Large-pore Metal-organic Frameworks Research Articles

Quantitative Simulations of Siloxane Adsorption in Metal-Organic Frameworks.

We present a transferable force field (FF) for simulating the bulk properties of linear and cyclic siloxanes and the adsorption of these species in metal-organic frameworks (MOFs). Unlike previous FFs for siloxanes, our FF accurately reproduces the vapor-liquid equilibria of each species in the bulk phase. The quality of our FF combined with the Universal Force Field using standard Lorentz-Berthelot combining rules for MOF atoms was assessed in a wide range of MOFs without open metal sites, showing good agreement with dispersion-corrected density functional theory calculations. Predictions with this FF show good agreement with the limited experimental data for siloxane adsorption in MOFs that is available. As an example of using the FF to predict adsorption properties in MOFs, we present simulations examining entropy effects in binary linear and cyclic siloxane mixture coadsorption in the large-pore MOF with structure code FOTNIN.

Solvent-Free Powder Synthesis and MOF-CVD Thin Films of the Large-Pore Metal–Organic Framework MAF-6

A simple solvent- and catalyst-free method is presented for the synthesis of the large-pore metal–organic framework (MOF) MAF-6 (RHO-Zn(eIm)2) based on the reaction of ZnO with 2-ethylimidazole vap...

Preserving Porosity of Mesoporous Metal–Organic Frameworks through the Introduction of Polymer Guests

High internal surface areas, an asset that is highly sought after in material design, has brought metal-organic frameworks (MOFs) to the forefront of materials research. In fact, a major focus in the field is on creating innovative ways to maximize MOF surface areas. Despite this, large-pore MOFs, particularly those with mesopores, continue to face problems with pore collapse upon activation. Herein, we demonstrate an easy method to inhibit this problem via the introduction of small quantities of polymer. For several mesoporous, isostructural MOFs, known as M2(NDISA) (where M = Ni2+, Co2+, Mg2+, or Zn2+), the accessible surface areas are increased dramatically, from 5 to 50 times, as the polymer effectively pins the MOFs open. Postpolymerization, the high surface areas and crystallinity are now readily maintained after heating the materials to 150 °C under vacuum. These activation conditions, which could not previously be attained due to pore collapse, also provide accessibility to high densities of open metal coordination sites. Molecular simulations are used to provide insight into the origin of instability of the M2(NDISA) series and to propose a potential mechanism for how the polymers immobilize the linkers, improving framework stability. Last, we demonstrate that the resulting MOF-polymer composites, referred to as M2(NDISA)-PDA, offer a perfect platform for the appendage/immobilization of small nanocrystals inside rendering high-performance catalysts. After decorating one of the composites with Pd (average size: 2 nm) nanocrystals, the material shows outstanding catalytic activity for Suzuki-Miyaura cross-coupling reactions.

Predicting the Features of Methane Adsorption in Large Pore Metal-Organic Frameworks for Energy Storage.

Currently, metal-organic frameworks (MOFs) are receiving significant attention as part of an international push to use their special properties in an extensive variety of energy applications. In particular, MOFs have exceptional potential for gas storage especially for methane and hydrogen for automobiles. However, using theoretical approaches to investigate this important problem presents various difficulties. Here we present the outcomes of a basic theoretical investigation into methane adsorption in large pore MOFs with the aim of capturing the unique features of this phenomenon. We have developed a pseudo one-dimensional statistical mechanical theory of adsorption of gas in a MOF with both narrow and large pores, which is solved exactly using a transfer matrix technique in the Osmotic Ensemble (OE). The theory effectively describes the distinctive features of adsorption of gas isotherms in MOFs. The characteristic forms of adsorption isotherms in MOFs reflect changes in structure caused by adsorption of gas and compressive stress. Of extraordinary importance for gas storage for energy applications, we find two regimes of Negative gas adsorption (NGA) where gas pressure causes the MOF to transform from the large pore to the narrow pore structure. These transformations can be induced by mechanical compression and conceivably used in an engine to discharge adsorbed gas from the MOF. The elements which govern NGA in MOFs with large pores are identified. Our study may help guide the difficult program of work for computer simulation studies of gas storage in MOFs with large pores.

Probing Metal-Organic Framework Design for Adsorptive Natural Gas Purification.

Parent and amine-functionalized analogues of metal-organic frameworks (MOFs), UiO-66(Zr), MIL-125(Ti), and MIL-101(Cr), were evaluated for their hydrogen sulfide (H2S) adsorption efficacy and post-exposure acid gas stability. Adsorption experiments were conducted through fixed-bed breakthrough studies utilizing multicomponent 1% H2S/99% CH4 and 1% H2S/10% CO2/89% CH4 natural gas simulant mixtures. Instability of MIL-101(Cr) materials after H2S exposure was discovered through powderX-ray diffraction and porosity measurements following adsorbent pelletization, whereas other materials retained their characteristic properties. Linker-based amine functionalities increased H2S breakthrough times and saturation capacities from their parent MOF analogues. Competitive CO2 adsorption effects were mitigated in mesoporous MIL-101(Cr) and MIL-101-NH2(Cr), in comparison to microporous UiO-66(Zr) and MIL-125(Ti) frameworks. This result suggests that the installation of H2S binding sites in large-pore MOFs could potentially enhance H2S selectivity. In situ Fourier transform infrared measurements in 10% CO2 and 5000 ppm H2S environments suggest that framework hydroxyl and amine moieties serve as H2S physisorption sites. Results from this study elucidate design strategies and stability considerations for engineering MOFs in sour gas purification applications.

Dual-Channel, Molecular-Sieving Core/Shell ZIF@MOF Architectures as Engineered Fillers in Hybrid Membranes for Highly Selective CO2 Separation.

A novel core/shell porous crystalline structure was prepared using a large pore metal organic framework (MOF, UiO-66-NH2, pore size, ∼ 0.6 nm) as core surrounded by a small pore zeolitic imidazolate framework (ZIF, ZIF-8, pore size, ∼ 0.4 nm) through a layer-by-layer deposition method and subsequently used as an engineered filler to construct hybrid polysulfone (PSF) membranes for CO2 capture. Compared to traditional fillers utilizing only one type of porous material with rigid channels (either large or small), our custom designed core/shell fillers possess clear advantages via pore engineering: the large internal channels of the UiO-66-NH2 MOFs create molecular highways to accelerate molecular transport through the membrane, while the thin shells with small pores (ZIF-8) or even smaller pores generated at the interface by the imperfect registry between the overlapping pores of ZIF and MOF enhance molecular sieving thus serving to distinguish slightly larger N2 molecules (kinetic diameter, 0.364 nm) from smaller CO2 molecules (kinetic diameter, 0.33 nm). The resultant core/shell ZIF@MOF and as-prepared hybrid PSF membranes were characterized by transmission electron microscopy, X-ray diffraction, wide-angle X-ray scattering, scanning electron microscopy, Fourier transform infrared, thermogravimetric analysis, differential scanning calorimetry, and contact angle tests. The dependence of the separation performance of the membranes on the MOF/ZIF ratio was also studied by varying the number of layers of ZIF coatings. The integrated PSF-ZIF@MOF hybrid membrane (40 wt % loading) with optimized ZIF coating cycles showed improved hydrophobicity and excellent CO2 separation performance by simultaneously increasing CO2 permeability (CO2 permeability of 45.2 barrer, 710% higher than PSF membrane) and CO2/N2 selectivity (CO2/N2 selectivity of 39, 50% higher than PSF membrane), which is superior to most reported hybrid PSF membranes. The strategy of using dual-channel molecular sieving core/shell porous crystals in hybrid membranes thus provides a promising means for CO2 capture from flue gas.

Exploiting Large-Pore Metal-Organic Frameworks for Separations through Entropic Molecular Mechanisms.

We review the molecular mechanisms behind adsorption and the separations of mixtures in metal-organic frameworks and zeolites. Separation mechanisms can be based on differences in the affinity of the adsorbate with the framework and on entropic effects. To develop next-generation adsorbents, the separation efficiency of the materials needs to be improved. The performance under industrially relevant conditions largely depends on two factors: 1) the separation selectivity and 2) the pore volume capacity of the material. Enthalpic mechanisms can lead to increased selectivities, but these are mostly restricted to the low loading regime, and hence these mechanisms are unable to make use of all of the large-pore volume that a metal-organic framework can provide. Industrial processes routinely operate in the pore saturation regime. In this Review, we focus on entropic molecular separation mechanisms that are effective under these conditions and, in particular, on a recent methodology to obtain high selectivities at high pore loading.

Formation of a quasi-solid structure by intercalated noble gas atoms in pores of Cu(I)-MFU-4l metal-organic framework.

The primary adsorption sites for Kr and Xe within the large-pore metal-organic framework Cu(I)-MFU-4l have been investigated by high-resolution synchrotron powder diffraction, revealing an enormous number of adsorption sites: in total, 10 crystallographically different positions for Xe and 8 positions for Kr were localized, the first five of which are located near metal atoms and the organic linker, and the remaining sites form a second adsorption layer in the pores.

Design, Synthesis, Characterization, and Catalytic Properties of a Large-Pore Metal-Organic Framework Possessing Single-Site Vanadyl(monocatecholate) Moieties

Through a combination of protecting groups, postsynthesis deprotection, and postsynthesis metallation, a homogeneously inaccessible, single-site vanadyl(monocatecholate) moiety can be incorporated into the dipyridyl struts of a Zn-based, pillared paddlewheel MOF. The resulting MOF, which has large pores, exhibits catalytic activity in the benzylic oxidation of tetralin in the presence of tert-butylhydroperoxide.

Two Large-Pore Metal–Organic Frameworks Derived from a Single Polytopic Strut

Two noninterpenetrated MOFs with strikingly different structures, NU-108-Cu and NU-108-Zn, were prepared from a single hexa-carboxylated ligand. NU-108-Cu contains paddlewheel-coordinated copper ions as nodes and is based on a 3,24 network associated with an inherently noncatenating rht-topology. Modifications introduced in the hexa-carboxylated struts (uniquely placed phenyl spacers) lead to substantial changes in pore sizes, relative to those found in other MOFs based on 3,24 networks and paddlewheel-coordinated copper ions. NU-108-Zn features a new net based on (3,3,6)-connecter and octadehral Zn4O nodes in which all struts lie in a–b planes.

Novel characterization of the adsorption sites in large pore metal–organic frameworks: combination of X-ray powder diffraction and thermal desorption spectroscopy

The preferred adsorption sites of xenon in the recently synthesized metal-organic framework MFU-4l(arge) possessing a bimodal pore structure (with pore sizes of 12 Å and 18.6 Å) were studied via the combination of low temperature thermal desorption spectroscopy and in situ X-ray powder diffraction. The diffraction patterns were collected at 110 K and 150 K according to the temperature of the desorption maxima. The maximum entropy method was used to reconstruct the electron density distribution of the structure and to localize the adsorbed xenon using refined data of the Xe-filled and empty sample. First principles calculations revealed that Xe atoms exclusively occupy the Wyckoff 32f position at approximately 2/3 2/3 2/3 along the body diagonal of the cubic crystal structure. At 110 K, Xe atoms occupy all 32 f positions (8 atoms per pore) while at 150 K the occupancy descends to 25% (2 atoms per pore). No Xe occupation of the small pores is observed by neither experimental measurements nor theoretical studies.

Efficient Calculation of Diffusion Limitations in Metal Organic Framework Materials: A Tool for Identifying Materials for Kinetic Separations

The very large number of distinct structures that are known for metal-organic frameworks (MOFs) and related materials presents both an opportunity and a challenge for identifying materials with useful properties for targeted applications. We show that efficient computational models can be used to evaluate large numbers of MOFs for kinetic separations of light gases based on finding materials with large differences between the diffusion coefficients of adsorbed gas species. We introduce a geometric approach that rapidly identifies the key features of a pore structure that control molecular diffusion and couple this with efficient molecular modeling calculations that predict the Henry's constant and diffusion activation energy for a range of spherical adsorbates. We demonstrate our approach for >500 MOFs and >160 silica zeolites. Our results indicate that many large pore MOFs will be of limited interest for separations based on kinetic effects, but we identify a significant number of materials that are predicted to have extraordinary properties for separation of gases such as CO(2), CH(4), and H(2).

Strategies for Characterization of Large-Pore Metal-Organic Frameworks by Combined Experimental and Computational Methods

A large-pore IRMOF-16-like material (1) was synthesized solvothermally and evacuated by two solvent removal procedures: the original chloroform (CHCl3) method and a new supercritical carbon dioxide (SCD) method. Using several experimental and geometric characterization tools, including thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and pore size analysis, we propose that 1 is a mixture of noncatenated IRMOF-16 and the corresponding 2-fold interwoven structure and is partially collapsed during the evacuation, especially some of the larger pores. Adsorption measurements using several gases at 77 and 298 K showed that the new SCD evacuation is superior to the conventional CHCl3 evacuation for increasing the adsorption kinetics as well as the adsorption capacity. This work illustrates a new strategy that combines several experimental methods, geometric calculations, and molecular simulations for the characterization of metal-organic frameworks (MOFs), especially those with large pores. This combination should be helpful for future characterization of new MOFs that possibly include some imperfections such as nonuniform catenation and partial collapse of the crystalline phase.