Abstract
"Breathing" metal-organic frameworks (MOFs) are an emerging class of soft porous crystals (SPCs) with potential for high working capacity for gas storage applications. However, most breathing MOFs have low stability and/or low surface area. Here we report a water-stable, high surface area, breathing MOF of ftw topology, NU-1105. While Zr6-oxo clusters as nodes introduce water stability in NU-1105, its high surface area and breathing character stem from its pyrene-based tetracarboxylate (Py-FP) linkers, in which the fluorene units (F) in the FP "arms" play a key role in promoting breathing behavior. During gas sorption studies, the "closed pore" (cp) 虠 "open pore" (op) transition of NU-1105 occurs at a propane pressure of ∼3 bar. At 1 bar, NU-1105 is in its cp form and adsorbs less propane than it would in its op form, highlighting improved working capacity. In situ powder X-ray diffraction during propane sorption was used to track the cp 虠 op transition, and molecular modeling was used to elucidate the structure of the op and cp forms of NU-1105. According to TD-DFT calculations, the proposed conformations of the Py-FP linkers in the op and cp forms are consistent with the measured excitation and emission spectra of the op and cp forms of NU-1105. Similar structural transitions are also observed in the porphyrinic MOF NU-1104 depending on the identity of the porphyrin core; we observed breathing behavior if the constituent Por-PTP linker is nonmetalated.
| Original language | English |
|---|---|
| Pages (from-to) | 13183-13190 |
| Number of pages | 8 |
| Journal | Journal of the American Chemical Society |
| Volume | 137 |
| Issue number | 40 |
| DOIs | |
| Publication status | Published - Oct 14 2015 |
Fingerprint
ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Ultraporous, water stable, and breathing zirconium-based metal-organic frameworks with ftw topology. / Deria, Pravas; Gómez-Gualdrón, Diego A.; Bury, Wojciech; Schaef, Herbert T.; Wang, Timothy C.; Thallapally, Praveen K.; Sarjeant, Amy A.; Snurr, Randall Q.; Hupp, Joseph T; Farha, Omar K.
In: Journal of the American Chemical Society, Vol. 137, No. 40, 14.10.2015, p. 13183-13190.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ultraporous, water stable, and breathing zirconium-based metal-organic frameworks with ftw topology
AU - Deria, Pravas
AU - Gómez-Gualdrón, Diego A.
AU - Bury, Wojciech
AU - Schaef, Herbert T.
AU - Wang, Timothy C.
AU - Thallapally, Praveen K.
AU - Sarjeant, Amy A.
AU - Snurr, Randall Q.
AU - Hupp, Joseph T
AU - Farha, Omar K.
PY - 2015/10/14
Y1 - 2015/10/14
N2 - "Breathing" metal-organic frameworks (MOFs) are an emerging class of soft porous crystals (SPCs) with potential for high working capacity for gas storage applications. However, most breathing MOFs have low stability and/or low surface area. Here we report a water-stable, high surface area, breathing MOF of ftw topology, NU-1105. While Zr6-oxo clusters as nodes introduce water stability in NU-1105, its high surface area and breathing character stem from its pyrene-based tetracarboxylate (Py-FP) linkers, in which the fluorene units (F) in the FP "arms" play a key role in promoting breathing behavior. During gas sorption studies, the "closed pore" (cp) 虠 "open pore" (op) transition of NU-1105 occurs at a propane pressure of ∼3 bar. At 1 bar, NU-1105 is in its cp form and adsorbs less propane than it would in its op form, highlighting improved working capacity. In situ powder X-ray diffraction during propane sorption was used to track the cp 虠 op transition, and molecular modeling was used to elucidate the structure of the op and cp forms of NU-1105. According to TD-DFT calculations, the proposed conformations of the Py-FP linkers in the op and cp forms are consistent with the measured excitation and emission spectra of the op and cp forms of NU-1105. Similar structural transitions are also observed in the porphyrinic MOF NU-1104 depending on the identity of the porphyrin core; we observed breathing behavior if the constituent Por-PTP linker is nonmetalated.
AB - "Breathing" metal-organic frameworks (MOFs) are an emerging class of soft porous crystals (SPCs) with potential for high working capacity for gas storage applications. However, most breathing MOFs have low stability and/or low surface area. Here we report a water-stable, high surface area, breathing MOF of ftw topology, NU-1105. While Zr6-oxo clusters as nodes introduce water stability in NU-1105, its high surface area and breathing character stem from its pyrene-based tetracarboxylate (Py-FP) linkers, in which the fluorene units (F) in the FP "arms" play a key role in promoting breathing behavior. During gas sorption studies, the "closed pore" (cp) 虠 "open pore" (op) transition of NU-1105 occurs at a propane pressure of ∼3 bar. At 1 bar, NU-1105 is in its cp form and adsorbs less propane than it would in its op form, highlighting improved working capacity. In situ powder X-ray diffraction during propane sorption was used to track the cp 虠 op transition, and molecular modeling was used to elucidate the structure of the op and cp forms of NU-1105. According to TD-DFT calculations, the proposed conformations of the Py-FP linkers in the op and cp forms are consistent with the measured excitation and emission spectra of the op and cp forms of NU-1105. Similar structural transitions are also observed in the porphyrinic MOF NU-1104 depending on the identity of the porphyrin core; we observed breathing behavior if the constituent Por-PTP linker is nonmetalated.
UR - http://www.scopus.com/inward/record.url?scp=84944259426&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84944259426&partnerID=8YFLogxK
U2 - 10.1021/jacs.5b08860
DO - 10.1021/jacs.5b08860
M3 - Article
AN - SCOPUS:84944259426
VL - 137
SP - 13183
EP - 13190
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 40
ER -