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Hydrogen storage in the dehydrated prussian blue analogues M3[Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn)
Authors:Kaye Steven S  Long Jeffrey R
Institution:Department of Chemistry, University of California, Berkeley, CA 94720-1460, USA.
Abstract:The porosity and hydrogen storage properties for the dehydrated Prussian blue analogues M3Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn) are reported. Argon sorption isotherms measured at 87 K afford BET surface areas ranging from 560 m2/g for Ni3Co(CN)6]2 to 870 m2/g for Mn3Co(CN)6]2; the latter value is comparable to the highest surface area reported for any known zeolite. All six compounds show significant hydrogen sorption at 77 K and 890 Torr, varying from 1.4 wt % and 0.018 kg H2/L for Zn3Co(CN)6]2 to 1.8 wt % and 0.025 kg H2/L for Cu3Co(CN)6]2. Fits to the sorption data employing the Langmuir-Freundlich equation give maximum uptake quantities, resulting in a predicted storage capacity of 2.1 wt % and 0.029 kg H2/L for Cu3Co(CN)6]2 at saturation. Enthalpies of adsorption for the frameworks were calculated from hydrogen isotherms measured at 77 and 87 K and found to increase with M varying in the order Mn < Zn < Fe < Co < Cu < Ni. In all cases, the binding enthalpies, which lie in the range of 5.3-7.4 kJ/mol, are higher than the 4.7-5.2 kJ/mol measured for Zn4O(1,4-benzenedicarboxylate)3.
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