Issue 7, 2024

Combination of dimensional reduction and active site addition strategies for preparing unique {RE9}-cluster-based MOFs: efficient CO2 fixation and Knoevenagel condensation

Abstract

The current application of porous catalytic materials for organic synthesis is always confined to comparatively simple small substrates because of the diffusion barrier. Therefore, in this study, dimensional reduction and active site addition strategies were employed for preparing unique porous {RE9}-cluster-based rare-earth metal–organic frameworks (MOFs) {[Me2NH2]4[RE9(pddb)63-O)23-OH)12(H2O)1.5(HCO2)3]·6.5DMF·11H2O}n (MOF-RE, RE = Tb, Y, and Dy) with high-density multiple active sites. It was found that MOF-RE are rare {RE9}-based two-dimensional (2D) networks including triangular-nanoporous (1.3 nm) and triangular-microporous (0.8 nm) channels decorated by abundant Lewis acid–base sites (open RE(III) sites and Npyridine atoms) on the inner surface. As anticipated, due to the coexistence of Lewis acid–base sites, activated samples exhibited better catalytic activity (a yield of 96%, and a TON value of 768 for styrene oxide) than most previously reported 3D MOF materials for the cycloaddition of CO2 and multifarious epoxides under moderate conditions. Moreover, as a heterogeneous catalyst, MOF-Tb, has excellent catalytic performance (with a TON value of 396 for benzaldehyde) for the Knoevenagel condensation reaction of malononitrile and aldehydes with high catalytic stability and recoverability. In addition, both reactions possessed high turnover numbers and frequencies. These dimensional reduction and active site addition tactics may permit the exploitation of new nanoporous MOF catalysts based on rare-earth clusters for useful and intricate organic conversions.

Graphical abstract: Combination of dimensional reduction and active site addition strategies for preparing unique {RE9}-cluster-based MOFs: efficient CO2 fixation and Knoevenagel condensation

Supplementary files

Article information

Article type
Research Article
Submitted
11 Des 2023
Accepted
16 Feb 2024
First published
07 Mac 2024

Inorg. Chem. Front., 2024,11, 2071-2080

Combination of dimensional reduction and active site addition strategies for preparing unique {RE9}-cluster-based MOFs: efficient CO2 fixation and Knoevenagel condensation

Y. Zhao, D. Wu, Y. Qiao, G. Yang, L. Ma and Y. Wang, Inorg. Chem. Front., 2024, 11, 2071 DOI: 10.1039/D3QI02527F

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