Results
Title

Phosphonate‐Modified UiO‐66 Brønsted Acid Catalyst and Its Use in Dehydra‐Decyclization of 2‐Methyltetrahydrofuran to Pentadienes.

Authors

Dorneles de Mello, Matheus; Kumar, Gaurav; Tabassum, Tarnuma; Jain, Sheetal K.; Chen, Tso‐Hsuan; Caratzoulas, Stavros; Li, Xinyu; Vlachos, Dionisios G.; Han, Songi‐I; Scott, Susannah L.; Dauenhauer, Paul; Tsapatsis, Michael

Abstract

Phosphorus‐modified all‐silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well‐defined sites, we report the incorporation of Brønsted acidity to metal–organic frameworks with the UiO‐66 topology, achieved by attaching phosphonic acid to the 1,4‐benzenedicarboxylate ligand and using it to form UiO‐66‐PO3H2 by post‐synthesis modification. Characterization reveals that UiO‐66‐PO3H2 retains stability similar to UiO‐66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra‐decyclization of 2‐methyltetrahydrofuran (2‐MTHF). For the later reaction, the reported catalyst exhibits site‐time yields and selectivity approaching that of phosphoric acid on all‐silica zeolites. Using solid‐state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.

Subjects

BRONSTED acids; ACID catalysts; PENTADIENES; BIOMASS conversion; METAL-organic frameworks; PHOSPHORIC acid

Publication

Angewandte Chemie, 2020, Vol 132, Issue 32, p13362

ISSN

0044-8249

Publication type

Academic Journal

DOI

10.1002/ange.202001332