Institut de Chimie des Milieux et des Matériaux de Poitiers

Within the framework of green chemistry, solvents occupy a strategic place. To be qualified as a green medium, these solvents have to meet different criteria such as availability, non-toxicity, biodegradability, recyclability, flammability, and low price among others. Up to now, the number of available green solvents are rather limited. Here we wish to discuss a new family of ionic fluids, so-called Deep Eutectic Solvents (DES), that are now rapidly emerging in the current literature. A DES is a fluid generally composed of two or three cheap and safe components that are capable of self-association, often through hydrogen bond interactions, to form a eutectic mixture with a melting point lower than that of each individual component. DESs are generally liquid at temperatures lower than 100 °C. These DESs exhibit similar physico-chemical properties to the traditionally used ionic liquids, while being much cheaper and environmentally friendlier. Owing to these remarkable advantages, DESs are now of growing interest in many fields of research. In this review, we report the major contributions of DESs in catalysis, organic synthesis, dissolution and extraction processes, electrochemistry and material chemistry. All works discussed in this review aim at demonstrating that DESs not only allow the design of eco-efficient processes but also open a straightforward access to new chemicals and materials.

International audience

International audience

This is a critical review on lignin valorization through oxidation reactions focusing on innovative approaches involving heterogeneous catalysis and unconventional activation methods and solvents.

H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.

Ti_nC_n−1T_x2D-sheets are functionalized using a new etching environment allowing the modification of their surface chemistry and production of rationalized TiO₂@MXene nanocomposites.

Presently, conventional technologies in water treatment are not efficient enough to completely mineralize refractory water contaminants. In this context, the implementation of catalytic processes could be an alternative. Despite the advantages provided in terms of kinetics of transformation, selectivity, and energy saving, numerous attempts have not yet led to implementation at an industrial scale. This review examines investigations at different scales for which controversies and limitations must be solved to bridge the gap between fundamentals and practical developments. Particular attention has been paid to the development of solar-driven catalytic technologies and some other emerging processes, such as microwave assisted catalysis, plasma-catalytic processes, or biocatalytic remediation, taking into account their specific advantages and the drawbacks. Challenges for which a better understanding related to the complexity of the systems and the coexistence of various solid-liquid-gas interfaces have been identified.

Highly active self-supported PdxBi catalysts are synthesized by the sacrificial support method. Self-supported PdxBi catalysts have a porous nanostructured morphology with high surface areas (in the range from 75 to 100 m(2) g(-1)), making PdxBi a state-of-the-art catalyst. Pd4Bi displays the highest activity toward glycerol oxidation. In situ Fourier transform infrared spectroscopy highlights the unique catalytic behavior of self-supported PdxBi materials due to their particular structure and morphology. The confinement of reactants and intermediates in pores acting as nanoreactors is responsible for the high selectivity as a function of the electrode potential: aldehyde and ketone at low potentials, hydroxypyruvate at moderate potentials, and CO2 at high potentials. Moreover, the selectivity depends on the electrode history: it is different for the positive potential scan direction than for the reverse direction, where the catalyst becomes selective toward the production of carboxylates.

Core Ideas OZCAR is a network of sites studying the critical zone. OZCAR covers various disciplines. OZCAR will help disciplines to work together for a better representation and modeling of the critical zone. The French critical zone initiative, called OZCAR (Observatoires de la Zone Critique–Application et Recherche or Critical Zone Observatories–Application and Research) is a National Research Infrastructure (RI). OZCAR‐RI is a network of instrumented sites, bringing together 21 pre‐existing research observatories monitoring different compartments of the zone situated between “the rock and the sky,” the Earth's skin or critical zone (CZ), over the long term. These observatories are regionally based and have specific initial scientific questions, monitoring strategies, databases, and modeling activities. The diversity of OZCAR‐RI observatories and sites is well representative of the heterogeneity of the CZ and of the scientific communities studying it. Despite this diversity, all OZCAR‐RI sites share a main overarching mandate, which is to monitor, understand, and predict (“earthcast”) the fluxes of water and matter of the Earth's near surface and how they will change in response to the “new climatic regime.” The vision for OZCAR strategic development aims at designing an open infrastructure, building a national CZ community able to share a systemic representation of the CZ, and educating a new generation of scientists more apt to tackle the wicked problem of the Anthropocene. OZCAR articulates around: (i) a set of common scientific questions and cross‐cutting scientific activities using the wealth of OZCAR‐RI observatories, (ii) an ambitious instrumental development program, and (iii) a better interaction between data and models to integrate the different time and spatial scales. Internationally, OZCAR‐RI aims at strengthening the CZ community by providing a model of organization for pre‐existing observatories and by offering CZ instrumented sites. OZCAR is one of two French mirrors of the European Strategy Forum on Research Infrastructure (eLTER‐ESFRI) project.

Abstract This present study provides an overview of the clay-mineral reactions involved in the chloritization process in a mixed-layer mineral series, and focuses on the properties of the resulting lowtemperature chlorites (formed at <220°C) in diagenetic and hydrothermal systems. According to the literature, most chlorite species occurring in low-temperature geological systems are derived fromspecific clay precursors except for direct precipitates from solution in veins. In addition, three main types of clay-mineral series have been associated with these chloritization processes: saponite-to-chlorite, berthierineto- chlorite and kaolinite-to-sudoite reactions. The conversion of saponite to chlorite results in the most common sequence of trioctahedral clay minerals related to the occurrence of Mg-Fe trioctahedral chlorite in a wide variety of hydrothermal and diagenetic to very low-grade metamorphism environments. Two models were proposed in the literature to describe the saponite-to-chlorite conversion through corrensite. The first model is a continuous transition model based on solid-state transformation (SST) mechanisms and is valid in rock-dominated systems (closed micro-systems with very low fluid-rock ratios). The second model is a stepwise transition model based on dissolution-crystallization mechanisms (DC) and is efficient in fluid-dominated systems (open systems with high fluid-rock ratio). The berthierine to Fechlorite transition results in a sequence of trioctahedral phases which are related to chloritization processes in iron-rich and reducing environments. This transformation is a cell-preserved phase transition dominated by a SST mechanismthat operates simultaneously in different domains of the parental mineral and may be considered as a polymorphic mineral reaction. Finally, the conversion of kaolinite to sudoite (Al-Mg ditrioctahedral chlorite) has not been documented like the other two aforementioned conversion series. Despite the scarcity of detailed investigations, the conversion of kaolinite to sudoite through tosudite is considered a stepwise mineral reaction that is dominated by a DC mechanism. From a compilation of literature data, it appears that several parameters of hydrothermal and diagenetic chlorites differ, including the minimal temperature, the textural and structural characteristics and the extents of compositional fields. In hydrothermal systems, discrete chlorite occurs at a minimal temperature near 200°C, regardless of its chemical composition. In diagenetic systems, discrete chlorite occurs at minimal temperatures that vary according to its crystal chemistry (100–120°C for Mg-chlorite as opposed to 40–120°C for Fe chlorite). The strong discrepancy between the lowest temperature at which Mg- and Fe-chlorite form in buried sediments and in geothermal systems should result from drastically different heating rates, heat-flow conditions and tectonism between basins at passivemargins and geothermal systems at active margins. The morphology, structure and compositional fields of the diagenetic Fe-rich chlorite may have been inherited from those of the berthierine precursor. All of the chlorite species formed through theDC mechanism have good geothermometry potential. However, the SST mechanism in which berthierine is transformed into chlorite could have unexplored consequences regarding the use of the chemistry (including stable isotope composition) of diagenetic Fe-chlorite for reconstructing the burial history of sediments. Further investigations regarding the formationmechanisms of mixed-layerminerals are required to provide us with insight to understand the chloritization process in low-temperature geological systems.

To investigate metal oxide surface catalysis, determining an appropriate Hubbard U-correction term is a challenge for the density functional theory (DFT) community and identifying realistic reaction intermediates and their corresponding X-ray photoelectron spectroscopy (XPS) shifts is a challenge for experimental researchers, when these methods are used independently. In this study, using CuO as a model transition metal oxide, we demonstrate that when DFT and XPS are applied synergistically, the determination of the U value and the identification of adsorbate/intermediate species on the surface (and their XPS shifts) can be done simultaneously. The experimental O 1s spectra of the as-synthesized CuO 2D-nanoleaves shows the presence of four different peaks with core level binding energies (CLBEs) of 529.7, 531.4, 533.2, and 534.6 eV. DFT is used to calculate the CLBE shifts for probable adsorbed moieties, in various adsorption configurations, on both, clean and vacancy defect containing surfaces. Comparison of experimental and theoretical CLBEs across the entire U value range of 0–9 eV narrows down the list to only four moieties, namely, O2 in the η1(O) configuration, H2O at the surface oxygen vacancy site, and adsorbed HCO3 and HCO2 (resembling adsorbed HCO3). Finally, the U value of 4–4.5 eV reproduces the experimental CLBE shifts correctly and thus, establishes these experimental XPS spectral peaks to the adsorbates and their geometries. The integrated approach elucidated in this article, results in the identification of adsorbates/intermediates (and their CLBEs) for the experimental XPS spectral analysis and the determination of an appropriate U value concurrently, to study metal oxide surface catalysis.

Mesopores are “highways” for mass transfer inside zeolite crystals and enhance the formation of mono-aromatic hydrocarbons from biomass pyrolysis.

This review describes the rapid evolution of chemistry in the context of a sustainable development of our society. Written in collaboration between scientists from different horizons, either from public organizations or chemical companies, we aim here at providing recommendations to accelerate the emergence of eco-designed products on the market.

Antimicrobial resistance (AMR) is a major global public health concern, shared by a large number of human and animal health actors. Within the framework of a One Health approach, actions should be implemented in the environmental realm, as well as the human and animal realms. The Government of France commissioned a report to provide policy and decision makers with an evidential basis for recommending or taking future actions to mitigate AMR in the environment. We first examined the mechanisms that underlie the emergence and persistence of antimicrobial resistance in the environment. This report drew up an inventory of the contamination of aquatic and terrestrial environments by AMR and antibiotics, anticipating that the findings will be representative of some other high-income countries. Effluents of wastewater treatment plants were identified as the major source of contamination on French territory, with spreading of organic waste products as a more diffuse and incidental contamination of aquatic environments. A limitation of this review is the heterogeneity of available data in space and time, as well as the lack of data for certain sources. Comparing the French Measured Environmental Concentrations (MECs) with predicted no effect concentrations (PNECs), fluoroquinolones and trimethoprim were identified as representing high and medium risk of favoring the selection of resistant bacteria in treated wastewater and in the most contaminated rivers. All other antibiotic molecules analyzed (erythromycin, clarithromycin, azithromycin, tetracycline) were at low risk of resistance selection in those environments. However, the heterogeneity of the data available impairs their full exploitation. Consequently, we listed indicators to survey AMR and antibiotics in the environment and recommended the harmonization of sampling strategies and endpoints for analyses. Finally, the objectives and methods used for the present work could comprise a useful example for how national authorities of countries sharing common socio-geographic characteristics with France could seek to better understand and define the environmental dimension of AMR in their particular settings.

Confirmed by DFT, a significant amount of platinum atoms are chemically bound to N of N-doped RGO.

We have performed first-principles evolutionary searches for stable Ti-N compounds and have found, in addition to the well-known rock-salt TiN, new ground states Ti3N2, Ti4N3, Ti6N5 at atmospheric pressure, and Ti2N and TiN2 at higher pressures. The latter nitrogen-rich structure contains encapsulated N2 dumbbells with a N-N distance of 1.348 Å at 60 GPa. TiN2 is predicted to be mechanically stable and quenchable. Our calculations on the mechanical properties (bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and hardness) are in excellent agreement with the available experimental data. Further analyses of the electronic density of states, crystal orbital Hamilton population and the electron localization function reveal that the hardness is enhanced by strengthening directional covalent bonds and disappearance of Ti-Ti metallic bonding.

NiO and NiO-CuO polycrystalline rodlike nanoparticles were confined and stabilized within the channels of ordered mesoporous SBA-15 silica by a simple and viable approach consisting in incipient wetness impregnation of the calcined support with aqueous solutions of metal nitrates followed by a mild drying step at 25 °C and calcination. As revealed by low- and high-angle XRD, N2 adsorption/desorption, HRTEM/EDXS and H2 TPR analyses, the morphostructural properties of NiO-CuO nanoparticles can be controlled by adjusting their chemical composition, creating the prerequisites to obtain high performance bimetallic catalysts. Experimental evidence by in situ XRD monitoring during the thermoprogrammed reduction indicates that the confined NiO-CuO nanoparticles evolve into thermostable and well-dispersed Ni-Cu heterostructures. The strong Cu-Ni and Ni-support interactions demonstrated by TPR and XPS were put forward to explain the formation of these new bimetallic structures. The optimal Ni-Cu/SBA-15 catalyst (i.e., Cu/(Cu+Ni) atomic ratio of 0.2) proved a greatly enhanced reducibility and H2 chemisorption capacity, and an improved activity in the hydrogenation of cinnamaldehyde, as compared with the monometallic Ni/SBA-15 or Cu/SBA-15 counterparts, which can be associated with the synergism between nickel and copper and high dispersion of active components on the SBA-15 host. The unique structure and controllable properties of both oxidic and metallic forms of Ni-Cu/SBA-15 materials make them very attractive for both fundamental research and practical catalytic applications.

A comprehensive overview of the catalysts developed for the electrooxidation of glycerol with the aim of producing selectively value-added compounds is proposed in the present contribution. By presenting the main results reported in the literature on glycerol electrooxidation in acidic and alkaline media, using different kinds of catalytic materials (monometallic catalysts based on platinum group metals and non-noble metals, multimetallic alloys, or modification of surfaces by adatoms, etc.) and under different experimental conditions, some general trends concerning the effects of catalyst composition and structure, of reaction medium and of the electrode potential to enhance the activity for the glycerol oxidation reaction and of the selectivity toward a unique value-added product will be presented and discussed. The objective is to provide a guideline for the development of electrochemical systems which allow performing the electrooxidation of glycerol at the rate and selectivity as high as possible.

Strain resulting from the collision of India with Asia has caused fundamental changes to Asian drainage patterns, but the timing and nature of these changes are poorly understood. One frequently proposed hypothesis involves the connection of the palaeo Tsangpo drainage to a precursor to the Irrawaddy River of central Myanmar in the Palaeogene. To test this hypothesis, we studied the provenance of Palaeogene fluvio-clastic sedimentary rocks that crop out in central Myanmar, namely the Late Middle Eocene–Early Oligocene Pondaung and Yaw Formations. Isotopic analysis on bulk-rock and petrographic data indicate a primary magmatic arc source, and a secondary source composed of recycled, metamorphosed basement material. Although the exact location of both sources is hardly distinguishable because Burmese and Tibetan provinces share common lithological features, the presence of low-grade metamorphic fragments, the heterogeneity in Sr–Nd isotopic values of bulk sediments and westward-directed palaeoflow orientations indicate a proximal source area located on the eastern Asian margin. Central Myanmar was the locus of westward-prograding deltas opening into the Indian Ocean, supplied by the unroofing of an Andean-type cordillera that extended along the Burmese margin. We found no evidence to support a palaeo Tsangpo–Irrawaddy River, at least during the Late Eocene. Supplementary material: Data locations, and isotopic and petrographic results are available at www.geolsoc.org.uk/SUP18655 .

electronic properties. Finally, the crucial role in the MXene's functionalization of the etchant used for its synthesis is evidenced by locally determining the [O]/[F] concentration ratio using the corresponding K edges. This ratio is shown to be drastically increased from 1.4 to 3.5 when using HF or LiF/HCl respectively.