The Nature of Structural Defects in ZIF‐8 Revealed with 1H and 31P MAS NMR and X‐ray Absorption Spectroscopy | Sciact - CRIS-system of Boreskov Institute of Catalysis

The Nature of Structural Defects in ZIF‐8 Revealed with 1H and 31P MAS NMR and X‐ray Absorption Spectroscopy Full article

Journal

Angewandte Chemie - International Edition
ISSN: 1433-7851 , E-ISSN: 1521-3773

Output data

Year: 2024, Article number : e202414823, Pages count : 8 DOI: 10.1002/anie.202414823

Tags

metal-organic framework, defects, solid state NMR, XAS, Cataly

Authors

Gabrienko Anton A. ¹ , Chaemchuen Somboon ^2,6 , Kou Zongkui ² , Ogiwara Naoki ³ , Kitagawa Hiroshi ⁴ , Khudozhitkov Alexander E. ¹ , Stepanov Alexander G. ¹ , Kolokolov Daniil I. ¹ , Verpoort Francis ^2,5

Affiliations

1	Boreskov Institute of Catalysis, Novosibirsk, Ac. Lavrentiev av. 5, Novosibirsk 630090, Russia
2	State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
3	Department of Basic Science, School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153–8902, Japan
4	Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502, Japan
5	Joint Institute of Chemical Research (FFMiEN), Peoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Str., 117198 Moscow, Russia
6	Department of Chemical Engineering, Faculty of Engineering, Mahidol University, Nakhon Pathom 73170, Thailand

Funding (1)

Ministry of Science and Higher Education of the Russian Federation

FWUR-2024-0032

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 1H MAS NMR spectrum. These species are of basic nature and may be responsible for the catalytic activity of the ZIF-8 material.

Gabrienko A.A. , Chaemchuen S. , Kou Z. , Ogiwara N. , Kitagawa H. , Khudozhitkov A.E. , Stepanov A.G. , Kolokolov D.I. , Verpoort F.
The Nature of Structural Defects in ZIF‐8 Revealed with 1H and 31P MAS NMR and X‐ray Absorption Spectroscopy
Angewandte Chemie - International Edition. 2024. e202414823 :1-8. DOI: 10.1002/anie.202414823 PMID OpenAlex

Submitted:	Aug 5, 2024
Accepted:	Sep 13, 2024
Published online:	Sep 18, 2024

PMID:	39291298
OpenAlex:	W4402612707

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