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Title: Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework

Abstract

A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Finally, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [5];  [4]; ORCiD logo [1]; ORCiD logo [6]
  1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  2. Physical and Computational Science Directorate, PNNL, Richland, Washington 99352, United States
  3. Environmental Molecular Sciences Laboratory, PNNL, Richland, Washington 99352, United States
  4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439-4858, United States
  5. Physical and Computational Science Directorate, PNNL, Richland, Washington 99352, United States; Materials Science and Engineering, University of Washington, Seattle, Washington 98195, United States
  6. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States; Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1422311
Report Number(s):
PNNL-SA-131981
Journal ID: ISSN 0897-4756; 48583; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 29; Journal Issue: 12
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Buru, Cassandra T., Li, Peng, Mehdi, B. Layla, Dohnalkova, Alice, Platero-Prats, Ana E., Browning, Nigel D., Chapman, Karena W., Hupp, Joseph T., and Farha, Omar K. Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b00750.
Buru, Cassandra T., Li, Peng, Mehdi, B. Layla, Dohnalkova, Alice, Platero-Prats, Ana E., Browning, Nigel D., Chapman, Karena W., Hupp, Joseph T., & Farha, Omar K. Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework. United States. doi:10.1021/acs.chemmater.7b00750.
Buru, Cassandra T., Li, Peng, Mehdi, B. Layla, Dohnalkova, Alice, Platero-Prats, Ana E., Browning, Nigel D., Chapman, Karena W., Hupp, Joseph T., and Farha, Omar K. Mon . "Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework". United States. doi:10.1021/acs.chemmater.7b00750.
@article{osti_1422311,
title = {Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework},
author = {Buru, Cassandra T. and Li, Peng and Mehdi, B. Layla and Dohnalkova, Alice and Platero-Prats, Ana E. and Browning, Nigel D. and Chapman, Karena W. and Hupp, Joseph T. and Farha, Omar K.},
abstractNote = {A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Finally, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.},
doi = {10.1021/acs.chemmater.7b00750},
journal = {Chemistry of Materials},
number = 12,
volume = 29,
place = {United States},
year = {Mon May 22 00:00:00 EDT 2017},
month = {Mon May 22 00:00:00 EDT 2017}
}
  • A Keggin-type polyoxometalate (H 3PW 12O 40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW 12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Lastly, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW 12@NU-1000 was shown to have a higher catalytic activity than eithermore » of the individual constituents alone.« less
  • Stepwise adsorption in a metal-organic framework with both micro- and meso-pores is caused by adsorbates first filling the micropores, then adsorbing along the mesopore walls, and finally filling the mesopores.
  • A polyoxometalate supported by the metal–organic framework, NU-1000, undergoes migration from the mesopore to the micropore when heated.
  • On account of their structural similarity to cofactors found in many metallo-enzymes, metalloporphyrins are obvious potential building blocks for catalytically active, metal-organic framework (MOF) materials. While numerous porphyrin-based MOFs have already been described, versions featuring highly accessible active sites and permanent microporosity are remarkably scarce. Indeed, of the more than 70 previously reported porphyrinic MOFs, only one has been shown to be both permanently microporous and contain internally accessible active sites for chemical catalysis. Attempts to generalize the design approach used in this single successful case have failed. Reported here, however, is the synthesis of an extended family of MOFsmore » that directly incorporate a variety of metalloporphyrins (specifically Al{sup 3+}, Zn{sup 2+}, Pd{sup 2+}, Mn{sup 3+}, and Fe{sup 3+} complexes). These robust porphyrinic materials (RPMs) feature large channels and readily accessible active sites. As an illustrative example, one of the manganese-containing RPMs is shown to be catalytically competent for the oxidation of alkenes and alkanes.« less
  • Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework MIL-101 without deposition of Pt nanoparticles on the external surfaces of framework by using a 'double solvents' method. The resulting Pt@MIL-101 composites with different Pt loadings represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis; solid-phase ammonia borane thermal dehy-drogenation and gas-phase CO oxidation. The observed excellent catalytic performances are at-tributed to the small Pt nanoparticles within the pores of MIL-101. 'We are thankful to AIST and METI for financial support. TA & AK are thankful formore » support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is operated by Battelle.'« less