Abstract
We report the design and synthesis of a metal-organic framework (MOF)-polythiophene composite that has comparable electronic conductivity to reported conductive 3-D MOFs, but with display and retention of high porosity, including mesoporosity. A robust zirconium MOF, NU-1000, was rendered electronically conductive by first incorporating, via solvent-assisted ligand incorporation (SALI), a carefully designed pentathiophene derivative at a density of one pentamer per hexa-zirconium node. Using a cast film of the intermediate composite (termed pentaSALI) on conductive glass, the incorporated oligothiophene was electrochemically polymerized to yield the conductive composite, Epoly. Depending on the doping level of the polythiophene in the composite, it can be tuned from an insulating state to a semiconduting state with conductivity of 1.3 × 10-7 (S cm-1), which is comparable to values reported for 3-D conductive MOFs. The porosity of the thin-film MOF-polythiophene composite was assessed using decane vapor uptake as determined by quartz crystal microgravimetry (QCM). The results indicate a porosity (pore volume) for Epoly essentially identical to that of bulk pentaSALI, and ∼74% of that of unmodified NU-1000. PentaSALI, and by inference Epoly, displays both micro- and mesoporosity, and features a BET surface area of nearly 1,600 m2·g-1, i.e., substantially larger than yet reported for any other electronically conductive MOF.
| Original language | English |
|---|---|
| Pages (from-to) | 12584-12591 |
| Number of pages | 8 |
| Journal | ACS Applied Materials and Interfaces |
| Volume | 9 |
| Issue number | 14 |
| DOIs | |
| Publication status | Published - Apr 12 2017 |
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Keywords
- electronic conductivity
- electropolymerization
- metal-organic framework
- polythiophene
- QCM porosity measurement
- solvent-assisted ligand incorporation
ASJC Scopus subject areas
- Materials Science(all)
Cite this
Rendering High Surface Area, Mesoporous Metal-Organic Frameworks Electronically Conductive. / Wang, Timothy C.; Hod, Idan; Audu, Cornelius O.; Vermeulen, Nicolaas A.; Nguyen, Sonbinh T.; Farha, Omar K.; Hupp, Joseph T.
In: ACS Applied Materials and Interfaces, Vol. 9, No. 14, 12.04.2017, p. 12584-12591.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Rendering High Surface Area, Mesoporous Metal-Organic Frameworks Electronically Conductive
AU - Wang, Timothy C.
AU - Hod, Idan
AU - Audu, Cornelius O.
AU - Vermeulen, Nicolaas A.
AU - Nguyen, Sonbinh T.
AU - Farha, Omar K.
AU - Hupp, Joseph T
PY - 2017/4/12
Y1 - 2017/4/12
N2 - We report the design and synthesis of a metal-organic framework (MOF)-polythiophene composite that has comparable electronic conductivity to reported conductive 3-D MOFs, but with display and retention of high porosity, including mesoporosity. A robust zirconium MOF, NU-1000, was rendered electronically conductive by first incorporating, via solvent-assisted ligand incorporation (SALI), a carefully designed pentathiophene derivative at a density of one pentamer per hexa-zirconium node. Using a cast film of the intermediate composite (termed pentaSALI) on conductive glass, the incorporated oligothiophene was electrochemically polymerized to yield the conductive composite, Epoly. Depending on the doping level of the polythiophene in the composite, it can be tuned from an insulating state to a semiconduting state with conductivity of 1.3 × 10-7 (S cm-1), which is comparable to values reported for 3-D conductive MOFs. The porosity of the thin-film MOF-polythiophene composite was assessed using decane vapor uptake as determined by quartz crystal microgravimetry (QCM). The results indicate a porosity (pore volume) for Epoly essentially identical to that of bulk pentaSALI, and ∼74% of that of unmodified NU-1000. PentaSALI, and by inference Epoly, displays both micro- and mesoporosity, and features a BET surface area of nearly 1,600 m2·g-1, i.e., substantially larger than yet reported for any other electronically conductive MOF.
AB - We report the design and synthesis of a metal-organic framework (MOF)-polythiophene composite that has comparable electronic conductivity to reported conductive 3-D MOFs, but with display and retention of high porosity, including mesoporosity. A robust zirconium MOF, NU-1000, was rendered electronically conductive by first incorporating, via solvent-assisted ligand incorporation (SALI), a carefully designed pentathiophene derivative at a density of one pentamer per hexa-zirconium node. Using a cast film of the intermediate composite (termed pentaSALI) on conductive glass, the incorporated oligothiophene was electrochemically polymerized to yield the conductive composite, Epoly. Depending on the doping level of the polythiophene in the composite, it can be tuned from an insulating state to a semiconduting state with conductivity of 1.3 × 10-7 (S cm-1), which is comparable to values reported for 3-D conductive MOFs. The porosity of the thin-film MOF-polythiophene composite was assessed using decane vapor uptake as determined by quartz crystal microgravimetry (QCM). The results indicate a porosity (pore volume) for Epoly essentially identical to that of bulk pentaSALI, and ∼74% of that of unmodified NU-1000. PentaSALI, and by inference Epoly, displays both micro- and mesoporosity, and features a BET surface area of nearly 1,600 m2·g-1, i.e., substantially larger than yet reported for any other electronically conductive MOF.
KW - electronic conductivity
KW - electropolymerization
KW - metal-organic framework
KW - polythiophene
KW - QCM porosity measurement
KW - solvent-assisted ligand incorporation
UR - http://www.scopus.com/inward/record.url?scp=85017539934&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85017539934&partnerID=8YFLogxK
U2 - 10.1021/acsami.6b16834
DO - 10.1021/acsami.6b16834
M3 - Article
AN - SCOPUS:85017539934
VL - 9
SP - 12584
EP - 12591
JO - ACS applied materials & interfaces
JF - ACS applied materials & interfaces
SN - 1944-8244
IS - 14
ER -