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

Abstract

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 openmore » up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

Authors:
 [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
Publication Date:
Research Org.:
Univ. of California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1426143
Grant/Contract Number:  
SC0008055
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Xue, Teng, Lin, Zhaoyang, Chiu, Chin-Yi, Li, Yongjia, Ruan, Lingyan, Wang, Gongming, Zhao, Zipeng, Lee, Chain, Duan, Xiangfeng, and Huang, Yu. Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol. United States: N. p., 2017. Web. doi:10.1126/sciadv.1600615.
Xue, Teng, Lin, Zhaoyang, Chiu, Chin-Yi, Li, Yongjia, Ruan, Lingyan, Wang, Gongming, Zhao, Zipeng, Lee, Chain, Duan, Xiangfeng, & Huang, Yu. Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol. United States. doi:10.1126/sciadv.1600615.
Xue, Teng, Lin, Zhaoyang, Chiu, Chin-Yi, Li, Yongjia, Ruan, Lingyan, Wang, Gongming, Zhao, Zipeng, Lee, Chain, Duan, Xiangfeng, and Huang, Yu. Fri . "Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol". United States. doi:10.1126/sciadv.1600615. https://www.osti.gov/servlets/purl/1426143.
@article{osti_1426143,
title = {Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol},
author = {Xue, Teng and Lin, Zhaoyang and Chiu, Chin-Yi and Li, Yongjia and Ruan, Lingyan and Wang, Gongming and Zhao, Zipeng and Lee, Chain and Duan, Xiangfeng and Huang, Yu},
abstractNote = {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.},
doi = {10.1126/sciadv.1600615},
journal = {Science Advances},
number = 1,
volume = 3,
place = {United States},
year = {2017},
month = {1}
}

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Works referenced in this record:

Allylic C−H Acetoxylation with a 4,5-Diazafluorenone-Ligated Palladium Catalyst: A Ligand-Based Strategy To Achieve Aerobic Catalytic Turnover
journal, November 2010

  • Campbell, Alison N.; White, Paul B.; Guzei, Ilia A.
  • Journal of the American Chemical Society, Vol. 132, Issue 43
  • DOI: 10.1021/ja105829t

Synthesis, Characterization, and Catalytic Applications of a Palladium-Nanoparticle-Cored Dendrimer
journal, December 2003

  • Gopidas, Karical R.; Whitesell, James K.; Fox, Marye Anne
  • Nano Letters, Vol. 3, Issue 12
  • DOI: 10.1021/nl0348490

Chiral Bisphosphine BINAP-Stabilized Gold and Palladium Nanoparticles with Small Size and Their Palladium Nanoparticle-Catalyzed Asymmetric Reaction
journal, December 2003

  • Tamura, Masaru; Fujihara, Hisashi
  • Journal of the American Chemical Society, Vol. 125, Issue 51
  • DOI: 10.1021/ja0369055

Transition-metal nanoparticles: synthesis, stability and the leaching issue
journal, January 2008

  • Pachón, Laura Durán; Rothenberg, Gadi
  • Applied Organometallic Chemistry, Vol. 22, Issue 6
  • DOI: 10.1002/aoc.1382

Recent advancements and challenges of palladiumII-catalyzed oxidation reactions with molecular oxygen as the sole oxidant
journal, January 2009

  • Gligorich, Keith M.; Sigman, Matthew S.
  • Chemical Communications, Issue 26
  • DOI: 10.1039/b902868d

Tailoring Molecular Specificity Toward a Crystal Facet: a Lesson From Biorecognition Toward Pt{111}
journal, January 2013

  • Ruan, Lingyan; Ramezani-Dakhel, Hadi; Chiu, Chin-Yi
  • Nano Letters, Vol. 13, Issue 2
  • DOI: 10.1021/nl400022g

Nanocrystals from solutions: catalysts
journal, January 2014

  • Wu, Yuen; Wang, Dingsheng; Li, Yadong
  • Chem. Soc. Rev., Vol. 43, Issue 7
  • DOI: 10.1039/C3CS60221D

Convenient and Efficient Pd-Catalyzed Regioselective Oxyfunctionalization of Terminal Olefins by Using Molecular Oxygen as Sole Reoxidant
journal, January 2006

  • Mitsudome, Takato; Umetani, Takuya; Nosaka, Naoya
  • Angewandte Chemie, Vol. 118, Issue 3
  • DOI: 10.1002/ange.200502886

Wacker-Type Oxidation of Internal Olefins Using a PdCl2/N,N-Dimethylacetamide Catalyst System under Copper-Free Reaction Conditions
journal, December 2009

  • Mitsudome, Takato; Mizumoto, Keiichi; Mizugaki, Tomoo
  • Angewandte Chemie International Edition, Vol. 49, Issue 7
  • DOI: 10.1002/anie.200905184

Dehydrogenation of cyclohexanones catalyzed by palladium(II) trifluoroacetate
journal, June 1982


Intramolecular Pd(II)-Catalyzed Aerobic Oxidative Amination of Alkenes: Synthesis of Six-Membered N -Heterocycles
journal, February 2012

  • Lu, Zhan; Stahl, Shannon S.
  • Organic Letters, Vol. 14, Issue 5
  • DOI: 10.1021/ol300030w

Rational Synthesis of Heterostructured Nanoparticles with Morphology Control
journal, May 2010

  • Wang, Chao; Tian, Wende; Ding, Yong
  • Journal of the American Chemical Society, Vol. 132, Issue 18
  • DOI: 10.1021/ja101305x

3-Mercaptobutyric Acid as an Effective Capping Agent for Highly Luminescent CdTe Quantum Dots: New Insight into the Selection of Mercapto Acids
journal, May 2012

  • Fang, Tan; Ma, Kaiguo; Ma, Lili
  • The Journal of Physical Chemistry C, Vol. 116, Issue 22
  • DOI: 10.1021/jp302820u

A Pt-Cluster-Based Heterogeneous Catalyst for Homogeneous Catalytic Reactions: X-ray Absorption Spectroscopy and Reaction Kinetic Studies of Their Activity and Stability against Leaching
journal, August 2011

  • Li, Yimin; Liu, Jack Hung-Chang; Witham, Cole A.
  • Journal of the American Chemical Society, Vol. 133, Issue 34
  • DOI: 10.1021/ja204191t

Confining the Nucleation and Overgrowth of Rh to the {111} Facets of Pd Nanocrystal Seeds: The Roles of Capping Agent and Surface Diffusion
journal, October 2013

  • Xie, Shuifen; Peng, Hsin-Chieh; Lu, Ning
  • Journal of the American Chemical Society, Vol. 135, Issue 44
  • DOI: 10.1021/ja408768e

Self-Assembly of a Catalytic Multivalent Peptide–Nanoparticle Complex
journal, May 2012

  • Zaramella, Davide; Scrimin, Paolo; Prins, Leonard J.
  • Journal of the American Chemical Society, Vol. 134, Issue 20
  • DOI: 10.1021/ja302754h

Polyol Synthesis of Ultrathin Pd Nanowires via Attachment-Based Growth and Their Enhanced Activity towards Formic Acid Oxidation
journal, August 2013

  • Wang, Yi; Choi, Sang-Il; Zhao, Xin
  • Advanced Functional Materials, Vol. 24, Issue 1
  • DOI: 10.1002/adfm.201302339

Straightforward Solvent-Free Heterogeneous Palladium-Catalyzed Synthesis of Arylamines from Nonaromatic Substrates by Dehydrogenative Alkylation
journal, August 2013

  • Sutter, Marc; Duclos, Marie-Christine; Guicheret, Boris
  • ACS Sustainable Chemistry & Engineering, Vol. 1, Issue 11
  • DOI: 10.1021/sc4002164

Inorganic concepts relevant to metal binding, activity, and toxicity in a biological system
journal, December 1991


Reaction-activated palladium catalyst for dehydrogenation of substituted cyclohexanones to phenols and H 2 without oxidants and hydrogen acceptors
journal, January 2015

  • Zhang, Jingwu; Jiang, Qiangqiang; Yang, Dejun
  • Chemical Science, Vol. 6, Issue 8
  • DOI: 10.1039/C5SC01044F

Aerobic Dehydrogenation of Cyclohexanone to Phenol Catalyzed by Pd(TFA) 2 /2-Dimethylaminopyridine: Evidence for the Role of Pd Nanoparticles
journal, May 2013

  • Pun, Doris; Diao, Tianning; Stahl, Shannon S.
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja403165u

Green, Catalytic Oxidation of Alcohols in Water
journal, March 2000


Oriented assembly of polyhedral plasmonic nanoparticle clusters
journal, April 2013

  • Henzie, J.; Andrews, S. C.; Ling, X. Y.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 17
  • DOI: 10.1073/pnas.1218616110

Platinum nanocrystals selectively shaped using facet-specific peptide sequences
journal, April 2011

  • Chiu, Chin-Yi; Li, Yujing; Ruan, Lingyan
  • Nature Chemistry, Vol. 3, Issue 5
  • DOI: 10.1038/nchem.1025

Multiscale Periodic Assembly of Striped Nanocrystal Superlattice Films on a Liquid Surface
journal, February 2011

  • Dong, Angang; Chen, Jun; Oh, Soong Ju
  • Nano Letters, Vol. 11, Issue 2
  • DOI: 10.1021/nl104208x

Green, Catalytic Oxidations of Alcohols
journal, September 2002

  • Sheldon, Roger A.; Arends, Isabel W. C. E.; ten Brink, Gerd-Jan
  • Accounts of Chemical Research, Vol. 35, Issue 9
  • DOI: 10.1021/ar010075n

Palladium-Catalyzed Aerobic Dehydrogenation of Substituted Cyclohexanones to Phenols
journal, June 2011


    Works referencing / citing this record:

    From recovered metal waste to high-performance palladium catalysts
    journal, January 2017

    • Jantan, Khairil A.; Kwok, Chuek Yee; Chan, Kuang Wen
    • Green Chemistry, Vol. 19, Issue 24
    • DOI: 10.1039/c7gc02678a

    From recovered metal waste to high-performance palladium catalysts
    journal, January 2017

    • Jantan, Khairil A.; Kwok, Chuek Yee; Chan, Kuang Wen
    • Green Chemistry, Vol. 19, Issue 24
    • DOI: 10.1039/c7gc02678a