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Synthesis, Characterization, and Post-Synthetic Modification of a Micro/Mesoporous Zirconium-Tricarboxylate Metal-Organic Framework: Towards the Addition of Acid Active Sites

Abstract

Zr-MOFs are characterized by their high thermal and chemical stability which may facilitate their application in heterogeneous catalysis. However, these applications could be restricted if large reactants exceed the MOF pore sizes leading to unavailable surface areas. In this work, we study the effect of acetic acid concentration, used as the modulator, on the formation of micro/mesoporous materials. This inclusion of a modulator during synthesis and its removal by an activation process generate materials with missing linker defects. We show that an increase in the concentration of modulator leads to an improvement of calculated apparent surface area and to a modification of MOF-808 pore structure by producing mesopores at the expense of micropores. Furthermore, we perform a post-synthetic modification (PSM) of the MOF-808. We observe the expected sulfation of the zirconium oxo-cluster but also the sulfonation of the organic ligand. Also, we find that only the families of mesopores and the larger micropores are interconnected within the material, and the ultramicropores seem to be isolated from the porous structure. The PSM process led to the addition of Lewis and Brønsted acid sites to the MOF-808. Experimental results are complemented by theoretical calculations using Density Functional Theory and Ab Initio Molecular Dynamics Simulations. The rationalization of the synthesis conditions effect and the post-synthetic sulfation process on the final properties presented in this paper can serve as a basis for engineering of defects towards the synthesis of solid acid catalysts from MOF 808.

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Publication details

The article was received on 15 Feb 2019, accepted on 20 Mar 2019 and first published on 20 Mar 2019


Article type: Paper
DOI: 10.1039/C9CE00218A
Citation: CrystEngComm, 2019, Accepted Manuscript

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    Synthesis, Characterization, and Post-Synthetic Modification of a Micro/Mesoporous Zirconium-Tricarboxylate Metal-Organic Framework: Towards the Addition of Acid Active Sites

    C. Ardila Suárez, A. M. Díaz, L. A. Díaz Vaca, P. B. Balbuena, V. G. Baldovino Medrano and G. Ramírez Caballero, CrystEngComm, 2019, Accepted Manuscript , DOI: 10.1039/C9CE00218A

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