FTIR spectroscopy and ab initio molecular modelling have been employed to probe the interaction between CO and Ni3(BTP)2, a thermally and chemically stable MOF. A combination of low pressure adsorption isotherms and FTIR spectroscopy has been utilised to study the material for its interaction with CO2 and H2. The experimental results indicate that despite an abundance of Ni2+ coordination vacancies in the activated sample, the molecular probes considered in this study do not interact with them. These findings are in alignment with the data obtained by molecular modelling, in which it is shown that the unreactive diamagnetic, low spin state is more stable. Due to the strong N-donor character of the pyrazolate ligands on this material, the electrostatic potential map of the optimized low spin structure does not show any evidence of a region of positive potential typical of open metal sites.

Stability vs. reactivity: understanding the adsorption properties of Ni3(BTP)2 by experimental and computational methods / G.C. Shearer, V. Colombo, S. Chavan, E. Albanese, B. Civalleri, A. Maspero, S. Bordiga. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - 42:18(2013), pp. 6450-6458. [10.1039/C3DT32944E]

Stability vs. reactivity: understanding the adsorption properties of Ni3(BTP)2 by experimental and computational methods

V. Colombo
Secondo
;
2013

Abstract

FTIR spectroscopy and ab initio molecular modelling have been employed to probe the interaction between CO and Ni3(BTP)2, a thermally and chemically stable MOF. A combination of low pressure adsorption isotherms and FTIR spectroscopy has been utilised to study the material for its interaction with CO2 and H2. The experimental results indicate that despite an abundance of Ni2+ coordination vacancies in the activated sample, the molecular probes considered in this study do not interact with them. These findings are in alignment with the data obtained by molecular modelling, in which it is shown that the unreactive diamagnetic, low spin state is more stable. Due to the strong N-donor character of the pyrazolate ligands on this material, the electrostatic potential map of the optimized low spin structure does not show any evidence of a region of positive potential typical of open metal sites.
Settore CHIM/03 - Chimica Generale e Inorganica
Settore CHIM/02 - Chimica Fisica
2013
Article (author)
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/223215
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