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

Ken Ichi Otake, Jingyun Ye, Mukunda Mandal, Timur Islamoglu, Cassandra T. Buru, Joseph T. Hupp, Massimiliano Delferro, Donald G Truhlar, Chris Cramer, Omar K. Farha

Research output: Contribution to journalArticle

2 Citations (Scopus)

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-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. These findings offer insights and methodology for the catalytic investigation of SSHCs in MOFs.

Original languageEnglish (US)
Pages (from-to)5383-5390
Number of pages8
JournalACS Catalysis
DOIs
StatePublished - Jan 1 2019

Fingerprint

Metals
Catalysts
Acids
Density functional theory
Hafnium
Vibrational spectroscopy
Catalyst deactivation
Level control
Palladium
Catalyst supports
Electronic properties
Oxides
Functional groups
Electronic structure
Structural properties
Catalyst activity
Agglomeration
X ray photoelectron spectroscopy
X rays

Keywords

  • metal-organic frameworks
  • oxidative Heck reaction
  • palladium catalyst
  • single-crystal X-ray diffraction
  • single-site heterogeneous catalyst

Cite this

Otake, K. I., Ye, J., Mandal, M., Islamoglu, T., Buru, C. T., Hupp, J. T., ... Farha, O. K. (2019). Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal-Organic Frameworks. ACS Catalysis, 5383-5390. https://doi.org/10.1021/acscatal.9b01043

Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal-Organic Frameworks. / Otake, Ken Ichi; Ye, Jingyun; Mandal, Mukunda; Islamoglu, Timur; Buru, Cassandra T.; Hupp, Joseph T.; Delferro, Massimiliano; Truhlar, Donald G; Cramer, Chris; Farha, Omar K.

In: ACS Catalysis, 01.01.2019, p. 5383-5390.

Research output: Contribution to journalArticle

Otake, Ken Ichi ; Ye, Jingyun ; Mandal, Mukunda ; Islamoglu, Timur ; Buru, Cassandra T. ; Hupp, Joseph T. ; Delferro, Massimiliano ; Truhlar, Donald G ; Cramer, Chris ; Farha, Omar K. / Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal-Organic Frameworks. In: ACS Catalysis. 2019 ; pp. 5383-5390.
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AU - Hupp, Joseph T.

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