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, the different selectivity observed experimentally for the Cu versusPd clusters is controlled by differences in the collective structural and redox dynamics of their ensembles.
- Authors:
-
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Univ. of California, Los Angeles, CA (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)
- Publication Date:
- Research Org.:
- Univ. of California, Los Angeles, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- US Air Force Office of Scientific Research (AFOSR); USDOD; European Commission (EC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Science - Office of Basic Energy Sciences - Scientific User Facilities Division; USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division; Air Force Research Laboratory (AFRL) - Air Force Office of Scientific Research (AFOSR); European Union - Horizon 2020 Research and Innovation Programme
- OSTI Identifier:
- 1594251
- Alternate Identifier(s):
- OSTI ID: 1755405; OSTI ID: 1773635
- Grant/Contract Number:
- SC0019152; AC02-06CH11357; FA9550-16-1-0141; 810310
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemCatChem
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 5; Journal ID: ISSN 1867-3880
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 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:https://doi.org/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:https://doi.org/10.1002/cctc.201901795. https://www.osti.gov/servlets/purl/1594251.
@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, the different selectivity observed experimentally for the Cu versusPd clusters is controlled by differences in the collective structural and redox dynamics of their ensembles.},
doi = {10.1002/cctc.201901795},
journal = {ChemCatChem},
number = 5,
volume = 12,
place = {United States},
year = {2019},
month = {11}
}
Web of Science
Works referenced in this record:
Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects
journal, April 2010
- Lei, Y.; Mehmood, F.; Lee, S.
- Science, Vol. 328, Issue 5975, p. 224-228
Electronic Structure Controls Reactivity of Size-Selected Pd Clusters Adsorbed on TiO2 Surfaces
journal, November 2009
- Kaden, W. E.; Wu, T.; Kunkel, W. A.
- Science, Vol. 326, Issue 5954
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
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
Catalytic oxidation over molecular sieves ion-exchanged with transition metal ions VI. A kinetic study of the oxidative dehydrogenation of cyclohexane over Y sieve ion-exchanged with cupric ion
journal, March 1975
- Mochida, I.
- Journal of Catalysis, Vol. 36, Issue 3
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
Catalysis by clusters with precise numbers of atoms
journal, July 2015
- Tyo, Eric C.; Vajda, Stefan
- Nature Nanotechnology, Vol. 10, Issue 7
Rare earth oxides doped NiO/γ-Al2O3 catalyst for oxidative dehydrogenation of cyclohexane
journal, June 2015
- AbdelDayem, Hany M.; Faiz, M.; Abdel-Samad, Hesham S.
- Journal of Rare Earths, Vol. 33, Issue 6
Oxidative dehydrogenation of cyclohexane over vanadate catalysts
journal, March 1991
- Kung, M.
- Journal of Catalysis, Vol. 128, Issue 1
Fluxionality of Catalytic Clusters: When It Matters and How to Address It
journal, February 2017
- Zhai, Huanchen; Alexandrova, Anastassia N.
- ACS Catalysis, Vol. 7, Issue 3
Reprint of: Oxidative dehydrogenation of cyclohexane and cyclohexene over supported gold, –palladium catalysts☆
journal, February 2011
- Dummer, Nicholas F.; Bawaked, Salem; Hayward, James
- Catalysis Today, Vol. 160, Issue 1
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
Cyclohexane oxidative dehydrogenation over copper oxide catalysts
journal, September 2016
- Nauert, Scott L.; Schax, Fabian; Limberg, Christian
- Journal of Catalysis, Vol. 341
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
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
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
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
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
Computational Design of Clusters for Catalysis
journal, April 2018
- Jimenez-Izal, Elisa; Alexandrova, Anastassia N.
- Annual Review of Physical Chemistry, Vol. 69, Issue 1
Study of Mn-based Catalysts for Oxidative Dehydrogenation of Cyclohexane to Cyclohexene
journal, November 2005
- Zhu, Haiou; Ge, Qingjie; Li, Wenzhao
- Catalysis Letters, Vol. 105, Issue 1-2
Catalysis Applications of Size-Selected Cluster Deposition
journal, November 2015
- Vajda, Stefan; White, Michael G.
- ACS Catalysis, Vol. 5, Issue 12
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
The Oxidative Dehydrogenation of Cyclohexane and Cyclohexene over Unsupported and Supported Molybdena Catalysts Prepared by Metal Oxide Vapor Deposition
journal, November 1996
- Alyea, Elmer C.; Keane, Mark A.
- Journal of Catalysis, Vol. 164, Issue 1
Oxidative dehydrogenation of cyclohexane over alumina-supported vanadium oxide nanoliths
journal, February 2010
- Feng, H.; Elam, J. W.; Libera, J. A.
- Journal of Catalysis, Vol. 269, Issue 2
Nanoalloying MgO-Deposited Pt Clusters with Si To Control the Selectivity of Alkane Dehydrogenation
journal, July 2018
- Jimenez-Izal, Elisa; Zhai, Huanchen; Liu, Ji-Yuan
- ACS Catalysis, Vol. 8, Issue 9
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
Catalytic oxidative dehydrogenation over Cu2+ exchanged NaY and KY zeolites
journal, January 1990
- Coughlan, Brendan; Keane, Mark A.
- Catalysis Letters, Vol. 4, Issue 3
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
Subnanometer cobalt oxide clusters as selective low temperature oxidative dehydrogenation catalysts
journal, February 2019
- Lee, Sungsik; Halder, Avik; Ferguson, Glen A.
- Nature Communications, Vol. 10, Issue 1
Formation of ilmenite-type CoTiO3 on TiO2 and its performance in oxidative dehydrogenation of cyclohexane with molecular oxygen
journal, November 2014
- Sarkar, Bipul; Pendem, Chandrashekar; Konathala, L. N. Sivakumar
- Catalysis Communications, Vol. 56
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
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
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
Effect of additives doping on catalytic properties of Mg3(VO4)2 catalysts in oxidative dehydrogenation of cyclohexane
journal, September 2013
- Jin, M.; Lu, P.; Yu, G. X.
- Catalysis Today, Vol. 212
The Progress of Catalyst for Cyclohexane Dehydrogenation Processes
journal, June 2014
- Guo, Jia Neng; Lin, Jin Zhi; Liu, Xin
- Advanced Materials Research, Vol. 953-954
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
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
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
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
Reactivity of Metal Clusters
journal, November 2016
- Luo, Zhixun; Castleman, A. W.; Khanna, Shiv N.
- Chemical Reviews, Vol. 116, Issue 23
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
- Baxter, Eric T.; Ha, Mai-Anh; Cass, Ashley C.
- ACS Catalysis, Vol. 7, Issue 5
A "Green" Route to Adipic Acid: Direct Oxidation of Cyclohexenes with 30 Percent Hydrogen Peroxide
journal, September 1998
- Sato, K.
- Science, Vol. 281, Issue 5383