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Ion adsorption in [B]-COOH and [S]-COOH was fast and Fabrication of porous polymer films by usingVieCwoAlrpticlepOhnalisnee
DOI: 10.1039/C8CC03292K
quantitative with 10 mM aq. NaOH, KOH and CsOH solutions demonstrated the applicability and versatility of the present
(Fig. S12a,b). In contrast, LiOH, was adsorbed more slowly in the approach, perhaps bridging the gap between LC based porous
porous polymer films of [S]-COOH or [B]-COOH than the other polymers and aluminosilicate, zeolite type porous solids.
alkali metal hydroxides. Complete conversion of [S]-COOH by 10
mM aq. LiOH solution took approximately 1 h. FT-IR analysis
Conflicts of interest
showed that the –C=O stretching vibration of –COOH groups at
1693 cm-1 gradually reduced in exchange for a new vibration
There are no conflicts to declare.
band at 1556 cm-1, which was assigned to the asymmetric
stretching vibration of carboxylate groups (Fig. 4a). Surprisingly,
[B]-COOH adsorbed Li+ ions even more slowly from solution. FT-
Acknowledgements
We thank Ritu Ghanghas from Indian Institute of Science,
IR analysis showed that formation of [B]-COOLi was not
complete even after 12 h (Fig. 4b). The slower adsorption of Li+
Bangalore for performing solid state 13C NMR experiments.
ions in case of [B]-COOH might be a consequence of the pores
staying in the collapsed state during conversion to the salt (Fig.
1g). The larger size of hydrated Li+ ions compared to the other
hydrated alkali metal ions likely causes the slower diffusion of
Li+ ions in the pores.2c While in case of [S]-COOH the pores
remained open before and after reaction with aq. LiOH solution,
allowing a faster uptake of Li+ when compared to [B]-COOH.
Notes and references
1
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Figure 4. (a,b) Monitoring reaction of [S]-COOH and [B]-COOH
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The assumption that the collapsed state of the pores in [B]-
COOH hinders the passage of Li+, was further confirmed by an
experiment, in which porous polymer [B]-COOH adsorbed Li+
ions quantitatively within 15 min., if the reaction was
performed in THF:H2O (1:1 v/v) instead of water (Fig. S13). In
the mixed solvent, the film swelled visibly, opening the
collapsed pores and allowing much faster uptake of Li+ ions. (Fig.
1g).
5
In conclusion, nanoporous polymers have been prepared
from a Colp phase. By judicious choice of chemical treatment,
porous polymer thin films with ≈1.1 nm diameter small pores or
≈1.6 nm diameter bigger pores were produced. Anionic porous
polymers bearing –COONa groups have been prepared
previously from LC derived polymers,4a,5a however, the pore size
of these polymers was not tunable. [S]-COONa and [B]-COONa
bearing –COONa groups in the pore surface selectively
adsorbed a cationic dye in preference over anionic dye, with 4.5
times more dye adsorbed in the big pores of [B]-COONa after 20
h. Unlike dye adsorption, the uptake of Li+ ions by the large
collapsed pores of [B]-COOH was much slower than in the small
open pores of [S]-COOH. The current work highlights different
factors that determine adsorption of dyes in [B]-COONa, [S]-
COONa and binding of alkali metal ions in [B]-COOH, [S]-COOH.
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