A radiopacidade e a resposta tecidual do cimento Portland (CP) acrescido de óxido de bismuto (OB) nas concentrações de 0, 15, 20, 30 e 50%, determinadas em peso, foram avaliadas. Para a análise da radiopacidade, foi seguida a norma ISO 6876/2001. A densidade radiográfica foi mensurada em milímetros de alumínio (mmAl) e a análise estatística realizada utilizando-se os testes de ANOVA e Tukey-Kramer (p<0,05). Para a análise da resposta tecidual foram selecionados 81 ratos albinos e cada um recebeu como implante, na região dorsal, dois tubos de polietileno preenchidos com os cimentos experimentais. Os ratos foram mortos após 15, 30 e 60 dias. Na análise microscópica foram avaliados dois parâmetros: células inflamatórias e fenômeno reparatório. Os escores foram determinados e submetidos à análise estatística, utilizando-se os testes não paramétricos de Kruskal-Wallis e Dunn (p<0,05). Os resultados demonstraram que os valores representativos da radiopacidade aumentaram, gradativamente, de acordo com a concentração de óxido de bismuto. A significância estatística foi verificada entre o CP/50%OB e os demais cimentos avaliados, e entre o CP puro e o CP/30%OB (p<0,05). A radiopacidade apresentada pelo CP puro foi abaixo do mínimo (3 mmAl) recomendado pelas normas nº 57 da ADA e da ISO 6876/2001. Na análise da resposta tecidual, em relação à intensidade do infiltrado inflamatório, ocorreu diminuição de 15 para 30 dias e de 15 para 60 dias, com significância estatística (p<0,05), apenas para o grupo II nos dois intervalos de tempos. Com referência ao fenômeno reparatório ocorreu, em geral, para todos os grupos aumento do tecido fibrocelular, do período de 15 para o de 60 dias. Os resultados obtidos permitiram concluir que 15 a 20% de óxido de bismuto é suficiente para proporcionar ao CP a radiopacidade mínima recomendada pelas normas ADA e ISO. A diminuição do infiltrado inflamatório associada ao aumento do tecido fibrocelular, fundamentam a ausência de citotoxicidade do óxido de bismuto incorporado ao CP. / The aim of the study was to evaluate the radiopacity and subcutaneous tissue response of Portland cement (PC) with different concentrations of bismuth oxide (BO). PC was mixed with 0, 15, 20, 30 and 50% of BO determined in weight. The radiopacity was performed according to the ISO 6876/2001 standard for dental root canal sealing materials Statistical analysis was performed using ANOVA and Tukey-Kramer tests (p<0.05). For biocompatibility test, eighty-one albino rats (Rattus norvegicus) were selected. Two subcutaneous pockets were created in animal dorsum and polyethylene tubes filled with the cements were implanted. The rats were sacrificed at 15, 30 and 60 days after implantation. Histological evaluations were classified according to inflammatory response and repair process and scores were established. Statistical analysis was performed using the Kruskal-Wallis and Dunn tests (p<0.05). The results showed that there were statistical differences in radiopacity among PC with 50% of BO and all the other evaluated concentrations (p<0.05). Also, there was statistical difference between PC with 30% of BO and PC without BO (p<0.05). No statistical differences were found for inflammatory response in all the evaluated groups in each period (p>0.05). For repair process evaluation was observed a significant increase in fiber cellular tissue through the periods for all the groups (p<0.05). The tests suggested that 15 to 20% of BO added to PC attended ISO requirements for radiopacity. For biological response, there were decreases in the inflammatory response associated with an increase in the repair process, suggesting the lack of toxicity of BO added to PC.

Neste trabalho foram realizados a síntese, o crescimento e a caracterização de cristais de Bi 12Ti1-xGaxO20 (BTGaO) para avaliar suas potencialidades tecnológicas em dispositivos do estado sólido, especificamente para registros holográficos. Através da síntese do estado sólido, foi possível determinar um limite máximo de 20% utilizando uma forma estequiométrica de substituição. Considerando a não-estequiometria do sistema Bi2O3:Ga2O3 obtivemos soluções sólidas completas. Os cristais de B12Ti1-xGaxO20 (BTGaO)foram obtidos pelo método de TSSG (Top Seed Solution Growth), utilizando como solvente excesso de Bi2O3 . Cristais de boa qualidade óptica e estrutural foram crescidos utilizando-se taxas de puxamento de 0,2 0,3 mm/h e rotação de 5- 30 rpm . Das medidas de composição dos cristais realizadas por microssonda (EDS) foi possível determinarmos o coeficiente de segregação efetivo do Ga em Bi12TiO20 como sendo maior do que um. Por meio de análise térmica diferencial (DTA) foi possível verificar que a temperatura de fusão diminui de acordo com os diferentes níveis de substituição. Verificamos que a introdução do Ga na matriz de BTO aumenta a atividade óptica (BTO puro de 6.4&#176;/mm; BTGaO-30% de substituição de 9.8&#176;/mm) e para o BGaO nominalmente puro encontramos um valor da ordem de 150% maior (15.9&#176;/mm). A corrente no escuro aumentou em quatro ordens de grandeza (ID=10-9 A) em relação àquela presente nos cristais de BTO nominalmente puro (ID=10-13 A) enquanto nenhuma fotocorrente foi detectada. O coeficiente de absorção óptica diminuiu em todo espectro visível e o coeficiente eletroóptico não apresentou variação significativa (5,20pm/V para o BTO e 5,4 - 5,6pm/V para os cristais de BTGaO). A análise das propriedades ópticas indicam que os cristais de Bi12Ti1-xGaxO20 são inadequados para registros holográfico no vermelho. Porém sua maior transparência na região do espectro visível pode qualificá-lo como um novo meio para dispositivos optoeletrônicos / In this work the synthesis, the growth and crystal characterization of Bi 12Ti1-xGaxO20 (BTGaO) have been carried out to evaluate its technological potentialities in solid state devices, specifically for holographic recorders. Through the synthesis of the solid state, it was possible to determine a maximum limit of 20% using an stoichioinetric form of substitution. Considering the non-stoichiometry of the Bi2O3:Ga203 system we got full solid solutions. The crystals of BTGaO have been gotten by the TSSG method (Top Seed Solution Growth), using as solvent excess of BiO3. Crystals with good optic and structural quality have been grown using pulling rates of 0.2-0.3 mm/h and rotation of 5-30rpm. From the measures of composition through microprobe(EDS) in crystals, it was possible to determine the effective coefficient of segregation of Ga in Bi12TiO20 as being bigger than one. By means of differential thermal analysis (DTA), it was possible to verify that the melting temperature diminishes in accordance with the different leveis of substitution. We verify the introduction of Ga in the host of BTO increases the optical activity (in pure BTO = 6.4&#176;/mm; 9.8&#176;/mm 30% of substitution) and for nominally pure BGaO vve find a value 150% higher (15.9&#176;/mm). The dark current increase in four orders of magnitude (ID=10-9 A) in relation to crystals of pure BTO (ID=10-13 A) while not any photocurrent was detected. The optical absorption coefficient diminishes in ali visible spectrum. The electrooptical coefficient did not present significant variation (5.20pm/V for BTO and 5.4-5.6pm/V for crystals of BTGaO). The analysis of the optical properties indicates that the crystals of Bi12Ti1-xGaxO20 are inadequate for holographic recorders. However its bigger transparency in the region of the visible specter can chancterize it as new medium for optoeletronical devices

Neste trabalho foram realizados a síntese, o crescimento e a caracterização de cristais de Bi 12Ti1-xGaxO20 (BTGaO) para avaliar suas potencialidades tecnológicas em dispositivos do estado sólido, especificamente para registros holográficos. Através da síntese do estado sólido, foi possível determinar um limite máximo de 20% utilizando uma forma estequiométrica de substituição. Considerando a não-estequiometria do sistema Bi2O3:Ga2O3 obtivemos soluções sólidas completas. Os cristais de B12Ti1-xGaxO20 (BTGaO)foram obtidos pelo método de TSSG (Top Seed Solution Growth), utilizando como solvente excesso de Bi2O3 . Cristais de boa qualidade óptica e estrutural foram crescidos utilizando-se taxas de puxamento de 0,2 0,3 mm/h e rotação de 5- 30 rpm . Das medidas de composição dos cristais realizadas por microssonda (EDS) foi possível determinarmos o coeficiente de segregação efetivo do Ga em Bi12TiO20 como sendo maior do que um. Por meio de análise térmica diferencial (DTA) foi possível verificar que a temperatura de fusão diminui de acordo com os diferentes níveis de substituição. Verificamos que a introdução do Ga na matriz de BTO aumenta a atividade óptica (BTO puro de 6.4&#176;/mm; BTGaO-30% de substituição de 9.8&#176;/mm) e para o BGaO nominalmente puro encontramos um valor da ordem de 150% maior (15.9&#176;/mm). A corrente no escuro aumentou em quatro ordens de grandeza (ID=10-9 A) em relação àquela presente nos cristais de BTO nominalmente puro (ID=10-13 A) enquanto nenhuma fotocorrente foi detectada. O coeficiente de absorção óptica diminuiu em todo espectro visível e o coeficiente eletroóptico não apresentou variação significativa (5,20pm/V para o BTO e 5,4 - 5,6pm/V para os cristais de BTGaO). A análise das propriedades ópticas indicam que os cristais de Bi12Ti1-xGaxO20 são inadequados para registros holográfico no vermelho. Porém sua maior transparência na região do espectro visível pode qualificá-lo como um novo meio para dispositivos optoeletrônicos / In this work the synthesis, the growth and crystal characterization of Bi 12Ti1-xGaxO20 (BTGaO) have been carried out to evaluate its technological potentialities in solid state devices, specifically for holographic recorders. Through the synthesis of the solid state, it was possible to determine a maximum limit of 20% using an stoichioinetric form of substitution. Considering the non-stoichiometry of the Bi2O3:Ga203 system we got full solid solutions. The crystals of BTGaO have been gotten by the TSSG method (Top Seed Solution Growth), using as solvent excess of BiO3. Crystals with good optic and structural quality have been grown using pulling rates of 0.2-0.3 mm/h and rotation of 5-30rpm. From the measures of composition through microprobe(EDS) in crystals, it was possible to determine the effective coefficient of segregation of Ga in Bi12TiO20 as being bigger than one. By means of differential thermal analysis (DTA), it was possible to verify that the melting temperature diminishes in accordance with the different leveis of substitution. We verify the introduction of Ga in the host of BTO increases the optical activity (in pure BTO = 6.4&#176;/mm; 9.8&#176;/mm 30% of substitution) and for nominally pure BGaO vve find a value 150% higher (15.9&#176;/mm). The dark current increase in four orders of magnitude (ID=10-9 A) in relation to crystals of pure BTO (ID=10-13 A) while not any photocurrent was detected. The optical absorption coefficient diminishes in ali visible spectrum. The electrooptical coefficient did not present significant variation (5.20pm/V for BTO and 5.4-5.6pm/V for crystals of BTGaO). The analysis of the optical properties indicates that the crystals of Bi12Ti1-xGaxO20 are inadequate for holographic recorders. However its bigger transparency in the region of the visible specter can chancterize it as new medium for optoeletronical devices

A radiopacidade e a resposta tecidual do cimento Portland (CP) acrescido de óxido de bismuto (OB) nas concentrações de 0, 15, 20, 30 e 50%, determinadas em peso, foram avaliadas. Para a análise da radiopacidade, foi seguida a norma ISO 6876/2001. A densidade radiográfica foi mensurada em milímetros de alumínio (mmAl) e a análise estatística realizada utilizando-se os testes de ANOVA e Tukey-Kramer (p<0,05). Para a análise da resposta tecidual foram selecionados 81 ratos albinos e cada um recebeu como implante, na região dorsal, dois tubos de polietileno preenchidos com os cimentos experimentais. Os ratos foram mortos após 15, 30 e 60 dias. Na análise microscópica foram avaliados dois parâmetros: células inflamatórias e fenômeno reparatório. Os escores foram determinados e submetidos à análise estatística, utilizando-se os testes não paramétricos de Kruskal-Wallis e Dunn (p<0,05). Os resultados demonstraram que os valores representativos da radiopacidade aumentaram, gradativamente, de acordo com a concentração de óxido de bismuto. A significância estatística foi verificada entre o CP/50%OB e os demais cimentos avaliados, e entre o CP puro e o CP/30%OB (p<0,05). A radiopacidade apresentada pelo CP puro foi abaixo do mínimo (3 mmAl) recomendado pelas normas nº 57 da ADA e da ISO 6876/2001. Na análise da resposta tecidual, em relação à intensidade do infiltrado inflamatório, ocorreu diminuição de 15 para 30 dias e de 15 para 60 dias, com significância estatística (p<0,05), apenas para o grupo II nos dois intervalos de tempos. Com referência ao fenômeno reparatório ocorreu, em geral, para todos os grupos aumento do tecido fibrocelular, do período de 15 para o de 60 dias. Os resultados obtidos permitiram concluir que 15 a 20% de óxido de bismuto é suficiente para proporcionar ao CP a radiopacidade mínima recomendada pelas normas ADA e ISO. A diminuição do infiltrado inflamatório associada ao aumento do tecido fibrocelular, fundamentam a ausência de citotoxicidade do óxido de bismuto incorporado ao CP. / The aim of the study was to evaluate the radiopacity and subcutaneous tissue response of Portland cement (PC) with different concentrations of bismuth oxide (BO). PC was mixed with 0, 15, 20, 30 and 50% of BO determined in weight. The radiopacity was performed according to the ISO 6876/2001 standard for dental root canal sealing materials Statistical analysis was performed using ANOVA and Tukey-Kramer tests (p<0.05). For biocompatibility test, eighty-one albino rats (Rattus norvegicus) were selected. Two subcutaneous pockets were created in animal dorsum and polyethylene tubes filled with the cements were implanted. The rats were sacrificed at 15, 30 and 60 days after implantation. Histological evaluations were classified according to inflammatory response and repair process and scores were established. Statistical analysis was performed using the Kruskal-Wallis and Dunn tests (p<0.05). The results showed that there were statistical differences in radiopacity among PC with 50% of BO and all the other evaluated concentrations (p<0.05). Also, there was statistical difference between PC with 30% of BO and PC without BO (p<0.05). No statistical differences were found for inflammatory response in all the evaluated groups in each period (p>0.05). For repair process evaluation was observed a significant increase in fiber cellular tissue through the periods for all the groups (p<0.05). The tests suggested that 15 to 20% of BO added to PC attended ISO requirements for radiopacity. For biological response, there were decreases in the inflammatory response associated with an increase in the repair process, suggesting the lack of toxicity of BO added to PC.

The thesis entitled “Variants of Complex Bismuth and Zirconium Oxides: Structure-Property Correlation Studies” consists of five chapters. A short introductory note outlines the synthetic procedures, characterization techniques and evaluated properties such as photocatalysis, second harmonic generation, ionic conductivity and thermal expansion in these materials. Chapter 1 deals with a new solid solution Pb3-xBi2x/3V2O8 (0.20 ≤ x ≤ 0.50), stabilizing the high temperature γ form of Pb3V2O8 in the system Pb3V2O8−BiVO4. Single-crystals of the composition x = 0.50 were grown and the structure is a new variant in palmierite structural type as determined by both single crystal X-ray and powder neutron diffraction. Several refinement strategies backed up by difference Fourier methods were used to arrive at the final crystal structure. ac impedance studies indicate conductivity of the order of 10-4 Ω-1 cm-1 for Pb2.5Bi1/3V2O8. Chapter 2 has two sections and describes the structure property correlation in bismuth based vanadate and phosphate eulytites. Section 2.1 discusses the crystal structure of Pb3Bi(VO4)3, the first eulytite compound containing [VO4]3- moieties. The compound displays incongruent melting behavior. Single-crystals were grown by melt-cool technique adding excess amount of BiVO4. The crystal structure has been characterized by both X-ray and neutron diffraction studies. Section 2.2 describes the crystal structures of four phosphate eulytites A3Bi(PO4)3 ( A = Ca, Cd, Sr, Pb). The crystals were grown from melt-cool technique with considerable difficulty as the compounds melt incongruently. While Pb3Bi(VO4)3 and Pb3Bi(PO4)3 have an unique position for one of the oxygen atoms, Sr3Bi(PO4)3, Ca3Bi(PO4)3, Cd3Bi(PO4)3 display split oxygen atomic sites. The SHG efficiencies measured on polycrystalline samples were 5.3, 3.8, 2.85, 1.21 and 0.64 times that of KDP (KH2PO4) for Pb3Bi(VO4)3, Cd3Bi(PO4)3, Sr3Bi(PO4)3, Pb3Bi(PO4)3 and Ca3Bi(PO4)3 respectively. Chapter 3 describes the isolation of the compound Sr2Bi2/3V2O8, a variant palmierite, in the phase diagram of SrO-Bi2O3-V2O5. The compound was synthesized by ceramic method and it is of interest to note that the Sr(1) site also accommodates Bi as found by single crystal X-ray studies unlike that found in the case described in chapter 1. Chapter 4 has two sections, dealing with synthesis, characterization and photocatalytic properties of trigonal and monoclinic polymorphs of ZrMo2O8, a negative thermal expansion material in its cubic form. Section 4.1 describes the synthesis of trigonal polymorph of ZrMo2O8 by both ceramic and combustion synthesis methods. SEM images show a particle size of 40-50 nm for combustion synthesized samples and 8-10 μm for solid state synthesized ZrMo2O8. The band gap obtained by UV-visible diffuse reflectance spectra for the combustion synthesized and solid state synthesized samples were 2.70 and 2.74 eV and the BET surface area were 1.0 m2/g and 10.0 m2/g. DFT electronic structure calculations reveal the indirect band gap nature of this polymorph. Photo-degradation studies performed on pollutant water show specific affinity to degrade dyes which do not possess anthraquinonic moieties. Section 4.2 describes the single-crystal structure determination and catalytic properties of monoclinic polymorph of ZrMo2O8. The band gap measured for the monoclinic form by UV-visible diffuse reflectance spectra was 2.57 eV. This polymorph was found to be specific towards the degradation of cationic dyes. Chapter 5 discusses a new solid solution ZrV2-xMo5x/6O7 (0 ≤ x ≤ 0.8) identified in the phase diagram of ZrO2−V2O5−MoO3. These compounds were synthesized via the solution combustion method. The resulting products were characterized by powder X-ray diffraction, solid-state UV-visible diffuse reflectance spectra, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The photo-catalytic activity shows specificity towards the degradation of non-azo dyes. Single-crystals were grown by melt-cool technique from the starting materials with twice the MoO3 quantity. Since, these crystals belong to a cubic system, space group Pa 3, they were tested for negative thermal expansion using variable temperature single-crystal XRD and indeed they exhibit this property above 370 K.

This study considered bismuth (III) oxide (Bi2O3) and antimony hexitatridecoxide (Sb6O13) as potential substitutes for the red lead (Pb3O4) and barium sulphate (BaSO4) oxidants currently used in time delay compositions for detonator assemblies. Fine silicon powders with a specific surface area of 2 - 10 m2/g were used as fuels. Some experiments were also done with a coarse manganese powder as fuel. Bi2O3 was synthesised by the thermal decomposition of (BiO) 2CO3 by heating at 460°C for 15 hours. The yield was near quantitative, ie. close to the 91,4% expected based on the complete conversion of the carbonate to the oxide. Sb6O13 was obtained by heating colloidal antimony pentoxide (Sb2O5) for 8 hours at 315°C. This resulted in a ca. 20 % mass loss and yielded a reactive black powder. In the Si-Bi2O3 system, compositions in the range 5 - 40% by mass Si were ignitable with shock tubing. Burn rates measured in lead tubes varied between 15 and 155 mm/s. This highest burn rate was obtained with 20% silicon. Addition of additives such as KMnO4 and boric oxide had little effect on the burn rate. The fast burning Si-Bi2O3 system is a potential replacement for the commercial Si - red lead system. The burning rate decreased with increasing compaction of the samples. Burn rate also decreased when the aluminium instead of lead tubes were used. This is attributed to a greater heat loss with the former. The combustion products were characterised using DTA, FT-IR, XRD and SEM. The results show that the combustion reactions led to reduction of the oxidant to the corresponding metal form. The Sb6O13-Si system requires an initiating composition such as Bi2O3-50%Si (Type 4). It is slow burning and thus a possible replacement for the commercial BaS04-Si system. The lowest sustainable and reproducible burn rate, in the absence of additives, was 4,8 mm/s. It was achieved using 10% silicon Type 4. Adding small amounts of fumed silica <2%) increased the burn rate. This is attributed to better mixing and compaction. However, lower burn rates (~2 mm/s) are possible if more fumed silica is added as inert diluent. Replacing the silicon fuel with manganese powder gave more exothermic and even slower burning compositions. / Dissertation (MSc)--University of Pretoria, 2008. / Graduate School of Technology Management (GSTM) / unrestricted

No description available.

Mit der vorliegenden Arbeit wurden neue Erkenntnisse bei der Aufklärung der Mechanismen, die für die Reaktivität von Übergangsmetall- und Metalloxid-Clustern verantwortlich sind, gewonnen. Dies ist aus zwei Gründen gelungen: Zum einen erlaubt die gradienten-korrigierte Dichtefunktional-Methode eine zuverlässige Beschreibung von strukturellen und energetischen Eigenschaften dieser Cluster, insbesondere durch die Entwicklung einer neuen Generation von Hybrid-Austausch- und Korrelations-Funktionalen im Rahmen der verallgemeinerten Gradienten-Näherung. Diese wurden erstmalig in entsprechenden quantenchemischen Programmen implementiert und getestet. Zum zweiten stellte die fruchtbare Zusammenarbeit mit den experimentellen Bereichen, eine Herausforderung für die Theorie dar, mittels der gewonnenen Erkenntnisse zur konzeptionellen Planung der Experimente beizutragen (A. Fielicke, Dissertation, Humboldt-Universität zu Berlin, 2001). / In this work the transition metal and metal oxide clusters has been investigated with the aim of gaining a better insight into the mechanisms which govern their reactivity. The theoretical study of the structural and energetic properties of the clusters has been carried out within the framework of the density functional theory by means of a new family of gradient-corrected hybrid density functionals which has been coded for the first time into quantum chemistry packages. The theoretical findings stimulated the experimental investigation of the gas phase reactivity of these species which confirmed the correctness of the reaction mechanism models proposed (A. Fielicke, Doctoral Thesis, Humboldt-Universität zu Berlin, 2001).

Nanoporous metal represents a particular form of a metal, which combines the characteristics of metals, such as good thermal and electrical conductivity, catalytic activity with the materials properties characteristic of nanoporosity, which include high surface area, low density, large number of pores, etc. Nanoporous metals have applications in various fields such as catalysis, hydrogen storage, electrochemical sensing, membranes, SERS, and supercapacitors. The three dimensional porous structures offer high specific surface area and large pore volumes, which enhance substrate diffusion within the porous structures and provide a large number of surface active sites for catalytic applications. However, synthesis of nanoporous metal based on conventional approach (template assisted synthesis and dealloying) suffers from scalability issue, specific for few metals, additional synthetic steps etc. Challenges still remain in this field to fabricate three dimensional porous metals where pores are interconnected (bicontinuous). Recently, development of the synthesis of nanoporous metal got a thrust by the advent of the concept of assembly of nanoparticles in either an ex-situ or in an in-situ manner. Objectives 1. Establish the synthetic strategy of metal nanosponge formation by capping agent dissolution method (ex-situ assembly) 2. Explore the catalytic activity of these metal nanosponges towards 4-nitrophenol reduction and alkene hydrogenation reactions 3. Elucidate the mechanism of formation of metal nanosponge in solution state (kinetic in-situ assembly of nanoparticles) using ammonia borane as a reducing agent in water under different conditions 4. Investigate the hydrogen storage properties and catalytic arene hydrogenation activities of metal nanosponges 5. Synthesis of bismuth oxide nanosponge using bismuth nanosponge as a template. Study of the photocatalytic dye degradation behavior using bismuth oxide nanosponge under visible light irradiation Significant results Synthesis of metal nanosponges was carried out using capping agent dissolution method wherein addition of water to M@BNHx polymer gives metal nanosponges. The B-H bond of BNHx polymer is unstable in the presence of water and gets hydrolyzed to give hydrogen gas bubbles which act as dynamic templates for the formation of metal nanosponges. The pristine nature of the surface of these metal nanosponges was elucidated by several analytical techniques. The catalytic activity of these metal nanosponges (Ag, Au, Pd, Pt, and Cu) was demonstrated using 4-nitrophenol reduction reaction in the presence of sodium borohydride as a reducing agent. Iridium nanosponge was obtained by capping agent dissolution method from Ir@BNHx polymer. Mesoporous high surface area iridium nanosponge was found to be an active catalyst for alkene hydrogenation reaction, whereas Ir@BNHx polymer does not exhibit any catalytic activity under similar reaction conditions. The effects of temperature, solvent, substrate to catalyst ratio, and pressure on catalyst activity were established using styrene as a substrate. The thermal stability (up to 300 oC) and robustness over several cycles were demonstrated for the iridium nanosponge. Several alkenes (linear alkene, cycloalkane, and conjugated alkene) were successfully hydrogenated using iridium nanosponge at room temperature and 4 bar hydrogen pressure. Generality of the synthetic procedure was explored by using different iridium precursors which gave iridium nanosponges exhibiting similar catalytic activity. Silver, gold, palladium, platinum, and copper nanosponges have been synthesized by chemical reduction method (in-situ kinetic assembly of nanoparticles) using ammonia borane as a reducing agent in water as a solvent. The effect of variables (metal salt to amine borane ratio, concentration of the reactants, solvent, temperature, and reducing agent) were thoroughly investigated using the silver system as a model. In the absence of a capping agent, metal salt reduction was carried out using amine borane which forms nanoparticles. In a high dielectric solvent, the colloidal particles attach together to form agglomerates. During the course of the reaction, hydrogen gas bubbles were generated which produce pores within the agglomerates leading to the formation of three dimensional nanosponge structures. Finally, the hydrogen storage properties (pressure composition isotherm and sorption kinetics) of these metal nanosponges were investigated under different conditions. These metal nanosponges exhibit reasonable, reversible storage characteristics: Ag (3 wt%), Pd (5.5 wt%), Pt (6 wt%), and Cu (2.5 wt%). Phase selective ruthenium nanosponge was synthesized using chemical reduction method. It was found that amine borane as a reducing agent for certain ruthenium precursors results in the hcp phase of ruthenium whereas, reduction using sodium borohydride affords fcc phase of ruthenium. Hcp and fcc phases of ruthenium were established using electron and X-ray diffraction methods. Surface characterization technique showed the pristine nature of ruthenium nanosponge. Both hcp and fcc ruthenium nanosponges were employed as catalysts for hydrogenation of benzene; it was found that hcp ruthenium is more active than fcc ruthenium for benzene hydrogenation to cyclohexane. Substrate to catalyst ratio, temperature, hydrogen pressure, and solvent effect were thoroughly investigated using benzene as a model substrate. It was found that hcp ruthenium nanosponge is capable of hydrogenating a variety of alkyl substituted benzenes under ambient conditions. The catalyst was found to be active over several cycles without any loss in its activity. Phosphine was used as a catalyst poison and hot filtration test was performed separately to show the true heterogeneous nature of the active catalyst. Hydrogen storage experiments were performed to understand the interaction of hydrogen with different phases of ruthenium. Bismuth nanosponge was synthesized using chemical reduction method. Synthesis of different polymorphs of bismuth oxide nanosponges (tetragonal, monoclinic and body centered cubic) were carried out by calcination of bismuth nanosponge at different temperature (300 oC, 500 oC, and 800 oC). The phase purity of bismuth oxide nanosponges were established using X-ray and electron diffraction method. It was found that surface area decreases with increasing the calcination temperature. Tetragonal bismuth oxide (300 oC annealed sample) nanosponge shows the highest photocatalytic activity as compared to other polymorphs. Mechanistic investigation suggests that hole and hydroxyl radical are responsible for dye degradation. Recyclability study demonstrated the formation of bismuth oxycarbonate which leads to a drop in catalytic activity. However, the tetragonal phase of bismuth oxide with high catalytic activity could be regenerated upon annealing at 300 oC for 3 h.

No description available.