Metal-organic frameworks (MOFs) have recently attracted intense research interest because of their permanent porous structures, large surface areas, and potential applications as novel adsorbents. The recent progress in adsorption-based CO(2) capture by MOFs is reviewed and summarized in this critical review. CO(2) adsorption in MOFs has been divided into two sections, adsorption at high pressures and selective adsorption at approximate atmospheric pressures. Keys to CO(2) adsorption in MOFs at high pressures and low pressures are summarized to be pore volumes of MOFs, and heats of adsorption, respectively. Many MOFs have high CO(2) selectivities over N(2) and CH(4). Water effects on CO(2) adsorption in MOFs are presented and compared with benchmark zeolites. In addition, strategies appeared in the literature to enhance CO(2) adsorption capacities and/or selectivities in MOFs have been summarized into three main categories, catenation and interpenetration, chemical bonding enhancement, and electrostatic force involvement. Besides the advantages, two main challenges of using MOFs in CO(2) capture, the cost of synthesis and the stability toward water vapor, have been analyzed and possible solutions and path forward have been proposed to address the two challenges as well (150 references).
The separation of molecules with similar size and shape is an important technological challenge. For example, rare gases can pose either an economic opportunity or an environmental hazard and there is a need to separate these spherical molecules selectively at low concentrations in air. Likewise, chiral molecules are important building blocks for pharmaceuticals, but chiral enantiomers, by definition, have identical size and shape, and their separation can be challenging. Here we show that a porous organic cage molecule has unprecedented performance in the solid state for the separation of rare gases, such as krypton and xenon. The selectivity arises from a precise size match between the rare gas and the organic cage cavity, as predicted by molecular simulations. Breakthrough experiments demonstrate real practical potential for the separation of krypton, xenon and radon from air at concentrations of only a few parts per million. We also demonstrate selective binding of chiral organic molecules such as 1-phenylethanol, suggesting applications in enantioselective separation.
Nuclear energy is among the most viable alternatives to our current fossil fuel-based energy economy. The mass deployment of nuclear energy as a low-emissions source requires the reprocessing of used nuclear fuel to recover fissile materials and mitigate radioactive waste. A major concern with reprocessing used nuclear fuel is the release of volatile radionuclides such as xenon and krypton that evolve into reprocessing facility off-gas in parts per million concentrations. The existing technology to remove these radioactive noble gases is a costly cryogenic distillation; alternatively, porous materials such as metal–organic frameworks have demonstrated the ability to selectively adsorb xenon and krypton at ambient conditions. Here we carry out a high-throughput computational screening of large databases of metal–organic frameworks and identify SBMOF-1 as the most selective for xenon. We affirm this prediction and report that SBMOF-1 exhibits by far the highest reported xenon adsorption capacity and a remarkable Xe/Kr selectivity under conditions pertinent to nuclear fuel reprocessing.
* S Supporting Information CONSPECTUS: The total world energy demand is predicted to rise significantly over the next few decades, primarily driven by the continuous growth of the developing world. With rapid depletion of nonrenewable traditional fossil fuels, which currently account for almost 86% of the worldwide energy output, the search for viable alternative energy resources is becoming more important from a national security and economic development standpoint. Nuclear energy, an emission-free, high-energy-density source produced by means of controlled nuclear fission, is often considered as a clean, affordable alternative to fossil fuel. However, the successful installation of an efficient and economically viable industrial-scale process to properly sequester and mitigate the nuclear-fission-related, highly radioactive waste (e.g., used nuclear fuel (UNF)) is a prerequisite for any further development of nuclear energy in the near future. Reprocessing of UNF is often considered to be a logical way to minimize the volume of high-level radioactive waste, though the generation of volatile radionuclides during reprocessing raises a significant engineering challenge for its successful implementation. The volatile radionuclides include but are not limited to noble gases (predominately isotopes of Xe and Kr) and must be captured during the process to avoid being released into the environment. Currently, energy-intensive cryogenic distillation is the primary means to capture and separate radioactive noble gas isotopes during UNF reprocessing. A similar cryogenic process is implemented during commercial production of noble gases though removal from air. In light of their high commercial values, particularly in lighting and medical industries, and associated high production costs, alternate approaches for Xe/Kr capture and storage are of contemporary research interest. The proposed pathways for Xe/Kr removal and capture can essentially be divided in two categories: selective absorption by dissolution in solvents and physisorption on porous materials. Physisorption-based separation and adsorption on highly functional porous materials are promising alternatives to the energy-intensive cryogenic distillation process, where the adsorbents are characterized by high surface areas and thus high removal capacities and often can be chemically fine-tuned to enhance the adsorbate−adsorbent interactions for optimum selectivity. Several traditional porous adsorbents such as zeolites and activated carbon have been tested for noble gas capture but have shown low capacity, selectivity, and lack of modularity. Metal− organic frameworks (MOFs) or porous coordination polymers (PCPs) are an emerging class of solid-state adsorbents that can be tailor-made for applications ranging from gas adsorption and separation to catalysis and sensing. Herein we give a concise summary of the background and development of Xe/Kr separation technologies with a focus on UNF reprocessing and the prospects of MOF-based adsorbents for that particular appl...
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