Issue 13, 2022

Isolated molybdenum-based microporous POMs for selective adsorption of gases

Abstract

Dodecanuclear, icosanuclear and octanuclear porous MOF-like POM materials [MoV12O122-O)43-O)12(Htrz)4(trz)4nH2O (n = 22, 1; n = 92, 2; Htrz = 1H-1,2,3-triazole), [MoV8O82-O)12(Htrz)8]½·[MoV12O122-O)43-O)12(Htrz)4(trz)4]·44H2O (3), and [MoV8O82-O)12(Htrz)8]·62H2O (4) have been obtained and well characterized. Higher Mo12 agglomerates have been fabricated in acidic solution, while isolated Mo8 species formed in weak alkaline conditions. Fortuitously, their additive 3 is precipitated in a neutral environment. Structural analyses indicate that there are diversiform pores present in 1–4, which are formed by polyoxometalates (POMs) themselves and intermolecular accumulations, or even induced by free disordered water molecules. Obvious downfield shifts have been found in the solid 13C NMR spectra for the coordinated 1,2,3-triazoles in 1 and 2. In particular, isolated single species of polyoxometalate-based porous framework POMOF 4 can be identified in the solution 13C NMR spectrum and further supported by solid and solution UV-vis spectroscopy. Moreover, gas adsorption tests indicate that 1 is the most promising CO2 adsorbent of these four materials, compared with other common gases O2, H2, CH4 and N2 under different pressures. The peculiarities of this sort of POMOFs, as well as the relationships and interactions with gases, have been discussed.

Graphical abstract: Isolated molybdenum-based microporous POMs for selective adsorption of gases

Supplementary files

Article information

Article type
Paper
Submitted
16 Jan 2022
Accepted
28 Feb 2022
First published
01 Mar 2022

Dalton Trans., 2022,51, 5239-5249

Isolated molybdenum-based microporous POMs for selective adsorption of gases

L. Deng, R. Lin and Z. Zhou, Dalton Trans., 2022, 51, 5239 DOI: 10.1039/D2DT00134A

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