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1. Unraveling the Crystal Structure of Sodium Tetrabenzylborate: Synthesis through the Sodium Borohydride Reduction of Benzaldehyde in the Solid State

Author

Carlos A. Castilla-Martinez, Dominique Granier, Pascal G. Yot, and Umit B. Demirci

Subjects
borate, tetraalkoxyborate, sodium borohydride, benzaldehyde, Inorganic chemistry, QD146-197
Abstract

We present the synthesis, characterization, and crystal structure of sodium tetrabenzylborate, a novel tetraalkoxyborate obtained via a direct mechanochemical reaction between benzaldehyde and sodium borohydride at room temperature. The molecular and crystal structures of this borate were investigated using 11B MAS NMR, IR spectroscopy, differential scanning calorimetry (DSC), and X-ray diffraction (XRD) analyses. Crystalline sodium tetrabenzylborate exists in two different crystal structures, which were elucidated using powder- and single-crystal-XRD analyses. At a low temperature (e.g., −100 °C), sodium tetrabenzylborate crystallizes in the monoclinic system with the space group P21 (No. 4), but at room temperature, it displays a crystallization in the tetragonal system with the space group I4¯ (No. 82). According to the DSC analysis, the phase transition occurs at −45 °C. Upon hydrolysis, sodium tetrabenzylborate undergoes direct transformation into benzyl alcohol, thereby confirming the ability of sodium borohydride to convert an aldehyde into its primary alcohol analog. The key findings from our analyses are presented herein.

Published
2024
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2. Synthesis: Molecular Structure, Thermal-Calorimetric and Computational Analyses, of Three New Amine Borane Adducts

Author

Kevin Turani-I-Belloto, Rodica Chiriac, François Toche, Eddy Petit, Pascal G. Yot, Johan G. Alauzun, and Umit B. Demirci

Subjects
adduct, amine borane, boranes, boron chemistry, dihydrogen bonds, Organic chemistry, QD241-441
Abstract

Cyclopropylamine borane C3H5NH2BH3 (C3AB), 2-ethyl-1-hexylamine borane CH3(CH2)3CH(C2H5)CH2NH2BH3 (C2C6AB) and didodecylamine borane (C12H25)2NHBH3 ((C12)2AB) are three new amine borane adducts (ABAs). They are synthesized by reaction of the corresponding amines with a borane complex, the reaction being exothermic as shown by Calvet calorimetry. The successful synthesis of each has been demonstrated by FTIR, Raman and NMR. For instance, the 11B NMR spectra show the presence of signals typical of the NBH3 environment, thereby implying the formation of B–N bonds. The occurrence of dihydrogen bonds (DHBs) for each of the ABAs has been highlighted by DSC and FTIR, and supported by DFT calculations (via the Mulliken charges for example). When heated, the three ABAs behave differently: C3AB and C2C6AB decompose from 68 to 100 °C whereas (C12)2AB is relatively stable up to 173 °C. That means that these ABAs are not appropriate as hydrogen carriers, but the ‘most’ stable (C12)2AB could open perspectives for the synthesis of advanced materials.

Published
2023
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3. Towards general network architecture design criteria for negative gas adsorption transitions in ultraporous frameworks

Author

Simon Krause, Jack D. Evans, Volodymyr Bon, Irena Senkovska, Paul Iacomi, Felicitas Kolbe, Sebastian Ehrling, Erik Troschke, Jürgen Getzschmann, Daniel M. Többens, Alexandra Franz, Dirk Wallacher, Pascal G. Yot, Guillaume Maurin, Eike Brunner, Philip L. Llewellyn, François-Xavier Coudert, and Stefan Kaskel

Subjects
Science
Abstract

Porous framework material DUT-49 was recently demonstrated to exhibit a unique counterintuitive negative gas adsorption (NGA) behaviour. Here the authors identify framework DUT-50 as an additional pressure amplifying material that features distinct NGA transitions, and suggest structural design criteria to access other such materials.

Published
2019
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4. Influence of Thermal and Mechanical Stimuli on the Behavior of Al-CAU-13 Metal–Organic Framework

Author

Michael T. Wharmby, Felicitas Niekiel, Jannik Benecke, Steve Waitschat, Helge Reinsch, Dominik Daisenberger, Norbert Stock, and Pascal G. Yot

Subjects
metal–organic frameworks, Al-CAU-13, thermal stimulus, mechanical stimulus, synchrotron powder X-ray thermodiffraction, in situ high pressure synchrotron powder X-ray diffraction, Chemistry, QD1-999
Abstract

The response of the metal–organic framework aluminum-1,4-cyclohexanedicarboxylate or Al-CAU-13 (CAU: Christian Albrecht University) to the application of thermal and mechanical stimuli was investigated using synchrotron powder X-ray diffraction (SPXRD). Variable temperature in situ SPXRD data, over the range 80–500 K, revealed a complex evolution of the structure of the water guest containing Al-CAU-13•H2O, the dehydration process from ca. 310 to 370 K, and also the evolution of the guest free Al-CAU-13 structure between ca. 370 and 500 K. Rietveld refinement allowed this complexity to be rationalized in the different regions of heating. The Berman thermal Equation of State was determined for the two structures (Al-CAU-13•H2O and Al-CAU-13). Diamond anvil cell studies at elevated pressure (from ambient to up to ca. 11 GPa) revealed similarities in the structural responses on application of pressure and temperature. The ability of the pressure medium to penetrate the framework was also found to be important: non-penetrating silicone oil caused pressure induced amorphization, whereas penetrating helium showed no plastic deformation of the structure. Third-order Vinet equations of state were calculated and show Al-CAU-13•H2O is a hard compound for a metal–organic framework material. The mechanical response of Al-CAU-13, with tetramethylpyrazine guests replacing water, was also investigated. Although the connectivity of the structure is the same, all the linkers have a linear e,e-conformation and the structure adopts a more open, wine-rack-like arrangement, which demonstrates negative linear compressibility (NLC) similar to Al-MIL-53 and a significantly softer mechanical response. The origin of this variation in behavior is attributed to the different linker conformation, demonstrating the influence of the S-shaped a,a-conformation on the response of the framework to external stimuli.

Published
2020
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5. Boron-Based (Nano-)Materials: Fundamentals and Applications

Author

Umit B. Demirci, Philippe Miele, and Pascal G. Yot

Subjects
benzoxaboronate, borane, borohydride, boron-based material, boron-treat steel, boron nitride, boronate, carborane, metallacarborane, polyborate, Crystallography, QD901-999
Abstract

The boron (Z = 5) element is unique. Boron-based (nano-)materials are equally unique. Accordingly, the present special issue is dedicated to crystalline boron-based (nano-)materials and gathers a series of nine review and research articles dealing with different boron-based compounds. Boranes, borohydrides, polyhedral boranes and carboranes, boronate anions/ligands, boron nitride (hexagonal structure), and elemental boron are considered. Importantly, large sections are dedicated to fundamentals, with a special focus on crystal structures. The application potentials are widely discussed on the basis of the materials’ physical and chemical properties. It stands out that crystalline boron-based (nano-)materials have many technological opportunities in fields such as energy storage, gas sorption (depollution), medicine, and optical and electronic devices. The present special issue is further evidence of the wealth of boron science, especially in terms of crystalline (nano-)materials.

Published
2016
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6. In situ Synchrotron X-ray Thermodiffraction of Boranes

Author

Pascal G. Yot, Philippe Miele, and Umit B. Demirci

Subjects
ammonia borane, hydrazine borane, hydrazine bisborane, hydrazinidoboranes, sodium triborane, synchrotron radiation X-ray powder thermodiffraction, Crystallography, QD901-999
Abstract

Boranes of low molecular weight are crystalline materials that have been much investigated over the past decade in the field of chemical hydrogen storage. In the present work, six of them have been selected to be studied by in situ synchrotron X-ray thermodiffraction. The selected boranes are ammonia borane NH3BH3 (AB), hydrazine borane N2H4BH3 (HB), hydrazine bisborane N2H4(BH3)2 (HBB), lithium LiN2H3BH3 (LiHB) and sodium NaN2H3BH3 (NaHB) hydrazinidoboranes, and sodium triborane NaB3H8 (STB). They are first investigated separately over a wide range of temperature (80–300 K), and subsequently compared. Differences in crystal structures, the existence of phase transition, evolutions of unit cell parameters and volumes, and variation of coefficients of thermal expansion can be observed. With respect to AB, HB and HBB, the differences are mainly explained in terms of molecule size, conformation and motion (degree of freedom) of the chemical groups (NH3, N2H4, BH3). With respect to LiHB, NaHB and STB, the differences are explained by a stabilization effect favored by the alkali cations via M···H interactions with four to five borane anions. The main results are presented and discussed herein.

Published
2016
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7. Structural Insight of MOFs under Combined Mechanical and Adsorption Stimuli

Author

Paul Iacomi, Frederico Alabarse, Roger Appleyard, Thomas Lemaire, Christophe Thessieu, Sujing Wang, Christian Serre, Guillaume Maurin, and Pascal G. Yot

Subjects
General Medicine, General Chemistry, Catalysis
Abstract

External control over the pore size of flexible metal-organic frameworks (MOFs) has recently emerged as an intriguing concept, with possible applications to gas storage and separation. In this work we present a new pressure cell capable for the first time of monitoring through in situ X-ray powder diffraction an adsorbent powder under combined uniaxial applied mechanical stress (up to 1 GPa) and gas pressure (up to 20 bar). The combined stress-pressure clamp (CSPC) cell was successfully exploited to follow the evolution of the CO

Published
2022
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8. Synthesis, Characterization, and Encapsulation Properties of Rigid and Flexible Porphyrin Cages Assembled from N -Heterocyclic Carbene–Metal Bonds

Author

Ludivine Poyac, Clémence Rose, Mohammad Wahiduzzaman, Aurélien Lebrun, Guillaume Cazals, Charles H. Devillers, Pascal G. Yot, Sébastien Clément, Sébastien Richeter, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire de Météorologie Physique (LaMP), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Clermont Auvergne (UCA), Laboratoire de Mesures Physiques, Université de Montpellier (UM), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
Inorganic Chemistry, 010405 organic chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 010402 general chemistry, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract

International audience

Published
2021
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9. A Series of Primary Alkylamine Borane Adducts C x H 2x+1 NH 2 BH 3 : Synthesis and Properties

Author

François Toche, Pascal G. Yot, Rodica Chiriac, Kevin Turani-I-Belloto, Umit B. Demirci, Dominique Granier, Eddy Petit, Johan G. Alauzun, María-José Valero-Pedraza, Didier Cot, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
Primary (chemistry), Series (mathematics), 010405 organic chemistry, Chemistry, Boranes, General Chemistry, Borane, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Adduct, chemistry.chemical_compound, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Dihydrogen bond, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021
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11. Crystals springing into action: metal–organic framework CUK-1 as a pressure-driven molecular spring

Author

Pascal G. Yot, Kyung Ho Cho, Jong-San Chang, Ji Sun Lee, Louis Vanduyfhuys, Dominique Granier, Jelle Wieme, Paul Iacomi, Veronique Van Speybroeck, Guillaume Maurin, Pierre Fertey, Université de Montpellier (UM), Korean Research Institute of Chemical Technology (KRICT), Korean Research Institute of Chemical Technology, Universiteit Gent = Ghent University [Belgium] (UGENT), Synchrotron SOLEIL (SSOLEIL), and Centre National de la Recherche Scientifique (CNRS)

Subjects
Work (thermodynamics), Molecular spring, 02 engineering and technology, Porosimetry, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Energy storage, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Hysteresis, Chemistry, Chemical physics, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], [CHIM.CRIS]Chemical Sciences/Cristallography, Metal-organic framework, 0210 nano-technology, Porous medium, Single crystal, ComputingMilieux_MISCELLANEOUS
Abstract

Mercury porosimetry and in situ high pressure single crystal X-ray diffraction revealed the wine-rack CUK-1 MOF as a unique crystalline material capable of a fully reversible mechanical pressure-triggered structural contraction. The near-absence of hysteresis upon cycling exhibited by this robust MOF, akin to an ideal molecular spring, is associated with a constant work energy storage capacity of 40 J g−1. Molecular simulations were further deployed to uncover the free-energy landscape behind this unprecedented pressure-responsive phenomenon in the area of compliant hybrid porous materials. This discovery is of utmost importance from the perspective of instant energy storage and delivery., Mercury porosimetry and in situ high pressure single crystal X-ray diffraction revealed the wine-rack CUK-1 MOF as a unique crystalline material capable of a fully reversible mechanical pressure-triggered structural contraction.

Published
2021
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12. Engineering micromechanics of soft porous crystals for negative gas adsorption

Author

Simon Krause, Daniel M. Többens, Pascal G. Yot, Sebastian Ehrling, Bin Zheng, François-Xavier Coudert, Irena Senkovska, Stefan Kaskel, Manfred S. Weiss, Dirk Wallacher, Paul Iacomi, Guillaume Maurin, Jack D. Evans, Volodymyr Bon, Philip L. Llewellyn, Synthetic Organic Chemistry, Technische Universität Dresden = Dresden University of Technology (TU Dresden), Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute of Computer Engineering (TUD), Helmholtz Centre for Materials and Energy (HZB), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH (HZB), Columbia University [New York], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), ANR-18-CE29-0009,MataReB,Matériaux à comportement adaptatif ciblé(2018), European Project: 742743,European Union’s Horizon 2020, Technische Universität Dresden (TUD), JEAcoustics, Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL), ANR-18-CE29-0009,MATAREB,MATERIALS WITH TARGETED RESPONSIVE BEHAVIOR(2018), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC)

Subjects
Work (thermodynamics), Materials science, Bistability, Energy landscape, Micromechanics, Large scale facilities for research with photons neutrons and ions, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Chemistry, Adsorption, Chemical physics, Metastability, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Surface modification, Metal-organic framework, 0210 nano-technology, Porosity
Abstract

Framework materials at the molecular level, such as metal–organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host–guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks' mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases stiffness, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons. Computational modeling shows how these modifications of the building blocks tune the activation barriers within the energy landscape of the guest-free bistable frameworks. Only frameworks with free energy barriers in the range of 800 to 1100 kJ mol−1 per unit cell, and moderate yield stress of 0.6 to 1.2 nN for single ligand buckling, exhibit adsorption-induced contraction and negative gas adsorption. Advanced experimental in situ methodologies give detailed insights into the structural transitions and the adsorption behavior. The new framework DUT-160 shows the highest magnitude of NGA ever observed for nitrogen adsorption at 77 K. Our computational and experimental analysis of the energetics and mechanical response functions of porous frameworks is an important step towards tuning activation barriers in dynamic framework materials and provides critical design principles for molecular building blocks leading to pressure amplifying materials., We characterise the elastic properties of molecular building blocks and how they impact the mechanical properties of soft porous crystals.

Published
2020
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13. Influence of Thermal and Mechanical Stimuli on the Behavior of Al-CAU-13 Metal–Organic Framework

Author

Steve Waitschat, Jannik Benecke, Norbert Stock, Michael T. Wharmby, Helge Reinsch, Dominik Daisenberger, Pascal G. Yot, Felicitas Niekiel, Deutsch Elektronen Synchrotron DESY, PETRA III, D-22607 Hamburg, Germany, Christian-Albrechts-Universität zu Kiel (CAU), Department of Chemistry, UCL, Christopher Ingold Laboratories, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Diffraction, Materials science, General Chemical Engineering, Thermodynamics, chemistry.chemical_element, 02 engineering and technology, Al-CAU-13, 010402 general chemistry, 01 natural sciences, Diamond anvil cell, Article, law.invention, lcsh:Chemistry, metal–organic frameworks, law, in situ high pressure synchrotron powder X-ray diffraction, Thermal, synchrotron powder X-ray thermodiffraction, General Materials Science, Helium, Rietveld refinement, 021001 nanoscience & nanotechnology, Synchrotron, 0104 chemical sciences, thermal stimulus, lcsh:QD1-999, chemistry, ddc:540, Compressibility, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Metal-organic framework, 0210 nano-technology, mechanical stimulus
Abstract

The response of the metal&ndash, organic framework aluminum-1,4-cyclohexanedicarboxylate or Al-CAU-13 (CAU: Christian Albrecht University) to the application of thermal and mechanical stimuli was investigated using synchrotron powder X-ray diffraction (SPXRD). Variable temperature in situ SPXRD data, over the range 80&ndash, 500 K, revealed a complex evolution of the structure of the water guest containing Al-CAU-13&bull, H2O, the dehydration process from ca. 310 to 370 K, and also the evolution of the guest free Al-CAU-13 structure between ca. 370 and 500 K. Rietveld refinement allowed this complexity to be rationalized in the different regions of heating. The Berman thermal Equation of State was determined for the two structures (Al-CAU-13&bull, H2O and Al-CAU-13). Diamond anvil cell studies at elevated pressure (from ambient to up to ca. 11 GPa) revealed similarities in the structural responses on application of pressure and temperature. The ability of the pressure medium to penetrate the framework was also found to be important: non-penetrating silicone oil caused pressure induced amorphization, whereas penetrating helium showed no plastic deformation of the structure. Third-order Vinet equations of state were calculated and show Al-CAU-13&bull, H2O is a hard compound for a metal&ndash, organic framework material. The mechanical response of Al-CAU-13, with tetramethylpyrazine guests replacing water, was also investigated. Although the connectivity of the structure is the same, all the linkers have a linear e,e-conformation and the structure adopts a more open, wine-rack-like arrangement, which demonstrates negative linear compressibility (NLC) similar to Al-MIL-53 and a significantly softer mechanical response. The origin of this variation in behavior is attributed to the different linker conformation, demonstrating the influence of the S-shaped a,a-conformation on the response of the framework to external stimuli.

Published
2020
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14. Cesium hydrazinidoborane, the last of the alkali hydrazinidoboranes, studied as potential hydrogen storage material

Author

Christophe Charmette, Umit B. Demirci, Carlos A. Castilla-Martinez, Pascal G. Yot, Dominique Granier, Jim Cartier, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
Materials science, Inorganic chemistry, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Borane, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Ion, chemistry.chemical_compound, Hydrogen storage, [CHIM]Chemical Sciences, Inert gas, ComputingMilieux_MISCELLANEOUS, Renewable Energy, Sustainability and the Environment, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Alkali metal, 0104 chemical sciences, Fuel Technology, chemistry, 13. Climate action, Caesium, 0210 nano-technology, Monoclinic crystal system
Abstract

Alkali hydrazinidoboranes MN2H3BH3 (M = Li, Na, K, Rb) have been developed for hydrogen storage. To complete the family of MN2H3BH3, we focused on cesium hydrazinidoborane CsN2H3BH3 (CsHB). It has been synthesized by reaction of cesium with hydrazine borane (N2H4BH3) at −20 °C under inert atmosphere, and it has been characterized. A crystalline solid (monoclinic, s.g. P21 (No. 4)) has been obtained. Its potential for hydrogen storage has been studied by combining different techniques. It was found that, under heating at constant heating rate (5 °C min−1) or at constant temperature (e.g. 120 °C), CsHB decomposes rather than it dehydrogenates. It releases several unwanted gaseous products (e.g. NH3, B2H6) together with H2, and transforms into a residue that poses safety issues because of shock-sensitivity and reactivity towards O2/H2O. Though the destabilization brought by Cs+ onto the anion [N2H3BH3]− has been confirmed, the effect is not efficient enough to avoid the aforementioned drawbacks. All of our results are presented herein and discussed within the context of solid-state hydrogen storage.

Published
2020
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15. Charting the Metal-Dependent High-Pressure Stability of Bimetallic UiO-66 Materials

Author

Jannick Jacobsen, Norbert Stock, Sven Rogge, Pascal G. Yot, Veronique Van Speybroeck, Francesco Muniz-Miranda, Guillaume Maurin, Jonas Gosch, Ines E. Collings, Sabine Devautour-Vinot, Steven Vandenbrande, Vanessa Ortiz, School of Physics [UNSW Sydney] (UNSW), University of New South Wales [Sydney] (UNSW), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Christian-Albrechts-Universität zu Kiel (CAU), Institute of Chemistry for Life and Health Sciences (iCLeHS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut fur Anorganische Chemie (CAU), Center for molecular modeling, and Universiteit Gent = Ghent University [Belgium] (UGENT)

Subjects
Materials science, Technology and Engineering, Letter, General Chemical Engineering, Biomedical Engineering, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, MOFS, Catalysis, Metal, DESIGN, [CHIM]Chemical Sciences, General Materials Science, Thermal stability, Bimetallic strip, ComputingMilieux_MISCELLANEOUS, Zirconium, Nanoporous, POROSITY, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Hafnium, Cerium, chemistry, Chemical engineering, Physics and Astronomy, MECHANICAL STABILITY, visual_art, ORGANIC FRAMEWORK UIO-66, visual_art.visual_art_medium, LINKER DEFECTS, 0210 nano-technology, BEHAVIOR, STORAGE, QUICKFF
Abstract

In theory, bimetallic UiO-66(Zr:Ce) and UiO-66(Zr:Hf) metal-organic frameworks (MOFs) are extremely versatile and attractive nanoporous materials as they combine the high catalytic activity of UiO-66(Ce) or UiO-66(Hf) with the outstanding stability of UiO-66(Zr). Using in situ high-pressure powder X-ray diffraction, however, we observe that this expected mechanical stability is not achieved when incorporating cerium or hafnium in UiO-66(Zr). This observation is akin to the earlier observed reduced thermal stability of UiO-66(Zr:Ce) compounds. To elucidate the atomic origin of this phenomenon, we chart the loss-of-crystallinity pressures of 22 monometallic and bimetallic UiO-66 materials and systematically isolate their intrinsic mechanical stability from their defect-induced weakening. This complementary experimental/computational approach reveals that the intrinsic mechanical stability of these bimetallic MOFs decreases nonlinearly upon cerium incorporation but remains unaffected by the zirconium: hafnium ratio. Additionally, all experimental samples suffer from defect-induced weakening, a synthesis-controlled effect that is observed to be independent of their intrinsic stability.

Published
2020
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16. Solvent Impact on the Properties of Benchmark Metal–Organic Frameworks: Acetonitrile‐Based Synthesis of CAU‐10, Ce‐UiO‐66, and Al‐MIL‐53

Author

Jannick Jacobsen, Guillaume Maurin, Julia Franke, Sebastian Leubner, Jürgen Senker, Norbert Stock, Helge Reinsch, Robert Stäglich, Jonas Gosch, Pascal G. Yot, Renée Siegel, Christian-Albrechts-Universität zu Kiel (CAU), Institut de Chimie (FRE 2446 CNRS), Université Louis Pasteur - Strasbourg I, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
solvent effects, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, metal–organic frameworks, Adsorption, NMR spectroscopy, Molecule, Acetonitrile, ComputingMilieux_MISCELLANEOUS, Full Paper, 010405 organic chemistry, Chemistry, microporous materials, Organic Chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, Atmospheric temperature range, Full Papers, 0104 chemical sciences, Solvent, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Physical chemistry, Metal-organic framework, Solvent effects
Abstract

Herein is reported the utilization of acetonitrile as a new solvent for the synthesis of the three significantly different benchmark metal–organic frameworks (MOFs) CAU‐10, Ce‐UiO‐66, and Al‐MIL‐53 of idealized composition [Al(OH)(ISO)], [Ce6O4(OH)4(BDC)6], and [Al(OH)(BDC)], respectively (ISO2−: isophthalate, BDC2−: terephthalate). Its use allowed the synthesis of Ce‐UiO‐66 on a gram scale. While CAU‐10 and Ce‐UiO‐66 exhibit properties similar to those reported elsewhere for these two materials, the obtained Al‐MIL‐53 shows no structural flexibility upon adsorption of hydrophilic or hydrophobic guest molecules such as water and xenon and is stabilized in its large‐pore form over a broad temperature range (130–450 K). The stabilization of the large‐pore form of Al‐MIL‐53 was attributed to a high percentage of noncoordinating −COOH groups as determined by solid‐state NMR spectroscopy. The defective material shows an unusually high water uptake of 310 mg g−1 within the range of 0.45 to 0.65 p/p°. In spite of showing no breathing effect upon water adsorption it exhibits distinct mechanical properties. Thus, mercury intrusion porosimetry studies revealed that the solid can be reversibly forced to breathe by applying moderate pressures (≈60 MPa)., Metal–organic frameworks: CAU‐10, Ce‐UiO‐66, and Al‐MIL‐53 were synthesized by utilizing acetonitrile as the solvent. The typical breathing behavior of Al‐MIL‐53 upon guest molecule adsorption was inhibited by a high concentration of defects. As shown by NMR spectroscopy these consist of noncoordinated −COOH groups. Breathing could be enforced by applying a pressure of about 60 MPa during mercury intrusion.

Published
2020
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17. Diammonium tetraborate dihydrate as hydrolytic by-product of ammonia borane in aqueous alkaline conditions

Author

Eddy Petit, María-José Valero-Pedraza, Karim Adil, Dominique Granier, Didier Cot, Umit B. Demirci, Damien Alligier, Pascal G. Yot, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Aqueous solution, Renewable Energy, Sustainability and the Environment, Chemistry, Precipitation (chemistry), Borax, Inorganic chemistry, Ammonia borane, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Hydrolysis, chemistry.chemical_compound, Fuel Technology, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Boron, ComputingMilieux_MISCELLANEOUS, Monoclinic crystal system
Abstract

Ammonia borane NH3BH3 is able to generate H2 by catalytic hydrolysis at ambient conditions. Such a potential has been much studied but the hydrolysis by-products, i.e. ammonium borates, have been little studied. As such we undertook a systematic work aiming at getting a sound understanding of the borates forming by hydrolysis. Contrary to what is commonly believed, NH3BH3 (10 M) in aqueous alkaline (pH = 8) solution is not completely stable. Spontaneous hydrolysis takes place, resulting in the formation of by-products and precipitation of borate crystals. This means that long-term storage of concentrated AB solution is not possible. The borate crystals were analyzed with the help of various techniques and was identified as being diammonium tetraborate dihydrate (NH4)2B4O5(OH)4⋅2H2O (263.39 g mol−1). The crystal structure was solved and found to be monoclinic with a space group P21. The borate is an analog of borax Na2B4O5(OH)4⋅8H2O. These results, among others, are reported in details hereafter and they are discussed in order to bring elements of response to the questions concerning storage of aqueous NH3BH3 and recyclability of such a borate.

Published
2020
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18. Mechanical-pressure induced response of the MOF Al-MIL-53-TDC

Author

Mohammad Wahiduzzaman, Jean-Paul Itié, Pascal G. Yot, Norbert Stock, Guillaume Maurin, Nele Reimer, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), and Christian-Albrechts-Universität zu Kiel (CAU)

Subjects
Work (thermodynamics), Phase transition, Chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Synchrotron, 0104 chemical sciences, law.invention, Ion, Inorganic Chemistry, Chemical engineering, Metal-organic frameworks Mechanical behavior High pressure X-ray powder diffraction Aluminium Nano-damper, law, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, [CHIM]Chemical Sciences, Metal-organic framework, Density functional theory, Physical and Theoretical Chemistry, 0210 nano-technology, Porosity, Powder diffraction
Abstract

International audience; The mechanical behavior of the recently synthesized flexible metal organic framework [Al(OH)(TDC)] with the well-known MIL-53 topology, built of 2,5-thiophenedicarboxylate (TDC2−) , OH– and Al3+ ions, named Al-MIL-53-TDC, has been explored using a combination of advanced characterization tools including mercury intrusion and high-pressure synchrotron X-ray powder diffraction, supported by Density Functional Theory calculations. This hybrid porous material was shown to exhibit a pressure-induced reversible structural contraction at ∼275 MPa associated with a unit cell volume change of ∼28.1% and a hysteresis loop once the pressure is released. This leads to an unprecedented energy work of 79 J g−1 that can be stored during one compression/decompression cycle for such a class of porous solids presenting a large-pore form ↔ closed-pore form phase transition. As such Al-MIL-53-TDC is at this time the best candidate of the MIL-53’s family for a future potential application where a nano-damper is required.Graphical abstract

Published
2018
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19. Unraveling the mechanical behaviour of hydrazine borane (NH2–NH2–BH3)

Author

Vibhav Yadav, Salem Ould Amara, Jean-Paul Itié, Umit B. Demirci, Guillaume Maurin, Pascal G. Yot, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Synchrotron SOLEIL (SSOLEIL), and Centre National de la Recherche Scientifique (CNRS)

Subjects
Bulk modulus, Materials science, Intermolecular force, General Physics and Astronomy, 02 engineering and technology, Crystal structure, Borane, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Hydrogen storage, chemistry.chemical_compound, chemistry, Chemical physics, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Compressibility, Density functional theory, Physical and Theoretical Chemistry, 0210 nano-technology, Anisotropy
Abstract

International audience; Crystalline B–N–H compounds of low molecular weight have been intensively investigated over the past two decades owing to their promises for chemical hydrogen storage. Hydrazine borane NH2–NH2–BH3 is one of the most recent examples of this family of materials. In the present work, we explored its structural behaviour under mechanical stimulus by synchrotron high pressure X-ray diffraction. It has been evidenced that hydrazine borane shows a gradual pressure-induced decrease of its unit cell dimension and the process is reversible when the applied pressure is released. The compressibility of this material was established to be relatively low (high bulk modulus) and highly anisotropic. As revealed by molecular simulations based on Density Functional Theory calculations, the mechanical behaviour of NH2–NH2–BH3 was correlated to the pressure-induced changes of its crystal structure in terms of intra- and intermolecular bond lengths and angles parameters.

Published
2018
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20. Calcium hydrazinidoborane: Synthesis, characterization, and promises for hydrogen storage

Author

Pascal G. Yot, Eddy Petit, Umit B. Demirci, Vibhav Yadav, Guillaume Maurin, Salem Ould-Amara, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Exothermic reaction, Calcium hydride, Materials science, Renewable Energy, Sustainability and the Environment, Intermolecular force, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Calcium, Borane, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Amorphous solid, chemistry.chemical_compound, Hydrogen storage, Crystallography, Fuel Technology, chemistry, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Monoclinic crystal system
Abstract

Viewing calcium hydrazinidoborane Ca(N2H3BH3)2 (9.3 wt% H) as a potential hydrogen storage material, we long sought to synthesize it by solid-solid reaction of calcium hydride CaH2 and hydrazine borane N2H4BH3. However, it was elusive because of unsuitable experimental conditions. In situ synchrotron thermodiffraction helped us to identify the key role played by the temperature in the formation of the new phase. From 45 °C, new diffraction peaks appear, and the DSC analysis shows an exothermic signal. Thermal activation is thus required to make solid-state CaH2 react with melted (liquid-state) N2H4BH3. The XRD pattern can be indexed using a mixture of two phases: (i) unreacted CaH2 as a minor phase (29 wt%) and (ii) the hitherto elusive Ca(N2H3BH3)2 (71 wt%). The as-formed Ca(N2H3BH3)2 crystallizes in a monoclinic Ic (No. 9) unit cell where the intermolecular interactions form chains (layers) along the a axis, resulting in intra-chain and inter-chain Ca⋅⋅⋅Ca distances as short as 4.39 and 7.04 A respectively. Beyond 90 °C, Ca(N2H3BH3)2 decomposes, as evidenced by the diffraction peaks fading, an exothermic signal revealed by DSC, a weight loss (5.3 wt% at 200 °C) observed by TGA, and a gas release (H2, and some N2, NH3, N2H4) monitored by MS. The as-formed thermolytic residue is amorphous and of complex polymeric composition. These results and the next challenges, are discussed herein.

Published
2020
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21. Alkaline aqueous solution of sodium decahydro-closo-decaborate Na2B10H10 as liquid anodic fuel

Author

Salem Ould-Amara, Dominique Granier, Eddy Petit, Pascal G. Yot, Umit B. Demirci, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Aqueous solution, 060102 archaeology, Renewable Energy, Sustainability and the Environment, 020209 energy, Sodium, Inorganic chemistry, chemistry.chemical_element, 06 humanities and the arts, 02 engineering and technology, Electrochemistry, Anode, Ion, chemistry, Electrode, 0202 electrical engineering, electronic engineering, information engineering, [CHIM]Chemical Sciences, 0601 history and archaeology, Cyclic voltammetry, Platinum, ComputingMilieux_MISCELLANEOUS
Abstract

The potential of the decahydro-closo-decaborate anion B10H102− in alkaline aqueous solution as anodic fuel was investigated by using cyclic voltammetry and three different bulk metal electrodes (platinum, gold and silver). The sodium salt NaB10H10 was first synthesized, fully characterized and assessed for its relative stability in alkaline medium for 25 days. Then, oxidation of B10H102− in alkaline aqueous solution was studied. With platinum, the electrochemical activity is nil. With gold and silver, oxidation takes place at >0 V vs. SCE, suggesting direct oxidation of B10H102−. A current density of e.g. 15.1 mA cm−2 at 0.51 V vs. SCE is produced, supporting an electrocatalytically activity for both electrodes. There is even some reversibility of the process (i.e. reduction of intermediate species) with silver. The most important oxidation products were identified as being B7-based anions for both silver and gold. Such results suggest the occurrence of partial oxidative degradation of B10H102− at positive potential and may open new application prospects to polyborate anions.

Published
2019
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22. Synthesis, characterization and modeling of self-assembled porphyrin nanorods

Author

Christel Gervais, Danielle Laurencin, Didier Cot, Sébastien Richeter, Yannick Guari, Sébastien Clément, Matthieu Paillet, Pascal G. Yot, Erik Elkaim, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
NMR crystallography, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, law, DFT modeling Tel : ++(33)467143971, Spectroscopy, solid state NMR, Tetraphenylborate, Chemistry, NMR cristallography, General Chemistry, self-assembly, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Porphyrin, Synchrotron, 0104 chemical sciences, Crystallography, Solid-state nuclear magnetic resonance, Nanorod, Self-assembly, 0210 nano-technology, nanorods, DFT modeling, porphyrin, Powder diffraction
Abstract

Porphyrin nanorods were prepared by ion-association between free-base meso 5,10,15,20-tetrakis-(4-[Formula: see text]-methylpyridinium)porphyrin cations and tetraphenylborate anions. The nanorods have variable lengths (up to a few micrometers long) and diameters ([Formula: see text]50–500 nm). Their structure at the molecular level was elucidated by combining multinuclear solid state NMR spectroscopy, synchrotron X-ray powder diffraction and DFT calculations.

Published
2019
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23. Rubidium hydrazinidoborane: Synthesis, characterization and hydrogen release properties

Author

Carlos A. Castilla-Martinez, Christophe Charmette, Pascal G. Yot, Dominique Granier, Umit B. Demirci, Guillaume Maurin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Européen des membranes (IEM), and Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)

Subjects
Materials science, Renewable Energy, Sustainability and the Environment, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Borane, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Alkali metal, 01 natural sciences, 0104 chemical sciences, Rubidium, Crystallography, Hydrogen storage, chemistry.chemical_compound, Fuel Technology, chemistry, [CHIM]Chemical Sciences, Lithium, Dehydrogenation, Isostructural, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS, Monoclinic crystal system
Abstract

In this work we present rubidium hydrazinidoborane RbN2H3BH3 (RbHB), the newest and last member of the alkali metal derivatives of hydrazine borane N2H4BH3 (HB). It is shown that HB readily reacts with metallic rubidium in THF at room temperature to form RbHB under argon atmosphere. The molecular and crystal structures of this new compound are discussed on the basis of FTIR spectroscopy, 11B MAS NMR spectroscopy, and powder X-ray diffraction analyses. RbHB crystallizes in a monoclinic P21 (No. 4) unit cell where each Rb+ cation adopts octahedral coordination surrounded by six [N2H3BH3]− anions, which are two more than for e.g. LiN2H3BH3 (with tetrahedral coordination) in accordance with the larger size of Rb+. RbHB is isostructural to potassium hydrazinidoborane KN2H3BH3. Its dehydrogenation properties, evaluated by using thermogravimetric analysis, differential scanning calorimetry, and isothermal analysis, are compared to those of the parent HB as well as to analogous compounds in order to evaluate the potential of RbHB as hydrogen storage material. According to the presented data, the dehydrogenation properties of RbHB are much better than those of HB and are comparable to those of the lithium derivative. Our main results are reported therein.

Published
2019
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24. Guest‐Assisted Proton Conduction in the Sulfonic Mesoporous MIL‐101 MOF

Author

Guillaume Maurin, Vanessa Ortiz, Pascal G. Yot, Jong-San Chang, Amine Geneste, Sabine Devautour-Vinot, Eriyakkadan S. Sanil, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Korean Research Institute of Chemical Technology (KRICT), Korean Research Institute of Chemical Technology, and Sungkyunkwan University [Suwon] (SKKU)

Subjects
Proton, 010405 organic chemistry, Chemistry, Organic Chemistry, Inorganic chemistry, sulfonic MOF, General Chemistry, Electrolyte, Conductivity, 010402 general chemistry, Thermal conduction, 7. Clean energy, 01 natural sciences, Biochemistry, 0104 chemical sciences, proton conduction, water and sulfuric acid-mediated proton migration, Molecule, [CHIM]Chemical Sciences, Relative humidity, Mesoporous material, Electrical conductor, post-synthesis modification, Grotthus mechanism
Abstract

Magalie Lefeuvre is acknowledged for the Elemental Analysis experiments.; International audience; 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 (H2SO4) 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.

Published
2019
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25. A High Proton Conductive Hydrogen-Sulfate Decorated Titanium Carboxylate Metal−Organic Framework

Author

Sabine Devautour-Vinot, Marco Daturi, Mohammad Wahiduzzaman, Josefine Schnee, Jong-San Chang, Pascal G. Yot, Alexandre Vimont, Richard Retoux, Sujing Wang, Ji Sun Lee, Guillaume Maurin, Vanessa Ortiz, Christian Serre, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire catalyse et spectrochimie (LCS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC), Korean Research Institute of Chemical Technology (KRICT), Korean Research Institute of Chemical Technology, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Sungkyunkwan University [Suwon] (SKKU), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Green chemistry, Proton conductivity, Materials science, General Chemical Engineering, Reaction mechanisms, Proton migration mechanism, Inorganic chemistry, Metal organic frameworks, chemistry.chemical_element, 02 engineering and technology, Conductivity, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Acidic sites, Proton transport, Environmental Chemistry, [CHIM]Chemical Sciences, Carboxylate, MOF, Titanium, Renewable Energy, Sustainability and the Environment, Postmodification, Fourier transform infrared spectroscopy, General Chemistry, Molecules, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Dielectric spectroscopy, chemistry, Metal-organic framework, Chemical stability, Clean-energy application, 0210 nano-technology, Proton conduction
Abstract

International audience; A hydrolytically stable titanium carboxylate-based metal−organic framework (MOF), incorporating hydrogen-sulfate functions bounded to Ti-metal sites and named MIP-177-SO4H-LT, was prepared using a green and simple synthesis protocol. This solid exhibits a very high proton conductivity of 2.6 × 10–2 S cm–1 at 298 K and 95% relative humidity as evidenced by impedance spectroscopy measurements. This high level of performance maintained over 7 days combined with a very good chemical stability and green synthesis route positions this MOF as a promising candidate for further deployment as a proton-exchange membrane. Ab initio Molecular Dynamics simulations and advanced characterization tools (IR, UV–vis, TGA–MS) were further coupled to reveal a water-mediated proton transport Grotthuss-like mechanism.

Published
2019
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26. Correction: Modulation of the mechanical energy storage performance of the MIL-47(V IV ) metal organic framework by ligand functionalization

Author

Pascal G. Yot, Mohammad Wahiduzzaman, Erik Elkaim, Pierre Fertey, Paul Fabry, Emmanuel Magnier, Thomas Devic, Christian Serre, Guillaume Maurin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inorganic Chemistry, 010405 organic chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 010402 general chemistry, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract

Correction for ‘Modulation of the mechanical energy storage performance of the MIL-47(VIV) metal organic framework by ligand functionalization’ by Pascal G. Yot et al., Dalton Trans., 2019, DOI: 10.1039/c8dt04214d.

Published
2019
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27. Evidence of an ordered ternary phase in the section Ni–Ti5Sn3 of the ternary Ti–Ni–Sn: Crystal structure and phase stability

Author

Marina Bulanova, Pascal G. Yot, Jean-Claude Tedenac, Catherine Colinet, Julia Fartushna, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Science et Ingénierie des Matériaux et Procédés (SIMaP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)

Subjects
Equation of state, Materials science, 02 engineering and technology, General Chemistry, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Gibbs free energy, symbols.namesake, Crystallography, Phase (matter), [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], symbols, General Materials Science, 0210 nano-technology, Ternary operation, ComputingMilieux_MISCELLANEOUS, Stoichiometry, Powder diffraction, Phase diagram
Abstract

In this paper we present the synchrotron and laboratory X-ray powder diffraction (S-XRPD) experiments made at normal conditions and also at different pressures (up to 2 GPa). Then crystal structure and equation of state (EoS) have been determined. These results are discussed together with experimental phase diagram. The binary phases of the Sn–Ti (Ti3Sn, Ti2Sn, Ti5Sn3) are often extended by a ternary addition. This was observed by us many times particularly in the Ga-Sn-Ti system where a ternary phase is observed. In the case of the Ni–Sn–Ti system, the question is still pending. Focusing on D88–Sn3Ti5 let remind that this phase is hexagonal, hP16, P63/mcm, prototype Mn5Si3. The point defect formation energies were obtained from first principles calculations. Four sublattices are introduced to account for the D88 structure and for the possibility of inserting atoms in the 2b sites of the structure P63/mcm. The 2b sites are not occupied in the stoichiometric compound at T 1⁄4 0 K. But the possibility exists that a few atoms occupy these sites at higher temperature or for off-stoichiometric alloys. For stoichiometric D88–Sn3Ti5 alloys, it was shown that the dominant thermal defects are composed of Sn atoms in interstitial positions 2b of the D88 structure and Ti atoms in antisite position on the sites preferentially occupied by Sn atoms. In the Sn-rich D88–Sn3Ti5, the constitutional defects are Sn atoms in interstitial positions. In the Ti-rich D88–Sn3Ti5, the constitutional defects are Ti atoms in antisite position. The chemical potentials as well as the Gibbs energy are obtained as function of composition for various temperatures.

Published
2020
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28. Pillared-layered metal-organic frameworks for mechanical energy storage applications

Author

Sven Rogge, Guillaume Maurin, Pascal G. Yot, Jong-San Chang, Michel Waroquier, Louis Vanduyfhuys, Su-Kyung Lee, Veronique Van Speybroeck, Jelle Wieme, Center for molecular modeling, Universiteit Gent = Ghent University [Belgium] (UGENT), School of Physics [UNSW Sydney] (UNSW), University of New South Wales [Sydney] (UNSW), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Korean Research Institute of Chemical Technology (KRICT), and Korean Research Institute of Chemical Technology

Subjects
STRUCTURAL TRANSITION, Materials science, MOLECULAR-DYNAMICS SIMULATIONS, ADSORPTION, Coordination polymer, FLEXIBILITY, BREATHING BEHAVIOR, 02 engineering and technology, PRESSURE, Force field (chemistry), MOFS, Molecular dynamics, chemistry.chemical_compound, Adsorption, COORDINATION POLYMER, General Materials Science, Volume contraction, ComputingMilieux_MISCELLANEOUS, Mechanical energy, Atmospheric pressure, STABILITY, Renewable Energy, Sustainability and the Environment, General Chemistry, 021001 nanoscience & nanotechnology, chemistry, Physics and Astronomy, Chemical physics, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], FORCE-FIELD, Metal-organic framework, 0210 nano-technology
Abstract

Herein we explore the unique potential of pillared-layered metal–organic frameworks of the DMOF-1 family for mechanical energy storage applications. In this work, we theoretically predict for the guest-free DMOF-1 a new contracted phase by exerting an external mechanical pressure of more than 200 MPa with respect to the stable phase at atmospheric pressure. The breathing transition is accompanied by a very large volume contraction of about 40%. The high transition pressures and associated volume changes make these materials highly promising with an outstanding mechanical energy work. Furthermore, we show that changing the nature of the metal allows to tune the behavior under mechanical pressure. The various phases were revealed by a combination of periodic density-functional theory calculations, force field molecular dynamics simulations and mercury intrusion experiments for DMOF-1(Zn) and DMOF-1(Cu). The combined experimental and theoretical approach allowed to discover the potential of these materials for new technological developments.

Published
2019
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30. Robust Monolithic Metal-Organic Framework with Hierarchical Porosity

Author

Patricia Horcajada, Sérgio M. F. Vilela, Pascal G. Yot, E.L. Solla, Pablo Salcedo-Abraira, Loïc Micheron, Instituto IMDEA Energy [Madrid], Instituto IMDEA Energía, Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidade de Vigo, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Metals and Alloys, Sorption, 02 engineering and technology, General Chemistry, Porosimetry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Intrusion, Chemical engineering, Robustness (computer science), Materials Chemistry, Ceramics and Composites, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Metal-organic framework, 0210 nano-technology, Porosity, Hierarchical porous
Abstract

International audience; Hierarchical porous UiO-66-NH2 cm-monolithic xero- and aero-gels with a controlled shape and mechanical robustness were successfully produced from ethanolic gels. Their remarkable controlled hierarchical porosity was effectively assessed using N2 sorption, Hg intrusion porosimetry and focused ion beam-scanning electron microscopy methods.

Published
2018
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31. Assessing the Potential of Sodium 1-Oxa- nido -dodecaborate NaB 11 H 12 O for Energy Storage

Author

Salem Ould-Amara, Eddy Petit, Umit B. Demirci, Marc Cretin, Sabine Devautour-Vinot, Pascal G. Yot, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Hydrogen, General Chemical Engineering, Sodium, medicine.medical_treatment, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Fuels, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Redox, lcsh:Chemistry, Batteries, Solid state electrochemistry, Fast ion conductor, medicine, [CHIM]Chemical Sciences, Hydrogen storage materials, Redox reaction, Aqueous solution, Chemistry, Dodecaborate, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, lcsh:QD1-999, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Alkali salt, Physical and chemical properties, 0210 nano-technology, Platinum, Electric transport processes and properties
Abstract

International audience; In the recent years, polyborate anions have been considered as possible candidates for energy. In aqueous solutions, they have been studied as either hydrogen carriers or anodic fuels. In the solid state (as an alkali salt), they have been seen as solid electrolytes. Herein, we focus on sodium 1-oxa-nido-dodecaborate NaB11H12O, a novel possible candidate for the aforementioned applications. The compound is soluble in water, and its stability depends on pH: under acidic conditions, it readily hydrolyzes while liberating hydrogen, and under alkaline conditions, it is stable, which is a feature searched for an anodic fuel. Over bulk platinum, gold, or silver electrode, oxidation takes place. The best performance has been noticed for the silver electrode. In the solid state, NaB11H12O shows Na+ conductivity at a high temperature of up to 150 °C. All of these properties are presented in detail, and hereafter they are discussed while giving indications of what have to be developed to open up more realistic prospectives for NaB11H12O in energy.

Published
2018
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32. Adsorption Contraction Mechanics: Understanding Breathing Energetics in Isoreticular Metal–Organic Frameworks

Author

François-Xavier Coudert, Jack D. Evans, Ulrich Stoeck, Sebastian Ehrling, Pascal G. Yot, Philip L. Llewellyn, Simon Krause, Stefan Kaskel, Paul Iacomi, Guillaume Maurin, Volodymyr Bon, Irena Senkovska, Technische Universität Dresden = Dresden University of Technology (TU Dresden), Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and ANR-17-CE08-0048,FUN,Etude fondamentale du comportement anormal d'un Matériau Flexible Nanoporeux sous l'effet de l'Adsorption(2017)

Subjects
Isothermal microcalorimetry, Work (thermodynamics), Materials science, Enthalpy, Thermodynamics, 02 engineering and technology, Porosimetry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Methane, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, General Energy, Adsorption, Volume (thermodynamics), chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Metal-organic framework, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract

International audience; A highly porous metal–organic framework DUT-48, isoreticular to DUT-49, is reported with a high surface area of 4560 m2·g–1 and methane storage capacity up to 0.27 g·g–1 (164 cm3·cm–3) at 6.5 MPa and 298 K. The flexibility of DUT-48 and DUT-49 under external and internal (adsorption-induced) pressure is analyzed and rationalized using a combination of advanced experimental and computational techniques. While both networks undergo a contraction by mechanical pressure, only DUT-49 shows adsorption-induced structural transitions and negative gas adsorption of n-butane and nitrogen. This adsorption behavior was analyzed by microcalorimetry measurements and molecular simulations to provide an explanation for the lack of adsorption-induced breathing in DUT-48. It was revealed that for DUT-48, a significantly lower adsorption enthalpy difference and a higher framework stiffness prevent adsorption-induced structural transitions and negative gas adsorption. The mechanical behavior of both DUT-48 and DUT-49 was further analyzed by mercury porosimetry experiments and molecular simulations. Both materials exhibit large volume changes under hydrostatic compression, demonstrating noteworthy potential as shock absorbers with unprecedented high work energies.

Published
2018
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33. Sodium borohydride and propylene glycol, an effective combination for the generation of 2.3 wt% of hydrogen

Author

Umit B. Demirci, Hanane Ould-Amara, Eddy Petit, Pascal G. Yot, Damien Alligier, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Hydrogen, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, 7. Clean energy, Polyvinyl alcohol, Catalysis, chemistry.chemical_compound, Hydrogen storage, Sodium borohydride, Propylene glycol, 0502 economics and business, [CHIM]Chemical Sciences, 050207 economics, Renewable Energy, Sustainability and the Environment, Chemistry, Precipitation (chemistry), 05 social sciences, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Alcoholysis, Fuel Technology, Gravimetric analysis, Methanol, 0210 nano-technology, Glycolysis, Nuclear chemistry
Abstract

International audience; Sodium borohydride NaBH4 (SB) readily and completely reacts with four equivalents of propylene glycol HOCH2CH(OH)CH3 (PG), resulting in the liberation of four equivalents of H2 at temperatures starting from 25 °C. Alcoholysis (or glycolysis) takes place. The system SB-4PG is then an attractive H2 generator thanks to an effective gravimetric hydrogen storage capacity of 2.3 wt%. It offers several other advantages: there is no need of catalyst; there is no precipitation of by-product; PG is among the safest alcohols (much safer than e.g. methanol). The potential of SB-4PG as H2 generator is thus illustrated and discussed herein.

Published
2018
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34. Exploration of the mechanical behavior of metal organic frameworks UiO-66(Zr) and MIL-125(Ti) and their NH2functionalized versions

Author

Thomas Devic, Christian Serre, Pascal G. Yot, Patricia Horcajada, Ke Yang, Vladimir Dmitriev, Florence Ragon, and Guillaume Maurin

Subjects
Diffraction, Bulk modulus, Materials science, Crystal density, Coordination number, Inorganic chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallinity, Chemical engineering, Metal-organic framework, 0210 nano-technology, Porosity, Linker
Abstract

The structural behaviour under mechanical stimuli of two metal organic frameworks, UiO-66(Zr) and MIL-125(Ti) and their amino-functionalized derivatives has been investigated by high-pressure powder X-ray diffraction up to 3.5 GPa. All these solids showed a gradual pressure-induced reversible decrease of their crystallinity and UiO-66(Zr)_NH2 material has been revealed as one of the most resilient MOFs reported so far corresponding to a very high bulk modulus. The mechanical behaviors of these MOFs have been correlated to their chemical and geometric features including the metal-oxygen coordination number, the nature of the organic linker, the porosity as well as their crystal density.

Published
2016
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35. Unraveling the mechanical behaviour of hydrazine borane (NH

Author

Pascal G, Yot, Vibhav, Yadav, Salem, Ould Amara, Jean-Paul, Itiè, Umit B, Demirci, and Guillaume, Maurin

Abstract

Crystalline B-N-H compounds of low molecular weight have been intensively investigated over the past two decades owing to their promises for chemical hydrogen storage. Hydrazine borane NH

Published
2018

36. Lithium Hydrazinidoborane Ammoniate LiN2H3BH3·0.25NH3, a Derivative of Hydrazine Borane

Author

Dominique Granier, Salem Ould-Amara, Umit B. Demirci, Pascal G. Yot, Rodica Chiriac, François Toche, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Thermogravimetric analysis, Hydrogen, Hydrazine, Inorganic chemistry, chemistry.chemical_element, ammonia carrier, ammoniate, borane, hydrazine borane, hydrazinidoborane, chemical hydrogen storage, 02 engineering and technology, Borane, 010402 general chemistry, 01 natural sciences, lcsh:Technology, Article, chemistry.chemical_compound, Hydrogen storage, General Materials Science, lcsh:Microscopy, lcsh:QC120-168.85, Lithium amide, lcsh:QH201-278.5, lcsh:T, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, lcsh:TA1-2040, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Lithium, lcsh:Descriptive and experimental mechanics, lcsh:Electrical engineering. Electronics. Nuclear engineering, 0210 nano-technology, lcsh:Engineering (General). Civil engineering (General), lcsh:TK1-9971, Derivative (chemistry)
Abstract

International audience; Boron-and nitrogen-based materials have shown to be attractive for solid-state chemical hydrogen storage owing to gravimetric hydrogen densities higher than 10 wt% H. Herein, we report a new derivative of hydrazine borane N 2 H 4 BH 3 , namely lithium hydrazinidoborane ammoniate LiN 2 H 3 BH 3 ·0.25NH 3. It is easily obtained in ambient conditions by ball-milling N 2 H 4 BH 3 and lithium amide LiNH 2 taken in equimolar amounts. Both compounds react without loss of any H atoms. The molecular and crystallographic structures of our new compound have been confirmed by NMR/FTIR spectroscopy and powder X-ray diffraction. The complexation of the entity LiN 2 H 3 BH 3 by some NH 3 has been also established by thermogravimetric and calorimetric analyses. In our conditions, LiN 2 H 3 BH 3 ·0.25NH 3 has been shown to be able to release H 2 at temperatures lower than the parent N 2 H 4 BH 3 or the counterpart LiN 2 H 3 BH 3. It also liberates non-negligible amounts of NH 3 at temperatures lower than 100 • C. This is actually quite detrimental for chemical H storage, but alternatively LiN 2 H 3 BH 3 ·0.25NH 3 might be seen as a potential NH 3 carrier.

Published
2017
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37. Mechanical properties of a gallium fumarate metal-organic framework: a joint experimental-modelling exploration

Author

Christian Serre, Paul Fabry, Louis Vanduyfhuys, Jean-Paul Itié, Veronique Van Speybroeck, Padmini Ramaswamy, Guillaume Maurin, Elsa Alvarez, Pascal G. Yot, Jelle Wieme, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Center for molecular modeling, Universiteit Gent = Ghent University [Belgium] (UGENT), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), BELSPO, ANR-12-BS10-0005,MODS,Des MOFs comme nano-amortisseurs ou nano-ressorts : une exploration des propriétés thermodynamiques et mécaniques des matériaux hybrides poreux de type Metal-Organic Frameworks(2012), European Project: 647755,H2020,ERC-2014-CoG,DYNPOR(2015), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Universiteit Gent = Ghent University (UGENT), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
ADSORPTION, Materials science, FLEXIBILITY, HIGH-PRESSURE BEHAVIOR, chemistry.chemical_element, TRANSITIONS, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, WAVE BASIS-SET, FLEXIBLE MIL-53(AL), Adsorption, Aluminium, General Materials Science, Gallium, ComputingMilieux_MISCELLANEOUS, MOF, Renewable Energy, Sustainability and the Environment, TOTAL-ENERGY CALCULATIONS, CARBON-DIOXIDE CAPTURE, General Chemistry, Porosimetry, Science General, 021001 nanoscience & nanotechnology, ZEOLITIC IMIDAZOLATE FRAMEWORKS, 0104 chemical sciences, Crystallography, Energy profile, chemistry, Chemical engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Metal-organic framework, 0210 nano-technology, Powder diffraction, Zeolitic imidazolate framework
Abstract

A gallium analogue of the commercially available Al-fumarate MOF A520 - recently identified as isotypic to MIL-53(Al)-BDC - has been synthesized for the first time and further characterized in its hydrated and dehydrated forms. The structural response under applied mechanical pressure of this MIL-53(Ga)-FA solid was investigated using advanced experimental techniques coupled with computational tools. Hg porosimetry and high-pressure X-ray powder diffraction (XRPD) experiments evidenced that the pristine dehydrated large pore form undergoes an irreversible structure contraction upon an applied pressure of 85 MPa with an associated volume change of similar to 14% which makes this material promising for mechanical energy storage applications, in particular as a shock absorber. The breathing behavior was further rationalized by performing a series of periodic Density Functional Theory (DFT) calculations with the construction of an energy profile as a function of volume for both MIL-53(Ga)-FA and its aluminium analogue. As such we unravelled the microscopic origin of the difference in pressure-induced behavior for the aluminium and gallium fumarate based materials.

Published
2017
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38. Impact of the Metal Centre and Functionalization on the Mechanical Behaviour of MIL-53 Metal-Organic Frameworks

Author

Gérard Férey, Christian Serre, Guillaume Maurin, Florence Ragon, Vincent Guillerm, Norbert Stock, Erik Elkaim, Paraskevas Parisiades, Patricia Horcajada, Ke Yang, Vladimir Dmitriev, Paul A. Wright, Thomas Devic, John P. S. Mowat, Pascal G. Yot, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Catalan Institute of Nanoscience and Nanotechnology (ICN2), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC)-Barcelona Institute of Science and Technology (BIST), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), European Synchrotron Radiation Facility (ESRF), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut fur Anorganische Chemie (CAU), Christian-Albrechts-Universität zu Kiel (CAU), University of St Andrews. School of Chemistry, and University of St Andrews. EaSTCHEM

Subjects
NDAS, Nanotechnology, Mechanical properties, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Metal, Substituent effects, [CHIM.CRIS]Chemical Sciences/Cristallography, QD, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Metal–organic frameworks, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, QD Chemistry, 0104 chemical sciences, X-ray diffraction, Phase transitions, visual_art, visual_art.visual_art_medium, Surface modification, Metal-organic framework, 0210 nano-technology
Abstract

The French National Agency for Research ANR “MODS” (ANR-12-BS10-0005) is thanked for its financial support. An extended series of MIL-53(M)_X metal–organic frameworks (MIL = Materials of Institute Lavoisier; M = Al, Cr, Fe, Sc; X = Cl, CH3, NO2) have been systematically investiaged to explore the impact of the nature of both the metal centre and the functions grafted on to the organic linker on the mechanical behaviour of this family of highly flexible hybrid porous frameworks under the application of an external pressure of up to 3 GPa. The high-pressure X-ray diffraction measurements allowed the characterization of the pressure-induced phase transitions of the hydrated structures, the associated volume changes/pressure transitions, and their mechanical resilience through the determination of their bulk moduli. Postprint Postprint

Published
2016
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39. Influence of the Organic Ligand Functionalization on the Breathing of the Porous Iron Terephthalate Metal Organic Framework Type Material upon Hydrocarbon Adsorption

Author

Christian Serre, Qingyuan Yang, François Fajula, Philippe Trens, Thomas Devic, Yaroslav Filinchuk, Trung Thuy Khuong, Sandrine Bourrelly, Pascal G. Yot, Gérard Férey, Guillaume Maurin, Philip L. Llewellyn, Naseem A. Ramsahye, Patricia Horcajada, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Chimie Provence (LCP), Université de Provence - Aix-Marseille 1-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), European Synchrotron Radiation Facility (ESRF), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Steric effects, chemistry.chemical_classification, Chemistry, Inorganic chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, General Energy, Adsorption, Hydrocarbon, Chemical engineering, Functional group, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Surface modification, Metal-organic framework, Physical and Theoretical Chemistry, 0210 nano-technology, Porosity, ComputingMilieux_MISCELLANEOUS, Powder diffraction
Abstract

A combination of manometry, X-ray powder diffraction (XRPD), and molecular modeling has been used to show that the functionalization of the flexible MIL-53(Fe)-X materials (MIL stands for Materials of the Lavoisier Institute; X = CH3, Cl, Br, NH2) modifies the adsorption process of normal alkanes, by facilitating pores filling as compared to that of the nonmodified MIL-53(Fe) analogue. The adsorption isotherms show that these materials undergo steps at pressures specific for each guest and functional group, associated with structural transitions as corroborated by the simulated isotherms and XRPD data. With the exception of methane, a transition from the closed pore form to the large pore form occurs through one intermediate pore form upon adsorption, thus differing from the case of the nonmodified MIL-53(Fe) where two intermediate pore forms are observed. The transitions are governed by a combination of factors, including energetic, kinetic, and steric aspects with, however, transition pressures becoming...

Published
2011
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40. Unusual Chain-Length Dependence of the Diffusion of n-Alkanes in the Metal-Organic Framework MIL-47(V): The Blowgun Effect

Author

Gérard Férey, Christian Serre, Nilton Rosenbach, Daniil I. Kolokolov, Pascal G. Yot, Hervé Jobic, Thomas Devic, Aziz Ghoufi, and Guillaume Maurin

Subjects
N alkanes, Chemistry, Organic Chemistry, Inorganic chemistry, 02 engineering and technology, General Chemistry, Neutron scattering, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Molecular dynamics, Chain length, Physical chemistry, Metal-organic framework, Diffusion (business), 0210 nano-technology
Published
2010
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41. Nanostructured ionic conductors: A study of Vycor®7930–LiI composites

Author

Nathalie Frolet, Michel Ribes, Annie Pradel, Stéphanie Albert, Pascal G. Yot, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Nanocomposite, Scanning electron microscope, Mechanical Engineering, Composite number, 02 engineering and technology, Porosimetry, Conductivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Mechanics of Materials, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Ionic conductivity, General Materials Science, Crystallite, Composite material, 0210 nano-technology, Porosity, ComputingMilieux_MISCELLANEOUS
Abstract

A series of three Vycor glass/LiI composites were prepared by impregnating molten LiI into a porous Vycor ® 7930 powdered glass. X-ray diffraction showed the presence of LiI and LiI, H 2 O crystallites of about 100 nm in size. Scanning electron microscopy confirmed that an optimisation of heat treatment could lead to a composite with optimal coating and filling of the pores of the matrix. An increase in the pore size, unavoidable and due to the residual water content of the Vycor, was measured by Hg porosimetry. Nevertheless the conductivity of the composites was increased compared to that of pure LiI, with a gain of two orders of magnitude for the best conductor, i.e. 0.5LiI–0.5Vycor.

Published
2008
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42. Mechanical energy storage performance of an aluminum fumarate metal-organic framework

Author

Nathalie Guillou, Christian Serre, Philip L. Llewellyn, Thomas Devic, Guillaume Maurin, Paul Fabry, Jean-Paul Itié, Julien Rodriguez, Veronique Van Speybroeck, Elsa Alvarez, Isabelle Beurroies, Louis Vanduyfhuys, Pascal G. Yot, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Center for molecular modeling, Universiteit Gent = Ghent University [Belgium] (UGENT), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and Universiteit Gent = Ghent University (UGENT)

Subjects
Work (thermodynamics), Materials science, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, EXPLORATION, Aluminium, Structural transition, Zeolite, ComputingMilieux_MISCELLANEOUS, MOF, PRESSURE WATER INTRUSION, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemistry, GUEST, Chemical engineering, chemistry, ZEOLITE, Mechanical energy storage, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Porous solids, Metal-organic framework, 0210 nano-technology
Abstract

The aluminum fumarate MOF A520 or MIL-53-FA is revealed to be a promising material for mechanical energy-related applications with performances in terms of work and heat energies which surpass those of any porous solids reported so far. Complementary experimental and computational tools are deployed to finely characterize and understand the pressure-induced structural transition at the origin of these unprecedented levels of performance.

Published
2016
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43. Characterisation of porous Vycor® 7930–AgI composites synthesised by electro-crystallisation

Author

Nathalie Frolet, Michel Ribes, Pascal G. Yot, Stéphanie Albert, Annie Pradel, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Morphology, Materials science, Scanning electron microscope, Composite number, Energy-dispersive X-ray spectroscopy, 02 engineering and technology, Composites synthesis, Porous glass, 010402 general chemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, law, Glass (PVG), General Materials Science, Crystallization, Composite material, Precipitation (chemistry), Silver iodide, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Porous Vycor(r), 0104 chemical sciences, Silver nitrate, Electro-crystallisation, chemistry, Mechanics of Materials, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology
Abstract

6 pages; International audience; The paper reports on the elaboration and characterisation of ‘‘porous glass–ionic conductor'' composite. The Vycor(r) 7930, a porous glass from Corning, was used as a bulk porous insulating matrix where silver iodide (beta-AgI) was inserted to obtain a Vycor(r)AgI composite. The precipitation of silver iodide (beta-AgI) inside the pores of Vycor(r) glass was obtained by electro-crystallisation with an applied voltage of 1.5 V using silver nitrate and sodium iodide solutions as precursors. The obtained ‘‘silver iodide–Vycor(r)'' composites were characterised by scanning electron microscopy coupled with energy dispersive spectroscopy. The influence of the electro-crystallisation time on the AgI precipitate microstructure was studied.

Published
2007
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44. ChemInform Abstract: Key Study on the Potential of Hydrazine Bisborane for Solid- and Liquid-State Chemical Hydrogen Storage

Author

Marc Cretin, Philippe Miele, Sergii Pylypko, Eddy Petit, Umit B. Demirci, Fabrice Salles, and Pascal G. Yot

Subjects
Hydrogen storage, chemistry.chemical_compound, Liquid state, Glovebox, Chemistry, Yield (chemistry), Inorganic chemistry, Hydrazine, General Medicine
Abstract

The title compound, N2H4(BH3)2, is prepared from a mixture of freshly ground [N2H5][HSO4] and NaBH4 in THF (Ar-filled glovebox, round-bottom flask, 40 °C, 42—90 h, 87% yield).

Published
2015
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45. Ionic conductivity in nanoporous composites SiO2/AgI

Author

Nathalie Frolet, Annie Pradel, Michel Ribes, Stéphanie Albert, Pascal G. Yot, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Nanoporous, Composite number, Ionic bonding, Composite, 02 engineering and technology, General Chemistry, Conductivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Dielectric spectroscopy, Pore controlled glass, Electric conductivity, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Melting point, Ionic conductivity, General Materials Science, Composite material, 0210 nano-technology, Porosity, AgI
Abstract

5 pages; International audience; In this work, porous silicate glasses were mixed with an ionic conductor AgI to obtain SiO2/AgI composites. The porous glasses were either commercial Vycor glass (VPG) from Corning or synthesised from phase separated SiO2–B2O3–Na2O glasses. Depending upon the elaboration process, glasses with different pore sizes were obtained (4, 20 and 40 nm). Composites comprising different amounts of AgI were prepared by heating above the melting point of AgI. SEM characterisation of the obtained composites indicated that heat treatment induced an increase in the pore sizes. The conductivity of the composites was measured by impedance spectroscopy. The maximum conductivity, twice as large as that of pure AgI, was obtained for the 50AgI/50VPG composite, i.e. that comprising the glasses with the smallest pores.

Published
2006
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46. Effects of temperature, reaction time and reducing agent content on the synthesis of macroporous foam glasses from waste funnel glasses

Author

François O. Méar, Michel Ribes, and Pascal G. Yot

Subjects
Materials science, Scanning electron microscope, Reducing agent, Mechanical Engineering, chemistry.chemical_element, Porosimetry, Condensed Matter Physics, Microstructure, chemistry, Mechanics of Materials, Phase (matter), General Materials Science, Composite material, Tin, Porosity, Lead oxide
Abstract

In this paper, the microstructures of cellular materials (foam glasses) synthesized from lead containing waste cathode ray tube glasses (funnel CRT glasses) are only investigated. This synthetic approach is a possible method for recycling PbO containing glasses (20–22 wt.%). In the present work, foam glasses were prepared using various concentrations of SiC or TiN as the reducing agent for various temperatures and reaction times. The reaction between the reducing agent and the lead oxide in the glasses produces a gaseous phase in the network (CO 2 and N 2 for SiC and TiN, respectively) and metallic lead. The gas expands, which results in a cellular structure, i.e., a porous body. Scanning electron microscopy was used with mercury porosimetry to study the microstructures of the resulting cellular materials as well as to determine their pore diameters and pore size distributions, and check for the presence of connecting “windows”. We correlate these intrinsic parameters with the elaboration parameters with the aim of optimizing the material synthesis process.

Published
2006
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47. 3D Reconstruction and Porosity Study of a Hierarchical Porous Monolithic Metal Organic Framework by FIB-SEM Nanotomography

Author

Patricia Horcajada, L. Micheron, J. Méndez, E.L. Solla, and Pascal G. Yot

Subjects
Materials science, 3D reconstruction, Metal-organic framework, 02 engineering and technology, Composite material, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, Porosity, 01 natural sciences, Instrumentation, Hierarchical porous, 0104 chemical sciences
Published
2016
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48. Diffusion of Benzene in the Breathing MetalpOrganic Framework MIL-53(Cr): A Joint Experimental-Computational Investigation

Author

Alexander G. Stepanov, Philippe Trens, Daniil I. Kolokolov, Hervé Jobic, Guillaume Maurin, Pascal G. Yot, Sébastien Rives, Jacques Ollivier, Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), IRCELYON-Approches thermodynamiques, analytiques et réactionnelles intégrées (ATARI), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Diffusion, Rotation around a fixed axis, 02 engineering and technology, Activation energy, [CHIM.CATA]Chemical Sciences/Catalysis, Neutron scattering, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, [SDE.ES]Environmental Sciences/Environmental and Society, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Molecular dynamics, chemistry.chemical_compound, General Energy, chemistry, Computational chemistry, Chemical physics, Phase (matter), Metal-organic framework, Physical and Theoretical Chemistry, 0210 nano-technology, Benzene
Abstract

A combination of experimental (quasi-elastic neutron scattering and 2H NMR) and computational (molecular dynamics) tools was used to uncover the molecular mobility of benzene trapped inside the flexible channel-type MIL-53 (Cr3+) MOF. This material was shown to undergo a contraction of the structure upon benzene adsorption with the formation of a narrow pore phase with a smaller aperture. This confinement was found to strongly influence the dynamics of the guest: benzene diffuses in a region centered in the middle of the pore by a 1D-jump translational mechanism along the tunnel ruled by the presence of the μ2-OH groups present at the MOF pore wall. This translational diffusion is combined with a fast uniaxial rotational motion around the C6-axis. Any other rotational motion that involves the tumbling of the phenyl rings about the channel axis is much less probable due to a high activation energy barrier (49 kJ mol–1). In this way benzene can be pictured as a rotating disc that diffuses rapidly through th...

Published
2015
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49. Key Study on the Potential of Hydrazine Bisborane for Solid- and Liquid-State Chemical Hydrogen Storage

Author

Sergii Pylypko, Marc Cretin, Umit B. Demirci, Fabrice Salles, Eddy Petit, Pascal G. Yot, Philippe Miele, Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, Hydrazine, Inorganic chemistry, Context (language use), [CHIM.MATE]Chemical Sciences/Material chemistry, 7. Clean energy, Catalysis, Inorganic Chemistry, Metal, chemistry.chemical_compound, symbols.namesake, Hydrogen storage, visual_art, symbols, visual_art.visual_art_medium, Dehydrogenation, Physical and Theoretical Chemistry, Fourier transform infrared spectroscopy, Raman spectroscopy
Abstract

International audience; Hydrazine bisborane N2H4(BH3)2 (HBB; 16.8 wt %) recently re-emerged as a potential hydrogen storage material. However, such potential is controversial: HBB was seen as a hazardous compound up to 2010, but now it would be suitable for hydrogen storage. In this context, we focused on fundamentals of HBB because they are missing in the literature and should help to shed light on its effective potential while taking into consideration any risk. Experimental/computational methods were used to get a complete characterization data sheet, including, e.g., XRD, NMR, FTIR, Raman, TGA, and DSC. From the reported results and discussion, it is concluded that HBB has potential in the field of chemical hydrogen storage given that both thermolytic and hydrolytic dehydrogenations were analyzed. In solid-state chemical hydrogen storage, it cannot be used in the pristine state (risk of explosion during dehydrogenation) but can be used for the synthesis of derivatives with improved dehydrogenation properties. In liquid-state chemical hydrogen storage, it can be studied for room-temperature dehydrogenation, but this requires the development of an active and selective metal-based catalyst. HBB is a thus a candidate for chemical hydrogen storage.

Published
2015
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50. Chemical vapor deposition growth of boron–carbon–nitrogen layers from methylamine borane thermolysis products

Author

F. Javier Garcia-Garcia, Filippo Mastrangelo, Eduardo Flores, Carlos Sánchez, Umit B. Demirci, Fernando J. Urbanos, Cristina Gómez Navarro, Herko P. van der Meulen, Maria Grazia Betti, Fabrice Leardini, Pascal G. Yot, José R. Ares, Isabel J. Ferrer, Guillermo López Polin, Carlo Mariani, Pablo Molina, Daniel Granados, Andrés R. Galvis, National Institute for Materials Science, Université des Antilles et de la Guyane - UFR des sciences médicales (UAG UFR SM), Université des Antilles et de la Guyane (UAG), Institut Européen des membranes (IEM), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), UAM. Departamento de Física de la Materia Condensada, and UAM. Departamento de Física de Materiales

Subjects
Materials science, Band gap, Inorganic chemistry, FOS: Physical sciences, chemistry.chemical_element, Bioengineering, 02 engineering and technology, Chemical vapor deposition, Borane, 010402 general chemistry, 01 natural sciences, chemical vapor deposition, chemistry.chemical_compound, Hexagons, Nanosheets, [CHIM]Chemical Sciences, General Materials Science, Electrical and Electronic Engineering, Boron, ComputingMilieux_MISCELLANEOUS, Condensed Matter - Materials Science, Boron Nitrides, Methylamine, Mechanical Engineering, graphene, Doping, Thermal decomposition, Física, Materials Science (cond-mat.mtrl-sci), General Chemistry, 021001 nanoscience & nanotechnology, 3. Good health, 0104 chemical sciences, boron nitride, chemistry, Mechanics of Materials, optical bandgap, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], borocarbonitrides, Composition (visual arts), 0210 nano-technology
Abstract

This is the Accepted Manuscript version of an article accepted for publication in Nanotechnology. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at https://doi.org/10.1088/1361-6528/aa9c07, This work investigates the growth of B-C-N layers by chemical vapor deposition using methylamine borane (MeAB) as the single-source precursor. MeAB has been synthesized and characterized, paying particular attention to the analysis of its thermolysis products, which are the gaseous precursors for B-C-N growth. Samples have been grown on Cu foils and transferred onto different substrates for their morphological, structural, chemical, electronic and optical characterizations. The results of these characterizations indicate a segregation of h-BN and graphene-like (Gr) domains. However, there is an important presence of B and N interactions with C at the Gr borders, and of C interacting at the h-BN-edges, respectively, in the obtained nano-layers. In particular, there is a significant presence of C-N bonds, at Gr/h-BN borders and in the form of N doping of Gr domains. The overall B:C:N contents in the layers is close to 1:3:1.5. A careful analysis of the optical bandgap determination of the obtained B-C-N layers is presented, discussed and compared with previous seminal works with samples of similar composition

Published
2017
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