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CALF-20, a Zn-triazolate-based metal-organic framework (MOF), is one of the most promising adsorbent materials for CO2 capture. However, competitive adsorption of water severely limits its performance when the relative humidity (RH) exceeds 40%, limiting the potential implementation of CALF-20 in practical settings where CO2 is saturated with moisture, such as post-combustion flue gas. In this work, three newly designed MOFs related to CALF-20, denoted as NU-220, CALF-20M-w, and CALF-20M-e that feature hydrophobic methyl-triazolate linkers are presented. Inclusion of methyl groups in the linker is proposed as a strategy to improve CO2 uptake in the presence of water. Notably, both CALF-20M-w and CALF-20M-e retain over 20% of their initial CO2 capture efficiency at 70% RH – a threshold at which CALF-20 shows negligible CO2 uptake. Grand canonical Monte Carlo (GCMC) simulations reveal that the methyl group hinders water network formation in the pores of CALF-20M-w and CALF-20M-e and enhances their CO2 selectivity over N2 in the presence of high moisture content. Moreover, calculated radial distribution functions indicate that introducing the methyl group into the triazolate linker increases the distance between water molecules and Zn coordination bonds, offering insights into the origin of the enhanced moisture stability observed for CALF-20M-w and CALF-20M-e relative to CALF-20. Overall, this straightforward design strategy has afforded more robust sorbents that can potentially meet the challenge of effectively capturing CO2 in practical industrial applications.
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Unveiling Temperature-Induced Structural Phase Transformations and CO 2 Binding Sites in CALF-20
The increase in atmospheric carbon dioxide concentration linked to climate change has created a need for new sorbents capable of separating CO2 from exhaust gases. Recently, an easily produced metal–organic framework, CALF-20, was shown to withstand over 450,000 adsorption/desorption cycles in steam and wet acid gases. Further development and industrial application of such materials require an understanding of the observed processes. Herein, we demonstrate that conditioning as-synthesized CALF-20 single crystal transforms it into a different phase, γ-CALF-20. The transformation resulted in significant structural changes, including the binding of water molecules to Zn(II), accompanied by a reduction of 9% in the unit cell volume. Our experimental findings were supported by the energy-volume dependence of CALF-20 in the presence and absence of water molecules calculated from density functional theory. We have also monitored the sorption process of the dominant greenhouse gas, CO2, on the initial phase of CALF-20 at atomic resolution using in situ single-crystal X-ray diffraction under specific pressure. The new understanding of CALF-20 chemistry from these studies should facilitate development of novel sorbents for gas adsorption technologies.
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- Award ID(s):
- 2119433
- PAR ID:
- 10648757
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Inorganic Chemistry
- Volume:
- 63
- Issue:
- 41
- ISSN:
- 0020-1669
- Page Range / eLocation ID:
- 19277 to 19286
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1021/acs.inorgchem.4c02952
