Issue 20, 2024

An adsorbate biased dynamic 3D porous framework for inverse CO2 sieving over C2H2

Abstract

Separating carbon dioxide (CO2) from acetylene (C2H2) is one of the most critical and complex industrial separations due to similarities in physicochemical properties and molecular dimensions. Herein, we report a novel Ni-based three-dimensional framework {[Ni43-OH)22-OH2)2(1,4-ndc)3](3H2O)}n (1,4-ndc = 1,4-naphthalenedicarboxylate) with a one-dimensional pore channel (3.05 × 3.57 Å2), that perfectly matches with the molecular size of CO2 and C2H2. The dehydrated framework shows structural transformation, decorated with an unsaturated Ni(II) centre and pendant oxygen atoms. The dynamic nature of the framework is evident by displaying a multistep gate opening type CO2 adsorption at 195, 273, and 298 K, but not for C2H2. The real time breakthrough gas separation experiments reveal a rarely attempted inverse CO2 selectivity over C2H2, attributed to open metal sites with a perfect pore aperture. This is supported by crystallographic analysis, in situ spectroscopic inspection, and selectivity approximations. In situ DRIFTS measurements and DFT-based theoretical calculations confirm CO2 binding sites are coordinatively unsaturated Ni(II) and carboxylate oxygen atoms, and highlight the influence of multiple adsorption sites.

Graphical abstract: An adsorbate biased dynamic 3D porous framework for inverse CO2 sieving over C2H2

Supplementary files

Article information

Article type
Edge Article
Submitted
08 Dec 2023
Accepted
07 Apr 2024
First published
17 Apr 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 7698-7706

An adsorbate biased dynamic 3D porous framework for inverse CO2 sieving over C2H2

N. Sikdar, S. Laha, R. Jena, A. Dey, F. A. Rahimi and T. K. Maji, Chem. Sci., 2024, 15, 7698 DOI: 10.1039/D3SC06611H

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