The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that highly crystalline porous solids, metal-organic frameworks, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known metal organic framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks, and for other applications.
Capturing CO2 from humid flue gases and atmosphere with porous materials remains costly because prior dehydration of the gases is required. A large number of microporous materials with physical adsorption capacity have been developed as CO2-capturing materials. However, most of them suffer from CO2 sorption capacity reduction or structure decomposition that is caused by co-adsorbed H2O when exposed to humid flue gases and atmosphere. We report a highly stable microporous coppersilicate. It has H2O-specific and CO2-specific adsorption sites but does not have H2O/CO2-sharing sites. Therefore, it readily adsorbs both H2O and CO2 from the humid flue gases and atmosphere, but the adsorbing H2O does not interfere with the adsorption of CO2. It is also highly stable after adsorption of H2O and CO2 because it was synthesized hydrothermally.
Conventional separation technologies to separate valuable commodities are energy intensive, consuming 15% of the worldwide energy. Mixed-matrix membranes, combining processable polymers and selective adsorbents, offer the potential to deploy adsorbent distinct separation properties into processable matrix. We report the rational design and construction of a highly efficient, mixed-matrix metal-organic framework membrane based on three interlocked criteria: (i) a fluorinated metal-organic framework, AlFFIVE-1-Ni, as a molecular sieve adsorbent that selectively enhances hydrogen sulfide and carbon dioxide diffusion while excluding methane; (ii) tailoring crystal morphology into nanosheets with maximally exposed (001) facets; and (iii) in-plane alignment of (001) nanosheets in polymer matrix and attainment of [001]-oriented membrane. The membrane demonstrated exceptionally high hydrogen sulfide and carbon dioxide separation from natural gas under practical working conditions. This approach offers great potential to translate other key adsorbents into processable matrix.
This review summarizes recent advances in the field of metal–organic framework (MOF)-based membranes with a special focus on their design strategies and applications for gas and liquid separations.
Chemical separations are of prime industrial importance; however, they consume a large portion of total industrial energy. Credibly, adsorbent-based separation methods offer the prospective to drastically lessen the energy demand of conventional energy-intensive separation processes. Prominently, a special class of porous materials, namely metal-organic frameworks (MOFs), are reasonably positioned to address various demanding separations in an energy-efficient manner. Out of a myriad of possible topologies for the construction of MOFs, face-transitive nets affording a sole type of window, preferably defined by three-or four-membered rings, can be regarded as ideal blueprints for the construction of MOFs for targeted separations. Intricate separations by MOFs based on some of these topologies are discussed, highlighting the effect of appropriate pore aperture and channel size with prerequisite functional groups on their separation performance. MOFs based on face-transitive nets offer great potential as effective fillers for the construction of practical mixed-matrix membranes (MMMs) with improved separation properties over conventional polymeric membranes.
The effective removal of (137) Cs(+) ions from contaminated groundwater and seawater and from radioactive nuclear waste solutions is crucial for public health and for the continuous operation of nuclear power plants. Various (137) Cs(+) removers have been developed, but more effective (137) Cs(+) removers are still needed. A novel microporous vanadosilicate with mixed-valence vanadium (V(4+) and V(5+) ) ions is now reported, which shows an excellent ability for Cs(+) capture and immobilization from groundwater, seawater, and nuclear waste solutions. This material is superior to other known materials in terms of selectivity, capacity, and kinetics, and at very low Cs(+) concentrations, it was found to be the most effective material for the removal of radioactive Cs(+) ions under the test conditions. This novel vanadosilicate also contains hexadeca-coordinated Cs(+) ions, which corresponds to the highest coordination number ever described.
Capture of trace amounts (parts per trillion or ppt level) of 90Sr from highly Na+-rich (5 M or 115 000 parts per million) liquid wastes produced from reprocessing of spent nuclear fuel rods is crucial for continuous operation of nuclear power plants.
The effective removal of 137Cs+ ions from contaminated groundwater and seawater and from radioactive nuclear waste solutions is crucial for public health and for the continuous operation of nuclear power plants. Various 137Cs+ removers have been developed, but more effective 137Cs+ removers are still needed. A novel microporous vanadosilicate with mixed‐valence vanadium (V4+ and V5+) ions is now reported, which shows an excellent ability for Cs+ capture and immobilization from groundwater, seawater, and nuclear waste solutions. This material is superior to other known materials in terms of selectivity, capacity, and kinetics, and at very low Cs+ concentrations, it was found to be the most effective material for the removal of radioactive Cs+ ions under the test conditions. This novel vanadosilicate also contains hexadeca‐coordinated Cs+ ions, which corresponds to the highest coordination number ever described.
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