The Nature of Structural Defects in ZIF-8 Revealed with 1H and 31P MAS NMR and X-Ray Absorption Spectroscopy

The metal–organic frameworks (MOFs) attract interest as potential catalysts whose catalytic properties are driven by defects. Several methods have been proposed for the defects-inducing synthesis of MOFs. However, the active species formed on the defective sites remain elusive and uncharacterized, as the spectroscopic fingerprints of these species are hidden by the regular structure signals. In this work, we have performed the synthesis of ZIF-8 MOF with defect-inducing procedures using fully deuterated 2-methylimidazolate ligands to enhance the defective sites′ visibility. By combining 1H and 31P MAS NMR spectroscopy and X-ray absorption spectroscopy, we have found evidence for the presence of different structural hydroxyl Zn−OH groups in the ZIF-8 materials. It is demonstrated that the ZIF-8 defect sites are represented by Zn−OH hydroxyl groups with the signals at 0.3 and −0.7 ppm in the 1H MAS NMR spectrum. These species are of basic nature and may be responsible for the catalytic activity of the ZIF-8 material. © 2025 Elsevier B.V., All rights reserved.