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Selective Propane Dehydrogenation With Single-site CoII On SiO2 By A Non-redox Mechanism

Bo Hu, Bo Hu, Andrew “Bean” Getsoian, Neil M. Schweitzer, Neil M. Schweitzer, Ujjal Das, Hacksung Kim, Hacksung Kim, J. Niklas, O. Poluektov, L. Curtiss, Peter C. Stair, Peter C. Stair, J. Miller, A. Hock, A. Hock
Published 2015 · Chemistry

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Abstract We report the synthesis, characterization, and catalytic performance for gas phase propane dehydrogenation of single-site Co 2+ ions supported on silica. Spectroscopic characterization by resonance Raman, electron paramagnetic resonance, and X-ray near-edge and extended absorption fine structure revealed that tetrahedrally coordinated Co 2+ ions are chemisorbed into the trisiloxane rings on the surface of amorphous silica. In situ XAS shows that Co is not oxidized by air nor reduced by hydrogen even at 650 °C. For catalytic propane dehydrogenation, single-site Co 2+ /SiO 2 exhibits selectivities >95% at 550 °C and >90% at 650 °C with stable activity over 24 h. Calculations with hybrid density functional theory support a non-redox mechanism for activation of C–H and H–H bonds by Co 2+ similar to that previously reported for single-site Zn 2+ /SiO 2 .
This paper references
10.1007/S10562-005-6521-7
Mechanistic Insight in the Ethane Dehydrogenation Reaction over Cr/Al2O3 Catalysts
U. Olsbye (2005)
10.1016/0021-9517(92)90337-H
The effects of structure on the catalytic activity and selectivity of V2O5/TiO2 for the reduction of NO by NH3
G. Went (1992)
10.1021/ja406608u
Catalytic hydrogenation activity and electronic structure determination of bis(arylimidazol-2-ylidene)pyridine cobalt alkyl and hydride complexes.
R. Yu (2013)
10.1021/OM400325X
Spin Crossover during β-Hydride Elimination in High-Spin Iron(II)– and Cobalt(II)–Alkyl Complexes
Sarina M Bellows (2013)
10.1201/9781420007282
Comprehensive handbook of chemical bond energies
Yu-ran Luo (2007)
10.1021/JA9725561
Control of Dispersion of Ni2+ Ions via Chelate Ligands in the Preparation of Ni/SiO2 Materials. A XAFS Study
J. Y. Carriat (1998)
10.1021/cr900122p
C-H bond activation and organometallic intermediates on isolated metal centers on oxide surfaces.
C. Copéret (2010)
10.1021/ja4108148
Bis(imino)pyridine cobalt-catalyzed alkene isomerization-hydroboration: a strategy for remote hydrofunctionalization with terminal selectivity.
Jennifer V. Obligacion (2013)
10.1021/ar400270x
Low-valent cobalt catalysis: new opportunities for C-H functionalization.
Ke Gao (2014)
10.1021/OM900916G
Cobalt(II)-Catalyzed Intermolecular Benzylic C−H Amination with 2,2,2-Trichloroethoxycarbonyl Azide (TrocN3)
H. Lu (2010)
10.1016/0926-860X(95)00056-9
Oxidative dehydrogenation of lower alkanes on vanadium oxide-based catalysts. The present state of the art and outlooks
E. A. Mamedov (1995)
10.1021/JP002102H
Structure and Properties of Cobalt-Exchanged H-ZSM5 Catalysts for Dehydrogenation and Dehydrocyclization of Alkanes
W. Li (2001)
10.1016/S0021-9517(02)00106-9
Design and synthesis of heterogeneous catalysts: the thermolytic molecular precursor approach
Kyle L. Fujdala (2003)
10.1021/JA00187A028
Silsesquioxanes as models for silica surfaces
F. Feher (1989)
10.1016/S0022-3093(05)80555-1
Origin of the Raman bands, D1 and D2, in high surface area and vitreous silicas
B. Humbert (1992)
10.1063/1.464913
Density-functional thermochemistry. III. The role of exact exchange
Axel D. Becke (1993)
10.1073/pnas.1405314111
Proton transfers are key elementary steps in ethylene polymerization on isolated chromium(III) silicates
Murielle F Delley (2014)
10.1021/ja204800a
Mechanism of cobalt(II) porphyrin-catalyzed C-H amination with organic azides: radical nature and H-atom abstraction ability of the key cobalt(III)-nitrene intermediates.
Volodymyr Lyaskovskyy (2011)
10.1107/S0567739476001551
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
R. D. Shannon (1976)
10.1021/IC950855Q
Nitrogen-14 NMR Study on Solvent Exchange of the Octahedral Cobalt(II) Ion in Neat 1,3-Propanediamine and n-Propylamine at Various Temperatures and Pressures. Tetrahedral-Octahedral Equilibrium of the Solvated Cobalt(II) Ion in n-Propylamine As Studied by EXAFS and Electronic Absorption Spectroscopy
Sen-ichi Aizawa Si (1996)
10.1039/A906550D
Non-oxidative reactions of propane on Zn/Na-ZSM5
Joseph A. Biscardi (1999)
10.1016/0022-2860(94)80039-1
Transition metal hydrides
A. Dedieu (1992)
10.1021/OM300804A
Intramolecular C(sp3)–H Bond Activation Reactions of Low-Valent Cobalt Complexes with Coordination Unsaturation
Zhenbo Mo (2012)
10.1063/1.467146
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
A. Schaefer (1994)
10.1073/pnas.1220240110
Surface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites
L. A. Williams (2012)
10.1021/ja507902z
Bis(phosphine)cobalt dialkyl complexes for directed catalytic alkene hydrogenation.
Max R Friedfeld (2014)
10.1021/ol100266u
Cobalt catalysis at the crossroads: cobalt-catalyzed Alder-ene reaction versus [2 + 2] cycloaddition.
G. Hilt (2010)
10.1021/ja408238n
Z-selective alkene isomerization by high-spin cobalt(II) complexes.
C. Chen (2014)
10.1007/BF03052816
The crystal structure of cobaltic acetylacetonate Co (C5H7O2)3
V. Padmanabhan (1958)
10.1021/JP013245M
Kinetics and Reaction Pathways for Propane Dehydrogenation and Aromatization on Co/H-ZSM5 and H-ZSM5
S. Y. Yu (2002)
10.1021/ja5060884
Bis(imino)pyridine cobalt-catalyzed dehydrogenative silylation of alkenes: scope, mechanism, and origins of selective allylsilane formation.
C. C. H. Atienza (2014)
10.1021/jp807676n
Influence of ligands on the dynamics of hydrogen elimination in cationic complexes of Co and Rh.
R. Xu (2008)
10.1006/JCAT.1998.2312
Reaction Pathways and Rate-Determining Steps in Reactions of Alkanes on H-ZSM5 and Zn/H-ZSM5 Catalysts☆
Joseph A. Biscardi (1999)
10.1021/ic50150a042
Magnetic exchange interactions in transition metal dimers. IV. High-spin cobalt(II)-2,2',2''-triaminotriethylamine complexes with oxalate inner-sphere and cyanate, thiocyanate, chloride, and azide outer-sphere bridges
D. Duggan (1975)
Intramolecular C(sp(3))-H Bond Activation Reactions of Low-Valent Cobalt Complexes with Coordination Unsaturation
莫贞波 (2012)
10.1016/S0920-5861(01)00411-4
Nature and reactivity of Co species in a cobalt-containing beta zeolite: an FTIR study
F. Geobaldo (2001)
10.1016/J.JCAT.2005.11.032
Thermolytic molecular precursor route to site-isolated vanadia–silica materials and their catalytic performance in methane selective oxidation
D. Ruddy (2006)
10.1021/JP991762N
Electron Spin Resonance of High-Spin Cobalt in Microporous Crystalline Cobalt-Containing Aluminophosphates
B. M. Weckhuysen (2000)
10.1006/JCAT.1998.2177
Structure and Density of Active Zn Species in Zn/H-ZSM5 Propane Aromatization Catalysts☆
Joseph A. Biscardi (1998)
10.1021/ol303479f
Cobalt-catalyzed acceptorless alcohol dehydrogenation: synthesis of imines from alcohols and amines.
G. Zhang (2013)
10.1021/ct0499783
Using Hessian Updating To Increase the Efficiency of a Hessian Based Predictor-Corrector Reaction Path Following Method.
H. Hratchian (2005)
10.1017/cbo9780511809194
Introduction to XAFS: A Practical Guide to X-ray Absorption Fine Structure Spectroscopy
G. Bunker (2010)
10.1021/I260027A022
Thermal Cracking of Propane. Kinetics and Product Distributions
A. G. Buekens (1968)
10.1021/ja3042383
γ-Alumina: the essential and unexpected role of water for the structure, stability, and reactivity of "defect" sites.
Raphael Wischert (2012)
10.1021/JP801339Q
A Theoretical Investigation of the Selective Oxidation of Methanol to Formaldehyde on Isolated Vanadate Species Supported on Titania
Anthony Goodrow (2007)
10.1002/ANIE.200390072
Homogeneous and heterogeneous catalysis: bridging the gap through surface organometallic chemistry.
C. Copéret (2003)
10.1021/ja410052u
A well-defined silica-supported tungsten oxo alkylidene is a highly active alkene metathesis catalyst.
Matthew P Conley (2013)
10.1016/J.TCA.2008.04.015
Characterization of cobalt oxides studied by FT-IR, Raman, TPR and TG-MS
Chih-wei Tang (2008)
10.1002/anie.201206051
Mild and homogeneous cobalt-catalyzed hydrogenation of C=C, C=O, and C=N bonds.
G. Zhang (2012)
10.1002/ANIE.199406391
A Novel Open‐Framework Cobalt Phosphate Containing a Tetrahedrally Coordinated Cobalt(II) Center: CoPO4 · 0.5 C2H10N2
J. Chen (1994)
10.1021/ja5003636
Iron catalyzed asymmetric hydrogenation of ketones.
Yan-yun Li (2014)
10.1107/S0567740878004331
Hexaamminecobalt(III) chloride
G. Kruger (1978)
10.1039/C1NJ20506D
Silica-supported single-site catalysts: to be or not to be? A conjecture on silica surfaces
D. Gajan (2011)
10.1021/IC052108R
Tetrahedral Co(II) coordination in alpha-type cobalt hydroxide: Rietveld refinement and X-ray absorption spectroscopy.
R. Ma (2006)
10.1007/s10562-014-1238-0
Polymerization on CO-Reduced Phillips Catalyst initiates through the C–H bond Activation of Ethylene on Cr–O Sites
Murielle F Delley (2014)
10.1021/ja103768r
'Carbene radicals' in Co(II)(por)-catalyzed olefin cyclopropanation.
Wojciech I. Dzik (2010)
10.1021/CS401116P
Propylene hydrogenation and propane dehydrogenation by a single-site Zn2+ on silica catalyst
Neil M. Schweitzer (2014)
10.1002/anie.201308983
Polymerization of ethylene by silica-supported dinuclear Cr(III) sites through an initiation step involving C-H bond activation.
Matthew P Conley (2014)
10.1021/JA068249P
Highly active, stable, and selective well-defined silica supported mo imido olefin metathesis catalysts.
F. Blanc (2007)
10.1021/JA00120A010
Surface Organometallic Chemistry of Inorganic Oxides: The Synthesis and Characterization of (.tplbond.SiO)Ta(:CHC(CH3)3)(CH2C(CH3)3)2 and (.tplbond.SiO)2Ta(:CHC(CH3)3)(CH2C(CH3)3)
V. Dufaud (1995)
10.1016/J.CATTOD.2007.10.024
Selective catalytic reduction of NO by C3H8 over CoOx/Al2O3: An investigation of structure–activity relationships
C. He (2008)
10.1098/rspa.2012.0056
Rational design of single-site heterogeneous catalysts: towards high chemo-, regio- and stereoselectivity
V. Dal Santo (2012)
10.1016/S0920-5861(96)00028-4
Structure and function of metal cations in light alkane reactions catalyzed by modified H-ZSM5
Joseph A. Biscardi (1996)
10.1021/JA071561U
Highly Active, Stable, and Selective Well-Defined Silica Supported Mo Imido Olefin Metathesis Cata-lysts [J. Am. Chem. Soc. 2007, 129, 1044−1045].
F. Blanc (2007)
10.1021/JP0623387
Incorporation of Co(II) in dealuminated BEA zeolite at lattice tetrahedral sites evidenced by XRD, FTIR, diffuse reflectance UV-Vis, EPR, and TPR.
S. Dzwigaj (2006)
10.1021/JA953524L
Synthesis, Characterization, and Reactivity, in the C−H Bond Activation of Cycloalkanes, of a Silica-Supported Tantalum(III) Monohydride Complex: (⋮SiO)2TaIII−H
Véronique Vidal (1996)
10.1021/cr5002436
Catalytic dehydrogenation of light alkanes on metals and metal oxides.
J. Sattler (2014)
10.1039/c0cs00044b
Resonance Raman and surface- and tip-enhanced Raman spectroscopy methods to study solid catalysts and heterogeneous catalytic reactions.
Hacksung Kim (2010)
10.1021/ja500712z
Cobalt-catalyzed C-H borylation.
Jennifer V. Obligacion (2014)
10.1021/ic400352r
Reversible carbon-carbon bond formation induced by oxidation and reduction at a redox-active cobalt complex.
C. C. H. Atienza (2013)
10.1016/0144-2449(89)90051-1
Stabilization of Co (III) in aluminophosphate molecular sieve frameworks
L. Iton (1989)
10.1139/V74-401
Kinetics and Mechanism of the Thermal Decomposition of Hexaamminecobalt(III) and Aquopentaamminecobalt(III) Ions in Acidic Aqueous Solution
A. M. Newton (1974)
10.1002/ELAN.200503361
Electrochemical Response of Cobalt(II) in the Presence of Ammonia
Xiaobo Ji (2006)
10.1002/chem.201203666
Mechanistic study on ligand-controlled cobalt-catalyzed regioselectivity-switchable hydroarylation of styrenes.
Z. Yang (2013)
10.1021/LA00075A004
Concentration of hydroxyl groups on the surface of amorphous silicas
L. T. Zhuravlev (1987)
10.1021/ar900203a
Metathesis of alkanes and related reactions.
Jean-Marie Basset (2010)
10.1039/B703088F
Co2+/ Co(0) redox couple revealed by EPR spectroscopy triggers preferential coordination of reactants during SCR of NOx with propene over cobalt-exchanged zeolites.
P. Pietrzyk (2007)



This paper is referenced by
10.1016/J.APCATA.2018.01.014
Vanadium-doped porous silica materials with high catalytic activity and stability for propane dehydrogenation reaction
P. Hu (2018)
10.1021/ic502696n
Heterolytic Activation of C-H Bonds on Cr(III)-O Surface Sites Is a Key Step in Catalytic Polymerization of Ethylene and Dehydrogenation of Propane.
Matthew P Conley (2015)
10.1039/C6CY00698A
Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES
Andrew “Bean” Getsoian (2016)
10.1016/J.APCATA.2017.12.025
Effect of cobalt loading on structure and catalytic behavior of CoO x /SiO 2 in CO 2 -assisted dehydrogenation of ethane
R. Koirala (2018)
10.1149/2.1181610JES
Increased Anodic Performance of La0.5Sr0.5Mn0.9Al0.1O3 by Doping with Co for Solid Oxide Fuel Cells Using Dry C3H8 Fuel
A. K. Bahrain (2016)
10.1016/J.CATCOM.2019.04.005
Effect of cobalt complex precursors on reactivity of cationic cobalt catalysts: Cyclohexane dehydrogenation
Kittisak Choojun (2019)
10.1021/JACS.6B08705
C-H Activation on Co,O Sites: Isolated Surface Sites versus Molecular Analogs.
D. Estes (2016)
10.1016/J.MEMSCI.2019.02.012
High-performance catalytic perovskite hollow fiber membrane reactor for oxidative propane dehydrogenation
Z. Wang (2019)
10.1039/c9cy01442j
Catalytic activation of ethylene C–H bonds on uniform d8 Ir(I) and Ni(II) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts
Nicholas R Jaegers (2019)
10.1016/S1872-2067(18)63196-1
Electronic interaction between single Pt atom and vacancies on boron nitride nanosheets and its influence on the catalytic performance in the direct dehydrogenation of propane
XiaoYing Sun (2019)
10.1038/s41560-019-0491-2
Fuels and energy carriers from single-site catalysts prepared via surface organometallic chemistry
C. Copéret (2019)
10.1002/cctc.201900530
Alkene Hydrosilylation on Oxide‐Supported Pt‐Ligand Single‐Site Catalysts
L. Chen (2019)
10.1016/j.jcat.2019.08.024
Dual functions of CoOx decoration in PtCo/CeO2 catalysts for the hydrogen-borrowing amination of alcohols to primary amines
Tao Tong (2019)
10.1021/acs.chemrev.6b00082
Isolated Surface Hydrides: Formation, Structure, and Reactivity.
C. Copéret (2016)
10.1016/J.JCAT.2019.02.012
The effect of phase composition and crystallite size on activity and selectivity of ZrO2 in non-oxidative propane dehydrogenation
Yaoyuan Zhang (2019)
10.1016/j.jcat.2019.12.037
Ultrasmall Co confined in the silanols of dealuminated beta zeolite: A highly active and selective catalyst for direct dehydrogenation of propane to propylene
Charn-Ying Chen (2020)
10.1002/cctc.201500916
Propane Dehydrogenation over In2O3–Ga2O3–Al2O3 Mixed Oxides
Shuai Tan (2016)
10.1021/ACSCATAL.6B02771
Supported Aluminum Catalysts for Olefin Hydrogenation
Jeffrey Camacho-Bunquin (2017)
10.1021/acsomega.8b00862
Zirconium Modification Promotes Catalytic Activity of a Single-Site Cobalt Heterogeneous Catalyst for Propane Dehydrogenation
Y. Zhao (2018)
10.1002/chem.201803515
Single-Site Heterogeneous Catalysts: From Synthesis to NMR Signal Enhancement.
Dudari B. Burueva (2019)
10.1016/j.apcata.2019.117291
Isolated Sn on mesoporous silica as a highly stable and selective catalyst for the propane dehydrogenation
Hong Wang (2020)
10.1002/slct.202001054
Effects of Dopants in PtSn/M‐Silicalite‐1 on Structural Property and on Catalytic Propane Dehydrogenation Performance
S. Zhou (2020)
10.1016/J.JCAT.2017.02.016
ZrO2-based unconventional catalysts for non-oxidative propane dehydrogenation: Factors determining catalytic activity
T. Otroshchenko (2017)
10.1016/J.JCAT.2017.05.022
Influence of the kind of VOx structures in VOx/MCM-41 on activity, selectivity and stability in dehydrogenation of propane and isobutane
U. Rodemerck (2017)
10.1021/ACS.JPCC.7B08113
Simulations of Ammonia Adsorption for the Characterization of Acid Sites in Metal-Doped Amorphous Silicates
A. Jystad (2017)
10.1021/ACS.ORGANOMET.6B00623
Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene
A. Getsoian (2017)
10.1021/acs.inorgchem.7b00443
Understanding the Lewis Acidity of Co(II) Sites on a Silica Surface.
D. Estes (2017)
10.1002/cctc.201701815
Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst
G. Zhang (2018)
10.1021/ACSCATAL.5B00248
Isolated FeII on Silica As a Selective Propane Dehydrogenation Catalyst
Bo Hu (2015)
10.1016/J.JCAT.2016.10.017
Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument
Jeffrey Camacho-Bunquin (2017)
10.1021/ACSSUSCHEMENG.7B01769
Reduced Cu–Co–Al Mixed Metal Oxides for the Ring-Opening of Furfuryl Alcohol to Produce Renewable Diols
Taylor P. Sulmonetti (2017)
10.1021/acs.chemrev.5b00373
Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities.
C. Copéret (2016)
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