TY - JOUR
T1 - Thermochemistry of zeolitic imidazolate frameworks of varying porosity
AU - Hughes, James T.
AU - Bennett, Thomas D.
AU - Cheetham, Anthony K.
AU - Navrotsky, Alexandra
N1 - Copyright:
Copyright 2013 Elsevier B.V., All rights reserved.
PY - 2013/1/16
Y1 - 2013/1/16
N2 - The first thermochemical analysis by room-temperature aqueous solution calorimetry of a series of zeolite imidazolate frameworks (ZIFs) has been completed. The enthalpies of formation of the evacuated ZIFs - ZIF-zni, ZIF-1, ZIF-4, CoZIF-4, ZIF-7, and ZIF-8 - along with as-synthesized ZIF-4 (ZIF-4·DMF) and ball-milling amorphized ZIF-4 (amZIF-4) were measured with respect to dense components: metal oxide (ZnO or CoO), the corresponding imidazole linker, and N,N dimethylformamide (DMF) in the case of ZIF-4·DMF. Enthalpies of formation of ZIFs from these components at 298 K are exothermic, but the ZIFs are metastable energetically with respect to hypothetical dense components in which zinc is bonded to nitrogen rather than oxygen. These enthalpic destabilizations increase with increasing porosity and span a narrow range from 13.0 to 27.1 kJ/mol, while the molar volumes extend from 135.9 to 248.8 cm3/mol; thus, almost doubling the molar volume results in only a modest energetic destabilization. The experimental results are supported by DFT calculations. The series of ZIFs studied tie in with previously studied MOF-5, creating a broader trend that mirrors a similar pattern by porous inorganic oxides, zeolites, zeotypes, and mesoporous silicas. These findings suggest that no immediate thermodynamic barrier precludes the further development of highly porous materials.
AB - The first thermochemical analysis by room-temperature aqueous solution calorimetry of a series of zeolite imidazolate frameworks (ZIFs) has been completed. The enthalpies of formation of the evacuated ZIFs - ZIF-zni, ZIF-1, ZIF-4, CoZIF-4, ZIF-7, and ZIF-8 - along with as-synthesized ZIF-4 (ZIF-4·DMF) and ball-milling amorphized ZIF-4 (amZIF-4) were measured with respect to dense components: metal oxide (ZnO or CoO), the corresponding imidazole linker, and N,N dimethylformamide (DMF) in the case of ZIF-4·DMF. Enthalpies of formation of ZIFs from these components at 298 K are exothermic, but the ZIFs are metastable energetically with respect to hypothetical dense components in which zinc is bonded to nitrogen rather than oxygen. These enthalpic destabilizations increase with increasing porosity and span a narrow range from 13.0 to 27.1 kJ/mol, while the molar volumes extend from 135.9 to 248.8 cm3/mol; thus, almost doubling the molar volume results in only a modest energetic destabilization. The experimental results are supported by DFT calculations. The series of ZIFs studied tie in with previously studied MOF-5, creating a broader trend that mirrors a similar pattern by porous inorganic oxides, zeolites, zeotypes, and mesoporous silicas. These findings suggest that no immediate thermodynamic barrier precludes the further development of highly porous materials.
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U2 - 10.1021/ja311237m
DO - 10.1021/ja311237m
M3 - Article
C2 - 23270310
AN - SCOPUS:84872512466
VL - 135
SP - 598
EP - 601
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 2
ER -