Adsorbents MOFs

A MOF constructed from rhodium paddlewheel clusters linked to porphyrinic ligands already discussed in Section 4.3.1.1 shows an interesting synergetic behavior when the porphyrinic rings are loaded with metals like Cu , Ni , or Pd . In the hydrogenation of olefins, the hydride species at the rhodium center is transferred to the coordinated olefin adsorbed on a metal ion in the center of the porphyrin ring to form an alkyl species, and next this alkyl species reacts with a hydride species activated at the rhodium center to form the alkane [81]. 

The potential of MIL-47 and MIL-53(A1) for adsorption of other types of aromatic adsorbates has also been explored, for instance, of dichlorobenzene, cresol, or alkylnaphthalene isomers [17, 98]. The removal of sulfur-containing aromatics from fuels via physisorption on MOFs has been investigated on several instances in literature, for instance, via the selective removal of thiophene from a stream of methane gas by MIL-47 [99], the removal of tetrahydrothiophene from methane by... 

Fig. 4. Comparison of the amount of H2 sites with that of super strongly adsorbed NHs with the heat of adsorption above 155 kJ mof. ...

In order to locate metal organic frameworks (MOFs) on the map of the technologies used for C02 capture applications, we will briefly describe the major technologies that have been employed and discuss their advantages and limitations. Figure 1 shows the different technologies used for C02 capture, whereas MOFs are used under the category of membranes and adsorbents. 

For future studies on MOF-based slurry systems, there is basic selection of criteria that needs to be satisfied by both MOF and the liquid solution. The selection of the MOF possessing the appropriate pore size for the preparation of the slurry system is very important to guarantee that the size of the liquid is large enough and does not occupy the pores which leaves no space for C02 to adsorb. Moreover, the structural stability of the MOF in the aqueous solution is essential so that it does not lose its porous framework nor its surface area. The selection of the liquid candidate is crucial, as it should not provide any extra mass transfer resistance for C02 molecules. Further, experimental and computational investigations are still required to understand the separation mechanism in slurry mixtures and to have insight into the different types of interactions between the gas, liquid, and solid materials. 

MOFCAT S1NTEF, Norway 36 since 01/09/2006 Functional MOFs as heterogeneous catalvsrs and adsorbents 1... 

Figure 7. Amount of hydrogen adsorbed at 77 K and 4 MPa versus the BET surface area for a series of activated carbons and for MOFs (taken from Reference36 note values represented here have been recalculated as wt.%).

As it has been discussed in previous section, from a practical point of view1, and also for comparison between adsorbents, hydrogen adsorption capacities should be reported in a volumetric basis, which makes necessary to know the sample density. Unfortunately, papers reporting hydrogen adsorption capacities of MOFs in volumetric basis use the crystal density of the materials, which is not realistic for this application because it does not include the inter-particle space. Crystal densities of MOFs can vary between 0.2 and 1.3 g cm 3 36 39, and similar to what happens with tap and packing densities of carbon materials, crystal densities of MOFs decreases when porosity increases. Therefore, as in the case of carbon materials (see Figure 5) a maximum is observed when the hydrogen uptake in volumetric basis is plotted versus the porosity of the MOFs samples, and a compromise between density and porosity is necessary from a practical point of view. 

MOF-Graphite oxides composites as adsorbents of toxic gases... 

The hydrogen sulfide adsorption on the HKUST-l/GO composites was only studied in moist conditions [44]. The choice was based on the presence of water in the ambient air and on the extensive studies of H2S reactive adsorption on carbonaceous materials where water was important for dissociation of hydrogen sulfide before its further reaction with surface active sites [5]. Here up to 20 wt% of H2S was adsorbed in the composite with the smallest content of GO. [44]. An increase in the GO content resulted in a decrease in the capacity but nevertheless it was higher than that on MOF... 

The composites described in this chapter present superior quality which is demonstrated by their surface properties and performance in comparison with the parent components, GO and MOF or other inorganic phases. The important aspect of these composite formations is taking advantage of the promising properties of both phases and the creation of the hybrid, which exhibits the surface features of both phases and, as a bonus, new unique properties created on the interface. Moreover, the specific behavior of the individual components when placed together can open the door for new applications, not foreseen in this concise chapter. One should see that the detailed characterization of these materials as adsorbents is only one example of their application, which we could explore in detail. Nevertheless, the zinc (hydr)oxide story, where the enhanced photoactivity and water splitting reactions were noticed while investigating the adsorption phenomena, is one more example of the open book of the usefulness of such new materials. 

Petit C, Bandosz TJ. Exploring the coordination chemistry of MOF/graphite oxide composites and their applications as adsorbents, Dalton Transactions, in press, 2012. 

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