Adsorption of carbon monoxide, dinitrogen, and carbon dioxide on the porous metal organic framework Mg-MOF-74 was investigated by means of a combined methodology comprising variable-temperature infrared spectroscopy and ab initio periodic DFT-D calculations using the CRYSTAL code. Both CO and N-2 were found to form nearly linear (Mg2+center dot center dot center dot CO and Mg2+center dot center dot center dot NN) adsorption complexes, in contrast with CO2, which forms an angular Mg2+center dot center dot center dot OCO complex. From IR spectra recorded at a variable-temperature, the standard adsorption enthalpy (Delta H-0) was found to be -29, -21, and -47 kJ mol(-1) for CO, N-2, and CO2, respectively. Calculated values of Delta H-0, including an empirical correction for dispersion forces, resulted to be in a reasonably good agreement with those experimentally obtained. Calculations also showed the very significant role played by dispersion forces, which account for about one-half of the adsorption enthalpy for each of the three adsorbates, CO, N-2, and CO2. The results are discussed in the broader context of the adsorption of the same gases on other MOFs and also on zeolites

Computational and Experimental Studies on the Adsorption of CO, N2, and CO2 on Mg-MOF-74

VALENZANO, LOREDANA;CIVALLERI, Bartolomeo;CHAVAN, SACHIN MARUTI;BORDIGA, Silvia
2010

Abstract

Adsorption of carbon monoxide, dinitrogen, and carbon dioxide on the porous metal organic framework Mg-MOF-74 was investigated by means of a combined methodology comprising variable-temperature infrared spectroscopy and ab initio periodic DFT-D calculations using the CRYSTAL code. Both CO and N-2 were found to form nearly linear (Mg2+center dot center dot center dot CO and Mg2+center dot center dot center dot NN) adsorption complexes, in contrast with CO2, which forms an angular Mg2+center dot center dot center dot OCO complex. From IR spectra recorded at a variable-temperature, the standard adsorption enthalpy (Delta H-0) was found to be -29, -21, and -47 kJ mol(-1) for CO, N-2, and CO2, respectively. Calculated values of Delta H-0, including an empirical correction for dispersion forces, resulted to be in a reasonably good agreement with those experimentally obtained. Calculations also showed the very significant role played by dispersion forces, which account for about one-half of the adsorption enthalpy for each of the three adsorbates, CO, N-2, and CO2. The results are discussed in the broader context of the adsorption of the same gases on other MOFs and also on zeolites
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Valenzano L.; Civalleri B.; Chavan S.; Palomino G. T.; Arean C. O.; Bordiga S.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/76077
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