Sulfate-modified MOF-808 as a superacid catalyst: a performance evaluation of Zr(<scp>iv</scp>) and Hf(<scp>iv</scp>) analogues in acetalization reactions
In this study, we report the synthesis and characterization of MOF-808-SO<sub>4</sub>-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-SO<sub>4</sub>-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.
Authors
- Ximena Zárate (ORCID: https://orcid.org/0000-0001-7400-6649)
- Jaime Llanos (ORCID: https://orcid.org/0000-0002-0804-3166)
- Ana Belén Dongil (ORCID: https://orcid.org/0000-0003-3445-5444)
- Yoan Hidalgo‐Rosa (ORCID: https://orcid.org/0000-0002-1391-435X)
- Ángel Leiva (ORCID: https://orcid.org/0000-0003-3744-1945)
- César Pazo-Carballo (ORCID: https://orcid.org/0000-0002-0952-7672)
- Douglas Olivares (ORCID: https://orcid.org/0000-0003-3854-3505)
- N. Escalona (ORCID: https://orcid.org/0000-0002-2628-4609)
- Eduardo Schott (ORCID: https://orcid.org/0000-0002-2546-304X)
- Vanesa Roa
- Sebastian Cea
Institutions
- Universidad Mayor (CL)
- Universidad de Antofagasta (CL)
- Pontificia Universidad Católica de Chile (CL)
- Universidad Católica del Norte (CL)
- Universidad Autónoma de Chile (CL)
- Instituto de Catálisis y Petroleoquímica (ES)
Publication Details
- Journal
- Dalton Transactions
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5dt00608b
- Citations
- 2
- Primary Topic
- Metal-Organic Frameworks: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 1.07
Funders
- Agencia Nacional de Investigación y Desarrollo
- Fondo Nacional de Desarrollo Científico y Tecnológico
- Fondo de Financiamiento de Centros de Investigación en Áreas Prioritarias
- Air Force Office of Scientific Research