely covered polymeric monolayer on the gold surface. In addition, the modified gold surface seems to exhibit a reversible redox behavior and is found to act as an electronic conductor, which allows rapid electron transfer. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)(6)](3-/4-) as a redox couple revealed that the modified electrode showed a much lower electron transfer resistance compared with bare gold. In addition, the modified electrode is found to catalyze the H(2)O(2) reduction very effectively, showing a catalytic current that varies linearly with the peroxide concentration in the range of 0.35 to 70 μM with a detection limit of 0.25 μM.

Adsorption and enhanced photocatalytic activity of the {0 0 0 1} faceted Sm-doped ZnIn2S4 microspheres.

In this study, the doping effect of samarium on the structure, morphology, adsorption and photocatalytic performance of hexagonal ZnIn2S4 microspheres was studied. The photocatalytic activity of Sm-doped ZnIn2S4 microspheres was evaluated for the photodegradation of Rhodamine B (RhB) and methyl orange (MO) under visible light irradiation. The samples were characterized by XRD, SEM, XPS, UV-vis, TEM, and N2 adsorption-desorption analysis. The results show that the hexagonal ZnIn2S4 microspheres are composed of nanoplates growing along c-axis with the predominant negative-charged S plane. Compared with the photodegadation of MO dye, the negative-charged {0 0 0 1} facets not only are beneficial for the adsorption of RhB by -N(Et)2 groups but also can accumulate the separation of photogenerated electrons and holes, enhancing photodegradation efficiency by direct-hole photocatalysis. Moreover, Sm is partially substituted for In in the crystal lattice for forming the doping energy level which promotes the separation of photoinduced electron-hole pairs and enhances absorption of visible light. Hexagonal 2% Sm-doped ZnIn2S4 microspheres with exposed {0 0 0 1} facets resulted in higher photodegradation efficiency of RhB under visible light irradiation.

Self Assembled Films of Porphyrins with Amine Groups at Different Positions: Influence of Their Orientation on the Corrosion Inhibition and the Electrocatalytic Activity

Self-assembled molecular films of two cobalt porphyrins with amine groups at different positions—(5,10,15,20-tetrakis-(2-aminophenyl) porphyrin-cobalt(II), [Co(II) (T(o-NH2)PP)] and (5,10,15,20-tetrakis-(4-aminophenyl) porphyrin-cobalt(II), [Co(II)(T(p-NH2)PP)]—were formed on a gold substrate. The functionalized surfaces were characterized using Raman spectroscopy, atomic force microscopy and electrochemical methods. Both modified gold surfaces completely mask the charge transfer of a [Fe(CN)6]3−/4− redox couple in solution, indicating the layer is highly resistive in behavior. Electrochemical impedance spectroscopy analyses revealed that the porphyrin film with amine groups at ortho positions shows a higher charge-transfer resistance with a better protective behavior compared to the para position modified surface. Raman, AFM and EIS data suggests that an ortho amine positioned molecule forms a more compact layer compared to the para-positioned molecule. This can be explained in terms of their orientation on the gold surface. [Co(II)(T(o-NH2)PP)] adopted a saddle shape orientation whereas [Co(II)(T(p-NH2)PP)] adopted a flat orientation on the gold surface. The porphyrin modified gold electrode catalyzes the oxygen reduction at lower potentials compared to the bare gold electrode. The shift in the overvoltage was higher in case of molecules with flat orientation compared to the saddle shaped oriented porphyrin molecules on the surface.

Synthesis, characterization, pyrolysis kinetics and conductivity studies of chloro substituted cobalt phthalocyanines

Cobalt(II) phthalocyanine (CoPc), cobalt(II) tetrachloro phthalocyanine (CoPcCl4), cobalt(II) octachloro phthalocyanine (CoPcCl8) and cobalt(II) hexadecachloro phthalocyanine (CoPcCl16) are synthesized pure and characterized using elemental analysis, UV-visible, IR-spectroscopy, magnetic susceptibility, X-ray crystallography, and thermogravimetry. All four complexes have monoclinic structure with different crystal lattice constants. Broidos, Coats-Redfern and Horowitz-Metzger relations were employed to calculate the kinetic and activation parameters associated with thermal decomposition of the above complexes. The compounds are analyzed for kinetic parameters, activation energies for decomposition and the Arrhenious pre-exponential factors, in their pyrolysis. Using these factors and standard equations, thermodynamic parameters such as enthalpy, entropy and free energies are calculated. The activation energies are evaluated based on their electrical conductivity conducted over the temperature range 30–200°C. The electrical conductivities observed at 30°C are in the order CoPcCl16 > CoPcCl4 > CoPcCl8 > CoPc. The relevant electrical conductivity data are reported.

Degradation study on the thermally stable nickel phthalocyanine sheet polymer

Poly (nickel phthalocyanine) which has exceptional thermal stability is synthesized. Knowledge of modes of degradation of this polymer is found to be necessary for its high temperature applications. This polymer showed very high thermal stability with maximum polymer decomposition temperatures (PDTmax) of 500 degreesC in air and 890 degreesC in N-2, with char yield 93% at 800 degreesC. Because of its excellent thermal stability, degradation study with MS as well as GC-MS techniques were found to be very difficult. The present publication deals with MS and GC-MS studies of nickel phthalocyanine sheet polymer at high temperatures ranging from 700 to 1000 degreesC. Tentative mechanisms are proposed for its modes of fragmentations and based on GC-MS studies, the most probable degradation products are identified