Anne Galarneau

• Institut Charles Gerhardt Montpellier

The advent of 3D printing has transformed the field of manufacturing, offering unprecedented opportunities to create complex structures. Digital light processing (DLP)‐based stereolithography has been widely adopted by material scientists, and DLP printers are now commonly available. However, despite its innovative nature, 3D printing remains limit...

The growing concern over water pollution and waste management requires innovative solutions that promote resource efficiency within a circular economy. This study aims to utilize rice husk (RH) as a sustainable feedstock to develop highly porous silica particles and generate valuable by-products, addressing the dual challenges of waste reduction an...

Avec le soutien d’une unité du CNRS de Montpellier, une équipe de recherche de l’Université de Pau et des Pays de l’Adour (UPPA) s’intéresse à la valorisation de la balle de riz, la cosse qui entoure ces petits grains bien connus. Leurs objectifs? Récupérer bio-huile et silice, deux super ingrédients présents dans ce déchet, qui pourraient servir d...

Hierarchical zeolite catalysts containing additional meso- or macropores have attracted significant interest due to their beneficial performance in various reactions involving bulky molecules. A surfactant-templated post-synthesis of zeolites in basic medium (NaOH) advances from the uniform mesopore size distribution and easy regulation of micro-to...

The extraction of silica particles from rice husks has been extensively studied. This review aims to present the most efficient approach to harnessing rice husk biomass and converting silica into high-value-added materials for direct applications to address current challenges like water purification. Rice husks, as a residue from agriculture, had b...

Among the different strategies to design highly shape-selective ZSM-5 to obtain para-xylene through toluene alkylation with methanol, the introduction of mesopores to increase reactant and product diffusion has been proposed but barely studied. In this study, we prepared mesoporous ZSM-5 catalysts, named ZSM5-MT(x), from commercial ZSM-5 (Si/Al = 1...

Mesoporous ZSM‐5 catalysts were prepared from a commercial ZSM‐5 (Si/Al=15), using a 2‐step micelle‐templating procedure. By varying the NaOH/Si synthesis ratio in the range of 0.3‐0.7, ZSM‐5 catalysts with different textural and acidic properties were obtained. Increasing the NaOH/Si ratio in the synthesis gel leads to zeolites that feature reduce...

A simple and reproducible approach for the synthesis of Cu-based heterogeneous catalysts, named flow chemisorption hydrolysis (flow-CH), is reported. The approach, derived from the CH method, allows size-controlled CuO nanoparticles (mean diameter 2.9 nm) to be obtained, that are highly and homogeneously dispersed into hierarchically meso-/macropor...

In this work, the laccase from Trametes versicolor was immobilized in highly porous silica monoliths (0.6-cm diameter, 0.5-cm length). These monoliths feature a unique homogeneous network of interconnected macropores (20 μm) with mesopores (20 nm) in the skeleton and a high specific surface area (330 m²/g). The enzymatic monoliths were applied to d...

Pharmaceutical products (PPs) are considered as emerging micropollutans in wastewaters, river and seawaters, and sediments. The biodegradation of PPs, such as ciprofloxacin, amoxicillin, sulfamethoxazole, and tetracycline by enzymes in aqueous solution was investigated. Laccase from Trametes versicolor was immobilized on silica monoliths with hiera...

Zeolites are well‐known microporous catalysts involved in many industrial applications. Their microporosity yet impedes diffusion of bulky molecules. To overcome this drawback, zeolites with hierarchical bimodal porosity, e. g. micropores and mesopores, are developed. In this context, it is important to develop/use methods able to evaluate accurate...

It is important to elucidate the role of the surface areas and pore volumes of hierarchical zeolites to understand their behavior as catalysts. Micro-and mesopore surface areas and volumes of the hierarchical MFI (Mobil Five zeolites) were assessed following several methods: (i) N2 adsorption at 77 K using classical and corrected t-plot analyses me...

Ionogels represent a route to biphasic materials, for the use of ionic liquids (ILs) for all solid devices. Confining ILs within host networks enhances their averaged dynamics, resulting in improved charge transport. Fragility, short relaxation times, low viscosity, and good ionic conductivity, all them appear to be related to the IL / host network...

In the frame of the development of solid ionogel electrolytes with enhanced ion transport properties, this paper investigates ionogel systems constituted by ∼80 wt% of ionic liquids (ILs) confined in meso-/macroporous silica monolith materials. The anion–cation coordination for two closely related ILs, either aprotic (AIL) butylmethylpyrrolidinium...

γ-Al 2 O 3 is promising for catalytic ozonation because it produces HO° radicals. To improve its basicity and/or its oxidative character, highly mesoporous γ-Al 2 O 3 was doped with different metals M alone or in mixture (M = Mg, Ca, Zn, Fe, Ba, Zr, Cu, Co, Ni, Ce, Ti, with 0.05 < M/Al < 0.5 molar ratio) prepared either by incipient wetness deposit...

Binderless pure silica zeolites (zeosils) spheres and hollow spheres with a diameter of 20 µm composed of silicalite-1 nanosheets particles were prepared by pseudomorphic transformation of spherical silica beads using different temperatures (110, 130, and 150 °C) and treatment times (1–5 days) in order to adapt the local dissolution rate of silica...

A flow-through bi-enzymatic reactor was developed to produce formate from CO2 gas. The reaction operates under ambient conditions without H2 and involves a high performance formate dehydrogenase from Methylobacterium extorquens AM1 (MeFoDH1). The tandem reaction comprises a clean in situ regeneration of the nicotinamide adenine dinucleotide (1,4-NA...

Enzymatic monolithic reactors were applied for the degradation of micropollutants through flow-through reactor configuration. Silica monoliths with uniform macro-/mesoporous structures (20 µm and 20 nm macro- and mesopores diameters) high porosity (83%) and high surface area (370 m2 g-1) were prepared. The monoliths were cladded in steel tubing and...

Silica monoliths with uniform macro-/mesoporous structures (20 µm and 20 nm macro-and mesopores diameters) high porosity (83%) and high surface area (370 m 2 g-1) were prepared. The monoliths were cladded in steel tubing and laccase from Trametes versicolor was immobilized by covalent grafting. Activity tests were carried out by passing 20 mg L-1 t...

Enzymatic monolithic reactors were applied for the degradation of micropollutants through flow-through reactor configuration. Silica monoliths with uniform macro-/mesoporous structures (20 µm and 20 nm macro- and mesopores diameters) high porosity (83%) and high surface area (370 m2 g-1) were prepared. The monoliths were cladded in steel tubing and...

Silica monoliths with uniform macro-/mesoporous structures (20 µm and 20 nm macro- and mesopores diameters, respectively), high porosity (83%) and high surface area (370 m² g⁻¹) were prepared. The monoliths were grafted with amino groups (0.9 mmol NH2 g⁻¹) and used to immobilize laccase from Trametes versicolor by covalent grafting with glutaraldeh...

n -Hexadecane hydroconversion has been investigated in a series of bifunctionnal metal/acid catalysts featuring distinct well-defined pore architectures. The acidic components were prepared from dealuminated Y zeolites with Si/Al of 15 and 30 post treated in alkaline medium to generate ordered or non-ordered secondary networks of mesopores and from...

Chemical phase separation and pseudomorphic transformation are very powerful tools for fine tuning the porous architecture of inorganic oxides. In this short review the basic principles of the preparation of centimetric bodies made of zeolites is introduced. The synthesis of monoliths with homogeneous distributions of interconnected macropores with...

C,N–TiO2 monoliths with homogeneous interconnected macro-/mesoporous hierarchical porosity, consisting in 83% anatase phase, exhibiting high visible light absorption were prepared in one pot synthesis. The hierarchical porosity was controlled by coupling a sol-gel method with a spinodal decomposition and the improved visible light absorption was ob...

The performances of binderless FAU-X monoliths (0.5 × 3 cm) build of nanocrystals featuring hierarchical trimodal porosity (micro-/meso-/macroporosity) in decontamination Cs-containing effluents have been evaluated. They have been compared to those obtained with newly synthesized FAU-X particles (1 mm) build with nanocrystals. Data have been confro...

Self-standing binderless FAU-X monoliths with hierarchical trimodal porosity have been synthesized for the first time by a double pseudomorphic transformation. Parent silica monoliths obtained by the combination of spinodal decomposition and sol-gel process have first been synthesized. The silica monoliths have been then transformed into silica-alu...

A methodology for determining from N2 adsorption isotherms at 77 K the micropore, mesopore, and external surface areas of hierarchical microporous/mesoporous materials is described. For FAU-Y zeolite, the microporous surface area calculated using the Rouquerol criterion and the BET equation is in accord with the geometrical surface determined by th...

The texture of mesoporous FAU-Y (FAUmes) prepared by surfactant-templating in basic media is a subject of debate. It is proposed that mesoporous FAU-Y consists of: (1) ordered mesoporous zeolite networks formed by a surfactant-assisted zeolite rearrangement process involving local dissolution and reconstruction of the crystalline framework, and (2)...

In this study we report that ethylene can be simultaneously and selectively converted into propylene and 1-butene through one-pot catalytic cascade reactions. In a single continuous flow reactor, and under identical mild conditions (60 °C, 3 MPa), without the use of co-catalyst, ethylene was first dimerized/isomerized over Ni-AlKIT-6 catalysts to f...

Doubly functionalized, hierarchical porosity silica monoliths were synthesized by post-grafting of sulfonic groups and in-situ growth of Pd nanoparticles in the order. PdNP of 3.1 nm size located in the mesopores of the material showed to be evenly distributed within 4.6% wt Pd monoliths. The system was explored in the continuous flow, catalytic pa...

We report the application of hierarchically porous zirconium phosphate monoliths with high surface area as acidic heterogeneous catalysts for the dehydration of xylose into furfural. Analyses by NH3-temperature programmed desorption and ³¹P solid state NMR reveal the presence of both Lewis and Brønsted acid sites in the as-synthesized zirconium pho...

LTA zeolites are used in many applications as diverse as chemistry, physics, medicine, agriculture. By exploiting the concept of pseudomorphic transformation, i.e. using silica monoliths featuring macro- and mesopores as silica source, we manage to shape LTA zeolites as centimetric monoliths (6 mm diameter, 5 cm length) with trimodal hierarchical p...

This themed issue, dedicated to François Fajula, includes the latest achievements in the field of ordered porous solids, which is among the most creative, fascinating and attractive fields of chemistry.

Silica monoliths featuring either mesopores or flow-through macropores and mesopores in their skeleton are prepared by combining spinodal phase separation and sol-gel condensation. The macroporous network is first generated by phase separation in acidic medium in the presence of polyethyleneoxides while mesoporosity is engineered in a second step i...

Experiment and molecular simulation are used to investigate adsorption in heterogeneous porous media consisting of hierarchical solids (combining different porosity scales) or composite solids (such as silver nanoparticles adsorbed at the external surface of zeolite). It is shown that adsorption in such heterogeneous materials can be written as a l...

A new monolithic carbonaceous material, 750-HMF-CarboHIPE is presented here. The new electrode has been tested as an anode material inside a microbial bioelectrochemical system. In a purposely designed continuous flow bioelectrochemical reactor, the new material showed high biocompatibility, with a continuous biofilm development that remained bioel...

Phosphatidylcholine isotropic mesophases are easily formed by membrane fusion in hydroalcoholic solution in the presence of condensating silica. The transformation of lamellar bilayers into a sponge phase proceeds with the increase of the concentration of ethanol until a monodispersed mesoporous silica with surface area 800 m2 g-1 can be formed by...

A systematic study of the effect of the mesopore diameter of silica monoliths with hierarchical porosity (meso-/macroporosity) on charge transport of confined ionic liquid with lithium salt is reported. Different measurements have been performed including ionic conductivity, Li+ transference number, and 7Li MAS NMR. For a concentration of 0.5 M of...

We show that nuclear magnetic relaxation experiments at variable magnetic fields (NMRD) provide non-invasive means for probing the spatial dependence of liquid diffusion close to solid interfaces. These experiments performed on samples of cylindrical and spherical nanopore geometries demonstrate that average diffusion coefficient parallel to the in...

Broad visible emissions dominant at green or red have been observed for the thermally-treated Ag(+) exchanged SOD zeolites, determined by the Ag(+) loading contents and the excitation wavelengths. Contrary to the notable reversible green/red dominant emission evolution in the Ag(+) exchanged LTA zeolites upon hydration/dehydration in air (or water...

The surface and textural properties of porous silicon (pSi) control many of its physical properties essential to its performance in key applications such as optoelectronics, energy storage, luminescence, sensing, and drug delivery. Here, we combine experimental and theoretical tools to demonstrate that the surface roughness at the nanometer scale o...

This special issue of the European Physical Journal Special Topics is dedicated to selected papers from the symposium "High surface area porous and granular materials" organized in the frame of the conference "Mat,riaux 2014", held on November 24-28, 2014 in Montpellier, France. Porous materials and granular materials gather a wide variety of heter...

Silica monoliths with hierarchical porosity (macro-/mesoporous), prepared by a combination of phase separation (spinodal decomposition) and sol–gel process, have demonstrated remarkable potential as supports for catalysts and adsorbents with improved efficiency and productivity of a number of applications. This is due to perfect homogeneous interco...

This article reviews the preparation, main characteristics and advantages of macroporous monolithic microreactors for the synthesis of fine chemicals by continuous flow catalytic processes. It focuses on different types of monolith (polymers, polymer/glass, silica, zeolites) exhibiting macropores of typically 2 to 10 μm, a large pore volume (1-2 mL...

Nowadays, heterogeneous catalytic ozonation appears as a promising way to treat industrial wastewaters containing refractory pollutants, which resist to biological treatments. Several oxides and minerals have been used and their behavior is subject to controversy with particularly the role of Lewis acid sites and/or basic sites and the effect of sa...

The t-plot method is a well-known technique which allows determining the micro- and/or mesoporous volumes and the specific surface area of a sample by comparison with a reference adsorption isotherm of a non-porous material having the same surface chemistry. In this paper, the validity of the t-plot method is discussed in the case of hierarchical p...

A carbon nitride array (CNA) material has been constructed using a sacrificial diatom template. A regular carbon nitride nanorod array could be replicated from the periodic and regular nanochannel array of the template. The directional charge transport properties and high light harvesting capability of the CNA gives much better performance in split...

a b s t r a c t Advanced oxidation processes (AOP) as ozonation coupled with inorganic materials have been recently demonstrated to be highly suitable for wastewater treatment. In petrochemical wastewa-ters, pollutants as alkylphenols are often detected. In this paper, we highlight the efficiency to couple ozone with zeolites as SOD, LTA and FAU-X...

A rapid and accurate ion chromatography (IC) method (limit of detection as low as 0.06 mg L-1) for fosfomycin concentration determination in pharmaceutical industrial wastewater was developed. This method was compared with the performance of high performance liquid chromatography determination (with a high detection limit of 96.0 mg L-1) and ultrav...

Adsorption and dynamics in hierarchical metal–organic frameworks are investigated by means of molecular simulation. The models of hierarchical porous solids are obtained by carving mesopores of different diameters out of a crystal of Cu-BTC (model A) or by inserting a microporous particle of Cu-BTC in an amorphous silica mesopore (model B). We show...

Removal of perfluorinated alkylated substances (PFAS) such as perfluorooctanoic acid (PFOA) from aqueous solution is an actual topic in light of their widespread diffusion and their persistence in the environment. The process of adsorption has been identified as an effective technique to eliminate PFAS in water, however the process efficiency stron...

Nitrogen adsorption at 77 K on metal–organic framework (MOF) is investigated by means of molecular simulations. We consider both regular Cu–BTC crystal and a MOF-based hierarchical porous solid consisting of a mesopore carved out of a Cu–BTC crystal. The t-plot method is applied to these solids by using a non-porous Cu–BTC surface as the reference...

The removal of heteroaromatic nitrogen and sulfur impurities from a model oil through extraction with ionic liquids (ILs) containing metal salts was performed in view of the purification of fuel feeds. Chloride and bis(trifluoromethanesulfonyl)imide salts of Cu+, Cu2+ and Fe3+ were used. The systems based on ILs and metal compounds were applied bot...

Positronium (Ps) has been the subject of several experimental and theoretical investigations due to its many scientific applications. In this work high positronium yield was found in engineered porous silica. The studied materials were pellets of swollen MCM-41 and of commercial Davicat 1700, obtained by different compression pressures, with mesopo...

Positronium (Ps) has been the subject of several experimental and theoretical investigations due to its many scientific applications. In this work high positronium yield was found in engineered porous silica. The studied materials were pellets of swollen MCM-41 and of commercial Davicat 1700, obtained by different compression pressures, with mesopo...

By reversing the biological metabolic reaction pathway of three dehydrogenases, a formate dehydrogenase, a formaldehyde dehydrogenase and an alcohol dehydrogenase, it was possible to transform CO2 into methanol by a cascade reaction. The activity of each enzyme was examined separately and then the relative amount of each enzyme for the cascade reac...

A hydrogen-bond donor resin HX was obtained by modifying resin H103 . The adsorption effect of resin HX on berberine was determined. The adsorbing kinetic and dynamic mechanisms of resin HX and resin H103 was compared. The results showed that, after modification, resin HX could form hydrogen-bond with berberine molecules. In the adsorption process,...

The grafting of the preformed Pc-L* (pyridine containing macrocyclic ligands) copper(I) complexes on different ordered and non-ordered silicas, and their use, under heterogeneous batch conditions, as catalysts for the olefin cyclopropanation are reported. High yields (up to 99%) and good recyclability in halogen-free solvent reactions were obtained...

Pseudomorphic transformation is a promising alternative to conventional approaches for the preparation of binderless preshaped zeolite beads. However this method was until now restricted to zeolites synthesized in low alkaline media (OH−/SiO2 ≪ 1) (ZSM-5, FER, BEA), where the silica dissolution rate was slow in comparison to zeolite crystallization...

Review: tutorial reviews; 60 refs.

Adsorption and transport in hierarchical porous solids with micro (~ 1 nm) and mesoporosities (> 2 nm) are investigated by molecular simulation. Two models of hierarchical solids are considered: microporous materials in which mesopores are carved out (model A) and mesoporous materials in which microporous nanoparticles are inserted (model B). Adsor...

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Selective catalysts for sustainable oxidation of alkanes are highly demanded because of the abundance of these molecules in the environment, the possibility to transform them into higher-value compounds, such as chemicals or synthetic fuels, and the fact that, kinetically speaking, this is a difficult reaction. Numerous chemical and biological cata...

This review presents the state of the art of molecular simulation and theory of adsorption, intrusion and freezing in porous silica. Both silica pores of a simple geometry and disordered porous silicas which exhibit morphological and topological disorders are considered. We provide a brief description of the numerical models of porous silicas avail...

Antimatter is barely known by the chemist community and this article has the vocation to explain how antimatter, in particular antihydrogen, can be obtained, as well as to show how mesoporous materials could be used as a further improvement for the production of antimatter at very low temperatures (below 1 K). The first experiments with mesoporous...

We study the slow dynamics of water evaporation out of hydrophobic cavities by using model porous silica materials grafted with octylsilanes. The cylindrical pores are monodisperse, with a radius in the range of 1-2 nm. Liquid water penetrates in the nanopores at high pressure and empties the pores when the pressure is lowered. The drying pressure...

Es besteht eine große Nachfrage nach selektiven Katalysatoren für die nachhaltige Oxidation von Alkanen, denn die in der Umwelt sehr häufig vorkommenden Alkane können dadurch in höherwertige Verbindungen, z. B. Chemikalien oder synthetische Brennstoffe, umgewandelt werden. Für diese – kinetisch gesehen – schwierige Reaktion wurde in den letzten Jah...

Well-dispersed Pd nanoparticles have been synthesized inside the mesoporosity of a silica monolith featuring hierarchical porosity of homogeneous interconnected macropores (4 microns) and mesopores (11 nm). These monoliths have been implemented as microreactors for selective hydrogenation reactions. Conversion and selectivity can be tuned by adjust...

Lyophobic heterogeneous systems (LHS) are made of mesoporous materials immersed in a non-wetting liquid. One application of LHS is the nonlinear damping of high frequency vibrations. The behaviour of LHS is characterized by P - ΔV cycles, where P is the pressure applied to the system, and ΔV its volume change due to the intrusion of the liquid into...

Pd nanoparticles are immobilized by a green procedure onto unconventional dual porosity titania monoliths. The material is used in catalytic continuous-flow hydrogenation reactions showing excellent efficiency, selectivity, and durability.

Sol-gel syntheses involving either neutral water or formic acid as a reactant have been investigated (1) to determine the best conditions to confine a maximum of ionic liquid (IL) inside silica-based matrixes and (2) to reach the highest porosity after removing the IL from the ion gels (washed gels). Several sets of ionogels were prepared from vari...

Pulsed field gradient (PFG) NMR is a powerful tool to examine diffusion of adsorbates in porous systems. The use of mesoporous silicas with uniform particle sizes allowed us to demonstrate the possibilities of this technique. In particular, we confirmed that, in the Mitra mathematical approach of diffusion, the surface-to-volume ratio is related to...

We report experimental nitrogen adsorption isotherms of organics-coated silicas, which exhibit a low-pressure desorption branch that does not meet the adsorption branch upon emptying of the pores. To address the physical origin of such a hysteresis loop, we propose an equilibrium thermodynamic model that enables one to explain this phenomenon. The...

The metal-organic framework Cu-BTC has been successfully synthesized as nanoparticles inside the mesopores of silica monoliths featuring a homogeneous macropore network enabling the use of Cu-BTC for continuous flow applications in liquid phase with low pressure drop. High productivity was reached with this catalyst for the Friedländer reaction.

Bimodal macro-/mesoporous silica monoliths (6 mm diameter, 1–4 cm length) were functionalized with aluminum oxide allowing the preparation of a new solid Lewis acid catalyst named Al-MonoSil. Al-MonoSil was used as catalytic microreactor for the in-flow implementation of the Diels–Alder reaction. Due to the interconnected and homogeneous system of...

A new rapid, very simple and one-step sol-gel strategy for the large-scale preparation of highly porous γ-Al2O3 is presented. The resulting mesoporous alumina materials feature high surface areas (400 m² g⁻¹), large pore volumes (0.8 mL g⁻¹) and the γ-Al2O3 phase is obtained at low temperature (500 °C). The main advantages and drawbacks of differen...

Metallothioneins (MTs) are low-molecular weight proteins (1–10 kDa), which are known to bind selectively metal ions such as Zn or Cd in metal–thiolate clusters. The present work describes the preparation of copper–metallothionein (Cu–MT) and its immobilization by covalent grafting on mesoporous silica for the selective uptake and recovery of Cu2+ f...

We explored the sensitivity of the (14)N quadrupolar interaction toward the characterization of surfactant-oxide interfaces. For the first time, experimental (14)N NMR spectra are recorded, modeled, and compared for three different mesostructured silica (hexagonal p6mm, cubic Ia3d, and lamellar) templated by hexadecyltrimethylammonium cations (CTA(...

Titanium-silica catalysts, obtained by grafting titanocene dichloride onto mesoporous silica (MCM-41 and MCM-48) and onto nanosized pyrogenic silica, were tested in the epoxidation of methyl oleate using aqueous hydrogen peroxide. All titanium-containing materials, combined with the slow addition of hydrogen peroxide, showed good catalytic activity...

The reaction of octylphosphonic acid with the surface of alumina nanoparticles has been investigated in order to prep. a close packing of grafted-alkyl chains. This goal was attained through a fitting selection of the exptl. conditions in terms of pH, reactant amt., reaction time and temp. DRX, TEM and 31P MAS NMR spectroscopy are all consistent wi...