Fabrice Leroux

• Head of Institute (ICCF) at University of Clermont Auvergne

Antioxidants play a crucial role in inhibiting polypropylene (PP) oxidative damage and extending polymer lifetime. However, the high migration rate and limited efficiency reduced protection, often requiring overdosing, which raises environmental and health issues. Herein, a more sustainable solution involves an ultrathin antioxidant intercalated la...

In this work, the layered double hydroxide (LDH) Mg2Al(OH)6 was intercalated with redox active ferrocene carboxylate anions in order to implement charge storage capability to the interlayer spaces of the LDH structure. Two sets of anions, namely mono‐ and dicarboxylic ferrocene, were intercalated to produce two different active materials: MgAl‐FcMo...

Chiara Bisio, Sébastien Cahen and Fabrice Leroux introduce the Dalton Transactions themed collection on intercalation compounds.

exhibit high ability to release inhibitor as well as to capture aggressive ions from aqueous solution. Epoxy containing organo-modified LDH filler intercalated with ethylenediamine-N,N′-disuccinate anions (EDDS), [Zn2Al(OH)6]+ [EDDS]4􀀀 0.25 . 2H2O (LDH-EDDS) with loading from 0% to 1.25% were coated onto carbon steel plates. The efficiency of these...

After a general overview of the overworld financial support for chemistry devoted to materials science and more specifically to intercalation layered compounds (ILCs), the strategies to synthesize such host structure...

Intercalation compounds represent a unique class of materials that can be anisotropic (1D and 2D-based topology) or isotropic (3D) by their guest/ host superlattice repetitive organization. Intercalation refers to the...

Dispersion degree of Prussian blue in layered double hydroxides was enhanced by co-intercalation of sodium dodecyl sulfate, and then the rate of solar vapor generation is increased by 35.9%.

This study presents the intercalation into Layered Double Hydroxides (LDHs) of two sulfonated organic molecules featuring the mesoionic triazolium scaffold. These sulfonated fluorophores exhibited excellent solubility in aqueous basic solutions,...

The advancement of lithium-ion batteries (LIBs) with high performance is crucial across various sectors, notably in space exploration. This advancement hinges on the development of innovative cathode materials. Our research...

This study presents the intercalation into Layered Double Hydroxides (LDHs) of two sulfonated organic molecules featuring the mesoionic triazolium scaffold. These sulfonated fluorophores exhibited excellent solubility in aqueous basic solutions, facilitating their compatibility with the synthesis of LDHs through coprecipitation methods. We applied...

Layered Double Hydroxides (LDHs) are a versatile class of 2D materials, which consist of layered di- and trivalent metal cation hydroxides with intercalated anions (1). They are used in many applications including energy storage electrodes, water purification or drug delivery (2, 3). In this new study, Anthraquinone-2-sulfonate (AQS) intercalated i...

A layered double hydroxide (LDH) compound LDH ([Mg 2 Al(OH) 6 ] ⁺ x 2 H 2 O) intercalated with a redox active organic anion, Anthraquinone-2-sulfonate (AQS), has been envisioned as an electrode material for high power aqueous based battery. The purpose is to use this interlayer redox active molecule for enhancement of the specific capacity at the L...

Strongly luminescent when diluted in aqueous solution, Sulforhodamine B (SRB) is an organic fluorescent molecule suffering from aggregation caused quenching (ACQ) in its solid state. Its co-intercalation in very small quantities (0.12 mol%) in a layered double hydroxide (LDH) matrix with phenylenedipropionate (PPA) anions, a di-functionalized new s...

N–acetyl–L–cysteine (NAC), a derivative of the L–cysteine amino acid, presents antioxidant and mucolytic properties of pharmaceutical interest. This work reports the preparation of organic-inorganic nanophases aiming for the development of drug delivery systems based on NAC intercalation into layered double hydroxides (LDH) of zinc–aluminum (Zn2Al–...

Nanostructure control is an important issue when using electroactive materials in energy conversion and storage devices. In this study, we report various methods of synthesis of nanostructured copper (II) hydroxide nitrate (Cu2(OH)3NO3) with a layered hydroxide salt (LHS) structure using various synthesis methods and investigate the correlation bet...

By selecting two electroactive species immobilized in a layered double hydroxide backbone (LDH) host, one able to act as a positive electrode material and the other as a negative one, it was possible to match their capacity to design an innovative energy storage device. Each electrode material is based on electroactive species, riboflavin phosphate...

Subject to the aggregation-caused quenching (ACQ) mechanism in the solid state, perylene and its derivatives turn to be fascinating organic fluorophores when separated from each other by their co-intercalation within a layered double hydroxide host structure. Such accommodation with surfactant spacers limits their stacking usually caused by π-π int...

The diterpenoid abietate (ABI) ion, the conjugate base of the phytochemical abietic acid, was intercalated into a series of layered double hydroxides (LDH) with Mg2FeyAl(1-y) composition envisioning the preparation of drug delivery systems. Experimental parameters were evaluated to achieve organic-inorganic hybrid iron-based LDH as single-phases en...

Perylene diimide-based dyes substituted by four sulfonate groups at their bay position are known to be extremely sensitive to their mutual π–π intermolecular interaction. They do not emit fluorescence in solid state. When co-hosted in LDH with a surfactant in extremely small quantities, an absolute photoluminescence quantum yield (PL QYabs) of abou...

Ethylenediamine-N,N′-disuccinate (EDDS) is successfully intercalated between layered double hydroxide (LDH) sheets leading to hybrid assembly [Zn2Al(OH)6]⁺ [EDDS]⁴⁻0.25 2H2O (LDH-EDDS⁴⁻). The electrochemical behavior of the carbon steel carried out in a neutral and aerated sodium chloride solution shows the surface reactivity of carbon steel is sig...

Conversion cathodes such as metal fluorides are particularly interesting for their theoretical capacities up to 711 mAh/g when used in Li-ion batteries. However, they generally suffer from high hysteresis and/or poor cyclability. To overcome these problems, ternary metal fluorides are being explored to improve electrochemical properties compared to...

Folic acid (FA; vitamin B9) and its associated sodium salts, strongly relevant for many scientific and technological applications - from nutrition to pharmacology and nanomedicine, suffer from a lack of characterization combining experimental and theoretical. In this work, a spectroscopic investigation of FA and its synthesized sodium salts in the...

The optical properties of sulforhodamine B (SRB) hosted in surfactant-modified layered double hydroxide (LDH) are explored using quantum yield efficiencies and temporal variations in luminescence. The effect of the spacer, known to provide a suitable SRB dilution in the solid state, is studied in-depth with respect to its relative content and its a...

Developing green thermal stabilizer for poly(vinyl chloride) (PVC) today is a great challenge for materials as polymer filler. Here, the “salt-oxide/hydroxide” route in mild conditions is used to fabricate a series of Mg2Al-CO3-LDH samples from Mg(OH)2 precursors with different average particle sizes from 202 ± 10 nm to 334 ± 13 nm. A linear correl...

Light-Emitting Materials In article number 2103411, Damien Bowyer, Fabrice Leroux, and co-workers, report a new elegant method adapted from host–guest chemistry; the so-called “size-matching of the interlamellar space” (SMIS) is of particular interest in accommodating cumbersome, optically active, and fragile entities such as InP/ZnS quantum dots (...

Poly(vinyl chloride) (PVC), an important thermoplastic polymer widely-used in various fields, requires the use of thermal stabilizers to enhance its thermal stability during polymer processing and practical applications because of the poor thermal stability. Layered double hydroxides (LDHs), two-dimensional anionic layered and versatile filler, are...

Hypothesis While controlled and efficient exfoliation of layered oxides often remains a time consuming challenge, the surface modification of inorganic nanosheets is of outmost importance for future applications. The functionalization of the bulk material prior to exfoliation should allow the application of tools developped for Van der Waals materi...

The architecture of Zn‐Al layered double hydroxides (LDHs), organo‐modified with bola‐amphiphiles molecules, is matching its interlayer space to the size of narrow‐band red‐emitting InP/ZnS core–shell quantum dots (QDs) to form original high‐performance functional organic–inorganic QD‐bola‐LDH hybrids. The success of size‐matching interlayer space...

There is an urgent need in exploring new cathode materials for Lithium batteries in order to increase their capacities. Conversion type cathodes are relevant replacement candidates and especially metal fluorides such as FeF 3 with a theoretical capacity of 712 mAh g ⁻¹ for three electrons at a voltage of 2.74 V vs . Li ⁺ /Li or CuF 2 with a theoret...

In this study, photoactive organic molecules (PAO) and polymer stabilizer (anti-oxidant (AO) and light stabilizer (UV)) are co-intercalated into the galleries of layered double hydroxides (LDH) to form a series of new hybrid luminescent LDH fillers, LDH-AO/PAO and LDH-UV/PAO, adjusting the anion ratio of PAO (%). The structure of the hybrid materia...

Synthetic conditions were evaluated to intercalate norbixin into layered double hydroxides (LDH). Norbixin was isolated from a hydrosoluble commercial annatto extract. LDH samples comprising M2+/Al3+ (M = Mg, Zn) were synthesized by coprecipitation and characterized by X-ray diffraction, thermal analysis coupled to mass spectrometry, vibrational sp...

When sulforhodamine B (SRB) is entrapped in a tightly packed hybrid material composed of dodecylsulfate anions interleaved in layered double hydroxide, the organic dye is considered as a possible red-emitting phosphor for white light-emitting diodes (WLEDs). To confirm such promising potential, a reliability study is here undertaken and the materia...

La ciprofloxacine (CIP) fait partie de la famille des fluoroquinolones qui sont des antibiotiques fréquemment utilisés en prescription médicale courante car ils possèdent un bon profil de tolérance, une excellente biodisponibilité et un large spectre antibactérien. Les effets secondaires de la CIP sont pour la plupart des réactions attendues : gast...

Correction for ‘Unravelling lithiation mechanisms of iron trifluoride by operando X-ray absorption spectroscopy and MCR-ALS chemometric tools’ by F. Eveillard et al. , New J. Chem. , 2020, 44 , 10153–10164, DOI: 10.1039/C9NJ06321H.

Domestic lighting using white light-emitting diodes (WLEDs) requires a choice of materials to be eco-friendly as well as economically viable. Revisiting the optical properties of sulforhodamine B (SRB) with a new focus – designing rare-earth-free phosphors – is found here to be highly promising. Relying on a Layered Double Hydroxide (LDH) host, the...

Fabrice Leroux, Heloise de Oliveira Pastore and Vera Regina L. Constantino introduce this New Journal of Chemistry themed issue entitled “Sustainability from intercalation compounds”.

A pyrazino-1,3a,6a-triazapentalene dye-based molecule was intercalated by direct co-precipitation method into the galleries of negatively charged layered double hydroxide (LDH) to form a new luminescent LDH filler. The materials of cation composition Zn/Al = 2 lead to well-defined organic inorganic assemblies. The structure of the hybrid materials...

Polybutylene succinate (PBS) were processed in melt extrusion by dispersion of organo-modified layered double hydroxide (LDH). Depending on the organic anion interleaved into LDH fillers (L-tyrosine (TYR), L-tryptophan (TRP), L-ascorbate (ASA) and 3-(4-hydroxyphenyl)propionate (HPP)), it was possible to control and tune the properties of the result...

The compound p-coumaric acid (HCou) is found in many foods and presents action in suppression of chronic diseases and protective effects on neurodegenerative disorders. This work presents the intercalation of...

The lithium-ion batteries are extensively used for electrochemical energy storage but their performances need to be continuously increased. One solution is to use alternative cathode materials such as iron trifluoride. However, its galvanostatic profile depends on the allotropic phase studied. To go further on such various lithiation mechanisms, qu...

Enhancing the compatbility between inorgnic filler and polymer to obtain functionalized composite has always been a key issue. An aqueous miscible organic (AMO) method is here successfully adapted for the conventional layered double hydroxides (LDH) fillers. Here, a series of D-LDH hybrid materials, intercalated by an organic antioxidant DBHP (D, 3...

3-(4-hydroxyphenyl)propionic acid, intercalated in Mg2Al/layered double hydroxide has been used as filler in biopolyesters containing succinate moiety, such as poly(propylene succinate) (PPS), poly(butylene succinate-co-butylene adipate) (PBSA) and poly(butylene succinate) (PBS) with the aim of inducing an effect similar to that of an increment of...

This paper describes the intercalation of ciprofloxacin (CIP), a bactericidal antibiotic, into the interlayer space of layered double hydroxides (LDH). To counter the problem of bacterial resistance and also to improve the properties of CIP drug, the drug carrier approach promises significant benefits. Through a tightly control of the synthesis par...

Correction for ‘Design, fabrication and anti-aging behavior of a multifunctional inorganic–organic hybrid stabilizer derived from co-intercalated layered double hydroxides for polypropylene’ by Qian Zhang et al. , Inorg. Chem. Front. , 2019, 6 , 2539–2549.

It is of great and increasing interest to develop multifunctional additives to enhance anti-aging performance of polypropylene (PP) and then enlarge its application fields. Here, hindered amine light stabilizer (H for HALS) and hindered phenolic antioxidant (D for DBHP) with low molecular weight were co-intercalated into layered double hydroxides (...

The project aim on the development of intercalated compounds based on layered double hydroxide (LDH) materials as carriers of bioactive species.

The luminescence of Fluorescein, an inexpensive dye, ought to be interesting for lighting application devices such as commercial LEDs. However, the molecule suffers from severe instability, making it inappropriate for such applications. As previously studied, fluorescein molecules may be hosted in a layered double hydroxide (LDH), and the role of s...

Olive mill wastewater (OMW) is the aqueous waste derived from the production of virgin olive oil. OMW typically contains a wide range of phenol-type molecules, which are natural antioxidants and/or antibacterials. In order to exploit the bioactive molecules and simultaneously decrease the environmental impact of such a food waste stream, OMW has be...

Background: High concentration of phosphate has been threatening human health and the ecosystem. Adsorption is one of high-efficiency and low-cost techniques to reduce the concentration of phosphate. This mini review aims to summarize the recent development of adsorption materials for phosphate removal. Method: We conducted a detailed search of “a...

A new luminescent composite film resulting from the dispersion of luminescent organic dyes in a single-layered hydroxide (SLH)- type inorganic matrix has been developed. Two fluorescent organic dyes emitting visible light upon blue LED excitation were investigated in this study: dicyanomethylene (DCM) and pyranine (HPTS). These dyes exhibit broad e...

Polybutylene succinate (PBS) nanocomposite materials were prepared using a melt compounding process. The Mg2Al-based PBS nanocomposites, dispersed with inorganic–organic hybrid materials (layered double hydroxides, LDHs), were functionalized with the amino acids L-histidine (HIS) and L-phenylalanine (PHE). The rheological and anti-ultraviolet (anti...

Olive Mill wastewater (OMW) is a food waste stream resulting from the production of virgin olive oil, rich in valuable natural biocompounds, such as vanillic acid, ferulic acid, protocatechuic acid, etc. In order to decrease its environmental impact and to exploit the antioxidant properties of its phenol-type molecules, OMW was intercalated into Zn...

This work explores the synthesis, physicochemical characterization, and in vivo biocompatibility of iron-based layered double hydroxides (LDHs) with molar ratio M²⁺/(Fe³⁺ + Al³⁺) equal to 2, Fe³⁺/Al³⁺ equal to 1, and chloride anions as charge-compensating ion (abbreviated Mg4FeAl-Cl and Zn4FeAl-Cl) prepared by the coprecipitation method. The higher...

An elegant and efficient approach consisting in the co-intercalation of stabilizing molecular anions is described here. The thermal stabilizer calcium diethyl bis[[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate] (Irganox 1425, MP-Ca) and a photo-oxidation stabilizer (hindered amine light stabilizer, HALS) are co-intercalated into th...

In the field of biodegradable polymers such as poly(Lactic Acid) (PLA), it is quite well known that their kinetics of hydrolysis strongly depend on the pH of the hydrolyzing medium. The idea explored during this study focused on PLA, is the addition of additives that are able to control the pH of water when it diffuses inside the polymer. For insta...

In-depth understanding of the thermal stability of polymer-clay nanocomposites requires the use of advanced time-resolved techniques combined with multivariate data analysis, as well as the preparation of layered nanofillers with well-defined composition. The layered double hydroxide (LDH) compounds Zn2Al(OH)6·nH2O, Zn2Al0.75Fe0.25(OH)6·nH2O, ZnCuA...

The insertion of phenylbutylamine into a layered perovskite of formula H2Bi0.1Sr0.85Ta2O7 (HST) has been investigated as a function of the synthesis conditions. For short reactions times (1.5 h), achieved using microwave assisted reactions, a short interlayer distance (2.2 nm) is obtained (PBA1-HST) whereas for long reaction times (18 h) achieved u...

The encapsulation of molecules of therapeutic interest is emerging as an attractive tool to increase the stability of an active ingredient, to control its release over time and to prevent drug overdose. In this drug delivery approach, several analgesic molecules are considered, including (2E)–2-cyano-3-(furan-3-yl)acrylic acid (CFAA), and the host...

Ten organic molecule models simulating the chemical functions of commercial superplasticizers used in the cement/concrete industry were intercalated into lamellar calcium aluminate hydrates to synthesize hybrid AFm phases. AFm phases, encountered in cement hydration chemistry, belong to the large Layered Double Hydroxide (LDH) family. The intercala...

Hybridization of layered double hydroxide (LDH) platelets of Zn2Al cation intra-sheet composition was performed with L-tyrosine (TYR), L-tryptophan (TRP) and 3-(4-hydroxyphenyl) propionic (HPP) acid, and the hybrid LDH materials were characterized by the means of conventional techniques as X-ray diffraction and thermal analysis to address their san...

Microwave-assisted functionalization of the layered Aurivillius phase Bi2SrTa2O9 by alcohols is thoroughly investigated. The grafting of linear aliphatic and bulky alcohols is studied as a function of the starting material, underlining the importance of the prefunctionalization of the layered perovskite, for instance by butylamine. In addition, the...

Hybrid materials based on layered double hydroxides (LDHs) exhibit great potential in diverse fields such as health care, polymer composites, environment, catalysis, and energy generation. Indeed, the compositional flexibility and the scalability of LDH structures, their low cost, and their ease of synthesis have made hybrid LDHs extremely attracti...

A low molecular weight hindered amine light stabilizer (HALS), contains 2, 2, 6, 6-tetramethyl piperidine functional group has been successfully prepared and intercalated into the interlayer region of Mg-Al layered double hydroxides (LDH) via a co-precipitation method to produce HALS-LDH. Furthermore, a series of HALS-LDH/PP nanocomposites were fab...

This work investigates emulsion templating to synthesize hexadecane oil/geopolymer composites. In a system with hexadecane as the internal (dispersed) phase and an alkali activated continuous phase without added surfactant, adding aluminosilicate clay particles does not increase resistance against creaming or coalescence, while adding a surfactant...

Welcome to this themed issue of Dalton Transactions entitled “Recent Developments in Intercalation Compounds: Chemistry and Applications”.

Nanocomposites based on poly(butylene succinate) (PBS) and hydrotalcite-type anionic clays (HTs) organo-modified with biomolecules characterized by antibacterial and/or antioxidant activity, such as L-ascorbic acid (ASA), phloretic acid (HPP), L-tyrosine (TYR) and L-tryptophan (TRP), have been prepared by in situ polymerization. From XRD analysis a...

High-performance heat-retention agent for multifunctional green agricultural film is today largely suitable to increase production yield as well as to save energy. Here, an adapted ammonia releasing hydrothermal method was used to produce a series of micrometer-sized carbonate-layered double hydroxides (CO3-LDH) precusors from 1.32 μm to 8.64 μm by...

In this work, a carbon replica derived from vinylbenzenesulfonate-intercalated layered double hydroxide (CR-LDH) was applied to remove the Dicamba organochlorine herbicide from aqueous solution. The samples were characterized by several experimental techniques such as X-ray diffraction (XRD), thermogravimetric analysis coupled to differential scann...

The disposal of polymeric waste is increasingly becoming an issue of international concern. The use of biodegradable polymers is a possible strategy to face most of the problems related to the disposal of the durable (non-biodegradable) polymers. Among biodegradable polymers, PLA (obtained from renewable sources) is a very attractive one, due to it...

A novel preparation route for layered hydroxide based hybrid phases has been investigated combining the polyol route with the in-situ generation of inorganic platelets, in the presence of amphiphilic polymer...

For many decorative applications like industrial and architectural paints, prevention of metal substrates from corrosion is a primary function of organic coatings. Triggered release of inhibitor species is generally accepted as a remedy for starting corrosion in case of coatings damage. A polyurethane based coating, doped with bola-amphiphiles of v...

3-(4-hydroxyphenyl)propionic acid (HPPA), a biobased hydroxy acid, has been used as organic modifier in Layered double hydroxides (LDHs) based on ZnAl and MgAl cations. PBS bionanocomposites have been prepared via in situ polymerization (with both types of clays) and melt blending (just with ZnAl-HPPA) obtaining completely green materials, potentia...

One of the major issues for poly (propylene) PP concerns its protection towards oxidative phenomena resulting in polymer failure. Using known anti-oxidant (AO), Irganox 1425, an original approach is taking advantage of the counterion, cations Ca2+, in building hydrocalumite inorganic sheets, and concomitantly providing the AO anions to be immobiliz...

The article describes the synthesis and properties of new ionogels for ion transport. A new preparation process using an organic linker, bis(3-(trimethoxysilyl)propyl)amine (BTMSPA), yields stable organosilica matrix materials. The second ionogel component, the ionic liquid 1-methyl-3-(4-sulfobutyl)imidazolium 4-methylbenzenesulfonate, [BmimSO3H][P...

A straightforward preparation of the antioxidant anion 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (DBHP), intercalated into layered double hydroxides (DBHP-LDH) via a co-precipitation method, and adjusting the (Mg, Zn, Al) metal ratio was reported. The influence of the Zn-containing LDH composition was studied by measuring the thermal stabilit...

Nanocomposite latex particles containing layered double hydroxide (LDH) platelets were synthesized using reversible addition-fragmentation chain transfer (RAFT) seeded emulsion polymerization. A random copolymer of acrylic acid (AA) and n-butyl acrylate (BA) was first synthesized by RAFT polymerization, and then electrostatically adsorbed on both n...

Additional PXRD analysis.

Increasing attention has been devoted to the design of layered double hydroxide (LDH)-based hybrid materials. In this work, we demonstrate the intercalation by anion exchange process of poly(acrylic acid) (PAA) and three different hydrophilic random copolymers of acrylic acid (AA) and n-butyl acrylate (BA) with molar masses ranging from 2000 to 420...

The invention relates to layered double hydroxides organo-modified by 3-(4-hydroxyphenyl)propionic acid (HPPA), by 2-(4-hydroxyphenyl)ethylsulfonic acid or by a hydroxyphenylpropenoic acid, and to composite polymer materials comprising same. The composite materials are advantageously made of biosourced polymers such as poly(butylene succinate). The...