skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on November 4, 2020

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]
  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.
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.
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.
@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}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on November 4, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects
journal, April 2010


Electronic Structure Controls Reactivity of Size-Selected Pd Clusters Adsorbed on TiO2 Surfaces
journal, November 2009


Evolution of Functional Cyclohexadiene-Based Synthetic Reagents:  The Importance of Becoming Aromatic
journal, October 2005

  • Walton, John C.; Studer, Armido
  • Accounts of Chemical Research, Vol. 38, Issue 10
  • DOI: 10.1021/ar050089j

Local Fluxionality of Surface-Deposited Cluster Catalysts: The Case of Pt 7 on Al 2 O 3
journal, March 2018

  • Zhai, Huanchen; Alexandrova, Anastassia N.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 7
  • DOI: 10.1021/acs.jpclett.8b00379

Dynamic Phase Diagram of Catalytic Surface of Hexagonal Boron Nitride under Conditions of Oxidative Dehydrogenation of Propane
journal, December 2018

  • Zhang, Zisheng; Jimenez-Izal, Elisa; Hermans, Ive
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 1
  • DOI: 10.1021/acs.jpclett.8b03373

Catalysis by clusters with precise numbers of atoms
journal, July 2015


Rare earth oxides doped NiO/γ-Al2O3 catalyst for oxidative dehydrogenation of cyclohexane
journal, June 2015


Oxidative dehydrogenation of cyclohexane over vanadate catalysts
journal, March 1991


Fluxionality of Catalytic Clusters: When It Matters and How to Address It
journal, February 2017


Reprint of: Oxidative dehydrogenation of cyclohexane and cyclohexene over supported gold, –palladium catalysts☆
journal, February 2011


Aerobic Oxidation of Cyclohexane Catalyzed by Size-Controlled Au Clusters on Hydroxyapatite: Size Effect in the Sub-2 nm Regime
journal, December 2010

  • Liu, Yongmei; Tsunoyama, Hironori; Akita, Tomoki
  • ACS Catalysis, Vol. 1, Issue 1
  • DOI: 10.1021/cs100043j

Cyclohexane oxidative dehydrogenation over copper oxide catalysts
journal, September 2016


Electron Counting in Solids: Oxidation States, Partial Charges, and Ionicity
journal, April 2017

  • Walsh, Aron; Sokol, Alexey A.; Buckeridge, John
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 9
  • DOI: 10.1021/acs.jpclett.7b00809

Size-Dependent Molecular Dissociation on Mass-Selected, Supported Metal Clusters
journal, September 1998

  • Heiz, U.; Vanolli, F.; Sanchez, A.
  • Journal of the American Chemical Society, Vol. 120, Issue 37
  • DOI: 10.1021/ja981181w

Pt–Zn Clusters on Stoichiometric MgO(100) and TiO 2 (110): Dramatically Different Sintering Behavior
journal, March 2015

  • Dadras, Jonny; Shen, Lu; Alexandrova, Anastassia
  • The Journal of Physical Chemistry C, Vol. 119, Issue 11
  • DOI: 10.1021/jp512277x

Oxidative Dehydrogenation of Cyclohexane on Cobalt Oxide (Co 3 O 4 ) Nanoparticles: The Effect of Particle Size on Activity and Selectivity
journal, September 2012

  • Tyo, Eric C.; Yin, Chunrong; Di Vece, Marcel
  • ACS Catalysis, Vol. 2, Issue 11
  • DOI: 10.1021/cs300479a

Metastable Structures in Cluster Catalysis from First-Principles: Structural Ensemble in Reaction Conditions and Metastability Triggered Reactivity
journal, February 2018

  • Sun, Geng; Sautet, Philippe
  • Journal of the American Chemical Society, Vol. 140, Issue 8
  • DOI: 10.1021/jacs.7b11239

Computational Design of Clusters for Catalysis
journal, April 2018


Study of Mn-based Catalysts for Oxidative Dehydrogenation of Cyclohexane to Cyclohexene
journal, November 2005


Catalysis Applications of Size-Selected Cluster Deposition
journal, November 2015


Characterization of Cr−MCM-41 and Al,Cr−MCM-41 Mesoporous Catalysts for Gas-Phase Oxidative Dehydrogenation of Cyclohexane
journal, February 2007

  • Lezanska, Maria; Szymanski, Grzegorz S.; Pietrzyk, Piotr
  • The Journal of Physical Chemistry C, Vol. 111, Issue 4
  • DOI: 10.1021/jp066498u

Oxidative dehydrogenation of cyclohexane over alumina-supported vanadium oxide nanoliths
journal, February 2010


Nanoalloying MgO-Deposited Pt Clusters with Si To Control the Selectivity of Alkane Dehydrogenation
journal, July 2018


Rutile-Deposited Pt–Pd clusters: A Hypothesis Regarding the Stability at 50/50 Ratio
journal, September 2014

  • Ha, Mai-Anh; Dadras, Jonny; Alexandrova, Anastassia
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs5011426

Catalytic oxidative dehydrogenation over Cu2+ exchanged NaY and KY zeolites
journal, January 1990

  • Coughlan, Brendan; Keane, Mark A.
  • Catalysis Letters, Vol. 4, Issue 3
  • DOI: 10.1007/BF00765938

Boron Switch for Selectivity of Catalytic Dehydrogenation on Size-Selected Pt Clusters on Al 2 O 3
journal, August 2017

  • Ha, Mai-Anh; Baxter, Eric T.; Cass, Ashley C.
  • Journal of the American Chemical Society, Vol. 139, Issue 33
  • DOI: 10.1021/jacs.7b05894

Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts
journal, February 2019


Formation of ilmenite-type CoTiO3 on TiO2 and its performance in oxidative dehydrogenation of cyclohexane with molecular oxygen
journal, November 2014


Dynamics of Subnanometer Pt Clusters Can Break the Scaling Relationships in Catalysis
journal, January 2019

  • Zandkarimi, Borna; Alexandrova, Anastassia N.
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 3
  • DOI: 10.1021/acs.jpclett.8b03680

A New Route to Control Product Selectivity in the Oxidative Dehydrogenation of Cyclohexane and Cyclohexene
journal, July 2004

  • Zhu, Yujun; Li, Jing; Yang, Xiangguang
  • Chemistry Letters, Vol. 33, Issue 7
  • DOI: 10.1246/cl.2004.822

Ensemble-Average Representation of Pt Clusters in Conditions of Catalysis Accessed through GPU Accelerated Deep Neural Network Fitting Global Optimization
journal, November 2016

  • Zhai, Huanchen; Alexandrova, Anastassia N.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 12
  • DOI: 10.1021/acs.jctc.6b00994

The Progress of Catalyst for Cyclohexane Dehydrogenation Processes
journal, June 2014


Hydrogenation of Ethylene and Dehydrogenation and Hydrogenolysis of Ethane on Pt(111) and Pt(211): A Density Functional Theory Study
journal, February 2010

  • Chen, Ying; Vlachos, Dionisios G.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 11
  • DOI: 10.1021/jp909163z

Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane
journal, February 2009

  • Vajda, Stefan; Pellin, Michael J.; Greeley, Jeffrey P.
  • Nature Materials, Vol. 8, Issue 3
  • DOI: 10.1038/nmat2384

Atomically precise (catalytic) particles synthesized by a novel cluster deposition instrument
journal, May 2014

  • Yin, C.; Tyo, E.; Kuchta, K.
  • The Journal of Chemical Physics, Vol. 140, Issue 17, Article No. 174201
  • DOI: 10.1063/1.4871799

Theoretical and Experimental Study of Vanadium-Based Fluorophosphate Cathodes for Rechargeable Batteries
journal, May 2014

  • Xu, Maowen; Xiao, Penghao; Stauffer, Shannon
  • Chemistry of Materials, Vol. 26, Issue 10
  • DOI: 10.1021/cm500106w

Reactivity of Metal Clusters
journal, November 2016


Ethylene Dehydrogenation on Pt 4,7,8 Clusters on Al 2 O 3 : Strong Cluster Size Dependence Linked to Preferred Catalyst Morphologies
journal, April 2017