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      Effect of thermal treatment on the synthesis of NiAl 2 O 4 spinel oxide using chitosan as precursor Translated title: (Efeito do tratamento térmico na síntese do óxido espinélio NiAl2O4 usando quitosana como precursor)

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          Abstract

          Abstract Nickel aluminate oxide (NiAl2O4) was prepared using chitosan as polymeric precursor and ammonia solution as a precipitating agent. In addition, nickel nitrate and aluminum nitrate salts were used as sources of Ni and Al, under stoichiometric amounts (molar ratio Ni:Al = 1:2). NiAl2O4 particles were prepared at different calcination temperatures and their properties were investigated. The synthesized materials were characterized by X-ray diffraction, infrared spectroscopy, atomic force microscopy, thermogravimetric analysis and nitrogen adsorption-desorption isotherms. The results showed that the thermal treatment process strongly influence on the formation of a single-phase structure of NiAl2O4 spinel. Nickel aluminate spinel with a porous structure and high surface area was obtained at temperatures above 700 ºC.

          Translated abstract

          Resumo Aluminato de níquel (NiAl2O4) foi preparado utilizando quitosana como precursor polimérico e uma solução amoniacal como um agente de precipitação. Além disso, sais de nitrato de níquel e de nitrato alumínio foram empregados como fontes de Ni e Al, em quantidades estequiométricas (razão molar Ni:Al = 1:2). Partículas de NiAl2O4 foram preparadas em diferentes temperaturas de calcinação e as suas propriedades foram investigadas. Os sólidos sintetizados foram caracterizados por difração de raios X, espectroscopia de infravermelho, microscopia de força atômica, análise termogravimétrica e isotermas de adsorção-dessorção de nitrogênio. Os resultados mostraram que o processo de tratamento térmico influencia fortemente sobre formação da fase espinélio NiAl2O4. Partículas de aluminato de níquel, com uma estrutura porosa e com alta área superficial, foram obtidas em temperaturas superiores a 700 °C.

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          Versatile Photocatalytic Systems for H2 Generation in Water Based on an Efficient DuBois-Type Nickel Catalyst

          The generation of renewable H2 through an efficient photochemical route requires photoinduced electron transfer (ET) from a light harvester to an efficient electrocatalyst in water. Here, we report on a molecular H2 evolution catalyst (NiP) with a DuBois-type [Ni(P2 R′N2 R″)2]2+ core (P2 R′N2 R″ = bis(1,5-R′-diphospha-3,7-R″-diazacyclooctane), which contains an outer coordination sphere with phosphonic acid groups. The latter functionality allows for good solubility in water and immobilization on metal oxide semiconductors. Electrochemical studies confirm that NiP is a highly active electrocatalyst in aqueous electrolyte solution (overpotential of approximately 200 mV at pH 4.5 with a Faradaic yield of 85 ± 4%). Photocatalytic experiments and investigations on the ET kinetics were carried out in combination with a phosphonated Ru(II) tris(bipyridine) dye (RuP) in homogeneous and heterogeneous environments. Time-resolved luminescence and transient absorption spectroscopy studies confirmed that directed ET from RuP to NiP occurs efficiently in all systems on the nano- to microsecond time scale, through three distinct routes: reductive quenching of RuP in solution or on the surface of ZrO2 (“on particle” system) or oxidative quenching of RuP when the compounds were immobilized on TiO2 (“through particle” system). Our studies show that NiP can be used in a purely aqueous solution and on a semiconductor surface with a high degree of versatility. A high TOF of 460 ± 60 h–1 with a TON of 723 ± 171 for photocatalytic H2 generation with a molecular Ni catalyst in water and a photon-to-H2 quantum yield of approximately 10% were achieved for the homogeneous system.
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              Cytochrome P450-catalyzed regio- and stereoselective phenol coupling of fungal natural products.

              For almost 100 years, phenoxy radical coupling has been known to proceed in nature. Because of the linkage of their molecular halves (regiochemistry) and the configuration of the biaryl axis (stereochemistry), biaryls are notoriously difficult to synthesize. Whereas the intramolecular enzymatic coupling has been elucidated in detail for several examples, the bimolecular intermolecular coupling could not be assigned to one single enzyme in the biosynthesis of axially chiral biaryls. As these transformations often take place regio- and stereoselectively, enzyme-catalyzed control is reasonable. We now report the identification and expression of fungal cytochrome P450 enzymes that catalyze regio- and stereoselective intermolecular phenol couplings. The cytochrome P450 enzyme KtnC from the kotanin biosynthetic pathway of Aspergillus niger was expressed in Saccharomyces cerevisiae. The recombinant cells catalyzed the coupling of the monomeric coumarin 7-demethylsiderin both regio- and stereoselectively to the 8,8'-dimer P-orlandin, a precursor of kotanin. The sequence information obtained from the kotanin biosynthetic gene cluster was used to identify in silico a similar gene cluster in the genome of Emericella desertorum, a producer of desertorin A, the 6,8'-regioisomer of orlandin. The cytochrome P450 enzyme DesC was also expressed in S. cerevisiae and was found to regio- and stereoselectively catalyze the coupling of 7-demethylsiderin to M-desertorin A. Our results show that fungi use highly specific cytochrome P450 enzymes for regio- and stereoselective phenol coupling. The enzymatic activities of KtnC and DesC are relevant for an understanding of the mechanism of this important biosynthetic step. These results suggest that bimolecular phenoxy radical couplings in nature can be catalyzed by phenol-coupling P450 heme enzymes, which might also apply to the plant kingdom.
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                Author and article information

                Contributors
                Role: ND
                Role: ND
                Role: ND
                Role: ND
                Role: ND
                Role: ND
                Role: ND
                Role: ND
                Role: ND
                Journal
                ce
                Cerâmica
                Cerâmica
                Associação Brasileira de Cerâmica (São Paulo )
                1678-4553
                December 2015
                : 61
                : 360
                : 477-481
                Affiliations
                [1 ] Universidade Federal de Santa Maria Brazil
                [2 ] Universidade Federal do Pampa Brazil
                Article
                S0366-69132015000400477
                10.1590/0366-69132015613601925
                b8981f5c-6470-47b8-99ef-5bc4fc435777

                http://creativecommons.org/licenses/by/4.0/

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                SciELO Brazil

                Self URI (journal page): http://www.scielo.br/scielo.php?script=sci_serial&pid=0366-6913&lng=en
                Categories
                MATERIALS SCIENCE, CERAMICS

                Ceramics
                nickel aluminate,synthesis,characterization,chitosan,porous material,aluminato de níquel,síntese,caracterização,quitosana,material poroso

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