Ultra-stable imine-based covalent organic frameworks for sulfuric acid recovery: an effect of interlayer hydrogen bonding

Banerjee, R., Halder, A., Karak, S., Addicoat, M. ORCID: 0000-0002-5406-7927, Bera, S., Chakraborty, A., Kunjattu, S.H., Pachfule, P. and Heine, T., 2018. Ultra-stable imine-based covalent organic frameworks for sulfuric acid recovery: an effect of interlayer hydrogen bonding. Angewandte Chemie (International Edition). ISSN 1433-7851

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Abstract

Covalent Organic Frameworks (COFs) have convened inordinate scientific attention from last few years because of their unique tunable porosity and long range ordered structures with high atomic precisions. Although the high crystalline nature with considerable porosity fashioned these novel materials as an eligible candidate for diverse applications, the ordered nano-channels with controllable pore aperture, especially regarding membrane separations in extreme conditions, have been poorly explored. Herein, we have demonstrated rapid and scalable synthesis of six new imine-linked highly crystalline and porous COFs via salt (p-toluenesulfonic acid) mediated solid state crystallization approach. These as-synthesized materials show exceptionally high chemical stability in harsh environments including conc. H2SO4 (36 N), conc. HCl (12 N) and NaOH (9N). This is exclusivly because of the presence of strong interlayer C–H***N H-bonding interactions among the individual layers. This H-bonding reinforce interlayer stacking interaction and provides a steric hindrance and hydrophobic environ-ment around the imine (–C=N) bonds making it safe from hydrolysis, as confirmed by Density Functional Theory (DFT) calculations. By taking advantage of processability of COF powders in salt mediated synthesis approach, the continuous, porous, crystalline, self-standing and crack-free COF membranes (COFMs) with high chemical stability have been transmut-ed, for their potential applications to separate various environmentally toxic materials from drinking water with high water flux. Moreover, owing to its highly robust backbone, the COFM have showed unprecedented Sulfuric acid (12 N) permeance reflecting its potential applications for sulfuric acid purification. Also, the as-synthesized COFMs exhibit exceptionally high permeance of acetonitrile (380 Lm-2h-1bar-1) and acetone (340 Lm-2h-1bar-1).

Item Type: Journal article
Publication Title: Angewandte Chemie (International Edition)
Creators: Banerjee, R., Halder, A., Karak, S., Addicoat, M., Bera, S., Chakraborty, A., Kunjattu, S.H., Pachfule, P. and Heine, T.
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA
Date: 2018
ISSN: 1433-7851
Identifiers:
NumberType
10.1002/anie.201802220DOI
Divisions: Schools > School of Science and Technology
Depositing User: Linda Sullivan
Date Added: 04 Apr 2018 11:32
Last Modified: 05 Apr 2018 07:24
URI: http://irep.ntu.ac.uk/id/eprint/33178

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