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

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

doi:10.1002/anie.202001332

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

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

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

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.

Original language	English (US)
Pages (from-to)	13260-13266
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	32
DOIs	https://doi.org/10.1002/anie.202001332
State	Published - Aug 3 2020

Bibliographical note

Funding Information:
This work was supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE‐SC0001004. M.D.dM.’s doctoral fellowship was partially supported by the Brazillian National Council for Scientific and Technological Development (CNPq) under grant 202982/2014‐9.

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

biomass conversion
metal–organic frameworks
phosphonates
solid Brønsted acids

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10.1002/anie.202001332

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Dorneles de Mello, M., Kumar, G., Tabassum, T., Jain, S. K., Chen, T. H., Caratzoulas, S., Li, X., Vlachos, D. G., Han, S. I., Scott, S. L., Dauenhauer, P., & Tsapatsis, M. (2020). Phosphonate-Modified UiO-66 Brønsted Acid Catalyst and Its Use in Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes. Angewandte Chemie - International Edition, 59(32), 13260-13266. https://doi.org/10.1002/anie.202001332

Dorneles de Mello, M, Kumar, G, Tabassum, T, Jain, SK, Chen, TH, Caratzoulas, S, Li, X, Vlachos, DG, Han, SI, Scott, SL, Dauenhauer, P & Tsapatsis, M 2020, 'Phosphonate-Modified UiO-66 Brønsted Acid Catalyst and Its Use in Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes', Angewandte Chemie - International Edition, vol. 59, no. 32, pp. 13260-13266. https://doi.org/10.1002/anie.202001332

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title = "Phosphonate-Modified UiO-66 Br{\o}nsted Acid Catalyst and Its Use in Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes",

abstract = "Phosphorus-modified all-silica zeolites exhibit activity and selectivity in certain Br{\o}nsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well-defined sites, we report the incorporation of Br{\o}nsted 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 Br{\o}nsted 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.",

keywords = "biomass conversion, metal–organic frameworks, phosphonates, solid Br{\o}nsted acids",

author = "\{Dorneles de Mello\}, Matheus and Gaurav Kumar and Tarnuma Tabassum and Jain, \{Sheetal K.\} and Chen, \{Tso Hsuan\} and Stavros Caratzoulas and Xinyu Li and Vlachos, \{Dionisios G.\} and Han, \{Songi I.\} and Scott, \{Susannah L.\} and Paul Dauenhauer and Michael Tsapatsis",

note = "Funding Information: This work was supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE‐SC0001004. M.D.dM.{\textquoteright}s doctoral fellowship was partially supported by the Brazillian National Council for Scientific and Technological Development (CNPq) under grant 202982/2014‐9. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

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doi = "10.1002/anie.202001332",

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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 - Funding Information: This work was supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE‐SC0001004. M.D.dM.’s doctoral fellowship was partially supported by the Brazillian National Council for Scientific and Technological Development (CNPq) under grant 202982/2014‐9. 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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SP - 13260

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 32

ER -

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

Abstract

Bibliographical note

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