ABSTRACT Nanoparticles of mesoporous MIL-100(Al, Cr or Fe) metalorganic frameworks were synthesiz... more ABSTRACT Nanoparticles of mesoporous MIL-100(Al, Cr or Fe) metalorganic frameworks were synthesized by a microwave-assisted solvothermal route with green solvents. The optimization of yield, crystallinity, and particle size was achieved through the control of synthetic parameters such as temperature, heating rate, and dwelling time. The particle size strongly depends on the metallic cation and the metal and linker precursors; nanoparticles smaller than 100 nm were obtained for iron and chromium based MIL-100. Finally, stable colloidal solutions of iron and chromium MIL-100 nanoparticles were used for thin layer dip-coating deposition, which resulted in high optical quality thin films, the porosity of which was investigated by environmental ellipsometric porosimetry.
The crystallization of metal-organic framework (MOF) materials is an extremely attractive way in ... more The crystallization of metal-organic framework (MOF) materials is an extremely attractive way in which to produce functional solid materials with complex three-dimensional structures, since an element of "design" is considered possible in their synthesis: the idea being that by using chosen metal polyhedral units linked by polydentate organic ligands with a known coordination preference, a network structure of desired connectivity may be formed. This synthetic approach is presently the focus of some considerable attention and is yielding many novel hybrid inorganic-organic solids, often that possess some porosity on the nanoscale suitable for applications, such as gas separation, molecular sieving, and shape-selective catalysis. Although these uses are already well-established in silicate zeolite chemistry, there are distinct advantages offered by the MOFs for uses under mild conditions. For example, the choice of framework metal may offer desirable binding sites for gases (currently the focus of much attention in the topical areas of storage of hydrogen, methane, or carbon dioxide ), the functionalization of organic linkers (either pre-or post-synthesis) may allow tuning of the porosity, reactivity, and the selectivity towards binding of guest molecules, and the use of chiral ligands may result in chiral framework materials. In addition, MOF structures also often show great flexibility in the solid state, giving them properties distinct from the traditional inorganic zeotype materials. To explore the extent to which new MOF materials may be "designed" it is now important to elucidate the fundamental physico-chemical details of the crystallization of MOF materials: knowledge of how complex extended network structures are assembled from simple chemical precursors in solution could ultimately permit some fine tuning of synthesis conditions to test and realize the ideas of design in synthesis. Only a few such studies have been reported to date. These include extended X-ray absorption fine structure (EXAFS) spectroscopy studies of reactive solutions to examine the presence of structural building units in solution, through the amorphous intermediate to final crystalline product; light scattering from clear solutions to observe the formation of colloidal nanocrystals; and mass spectrometry to examine the interaction of Mg 2+ ions with (+)camphoric acid to identify possible building units for the construction of a MOF. Shoaee et al. recently used atomic force microscopy (AFM) to examine a growing face of a copper MOF after injection of a reactive solution and suggested that the growth unit from solution was actually smaller than the paddle-wheel-shaped building unit identified in its crystal structure. The study of MOF crystallization mechanism has so far been concerned with the local structure of solution species prior to the appearance of crystal order, but it is important to examine crystal growth over all length scales to build up a complete picture of crystallization. Herein, we describe observations of the emergence of the crystal order of MOFs from reactive solutions, above room temperature, by using the time-resolved energy-dispersive Xray diffraction (EDXRD) method for two established transition-metal carboxylate MOFs. The technique has been used successfully for the in situ study of the crystallization of a variety of inorganic materials, although to date it has not been applied to the study of hybrid MOF materials. Its advantage lies in the use of high intensity white beam X-rays, which allows the non-invasive penetration of laboratory-scale reaction vessels under elevated temperature and autogeneous pressure. Thus the evolution of Bragg peaks as a function of reaction conditions and time can be monitored with a time resolution of less than 1 min.
In a recent systematic study on the influence of the reaction temperature on the structure format... more In a recent systematic study on the influence of the reaction temperature on the structure formation in the system CdCl2/H(HO3PCH2)2NH-CH2C6H4-COOH (H5L) /NaOH, [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O was obtained as a microcrystalline compound. We have now been able to elucidate the structure from single-crystal data: triclinic, P; a=5.4503(9), b=12.880(2), and c=16.417(3) A; alpha=67.841(6) degrees, beta=80.633(6) degrees, gamma=87.688(8) degrees, V=1052.9(3) A3; Z=1; R1=0.1143, R2=0.2108 (all data); 0.0705, 0.1823 ((I>2sigmaI)). The structure of [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O is built up of cadmium phosphonate layers connected by water-mediated hydrogen bonds between aryl-carboxylic acid groups and water molecules coordinated to Cd2+ ions of adjacent layers (C-OH...H2O...H2O-Cd2+). The title compound was characterized by IR spectroscopy and energy dispersive X-ray, elemental, and thermogravimetric analyses. Furthermore, temperature-dependent X-ray diffraction data are presented. [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O can be reversibly dehydrated, and mechanical stress and grinding in the presence of water leads to the intercalation of additional water molecules.
The adsorption of short linear alkanes has been explored in the highly flexible MIL-53(Cr) porous... more The adsorption of short linear alkanes has been explored in the highly flexible MIL-53(Cr) porous metal-organic framework by means of molecular simulations based on configurational bias grand canonical Monte Carlo. The unusual shape of the adsorption isotherms with the existence of steps has been successfully modelled by creating a (narrow pore, large pore) phase mixture domain, the composition of which varies with pressure. A further step consisted of combining our computational approach with several experimental tools including microcalorimetry, gravimetry and in situ X-ray diffraction, to fully characterize the adsorption behaviour of the isostructural MIL-47(V) rigid MOF, i.e. the preferential arrangement of each type of alkane inside the pores and the resulting interaction energy. Finally, relationships are established between the adsorption enthalpies and both alkyl chain length and polarisability of the alkanes that can be further utilised to predict the energetics of the adsorption process for longer alkane chains.
... Views of the structure (Figure 2) show that this new nickel glutarate, denoted MIL-77, presen... more ... Views of the structure (Figure 2) show that this new nickel glutarate, denoted MIL-77, presents an open 3D network of edge-sharing nickel octahedra. ... vacuum gives a typical Type-1 isotherm and a surface area of 346(10) m 2 g −1 which clearly indicates notable porosity for this ...
This critical review focuses on a strange behaviour of crystallized solid matter: its reversible ... more This critical review focuses on a strange behaviour of crystallized solid matter: its reversible swelling with large magnitude. This will be of interest for experts in porous solids but also for solid state chemists and physicists. Some examples, classified according to the dimensionality of the inorganic subnetwork, present the general requirements and the structural rules which govern the existence of this phenomenon. Its consequences concern specific applications related to sensors, energy savings, sustainable development and health (100 references).
One of the technological problems that face society today is the environmentally friendly and eco... more One of the technological problems that face society today is the environmentally friendly and economically feasible separation, recovery, and recovery/reuse of vapors and gases. Several examples are currently of interest: the selective recovery of solvents, the recovery of greenhouse gases, and the purification of hydrogen. Many processes include an adsorption step in which microporous adsorbents, such as activated carbon and zeolites, are used. Recently a new class of porous materials have found interest: these metal organic frameworks (MOFs) or metal coordination polymers are built up from inorganic subnetworks and organic complexing molecules (phosphonates, carboxylates, sulfonates). These subnetworks often contain divalent or trivalent cations connected by organic groups such as carboxylates. Such structures possess tunnels or cavities with pore sizes between 3 and 35 . Several of these organic-inorganic hybrid porous solids have the interesting feature of being selectively flexible during the adsorption process by means of a breathing or gate-opening process, which depends on the nature of the adsorptive. Examples discovered by Ferey and coworkers include flexible porous carboxylates formed by chains of metallic centers (MIL-53, -69) and with metalcenter trimers (MIL-88A). These solids have shown to "breath" with unprecedented increases in volume between 50 and 85 % depending on the nature of the fluid. A consequence of this particular property is the possibility to develop novel selective separation and storage processes that could be less expensive than existing processes.
... DA; Thode, CJ; Williams, ME Chem. Mater. ... Kyriakos C. Stylianou, Romain Heck, Samantha Y. ... more ... DA; Thode, CJ; Williams, ME Chem. Mater. ... Kyriakos C. Stylianou, Romain Heck, Samantha Y. Chong, John Bacsa, James TA Jones, Yaroslav Z. Khimyak, Darren Bradshaw and Matthew J. Rosseinsky. Journal of the American Chemical Society 2010 132 (12), pp 41194130. ...
A variety of spectroscopic techniques combined with in situ pressure-controlled X-ray diffraction... more A variety of spectroscopic techniques combined with in situ pressure-controlled X-ray diffraction and molecular simulations have been utilized to characterize the five-step phase transition observed upon N 2 adsorption within the high-surface area metal-organic framework Co(BDP) (BDP 2-) 1,4-benzenedipyrozolate). The computationally assisted structure determinations reveal structural changes involving the orientation of the benzene rings relative to the pyrazolate rings, the dihedral angles for the pyrazolate rings bound at the metal centers, and a change in the metal coordination geometry from square planar to tetrahedral. Variable-temperature magnetic susceptibility measurements and in situ infrared and UV-vis-NIR spectroscopic measurements provide strong corroborating evidence for the observed changes in structure. In addition, the results from in situ microcalorimetry measurements show that an additional heat of 2 kJ/ mol is required for each of the first four transitions, while 7 kJ/mol is necessary for the last step involving the transformation of Co II from square planar to tetrahedral. Based on the enthalpy, a weak N 2 interaction with the open Co II coordination sites is proposed for the first four phases, which is supported by Monte Carlo simulations.
Comptes Rendus De L Academie Des Sciences Serie Ii Fascicule C-chimie, 2001
Hydrothermal reaction of cobalt (II) salts with pimelate ions produces the new compound Co(C7H10O... more Hydrothermal reaction of cobalt (II) salts with pimelate ions produces the new compound Co(C7H10O4). It crystallises in the orthorhombic space group Pcca 〚a = 37.477 8(8) Å, b = 4.772 4(1) Å, c = 9.330 2(1) Å〛 and its structure was solved by single crystal X-ray diffraction. The neutral three-dimensional framework is built up from isolated cobalt tetrahedra bridged by pimelate ions. The connection involves the formation of two types of small
Angewandte Chemie (International ed. in English), 2007
Metal-organic frameworks (MOFs) are promising multifunctional materials which can combine the pro... more Metal-organic frameworks (MOFs) are promising multifunctional materials which can combine the properties of porous materials (catalysis, shape-selective absorption, gas storage, and purification) with those of dense inorganic phases (magnetism and optics). The performances of the new class of micro-and mesoporous metal-organic frameworks favorably compare with zeolites in terms of either CO 2 capture, hydrogen sorption, or capabilities to host a wide variety of aqueous or nonaqueous solvent molecules for energy applications. These properties arise from the presence of large-size tunnels or cages within their skeleton, built up from organic (often polycarboxylates) and inorganic moieties of variable dimensionalities (clusters, chains, or slabs). Herein we report the first use of these materials as rechargeable intercalation electrodes with promise for application in the positive electrode in Li-based batteries.
In the domain of porous solids with inorganic or hybrid frameworks, the combination of mastered c... more In the domain of porous solids with inorganic or hybrid frameworks, the combination of mastered chemistry and of computer simulations pushes forward the limits of the classical approach and allows the full determination from powder diffraction data of architectures with cells of several hundred thousand cubic angstroms with hierarchies of giant pores and unprecedented Langmuir surfaces. The different limits induced by this new approach are analyzed.
Chemical communications (Cambridge, England), Jan 21, 2003
Hydrogen adsorption has been studied in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-... more Hydrogen adsorption has been studied in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-CO2) (M = Al3+, Cr3+); these solids show a hydrogen storage capacity of 3.8 and 3.1 wt.% respectively when loaded at 77 K under 1.6 MPa.
We report here a new family of isoreticular MOFs, comprising three larger analogues of the nanopo... more We report here a new family of isoreticular MOFs, comprising three larger analogues of the nanoporous metallocarboxylate MIL-88; these solids were synthesized using a controlled SBU approach and the three crystal structures were solved using an original simulation-assisted structure determination method in direct space.
A new three-dimensional chromium(III) naphthalene tetracarboxylate, CrIII3O(H2O)2F{C10H4(CO2)4}1.... more A new three-dimensional chromium(III) naphthalene tetracarboxylate, CrIII3O(H2O)2F{C10H4(CO2)4}1.5.6H2O (MIL-102), has been synthesized under hydrothermal conditions from an aqueous mixture of Cr(NO3)3.9H2O, naphthalene-1,4,5,8-tetracarboxylic acid, and HF. Its structure, solved ab initio from X-ray powder diffraction data, is built up from the connection of trimers of trivalent chromium octahedra and tetracarboxylate moieties. This creates a three-dimensional structure with an array of small one-dimensional channels filled with free water molecules, which interact through hydrogen bonds with terminal water molecules and oxygen atoms from the carboxylates. Thermogravimetric analysis and X-ray thermodiffractometry indicate that MIL-102 is stable up to approximately 300 degrees C and shows zeolitic behavior. Due to topological frustration effects, MIL-102 remains paramagnetic down to 5 K. Finally, MIL-102 exhibits a hydrogen storage capacity of approximately 1.0 wt % at 77 K when loaded at 3.5 MPa (35 bar). The hydrogen uptake is discussed in relation with the structural characteristics and the molecular simulation results. The adsorption behavior of MIL-102 at 304 K resembles that of small-pore zeolites, such as silicalite. Indeed, the isotherms of CO2, CH4, and N2 show a maximum uptake at 0.5 MPa, with no further significant adsorption up to 3 MPa. Crystal data for MIL-102: hexagonal space group P(-)6 (No. 169), a = 12.632(1) A, c = 9.622(1) A.
The Room-Temperature Crystallization of a One-Dimensional Gallium Fluorophosphate, Ga(HPO 4 ) 2 F... more The Room-Temperature Crystallization of a One-Dimensional Gallium Fluorophosphate, Ga(HPO 4 ) 2 F·H 3 N (CH 2 ) 3 NH 3 ·2H 2 O, a Precursor to Three-Dimensional Microporous Gallium Fluorophosphates.
A large-pore, zeolitic nickel(II) phosphate, VSB-1, has been prepared under hydrothermal conditio... more A large-pore, zeolitic nickel(II) phosphate, VSB-1, has been prepared under hydrothermal conditions. The unidimensional pore system is delineated by 24 NiO6 and PO4 polyhedra and has a free diameter of approximately 9 Å. It becomes microporous on calcination in air at 623 K, yielding a BET surface area of 82 m2·g−1, and is stable in air to approximately 823 K.
ABSTRACT Nanoparticles of mesoporous MIL-100(Al, Cr or Fe) metalorganic frameworks were synthesiz... more ABSTRACT Nanoparticles of mesoporous MIL-100(Al, Cr or Fe) metalorganic frameworks were synthesized by a microwave-assisted solvothermal route with green solvents. The optimization of yield, crystallinity, and particle size was achieved through the control of synthetic parameters such as temperature, heating rate, and dwelling time. The particle size strongly depends on the metallic cation and the metal and linker precursors; nanoparticles smaller than 100 nm were obtained for iron and chromium based MIL-100. Finally, stable colloidal solutions of iron and chromium MIL-100 nanoparticles were used for thin layer dip-coating deposition, which resulted in high optical quality thin films, the porosity of which was investigated by environmental ellipsometric porosimetry.
The crystallization of metal-organic framework (MOF) materials is an extremely attractive way in ... more The crystallization of metal-organic framework (MOF) materials is an extremely attractive way in which to produce functional solid materials with complex three-dimensional structures, since an element of "design" is considered possible in their synthesis: the idea being that by using chosen metal polyhedral units linked by polydentate organic ligands with a known coordination preference, a network structure of desired connectivity may be formed. This synthetic approach is presently the focus of some considerable attention and is yielding many novel hybrid inorganic-organic solids, often that possess some porosity on the nanoscale suitable for applications, such as gas separation, molecular sieving, and shape-selective catalysis. Although these uses are already well-established in silicate zeolite chemistry, there are distinct advantages offered by the MOFs for uses under mild conditions. For example, the choice of framework metal may offer desirable binding sites for gases (currently the focus of much attention in the topical areas of storage of hydrogen, methane, or carbon dioxide ), the functionalization of organic linkers (either pre-or post-synthesis) may allow tuning of the porosity, reactivity, and the selectivity towards binding of guest molecules, and the use of chiral ligands may result in chiral framework materials. In addition, MOF structures also often show great flexibility in the solid state, giving them properties distinct from the traditional inorganic zeotype materials. To explore the extent to which new MOF materials may be "designed" it is now important to elucidate the fundamental physico-chemical details of the crystallization of MOF materials: knowledge of how complex extended network structures are assembled from simple chemical precursors in solution could ultimately permit some fine tuning of synthesis conditions to test and realize the ideas of design in synthesis. Only a few such studies have been reported to date. These include extended X-ray absorption fine structure (EXAFS) spectroscopy studies of reactive solutions to examine the presence of structural building units in solution, through the amorphous intermediate to final crystalline product; light scattering from clear solutions to observe the formation of colloidal nanocrystals; and mass spectrometry to examine the interaction of Mg 2+ ions with (+)camphoric acid to identify possible building units for the construction of a MOF. Shoaee et al. recently used atomic force microscopy (AFM) to examine a growing face of a copper MOF after injection of a reactive solution and suggested that the growth unit from solution was actually smaller than the paddle-wheel-shaped building unit identified in its crystal structure. The study of MOF crystallization mechanism has so far been concerned with the local structure of solution species prior to the appearance of crystal order, but it is important to examine crystal growth over all length scales to build up a complete picture of crystallization. Herein, we describe observations of the emergence of the crystal order of MOFs from reactive solutions, above room temperature, by using the time-resolved energy-dispersive Xray diffraction (EDXRD) method for two established transition-metal carboxylate MOFs. The technique has been used successfully for the in situ study of the crystallization of a variety of inorganic materials, although to date it has not been applied to the study of hybrid MOF materials. Its advantage lies in the use of high intensity white beam X-rays, which allows the non-invasive penetration of laboratory-scale reaction vessels under elevated temperature and autogeneous pressure. Thus the evolution of Bragg peaks as a function of reaction conditions and time can be monitored with a time resolution of less than 1 min.
In a recent systematic study on the influence of the reaction temperature on the structure format... more In a recent systematic study on the influence of the reaction temperature on the structure formation in the system CdCl2/H(HO3PCH2)2NH-CH2C6H4-COOH (H5L) /NaOH, [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O was obtained as a microcrystalline compound. We have now been able to elucidate the structure from single-crystal data: triclinic, P; a=5.4503(9), b=12.880(2), and c=16.417(3) A; alpha=67.841(6) degrees, beta=80.633(6) degrees, gamma=87.688(8) degrees, V=1052.9(3) A3; Z=1; R1=0.1143, R2=0.2108 (all data); 0.0705, 0.1823 ((I>2sigmaI)). The structure of [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O is built up of cadmium phosphonate layers connected by water-mediated hydrogen bonds between aryl-carboxylic acid groups and water molecules coordinated to Cd2+ ions of adjacent layers (C-OH...H2O...H2O-Cd2+). The title compound was characterized by IR spectroscopy and energy dispersive X-ray, elemental, and thermogravimetric analyses. Furthermore, temperature-dependent X-ray diffraction data are presented. [Cd3(H2O)3((O3PCH2)2NH-CH2C6H4-COOH)2].11H2O can be reversibly dehydrated, and mechanical stress and grinding in the presence of water leads to the intercalation of additional water molecules.
The adsorption of short linear alkanes has been explored in the highly flexible MIL-53(Cr) porous... more The adsorption of short linear alkanes has been explored in the highly flexible MIL-53(Cr) porous metal-organic framework by means of molecular simulations based on configurational bias grand canonical Monte Carlo. The unusual shape of the adsorption isotherms with the existence of steps has been successfully modelled by creating a (narrow pore, large pore) phase mixture domain, the composition of which varies with pressure. A further step consisted of combining our computational approach with several experimental tools including microcalorimetry, gravimetry and in situ X-ray diffraction, to fully characterize the adsorption behaviour of the isostructural MIL-47(V) rigid MOF, i.e. the preferential arrangement of each type of alkane inside the pores and the resulting interaction energy. Finally, relationships are established between the adsorption enthalpies and both alkyl chain length and polarisability of the alkanes that can be further utilised to predict the energetics of the adsorption process for longer alkane chains.
... Views of the structure (Figure 2) show that this new nickel glutarate, denoted MIL-77, presen... more ... Views of the structure (Figure 2) show that this new nickel glutarate, denoted MIL-77, presents an open 3D network of edge-sharing nickel octahedra. ... vacuum gives a typical Type-1 isotherm and a surface area of 346(10) m 2 g −1 which clearly indicates notable porosity for this ...
This critical review focuses on a strange behaviour of crystallized solid matter: its reversible ... more This critical review focuses on a strange behaviour of crystallized solid matter: its reversible swelling with large magnitude. This will be of interest for experts in porous solids but also for solid state chemists and physicists. Some examples, classified according to the dimensionality of the inorganic subnetwork, present the general requirements and the structural rules which govern the existence of this phenomenon. Its consequences concern specific applications related to sensors, energy savings, sustainable development and health (100 references).
One of the technological problems that face society today is the environmentally friendly and eco... more One of the technological problems that face society today is the environmentally friendly and economically feasible separation, recovery, and recovery/reuse of vapors and gases. Several examples are currently of interest: the selective recovery of solvents, the recovery of greenhouse gases, and the purification of hydrogen. Many processes include an adsorption step in which microporous adsorbents, such as activated carbon and zeolites, are used. Recently a new class of porous materials have found interest: these metal organic frameworks (MOFs) or metal coordination polymers are built up from inorganic subnetworks and organic complexing molecules (phosphonates, carboxylates, sulfonates). These subnetworks often contain divalent or trivalent cations connected by organic groups such as carboxylates. Such structures possess tunnels or cavities with pore sizes between 3 and 35 . Several of these organic-inorganic hybrid porous solids have the interesting feature of being selectively flexible during the adsorption process by means of a breathing or gate-opening process, which depends on the nature of the adsorptive. Examples discovered by Ferey and coworkers include flexible porous carboxylates formed by chains of metallic centers (MIL-53, -69) and with metalcenter trimers (MIL-88A). These solids have shown to "breath" with unprecedented increases in volume between 50 and 85 % depending on the nature of the fluid. A consequence of this particular property is the possibility to develop novel selective separation and storage processes that could be less expensive than existing processes.
... DA; Thode, CJ; Williams, ME Chem. Mater. ... Kyriakos C. Stylianou, Romain Heck, Samantha Y. ... more ... DA; Thode, CJ; Williams, ME Chem. Mater. ... Kyriakos C. Stylianou, Romain Heck, Samantha Y. Chong, John Bacsa, James TA Jones, Yaroslav Z. Khimyak, Darren Bradshaw and Matthew J. Rosseinsky. Journal of the American Chemical Society 2010 132 (12), pp 41194130. ...
A variety of spectroscopic techniques combined with in situ pressure-controlled X-ray diffraction... more A variety of spectroscopic techniques combined with in situ pressure-controlled X-ray diffraction and molecular simulations have been utilized to characterize the five-step phase transition observed upon N 2 adsorption within the high-surface area metal-organic framework Co(BDP) (BDP 2-) 1,4-benzenedipyrozolate). The computationally assisted structure determinations reveal structural changes involving the orientation of the benzene rings relative to the pyrazolate rings, the dihedral angles for the pyrazolate rings bound at the metal centers, and a change in the metal coordination geometry from square planar to tetrahedral. Variable-temperature magnetic susceptibility measurements and in situ infrared and UV-vis-NIR spectroscopic measurements provide strong corroborating evidence for the observed changes in structure. In addition, the results from in situ microcalorimetry measurements show that an additional heat of 2 kJ/ mol is required for each of the first four transitions, while 7 kJ/mol is necessary for the last step involving the transformation of Co II from square planar to tetrahedral. Based on the enthalpy, a weak N 2 interaction with the open Co II coordination sites is proposed for the first four phases, which is supported by Monte Carlo simulations.
Comptes Rendus De L Academie Des Sciences Serie Ii Fascicule C-chimie, 2001
Hydrothermal reaction of cobalt (II) salts with pimelate ions produces the new compound Co(C7H10O... more Hydrothermal reaction of cobalt (II) salts with pimelate ions produces the new compound Co(C7H10O4). It crystallises in the orthorhombic space group Pcca 〚a = 37.477 8(8) Å, b = 4.772 4(1) Å, c = 9.330 2(1) Å〛 and its structure was solved by single crystal X-ray diffraction. The neutral three-dimensional framework is built up from isolated cobalt tetrahedra bridged by pimelate ions. The connection involves the formation of two types of small
Angewandte Chemie (International ed. in English), 2007
Metal-organic frameworks (MOFs) are promising multifunctional materials which can combine the pro... more Metal-organic frameworks (MOFs) are promising multifunctional materials which can combine the properties of porous materials (catalysis, shape-selective absorption, gas storage, and purification) with those of dense inorganic phases (magnetism and optics). The performances of the new class of micro-and mesoporous metal-organic frameworks favorably compare with zeolites in terms of either CO 2 capture, hydrogen sorption, or capabilities to host a wide variety of aqueous or nonaqueous solvent molecules for energy applications. These properties arise from the presence of large-size tunnels or cages within their skeleton, built up from organic (often polycarboxylates) and inorganic moieties of variable dimensionalities (clusters, chains, or slabs). Herein we report the first use of these materials as rechargeable intercalation electrodes with promise for application in the positive electrode in Li-based batteries.
In the domain of porous solids with inorganic or hybrid frameworks, the combination of mastered c... more In the domain of porous solids with inorganic or hybrid frameworks, the combination of mastered chemistry and of computer simulations pushes forward the limits of the classical approach and allows the full determination from powder diffraction data of architectures with cells of several hundred thousand cubic angstroms with hierarchies of giant pores and unprecedented Langmuir surfaces. The different limits induced by this new approach are analyzed.
Chemical communications (Cambridge, England), Jan 21, 2003
Hydrogen adsorption has been studied in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-... more Hydrogen adsorption has been studied in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-CO2) (M = Al3+, Cr3+); these solids show a hydrogen storage capacity of 3.8 and 3.1 wt.% respectively when loaded at 77 K under 1.6 MPa.
We report here a new family of isoreticular MOFs, comprising three larger analogues of the nanopo... more We report here a new family of isoreticular MOFs, comprising three larger analogues of the nanoporous metallocarboxylate MIL-88; these solids were synthesized using a controlled SBU approach and the three crystal structures were solved using an original simulation-assisted structure determination method in direct space.
A new three-dimensional chromium(III) naphthalene tetracarboxylate, CrIII3O(H2O)2F{C10H4(CO2)4}1.... more A new three-dimensional chromium(III) naphthalene tetracarboxylate, CrIII3O(H2O)2F{C10H4(CO2)4}1.5.6H2O (MIL-102), has been synthesized under hydrothermal conditions from an aqueous mixture of Cr(NO3)3.9H2O, naphthalene-1,4,5,8-tetracarboxylic acid, and HF. Its structure, solved ab initio from X-ray powder diffraction data, is built up from the connection of trimers of trivalent chromium octahedra and tetracarboxylate moieties. This creates a three-dimensional structure with an array of small one-dimensional channels filled with free water molecules, which interact through hydrogen bonds with terminal water molecules and oxygen atoms from the carboxylates. Thermogravimetric analysis and X-ray thermodiffractometry indicate that MIL-102 is stable up to approximately 300 degrees C and shows zeolitic behavior. Due to topological frustration effects, MIL-102 remains paramagnetic down to 5 K. Finally, MIL-102 exhibits a hydrogen storage capacity of approximately 1.0 wt % at 77 K when loaded at 3.5 MPa (35 bar). The hydrogen uptake is discussed in relation with the structural characteristics and the molecular simulation results. The adsorption behavior of MIL-102 at 304 K resembles that of small-pore zeolites, such as silicalite. Indeed, the isotherms of CO2, CH4, and N2 show a maximum uptake at 0.5 MPa, with no further significant adsorption up to 3 MPa. Crystal data for MIL-102: hexagonal space group P(-)6 (No. 169), a = 12.632(1) A, c = 9.622(1) A.
The Room-Temperature Crystallization of a One-Dimensional Gallium Fluorophosphate, Ga(HPO 4 ) 2 F... more The Room-Temperature Crystallization of a One-Dimensional Gallium Fluorophosphate, Ga(HPO 4 ) 2 F·H 3 N (CH 2 ) 3 NH 3 ·2H 2 O, a Precursor to Three-Dimensional Microporous Gallium Fluorophosphates.
A large-pore, zeolitic nickel(II) phosphate, VSB-1, has been prepared under hydrothermal conditio... more A large-pore, zeolitic nickel(II) phosphate, VSB-1, has been prepared under hydrothermal conditions. The unidimensional pore system is delineated by 24 NiO6 and PO4 polyhedra and has a free diameter of approximately 9 Å. It becomes microporous on calcination in air at 623 K, yielding a BET surface area of 82 m2·g−1, and is stable in air to approximately 823 K.
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Papers by Gérard Férey