Sulfate-modified MOF-808 as a superacid catalyst: a performance evaluation of Zr(iv) and Hf(iv) analogues in acetalization reactions

Abstract

In this study, we report the synthesis and characterization of MOF-808-SO4-M (M = Zr(IV), Hf(IV)), derived from MOF-808-M precursors. The introduction of sulfate groups enhances the Brønsted acidity of these materials, significantly improving their catalytic performance in the benzaldehyde acetalization reaction. The materials were characterized using powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FT-IR), nitrogen adsorption–desorption analysis, thermogravimetric analysis (TGA), energy-dispersive spectroscopy (EDS), and Hammett indicator tests. Catalytic evaluation revealed that MOF-808-SO4-Zr exhibited significantly higher conversion compared to its Hf-based analogue, a difference attributed to its greater density of acid sites, as confirmed by temperature-programmed surface reaction (TPSR) analysis. These experimental results were further supported by density functional theory (DFT) calculations, which provided insights into the acidic properties and catalytic behavior of the materials.

Graphical abstract: Sulfate-modified MOF-808 as a superacid catalyst: a performance evaluation of Zr(iv) and Hf(iv) analogues in acetalization reactions

Supplementary files

Article information

Article type
Paper
Submitted
13 Mar 2025
Accepted
19 May 2025
First published
27 May 2025
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2025, Advance Article

Sulfate-modified MOF-808 as a superacid catalyst: a performance evaluation of Zr(IV) and Hf(IV) analogues in acetalization reactions

V. Roa, S. Cea, C. Pazo, J. Llanos, D. Olivares, N. Escalona, Á. Leiva, Y. Hidalgo-Rosa, X. Zarate, A. B. Dongil and E. Schott, Dalton Trans., 2025, Advance Article , DOI: 10.1039/D5DT00608B

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