With the ever-growing sales of electric vehicles (EVs) in the world and uncontrolled consumption of nonrenewable lithium resources for lithium-ion batteries (LIBs), new materials were proposed to reinforce the recycling technologies that are currently in use. For such purpose, the design and synthesis of a new crown etherbearing monomer, namely 2-(benzo-12-crown-4-ether)ethyl methacrylamide (BCEEM), its copolymerization with N-isopropylacrylamide (NiPAAm) and its adsorption properties were studied. While crown ethers (CEs) are well known for their metal adsorption properties, NiPAAm brought thermoresponsive properties to the copolymer, allowing for sorption at certain temperatures, and great processability through precipitation at other temperatures. With varied BCEEM/NiPAAm ratios, Lower Critical Solution Temperatures (LCST) ranged from 6 to 26.5 degrees C. Regarding the sorption performances by the CEs, several parameters were varied, such as pH, temperature and Li/CE ratio. Under optimized experimental conditions, the lithium sorption isotherm highlighted a maximum adsorption capacity of 0.075 mmol/g polymer (0.55 mg.g- 1), which is in the lower limit compared to similar CE studies reported in the literature. Moreover, competitive sorption studied in multicomponent solutions (Li, Co, Ni, Mn) simulating lithium-ion batteries (LIB) leachates (containing mostly lithium and cobalt), as well as in solutions with increased amounts of nickel and manganese, showed that selectivity towards lithium (and to a lesser extent cobalt) appeared to depend on the relative concentration of these two elements compared to Ni and Mn. In leachate-like conditions, the copolymer showed selectivity towards Li and Co whereas the selectivity evolved towards Ni and Mn as the initial concentration of Ni and Mn increased. DLS and ITC measurements were undergone to comprehend the obtained sorption capacities and selectivity from a mechanistic and thermodynamic point of view. While DLS measurements indicated potential salting-out effect of the ions causing degradation of water and metal interactions with the CEs, ITC experiments shed light on the potential culprit: the rigidity and hydrophobicity of the benzo-group.

This work presents supramolecular coassembled nucleobase copolymers with transitional morphologies upon pH changes (from 7.4 to 10). Uracil- and adenine-containing copolymers were prepared by RAFT, which allowed us to finely tailor the polymerization degree and the composition. The coassembled formulations prepared in an aqueous buffer at two distinct pH (7.4 and 10) formed spherical morphologies at physiological pH. The increase of the pH induced the apparition of various large, irreversible anisotropic supramolecular architectures. Isothermal titration calorimetry revealed that the coassembly at pH 7.4 was mainly guided by H-bonds between complementary nucleobases, while the experiments conducted at pH 10 showed that the assemblies were mainly driven by hydrophobic interactions. These results highlight that the nature of supramolecular interactions (H-bonds or hydrophobic interactions) has a great influence on the morphology of nucleobase-containing coassemblies when changing the pH. These findings may provide further perspectives in the field of advanced nanomaterials.

We report the ionothermal carbonization (ITC) of lignocellulosic biomass in imidazolium tetrachloroferrate ionic liquids (ILs) as an advantageous approach for the preparation of nanostructured carbonaceous materials, namely, ionochars. In a previous study, we investigated the role of the imidazolium cation and demonstrated the possibility of controlling both the textural and morphological properties of ionochars by cation engineering. Although essential for providing intermediate Lewis acidity and relatively high thermal stability, the role of the chloroferrate anion is still open to debate. Herein, we investigated the ITC of sugarcane bagasse and its main component, cellulose, in 1-alkyl-3-methylimidazolium ILs with different chloroferrate anions. We identified anionic speciation and its impact on the properties of the IL by Raman spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The obtained ionochars were characterized by gas physisorption, electron microscopy, Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and 13C solid-state CP-MAS NMR spectroscopy. We show that the anionic species have a predominant impact on the textural and morphological properties of the ionochars.

CH 3 -functionalised imogolite nanotubes form extended bundles and the accessibility of their porous structure may vary depending on the surrounding medium.

Original α-aminobisphosphonate-based copolymers were synthesized and successfully used for actinide complexation. For this purpose, poly(α-chloro-ε-caprolactone-co-ε-caprolactone)-b-poly(ethylene glycol)-b-poly(α-chloro-ε-caprolactone-co-ε-caprolactone) copolymers were first prepared by ring-opening copolymerization of ε-caprolactone (εCL) and α-chloro-ε-caprolactone using poly(ethylene glycol) (PEG) as a macro-initiator and tin(II) octanoate as a catalyst. The chloride functions were then converted to azide moieties by chemical modification, and finally α-aminobisphosphonate alkyne ligand (TzBP) was grafted using click chemistry, to afford well-defined poly(αTzBPεCL-co-εCL)-b-PEG-b-poly(αTzBPεCL-co-εCL) copolymers. Three copolymers, showing different α-aminobisphosphonate group ratios, were prepared (7, 18, and 38%), namely, CP8, CP9, and CP10, respectively. They were characterized by 1H and 31P NMR and size exclusion chromatography. Sorption properties of these copolymers were evaluated by isothermal titration calorimetry (ITC) with neodymium [Nd(III)] and cerium [Ce(III)] cations, used as surrogates of actinides, especially uranium and plutonium, respectively. ITC enabled the determination of the full thermodynamic profile and the calculation of the complete set of thermodynamic parameter (ΔH, TΔS, and ΔG), with the Ka constant and the n stoichiometry. The results showed that the number of cations sorbed by the functional copolymers logically increased with the number of bisphosphonate functions borne by the macromolecular chain, independently of the complexed cation. Additionally, CP9 and CP10 copolymers showed higher sorption capacities [21.4 and 34.0 mg·g-1 for Nd(III) and 9.6 and 14.3 mg·g-1 for Ce(III), respectively] than most of the systems previously described in the literature. CP9 also showed a highest binding constant (7000 M-1). These copolymers, based on non-toxic and biocompatible poly(ε-caprolactone) and PEG, are of great interest for external body decontamination of actinides as they combine high number of complexing groups, thus leading to great decontamination efficiency, and limited diffusion through the skin due to their high-molecular weight, thus avoiding additional possible internal contamination.

NaLa(SO4)2,H2O crystalline powder was obtained under hydrothermal conditions at 220 degrees C. A coupled TGA/DTA experiment of NaLa(SO4)2,H2O exhibits a weight loss at 260 degrees C corresponding to the dehydration and an endo-thermal peak at 774 degrees C. To elucidate the transformation mechanism as a function of temperature, single crystals have been grown at 80 degrees C, 300 and 800 degrees C. For each phase, single crystals have been isolated and structure determination was performed. As already published, NaLa(SO4)2,H2O crystallizes in a P3121 space group. However, the dehydration at 260 degrees C is not a simple loss of the water molecule but a radical change in the structure. The removal of the water molecules inside the tunnels formed by the framework leads to a change in the coor-dination of the LaO9 Lanthanum-based polyhedrons. The compound obtained after dehydration is a new triple sulfate of the formula Na3La(SO4)3 crystallizing in the R-3 space group (a = 14.0976(1) angstrom; c = 8.1267(1) angstrom) with LaO12 icosahedrons. Millimeter size single crystals of this new phase have been grown under hydrothermal conditions (300 degrees C, 157 bars). After the endothermal peak at 774 degrees C, Na3La(SO4)3 decomposes by forming the anhydrous double sulfate NaLa(SO4)2 crystallizing in the P-1 space group with LaO10 polyhedrons. The structure of the three (NaLa)-compounds at RT, 300 degrees C and 800 degrees C is compatible with the expected Raman signatures. Finally, a complete transformation of NaLa(SO4)2,H2O up to 800 degrees C is proposed. After 1000 degrees C, the compound decomposes chemically with a large weight loss.

Water-soluble polymers are attractive materials for pollutants removal thanks to their ability to easily interact with soluble metal cations. In the present contribution, the chemical modification of biocompatible and non-toxic poly(vinyl alcohol) (PVA) was achieved with ethylene diamine tetraacetic acid (EDTA) groups, thus leading to new water-soluble polymers, named PVA(EDTA). Modification was carried out using Mitsunobu?s reaction as an original pathway to obtain statistical copolymers with different EDTA functionalization rates in the PVA chains. Preliminary study about the variation of EDTA rate and chain length permitted determining the optimal polymeric structures. Then, sorption properties of heavy metal (i.e. Co(II), Ni(II), Zn(II), Pb(II), Cd(II), Cu(II)) on structures containing 15% of chelating agent were determined by performing thorough adsorption isotherms or determining removal percentage, at a high or low concentration, respectively. Additionally, the performances of the polymers were tested in a more complex effluent constituted by previous pollutants in the presence of Ca(II) and Mn(II) cations. We demonstrated that water-soluble PVA(EDTA) led to a great improvement of sorption properties in comparison with PVA. Indeed, results obtained showed high sorption capacities for Pb(II), Ni(II), Zn (II), and good selectivity towards some cations, in consistency with EDTA-metal complex formation constants. Isotherm Titration Calorimetry measurements allowed evidencing the complexation stoichiometry, and determining the interaction constant and the enthalpy. This study highlighted the interest of modifying basic commercial polymers with chelating agents for further applications based on Polymer Enhanced Ultrafiltration (PEUF) process.

19 Metal-organic frameworks (MOFs)/Graphene oxide (GO) composites are of growing interest due 20 to their properties which can exceed those of the pure components, including post-combustion CO2 21 capture. Series of composites suitable for CO2 capture under flue gas conditions based on the 22 microporous water stable MIL-91(Ti) have been prepared with different GO contents, following 23 two routes, in situ and post-synthetic. It was observed that the 5wt% GO in situ composite exhibits 24 a semi-conducting behavior, while the post-synthetic materials are insulating, even with high 25

a. Institut des Matériaux Poreux de Paris, ESPCI Paris, Ecole Normale Supérieure, CNRS, PSL University, 75005 Paris, France. b. ICGM, Univ. Montpellier, CNRS, ENSCM, Montpellier, France. c. Institut Lavoisier de Versailles, UMR 8180 CNRS, Université de Versailles St Quentin en Yvelines, Université Paris Saclay, Versailles, France. d. Service de Thermodynamique et de Physique mathématique, Faculté Polytechnique, Université de Mons, 7000 Mons, Belgium. e. Fraunhofer Institute for Chemical Technology ICT Joseph-von-Fraunhofer St. 7, 76327 Pfinztal, Germany. f. Université Paris-Saclay, CNRS, Centre de Nanosciences et de Nanotechnologies, 91120, Palaiseau, France.

Metal–organic frameworks/graphene oxide in situ composites are promising candidates for the CO2 capture microwave swing adsorption process.

The performances of binderless FAU-X monoliths (0.5 x 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 nano crystals. Data have been confronted to those recently reported for a benchmark reference Cs+ adsorbent Sorbmatech (R), based on copper hexacyanoferrate nanoparticles (15 nm) immobilized into mesoporous silica particles (250-500 pm) (Cu-HCF@SiO2). FAU-X monoliths show high rate of adsorption in batch in less than 2 min, much faster than Cs+ adsorption in FAU-X particles (60 min). This result highlights the importance of a homogeneous macropore network in adsorbents to enhance mass transport and access to the zeolite active sites. FAU-X monoliths with 20 mu m macropore diameter have been used in continuous flow experiments for sequestering Cs+ (0.5 mmol/L) in mineral drinking water containing competing cations (Ca2+, Mg2+, Na+, K+) with flow rates of 0.5-1 mL/min, corresponding to Darcy rates of 1.5-3 m/h. FAU-X monoliths are very efficient for Cs+ removal and show ideal steep breakthrough curves characteristic of fast diffusion. FAU-X monoliths are as excellent as Cu-HCF@SiO2 and could represent an alternative adsorbent for safer processes, avoiding the handling of powders or particles. Above all, this study reveals the unique hydrodynamic behavior of FAU-X monoliths and opens the route for process intensification using FAU-X in continuous flow.

Post-synthesis modification of MIL-101(Cr)-NO2 was explored in order to decorate the organic backbone by propyl-sulfonic groups, with the aim to incorporate mobile and acidic protons for solid-state proton electrolyte applications. The resulting solid switched from insulating towards proton superconductive behavior under humidity, while the conductivity recorded at 363 K and 95 % relative humidity reached 4.8×10-3  S cm-1 . Propitiously, the impregnation of the material by strong acidic molecules (H2 SO4 ) further boosted the proton conductivity performances up to the remarkable σ value of 1.3×10-1  S cm-1 at 363 K/95 % RH, which reaches the performances of the best proton conductive MOF reported so far.

An alternative microwave-assisted hydrothermal route for the preparation of manganate nanoflowers under basic conditions has been proposed in view of potential uses in selective retention of strontium from multicomponent aqueous streams. Based on the combination of such characterization techniques as Scanning and Transmission Electronic Microscopy, X-ray photoelectron spectroscopy, and X-ray Diffraction, as well as taking advantage of the computer-aided structure simulation, homogeneous nanoflower morphology possessing a layered structure and K+ compensating cations was evidenced as corresponding to the KMn4O8 chemical formula. The nanoflower sample was subsequently tested for the selective adsorption of strontium and cesium by measuring the individual adsorption isotherms from single-solute and multicomponent aqueous solutions. The material appeared selective towards strontium against cesium even in multicomponent solutions provided that the concentration of calcium remained low. This difference in the retention selectivity was rationalized based on the Density Functional Theory (DFT) calculations of the energy of adsorption and direct calorimetry measurements of the enthalpy of displacement for the individual cations.

In this study, binding of linear poly(l-lysine) to a series of acrylamide and 2-acrylamido-2-methyl-1-propanesulfonate copolymers was examined by isothermal titration calorimetry (ITC). Binding constant and stoichiometry were systematically determined at different ionic strengths and for different polyanion charge densities varying between 15% and 100%. The range of investigated ionic strengths was carefully adjusted according to the polyanion charge densities to get measurable binding constants (i.e., formation binding constant typically comprised between 104 and 106 M-1) by isothermal titration calorimetry (ITC). The number of released counterions during the polyelectrolyte complex formation was determined from the log-log dependence of the binding constant according to the ionic strength and was compared to the total number of condensed counterions estimated from the Manning theory. Experimental results obtained by ITC are in very good agreement with those previously obtained by frontal analysis continuous capillary electrophoresis (FACCE) and can be used to model and predict the binding parameters at any ionic strength or any polyanion charge density. Thermodynamic parameters of the complexation between the oppositely charged polyelectrolytes confirm that the complex formation was entropically driven together with a favorable (but minor) enthalpic contribution. For the first time, specificities, advantages/disadvantages of ITC, and FACCE techniques for studying polyelectrolyte complexations are compared and discussed, using the same experimental conditions.

Ammonium based hybrid ionosilicas were prepared from tetrasilylated ammonium precursors. The formed material exhibited high specific surface area together with mesoporosity. Our results indicate that ionosilicas display high exchange capacity for iodide. They were submitted to 10MeV electron irradiation at a total dose of 1.7MGy. Irradiation was shown not to alter the properties of ionosilica: the morphological, textural and surface properties of the material are hardly modified. The sorption properties (sorption capacity and cumulative displacement enthalpy) are similar before and after electron irradiation. This high radiolytical stability confirms that these innovative materials have therefore high potential as anion traps for future applications in decontamination processes or long term storage of radioactive waste.