Bridging Zeolites and Metal-Organic Frameworks: Alkali Metal Cation Modulation in Zn-based UTSA-16
- 1Dipartimento di Chimica, Centro NIS, Unità di Ricerca INSTM, Università di Torino, Via G. Quarello 15/A and Via P. Giuria 7, Torino, Italy, I-10125
- 2Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Giuseppe Moruzzi 13, Pisa, Italy, 56124
Abstract
We present the first modulation of different alkali metal cations in Zn-based UTSA-16 metal-organic frameworks (MOFs), achieved through the use of different alkali metal hydroxides (KOH, NaOH and LiOH) during the synthesis. Optimisation of the stoichiometric ratio of reagents enabled the synthesis of phasepure UTSA-16(K) free from residual traces of undesired phases and exhibiting enhanced surface area and adsorption performance. This optimised protocol allowed the direct synthesis of other UTSA-16 frameworks containing Li + and Na + . Systematic variation of the alkali metal composition revealed pronounced site selectivity, proving that K + and Na+ are compatible with both the crystallographically defined structural and extra-framework cation environments, whereas Li + incorporation requires the presence of K + or Na + , supporting its preferential occupation of extra-framework positions. N 2 and CO 2 adsorption measurements, combined with in situ IR spectroscopy with CO, proved that cation composition affects both pore accessibility and local adsorption environment. In particular, materials containing predominantly extra-framework Li + exhibit distinct adsorption and spectroscopic behaviour depending on the occupancy of the structural cation site and revealing an interplay between the two cation populations. These findings show that the adsorption properties of UTSA-16 cannot be rationalised only considering the nature or size of the extra-framework cation. Instead, the organisation of charge-balancing cations within the framework is a key parameter affecting the adsorption environment. This behaviour provides a conceptual link between UTSA-16 and zeolites, where the nature and location of charge-balancing cations are essential to control the adsorption properties.
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BibTeX
@misc{guiotto2026bridging,
title = {{Bridging Zeolites and Metal-Organic Frameworks: Alkali Metal Cation Modulation in Zn-based UTSA-16}},
author = {Virginia Guiotto and Nicole Polzella and Giulio Bresciani and Francesca Nerli and Matteo Signorile and Silvia Bordiga and Marco Taddei and Valentina Crocellà},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010436/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010436/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Bridging Zeolites and Metal-Organic Frameworks: Alkali Metal Cation Modulation in Zn-based UTSA-16
AU - Virginia Guiotto
AU - Nicole Polzella
AU - Giulio Bresciani
AU - Francesca Nerli
AU - Matteo Signorile
AU - Silvia Bordiga
AU - Marco Taddei
AU - Valentina Crocellà
PY - 2026
DA - 2026/10/13
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010436/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010436/v1
AB - We present the first modulation of different alkali metal cations in Zn-based UTSA-16 metal-organic frameworks (MOFs), achieved through the use of different alkali metal hydroxides (KOH, NaOH and LiOH) during the synthesis. Optimisation of the stoichiometric ratio of reagents enabled the synthesis of phasepure UTSA-16(K) free from residual traces of undesired phases and exhibiting enhanced surface area and adsorption performance. This optimised protocol allowed the direct synthesis of other UTSA-16 frameworks containing Li + and Na + . Systematic variation of the alkali metal composition revealed pronounced site selectivity, proving that K + and Na+ are compatible with both the crystallographically defined structural and extra-framework cation environments, whereas Li + incorporation requires the presence of K + or Na + , supporting its preferential occupation of extra-framework positions. N 2 and CO 2 adsorption measurements, combined with in situ IR spectroscopy with CO, proved that cation composition affects both pore accessibility and local adsorption environment. In particular, materials containing predominantly extra-framework Li + exhibit distinct adsorption and spectroscopic behaviour depending on the occupancy of the structural cation site and revealing an interplay between the two cation populations. These findings show that the adsorption properties of UTSA-16 cannot be rationalised only considering the nature or size of the extra-framework cation. Instead, the organisation of charge-balancing cations within the framework is a key parameter affecting the adsorption environment. This behaviour provides a conceptual link between UTSA-16 and zeolites, where the nature and location of charge-balancing cations are essential to control the adsorption properties.
ER -