The microporous metal-organic framework Ni2(dhtp) (H4dhtp ) 2,5-dihydroxyterephtalic acid) is a 3D network that maintains crystallinity and porosity after solvent removal. A mild thermal treatment in high vacuo at 393 K removes completely water allowing to obtain a MOF material with honeycomb structure able to strongly coordinate CO at room temperature. In this contribution, the reactivity toward CO of CPO-27-Ni has been studied by the combined use of infrared, extended X-ray absorption fine structure, X-ray absorption near edge structure, and UV-vis spectropies and microcalorimetry. Most of the Ni2+ sites are involved in the interaction (about 80%), forming 1:1 linear adducts whose interaction enthalpy is slightly above 50 kJ/mol. In the presence of CO, a large modification of the vibrational and electronic properties of the material with respect to the dehydrated one has been observed.

CO adsorption on CPO-27-Ni coordination polymer: spectroscopic features and interaction energy

CHAVAN, SACHIN MARUTI;VITILLO, Jenny Grazia;GROPPO, Elena Clara;BONINO, Francesca Carla;LAMBERTI, Carlo;BORDIGA, Silvia
2009

Abstract

The microporous metal-organic framework Ni2(dhtp) (H4dhtp ) 2,5-dihydroxyterephtalic acid) is a 3D network that maintains crystallinity and porosity after solvent removal. A mild thermal treatment in high vacuo at 393 K removes completely water allowing to obtain a MOF material with honeycomb structure able to strongly coordinate CO at room temperature. In this contribution, the reactivity toward CO of CPO-27-Ni has been studied by the combined use of infrared, extended X-ray absorption fine structure, X-ray absorption near edge structure, and UV-vis spectropies and microcalorimetry. Most of the Ni2+ sites are involved in the interaction (about 80%), forming 1:1 linear adducts whose interaction enthalpy is slightly above 50 kJ/mol. In the presence of CO, a large modification of the vibrational and electronic properties of the material with respect to the dehydrated one has been observed.
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http://pubs.acs.org/doi/abs/10.1021/jp809872w
MOF; coordination polymer; CPO-27-Ni; CO adsorption; microcalorimetry; FTIR; EXAFS; XANES; adsorption hentalpy; local environment; C-O stertching frequency
S. Chavan; J. G. Vitillo; E. Groppo; F. Bonino; C. Lamberti; P. D. C. Dietzel; S. Bordiga
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/58946
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