Adsorption−Desorption Induced Structural Changes of Cu-MOF Evidenced by Solid State NMR and EPR Spectroscopy
Yijiao Jiang, Jun Huang, Besnik Kasumaj, Gunnar Jeschke, Michael Hunger, Tamas Mallat and Alfons Baiker
Adsorption−desorption induced structural changes of Cu(bpy)(H2O)2(BF4),(bpy) (bpy = 4,4′-bipyridine) [Cu-MOF] have been evidenced by combined NMR and EPR spectroscopy. Upon adsorption of probe molecules even at a few mbar, EPR spectra show that they are activated to form complexes at Cu(II) sites, which results in a change of the Cu-MOF’s structure as indicated by a high-field shift of the 11B MAS NMR. After desorption, both EPR and 11B MAS NMR spectra evidenced that the structure of the Cu-MOF reversibly shifted to the original state. This observation indicates that MOFs can undergo structural changes during processes where adsorption−desorption steps are involved such as gas storage, separation, and catalysis.