a b s t r a c t Keywords: Palygorskite TiO 2 Photocatalysis Inorganic-inorganic nanocomposites Orange G pollutantThis study deals with the synthesis of TiO 2 supported Moroccan palygorskite fibers and their use as photocatalyst for the removal of Orange G pollutant from wastewater. The TiO 2 -palygorskite nanocomposite synthesis was accomplished according to a colloidal route involving a cationic surfactant as template (hexadecyltrimethylammonium bromide) assuring hence organophilic environment for the formation of TiO 2 nanoparticles. The clay minerals samples were characterized before and after functionalization with TiO 2 . Anatase crystallizes above ca. 450°C and remarkably remains stable up to 900°C. In contrast, pure TiO 2 xerogel obtained from titanium tetraisopropoxide (TTIP) showed before calcination a nanocrystalline structure of anatase. By increasing the temperature, anatase readily transforms into rutile beyond 600°C. The remarkable stability at high temperature of anatase particles immobilized onto palygorskite microfibers was due to the hindrance of particles growth by sintering. Homogeneous monodisperse distribution of anatase particles with an average size of 8 nm was found by TEM and XRD onto palygorskite fibers. This anatase particle size remains below the nucleus critical size (ca. 11 nm) required for anatase-rutile transition. The TiO 2 supported palygorskite sample annealed in air at 600°C for 1 h exhibits the highest photocatalytic activity towards the degradation of Orange G compared to nanocomposite samples prepared under different conditions as well as pure TiO 2 powders obtained from the xerogel route or commercially available as Degussa P25.
Ceramic clays are among the most complicated of ceramic systems because of the very intricate relationship between the behavior of minerals during ceramic processing and their modifications during heating. A major challenge is to predict the phase changes in clay ceramics. The aims of this study were to establish reference data of ceramic products that can be formed based on the mineralogical compositions of the local raw materials. These data, in turn, can be compared with archeological ceramics in order to study their origins.The mineralogical compositions and modifications during firing (550–1100°C under oxidizing conditions) of seven clayey materials sampled from the main clay deposits of northern Morocco were evaluated by X-ray powder diffraction. Two groups of clays were distinguished according to the type of neoformed high-temperature minerals: non-calcareous clays and calcareous clays. For the non-calcareous raw materials, spinel was produced at 950°C. Cristobalite and mullite were formed at temperatures in excess of 1000°C from clays that contain illite, kaolinite, and chlorite. In clays containing vermiculite and large amounts of chlorite, hematite was formed at temperatures in excess of 950°C. Firing of calcareous clays at temperatures >950°C yielded Ca-silicates (diopside, gehlenite and wollastonite), spinel, cristobalite, hematite, and feldspars. Mullite may also form in the calcareous clay products when the carbonate content exceeds 10%.
International audienceThis study is devoted to the physicochemical and mineralogical characterizations of palygorskite from Marrakech High Atlas, Morocco. The raw clay and its Na?-saturated\ 2 lm fraction were characterized using chemical, structural, and thermal analytical techniques. Measurements of specific surface area and porous volume are reported. The clay fraction was found to be made up of 95 %of palygorskite and 5 % of sepiolite. An original feature of this palygorskite is its deficiency in zeolitic H2O. The half-cell structural formula of its dehydrated form was determined on the basis of 21 oxygens to be (Si7.92Al0.08)(Mg2.15Al1.4Fe0.4Ti0.05h1)(Ca0.03 Na0.08K0.04)O21, while the hydrated form could be formulated as (Si7.97Al0.03)(Mg2.17Al1.46Fe0.40Ti0.05)(Ca0.03Na0.07K0,03) O20.18(OH)1.94(OH2)3.8812.43H2O. These formulas showthat the (Al3??Fe3?)/Mg2? ratio is around 0.84, revealing a pronounced dioctahedral character. Further, inside its octahedral sheet, it was determined that the inner M1 sites are occupied by vacancies, whereas the M2 sites are shared between 90 % of trivalent cations (78 % for Al3? and 22 % for Fe3?), 7.5 % of Mg2+, and 2.5 % of Ti4+, all of them linked to 1.94 of structural hydroxyls. The two remaining Mg2+ by half-cell occupy edge M3 sites and are coordinated to 3.88 molecules of OH2. Channels of this palygorskite are deficient in zeolitic H2O since they contain only 2.43 H2O molecules.A correlation was found between these results and the observation of very intense and well-resolved FTIR bands arising from dioctahedral domains (mainly Al2OH, Fe2OH, and AlFeOH) along with very small responses from a trioctahedral domain (Mg3OH). Accordingly, a schematic representation of the composition of the octahedral sheet was proposed. The cation exchange capacity, specific surface area, and total pore volume were also assessed to be ca. 21.2 meq/100 g, 116 m2/g, and 0.458 cm3/g, respectively
The composition of Rhassoul clay is controversial regarding the nature of the pure-mineral clay fraction which is claimed to be stevensite rather than saponite. In this study, the raw and mineral fractions were characterized using various techniques including Fourier transform infrared spectroscopy and magic angle spinning nuclear magnetic resonance (MAS NMR). The isolated fine clay mineral fraction contained a larger amount of Al (>1 wt.%) than that reported for other stevensite occurrences. The 27Al MAS NMR technique confirmed that the mineral is stevensite in which the Al is equally split between the tetrahedral and octahedral coordination sites. The 29Si NMR spectrum showed a single unresolved resonance indicating little or no short-range ordering of silicon. The chemical composition of the stevensite from Jbel Rhassoul was determined to be ((Na0.25K0.20)(Mg5.04Al0.37Fe0.20☐0.21)5.61(Si7.76Al0.24)8O20(OH)4). This formula differs from previous compositions described from this locality and shows it to be an Al-bearing lacustrine clay mineral.
This study focuses on the mineralogical and geotechnical characterization of northern Moroccan clays from the Tangier and Tetouan areas and compares them with the main clay deposits used in the Moroccan ceramic industry (from Meknes, Fes, Salé and Safi regions). Sampled clays were analysed by X-ray diffraction on bulk and clay (<2 μm) fractions to identify the mineralogical assemblages of the clay outcrops. Further analyses were conducted to determine the particle size distribution (laser diffraction particle analyser), the total organic matter content (Loss- On-Ignition measurements) and the Atterberg limits of the raw clays. The study aims at investigating the spatial variability of the clay samples and at evaluating their potential application as raw materials in the ceramic industry.Tetouan and Tangier clays are characterized by diversified mineralogical assemblages (in particular a variable proportion of clay, quartz and calcite) compared with the Meknes, Fes, Salé and Safi clays (high clay content, quartz and calcite). The clay fraction of the Tetouan and Tangier samples is dominated by illite and kaolinite with variable amounts of chlorite, smectite and/or vermiculite. Illite is the dominant phase in the Meknes, Fes, Safi and Salé clays, but is associated with kaolinite. No direct relationship between the mineral assemblage composition and the lithology of the series was found.The clays materials studied consist generally of fine particles with medium to high plasticity and low organic matter content. Due to their mineralogy, grain-size distribution and plasticity the clays appear to be suitable as raw material for the growing Morocco ceramic industry.
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