Photocatalyseurs à base de Ag2CO3 et TiO2 déposés par voie humide (sol-gel, précipitation) et sèche (mécanosynthèse) sur des supports argileux d'origine naturelle

Ce travail rapporte l'élaboration par voies humides (sol-gel, précipitation) et sèche (mécanosynthèse) de photocatalyseurs originaux à l’état de poudre pure ou supportées sur des fibres de palygorskite (Pal), composant d’une argile brute naturelle d’origine marocaine. TiO2 seul, non dopé ou dopé au soufre, et couplé avec CuO fut utilisé comme composant actif principal. Ag2CO3 fut également étudié comme composant alternatif en raison de sa forte activité dans le domaine du visible. Ces photocatalyseurs furent testés pour la dégradation de polluants modèles anionique (orange G, OG) et cationique (rouge neutre, RN) en milieux aqueux, sous irradiation artificielle UV, Visible et Solaire, ainsi que sous ensoleillement naturel extérieur. Les caractérisations multi-échelles effectuées sur les différents photocatalyseurs développés ont essentiellement démontré : - L’immobilisation par sol-gel de nanoparticules (NPs) de TiO2 et CuO sur Pal avec formation d’hétérojonctions entre ces oxydes, produisant une activité photocatalytique sous UV avérée mais toutefois trop limitée ; - La formation par précipitation de nanocomposites à base de NPs Ag2CO3 déposées sur les fibres de Pal. Selon la durée de maintien des réactifs en digestion et un protocole de cycles thermiques couplés à du vieillissement sous atmosphère de CO2, il a été possible d’obtenir Ag2CO3 sous sa forme structurale métastable hexagonale (H) et stable monoclinique (m), ou de contrôler la proportion des 2 phases dans les composites Ag2CO3/Pal. Ces nouveaux photocatalyseurs sont actifs dans le visible et les nanocomposites biphasés H+m se sont avérés plus actifs que les monophasés. - L’élaboration par mécanosynthèse de TiO2 anatase supporté sur Pal et de TiO2 principalement anatase en coexistence remarquable avec une phase monoclinique métastable B dans le cas du dopage au soufre. TiO2-S est très actif dans le visible tandis que TiO2-Pal manifeste une activité sous UV en présentant l’avantage de pouvoir exploiter les propriétés de l’argile pour développer une multifonctionnalité (photocatalyse-adsorption). Ces photocatalyseurs sont actifs sous forme de poudres dispersés et de revêtements sous irradiation solaire. La cinétique de dégradation du polluant modèle a pu être modélisée

Supported Photocatalyst Based on CuO–TiO2/Palygorskite Nanocomposite Material for Wastewater Treatment

This study deals with the immobilization of mixtures of two semiconductor oxides CuO and TiO2 on fibrous palygorskite clay mineral in order to evaluate their photocatalytic activity for removing Orange G dye as model pollutant from aqueous solutions. The elaboration of CuO–TiO2/Palygorskite nanocomposites was carried out by impregnation with Cu2+ of before hand synthesized TiO2 supported palygorskite (Pal) followed by air annealing for 5 h at 550 °C. In the composite materials, different CuO to CuO + TiO2 molar ratios were used in order to obtain a CuO content in the range 13–30 mol.%. XRD, SEM and TEM equipped with elemental EDS analysis are concordant for showing the crystallization of anatase TiO2 along with CuO whose average size of nanoparticles (NPs) are in the range 6 to 20 nm as determined by TEM. By increasing the CuO content the average size of this oxide remains constant at about 10 nm while that of TiO2 NPs is slightly decreasing from 8.4 to 5.1 nm. Both oxide NPs were successfully attached on palygorskite fibers where they form CuO–TiO2 heterojunctions (grain boundaries like). The CuO–TiO2/Pal supported photocatalyst containing 23% of CuO was found to be the most photoactive material but itremained less active than TiO2/Palygorskite supported photocatalyst. The photocatalytic activity of the mixed nanocomposites is not readily correlated with only one of their main features as CuO content or the average crystallite size of functional oxides indicating that if there are synergistic effects there are also antagonistic effects in particular for high CuO contents

On the key role of the surface of palygorskite nanofibers in the stabilization of hexagonal metastable β-Ag2CO3 phase in palygorskite-based nanocomposites

This study reports an original remarkable effect of fibrous palygorskite clay mineral in the stabilization at the ambient temperature of the metastable hexagonal β-phase of Ag2CO3 along with the stable monoclinic one (m-Ag2CO3) and the refinement of their particles size (≈5–10 nm). These structural and microstructural features likely arise owing to heterogeneous nucleation induced by the surface of palygorskite fibers between CO32– anions in solution and Ag+ exchanged palygorskite (Ag+-Pal) as reactants kept maturing for short periods, which should not exceed 1 h. Besides, the phase composition of Ag2CO3 supported on palygorskite, namely β- and m-structures can be monitored by carrying on appropriate low temperature treatments under CO2 atmosphere coupled with aging during several months in such a way that either pure β or m single-phases as well as biphased mixtures with controlled composition can be obtained. Taking into account experimental results and literature data, a growth mechanism is discussed

Influence of the crystal structure of Ag2CO3 on the photocatalytic activity under visible light of Ag2CO3-Palygorskite nanocomposite material

In a companion paper, it has been demonstrated the remarkably beneficial effect of palygorskite clay (Pal) fibers as support material coupled to appropriate thermal treatments and aging under CO2 atmosphere in monitoring the phase composition of Ag2CO3-Pal composite. In this new nanocomposite material, the structure of the functional component Ag2CO3 can be controlled from 100% stable monoclinic (m) to 100% metastable hexagonal β through an adjusted mixture of m- and β-Ag2CO3. The present study deals with the assessment of the visible photocatalytic properties of these various nanocomposite materials towards the removal of Orange G dye from aqueous solutions. It was found that the Ag2CO3-Pal nanocomposite in which Ag2CO3 was single-phased and crystallized with the stable monoclinic structure was more active than the one crystallizing entirely with the metastable β-Ag2CO3 structure. Nevertheless, the composite material containing a mixture of both Ag2CO3 phases with a relative content of 32% of β- and 68% of m-phase was found to be the most photoactive compound of the series. This behavior reveals likely a synergetic effect between both phases in the photocatalytic degradation of the dye under visible light

Comprehensive physicochemical study of dioctahedral palygorskite-rich clay from Marrakech High Atlas (Morocco)

This 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

Ag2CO3 and TiO2 based photocatalysts deposited by wet (sol-gel, precipitation) and dried (mechanosynthesis) routes on natural clayey supports

Ce travail rapporte l'élaboration par voies humides (sol-gel, précipitation) et sèche (mécanosynthèse) de photocatalyseurs originaux à l’état de poudre pure ou supportées sur des fibres de palygorskite (Pal), composant d’une argile brute naturelle d’origine marocaine. TiO2 seul, non dopé ou dopé au soufre, et couplé avec CuO fut utilisé comme composant actif principal. Ag2CO3 fut également étudié comme composant alternatif en raison de sa forte activité dans le domaine du visible. Ces photocatalyseurs furent testés pour la dégradation de polluants modèles anionique (orange G, OG) et cationique (rouge neutre, RN) en milieux aqueux, sous irradiation artificielle UV, Visible et Solaire, ainsi que sous ensoleillement naturel extérieur. Les caractérisations multi-échelles effectuées sur les différents photocatalyseurs développés ont essentiellement démontré : - L’immobilisation par sol-gel de nanoparticules (NPs) de TiO2 et CuO sur Pal avec formation d’hétérojonctions entre ces oxydes, produisant une activité photocatalytique sous UV avérée mais toutefois trop limitée ; - La formation par précipitation de nanocomposites à base de NPs Ag2CO3 déposées sur les fibres de Pal. Selon la durée de maintien des réactifs en digestion et un protocole de cycles thermiques couplés à du vieillissement sous atmosphère de CO2, il a été possible d’obtenir Ag2CO3 sous sa forme structurale métastable hexagonale (H) et stable monoclinique (m), ou de contrôler la proportion des 2 phases dans les composites Ag2CO3/Pal. Ces nouveaux photocatalyseurs sont actifs dans le visible et les nanocomposites biphasés H+m se sont avérés plus actifs que les monophasés. - L’élaboration par mécanosynthèse de TiO2 anatase supporté sur Pal et de TiO2 principalement anatase en coexistence remarquable avec une phase monoclinique métastable B dans le cas du dopage au soufre. TiO2-S est très actif dans le visible tandis que TiO2-Pal manifeste une activité sous UV en présentant l’avantage de pouvoir exploiter les propriétés de l’argile pour développer une multifonctionnalité (photocatalyse-adsorption). Ces photocatalyseurs sont actifs sous forme de poudres dispersés et de revêtements sous irradiation solaire. La cinétique de dégradation du polluant modèle a pu être modélisée.This work reports the development of different photocatalysts using either wet route (sol-gel and precipitation methods) or dry route (mecanosynthesis followed by annealing). The photocatalysts are TiO2 (pure or doped with sulfur) nanoparticles (NPs), TiO2 coupled with CuO and Ag2CO3 supported on natural fibrous clay from Morocco called palygorskite (Pal). The degradation of model anionic dyes (orange G, OG) and cationic dyes (neutral red, NR) in aqueous solution were investigated under artificial radiation (UV and visible) and natural sunlight. The multi-scale chemical and structural characterization and the properties investigated on the different photocatalysts showed the following results: -Immobilization of both TiO2 and CuO NPs on palygorskite by sol-gel method. Despite the heterojunctions between these functional oxides the photocatalysts exhibit a limited activity under UV irradiation. - Elaboration of nanocomposites made of Ag2CO3 NPs deposited on Pal fibers using the precipitation method. Depending on the time of reactant digestion, the number of thermal cycles and the aging for several months, Ag2CO3 adopts remarkably, in these nanocomposites, the exclusive forms of metastable hexagonal structure (H), or the stable monoclinic one (m) or a mixture of both phases with different proportions depending on the mass ratio of Ag2CO3/Pal. All Ag2CO3-Pal nanocomposites are active in the visible range for the elimination of OG. The nanocomposites in the biphasic form H + m are more active than single phases samples either in the form H or m. - Preparation of anatase TiO2 supported on Pal and TiO2 as a mixture of mainly TiO2 anatase and a minority of a remarkable monoclinic phase B by a mechanical alloying method. The NPs surfaces of these photocatalysts are acidified by grafting the sulfate groups (SO42-) and the anionic network is lightly doped with substituting O2- by S2-. These specific characteristics have made TiO2-S very active in the visible for the degradation of OG, while TiO2-Pal composite exhibits an activity under UV. Both types of photocatalysts in the form of powders dispersed in the OG solutions have proved to be active under sunlight and as well in the form of coating. TiO2-Pal has showed allows the adsorption of cationic entities RN facilitating their subsequent photodegradation

A simple and fast spectroscopy-based technique for Covid-19 diagnosis

AbstractThe coronavirus pandemic, which appeared in Wuhan, China, in December 2019, rapidly spread all over the world in only a few weeks. Faster testing techniques requiring less resources are key in managing the pandemic, either to enable larger scale testing or even just provide developing countries with limited resources, particularly in Africa, means to perform tests to manage the crisis. Here, we report an unprecedented, rapid, reagent-free and easy-to-use screening spectroscopic method for the detection of SARS-CoV-2 on RNA extracts. This method, validated on clinical samples collected from 280 patients with quantitative predictive scores on both positive and negative samples, is based on a multivariate analysis of FTIR spectra of RNA extracts. This technique, in agreement with RT-PCR, achieves 97.8% accuracy, 97% sensitivity and 98.3% specificity while reducing the testing time post RNA extraction from hours to minutes. Furthermore, this technique can be used in several laboratories with limited resources.</jats:p