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Title: In Situ Spectroscopic Investigation into the Active Sites for Crotonaldehyde Hydrogenation at the Pt Nanoparticle–Co3O4 Interface

Abstract

The hydrogenation of crotonaldehyde by platinum nanoparticles supported on cobalt oxide was used as a reaction to probe the effect of the interface between the two materials on the activity and selectivity of the catalyst. Four potential products can be formed by this reaction: propylene, butyraldehyde, crotyl alcohol, and butanol. When Pt nanoparticles are supported on SiO2, an inert support, only propylene and butyraldehyde are formed. However, when Pt is supported on cobalt oxide, the alcohols make up roughly 40% of the total activity, indicating that cobalt oxide plays a pivotal role in the reaction, much like other active supports such as TiO2. To elucidate the mechanism of alcohol formation, in situ sum frequency generation vibrational spectroscopy (SFG) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) were utilized to probe the reactant adsorption and intermediate formation and the chemical state of the materials under working catalytic conditions. The SFG data indicate that crotonaldehyde adsorbs on the oxide surface, likely through the aldehyde oxygen as well as on the Pt surface through the alkene group. AP-XPS results show that the surface of the Co3O4 support becomes partially reduced under the reaction conditions and Pt exists in its metallic state. Taking these results together,more » we propose in this paper that the crotonaldehyde adsorbs at reduced oxide surface sites and that this adsorption mode is responsible for the production of alcohol products. A platinum nanoparticle density dependence study was also undertaken to change the abundance of interface sites and study their effect on the reaction. The selectivity between the two alcohol products was altered as a function of the Pt nanoparticle density: higher selectivity toward butanol and lower selectivity toward crotyl alcohol was obtained with increasing density, while propylene and butyraldehyde selectivities were constant with respect to density. Finally, on the basis of the data presented, we propose that butanol is preferentially formed at the metal–oxide interface, while crotyl alcohol is formed at oxide surface sites by reaction with spillover hydrogen.« less

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
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:
1393085
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 10; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ambient-pressure XPS; cobalt oxide; hydrogenation; in situ characterization; sum frequency generation; support effects

Citation Formats

Kennedy, Griffin, Melaet, Gérôme, Han, Hui-Ling, Ralston, Walter T., and Somorjai, Gabor A.. In Situ Spectroscopic Investigation into the Active Sites for Crotonaldehyde Hydrogenation at the Pt Nanoparticle–Co3O4 Interface. United States: N. p., 2016. Web. https://doi.org/10.1021/acscatal.6b01640.
Kennedy, Griffin, Melaet, Gérôme, Han, Hui-Ling, Ralston, Walter T., & Somorjai, Gabor A.. In Situ Spectroscopic Investigation into the Active Sites for Crotonaldehyde Hydrogenation at the Pt Nanoparticle–Co3O4 Interface. United States. https://doi.org/10.1021/acscatal.6b01640
Kennedy, Griffin, Melaet, Gérôme, Han, Hui-Ling, Ralston, Walter T., and Somorjai, Gabor A.. Sat . "In Situ Spectroscopic Investigation into the Active Sites for Crotonaldehyde Hydrogenation at the Pt Nanoparticle–Co3O4 Interface". United States. https://doi.org/10.1021/acscatal.6b01640. https://www.osti.gov/servlets/purl/1393085.
@article{osti_1393085,
title = {In Situ Spectroscopic Investigation into the Active Sites for Crotonaldehyde Hydrogenation at the Pt Nanoparticle–Co3O4 Interface},
author = {Kennedy, Griffin and Melaet, Gérôme and Han, Hui-Ling and Ralston, Walter T. and Somorjai, Gabor A.},
abstractNote = {The hydrogenation of crotonaldehyde by platinum nanoparticles supported on cobalt oxide was used as a reaction to probe the effect of the interface between the two materials on the activity and selectivity of the catalyst. Four potential products can be formed by this reaction: propylene, butyraldehyde, crotyl alcohol, and butanol. When Pt nanoparticles are supported on SiO2, an inert support, only propylene and butyraldehyde are formed. However, when Pt is supported on cobalt oxide, the alcohols make up roughly 40% of the total activity, indicating that cobalt oxide plays a pivotal role in the reaction, much like other active supports such as TiO2. To elucidate the mechanism of alcohol formation, in situ sum frequency generation vibrational spectroscopy (SFG) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) were utilized to probe the reactant adsorption and intermediate formation and the chemical state of the materials under working catalytic conditions. The SFG data indicate that crotonaldehyde adsorbs on the oxide surface, likely through the aldehyde oxygen as well as on the Pt surface through the alkene group. AP-XPS results show that the surface of the Co3O4 support becomes partially reduced under the reaction conditions and Pt exists in its metallic state. Taking these results together, we propose in this paper that the crotonaldehyde adsorbs at reduced oxide surface sites and that this adsorption mode is responsible for the production of alcohol products. A platinum nanoparticle density dependence study was also undertaken to change the abundance of interface sites and study their effect on the reaction. The selectivity between the two alcohol products was altered as a function of the Pt nanoparticle density: higher selectivity toward butanol and lower selectivity toward crotyl alcohol was obtained with increasing density, while propylene and butyraldehyde selectivities were constant with respect to density. Finally, on the basis of the data presented, we propose that butanol is preferentially formed at the metal–oxide interface, while crotyl alcohol is formed at oxide surface sites by reaction with spillover hydrogen.},
doi = {10.1021/acscatal.6b01640},
journal = {ACS Catalysis},
number = 10,
volume = 6,
place = {United States},
year = {2016},
month = {9}
}

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Works referenced in this record:

Strong Interactions in Supported-Metal Catalysts
journal, March 1981


Combined action of metal and semiconductor catalysts
journal, June 1968

  • Schwab, G. M.; Koller, K.
  • Journal of the American Chemical Society, Vol. 90, Issue 12
  • DOI: 10.1021/ja01014a016

Designed Catalysts from Pt Nanoparticles Supported on Macroporous Oxides for Selective Isomerization of n -Hexane
journal, May 2014

  • An, Kwangjin; Alayoglu, Selim; Musselwhite, Nathan
  • Journal of the American Chemical Society, Vol. 136, Issue 19
  • DOI: 10.1021/ja5018656

Enhanced CO Oxidation Rates at the Interface of Mesoporous Oxides and Pt Nanoparticles
journal, October 2013

  • An, Kwangjin; Alayoglu, Selim; Musselwhite, Nathan
  • Journal of the American Chemical Society, Vol. 135, Issue 44
  • DOI: 10.1021/ja4088743

Titanium Oxide/Platinum Catalysis: Charge Transfer from a Titanium Oxide Support Controls Activity and Selectivity in Methanol Oxidation on Platinum
journal, October 2011

  • Hervier, Antoine; Baker, L. Robert; Komvopoulos, Kyriakos
  • The Journal of Physical Chemistry C, Vol. 115, Issue 46
  • DOI: 10.1021/jp2066327

Role of Hot Electrons and Metal–Oxide Interfaces in Surface Chemistry and Catalytic Reactions
journal, March 2015

  • Park, Jeong Young; Baker, L. Robert; Somorjai, Gabor A.
  • Chemical Reviews, Vol. 115, Issue 8
  • DOI: 10.1021/cr400311p

Dependence of Gas-Phase Crotonaldehyde Hydrogenation Selectivity and Activity on the Size of Pt Nanoparticles (1.7–7.1 nm) Supported on SBA-15
journal, November 2008

  • Grass, Michael E.; Rioux, Robert M.; Somorjai, Gabor A.
  • Catalysis Letters, Vol. 128, Issue 1-2
  • DOI: 10.1007/s10562-008-9754-4

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

  • Englisch, Martin; Jentys, Andreas; Lercher, Johannes A.
  • Journal of Catalysis, Vol. 166, Issue 1
  • DOI: 10.1006/jcat.1997.1494

Hydrogenation of the α,β-Unsaturated Aldehydes Acrolein, Crotonaldehyde, and Prenal over Pt Single Crystals: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study
journal, July 2009

  • Kliewer, Christopher J.; Bieri, Marco; Somorjai, Gabor A.
  • Journal of the American Chemical Society, Vol. 131, Issue 29
  • DOI: 10.1021/ja8092532

Crotonaldehyde Hydrogenation on Pt/TiO2and Ni/TiO2SMSI Catalysts
journal, April 1999


In Situ Microscopy and Spectroscopy Applied to Surfaces at Work
journal, October 2015


Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on crotonaldehyde by ab initio and DFT methods
journal, December 2011

  • Jayaprakash, A.; Arjunan, V.; Jose, Sujin P.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 83, Issue 1
  • DOI: 10.1016/j.saa.2011.08.054

Remote Plasma Atomic Layer Deposition of Co3O4 Thin Films
journal, January 2011

  • Donders, M. E.; Knoops, H. C. M.; van, M. C. M.
  • Journal of The Electrochemical Society, Vol. 158, Issue 4
  • DOI: 10.1149/1.3552616

High-Surface-Area Catalyst Design:  Synthesis, Characterization, and Reaction Studies of Platinum Nanoparticles in Mesoporous SBA-15 Silica
journal, February 2005

  • Rioux, R. M.; Song, H.; Hoefelmeyer, J. D.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 6
  • DOI: 10.1021/jp048867x

Effect of organic capping layers over monodisperse platinum nanoparticles upon activity for ethylene hydrogenation and carbon monoxide oxidation
journal, July 2009


New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2
journal, May 2010

  • Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda
  • Review of Scientific Instruments, Vol. 81, Issue 5
  • DOI: 10.1063/1.3427218

Beamline 10.3.2 at ALS: a hard X-ray microprobe for environmental and materials sciences
journal, April 2004

  • Marcus, Matthew A.; MacDowell, Alastair A.; Celestre, Richard
  • Journal of Synchrotron Radiation, Vol. 11, Issue 3
  • DOI: 10.1107/S0909049504005837

    Works referencing / citing this record:

    Enhanced catalytic activity for CO oxidation by the metal–oxide perimeter of TiO 2 /nanostructured Au inverse catalysts
    journal, January 2018

    • Lee, Si Woo; Song, Jun Tae; Kim, Jaehoon
    • Nanoscale, Vol. 10, Issue 8
    • DOI: 10.1039/c7nr08168e

    Phosphorus-Doped and Lattice-Defective Carbon as Metal-like Catalyst for the Selective Hydrogenation of Nitroarenes
    journal, October 2017


    Interplay between the metal-support interaction and stability in Pt/Co 3 O 4 (111) model catalysts
    journal, January 2018

    • Lykhach, Yaroslava; Faisal, Firas; Skála, Tomáš
    • Journal of Materials Chemistry A, Vol. 6, Issue 45
    • DOI: 10.1039/c8ta08142e

    Oxide-Nanotrap-Anchored Platinum Nanoparticles with High Activity and Sintering Resistance by Area-Selective Atomic Layer Deposition
    journal, January 2017


    Chemoselective Hydrogenation of Cinnamaldehyde on Iron-Oxide Modified Pt/MoO 3−y Catalysts
    journal, October 2018

    • Shu, Yijin; Chen, Ting; Chan, Hang Cheong
    • Chemistry - An Asian Journal, Vol. 13, Issue 23
    • DOI: 10.1002/asia.201801281

    Origin of synergistic effects in bicomponent cobalt oxide-platinum catalysts for selective hydrogenation reaction
    journal, September 2019


    Oxide‐Nanotrap‐Anchored Platinum Nanoparticles with High Activity and Sintering Resistance by Area‐Selective Atomic Layer Deposition
    journal, February 2017

    • Liu, Xiao; Zhu, Qianqian; Lang, Yun
    • Angewandte Chemie International Edition, Vol. 56, Issue 6
    • DOI: 10.1002/anie.201611559