Yanshuo Li

Zeolitic Imidazolate Framework Membrane with Molecular Sieving Properties by Microwave-Assisted Solvothermal Synthesis

A zeolitic imidazolate framework (ZIF-8) as member of the metal-organic framework family has been crystallized as a thin porous layer on an asymmetric ceramic support. Hydrogen can be selected from other gases by molecular sieving.

Molecular Sieve Membrane: Supported Metal–Organic Framework with High Hydrogen Selectivity

Microporous membranes with pore apertures below the nanolevel can exhibit size selectivity by serving as a molecular sieve, which is promising for overcoming Robeson s “upperbound” limits in membrane-based gas separation. Zeolites, polymers of intrinsic microporosity (PIMs), metal oxides, and active carbon are the typical materials used for this purpose. Metal–organic frameworks (MOFs) have attracted much research interest in recent years, and are emerging as a new family of molecular sieves. MOFs are novel porous crystalline materials consisting of metal ions or clusters interconnected by a variety of organic linkers. In addition to promising applications in adsorptive gas separation and storage or in catalysis, their unique properties, such as their highly diversified structures, large range in pore sizes, very high surface areas, and specific adsorption affinities, make MOFs excellent candidates for use in the construction of molecular sieve membranes with superior performance. The preparation of MOF membranes for gas separation is rapidly becoming a research focus. A number of attempts have been made to prepare supported-MOF membranes; however, progress is very limited and so far there are only very few reports of continuous MOF films on porous supports being used as separating membranes. Recently, Guo et al. reported a copper-net-supported HKUST-1 (Cu3(BTC)2; BTC= benzene-1,3,5-tricarboxylate) membrane exhibiting a H2/N2 selectivity of 7 [13] (separation factor of H2 over N2 is calculated as the permeate-to-retentate composition ratio of H2, divided by the same ratio for N2 as proposed by IUPAC) ; this is the first MOF membrane to show gasseparation performance beyond Knudsen diffusion behavior. Very recently, Ranjan and Tsapatsis prepared a microporous metal–organic framework [MMOF, Cu(hfipbb)(H2hfipbb)0.5; hfipbb= 4,4’-(hexafluoroisopropylidene)bis(benzoic acid)] membrane by seeded growth on an alumina support. The ideal selectivity for H2/N2, based on single permeation tests, was 23 at 190 8C. This higher selectivity, compared to the report from Guo et al., might be a result of the smaller effective pore size (ca. 0.32 nm of MMOF versus 0.9 nm of HKUTS-1), which results in a relatively low H2 permeance of this MMOF membrane (10 9 molm 2 s Pa 1 at 190 8C). The authors attributed this finding to the blockage of the onedimensional (1D) straight-pore channels in the membrane. Therefore, with regard to H2 separation, small-pore MOFs having three-dimensional (3D) channel structures are considered to be ideal membrane materials. Zeolitic imidazolate frameworks (ZIFs), a subfamily of MOFs, consist of transition metals (Zn, Co) and imidazolate linkers which form 3D tetrahedral frameworks and frequently resemble zeolite topologies. A number of ZIFs exhibit exceptional thermal and chemical stability. Another important feature of ZIFs is their hydrophobic surfaces, which give ZIF membranes certain advantages over zeolite membranes and sol–gel-derived silica membranes in the separation of H2 in the presence of steam. Very recently we reported the first result from permeation measurements on a ZIF-8 membrane. The ZIF-8 membrane showed a H2/CH4 separation factor greater than 10. Whereas the ZIF-8 pores (0.34 nm) are slightly larger than the kinetic diameter of CO2 (0.33 nm), and are very flexible, the H2/CO2 separation on this ZIF-8 membrane showed Knudsen selectivity. In the current work, we therefore chose ZIF-7 as a promising candidate for the development of a H2-selective membrane to satisfy the above requirements. ZIF-7 (Zn(bim)2) is formed by bridging benzimidazolate (bim) anions and zinc cations with soladite (SOD) topology. The pore size of ZIF-7 (the hexagonal window size in the SOD cage) estimated from crystallographic data is about 0.3 nm, which is just in between the size of H2 (0.29 nm) and CO2 (0.33 nm). We could therefore expect a ZIF-7 membrane to achieve a high selectivity of H2 over CO2 and other gases through a molecular sieving effect. In many cases, it was reported that the heterogeneous nucleation density of MOF crystals on ceramic supports is very low, 14] which makes it extremely difficult to prepare supported-MOF membranes by an in situ synthesis route. Chemical modifications of substrate surfaces have been proposed to direct the nucleation and orientation of the deposited MOF layers. Based on our knowledge in the development of zeolite membranes, we adopted a seeded secondary growth method for the ZIF-7 membrane prepara[*] Prof. Dr. Y.-S. Li, F.-Y. Liang, H. Bux, A. Feldhoff, Prof. Dr. J. Caro Institute of Physical Chemistry and Electrochemistry and the Laboratory for Nano and Quantum Engineering (LNQE) in cooperation with the Center for Solid State Research and New Materials, Leibniz Universit t Hannover Callinstrasse 3A, 30167 Hannover (Germany) Fax: (+49)511-762-19121 E-mail: yanshuo.li@pci.uni-hannover.de juergen.caro@pci.uni-hannover.de

Metal-organic framework nanosheets as building blocks for molecular sieving membranes

Layered metal-organic frameworks would be a diverse source of crystalline sheets with nanometer thickness for molecular sieving if they could be exfoliated, but there is a challenge in retaining the morphological and structural integrity. We report the preparation of 1-nanometer-thick sheets with large lateral area and high crystallinity from layered MOFs. They are used as building blocks for ultrathin molecular sieve membranes, which achieve hydrogen gas (H2) permeance of up to several thousand gas permeation units (GPUs) with H2/CO2 selectivity greater than 200. We found an unusual proportional relationship between H2 permeance and H2 selectivity for the membranes, and achieved a simultaneous increase in both permeance and selectivity by suppressing lamellar stacking of the nanosheets. Crystalline sheets exfoliated from layered metal-organic framework materials are formed into selective membranes. Metal-organic framework material membranes There continues to be a lot of interest in developing membranes for gas separations that go beyond the current polymer membranes used commercially for this purpose. Peng et al. took a porous metal-organic framework material with a layered structure and exfoliated it to give nanometer-thick molecular sieves. The membranes were exceptionally good at separating hydrogen gas from carbon dioxide both in terms of permeance and selectivity. Science, this issue p. 1356

Controllable Synthesis of Metal–Organic Frameworks: From MOF Nanorods to Oriented MOF Membranes

Tailoring of the crystal size and morphology of metal-organic framework (mof) materials and manipulation of mof films is possible by the solvothermal synthesis route introduced here. a c-out-of-plane zif-7 membrane (see figure) is obtained through evolutionary selection in a van der drift-type growth originating from randomly oriented seed layers. highly oriented mof thin films are important as molecular sieve membranes.

An Organophilic Pervaporation Membrane Derived from Metal–Organic Framework Nanoparticles for Efficient Recovery of Bio-Alcohols†

adsorption of water before the onset of capillary condensation. [12] All the above-mentioned characteristics suggest that ZIF-8 nanoparticles could be used as fillers in mixed-matrix membranes (MMMs) for the recovery of organic compounds from aqueous solutions by adopting organophilic pervaporation (OPV) technology. Pervaporation is a membrane process based on a sorption–diffusion mechanism, and is considered the most promising technology for molecular-scale liquid/ liquid separations. [13] Herein we show that both pervaporation

Improvement of hydrothermal stability of zeolitic imidazolate frameworks

The metal-organic framework ZIF-8, which undergoes hydrolysis under hydrothermal conditions, is endowed with high water-resistance after a shell-ligand-exchange-reaction. The stabilized ZIF-8 retains its structural characteristics with improved application performances in adsorption and membrane separation.

Confinement of Ionic Liquids in Nanocages: Tailoring the Molecular Sieving Properties of ZIF-8 for Membrane-Based CO2 Capture

Fine-tuning of effective pore size of microporous materials is necessary to achieve precise molecular sieving properties. Herein, we demonstrate that room temperature ionic liquids can be used as cavity occupants for modification of the microenvironment of MOF nanocages. Targeting CO2 capture applications, we tailored the effective cage size of ZIF-8 to be between CO2 and N2 by confining an imidazolium-based ionic liquid [bmim][Tf2 N] into ZIF-8s SOD cages by in-situ ionothermal synthesis. Mixed matrix membranes derived from ionic liquid-modified ZIF-8 exhibited remarkable combinations of permeability and selectivity that transcend the upper bound of polymer membranes for CO2 /N2 and CO2 /CH4 separation. We observed an unusual response of the membranes to varying pressure, that is, an increase in the CO2 /CH4 separation factor with pressure, which is highly desirable for practical applications in natural gas upgrading.

Fabrication of Highly b-Oriented MFI Film with Molecular Sieving Properties by Controlled In-Plane Secondary Growth

Here we report a facile method to fabricate highly b-oriented and submicrometer thin MFI films on substrates. Neither an anhydrous environment nor a specifically designed structure-directing agent (SDA) is required in the whole process, and by innovation of the secondary growth process, twin growth of the b-oriented seed layer is effectively suppressed with TPAOH as the SDA for the first time. Furthermore, various substrates with different surface conditions can be directly used as substrates without premodification. A Pt electrode also was successfully used as a substrate to grow this high quality MFI film, showing excellent molecular sieving ability in aqueous solution.

Two-Dimensional Metal–Organic Framework Nanosheets for Membrane-Based Gas Separation

Metal-organic framework (MOF) nanosheets could serve as ideal building blocks of molecular sieve membranes owing to their structural diversity and minimized mass-transfer barrier. To date, discovery of appropriate MOF nanosheets and facile fabrication of high performance MOF nanosheet-based membranes remain as great challenges. A modified soft-physical exfoliation method was used to disintegrate a lamellar amphiprotic MOF into nanosheets with a high aspect ratio. Consequently sub-10 nm-thick ultrathin membranes were successfully prepared, and these demonstrated a remarkable H2 /CO2 separation performance, with a separation factor of up to 166 and H2 permeance of up to 8×10-7  mol m-2  s-1  Pa-1 at elevated testing temperatures owing to a well-defined size-exclusion effect. This nanosheet-based membrane holds great promise as the next generation of ultrapermeable gas separation membrane.

Metal‐Substituted Zeolitic Imidazolate Framework ZIF‐108: Gas‐Sorption and Membrane‐Separation Properties

A series of dual-metal zeolitic imidazolate framework (ZIF) crystals with SOD and RHO topologies was synthesised by metal substitution from ZIF-108 (Zn(2-nitroimidazolate)2 , SOD topology) as the parent material. This was based on the concept that metal substitution of ZIF-108 requires a much lower activation energy than homogenous nucleation owing to the metastability of ZIF-108. In-depth investigations of the formation processes of the daughter ZIFs indicated that the transformation of ZIF-108 is a dissolution/heterogeneous nucleation process. Typical isostructural Co(2+) substitution mainly occurs at the outer surface of ZIF-108 and results in a core-shell structure. On the contrary, the Cu(2+) -substituted ZIF has a RHO topology with a homogeneous distribution of Cu(2+) ions in the structure. Substitution with Ni(2+) resulted in a remarkable enhancement in adsorption selectivity toward CO(2) over N(2) by a factor of up to 227. With Co(2+) -substituted nanoparticles as inorganic filler, a mixed matrix membrane based on polysulfone displayed greatly improved performance in the separation of H(2)/CH(4), CO(2)/N(2) and CO(2)/CH(4).