Intimately mixed copper, cobalt, and iron fluorides resulting from the insertion of fluorine into a LDH template.

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 is dedicated to pioneering a new category of cathodes using fluorinated multimetallic materials, with a specific focus on diverging from the traditional Ni, Co, and Mn-based NMC chemistries by substituting nickel and manganese with copper and iron which are more sustainable elements. Our goal is also to enhance the robustness of cathodes upon cycling by substituting oxygen with fluorine as the metal-ligand. To achieve this, an intimate composite blend of CuF2 and FeF3, through the multi-metallic template fluorination (MMTF) methodology using a layered double hydroxide (LDH) as a precursor has been designed. Each of these components was carefully selected for its distinct attributes, including high redox potential, elevated energy density, substantial theoretical capacity, and improved cyclability. The composition denoted as (Cu1.5Co0.5)2+(Fe0.75Al0.25)3+ has been selected for fluorination because it maximizes Fe3+ and Cu2+ amount in the screened LDHs. Subsequently, this particular LDH was fluorinated through solid-gas fluorination at different temperatures (200, 350, and 500 °C) using gaseous molecular fluorine (F2). A comprehensive characterization of these materials using various techniques, including X-ray diffraction (XRD), 57Fe Mössbauer spectrometry, scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX), and inductively coupled plasma analyses (ICP-AES) was conducted, and the evolution of LDH upon fluorination has revealed an intermediate porous texture particularly sensitive to hydration. Two original crystallographic phases are else obtained by fluorination: one formed by the hydration of the amorphous intermediate compound: Cu3Fe1.5Al0.5F12(H2O)12 an anti-perovskite structure and another stabilized through the combination of solid gas fluorination and LDH precursor yielding an original CoFeF5-type phase. Raman operando during cyclic voltammetry measurement applied on a sample fluorinated at 500 °C and used as a cathode in front of lithium metal was finally conducted to validate redox activity and mechanism.

Hierarchical superparamagnetic metal-organic framework nanovectors as anti-inflammatory nanomedicines.

Among a plethora of drug nanocarriers, biocompatible nanoscale metal-organic frameworks (nanoMOFs) with a large surface area and an amphiphilic internal microenvironment have emerged as promising drug delivery platforms, mainly for cancer therapy. However, their application in biomedicine still suffers from shortcomings such as a limited chemical and/or colloidal stability and/or toxicity. Here, we report the design of a hierarchically porous nano-object (denoted as USPIO@MIL) combining a benchmark nanoMOF (that is, MIL-100(Fe)) and ultra-small superparamagnetic iron oxide (USPIO) nanoparticles (that is, maghemite) that is synthesized through a one-pot, cost-effective and environmentally friendly protocol. The synergistic coupling of the physico-chemical and functional properties of both nanoparticles confers to these nano-objects valuable features such as high colloidal stability, high biodegradability, low toxicity, high drug loading capacity as well as stimuli-responsive drug release and superparamagnetic properties. This bimodal MIL-100(Fe)/maghemite nanocarrier once loaded with anti-tumoral and anti-inflammatory drugs (doxorubicin and methotrexate) shows high anti-inflammatory and anti-tumoral activities. In addition, the USPIO@MIL nano-object exhibits excellent relaxometric properties and its applicability as an efficient contrast agent for magnetic resonance imaging is herein demonstrated. This highlights the high potential of the maghemite@MOF composite integrating the functions of imaging and therapy as a theranostic anti-inflammatory formulation.

Deciphering the Thermal and Electrochemical Behaviors of Dual Redox-Active Iron Croconate Violet Coordination Complexes.

Interest in coordination compounds based on non-innocent ligands (NILs) for electrochemical energy storage has risen in the last few years. We have focused our attention on an overlooked redox active linker, croconate violet, which has not yet been addressed in this field although closely related to standard NILs such as catecholate and tetracyanoquinodimethane. Two anionic complexes consisting of Fe(II) and croconate violet (-2) with balancing potassium cations were isolated and structurally characterized. By a combination of in situ and ex situ techniques (powder and single-crystal X-ray diffraction, infrared, and 57Fe Mössbauer spectroscopies), we have shown that their dehydration occurs through complex patterns, whose reversibility depends on the initial crystal structure but that the structural rearrangements around the iron cations occur without any oxidation. While electrochemical studies performed in solution clearly show that both the organic and inorganic parts can be reversibly addressed, in the solid state, poor charge storage capacities were initially measured, mainly due to the solubilization of the solids in the electrolyte. By optimizing the formulation of the electrode and the composition of the electrolyte, a capacity of >100 mA h g-1 after 10 cycles could be achieved. This suggests that this family of redox active linkers deserves to be investigated for solid-state electrochemical energy storage, although it requires the solving of the issues related to the solubilization of the derived coordination compounds.

Structure-Property-Function Relationships of Iron Oxide Multicore Nanoflowers in Magnetic Hyperthermia and Photothermia.

Magnetite and maghemite multicore nanoflowers (NFs) synthesized using the modified polyol-mediated routes are to date among the most effective nanoheaters in magnetic hyperthermia (MHT). Recently, magnetite NFs have also shown high photothermal (PT) performances in the most desired second near-infrared (NIR-II) biological window, making them attractive in the field of nanoparticle-activated thermal therapies. However, what makes magnetic NFs efficient heating agents in both modalities still remains an open question. In this work, we investigate the role of many parameters of the polyol synthesis on the final NFs' size, shape, chemical composition, number of cores, and crystallinity. These nanofeatures are later correlated to the magnetic, optical, and electronic properties of the NFs as well as their collective macroscopic thermal properties in MHT and PT to find relationships between their structure, properties, and function. We evidence the critical role of iron(III) and heating ramps on the elaboration of well-defined NFs with a high number of multicores. While MHT efficiency is found to be proportional to the average number of magnetic cores within the assemblies, the optical responses of the NFs and their collective photothermal properties depend directly on the mean volume of the NFs (as supported by optical cross sections numerical simulations) and strongly on the structural disorder in the NFs, rather than the stoichiometry. The concentration of defects in the nanostructures, evaluated by photoluminescence and Urbach energy (EU), evidence a switch in the optical behavior for a limit value of EU = 0.4 eV where a discontinuous transition from high to poor PT efficiency is also observed.

Unveiling the role of surface, size, shape and defects of iron oxide nanoparticles for theranostic applications.

Iron oxide nanoparticles (IONPs) are well-known contrast agents for MRI for a wide range of sizes and shapes. Their use as theranostic agents requires a better understanding of their magnetic hyperthermia properties and also the design of a biocompatible coating ensuring their stealth and a good biodistribution to allow targeting of specific diseases. Here, biocompatible IONPs of two different shapes (spherical and octopod) were designed and tested in vitro and in vivo to evaluate their abilities as high-end theranostic agents. IONPs featured a dendron coating that was shown to provide anti-fouling properties and a small hydrodynamic size favoring an in vivo circulation of the dendronized IONPs. While dendronized nanospheres of about 22 nm size revealed good combined theranostic properties (r2 = 303 mM s-1, SAR = 395 W gFe-1), octopods with a mean size of 18 nm displayed unprecedented characteristics to simultaneously act as MRI contrast agents and magnetic hyperthermia agents (r2 = 405 mM s-1, SAR = 950 W gFe-1). The extensive structural and magnetic characterization of the two dendronized IONPs reveals clear shape, surface and defect effects explaining their high performance. The octopods seem to induce unusual surface effects evidenced by different characterization techniques while the nanospheres show high internal defects favoring Néel relaxation for magnetic hyperthermia. The study of octopods with different sizes showed that Néel relaxation dominates at sizes below 20 nm while the Brownian one occurs at higher sizes. In vitro experiments demonstrated that the magnetic heating capability of octopods occurs especially at low frequencies. The coupling of a small amount of glucose on dendronized octopods succeeded in internalizing them and showing an effect of MH on tumor growth. All measurements evidenced a particular signature of octopods, which is attributed to higher anisotropy, surface effects and/or magnetic field inhomogeneity induced by tips. This approach aiming at an analysis of the structure-property relationships is important to design efficient theranostic nanoparticles.

Iron Stearate Structures: An Original Tool for Nanoparticles Design.

Iron carboxylates are widely used as iron precursors in the thermal decomposition process or considered as in situ formed intermediate precursors. Their molecular and three-dimensional (3D)-structural nature has been shown to affect the shape, size, and composition of the resulting iron oxide nanoparticles (NPs). Among carboxylate precursors, stearates are particularly attractive because of their higher stability to aging and hydration and they are used as additives in many applications. Despite the huge interest of iron stearates, very few studies aimed up to now at deciphering their full metal-ligand structures and the mechanisms allowing us to achieve in a controlled manner the bottom-up NP formation. In this work, we have thus investigated the molecular structure and composition of two iron stearate precursors, synthesized by introducing either two (FeSt2) or three (FeSt3) stearate (St) chains. Interestingly, both iron stearates consist of lamellar structures with planes of iron polynuclear complexes (polycations) separated with stearate chains in all-trans conformation. The iron content in polycations was found very different between both iron stearates. Their detailed characterizations indicate that FeSt2 is mainly composed of [Fe3-(µ3-O)St6·xH2O]Cl, with no (or few) free stearate, whereas FeSt3 is a mixture of mainly [Fe7(µ3-O(H))6(µ2-OH)xSt12-2x]St with some [Fe3(µ3-O)St6·xH2O]St and free stearic acid. The formation of bigger polynuclear complexes with FeSt3 was related to higher hydrolysis and condensation rates within the iron(III) chloride solution compared to the iron(II) chloride solution. These data suggested a nucleation mechanism based on the condensation of polycation radicals generated by the catalytic departure of two stearate chains from an iron polycation-based molecule.

Rheological, Microstructural and Thermal Properties of Magnetic Poly(Ethylene Oxide)/Iron Oxide Nanocomposite Hydrogels Synthesized Using a One-Step Gamma-Irradiation Method.

Magnetic polymer gels are a new promising class of nanocomposite gels. In this work, magnetic PEO/iron oxide nanocomposite hydrogels were synthesized using the one-step -irradiation method starting from poly(ethylene oxide) (PEO) and iron(III) precursor alkaline aqueous suspensions followed by simultaneous crosslinking of PEO chains and reduction of Fe(III) precursor. -irradiation dose and concentrations of Fe3+, 2-propanol and PEO in the initial suspensions were varied and optimized. With 2-propanol and at high doses magnetic gels with embedded magnetite nanoparticles were obtained, as confirmed by XRD, SEM and Mössbauer spectrometry. The quantitative determination of -irradiation generated Fe2+ was performed using the 1,10-phenanthroline method. The maximal Fe2+ molar fraction of 0.55 was achieved at 300 kGy, pH = 12 and initial 5% of Fe3+. The DSC and rheological measurements confirmed the formation of a well-structured network. The thermal and rheological properties of gels depended on the dose, PEO concentration and initial Fe3+ content (amount of nanoparticles synthesized inside gels). More amorphous and stronger gels were formed at higher dose and higher nanoparticle content. The properties of synthesized gels were determined by the presence of magnetic iron oxide nanoparticles, which acted as reinforcing agents and additional crosslinkers of PEO chains thus facilitating the one-step gel formation.

Stabilization of a mixed iron vanadium based hexagonal tungsten bronze hydroxyfluoride HTB-(Fe0.55V0.45)F2.67(OH)0.33 as a positive electrode for lithium-ion batteries.

In our search for novel insertion compounds for Li-based batteries, we have identified a new mixed iron vanadium based Hexagonal Tungsten Bronze (HTB) type phase. Its synthesis involves two steps which consist first of preparing mixed metal hydrated fluoride Fe1.64V1.36F8(H2O)2 by a microwave assisted thermal process, followed by thermal treatment under air to obtain metastable HTB-(Fe0.55V0.45)F2.67(OH)0.33 hydroxyfluoride. 57Fe Mössbauer spectrometry demonstrates the presence of oxidation states Fe2+ and Fe3+ in Fe1.64V1.36F8(H2O)2 as opposed to only Fe3+ in HTB-(Fe0.55V0.47)F2.67(OH)0.33. Moreover, the Mössbauer spectra recorded at 77 K reveal that none of the compounds shows magnetic ordering owing to the presence of V3+ distributed over the crystallographic sites of Fe3+. Complementary X-ray spectroscopy and Rietveld refinement further confirm the successful synthesis of HTB-(Fe0.55V0.45)F2.67(OH)0.33. Electrochemically, the new HTB-(Fe0.55V0.45)F2.67(OH)0.33 shows a first discharge capacity of 181 mA h g-1 with 67% of this capacity remaining upon cycling. Unlike HTB-FeF2.66(OH)0.34, the structure remains stable after the first discharge confirming the positive effect of vanadium in the HTB network.

Chemical Inhomogeneity in Iron Oxide@CoO Core-Shell Nanoparticles: A Local Probe Study Using Zero-Field and In-Field 57Fe Mössbauer Spectrometry.

Core-shell magnetic nanoparticles type Fe3-xO4 (≈10 nm)@CoO (≈3 nm) prepared by forced hydrolysis in polyol medium have been investigated through the combined use of dc magnetization measurements by SQUID and local analysis by 57Fe Mössbauer spectrometry. A shift of the hysteresis loop along the field axis was observed, which highlights the presence of exchange bias coupling in these nanoparticles. This exchange bias coupling is accompanied by an unexpected high value of coercive field in hysteresis loop in mode ZFC. A local probe study using both zero-field and in-field Mössbauer spectrometry reveals complex hyperfine structures. Great attention is paid to the fitting procedure: it is concluded that Fe3-xO4@CoO nanoparticles result from a mixture of magnetite and maghemite phases in addition to the formation of an interface-like layer close to a cobalt ferrite. Such a structure explains both the high coercive field value observed by SQUID and the presence of exchange bias coupling.

Microwave Absorption and the Magnetic Hyperthermia Applications of Li0.3Zn0.3Co0.1Fe2.3O4 Nanoparticles in Multiwalled Carbon Nanotube Matrix.

Nanoparticles of Li0.3Zn0.3Co0.1Fe2.3O4 (LZC) were prepared by the sol-gel method and dried in a furnace at ∼200 °C. The dried sample was annealed at 500, 600, 700, and 800 °C for 5 h each. Rietveld analysis of X-ray diffraction patterns confirms the cubic Fd3̅m phase formation with lattice parameters ranged from 8.376 up to 8.390 Å and allows the crystallite sizes (dcryst) to be estimated. To enhance microwave (MW) absorption as well as the effectiveness for hyperthermia treatment, nanoparticles are taken in the matrix of multiwalled carbon nanotubes (MWCNTs) and the morphology of the so-prepared samples (LZC@MWCNT) was studied by scanning electron microscopy and transmission electron microscopy analyses. Both static and dynamic magnetic properties were investigated on the samples of LZC nanoparticles and compared to those of the samples of LZC@MWCNT. The samples annealed at 500, 600, and 800 °C are excellent candidates in cancer treatment as ac magnetic heating analysis shows that the hyperthermia temperature (42 °C) was successfully achieved for an applied ac magnetic field of 420 Oe and 300 kHz frequency. MW absorption study also reveals that the samples of LZC@MWCNT could be used as a potential MW absorbing material for which a maximum reflection loss (RL) of ∼-21 dB was achieved at a frequency of 15.27 GHz for only 1 mm layer thickness.

Atomic scale modeling of iron-doped biphasic calcium phosphate bioceramics.

Biphasic calcium phosphates (BCPs) are bioceramics composed of hydroxyapatite (HAp, Ca10(PO4)6(OH)2) and beta-Tricalcium Phosphate (ß-TCP, Ca3(PO4)2). Because their chemical and mineral composition closely resembles that of the mineral component of bone, they are potentially interesting candidates for bone repair surgery, and doping can advantageously be used to improve their biological behavior. However, it is important to describe the doping mechanism of BCP thoroughly in order to be able to master its synthesis and then to fully appraise the benefit of the doping process. In the present paper we describe the ferric doping mechanism: the crystallographic description of our samples, sintered at between 500°C and 1100°C, was provided by Rietveld analyses on X-ray powder diffraction, and the results were confirmed using X-ray absorption spectroscopy and 57Fe Mössbauer spectrometry. The mechanism is temperature-dependent, like the previously reported zinc doping mechanism. Doping was performed on the HAp phase, at high temperature only, by an insertion mechanism. The Fe3+ interstitial site is located in the HAp hexagonal channel, shifted from its centre to form a triangular three-fold coordination. At lower temperatures, the Fe3+ are located at the centre of the channel, forming linear two-fold coordinated O-Fe-O entities. The knowledge of the doping mechanism is a prerequisite for a correct synthesis of the targeted bioceramic with the adapted (Ca+Fe)/P ratio, and so to be able to correctly predict its potential iron release or magnetic properties. STATEMENT OF SIGNIFICANCE: Biphasic calcium phosphates (BCPs) are bioceramics composed of hydroxyapatite (HAp, Ca10(PO4)6(OH)2) and beta-Tricalium Phosphate (ß-TCP, Ca3(PO4)2). Because their chemical and mineral composition closely resembles that of the mineral component of bone, they are potentially interesting candidates for bone repair surgery. Doping can advantageously be used to improve their biological behaviors and/or magnetic properties; however, it is important to describe the doping mechanism of BCP thoroughly in order to fully appraise the benefit of the doping process. The present paper scrutinizes in detail the incorporation of ferric cation in order to correctly interpret the behavior of the iron-doped bioceramic in biological fluid. The temperature dependent mechanism has been fully described for the first time. And it clearly appears that temperature can be used to design the doping according to desired medical application: blood compatibility, remineralization, bactericidal or magnetic response.

Tuning the iron redox state inside a microporous porphyrinic metal organic framework.

Two new 3D porphyrin-based metal organic frameworks were obtained by solvothermally reacting iron(iii) chloride, a free base (5,10,15,20-tetrakis[4-(2,3,4,5-tetrazolyl)phenyl]porphyrin) (H2TTPP) and either pyrazine or 1,4-diazabicyclo[2.2.2]octane (DABCO). Both MOFs displayed a 3-D open framework of the fry topology, where the inorganic building unit is a chain of corner-sharing FeN4O2 octahedra and the porphyrinic linker is metallated with iron during the reaction course, with the N-donor base bridging the iron of the porphyrinic cores. Through thorough structural and spectroscopic analyses of the pyrazine containing material the chemical formula [FeIIpzTTP(FeDMF1-xFeOHx)]n was inferred (x ≥ 0.25). Whereas the already reported carboxylate analogue is built up from a pure iron(iii) inorganic chain, here spectroscopic and structural studies evidenced a mixed valence iron(ii/iii) state, evidencing that, in agreement with the HSAB theory, the substitution of a carboxylate function by a tetrazolate one allows redox tuning. Finally, both materials feature one-dimensional channels of ca. 8 × 12 Å within the structures with permanent microporosity.

Genetic manipulation of iron biomineralization enhances MR relaxivity in a ferritin-M6A chimeric complex.

Ferritin has gained significant attention as a potential reporter gene for in vivo imaging by magnetic resonance imaging (MRI). However, due to the ferritin ferrihydrite core, the relaxivity and sensitivity for detection of native ferritin is relatively low. We report here on a novel chimeric magneto-ferritin reporter gene - ferritin-M6A - in which the magnetite binding peptide from the magnetotactic bacteria magnetosome-associated Mms6 protein was fused to the C-terminal of murine h-ferritin. Biophysical experiments showed that purified ferritin-M6A assembled into a stable protein cage with the M6A protruding into the cage core, enabling magnetite biomineralisation. Ferritin-M6A-expressing C6-glioma cells showed enhanced (per iron) r2 relaxivity. MRI in vivo studies of ferritin-M6A-expressing tumour xenografts showed enhanced R2 relaxation rate in the central hypoxic region of the tumours. Such enhanced relaxivity would increase the sensitivity of ferritin as a reporter gene for non-invasive in vivo MRI-monitoring of cell delivery and differentiation in cellular or gene-based therapies.

Iron-Doped (La,Sr)MnO3 Manganites as Promising Mediators of Self-Controlled Magnetic Nanohyperthermia.

Fe-doped La0.77Sr0.23Mn1 - y Fe y O3 nanoparticles have been synthesized by sol-gel method, and ceramic samples based on them were sintered at 1613 K. Crystallographic and magnetic properties of obtained nanoparticles and ceramic samples have been studied. It has been established that cell volume for nanoparticles increases with growing of iron content, while this dependence displays an opposite trend in the case of ceramic samples. Mössbauer investigations have shown that in all samples, the oxidation state of iron is +3. According to magnetic studies, at room temperature, both nanoparticles and ceramic samples with y ≤ 0.06 display superparamagnetic properties and samples with y ≥ 0.08 are paramagnetic. Magnetic fluids based on La0.77Sr0.23Mn1 - y Fe y O3 nanoparticles and aqua solution of agarose have been prepared. It has been established that heating efficiency of nanoparticles under an alternating magnetic field decreases with growing of iron content.

New iron tetrazolate frameworks: synthesis, temperature effect, thermal behaviour, Mössbauer and magnetic studies.

The exploration of the FeF3/FeF2-Hamtetraz-HF system in dimethylformamide by solvothermal synthesis evidences two isostructural 3D hybrid fluoroferrates. They are prepared from the same starting mixture at two different synthesis temperatures: 120 °C for [Hdma]·(Fe4(II)Fe(III)F8(H2O)2(amtetraz)4) () and 140 °C for [Hdma]1.5·(Fe4.5(II)Fe0.5(III)F7(H2O)(HCOO)(amtetraz)4) (). Both compounds are characterized by single crystal X-ray diffraction, X-ray thermodiffraction, TGA analysis, Mössbauer spectrometry and SQUID magnetometry. They crystallize in the monoclinic system and are built from two distinct chains connected by aminotetrazolate anions. The first chain ∞(Fe(II)FN4) is common to and and can be found in numerous fluorides. In the second chain ∞(Fe3X12) (X = F, N, O), iron cations adopt both valence states Fe(ii)/Fe(iii). The hydrolysis of DMF implies the formation of a [Hdma](+) cation and a (HCOO)(-) anion. The presence of Fe(3+) in both phases is evidenced by (57)Fe Mössbauer spectrometry. The magnetic properties are studied and two transitions from a paramagnetic regime to a long range ordered state below 30 K and 5 K are identified.

A novel and easy chemical-clock synthesis of nanocrystalline iron-cobalt bearing layered double hydroxides.

A novel synthesis of cobalt-iron layered double hydroxide (LDH) with interlayer chlorides was investigated. The method consists in mixing concentrated solutions of hexaamminecobalt(III) trichloride with ferrous chloride at room temperature and in anoxic conditions. Four initial Fe/Co atomic ratios have been tried out (0.12, 0.6, 1.2 and 1.8). Neither heating nor addition of alkali was employed for adjusting the pH and precipitating the metal hydroxides. Still, each mixture led to the spontaneous precipitation of a LDH-rich solid having a crystal-chemistry that depended on the initial solution Fe/Co. These LDHs phases were carefully characterized by mean of X-ray diffraction, (57)Fe Mössbauer spectrometry, transmission electron microscopy and chemical analysis (total dissolution and phenanthroline method). Solution Eh and pH were also monitored during the synthesis. Increasing initial Fe/Co ratio impacted the dynamic of the observed stepwise reaction and the composition of the resulting product. Once the two solutions are mixed, a spontaneous and abrupt color change occurs after an induction time which depends on the starting Fe/Co ratio. This makes the overall process acting as a chemical clock. This spontaneous generation of CoFe-LDH arises from the interplay between redox chemistries of iron and cobalt-ammonium complexes.

A magnetic nanogel based on O-carboxymethylchitosan for antitumor drug delivery: synthesis, characterization and in vitro drug release.

This paper studied the synthesis, characterization and use of the magnetic chitosan nanogel for carrying meleimidic compounds. The hydrogel polymer was prepared using O-carboxymethylchitosan, which was crosslinked with epichlorohydrin for subsequent incorporation of iron oxide magnetic nanoparticles. The characterization revealed that the magnetic material comprises about 10% of the hydrogel. This material is comprised of magnetite and maghemite and exhibits ferro-ferrimagnetic behavior. The average particle size is 4.2 nm. There was high incorporation efficiency of maleimides in the magnetic nanogel. The release was of sustained character and there was a greater release when an external magnetic field was applied. The mathematical model that best explained the process of drug release by the magnetic hydrogel was that of Peppas-Sahlin. The magnetic nanogel proved to be an excellent candidate for use in drug-delivery systems.

Modelling CEC variations versus structural iron reduction levels in dioctahedral smectites. Existing approaches, new data and model refinements.

A model was developed to describe how the 2:1 layer excess negative charge induced by the reduction of Fe(III) to Fe(II) by sodium dithionite buffered with citrate-bicarbonate is balanced and applied to nontronites. This model is based on new experimental data and extends structural interpretation introduced by a former model [36-38]. The 2:1 layer negative charge increase due to Fe(III) to Fe(II) reduction is balanced by an excess adsorption of cations in the clay interlayers and a specific sorption of H(+) from solution. Prevalence of one compensating mechanism over the other is related to the growing lattice distortion induced by structural Fe(III) reduction. At low reduction levels, cation adsorption dominates and some of the incorporated protons react with structural OH groups, leading to a dehydroxylation of the structure. Starting from a moderate reduction level, other structural changes occur, leading to a reorganisation of the octahedral and tetrahedral lattice: migration or release of cations, intense dehydroxylation and bonding of protons to undersaturated oxygen atoms. Experimental data highlight some particular properties of ferruginous smectites regarding chemical reduction. Contrary to previous assumptions, the negative layer charge of nontronites does not only increase towards a plateau value upon reduction. A peak is observed in the reduction domain. After this peak, the negative layer charge decreases upon extended reduction (>30%). The decrease is so dramatic that the layer charge of highly reduced nontronites can fall below that of its fully oxidised counterpart. Furthermore, the presence of a large amount of tetrahedral Fe seems to promote intense clay structural changes and Fe reducibility. Our newly acquired data clearly show that models currently available in the literature cannot be applied to the whole reduction range of clay structural Fe. Moreover, changes in the model normalising procedure clearly demonstrate that the investigated low tetrahedral bearing nontronites (SWa-1, GAN and NAu-1) all exhibit the same behaviour at low reduction levels. Consequently, we restricted our model to the case of moderate reduction (<30%) in low tetrahedral Fe-bearing nontronites. Our adapted model provides the relative amounts of Na(+) (p) and H(+) (ni) cations incorporated in the structure as a function of the amount of Fe reduction. Two equations enable the investigated systems to be described: p=m/(1+Kr·ω·mrel) and ni=Kr·ω·m·mrel/(1+Kr·ω·mrel); where m is the Fe(II) content, mrel, the reduction level (m/mtot), ω, the cation exchange capacity (CEC, and Kr, an empirical constant specific to the system.

On the use of amine-borane complexes to synthesize iron nanoparticles.

The effectiveness of amine-borane as reducing agent for the synthesis of iron nanoparticles has been investigated. Large (2-4 nm) Fe nanoparticles were obtained from [Fe{N(SiMe3)2}2]. Inclusion of boron in the nanoparticles is clearly evidenced by extended X-ray absorption fine structure spectroscopy and Mössbauer spectrometry. Furthermore, the reactivity of amine-borane and amino-borane complexes in the presence of pure Fe nanoparticles has been investigated. Dihydrogen evolution was observed in both cases, which suggests the potential of Fe nanoparticles to promote the release of dihydrogen from amine-borane and amino-borane moieties.

Adsorption of hydrogen gas and redox processes in clays.

In order to assess the adsorption properties of hydrogen gas and reactivity of adsorbed hydrogen, we measured H(2)(g) adsorption on Na synthetic montmorillonite-type clays and Callovo-Oxfordian (COx) clayrock using gas chromatography. Synthetic montmorillonites with increasing structural Fe(III) substitution (0 wt %, 3.2 wt %, and 6.4 wt % Fe) were used. Fe in the synthetic montmorillonites is principally present as structural Fe(III) ions. We studied the concomitant reduction of structural Fe(III) in the clays using (57)Fe Mössbauer spectrometry. The COx, which mainly contains smectite/illite and calcite minerals, is also studied together with the pure clay fraction of this clayrock. Experiments were performed with dry clay samples which were reacted with hydrogen gas at 90 and 120 °C for 30 to 45 days at a hydrogen partial pressure close to 0.45 bar. Results indicate that up to 0.11 wt % of hydrogen is adsorbed on the clays at 90 °C under 0.45 bar of relative pressure. (57)Fe Mössbauer spectrometry shows that up to 6% of the total structural Fe(III) initially present in these synthetic clays is reduced upon adsorption of hydrogen gas. No reduction is observed with the COx sample in the present experimental conditions.