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.

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

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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.

OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible. This is an author-deposited version published in : http://oatao.univ-toulouse.fr/ Eprints ID : 14098To link to this article :Abstract-The mechanism of formation of detrital, beidellite-rich clay occurring in the Agadir basin (Morocco) is well documented, but its detailed characterization is incomplete which limits its application. The aim of the present study was to provide further details of the mineralogical and physico-chemical characteristics of this clay. Bulk raw clay and its Na + -saturated, <2 mm fraction were characterized using chemical, structural, and thermal techniques. Measurements of induced streaming potential (e.g. particle charge) and of specific surface area and porous volume are reported. The raw clay contained carbonate and quartz as associated minerals along with phyllosilicates (<2 mm particle size). X-ray diffraction and scanning electron microscopy analyses showed that the <2 mm fraction was dominated by a dioctahedral smectite. Because dehydroxylation of this mineral occurred at 510ºC, and because it re-expanded in ethylene glycol after Li + -saturation followed by heating at 240ºC for 24 h, the mineral was shown to be a beidellite rather than montmorillonite. This assertion was further supported by 27 Al and 29 Si magic-angle spinning nuclear magnetic resonance spectra showing predominantly negative charges in the tetrahedral sheets due to notable Al-for-Si substitutions. The chemical composition of the <2 mm fraction showed an Fe 2 O 3 content which was~7.52 wt.% greater than those of other beidellite occurrences but not so much that it would be identified as a nontronite. The absence of stretching and bending absorption bands corresponding to characteristic (Fe 2 OH) units in mid-infrared spectra and their corresponding fundamental overtones or combination bands in near-infrared spectra supported this notion. The structural formula of the beidellite in the present study was determined to be (Si 7.51 Al 0.49 )(Al 2.99 Fe 0.68 Mg 0.33 ) (Ca 0.03 Na 0.54 Mg 0.11 )O 20 (OH) 4 , having dioctahedral ferruginous characteristics with almost 60% of the negative charge found in tetrahedral sheets. The cation exchange capacity determined from the structural formula was~108 meq/100 g. The specific surface area and total pore volume were~82.2 m 2 /g and 0.136 cm 3 /g, respectively. Interestingly, a detrital rather than a hydrothermal-alteration origin, as reported for other beidellite occurrences, explains its natural abundance and emphasizes the great interest in it.