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It is important to note that almost all reported values for the methane adsorption capacities in MOF materials are based on the ideal densities of MOF crystals. In practice, MOF materials are usually in microcrystalline powder forms. When the "packing factor" of the powders is taken into account, the actual volumetric adsorption capacities would be less than the reported, ideal values. Therefore, there are still strong driving forces for discovering new MOF materials with even higher ideal adsorption capacities than that reported for PCN-14.
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Note that, in the literature, Zn2(dhtp) was also called MOF-74, while some other M2(dhtp)'s were named CPO-27-M. Also note that although dhtp is widely used in the literature to represent the organic linker in this series of MOF compounds, a more appropriate name might be 2,5-dioxido-1,4-benzene-dicarboxylate (DOBDC), as suggested recently in ref 10e. For historic reasons, here we continue to use the well-known dhtp representation.
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Note that, in the literature, Zn2(dhtp) was also called MOF-74, while some other M2(dhtp)'s were named CPO-27-M. Also note that although "dhtp" is widely used in the literature to represent the organic linker in this series of MOF compounds, a more appropriate name might be "2,5-dioxido-1,4-benzene-dicarboxylate (DOBDC)", as suggested recently in ref 10e. For historic reasons, here we continue to use the well-known "dhtp" representation.
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Only for a single-crystal bulk sample, such an ideal adsorption capacity becomes the real storage capacity. So far we have not been able to grow single crystals large enough for isotherm measurements. The assembly of microcrystalline MOF powders into a bulk material is an engineering issue. Our preliminary effort on packing MOF powders into a bulk pellet sample under hydrostatic pressure shows that a packing density of 80-85% can be easily achieved without collapsing the MOF crystal. This packing density might be further improved in the future but would certainly still be less than that of a single crystal. Here we focus on the ideal volumetric capacities derived using the MOF crystal densities, to compare the intrinsic properties of different MOFs.
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Only for a single-crystal bulk sample, such an ideal adsorption capacity becomes the real storage capacity. So far we have not been able to grow single crystals large enough for isotherm measurements. The assembly of microcrystalline MOF powders into a bulk material is an engineering issue. Our preliminary effort on packing MOF powders into a bulk pellet sample under hydrostatic pressure shows that a packing density of 80-85% can be easily achieved without collapsing the MOF crystal. This packing density might be further improved in the future but would certainly still be less than that of a single crystal. Here we focus on the ideal volumetric capacities derived using the MOF crystal densities, to compare the intrinsic properties of different MOFs.
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Note that the absolute adsorption is the total amount of gas introduced to the sample cell minus the amount outside the sample in the gas phase; thus, it accounts for the total amount of adsorbate molecules residing in pores. The excess adsorption is the absolute amount of gas contained in the sample pores less the amount of gas that would be present in the pores in the absence of gas-solid intermolecular forces. Excess adsorption capacity is a material property; thus it is what is usually reported in the literature and can be used to compare different materials. When one compares the performance of materialsbased gas storage with compressed gas storage, absolute adsorption capacity is the more proper one to use
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Note that the absolute adsorption is the total amount of gas introduced to the sample cell minus the amount outside the sample in the gas phase; thus, it accounts for the total amount of adsorbate molecules residing in pores. The excess adsorption is the absolute amount of gas contained in the sample pores less the amount of gas that would be present in the pores in the absence of gas-solid intermolecular forces. Excess adsorption capacity is a "material property"; thus it is what is usually reported in the literature and can be used to compare different materials. When one compares the performance of "materialsbased gas storage" with "compressed gas storage", "absolute adsorption capacity" is the more proper one to use.
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