Abstract
HKUST-1, a metal-organic framework (MOF) material containing Cu II-paddlewheel-type nodes and 1,3,5-benzenetricarboxylate struts, features accessible Cu II sites to which solvent or other desired molecules can be intentionally coordinated. As part of a broader investigation of ionic conductivity in MOFs, we unexpectedly observed substantial proton conductivity with the "as synthesized" version of this material following sorption of methanol. Although HKUST-1 is neutral, coordinated water molecules are rendered sufficiently acidic by Cu II to contribute protons to pore-filling methanol molecules and thereby enhance the alternating-current conductivity. At ambient temperature, the chemical identities of the node-coordinated and pore-filling molecules can be independently varied, thus enabling the proton conductivity to be reversibly modulated. The proton conductivity of HKUST-1 was observed to increase by ∼75-fold, for example, when node-coordinated acetonitrile molecules were replaced by water molecules. In contrast, the conductivity became almost immeasurably small when methanol was replaced by hexane as the pore-filling solvent.
| Original language | English |
|---|---|
| Pages (from-to) | 51-54 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 134 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - Jan 11 2012 |
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ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Coordination-chemistry control of proton conductivity in the iconic metal-organic framework material HKUST-1. / Jeong, Nak Cheon; Samanta, Bappaditya; Lee, Chang Yeon; Farha, Omar K.; Hupp, Joseph T.
In: Journal of the American Chemical Society, Vol. 134, No. 1, 11.01.2012, p. 51-54.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Coordination-chemistry control of proton conductivity in the iconic metal-organic framework material HKUST-1
AU - Jeong, Nak Cheon
AU - Samanta, Bappaditya
AU - Lee, Chang Yeon
AU - Farha, Omar K.
AU - Hupp, Joseph T
PY - 2012/1/11
Y1 - 2012/1/11
N2 - HKUST-1, a metal-organic framework (MOF) material containing Cu II-paddlewheel-type nodes and 1,3,5-benzenetricarboxylate struts, features accessible Cu II sites to which solvent or other desired molecules can be intentionally coordinated. As part of a broader investigation of ionic conductivity in MOFs, we unexpectedly observed substantial proton conductivity with the "as synthesized" version of this material following sorption of methanol. Although HKUST-1 is neutral, coordinated water molecules are rendered sufficiently acidic by Cu II to contribute protons to pore-filling methanol molecules and thereby enhance the alternating-current conductivity. At ambient temperature, the chemical identities of the node-coordinated and pore-filling molecules can be independently varied, thus enabling the proton conductivity to be reversibly modulated. The proton conductivity of HKUST-1 was observed to increase by ∼75-fold, for example, when node-coordinated acetonitrile molecules were replaced by water molecules. In contrast, the conductivity became almost immeasurably small when methanol was replaced by hexane as the pore-filling solvent.
AB - HKUST-1, a metal-organic framework (MOF) material containing Cu II-paddlewheel-type nodes and 1,3,5-benzenetricarboxylate struts, features accessible Cu II sites to which solvent or other desired molecules can be intentionally coordinated. As part of a broader investigation of ionic conductivity in MOFs, we unexpectedly observed substantial proton conductivity with the "as synthesized" version of this material following sorption of methanol. Although HKUST-1 is neutral, coordinated water molecules are rendered sufficiently acidic by Cu II to contribute protons to pore-filling methanol molecules and thereby enhance the alternating-current conductivity. At ambient temperature, the chemical identities of the node-coordinated and pore-filling molecules can be independently varied, thus enabling the proton conductivity to be reversibly modulated. The proton conductivity of HKUST-1 was observed to increase by ∼75-fold, for example, when node-coordinated acetonitrile molecules were replaced by water molecules. In contrast, the conductivity became almost immeasurably small when methanol was replaced by hexane as the pore-filling solvent.
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U2 - 10.1021/ja2110152
DO - 10.1021/ja2110152
M3 - Article
VL - 134
SP - 51
EP - 54
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 1
ER -