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Title: Tandem catalysis by palladium nanoclusters encapsulated in metal–organic frameworks

Abstract

A bifunctional Zr-MOF catalyst containing palladium nanoclusters (NCs) has been developed. The formation of Pd NCs was confirmed by transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS). Combining the oxidation activity of Pd NCs and the acetalization activity of the Lewis acid sites in UiO-66-NH 2, this catalyst (Pd@UiO-66-NH 2) exhibits excellent catalytic activity and selectivity in a one-pot tandem oxidation-acetalization reaction. This catalyst shows 99.9% selectivity to benzaldehyde ethylene acetal in the tandem reaction of benzyl alcohol and ethylene glycol at 99.9% conversion of benzyl alcohol. We also examined various substituted benzyl alcohols and found that alcohols with electron-donating groups showed better conversion and selectivity compared to those with electron-withdrawing groups. As a result, we further proved that there was no leaching of active catalytic species during the reaction and the catalyst can be recycled at least five times without significant deactivation.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1225525
Report Number(s):
IS-J-8534
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
200021-129511
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 4; Journal Issue: 10; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; tandem catalysis; acetalization; bifunctional catalysts; UiO-66; Zr-MOF; nanoclusters; heterogeneous catalysis

Citation Formats

Li, Xinle, Guo, Zhiyong, Xiao, Chaoxian, Goh, Tian Wei, Tesfagaber, Daniel, and Huang, Wenyu. Tandem catalysis by palladium nanoclusters encapsulated in metal–organic frameworks. United States: N. p., 2014. Web. doi:10.1021/cs5006635.
Li, Xinle, Guo, Zhiyong, Xiao, Chaoxian, Goh, Tian Wei, Tesfagaber, Daniel, & Huang, Wenyu. Tandem catalysis by palladium nanoclusters encapsulated in metal–organic frameworks. United States. doi:10.1021/cs5006635.
Li, Xinle, Guo, Zhiyong, Xiao, Chaoxian, Goh, Tian Wei, Tesfagaber, Daniel, and Huang, Wenyu. Mon . "Tandem catalysis by palladium nanoclusters encapsulated in metal–organic frameworks". United States. doi:10.1021/cs5006635. https://www.osti.gov/servlets/purl/1225525.
@article{osti_1225525,
title = {Tandem catalysis by palladium nanoclusters encapsulated in metal–organic frameworks},
author = {Li, Xinle and Guo, Zhiyong and Xiao, Chaoxian and Goh, Tian Wei and Tesfagaber, Daniel and Huang, Wenyu},
abstractNote = {A bifunctional Zr-MOF catalyst containing palladium nanoclusters (NCs) has been developed. The formation of Pd NCs was confirmed by transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS). Combining the oxidation activity of Pd NCs and the acetalization activity of the Lewis acid sites in UiO-66-NH2, this catalyst (Pd@UiO-66-NH2) exhibits excellent catalytic activity and selectivity in a one-pot tandem oxidation-acetalization reaction. This catalyst shows 99.9% selectivity to benzaldehyde ethylene acetal in the tandem reaction of benzyl alcohol and ethylene glycol at 99.9% conversion of benzyl alcohol. We also examined various substituted benzyl alcohols and found that alcohols with electron-donating groups showed better conversion and selectivity compared to those with electron-withdrawing groups. As a result, we further proved that there was no leaching of active catalytic species during the reaction and the catalyst can be recycled at least five times without significant deactivation.},
doi = {10.1021/cs5006635},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 10,
volume = 4,
place = {United States},
year = {2014},
month = {8}
}

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Cited by: 70 works
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Works referencing / citing this record:

Titanium-Carboxylate Metal-Organic Framework Based on an Unprecedented Ti-Oxo Chain Cluster
journal, October 2018

  • Keum, Yesub; Park, Seonghun; Chen, Ying-Pin
  • Angewandte Chemie International Edition, Vol. 57, Issue 45
  • DOI: 10.1002/anie.201809762

Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
journal, November 2018

  • Yang, Shuliang; Peng, Li; Bulut, Safak
  • Chemistry - A European Journal, Vol. 25, Issue 9
  • DOI: 10.1002/chem.201803157

Metal organic frameworks from extended, conjugated pentiptycene-based ligands
journal, January 2015

  • Crane, Angela K.; White, Nicholas G.; MacLachlan, Mark J.
  • CrystEngComm, Vol. 17, Issue 26
  • DOI: 10.1039/c5ce00886g

Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation–acetalization of olefins
journal, January 2016

  • Wang, Peng; Liu, Huan; Li, Yong-Qi
  • Catalysis Science & Technology, Vol. 6, Issue 11
  • DOI: 10.1039/c5cy01827g

Size-confined growth of atom-precise nanoclusters in metal–organic frameworks and their catalytic applications
journal, January 2016

  • Liu, Lingli; Song, Yongbo; Chong, Hanbao
  • Nanoscale, Vol. 8, Issue 3
  • DOI: 10.1039/c5nr06930k

An unprecedented anionic Ln-MOF with a cage-within-cage motif: spontaneous reduction and immobilization of ion-exchanged Pd( ii ) to Pd-NPs in the framework
journal, January 2015

  • Han, Yun-Hu; Tian, Chong-Bin; Lin, Ping
  • Journal of Materials Chemistry A, Vol. 3, Issue 48
  • DOI: 10.1039/c5ta04937g

Titanium-Carboxylate Metal-Organic Framework Based on an Unprecedented Ti-Oxo Chain Cluster
journal, October 2018

  • Keum, Yesub; Park, Seonghun; Chen, Ying-Pin
  • Angewandte Chemie International Edition, Vol. 57, Issue 45
  • DOI: 10.1002/anie.201809762

Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
journal, November 2018

  • Yang, Shuliang; Peng, Li; Bulut, Safak
  • Chemistry - A European Journal, Vol. 25, Issue 9
  • DOI: 10.1002/chem.201803157

Metal organic frameworks from extended, conjugated pentiptycene-based ligands
journal, January 2015

  • Crane, Angela K.; White, Nicholas G.; MacLachlan, Mark J.
  • CrystEngComm, Vol. 17, Issue 26
  • DOI: 10.1039/c5ce00886g

Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation–acetalization of olefins
journal, January 2016

  • Wang, Peng; Liu, Huan; Li, Yong-Qi
  • Catalysis Science & Technology, Vol. 6, Issue 11
  • DOI: 10.1039/c5cy01827g

Size-confined growth of atom-precise nanoclusters in metal–organic frameworks and their catalytic applications
journal, January 2016

  • Liu, Lingli; Song, Yongbo; Chong, Hanbao
  • Nanoscale, Vol. 8, Issue 3
  • DOI: 10.1039/c5nr06930k

An unprecedented anionic Ln-MOF with a cage-within-cage motif: spontaneous reduction and immobilization of ion-exchanged Pd( ii ) to Pd-NPs in the framework
journal, January 2015

  • Han, Yun-Hu; Tian, Chong-Bin; Lin, Ping
  • Journal of Materials Chemistry A, Vol. 3, Issue 48
  • DOI: 10.1039/c5ta04937g

Utilisation of gold nanoparticles on amine-functionalised UiO-66 (NH 2 -UiO-66) nanocrystals for selective tandem catalytic reactions
journal, January 2016

  • Hinde, Christopher S.; Webb, William R.; Chew, Benny K. J.
  • Chemical Communications, Vol. 52, Issue 39
  • DOI: 10.1039/c6cc02169g