Guest-tuned proton conductivity of a porphyrinylphosphonate-based hydrogen-bonded organic framework
Hydrogen-bonded organic frameworks (HOFs), similar to their MOF analogues, exhibit great potential in proton conduction applications. Herein, a porous HOF namely [(NiH 4 TPPP)(Me 2 NH 2 ) 4 (DMF)(H 2 O) 4 ] (UPC-H5) was synthesized from phosphonate-based porphyrinato nickel (NiH 8 TPPP), and its pro...
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Published in | Journal of materials chemistry. A, Materials for energy and sustainability Vol. 9; no. 5; pp. 2683 - 2688 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
Cambridge
Royal Society of Chemistry
01.01.2021
|
Subjects | |
Online Access | Get full text |
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Summary: | Hydrogen-bonded organic frameworks (HOFs), similar to their MOF analogues, exhibit great potential in proton conduction applications. Herein, a porous HOF namely [(NiH
4
TPPP)(Me
2
NH
2
)
4
(DMF)(H
2
O)
4
] (UPC-H5) was synthesized from phosphonate-based porphyrinato nickel (NiH
8
TPPP), and its proton conductivity is regulated through a two-step guest change. Firstly, immersing UPC-H5 in CH
2
Cl
2
to exchange lattice solvent molecules for 24 h followed by heating under vacuum afforded the lattice solvent molecule-free HOF [(NiH
4
TPPP)(Me
2
NH
2
)
4
] (UPC-H5a) with the pristine framework still retained. Secondly, exposing UPC-H5a to vapors of 25% aqueous ammonia for 24 h at room temperature gave a new derivative UPC-H5a@NH
3
·H
2
O with the molecular formula [(NiH
4
TPPP)(Me
2
NH
2
)
2
(NH
4
)
2
(H
2
O)
4
] according to elemental and thermal analyses. At 30 °C and 95% R.H., the proton conductivity of UPC-H5, UPC-H5a, and UPC-H5a@NH
3
·H
2
O amounts to 5.59 × 10
−4
, 7.00 × 10
−3
, and 1.47 × 10
−2
S cm
−1
, respectively, which increases to 1.85 × 10
−3
, 3.42 × 10
−2
, and 1.59 × 10
−1
S cm
−1
at 80 °C and 99% R.H., clearly showing the effect of guest regulation on the proton conductivity of the HOF-based materials. In addition, this result is also helpful towards understanding the important role of guests in the formation of their proton conduction pathways.
A porous porphyrin-based hydrogen-bonded organic framework (HOF) was constructed, and its proton conductivity was improved through a two-step guest-tuned strategy. After regulation, the proton conductivity of the HOF reaches 1.59 × 10
−1
S cm
−1
at 80 °C and 99% RH. |
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Bibliography: | CCDC For ESI and crystallographic data in CIF or other electronic format see DOI Electronic supplementary information (ESI) available: Synthetic details, FTIR images, PXRD patterns, TGA results etc. 10.1039/d0ta07207a 1976307 |
ISSN: | 2050-7488 2050-7496 |
DOI: | 10.1039/d0ta07207a |