TY - JOUR
T1 - Phosphonate-Modified UiO-66 Brønsted Acid Catalyst and Its Use in Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes
AU - Dorneles de Mello, Matheus
AU - Kumar, Gaurav
AU - Tabassum, Tarnuma
AU - Jain, Sheetal K.
AU - Chen, Tso Hsuan
AU - Caratzoulas, Stavros
AU - Li, Xinyu
AU - Vlachos, Dionisios G.
AU - Han, Songi I.
AU - Scott, Susannah L.
AU - Dauenhauer, Paul
AU - Tsapatsis, Michael
N1 - Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/8/3
Y1 - 2020/8/3
N2 - 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.
AB - 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.
KW - biomass conversion
KW - metal–organic frameworks
KW - phosphonates
KW - solid Brønsted acids
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U2 - 10.1002/anie.202001332
DO - 10.1002/anie.202001332
M3 - Article
C2 - 32413202
AN - SCOPUS:85085759116
SN - 1433-7851
VL - 59
SP - 13260
EP - 13266
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 32
ER -
