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identify the complex as the square-planar [Co(CN)4]-2 complex with an axial position occupied by a framework oxygen.23 This complex was stable to repeated cycling in air and, even in the low concentrations achieved, increased the amount of oxygen adsorbed over that of the pure Na-Y zeolite. Because of the apparent success of Drago and coworkers in stabilizing their cyanocobaltate complex by anchoring to framework oxygen in zeolite Y, we attemped to do the same with Co(fluomine). Table 2 gives the experimental and theoretical O2- binding capacities for the free Co(fluomine) and Co(salen) complexes and for the Co(fluomine) attached to the various substrates. One can see by comparing the experimental results to the predicted values, the free Co(fluomine) and Co(salen) form 1:2 (O2:Co2+) adducts (type Ib shown in Figure 9). This is consistent with previously reported results.2 In the case of the Co(fluomine)-LSX, it is possible that the complex forms 1:1 (O2:Co2+) adducts (type Ia in Figure 9) rather than the 1:2 ones observed with the free complex. This is due to the isolation of the Co(fluomine) within the zeolite cavity that prevents interaction between Co(fluomine) molecules. It is also possible that there is some amount of Co(fluomine) attached to the outside surface of the zeolite or some free Co(fluomine) forming 1:2 adducts. Unlike the X zeolite, the MCM-41 does not have a cavity structure; but, rather a channel structure with large pore openings (of approximately 40Å in diameter). This open pore structure may not isolate the complexes and thus will allow the formation of 1:2 (O2:Co2+) adducts. However, it is difficult to determine from the experimental capacity the type of bonding in this material. The same can be said for the Co(fluomine)-IXR since the measured capacity is very low. 168PDF Image | PSA USING SUPERIOR ADSORBENTS
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