Hydrogen storage in copper prussian blue analogues: Evidence of H <inf>2</inf> coordination to the copper atom

L. Reguera, C. P. Krap, J. Balmaseda, E. Reguera

Research output: Contribution to journalArticle

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Abstract

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 a 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, Cu 3[Fe(CN)6]2, Cu2[Fe(CN) 6], Cu[Pt(CN)6], and Cu3-xMn x[Co(CN)6]2, where 0 ≤ x ≤ 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 Mössbauer spectroscopies. © 2008 American Chemical Society.
Original languageAmerican English
Pages (from-to)15893-15899
Number of pages14303
JournalJournal of Physical Chemistry C
DOIs
StatePublished - 9 Oct 2008

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Hydrogen storage
Copper
analogs
copper
Atoms
Hydrogen
hydrogen
atoms
Adsorption
orbitals
adsorption
Molecules
ferric ferrocyanide
Electrons
interactions
thermogravimetry
configurations
electronics
Carrier concentration
availability

Cite this

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title = "Hydrogen storage in copper prussian blue analogues: Evidence of H 2 coordination to the copper atom",
abstract = "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 a 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, Cu 3[Fe(CN)6]2, Cu2[Fe(CN) 6], Cu[Pt(CN)6], and Cu3-xMn x[Co(CN)6]2, where 0 ≤ x ≤ 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 M{\"o}ssbauer spectroscopies. {\circledC} 2008 American Chemical Society.",
author = "L. Reguera and Krap, {C. P.} and J. Balmaseda and E. Reguera",
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Hydrogen storage in copper prussian blue analogues: Evidence of H <inf>2</inf> coordination to the copper atom. / Reguera, L.; Krap, C. P.; Balmaseda, J.; Reguera, E.

In: Journal of Physical Chemistry C, 09.10.2008, p. 15893-15899.

Research output: Contribution to journalArticle

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T1 - Hydrogen storage in copper prussian blue analogues: Evidence of H 2 coordination to the copper atom

AU - Reguera, L.

AU - Krap, C. P.

AU - Balmaseda, J.

AU - Reguera, E.

PY - 2008/10/9

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N2 - 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 a 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, Cu 3[Fe(CN)6]2, Cu2[Fe(CN) 6], Cu[Pt(CN)6], and Cu3-xMn x[Co(CN)6]2, where 0 ≤ x ≤ 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 Mössbauer spectroscopies. © 2008 American Chemical Society.

AB - 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 a 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, Cu 3[Fe(CN)6]2, Cu2[Fe(CN) 6], Cu[Pt(CN)6], and Cu3-xMn x[Co(CN)6]2, where 0 ≤ x ≤ 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 Mössbauer spectroscopies. © 2008 American Chemical Society.

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