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Title: Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol

Journal Article · · Science Advances
 [1];  [2];  [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [1];  [2];  [3]; ORCiD logo [4]
  1. Univ. of California, Los Angeles, CA (United States). Department of Materials Science and Engineering
  2. Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry
  3. Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry and California NanoSystems Institute
  4. Univ. of California, Los Angeles, CA (United States). Department of Materials Science and Engineering and California NanoSystems Institute
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Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts to date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.

Research Organization:
Univ. of California, Los Angeles, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
SC0008055
OSTI ID:
1426143
Journal Information:
Science Advances, Vol. 3, Issue 1; ISSN 2375-2548
Publisher:
AAASCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

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Cited By (5)

Palladium-Catalyzed Regioselective Oxidative Annulation of Cyclohexanones and 2-Aminophenyl Ketones Using Molecular Oxygen as the Sole Oxidant journal October 2017
The Effect of Residual Palladium Catalyst Contamination on the Photocatalytic Hydrogen Evolution Activity of Conjugated Polymers journal October 2018
From recovered metal waste to high-performance palladium catalysts journal January 2017
Retracted Article: A miraculous chiral Ir–Rh bimetallic nanocatalyst for asymmetric hydrogenation of activated ketones journal January 2018
Electrophilic substitution reaction as a facile and general approach for reactive removal of native ligands from nanocrystals surface journal October 2018

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