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 »
- Authors:
-
[1];
[1];
[4]
- Univ. of California, Los Angeles, CA (United States). Department of Materials Science and Engineering
- Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry
- Univ. of California, Los Angeles, CA (United States). Department of Chemistry and Biochemistry and California NanoSystems Institute
- 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. https://doi.org/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. https://doi.org/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}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 20 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
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
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
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
Transition-metal nanoparticles: synthesis, stability and the leaching issue
journal, January 2008
- Pachón, Laura Durán; Rothenberg, Gadi
- Applied Organometallic Chemistry, Vol. 22, Issue 6
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
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
Efficient Dehydrogenation of Amines and Carbonyl Compounds Catalyzed by a Tetranuclear Ruthenium-μ-oxo-μ-hydroxo-hydride Complex
journal, February 2009
- Yi, Chae S.; Lee, Do W.
- Organometallics, Vol. 28, Issue 4
One-Pot Syntheses of α,β-Unsaturated Carbonyl Compounds through Palladium-Mediated Dehydrogenation of Ketones, Aldehydes, Esters, Lactones and Amides
journal, May 2010
- Muzart, Jacques
- European Journal of Organic Chemistry, Vol. 2010, Issue 20
Nanocrystals from solutions: catalysts
journal, January 2014
- Wu, Yuen; Wang, Dingsheng; Li, Yadong
- Chem. Soc. Rev., Vol. 43, Issue 7
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
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
Dehydrogenation of cyclohexanones catalyzed by palladium(II) trifluoroacetate
journal, June 1982
- Muzart, J.; Pete, J. P.
- Journal of Molecular Catalysis, Vol. 15, Issue 3
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
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
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
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
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
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
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
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
Inorganic concepts relevant to metal binding, activity, and toxicity in a biological system
journal, December 1991
- Hoeschele, James D.; Turner, James E.; England, M. Wendy
- Science of The Total Environment, Vol. 109-110
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
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
Green, Catalytic Oxidation of Alcohols in Water
journal, March 2000
- Brink, G. t.
- Science, Vol. 287, Issue 5458
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
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
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
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
Palladium-Catalyzed Aerobic Dehydrogenation of Substituted Cyclohexanones to Phenols
journal, June 2011
- Izawa, Y.; Pun, D.; Stahl, S. S.
- Science, Vol. 333, Issue 6039
Straightforward heterogeneous palladium catalyzed synthesis of aryl ethers and aryl amines via a solvent free aerobic and non-aerobic dehydrogenative arylation
journal, January 2013
- Sutter, Marc; Sotto, Nicolas; Raoul, Yann
- Green Chem., Vol. 15, Issue 2
Wacker-Type Oxidation of Internal Olefins Using a PdCl 2 / N , N -Dimethylacetamide Catalyst System under Copper-Free Reaction Conditions
journal, February 2010
- Mitsudome, Takato; Mizumoto, Keiichi; Mizugaki, Tomoo
- Angewandte Chemie, Vol. 122, Issue 7
Convenient and Efficient Pd-Catalyzed Regioselective Oxyfunctionalization of Terminal Olefins by Using Molecular Oxygen as Sole Reoxidant.
journal, May 2006
- Mitsudome, Takato; Umetani, Takuya; Nosaka, Naoya
- ChemInform, Vol. 37, Issue 21
Works referencing / citing this record:
Palladium-Catalyzed Regioselective Oxidative Annulation of Cyclohexanones and 2-Aminophenyl Ketones Using Molecular Oxygen as the Sole Oxidant
journal, October 2017
- Mu, Wan-Lu; Wang, Meirong; Li, Hui-Jing
- Advanced Synthesis & Catalysis, Vol. 359, Issue 23
The Effect of Residual Palladium Catalyst Contamination on the Photocatalytic Hydrogen Evolution Activity of Conjugated Polymers
journal, October 2018
- Kosco, Jan; Sachs, Michael; Godin, Robert
- Advanced Energy Materials, Vol. 8, Issue 34
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
Retracted Article: A miraculous chiral Ir–Rh bimetallic nanocatalyst for asymmetric hydrogenation of activated ketones
journal, January 2018
- Xue, Xiuru; Zhao, Zhaohui; Wang, Yanhua
- Organic Chemistry Frontiers, Vol. 5, Issue 24
Electrophilic substitution reaction as a facile and general approach for reactive removal of native ligands from nanocrystals surface
journal, October 2018
- Zhao, Kai; Niu, Wenbin; Wang, Yunpeng
- Nanotechnology, Vol. 30, Issue 1