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Title: Metal Nanoparticles Catalyzed Selective Carbon–Carbon Bond Activation in the Liquid Phase

Abstract

Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. Here, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy.

Authors:
 [1];  [2];  [2];  [2];  [2];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Department of Chemistry, University of California, Berkeley, California 94720, United States; Chemical Science Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
  2. Department of Chemistry, University of California, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1336474
Alternate Identifier(s):
OSTI ID: 1464139
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 27; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Ye, Rong, Yuan, Bing, Zhao, Jie, Ralston, Walter T., Wu, Chung-Yeh, Unel Barin, Ebru, Toste, F. Dean, and Somorjai, Gabor A. Metal Nanoparticles Catalyzed Selective Carbon–Carbon Bond Activation in the Liquid Phase. United States: N. p., 2016. Web. doi:10.1021/jacs.6b03977.
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Ye, Rong, Yuan, Bing, Zhao, Jie, Ralston, Walter T., Wu, Chung-Yeh, Unel Barin, Ebru, Toste, F. Dean, & Somorjai, Gabor A. Metal Nanoparticles Catalyzed Selective Carbon–Carbon Bond Activation in the Liquid Phase. United States. https://doi.org/10.1021/jacs.6b03977
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Ye, Rong, Yuan, Bing, Zhao, Jie, Ralston, Walter T., Wu, Chung-Yeh, Unel Barin, Ebru, Toste, F. Dean, and Somorjai, Gabor A. Mon . "Metal Nanoparticles Catalyzed Selective Carbon–Carbon Bond Activation in the Liquid Phase". United States. https://doi.org/10.1021/jacs.6b03977.
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@article{osti_1336474,
title = {Metal Nanoparticles Catalyzed Selective Carbon–Carbon Bond Activation in the Liquid Phase},
author = {Ye, Rong and Yuan, Bing and Zhao, Jie and Ralston, Walter T. and Wu, Chung-Yeh and Unel Barin, Ebru and Toste, F. Dean and Somorjai, Gabor A.},
abstractNote = {Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. Here, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy.},
doi = {10.1021/jacs.6b03977},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 138,
place = {United States},
year = {Mon Jun 20 00:00:00 EDT 2016},
month = {Mon Jun 20 00:00:00 EDT 2016}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/jacs.6b03977
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