Catalytic C-O bond hydrogenolysis of tetrahydrofuran-dimethanol over metal supported WOx/TiO2 catalysts

He, Jiayue; Burt, Samuel P.; Ball, Madelyn R.; Hermans, Ive; Dumesic, James A.; Huber, George W.

doi:10.1016/j.apcatb.2019.117945

Title: Catalytic C-O bond hydrogenolysis of tetrahydrofuran-dimethanol over metal supported WO_x/TiO₂ catalysts

Abstract

M-WO_x/TiO₂ (M = Pt-, Rh-, Pd-, and Ru) catalysts were prepared and studied for tetrahydrofuran-dimethanol (THFDM) hydrogenolysis. All catalysts have a small metal particle size (< 2 nm) but show catalytic activities that differ by two orders of magnitude. From a combination of CO chemisorption and STEM, we conclude that this wide gap in activity is primarily due to overgrowth of WO_x/TiO₂ covering the metal particle of the less-active catalysts. This overgrowth decreases the number of exposed hydrogenation sites in these catalysts, lowering the overall reaction rate. The catalyst with the highest activity (Pt-WO_x/TiO₂) was studied at various pressures of H₂, with catalytic activity passing through a maximum with increasing pressure. This is likely due to changes in the oxidation state of W^δ+ on the catalyst surface, which changes from W⁶⁺ to W⁵⁺ and W⁴⁺ with increasing hydrogen pressure. Moreover, H₂ can strongly adsorb on the catalyst surface and inhibit the activity at high hydrogen pressure. The apparent activation energy of THFDM conversion over Pt-WO_x/TiO₂ is 47 kJ·mol^-1. Pt-WO_x/TiO₂ showed a decrease in conversion from 45% to 23% over 46 h on stream in a continuous flow reactor. Catalyst deactivation is likely due to leaching of W. THFDM can bemore »« less

Authors:

He, Jiayue ^[1]; Burt, Samuel P. ^[1]; Ball, Madelyn R. ^[1]; Hermans, Ive ^[1];

^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States)

Publication Date:: Wed Jul 10 00:00:00 EDT 2019

Research Org.:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; USDOE

OSTI Identifier:: 1799261

Alternate Identifier(s):: OSTI ID: 1778293

Grant/Contract Number:: EE0006878

Resource Type:: Accepted Manuscript

Journal Name:: Applied Catalysis B: Environmental

Additional Journal Information:: Journal Volume: 258; Journal ID: ISSN 0926-3373

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biochemicals; biomass; 1,6-hexanediol; catalyst

Citation Formats


                    He, Jiayue, Burt, Samuel P., Ball, Madelyn R., Hermans, Ive, Dumesic, James A., and Huber, George W. Catalytic C-O bond hydrogenolysis of tetrahydrofuran-dimethanol over metal supported WOx/TiO2 catalysts.  United States: N. p., 2019. 
Web.  doi:10.1016/j.apcatb.2019.117945.

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                    He, Jiayue, Burt, Samuel P., Ball, Madelyn R., Hermans, Ive, Dumesic, James A., & Huber, George W. Catalytic C-O bond hydrogenolysis of tetrahydrofuran-dimethanol over metal supported WOx/TiO2 catalysts.  United States.  https://doi.org/10.1016/j.apcatb.2019.117945

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                    He, Jiayue, Burt, Samuel P., Ball, Madelyn R., Hermans, Ive, Dumesic, James A., and Huber, George W. Wed .  
"Catalytic C-O bond hydrogenolysis of tetrahydrofuran-dimethanol over metal supported WOx/TiO2 catalysts".  United States.  https://doi.org/10.1016/j.apcatb.2019.117945.  https://www.osti.gov/servlets/purl/1799261.

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@article{osti_1799261,

  title        = {Catalytic C-O bond hydrogenolysis of tetrahydrofuran-dimethanol over metal supported WOx/TiO2 catalysts},

  author       = {He, Jiayue and Burt, Samuel P. and Ball, Madelyn R. and Hermans, Ive and Dumesic, James A. and Huber, George W.},

  abstractNote = {M-WOx/TiO2 (M = Pt-, Rh-, Pd-, and Ru) catalysts were prepared and studied for tetrahydrofuran-dimethanol (THFDM) hydrogenolysis. All catalysts have a small metal particle size (< 2 nm) but show catalytic activities that differ by two orders of magnitude. From a combination of CO chemisorption and STEM, we conclude that this wide gap in activity is primarily due to overgrowth of WOx/TiO2 covering the metal particle of the less-active catalysts. This overgrowth decreases the number of exposed hydrogenation sites in these catalysts, lowering the overall reaction rate. The catalyst with the highest activity (Pt-WOx/TiO2) was studied at various pressures of H2, with catalytic activity passing through a maximum with increasing pressure. This is likely due to changes in the oxidation state of Wδ+ on the catalyst surface, which changes from W6+ to W5+ and W4+ with increasing hydrogen pressure. Moreover, H2 can strongly adsorb on the catalyst surface and inhibit the activity at high hydrogen pressure. The apparent activation energy of THFDM conversion over Pt-WOx/TiO2 is 47 kJ·mol-1. Pt-WOx/TiO2 showed a decrease in conversion from 45% to 23% over 46 h on stream in a continuous flow reactor. Catalyst deactivation is likely due to leaching of W. THFDM can be efficiently converted to 1,2,6-hexanetriol (HTO) in the presence of Pt/TiO2 and homogeneous W salts.},

  doi          = {10.1016/j.apcatb.2019.117945},

  journal      = {Applied Catalysis B: Environmental},

  number       = ,

  volume       = 258,

  place        = {United States},

  year         = {Wed Jul 10 00:00:00 EDT 2019},

  month        = {Wed Jul 10 00:00:00 EDT 2019}

}

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Title: Catalytic C-O bond hydrogenolysis of tetrahydrofuran-dimethanol over metal supported WOx/TiO2 catalysts

Abstract

Citation Formats

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Asymmetric Hydrogenations (Nobel Lecture) Copyright© The Nobel Foundation 2002. We thank the Nobel Foundation, Stockholm, for permission to print this lecture. journal, June 2002

Title: Catalytic C-O bond hydrogenolysis of tetrahydrofuran-dimethanol over metal supported WO_x/TiO₂ catalysts

Chemoselective Hydrogenolysis of Tetrahydropyran-2-methanol to 1,6-Hexanediol over Rhenium-Modified Carbon-Supported Rhodium Catalysts
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Enhanced activity of Pd/TiO2 catalysts for the CO/H2 reaction in the absence of strong metal-support interactions (SMSI)
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Effect of carbon supports on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-methanol
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Dehydration of cellulose to levoglucosenone using polar aprotic solvents
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Caprolactam from Renewable Resources: Catalytic Conversion of 5-Hydroxymethylfurfural into Caprolactone
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Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases
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Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
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A new perspective in bio-refining: levoglucosenone and cleaner lignin from waste biorefinery hydrolysis lignin by selective conversion of residual saccharides
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Comparison of Metal-Support Interactions in Pt/TiO2 and Pt/CeO2
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Mechanisms of selective cleavage of C–O bonds in di-aryl ethers in aqueous phase
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Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts
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Hydrogenation of CO2 over sprayed Ru/TiO2 fine particles and strong metal–support interaction
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New approaches to the Pt/WO /Al2O3 catalytic system behavior for the selective glycerol hydrogenolysis to 1,3-propanediol
journal, March 2015

Catalyst studies on the ring opening of tetrahydrofuran–dimethanol to 1,2,6-hexanetriol
journal, July 2013

Direct observation of the surfaces of small metal crystallites: rhodium supported on titania
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SiO2 promoted Pt/WOx/ZrO2 catalysts for the selective hydrogenolysis of glycerol to 1,3-propanediol
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Catalyst support effects on hydrogen spillover
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Models of strong metal-support interaction (SMSI) in Pt on TiO2 catalysts
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Advanced Electron Microscopy Characterization of Nanostructured Heterogeneous Catalysts
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On the reduction of tungsten trioxide accelerated by platinum and water
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Imaging of low temperature induced SMSI on Pd/TiO2 catalysts
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Comparative XPS study of Rh/Al2O3 and Rh/TiO2 as catalysts for NaBH4 hydrolysis
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Resolving ruthenium: XPS studies of common ruthenium materials
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XPES studies of oxides of second- and third-row transition metals including rare earths
journal, January 1980

Hydrogenolysis of Glycerol to 1,3-propanediol under Low Hydrogen Pressure over WO _x -Supported Single/Pseudo-Single Atom Pt Catalyst
journal, February 2016

Cluster ruthenium hydrogenation catalysts
journal, May 1978

Synthesis of 1,6-Hexanediol from Cellulose Derived Tetrahydrofuran-Dimethanol with Pt-WO _x /TiO ₂ Catalysts
journal, January 2018

Highly selective heterogeneous palladium-catalyzed hydrogenations using triethoxysilane and water
journal, May 1990

Selective hydrogenolysis and hydrogenation using metal catalysts directly modified with metal oxide species
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Ni-Catalyzed Cleavage of Aryl Ethers in the Aqueous Phase
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Dynamical Observation and Detailed Description of Catalysts under Strong Metal–Support Interaction
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Oxygenated commodity chemicals from chemo-catalytic conversion of biomass derived heterocycles
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XPS and FTIR Study of Ru/Al ₂ O ₃ and Ru/TiO ₂ Catalysts: Reduction Characteristics and Interaction with a Methane−Oxygen Mixture
journal, June 1999

Study of properties of Al2O3 and TiO2 supported palladium catalysts in reactions of tetrachloromethane hydrogenation
journal, April 2012

Strong metal-support interactions. Group 8 noble metals supported on titanium dioxide
journal, January 1978

Selective Hydrogenolysis of Polyols and Cyclic Ethers over Bifunctional Surface Sites on Rhodium–Rhenium Catalysts
journal, August 2011

Behavior of H2 chemisorption on Ru/TiO2 surface and its application in evaluation of Ru particle sizes compared with TEM and XRD analyses
journal, February 2008

Pd/CeO2?TiO2 catalyst for CO oxidation at low temperature: a TPR study with H2 and CO as reducing agents
journal, July 2004

Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures
journal, January 2017

Structure Sensitivity of the Hydrogenation of Crotonaldehyde over Pt/SiO2and Pt/TiO2
journal, February 1997

New catalytic strategies for α,ω-diols production from lignocellulosic biomass
journal, January 2017

Reaction mechanism of the glycerol hydrogenolysis to 1,3-propanediol over Ir–ReOx/SiO2 catalyst
journal, June 2011

Hydrogenation of levoglucosenone to renewable chemicals
journal, January 2017

The kinetics and mechanism of spillover
journal, February 1974

The synthesis of highly dispersed noble and base metals on silica via strong electrostatic adsorption: I. Amorphous silica
journal, December 2008

Strong metal-support interactions
journal, November 1987

Asymmetric Hydrogenations (Nobel Lecture) Copyright© The Nobel Foundation 2002. We thank the Nobel Foundation, Stockholm, for permission to print this lecture.
journal, June 2002