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Título : Hydrogen Storage in Copper Prussian Blue Analogues: Evidence of H2 Coordination to the Copper Atom
Fecha de publicación : 16-ene-2013
Editorial : J. Phys. Chem.
Descripción : The hydrogen adsorption in porous Prussian blue analogues shows the highest value for copper, suggesting the possibility that a direct interaction between the copper atom and the hydrogen molecule is established. The bonding of copper (2+) to the CN group of cyanometallates shows a unique behavior. The trend of copper to receive electrons in its 3d hole to adopt an electronic configuration close to 3d10 is complemented by the ability of the CN group to donate electrons from its 5σ orbital, which has certain antibonding character. Because of this cooperative effect, the electronic configuration of the copper atom at the cavity surface is close to Cu(+). The resulting large availability of electron density on the copper atom favors its interaction with the antibonding σ* orbital of the hydrogen molecule. The charge removed from the metal t2g orbitals is compensated (donated) by H2 through a side-on σ interaction. From these combined mechanisms, where H2 behaves as an acceptor-donor ligand for the copper atom, the high ability that copper hexacyanometallates show for the hydrogen storage could be explained. This hypothesis is supported by the obtained hydrogen adsorption data for Cu3[Ir(CN)6]2, Cu3[Fe(CN)6]2, Cu2[Fe(CN)6], Cu[Pt(CN)6], and Cu3-xMnx[Co(CN)6]2, where 0 e x e 3, and also by the estimated values for the involved adsorption heats. The studied samples were previously characterized using X-ray diffraction, thermogravimetry, and infrared and Mo¨ssbauer spectroscopies.
URI : http://www.repositoriodigital.ipn.mx/handle/123456789/11166
Otros identificadores : J. Phys. Chem. C 2008, 112, 15893–15899
Aparece en las colecciones: Doctorado

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