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Title: Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks

Abstract

Single-site heterogeneous catalysts (SSHCs) play important roles in fundamental science and technology, owing to the molecular level control of structure–support interactions that is possible in these systems. Recently, SSHCs supported by acidic oxides have attracted particular interest because catalytically active metal centers can be formed at the surface sites. Here, we incorporated a palladium SSHC in phosphated and sulfated metal–organic frameworks (MOFs), hafnium-based MOF-808 (Hf-MOF-808-PO 4 and Hf-MOF-808-SO 4). The structural and electronic properties of the Pd(II) sites coordinated to the acidic sites in these MOFs were investigated through X-ray photoelectron spectroscopy, vibrational spectroscopy, X-ray crystallographic techniques, catalytic studies, and quantum mechanical electronic structure calculations employing density functional theory. We demonstrated that the presence of node-bound acidic functional groups stabilizes the Pd(II) site in these MOFs, resulting in enhanced catalytic activities (compared to in the nonacid functionalized Hf-MOF-808) in the oxidative Heck reaction where Pd(II) is the active species. The density functional calculations support the interpretation that the acid functionalization of the MOF node can stabilize the Pd(0) intermediate state during the catalytic reactions, thereby suppressing Pd(0) aggregation leading to catalyst deactivation. Furthermore, these findings offer insights and methodology for the catalytic investigation of SSHCs in MOFs.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Northwestern Univ., Evanston, IL (United States); Kyoto Univ., Kyoto (Japan)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1526641
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 6; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal−organic frameworks; single-site heterogeneous catalyst; oxidative Heck reaction; palladium catalyst; single-crystal X-ray diffraction

Citation Formats

Otake, Ken-ichi, Ye, Jingyun, Mandal, Mukunda, Islamoglu, Timur, Buru, Cassandra T., Hupp, Joseph T., Delferro, Massimiliano, Truhlar, Donald G., Cramer, Christopher J., and Farha, Omar K. Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks. United States: N. p., 2019. Web. doi:10.1021/acscatal.9b01043.
Otake, Ken-ichi, Ye, Jingyun, Mandal, Mukunda, Islamoglu, Timur, Buru, Cassandra T., Hupp, Joseph T., Delferro, Massimiliano, Truhlar, Donald G., Cramer, Christopher J., & Farha, Omar K. Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks. United States. doi:10.1021/acscatal.9b01043.
Otake, Ken-ichi, Ye, Jingyun, Mandal, Mukunda, Islamoglu, Timur, Buru, Cassandra T., Hupp, Joseph T., Delferro, Massimiliano, Truhlar, Donald G., Cramer, Christopher J., and Farha, Omar K. Mon . "Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks". United States. doi:10.1021/acscatal.9b01043.
@article{osti_1526641,
title = {Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks},
author = {Otake, Ken-ichi and Ye, Jingyun and Mandal, Mukunda and Islamoglu, Timur and Buru, Cassandra T. and Hupp, Joseph T. and Delferro, Massimiliano and Truhlar, Donald G. and Cramer, Christopher J. and Farha, Omar K.},
abstractNote = {Single-site heterogeneous catalysts (SSHCs) play important roles in fundamental science and technology, owing to the molecular level control of structure–support interactions that is possible in these systems. Recently, SSHCs supported by acidic oxides have attracted particular interest because catalytically active metal centers can be formed at the surface sites. Here, we incorporated a palladium SSHC in phosphated and sulfated metal–organic frameworks (MOFs), hafnium-based MOF-808 (Hf-MOF-808-PO4 and Hf-MOF-808-SO4). The structural and electronic properties of the Pd(II) sites coordinated to the acidic sites in these MOFs were investigated through X-ray photoelectron spectroscopy, vibrational spectroscopy, X-ray crystallographic techniques, catalytic studies, and quantum mechanical electronic structure calculations employing density functional theory. We demonstrated that the presence of node-bound acidic functional groups stabilizes the Pd(II) site in these MOFs, resulting in enhanced catalytic activities (compared to in the nonacid functionalized Hf-MOF-808) in the oxidative Heck reaction where Pd(II) is the active species. The density functional calculations support the interpretation that the acid functionalization of the MOF node can stabilize the Pd(0) intermediate state during the catalytic reactions, thereby suppressing Pd(0) aggregation leading to catalyst deactivation. Furthermore, these findings offer insights and methodology for the catalytic investigation of SSHCs in MOFs.},
doi = {10.1021/acscatal.9b01043},
journal = {ACS Catalysis},
number = 6,
volume = 9,
place = {United States},
year = {2019},
month = {4}
}

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This content will become publicly available on April 29, 2020
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