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Title: Thermal Stabilization of Metal–Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting

Abstract

Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOP-based catalytic single sites, preventing their aggregation even after exposure to air at 600 degrees C. We describe the nanocasting of NU-1000, a MOP with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 degrees C in air. Density functional theory calculations show a correlation betweenmore » the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [4];  [1];  [1];  [5];  [6];  [5];  [1];  [4];  [7];  [1];  [1];  [2];  [1]
  1. Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
  2. Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, United States
  3. Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States; Department of Chemistry, Austin College, 900 North Grand Avenue, Sherman, Texas 75090, United States
  4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
  5. Department of Chemistry and Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  6. Department of Chemistry and Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States; Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
  7. College of Science and Engineering Characterization Facility, University of Minnesota, 100 Union Street SE, Minneapolis, Minnesota 55455, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1392931
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 8; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
MOFs; NU-1000; Zr-MOFs; catalysis; cluster stabilization; metal-organic framework; nanocasting; oxozirconium clusters

Citation Formats

Malonzo, Camille D., Shaker, Sammy M., Ren, Limin, Prinslow, Steven D., Platero-Prats, Ana E., Gallington, Leighanne C., Borycz, Joshua, Thompson, Anthony B., Wang, Timothy C., Farha, Omar K., Hupp, Joseph T., Lu, Connie C., Chapman, Karena W., Myers, Jason C., Penn, R. Lee, Gagliardi, Laura, Tsapatsis, Michael, and Stein, Andreas. Thermal Stabilization of Metal–Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting. United States: N. p., 2016. Web. doi:10.1021/jacs.5b12688.
Malonzo, Camille D., Shaker, Sammy M., Ren, Limin, Prinslow, Steven D., Platero-Prats, Ana E., Gallington, Leighanne C., Borycz, Joshua, Thompson, Anthony B., Wang, Timothy C., Farha, Omar K., Hupp, Joseph T., Lu, Connie C., Chapman, Karena W., Myers, Jason C., Penn, R. Lee, Gagliardi, Laura, Tsapatsis, Michael, & Stein, Andreas. Thermal Stabilization of Metal–Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting. United States. https://doi.org/10.1021/jacs.5b12688
Malonzo, Camille D., Shaker, Sammy M., Ren, Limin, Prinslow, Steven D., Platero-Prats, Ana E., Gallington, Leighanne C., Borycz, Joshua, Thompson, Anthony B., Wang, Timothy C., Farha, Omar K., Hupp, Joseph T., Lu, Connie C., Chapman, Karena W., Myers, Jason C., Penn, R. Lee, Gagliardi, Laura, Tsapatsis, Michael, and Stein, Andreas. Fri . "Thermal Stabilization of Metal–Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting". United States. https://doi.org/10.1021/jacs.5b12688.
@article{osti_1392931,
title = {Thermal Stabilization of Metal–Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting},
author = {Malonzo, Camille D. and Shaker, Sammy M. and Ren, Limin and Prinslow, Steven D. and Platero-Prats, Ana E. and Gallington, Leighanne C. and Borycz, Joshua and Thompson, Anthony B. and Wang, Timothy C. and Farha, Omar K. and Hupp, Joseph T. and Lu, Connie C. and Chapman, Karena W. and Myers, Jason C. and Penn, R. Lee and Gagliardi, Laura and Tsapatsis, Michael and Stein, Andreas},
abstractNote = {Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOP-based catalytic single sites, preventing their aggregation even after exposure to air at 600 degrees C. We describe the nanocasting of NU-1000, a MOP with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 degrees C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.},
doi = {10.1021/jacs.5b12688},
url = {https://www.osti.gov/biblio/1392931}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 8,
volume = 138,
place = {United States},
year = {2016},
month = {2}
}

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