Yujie Ban

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

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.

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).

Microstructural Engineering and Architectural Design of Metal–Organic Framework Membranes

In the past decade, a huge development in rational design, synthesis, and application of molecular sieve membranes, which typically included zeolites, metal-organic frameworks (MOFs), and graphene oxides, has been witnessed. Owing to high flexibility in both pore apertures and functionality, MOFs in the form of membranes have offered unprecedented opportunities for energy-efficient gas separations. Reports on the fabrication of well-intergrown MOF membranes first appeared in 2009. Since then there has been tremendous growth in this area along with an exponential increase of MOF-membrane-related publications. In order to compete with other separation and purification technologies, like cryogenic distillation, pressure swing adsorption, and chemical absorption, separation performance (including permeability, selectivity, and long-term stability) of molecular sieve membranes must be further improved in an attempt to reach an economically attractive region. Therefore, microstructural engineering and architectural design of MOF membranes at mesoscopic and microscopic levels become indispensable. This review summarizes some intriguing research that may potentially contribute to large-scale applications of MOF membranes in the future.

High performance carbon molecular sieving membranes derived from pyrolysis of metal–organic framework ZIF-108 doped polyimide matrices

Carbon molecular sieve membranes (CMSMs) were fabricated by pyrolysis of MOF-doped polyimide mixed matrix membranes. ZIF-108 (Zn(2-nitroimidazolate)2) was used as a dopant to tailor the micropores of the as-prepared CMSMs into narrow ultramicropores, providing a remarkable combination of permeability and selectivity of membranes in CO2/CH4, O2/N2 and N2/CH4 separation.