27 research outputs found
Hydrogenation of Acetophenone in the Presence of Ru Catalysts Supported on Amine Groups Functionalized Polymer
Titania-Clay Mineral Composites for Environmental Catalysis and Photocatalysis
The use of titania-based composite materials in the field of heterogeneous catalysis and photocatalysis has a long and rich history. Hybrid structures combining titania nanoparticles with clay minerals have been extensively investigated for nearly four decades. The attractiveness of clay minerals as components of functional materials stems primarily from their compositional versatility and the possibility of using silicate lamellae as prefabricated building blocks ready to be fitted into the desired nanoconstruction. This review focuses on the evolution over the years of synthetic strategies employed for the manufacturing of titania–clay mineral composites with particular attention to the role of the adopted preparative approach in shaping the physical and chemical characteristics of the materials and enabling, ultimately, tuning of their catalytic and/or photocatalytic performance
Rehydration Driven Na-Activation of Bentonite—Evolution of the Clay Structure and Composition
A new method of Na-activation of raw bentonite, rich in Ca-montmorillonite, consisting of combined thermal treatment at 200 °C, followed by immediate impregnation with aqueous solution of Na2CO3 of concentration corresponding to 0.5, 1.0, 1.5, or 2.0 cation exchange capacity (CEC) of clay, was investigated. Structural and compositional evolution of the activated solids after 1, 2, 3, and 4 weeks of storage was monitored by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). XRD analysis indicated that within the investigated period of ageing transformation to Na-rich montmorillonite required Na2CO3 concentration of at least 1.0 CEC. FTIR spectra showed that, depending on the Na2CO3 concentration and ageing time, formation of Na-rich montmorillonite was accompanied by precipitation of poorly crystalline calcite, amorphous calcium carbonate, gaylussite (a double calcium-sodium carbonate), and portlandite (Ca(OH)2)
Composites of Montmorillonite and Titania Nanoparticles Prepared by Inverse Microemulsion Method: Physico-Chemical Characterization
TiO2/montmorillonite composites were synthesized using inverse micellar route for the preparation of titania nanoparticles (4–6 nm diameter) in 1-hexanol and for the dispersion of one of the clay components. Two series of composites were obtained: one derived from cetyltrimethylammonium organomontmorillonite (CTA-Mt), exfoliated in 1-hexanol, and the other from sodium form of montmorillonite (Na-Mt) dispersed by formation of an inverse microemulsion in 1-hexanol. The TiO2 content ranged from 16 to 64 wt.%. The composites were characterized with X-ray diffraction, scanning/transmission electron microscopy/energy dispersive X-ray spectroscopy, thermal analysis, and N2 adsorption-desorption isotherms. The Na-Mt-derived component was shown to undergo transformation to CTA-Mt, as indicated by basal spacing of 17.5 nm, due to the interaction with the CTABr surfactant in inverse microemulsion. It was also better dispersed and intermixed with TiO2 nanoparticles. As a result, the TiO2/Na-Mt series displayed superior textural properties, with specific surface area up to 256 m2g−1 and pore volume up to 0.247 cm3g−1 compared with 208 m2g−1 and 0.231 cm3g−1, respectively, for the TiO2/CTA-Mt counterpart. Members of both series were uniformly mesoporous, with the dominant pore size around 5 nm, i.e., comparable with the dimensions of titania nanoparticles. The advantage of the adopted synthesis method is discussed in the context of other preparative procedures used for manufacturing of titania-clay composites
Structural Transformations of Hydrolysates Obtained from Ti-, Zr-, and Ti, Zr-Solutions Used for Clay Pillaring: Towards Understanding of the Mixed Pillars Nature
Structural characteristics of hydrolysates formed from the aqueous Ti-, Zr-, and Ti, Zr-pillaring solutions prepared from inorganic precursors (TiCl4 and ZrOCl2), was investigated and compared with that of precipitates obtained from the same solutions after a slight alkalization of pH to the values reported for the conditions of clay pillaring. The materials were recovered by lyophilization and subsequently subjected to calcination at 500, 800 and 1000 °C. Of special interest was the effect of pH on the possible formation of mixed Ti, Zr-oxide species. Powder X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscope/energy dispersive spectrometer (SEM/EDS) analysis showed that even a relatively moderate alteration of pH in Ti-, Zr-, or Ti, Zr-precursor solutions caused substantial changes in the outcome of hydrolytic transformations, manifested by different phase and/or chemical composition of the resulting hydrolysates. Analysis of thermal evolution of hydrolysates showed that alkalization facilitated the transformation of anatase into rutile in materials obtained from Ti-pillaring solution, but retarded tetragonal to monoclinic zirconia conversion in samples derived from Zr-pillaring agent. The most striking effect was observed for the mixed Ti, Zr-pillaring solution, where an increase of pH enabled the formation of zirconium titanate as the only crystalline phase, rather than a multiphase mixture of anatase, monoclinic zirconia and zirconium titanate obtained from the more acidic precursor. The finding supports the model of mixed Ti-O-Zr network in props generated in Ti, Zr-pillared montmorillonites
Synthesis of Nanocrystalline Mg-Al Hydrotalcites in the Presence of Starch—the Effect on Structure and Composition
The study describes the synthesis of Mg-Al hydrotalcite (Ht) with the use of starch as a structure controlling biotemplate. Syntheses were carried out at room temperature, by co-precipitation at pH = 10. The investigated synthesis parameters included the nature of the precipitating agent (NaOH/Na2CO3 or NH3aq/(NH4)2CO3), the nature of starch (potato, corn and cassava), the method of starch addition to reagents, the method of drying and the effect of washing. The materials were examined with X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy and infrared spectroscopy. The data show that synthesis of Ht materials in the presence of starch, with use of the ammonia-based precipitant, enabled preparation of nanocrystalline Ht with very fine (<50 nm) particle size. All investigated starches had a similar effect on the crystallinity and the grain size of Ht precipitates. Ht with the smallest nanocrystals was obtained when starch was present in all solutions used for synthesis, and the final product subjected to freeze drying. Washing with water was found to enhance recrystallization and exchange of nitrates for carbonates. Infrared spectra showed that an interaction exists between the biopolymer template and the Ht particles, resulting in a higher degree of order within the Ht-adhering starch component
Keggin-Type Heteropoly Salts as Bifunctional Catalysts in Aerobic Baeyer-Villiger Oxidation
The cobalt, manganese, and iron salts of tungstophosphoric or molybdophosphoric acid with growing content of metals were applied for the first time as catalysts in the Baeyer-Villiger (BV) oxidation of cyclohexanone to ε-caprolactone with molecular oxygen. The catalysts were characterized with Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF), and ethanol decomposition reaction. Introduction of transition metals into the heteropoly structure increases the activity of resulting heteropoly salts in comparison with parent heteropolyacids. It was shown that the most active catalysts are salts of the heteropoly salts with one metal atom introduced and one proton left (HMPX) type, (where M = Co, Fe, Mn, and X = W, Mo) with the metal to proton ratio equal one. Among all of the studied catalysts, the highest catalytic activity was observed for HCoPW. The effect indicates that both the acidic and redox properties are required to achieve the best performance. The Baeyer-Villiger (BV) oxidation mechanism proposed identifies the participation of heteropoly compounds in three steps of the investigated reaction: oxidation of aldehyde to peracid (redox function), activation of carbonyl group (Lewis acidity), and decomposition of the Criegee adduct to ε-caprolactone (Brønsted acidity)
Waste into Fuel—Catalyst and Process Development for MSW Valorisation
The present review paper highlights recent progress in the processing of potential municipal solid waste (MSW) derived fuels. These wastes come from the sieved fraction (∅ < 40 mm), which, after sorting, can differ in biodegradable fraction content ranging from 5–60%. The fuels obtained from these wastes possess volumetric energy densities in the range of 15.6–26.8 MJL−1 and are composed mainly of methanol, ethanol, butanol, and carboxylic acids. Although these waste streams are a cheap and abundant source (and decrease the fraction going to landfills), syngas produced from MSW contains various impurities such as organic compounds, nitrogen oxides, sulfur, and chlorine components. These limit its use for advanced electricity generation especially for heat and power generation units based on high temperature fuel cells such as solid oxide fuel cells (SOFC) or molten carbonate fuel cells (MCFC). In this paper, we review recent research developments in the continuous MSW processing for syngas production specifically concentrating on dry reforming and the catalytic sorbent effects on effluent and process efficiency. A particular emphasis is placed on waste derived biofuels, which are currently a primary candidate for a sustainable biofuel of tomorrow, catalysts/catalytic sorbents with decreased amounts of noble metals, their long term activity, and poison resistance, and novel nano-sorbent materials. In this review, future prospects for waste to fuels or chemicals and the needed research to further process technologies are discussed
Fine Crystalline Mg-Al Hydrotalcites as Catalysts for Baeyer-Villiger Oxidation of Cyclohexanone with H2O2
The catalytic activity of Mg-Al hydrotalcite (HT) materials in base-catalyzed reactions is known to be promoted by the low crystallinity of the HT solid. In the present work, two routes enabling the preparation of finely crystalline Mg-Al HT materials were explored: (1) the inverse microemulsion technique, and (2) co-precipitation in the presence of starch. Carbonate, chloride and bromide forms of HT were prepared, examined with X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy and infrared spectroscopy, and used as catalysts in the Baeyer–Villiger oxidation of cyclohexanone to ε-caprolactone with a H2O2/acetonitrile system. The bromide forms proved significantly less active than the chlorides and carbonates, as they promoted nonselective consumption of H2O2. The fine crystalline materials were more active than the more crystalline HT references obtained by conventional co-precipitation. Catalysts prepared by inverse microemulsion were less crystalline and more active than the starch-templated ones, but suffered stronger deactivation by the acidic reaction environment. Alkalization of the reaction medium with NaHCO3 stabilized the HT materials and increased the ε-caprolactone yield, which became comparable for both types of fine crystalline catalysts—thus pointing to the synthesis involving a simple and cheap starch templating approach as being a particularly attractive one