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

Halder, Avik; Ha, Mai‐Anh; Zhai, Huanchen; Yang, Bing; Pellin, Michael J.; Seifert, Sönke; Alexandrova, Anastassia N.; Vajda, Stefan

doi:10.1002/cctc.201901795

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

Journal Article · Mon Nov 04 00:00:00 UTC 2019 · ChemCatChem

DOI: https://doi.org/10.1002/cctc.201901795 · OSTI ID:1594251

Halder, Avik ^[1]; Ha, Mai‐Anh ^[2]; Zhai, Huanchen ^[2]; Yang, Bing ^[3]; Pellin, Michael J. ^[4]; Seifert, Sönke ^[4]; Alexandrova, Anastassia N. ^[5]; Vajda, Stefan ^[6]

Argonne National Lab. (ANL), Lemont, IL (United States); University of California, Los Angeles
Univ. of California, Los Angeles, CA (United States)
Argonne National Lab. (ANL), Lemont,, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of California, Los Angeles, CA (United States); California NanoSystems Inst., Los Angeles, CA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Chicago, IL (United States); Czech Academy of Sciences, Prague (Czech Republic)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: European Commission; US Air Force Office of Scientific Research (AFOSR); USDOD; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357; SC0019152

OSTI ID:: 1594251

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 5 Vol. 12; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
cluster dynamics
cyclohexane oxidative dehydrogenation
deposited clusters
selectivity control
size-selected subnanometer clusters

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

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