Abstract
Instability of most prototypical metal organic frameworks (MOFs) in the presence of moisture is always a limitation for industrial scale development. In this work, we examine the dissociation mechanism of microporous paddle wheel frameworks M(bdc)(ted)0.5 [M = Cu, Zn, Ni, Co; bdc = 1,4-benzenedicarboxylate; ted = triethylenediamine] in controlled humidity environments. Combined in situ IR spectroscopy, Raman, and Powder X-ray diffraction measurements show that the stability and modification of isostructual M(bdc)(ted)0.5 compounds upon exposure to water vapor critically depend on the central metal ion. A hydrolysis reaction of water molecules with Cu-O-C is observed in the case of Cu(bdc)(ted)0.5. Displacement reactions of ted linkers by water molecules are identified with Zn(bdc)(ted)0.5 and Co(bdc)(ted)0.5. In contrast,. Ni(bdc)(ted)0.5 is less susceptible to reaction with water vapors than the other three compounds. In addition, the condensation of water vapors into the framework is necessary to initiate the dissociation reaction. These findings, supported by supported by first principles theoretical van der Waals density functional (vdW-DF) calculations of overall reaction enthalpies, provide the necessary information for determining operation conditions of this class of MOFs with paddle wheel secondary building units and guidance for developing more robust units.
| Original language | English |
|---|---|
| Pages (from-to) | 3153-3167 |
| Number of pages | 15 |
| Journal | Chemistry of Materials |
| Volume | 24 |
| Issue number | 16 |
| DOIs | |
| Publication status | Published - Aug 28 2012 |
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Keywords
- hydration
- in situ IR spectroscopy
- metal organic frameworks
- paddle wheel
- Raman
- secondary building units
- X-ray diffraction
ASJC Scopus subject areas
- Materials Chemistry
- Chemical Engineering(all)
- Chemistry(all)
Cite this
Stability and hydrolyzation of metal organic frameworks with paddle-wheel SBUs upon hydration. / Tan, Kui; Nijem, Nour; Canepa, Pieremanuele; Gong, Qihan; Li, Jing; Thonhauser, Timo; Chabal, Yves J.
In: Chemistry of Materials, Vol. 24, No. 16, 28.08.2012, p. 3153-3167.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Stability and hydrolyzation of metal organic frameworks with paddle-wheel SBUs upon hydration
AU - Tan, Kui
AU - Nijem, Nour
AU - Canepa, Pieremanuele
AU - Gong, Qihan
AU - Li, Jing
AU - Thonhauser, Timo
AU - Chabal, Yves J.
PY - 2012/8/28
Y1 - 2012/8/28
N2 - Instability of most prototypical metal organic frameworks (MOFs) in the presence of moisture is always a limitation for industrial scale development. In this work, we examine the dissociation mechanism of microporous paddle wheel frameworks M(bdc)(ted)0.5 [M = Cu, Zn, Ni, Co; bdc = 1,4-benzenedicarboxylate; ted = triethylenediamine] in controlled humidity environments. Combined in situ IR spectroscopy, Raman, and Powder X-ray diffraction measurements show that the stability and modification of isostructual M(bdc)(ted)0.5 compounds upon exposure to water vapor critically depend on the central metal ion. A hydrolysis reaction of water molecules with Cu-O-C is observed in the case of Cu(bdc)(ted)0.5. Displacement reactions of ted linkers by water molecules are identified with Zn(bdc)(ted)0.5 and Co(bdc)(ted)0.5. In contrast,. Ni(bdc)(ted)0.5 is less susceptible to reaction with water vapors than the other three compounds. In addition, the condensation of water vapors into the framework is necessary to initiate the dissociation reaction. These findings, supported by supported by first principles theoretical van der Waals density functional (vdW-DF) calculations of overall reaction enthalpies, provide the necessary information for determining operation conditions of this class of MOFs with paddle wheel secondary building units and guidance for developing more robust units.
AB - Instability of most prototypical metal organic frameworks (MOFs) in the presence of moisture is always a limitation for industrial scale development. In this work, we examine the dissociation mechanism of microporous paddle wheel frameworks M(bdc)(ted)0.5 [M = Cu, Zn, Ni, Co; bdc = 1,4-benzenedicarboxylate; ted = triethylenediamine] in controlled humidity environments. Combined in situ IR spectroscopy, Raman, and Powder X-ray diffraction measurements show that the stability and modification of isostructual M(bdc)(ted)0.5 compounds upon exposure to water vapor critically depend on the central metal ion. A hydrolysis reaction of water molecules with Cu-O-C is observed in the case of Cu(bdc)(ted)0.5. Displacement reactions of ted linkers by water molecules are identified with Zn(bdc)(ted)0.5 and Co(bdc)(ted)0.5. In contrast,. Ni(bdc)(ted)0.5 is less susceptible to reaction with water vapors than the other three compounds. In addition, the condensation of water vapors into the framework is necessary to initiate the dissociation reaction. These findings, supported by supported by first principles theoretical van der Waals density functional (vdW-DF) calculations of overall reaction enthalpies, provide the necessary information for determining operation conditions of this class of MOFs with paddle wheel secondary building units and guidance for developing more robust units.
KW - hydration
KW - in situ IR spectroscopy
KW - metal organic frameworks
KW - paddle wheel
KW - Raman
KW - secondary building units
KW - X-ray diffraction
UR - http://www.scopus.com/inward/record.url?scp=84870670659&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84870670659&partnerID=8YFLogxK
U2 - 10.1021/cm301427w
DO - 10.1021/cm301427w
M3 - Article
VL - 24
SP - 3153
EP - 3167
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 16
ER -