Recent advances and perspectives on intercalation layered compounds part 1: design and applications in the field of energy.

Herein, initially, we present a general overview of the global financial support for chemistry devoted to materials science, specifically intercalation layered compounds (ILCs). Subsequently, the strategies to synthesise these host structures and the corresponding guest-host hybrid assemblies are exemplified on the basis of some families of materials, including pillared clays (PILCs), porous clay heterostructures (PCHs), zirconium phosphate (ZrP), layered double hydroxides (LDHs), graphite intercalation compounds (GICs), graphene-based materials, and MXenes. Additionally, a non-exhaustive survey on their possible application in the field of energy through electrochemical storage, mostly as electrode materials but also as electrolyte additives, is presented, including lithium technologies based on lithium ion batteries (LIBs), and beyond LiBs with a focus on possible alternatives such XIBs (X = Na (NIB), K (KIB), Al (AIB), Zn (ZIB), and Cl (CIB)), reversible Mg batteries (RMBs), dual-ion batteries (DIBs), Zn-air and Zn-sulphur batteries and supercapacitors as well as their relevance in other fields related to (opto)electronics. This selective panorama should help readers better understand the reason why ILCs are expected to meet the challenge of tomorrow as electrode materials.

Recent advances and perspectives for intercalation layered compounds. Part 2: applications in the field of catalysis, environment and health.

Intercalation compounds represent a unique class of materials that can be anisotropic (1D and 2D-based topology) or isotropic (3D) through their guest/host superlattice repetitive organisation. Intercalation refers to the reversible introduction of guest species with variable natures into a crystalline host lattice. Different host lattice structures have been used for the preparation of intercalation compounds, and many examples are produced by exploiting the flexibility and the ability of 2D-based hosts to accommodate different guest species, ranging from ions to complex molecules. This reaction is then carried out to allow systematic control and fine tuning of the final properties of the derived compounds, thus allowing them to be used for various applications. This review mainly focuses on the recent applications of intercalation layered compounds (ILCs) based on layered clays, zirconium phosphates, layered double hydroxides and graphene as heterogeneous catalysts, for environmental and health purposes, aiming at collecting and discussing how intercalation processes can be exploited for the selected applications.

Basic Properties of MgAl-Mixed Oxides in CO2 Adsorption at High Temperature.

The increase of consciousness towards global warming and the need to reduce greenhouse gas emissions lead to the necessity of finding alternative applications based on easy-to-use materials in order to control and reduce global CO2 emissions. Layered Double Hydroxides (LDHs) and LDH-derived materials are potentially good adsorbents for CO2, thanks to their low cost, easy synthesis, high sorption capacity, and surface basicity. They have been intensively studied in CO2 capture at high temperature, presenting variable sorption capacities for MgAl LDHs with the same composition, but prepared under different synthesis conditions. The ambient temperature coprecipitation synthesis method is an attractive one-step procedure to synthesize LDHs under mild conditions, with low energy consumption and short synthesis time. The present study is based on the synthesis and characterization of hydrotalcites by a mild-conditions coprecipitation process and the production of derived mixed oxides to be used as CO2 adsorbents. A critical comparison to similar materials is reported. Moreover, the effect of the surface basicity of the derived mixed oxides (measured by adsorption calorimetry) and the CO2 sorption capacity are discussed, showing a linear correlation between the amount of weak and very strong basic sites and the CO2 adsorption behavior.

In situ preparation of compounds using silanized mPEG inspired by talc-like structures.

Composite materials show improved properties compared to pristine materials, in particular when the filler is dispersed homogeneously in the matrix. For polymer-clay composites, different strategies exist to improve clay mineral dispersion in the polymer matrix. In this study, an innovative approach is suggested which consists of forming a talc-like structure directly in a polymer matrix using a silanized polymer as the silicon source. Poly(ethylene glycol) methyl ether of different average molar masses (Mn = 350, 500, 750, 1900 g mol-1) were functionalized with (3-isocyanatopropyl)triethoxysilane and added to the ethanolic solutions of magnesium nitrate. 1H-29Si CPMAS solid state NMR experiments revealed partial condensation of silane compounds, and FTIR analysis confirmed the presence of both Si-O and Mg-O bonds, but an additional proof of the Si-O-Mg bond is needed to prove the formation of such a structure.

Synthetic beidellite clay as nanocarrier for delivery of antitumor oxindolimine-metal complexes.

Studies on the immobilization of oxindolimine­copper(II) or zinc(II) complexes [ML] in synthetic beidellite (BDL) clay were developed to obtain a suitable inorganic carrier capable of promoting the modified-release of metallopharmaceuticals. Previous investigations have shown that the studied metal complexes are promising antitumor agents, targeting DNA, mitochondria, and some proteins. They can bind to DNA, causing oxidative damage via formation of reactive oxygen species (ROS). In mitochondria they lead to a decrease in membrane potential, acting as decoupling agents, and therefore efficiently inducing apoptosis. Additionally, they inhibit human topoisomerase IB and cyclin dependent kinases, proteins involved in the cell cycle. BDL clays in the sodium form were synthesized under hydrothermal conditions and characterized by a set of physicochemical techniques while the BDL-[ML] hybrid materials were prepared by ion exchange method. The characterization of pristine clay and the obtained hybrids were performed by Infrared, Raman, electron paramagnetic resonance and energy dispersive X-ray spectroscopies, thermogravimetric analysis, scanning electron microscopy, X-ray powder diffraction, specific surface area, zeta potential and surface ionic charge measurements. The [ML] release assays under the same cell incubation conditions were performed monitoring metals by X-ray fluorescence. The BDL-[CuL] hybrid materials were stable and able to derail tumor HeLa cells, with corresponding IC50 values in the 0.11-0.41 mg mL-1 range. By contrast, the analogous hybrid samples of zinc(II) and the pristine BDL proved to be non-toxic facing the same cells. These results indicate a promising possibility of using synthetic beidellite as a carrier of such antitumor metal complexes.

New Materials and Technologies for Wastewater Treatment.

This Special Issue (SI) contains the successful submissions [...].

Review: Clay-Modified Electrodes in Heterogeneous Electro-Fenton Process for Degradation of Organic Compounds: The Potential of Structural Fe(III) as Catalytic Sites.

Advanced oxidation processes are considered as a promising technology for the removal of persistent organic pollutants from industrial wastewaters. In particular, the heterogeneous electro-Fenton (HEF) process has several advantages such as allowing the working pH to be circumneutral or alkaline, recovering and reusing the catalyst and avoiding the release of iron in the environment as a secondary pollutant. Among different iron-containing catalysts, studies using clay-modified electrodes in HEF process are the focus in this review. Fe(III)/Fe(II) within the lattice of clay minerals can possibly serve as catalytic sites in HEF process. The description of the preparation and application of clay-modified electrodes in the degradation of model pollutants in HEF process is detailed in the review. The absence of mediators responsible for transferring electrons to structural Fe(III) and regenerating catalytic Fe(II) was considered as a milestone in the field. A comprehensive review of studies investigating the use of electron transfer mediators as well as the mechanism behind electron transfer from and to the clay mineral structure was assembled in order to uncover other milestones to be addressed in this study area.

Layered double hydroxides and LDH-derived materials in chosen environmental applications: a review.

With increasing global warming awareness, layered double hydroxides (LDHs), hydrotalcites, and their related materials are key components to reduce the environmental impact of human activities. Such materials can be synthesized quickly with high efficiency by using different synthesis processes. Moreover, their properties' tunability is appreciated in various industrial processes. Regarding physical and structural properties, such materials can be applied in environmental applications such as the adsorption of atmospheric and aqueous pollutants, hydrogen production, or the formation of 5-hydroxymethylfurfural (5-HMF). After the first part that was dedicated to the synthesis processes of hydrotalcites, the present review reports on specific environmental applications chosen as examples in various fields (green chemistry and depollution) that have gained increasing interest in the last decades, enlightening the links between structural properties, synthesis route, and application using lamellar materials.

Laponites® for the Recovery of 133Cs, 59Co, and 88Sr from Aqueous Solutions and Subsequent Storage: Impact of Grafted Silane Loads.

In this study, silylated Laponites® (LAP) were synthetized with various loads of 3-aminopropyltriethoxysilane (APTES) to evaluate their adsorption properties of 133Cs, 59Co, and 88Sr during single-solute and competitive experiments. The increase in the initial load of APTES increased the adsorbed amount of APTES in the resulted grafted clay. The characterization of LAP-APTES exhibited a covalent binding between APTES and LAP and emphasized the adsorption sites of APTES for each tested load. In comparison with raw LAP, LAP-APTES displayed significantly higher adsorption properties of Co2+, Cs+, and Sr2+. The competitive adsorption of these three contaminants provides a deeper understanding of the affinity between adsorbate and adsorbent. Therefore, Co2+ displayed a strong and specific adsorption onto LAP-APTES. Except for Cs+, the adsorption capacity was improved with increasing the load of APTES. Finally, the desorption behavior of the three contaminants was tested in saline solutions. Cs+ and Sr2+ were significantly released especially by inorganic cations displaying the same valence. Conversely, desorption of Co2+ was very low whatever the saline solution. LAP-APTES, therefore, presented suitable adsorption properties for the removal of radionuclides especially for Co2+, making this material suitable to improve the decontamination of radioactive wastewaters.

Inorganic and Hybrid (Organic⁻Inorganic) Lamellar Materials for Heavy metals and Radionuclides Capture in Energy Wastes Management-A Review.

The energy industry (nuclear, battery, mining industries, etc.) produces a large quantity of hazardous effluents that may contain radionuclides (137Cs and 90Sr in particular) and heavy metals. One of the hardest tasks of environmental safety and sustainable development is the purification of wastewater holding these pollutants. Adsorption is one of the most powerful methods for extracting toxic compounds from wastewater. This study reviews the usefulness of clay minerals as adsorbent for removing these hazardous elements to clean up energy production processes. Phyllosilicates are able to extract several heavy metals from effluent, as widely examined. A particular focus is given to synthetic phyllosilicates and their abilities to entrap heavy metals with a special attention paid to those synthesized by sol-gel route. Indeed, this method is attractive since it allows the development of organic-inorganic hybrids from organosilanes presenting various functions (amino, thiol, etc.) that can interact with pollutants. Regarding these pollutants, a part of this review focuses on the interaction of lamellar materials (natural and synthetic phyllosilicates as well as layered double hydroxide) with heavy metals and another part deals with the adsorption of specific radionuclides, cesium and strontium.

Systems for stimuli-controlled release: Materials and applications.

The design and development of delivery controlled systems of molecules of interest has attracted great interest over the last years. pH variation, light irradiation, temperature increasing, variation of the redox potential and the application of a magnetic field are among the most widely used stimuli that can be used to induce the release of an active molecule in a medium. The dominance of pH and photo-controlled release is clearly highlighted by the numerous articles published in these fields as well as all the related applications. In the case of pH-controlled release, two main parameters govern the release: the solubility of the active molecule in the releasing medium and the stability of the carrier materials. In the photo-controlled release, the carrier needs to contain a photosensible functionality; this stimulus can be successfully applied in the medical field when red light, that is able to penetrate the human tissues, is used. A large panel of applications of controlled release can be identified in the pharmaceuticals, agriculture, cosmetics, chemistry and dyes industry fields. More recently, biological, enzymatic, and mechanical (ultrasounds, stretching, shear stress) stimuli have been developed for target applications, in particular for drugs and hormones release. Consequently, many types of materials (polymers, silica, oxides, MOF…) can be used as carrier in relation to their compatibility with the active molecule and the type of releasing medium. This review aims to gives a useful overview on the materials, applications and mechanisms implied in stimuli-controlled release.

Spectroscopic Studies of the Interactions between a Cationic Cyanine Dye and a Synthetic Phyllosilicate: From Photophysics to Hybrid Materials.

The interaction of the cationic organic dye Astrazon orange R (AO-R) with the synthetic phyllosilicate Laponite leads to very interesting hybrid materials. Indeed, the Laponite nanoparticles modify the photophysical properties of AO-R, inducing a stabilization of its excited emissive state by preventing ultrafast isomerization. The long-lived emissive clay-dye hybrid complex can be used to develop efficient photoinitiating systems, leading to organic-inorganic hybrid crosslinked polymer materials.

Enhanced interlayer trapping of a tetracycline antibiotic within montmorillonite layers in the presence of Ca and Mg.

The formation of a ternary antibiotic-metal-clay complex is hypothesized as the primary adsorption mechanism responsible for the increased adsorption of tetracycline antibiotics on smectites in the presence of divalent metal cations under circumneutral and higher pH conditions. To evaluate this hypothesis, we conducted a spectroscopic investigation of oxytetracycline (OTC) interacting with Na-montmorillonite in the presence and absence of Ca or Mg salts at pH 6 and pH 8. Despite a two-fold increase in OTC adsorbed in the presence of Ca or Mg, both solid-state nuclear magnetic resonance and infrared signatures of the OTC functional groups involved in metal complexation implied that the formation of an inner-sphere ternary complexation was not significant in stabilizing the adsorbate structures. The spectroscopic data further indicated that the positively-charged amino group mediated the OTC adsorption both in the absence and presence of the divalent metal cations. Focusing on the experiments with Mg, X-ray diffraction analysis revealed that the metal-promoted adsorption was coupled with an increased intercalation of OTC within the montmorillonite layers. The resulting interstratified clay layers were characterized by simulating X-ray diffraction of theoretical stacking compositions using molecular dynamics-optimized montmorillonite layers with and without OTC. The simulations uncovered the evolution of segregated interstratification patterns that demonstrated how increased access to smectite interlayers in the presence of the divalent metal cations enhanced adsorption of OTC. Our findings suggest that specific aqueous structures of the clay crystallites in response to the co-presence of Mg and OTC in solution served as precursors to the interlayer trapping of the antibiotic species. Elucidation of these structures is needed for further insights on how aqueous chemistry influences the role of smectite clay minerals in trapping organic molecules in natural and engineered soil particles.

Ammonium and potassium removal from swine liquid manure using clinoptilolite, chabazite and faujasite zeolites.

This study concerns cationic exchanges performed in order to remove ammonium and potassium cations from manure by using various zeolites: clinoptilolite, chabazite and NaX faujasite. First, the effect of temperature (25 °C and 40 °C) on the exchange rate between zeolites and an ammonium chloride solution was investigated. Then, cationic exchanges were performed on these three zeolites using on one side a mixed ammonium and potassium chloride solution reproducing the chemical composition of a swine manure and on the other side the corresponding liquid manure. No significant difference was observed on the exchange rate and the trapping of ammonium cations by changing the temperature (25 or 40 °C). Clinoptilolite showed a good selectivity towards ammonium cations using model (NH4Cl, and mixed NH4Cl/KCl) solutions but is less efficient with the liquid manure. Chabazite and faujasite were found more efficient than clinoptilolite for trapping ammonium cations. However, NaX faujasite enables trapping 3 times more ammonium cations than chabazite from manure (60 and 20 mg/g, respectively). Moreover, chabazite allowed to trap the same amount of potassium cations than NaX faujasite (33 and 35 mg/g, respectively).

Hydrophilic/hydrophobic film patterning by photodegradation of self-assembled alkylsilane multilayers and its applications.

While the photopatterning of self-assembled monolayers (SAMs) has been extensively investigated, much less attention has been given to highly ordered multilayer systems. By being both thicker (0.5-2 µm) and more stable (cross-linked) than SAMs, patterned hybrid multilayers lend themselves more easily to the development of technology-relevant materials and characterization. This paper describes a facile two-step UV approach to patterning an alkylsilane multilayer by combining photoinduced self-assembly for multilayer synthesis and photodegradation through a mask for creating patterns within the film. In this second stage, a spatially resolved removal of the alkyl tail via a photooxidation mechanism took place, yielding regular and uniform silica microdomains. The result was a regular array of features (alkylsiloxane/silica) differing in chemical composition (hybrid/inorganic), ordering (crystal-like/disordered), and wettability (hydrophobic/hydrophilic). Such a photopatterned film was of utility for a range of applications in which water droplets, inorganic crystals, or aqueous polymer dispersions were selectively deposited in the hydrophilic silica microwells.

Competitive Fe(II)-Zn(II) uptake on a synthetic montmorillonite.

The interaction of Fe(II) with clay minerals is of particular relevance in global geochemical processes controlling metal and nutrient cycles and the fate of contaminants. In this context, the influence of competitive sorption effects between Fe(II) and other relevant transition metals on their uptake characteristics and mobility remains an important issue. Macroscopic sorption experiments combined with surface complexation modeling and extended X-ray absorption fine structure (EXAFS) spectroscopy were applied to elucidate competitive sorption processes between divalent Fe and Zn at the clay mineral-water interface. Sorption isotherms were measured on a synthetic iron-free montmorillonite (IFM) under anoxic conditions (O2 <0.1 ppm) for the combinations of Zn(II)/Fe(II) and Fe(II)/Zn(II), where the former metal in each pair represents the trace metal (<10(-7) M) and the latter the competing metal at higher concentrations (10(-7) to 10(-3) M). Results of the batch sorption and EXAFS measurements indicated that Fe(II) is competing with trace Zn(II) for the same type of strong sites if Fe(II) is present in excess, whereas no competition between trace Fe(II) and Zn(II) was observed if Zn(II) is present at high concentrations. The noncompetitive behavior suggests the existence of sorption sites which have a higher affinity for Fe(III), where surface-induced oxidation of the sorbed Fe(II) to Fe(III) occurred, and which are not accessible for Zn(II). The understanding of this competitive uptake mechanism between Fe(II) and Zn(II) is of great importance to assess the bioavailability and mobility of transition metals in the natural environment.

Fe(II) sorption on a synthetic montmorillonite. A combined macroscopic and spectroscopic study.

Extended X-ray absorption fine structure (EXAFS) and Mössbauer spectroscopy combined with macroscopic sorption experiments were employed to investigate the sorption mechanism of Fe(II) on an iron-free synthetic montmorillonite (Na-IFM). Batch sorption experiments were performed to measure the Fe(II) uptake on Na-IFM at trace concentrations as a function of pH and as a function of sorbate concentration at pH 6.2 and 6.7 under anoxic conditions (O2 < 0.1 ppm). A two-site protolysis nonelectrostatic surface complexation and cation exchange sorption model was used to quantitatively describe the uptake of Fe(II) on Na-IFM. Two types of clay surface binding sites were required to model the Fe(II) sorption, the so-called strong (≡S(S)OH) and weak (≡S(W)OH) sites. EXAFS data show spectroscopic differences between Fe sorbed at low and medium absorber concentrations that were chosen to be characteristic for sorption on strong and weak sites, respectively. Data analysis indicates that Fe is located in the continuity of the octahedral sheet at trans-symmetric sites. Mössbauer spectroscopy measurements confirmed that iron sorbed on the weak edge sites is predominantly present as Fe(II), whereas a significant part of surface-bound Fe(III) was produced on the strong sites (∼12% vs ∼37% Fe(III) species to total sorbed Fe).

Hydrothermal Synthesis and Characterization of Ni-Al Montmorillonite-Like Phyllosilicates.

This work describes the first hydrothermal synthesis in fluoride medium of Ni-Al montmorillonite-like phyllosilicates, in which the only metallic elements in the octahedral sheet are Ni and Al. X-ray diffraction, chemical analysis, thermogravimetric and differential thermal analysis, scanning electron microscopy and transmission electron microscopy confirm that the synthesized samples are montmorillonite-like phyllosilicates having the expected chemical composition. The specific surface areas of the samples are relatively large (>100 m² g-¹) compared to naturally occurring montmorillonites. 29Si and 27Al nuclear magnetic resonance (NMR) indicate substitutions of Al for Si in the tetrahedral sheet. 19F NMR and Ni K-edge extended X-ray absorption fine structure (EXAFS) local probes highlight a clustering of the metal elements and of the vacancies in the octahedral sheet of the samples. These Ni-Al phyllosilicates exhibit a higher local order than in previously synthesized Zn-Al phyllosilicates. Unlike natural montmorillonites, where the distribution of transition metal cations ensures a charge equilibrium allowing a stability of the framework, synthetic montmorillonites entail clustering and instability of the lattice when the content of divalent element in the octahedral sheet exceeds ca. 20%. Synthesis of Ni-Al montmorillonite-like phyllosilicates, was successfully achieved for the first time. These new synthetic materials may find potential applications as catalysts or as materials with magnetic, optical or staining properties.

A Novel Fluoride Route for the Synthesis of Aluminosilicate Nanotubes.

In this work we present a novel method for synthesis of aluminosilicate nanotubes: the fluoride route. F-containing imogolite (F-IMO) exhibits an improved crystallization rate and improved yield. The structure of F-IMO was investigated and compared with F-free imogolite (IMO) by means of X-ray diffraction (XRD) and Fourier transformed infrared spectroscopy (FTIR) confirming imogolite structure. Solid state nuclear magnetic resonance (NMR) analyses show an increased crystallization rate for F-IMO and confirm the incorporation of fluorine ion in the structure.

Photopatterning of multilayer n-alkylsilane films.

Surface photopatterning of organosilane self-assembled monolayers (SAM) has received increasing attention since its introduction 20 years ago. Herein we report for the first time a cost-efficient soft photopatterning technique affording amplified 3D multilayer structures. The essential chemistry relies on a spatially controlled photoacid-catalyzed hydrolysis and polycondensation of n-alkyltrimethoxysilane precursors (n-C(12)H(25)Si(OCH(3))(3),). Amphiphilic siloxane species are photogenerated locally and are able to self-assemble spontaneously into a long-range-ordered lamellar mesostructure.