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Title: Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics

Abstract

Supported subnanometer clusters can exhibit precious catalytic properties not observed in their bulk analogues. Partially-oxidized Pd and Cu clusters are reported to catalyze the oxidative dehydrogenation of cyclohexane with high activity, and with distinctly different selectivity, producing primarily benzene or cyclohexene, respectively. Under reaction conditions, the structure and oxidation state of the two catalysts evolve differently which leads to either the desorption of the cyclohexene intermediate or to its deeper dehydrogenation. Under the applied reaction conditions the initially oxidized Pd and Cu clusters undergo partial reduction, which we show to be required for the selectivity to emerge. Both systems also have thermal access to multiple distinct structural forms yielding statistical ensembles. The structures within these ensembles evolve with the changing nature of the bound reaction intermediates differently for the two metals; the evolution is found pronounced in the Cu clusters, but only modest in Pd. Ultimately, we find the different selectivity observed experimentally for the Cu versus Pd clusters is controlled by differences in the collective structural and redox dynamics of their ensembles.

Authors:
 [1];  [2];  [2];  [3];  [1];  [1];  [4];  [5]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Univ. of California, Los Angeles, CA (United States)
  3. Argonne National Lab. (ANL), Lemont,, IL (United States)
  4. Univ. of California, Los Angeles, CA (United States); California NanoSystems Inst., Los Angeles, CA (United States)
  5. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Chicago, IL (United States); Czech Academy of Sciences, Prague (Czech Republic)
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). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; US Air Force Office of Scientific Research (AFOSR); USDOD; European Commission (EC)
OSTI Identifier:
1594251
Grant/Contract Number:  
SC0019152; AC02-06CH11357; FA9550-16-1-0141; 810310
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Name: ChemCatChem; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
cluster dynamics; cyclohexane oxidative dehydrogenation; deposited clusters; selectivity control; size-selected subnanometer clusters

Citation Formats

Halder, Avik, Ha, Mai‐Anh, Zhai, Huanchen, Yang, Bing, Pellin, Michael J., Seifert, Sönke, Alexandrova, Anastassia N., and Vajda, Stefan. Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics. United States: N. p., 2019. Web. doi:10.1002/cctc.201901795.
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Halder, Avik, Ha, Mai‐Anh, Zhai, Huanchen, Yang, Bing, Pellin, Michael J., Seifert, Sönke, Alexandrova, Anastassia N., & Vajda, Stefan. Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics. United States. doi:10.1002/cctc.201901795.
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Halder, Avik, Ha, Mai‐Anh, Zhai, Huanchen, Yang, Bing, Pellin, Michael J., Seifert, Sönke, Alexandrova, Anastassia N., and Vajda, Stefan. Mon . "Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics". United States. doi:10.1002/cctc.201901795.
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@article{osti_1594251,
title = {Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters: Selectivity Control by Specific Cluster Dynamics},
author = {Halder, Avik and Ha, Mai‐Anh and Zhai, Huanchen and Yang, Bing and Pellin, Michael J. and Seifert, Sönke and Alexandrova, Anastassia N. and Vajda, Stefan},
abstractNote = {Supported subnanometer clusters can exhibit precious catalytic properties not observed in their bulk analogues. Partially-oxidized Pd and Cu clusters are reported to catalyze the oxidative dehydrogenation of cyclohexane with high activity, and with distinctly different selectivity, producing primarily benzene or cyclohexene, respectively. Under reaction conditions, the structure and oxidation state of the two catalysts evolve differently which leads to either the desorption of the cyclohexene intermediate or to its deeper dehydrogenation. Under the applied reaction conditions the initially oxidized Pd and Cu clusters undergo partial reduction, which we show to be required for the selectivity to emerge. Both systems also have thermal access to multiple distinct structural forms yielding statistical ensembles. The structures within these ensembles evolve with the changing nature of the bound reaction intermediates differently for the two metals; the evolution is found pronounced in the Cu clusters, but only modest in Pd. Ultimately, we find the different selectivity observed experimentally for the Cu versus Pd clusters is controlled by differences in the collective structural and redox dynamics of their ensembles.},
doi = {10.1002/cctc.201901795},
journal = {ChemCatChem},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {11}
}
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DOI:  10.1002/cctc.201901795
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