Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles

Abstract

Catalytic oxidation of alcohols is an essential process for energy conversion, production of fine chemicals and pharmaceutical intermediates. Although it has been broadly utilized in industry, the basic understanding for catalytic alcohol oxidations at a molecular level, especially under both gas and liquid phases, is still lacking. In this paper, we systematically summarized our work on catalytic alcohol oxidation over size-controlled Pt nanoparticles. The studied alcohols included methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol. The turnover rates of different alcohols on Pt nanoparticles and also the apparent activation energy in gas and liquid phase reactions were compared. The Pt nanoparticle size dependence of reaction rates and product selectivity was also carefully examined. Water showed very distinct effects for gas and liquid phase alcohol oxidations, either as an inhibitor or as a promoter depending on alcohol type and reaction phase. A deep understanding of different alcohol molecular orientations on Pt surface in gas and liquid phase reactions was established using sum-frequency generation spectroscopy analysis for in situ alcohol oxidations, as well as density functional theory calculation. This approach can not only explain the entirely different behaviors of alcohol oxidations in gas and liquid phases, but can also provide guidance for future catalyst/processmore » design.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [2];  [2];  [1];  [1];  [1]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1489656
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Catalysts
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2073-4344
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalytic alcohol oxidation; gas phase; liquid phase; Pt nanoparticles; sum-frequency generation spectroscopy; surface molecular orientation; density functional theory calculation

Citation Formats

Liu, Fudong, Wang, Hailiang, Sapi, Andras, Tatsumi, Hironori, Zherebetskyy, Danylo, Han, Hui-Ling, Carl, Lindsay, and Somorjai, Gabor. Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles. United States: N. p., 2018. Web. doi:10.3390/catal8060226.
Copy to clipboard
Liu, Fudong, Wang, Hailiang, Sapi, Andras, Tatsumi, Hironori, Zherebetskyy, Danylo, Han, Hui-Ling, Carl, Lindsay, & Somorjai, Gabor. Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles. United States. https://doi.org/10.3390/catal8060226
Copy to clipboard
Liu, Fudong, Wang, Hailiang, Sapi, Andras, Tatsumi, Hironori, Zherebetskyy, Danylo, Han, Hui-Ling, Carl, Lindsay, and Somorjai, Gabor. Sun . "Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles". United States. https://doi.org/10.3390/catal8060226. https://www.osti.gov/servlets/purl/1489656.
Copy to clipboard
@article{osti_1489656,
title = {Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles},
author = {Liu, Fudong and Wang, Hailiang and Sapi, Andras and Tatsumi, Hironori and Zherebetskyy, Danylo and Han, Hui-Ling and Carl, Lindsay and Somorjai, Gabor},
abstractNote = {Catalytic oxidation of alcohols is an essential process for energy conversion, production of fine chemicals and pharmaceutical intermediates. Although it has been broadly utilized in industry, the basic understanding for catalytic alcohol oxidations at a molecular level, especially under both gas and liquid phases, is still lacking. In this paper, we systematically summarized our work on catalytic alcohol oxidation over size-controlled Pt nanoparticles. The studied alcohols included methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol. The turnover rates of different alcohols on Pt nanoparticles and also the apparent activation energy in gas and liquid phase reactions were compared. The Pt nanoparticle size dependence of reaction rates and product selectivity was also carefully examined. Water showed very distinct effects for gas and liquid phase alcohol oxidations, either as an inhibitor or as a promoter depending on alcohol type and reaction phase. A deep understanding of different alcohol molecular orientations on Pt surface in gas and liquid phase reactions was established using sum-frequency generation spectroscopy analysis for in situ alcohol oxidations, as well as density functional theory calculation. This approach can not only explain the entirely different behaviors of alcohol oxidations in gas and liquid phases, but can also provide guidance for future catalyst/process design.},
doi = {10.3390/catal8060226},
journal = {Catalysts},
number = 6,
volume = 8,
place = {United States},
year = {2018},
month = {5}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.3390/catal8060226
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Turnover rates of alcohol oxidation to carbonyl compounds in gas and liquid phases over 6 nm Pt/MCF-17 (4.5 nm Pt/MCF-17 for 1-PrOH oxidation). Gas phase reaction: 1.33 kPa alcohol, 6.67 kPaO2, 94.66 kPa He, 60 °C reaction temperature for MeOH, EtOH, 1-PrOH, 2-PrOH and 80 °C reaction temperaturemore » for 2-BuOH. Liquid phase reaction: 15 mL alcohol, dissolved oxygen under 100 kPa for MeOH, EtOH, 1-PrOH, 2-PrOH (60 °C reaction temperature) and 300 kPa for 2-BuOH (80 °C reaction temperature). Liquid phase reaction (1000 times diluted): 15 mL heptane, 15 μL alcohol with dissolved oxygen under 100 kPa for MeOH, EtOH, 1-PrOH, 2-PrOH at 60 °C reaction temperature. The vapor pressure of MeOH, EtOH, 1-PrOH, 2-PrOH at 20 and 60 °C is also presented herein. (TOF data for MeOH, EtOH, 1-PrOH, 2-PrOH, 2-BuOH oxidations were reported in [9,19–22], respectively).« less
All figures and tables (12 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts
journal, June 2004

  • Mallat, Tamas; Baiker, Alfons
  • Chemical Reviews, Vol. 104, Issue 6
  • DOI: 10.1021/cr0200116

Oxidation of alcohols with molecular oxygen on platinum metal catalysts in aqueous solutions
journal, March 1994

Cooperative Catalysis for Selective Alcohol Oxidation with Molecular Oxygen
journal, July 2016

  • Slot, Thierry K.; Eisenberg, David; van Noordenne, Dylan
  • Chemistry - A European Journal, Vol. 22, Issue 35
  • DOI: 10.1002/chem.201602964

Selective oxidation of alcohols and aldehydes on metal catalysts
journal, March 2000

Multiple steady-states for the oxidation of aqueous ethanol with oxygen on a carbon supported platinum catalyst
journal, January 1995

  • Jelemensky, L.; Kuster, B. F. M.; Marin, G. B.
  • Catalysis Letters, Vol. 30, Issue 1-4
  • DOI: 10.1007/BF00813693

Van der Waals density functionals applied to solids
journal, May 2011

Vapor pressure of primary n-alkyl chlorides and alcohols
journal, January 1969

  • Kemme, Herbert R.; Kreps, Saul I.
  • Journal of Chemical & Engineering Data, Vol. 14, Issue 1
  • DOI: 10.1021/je60040a011

Reaction intermediates of ethanol electro-oxidation on platinum investigated by SFG spectroscopy
journal, June 2013

The water solubility of 2-butanol: A widespread error
journal, November 1991

Catalytic 1-Propanol Oxidation on Size-Controlled Platinum Nanoparticles at Solid–Gas and Solid–Liquid Interfaces: Significant Differences in Kinetics and Mechanisms
journal, April 2018

  • Liu, Fudong; Han, Hui-Ling; Carl, Lindsay M.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 13
  • DOI: 10.1021/acs.jpcc.8b00405

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Au–Pd nanoalloys supported on Mg–Al mixed metal oxides as a multifunctional catalyst for solvent-free oxidation of benzyl alcohol
journal, January 2013

  • Feng, Junting; Ma, Chao; Miedziak, Peter J.
  • Dalton Transactions, Vol. 42, Issue 40
  • DOI: 10.1039/c3dt51855h

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Sum Frequency Generation Study of the Interfacial Layer in Liquid-Phase Heterogeneously Catalyzed Oxidation of 2-Propanol on Platinum: Effect of the Concentrations of Water and 2-Propanol at the Interface
journal, November 2013

  • Thompson, Christopher M.; Carl, Lindsay M.; Somorjai, Gabor A.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 49
  • DOI: 10.1021/jp408123u

Oxidation of 2-propanol to acetone by dioxygen on a platinized electrode under open-circuit conditions
journal, January 1989

  • DiCosimo, Robert; Whitesides, George M.
  • The Journal of Physical Chemistry, Vol. 93, Issue 2
  • DOI: 10.1021/j100339a051

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992

Selective oxidation of alcohols and aldehydes over supported metal nanoparticles
journal, January 2013

  • Davis, Sara E.; Ide, Matthew S.; Davis, Robert J.
  • Green Chem., Vol. 15, Issue 1
  • DOI: 10.1039/C2GC36441G

Heterogeneously Catalyzed Alcohol Oxidation for the Fine Chemical Industry
journal, August 2014

  • Ciriminna, Rosaria; Pandarus, Valerica; Béland, Francois
  • Organic Process Research & Development, Vol. 19, Issue 11
  • DOI: 10.1021/acs.oprd.5b00204

Control of selectivity in allylic alcohol oxidation on gold surfaces: the role of oxygen adatoms and hydroxyl species
journal, January 2015

  • Mullen, Gregory M.; Zhang, Liang; Evans, Edward J.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 6
  • DOI: 10.1039/C4CP04739G

Oxygen and Hydroxyl Species Induce Multiple Reaction Pathways for the Partial Oxidation of Allyl Alcohol on Gold
journal, April 2014

  • Mullen, Gregory M.; Zhang, Liang; Evans, Edward J.
  • Journal of the American Chemical Society, Vol. 136, Issue 17
  • DOI: 10.1021/ja502347d

Efficient Implementation of a van der Waals Density Functional: Application to Double-Wall Carbon Nanotubes
journal, August 2009

Gas management and multiphase flow in direct alcohol fuel cells
journal, May 2014

Effects of Nanoparticle Size and Metal/Support Interactions in Pt-Catalyzed Methanol Oxidation Reactions in Gas and Liquid Phases
journal, September 2014

Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO 2 Catalysts
journal, January 2006

Dramatically Different Kinetics and Mechanism at Solid/Liquid and Solid/Gas Interfaces for Catalytic Isopropanol Oxidation over Size-Controlled Platinum Nanoparticles
journal, July 2014

  • Wang, Hailiang; Sapi, Andras; Thompson, Christopher M.
  • Journal of the American Chemical Society, Vol. 136, Issue 29
  • DOI: 10.1021/ja505641r

Recent advances in the heterogeneously catalysed aerobic selective oxidation of alcohols
journal, September 2010

  • Vinod, C. Prabhakaran; Wilson, Karen; Lee, Adam F.
  • Journal of Chemical Technology & Biotechnology, Vol. 86, Issue 2
  • DOI: 10.1002/jctb.2504

Selective oxidation of alcohols by supported gold nanoparticles: recent advances
journal, January 2016

  • Sharma, Anuj S.; Kaur, Harjinder; Shah, Dipen
  • RSC Advances, Vol. 6, Issue 34
  • DOI: 10.1039/C5RA25646A

Recent advances in catalysts for direct methanol fuel cells
journal, January 2011

  • Zhao, Xiao; Yin, Min; Ma, Liang
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c1ee01307f

Alcohol Oxidation at Platinum–Gas and Platinum–Liquid Interfaces: The Effect of Platinum Nanoparticle Size, Water Coadsorption, and Alcohol Concentration
journal, March 2017

  • Tatsumi, Hironori; Liu, Fudong; Han, Hui-Ling
  • The Journal of Physical Chemistry C, Vol. 121, Issue 13
  • DOI: 10.1021/acs.jpcc.7b01432

Diffusion coefficients of nitrogen and oxygen in water
journal, January 1967

  • Ferrell, Ralph T.; Himmelblau, David M.
  • Journal of Chemical & Engineering Data, Vol. 12, Issue 1
  • DOI: 10.1021/je60032a036

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts
journal, September 2004

Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021

Van der Waals density functionals applied to solids
text, January 2011

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Recent Progress in Catalytic Oxidative Transformations of Alcohols by Supported Gold Nanoparticles
    journal, February 2019

    • Hui, Yonghai; Zhang, Shiqi; Wang, Wentao
    • Advanced Synthesis & Catalysis, Vol. 361, Issue 10
    • DOI: 10.1002/adsc.201801595
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1 (p. 4)figure
      Figure 2 (p. 5)figure
      Figure 3 (p. 6)figure
      Figure 4 (p. 7)figure
      Figure 5 (p. 8)figure
      Figure 6 (p. 10)figure
      Figure 7 (p. 11)figure
      Table 1 (p. 11)table
      Figure 8 (p. 12)figure
      Figure 9 (p. 12)figure
      Table 2 (p. 12)table
      Figure 10 (p. 13)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: