3There is great current interest in the use of porous materials for substrate storage and separations, catalysis, drug delivery, and sensing. [1][2][3][4][5] Understanding the host-guest interactions in these systems is vital if new generations of improved materials are to be developed. However, gaining such insight is challenging and often not feasible in large void materials due to lack of order in porous systems such as carbon, mesoporous silica and zeolites, 5 and also because the nature of these host-guest interactions is often based upon very weak and dynamic supramolecular contacts such as hydrogen-bond, π···π stacking, van der Waals, electrostatic or dipole interactions. Such supramolecular binding usually involves many hydrogen atoms and undergoes dynamic processes that are difficult to probe directly by experiment. 2,6 Recent studies on porous metal-organic frameworks (MOFs) for hydrogen storage, 7,8 carbon capture, 1 and hydrocarbon separations 9,10 have shown, in exceptional cases, location of guest molecules within the host via advanced crystallography studies, providing invaluable structural rationale for their function and properties. Most of these successes have been achieved within host systems that display strong confinement effects on the guest molecules and/or have specific relatively strong binding sites such as open metal centers. 7-12 However, host-guest systems involving primarily soft supramolecular interactions usually lead to serious positional disorder of the guest molecules, and hydrogen atoms involved in these binding processes are not readily seen or defined from crystallography studies, 13,14 leading to problems in defining the dynamics and motions of such host-guest systems.As a result, information on molecular binding dynamics and the motion of guests within the confined space of MOF hosts is largely lacking. Herein, we report the application of combined inelastic, quasi-elastic and elastic neutron scattering and synchrotron X-ray diffraction coupled to density functional theory (DFT) calculations to directly visualise the dynamics of host-guest interactions between adsorbed C 2 -hydrocarbons and the hydroxylfunctionalised porous MOF NOTT-300, which exhibits high selectivity and uptake capacity for unsaturated hydrocarbons. Moreover, direct observation of the mobility and diffusion for these adsorbed hydrocarbons within NOTT-300 has been achieved, representing important methodologies for their potential kinetic separations. These complementary experiments using dynamic, kinetic and static approaches lead to the same conclusion: four types of soft supramolecular interactions cooperatively bind guest molecules in these functionalised cavities, and these finetuned interactions lead to optimal uptake kinetics and binding dynamics affording excellent selectivities between these hydrocarbons. Results and discussionMaterial and characterisation. and 5, respectively. These selectivities are, however, subject to uncertainties associated with isotherm measurement of the extremely low ...
Understanding the mechanism by which porous solids trap harmful gases such as CO(2) and SO(2) is essential for the design of new materials for their selective removal. Materials functionalized with amine groups dominate this field, largely because of their potential to form carbamates through H(2)N(δ(-))···C(δ(+))O(2) interactions, thereby trapping CO(2) covalently. However, the use of these materials is energy-intensive, with significant environmental impact. Here, we report a non-amine-containing porous solid (NOTT-300) in which hydroxyl groups within pores bind CO(2) and SO(2) selectively. In situ powder X-ray diffraction and inelastic neutron scattering studies, combined with modelling, reveal that hydroxyl groups bind CO(2) and SO(2) through the formation of O=C(S)=O(δ(-))···H(δ(+))-O hydrogen bonds, which are reinforced by weak supramolecular interactions with C-H atoms on the aromatic rings of the framework. This offers the potential for the application of new 'easy-on/easy-off' capture systems for CO(2) and SO(2) that carry fewer economic and environmental penalties.
The key requirement for a portable store of natural gas is to maximize the amount of gas within the smallest possible space. The packing of methane (CH4) in a given storage medium at the highest possible density is, therefore, a highly desirable but challenging target. We report a microporous hydroxyl-decorated material, MFM-300(In) (MFM = Manchester Framework Material, replacing the NOTT designation), which displays a high volumetric uptake of 202 v/v at 298 K and 35 bar for CH4 and 488 v/v at 77 K and 20 bar for H2. Direct observation and quantification of the location, binding, and rotational modes of adsorbed CH4 and H2 molecules within this host have been achieved, using neutron diffraction and inelastic neutron scattering experiments, coupled with density functional theory (DFT) modeling. These complementary techniques reveal a very efficient packing of H2 and CH4 molecules within MFM-300(In), reminiscent of the condensed gas in pure component crystalline solids. We also report here, for the first time, the experimental observation of a direct binding interaction between adsorbed CH4 molecules and the hydroxyl groups within the pore of a material. This is different from the arrangement found in CH4/water clathrates, the CH4 store of nature.
Metal–organic frameworks (MOFs) are usually synthesized using a single type of metal ion, and MOFs containing mixtures of different metal ions are of great interest and represent a methodology to enhance and tune materials properties. We report the synthesis of [Ga2(OH)2(L)] (H4L = biphenyl-3,3′,5,5′-tetracarboxylic acid), designated as MFM-300(Ga2), (MFM = Manchester Framework Material replacing NOTT designation), by solvothermal reaction of Ga(NO3)3 and H4L in a mixture of DMF, THF, and water containing HCl for 3 days. MFM-300(Ga2) crystallizes in the tetragonal space group I4122, a = b = 15.0174(7) Å and c = 11.9111(11) Å and is isostructural with the Al(III) analogue MFM-300(Al2) with pores decorated with −OH groups bridging Ga(III) centers. The isostructural Fe-doped material [Ga1.87Fe0.13(OH)2(L)], MFM-300(Ga1.87Fe0.13), can be prepared under similar conditions to MFM-300(Ga2) via reaction of a homogeneous mixture of Fe(NO3)3 and Ga(NO3)3 with biphenyl-3,3′,5,5′-tetracarboxylic acid. An Fe(III)-based material [Fe3O1.5(OH)(HL)(L)0.5(H2O)3.5], MFM-310(Fe), was synthesized with Fe(NO3)3 and the same ligand via hydrothermal methods. [MFM-310(Fe)] crystallizes in the orthorhombic space group Pmn21 with a = 10.560(4) Å, b = 19.451(8) Å, and c = 11.773(5) Å and incorporates μ3-oxo-centered trinuclear iron cluster nodes connected by ligands to give a 3D nonporous framework that has a different structure to the MFM-300 series. Thus, Fe-doping can be used to monitor the effects of the heteroatom center within a parent Ga(III) framework without the requirement of synthesizing the isostructural Fe(III) analogue [Fe2(OH)2(L)], MFM-300(Fe2), which we have thus far been unable to prepare. Fe-doping of MFM-300(Ga2) affords positive effects on gas adsorption capacities, particularly for CO2 adsorption, whereby MFM-300(Ga1.87Fe0.13) shows a 49% enhancement of CO2 adsorption capacity in comparison to the homometallic parent material. We thus report herein the highest CO2 uptake (2.86 mmol g–1 at 273 K at 1 bar) for a Ga-based MOF. The single-crystal X-ray structures of MFM-300(Ga2)-solv, MFM-300(Ga2), MFM-300(Ga2)·2.35CO2, MFM-300(Ga1.87Fe0.13)-solv, MFM-300(Ga1.87Fe0.13), and MFM-300(Ga1.87Fe0.13)·2.0CO2 have been determined. Most notably, in situ single-crystal diffraction studies of gas-loaded materials have revealed that Fe-doping has a significant impact on the molecular details for CO2 binding in the pore, with the bridging M–OH hydroxyl groups being preferred binding sites for CO2 within these framework materials. In situ synchrotron IR spectroscopic measurements on CO2 binding with respect to the −OH groups in the pore are consistent with the above structural analyses. In addition, we found that, compared to MFM-300(Ga2), Fe-doped MFM-300(Ga1.87Fe0.13) shows improved catalytic properties for the ring-opening reaction of styrene oxide, but similar activity for the room-temperature acetylation of benzaldehyde by methanol. The role of Fe-doping in these systems is discussed as a mechanism for enhancing porosity and the s...
We report the adsorption of C2H2, CO2 and SO2 in a new, ultra-stable Cr(III)-based MOF, MFM-300(Cr), {[Cr2(OH)2(L)], H4L = biphenyl-3,3',5,5'-tetracarboxylic acid}. MFM-300(Cr) shows uptakes of 7.37, 7.73 and 8.59 mmol...
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