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

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)

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

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

Removal of amoxicillin and ampicillin using manganese dioxide/montmorillonite composite

BACKGROUND Clay-based materials represent great potential for the development of efficient and environmentally friendly sorbents. The study focuses on a laboratory-obtained manganese dioxide/montmorillonite (MnO2/MMT) composite for removal of two types of antibiotics - amoxicillin (AMX) and ampicillin (AMP) - from aqueous solution. RESULTS The composite was successfully prepared using a reduction procedure involving the reaction between potassium permanganate (KMnO4) and hydrochloric acid (HCl) to form MnO2 followed by the addition of MMT. X-ray analysis, scanning electron microscopy, X-ray fluorescence and Fourier transform infrared spectroscopy were performed for characterization of physicochemical and structural properties, simultaneous thermogravimetry and differential scanning calorimetry for estimation of thermal stability and high-performance liquid chromatography for determination of antibiotic equilibrium concentrations in aqueous solution. The precipitated MnO2 component, manifested by long fibers, corresponded to the tunnel structure of cryptomelane. In the case of MnO2/MMT it is evident that MnO2 developed short fibers with the participation of the MMT matrix. The thermal data suggested that the MnO2 phase upon contact with the clay support showed better thermal stability. The final decomposition of Mn2O3 was shifted to higher temperature of 985 degrees C. Adsorption procedure in a batch regimen showed sufficient sorption ability for both antibiotics with over 90% efficiency. For AMP the value of q(max) was about 45 mg g(-1) and for AMX it was only 21 mg g(-1). CONCLUSIONS The results provided valuable information for the design of a potentially inexpensive clay-based adsorbent and demonstrated the removal of two types of broad-spectrum beta-lactam antibiotics from aqueous solution to a sufficient degree.Web of Scienc