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Title: Towards ALD thin film stabilized single-atom Pd 1 catalysts

Abstract

Supported precious metal single-atom catalysts have shown interesting activity and selectivity in recent studies. However, agglomeration of these highly mobile mononuclear surface species can eliminate their unique catalytic properties. Here we study a strategy for synthesizing thin film stabilized single-atom Pd1 catalysts using atomic layer deposition (ALD). The thermal stability of the Pd1 catalysts is significantly enhanced by creating a nanocavity thin film structure. In situ infrared spectroscopy and Pd K-edge X-ray absorption spectroscopy (XAS) revealed that the Pd1 was anchored on the surface through chlorine sites. The thin film stabilized Pd1 catalysts were thermally stable under both oxidation and reduction conditions. The catalytic performance in the methanol decomposition reaction is found to depend on the thickness of protecting layers. While Pd1 catalysts showed promising activity at low temperature in a methanol decomposition reaction, 14 cycle TiO2 protected Pd1 was less active at high temperature. Pd L3 edge XAS indicated that the low reactivity compared with Pd nanoparticles is due to the strong adsorption of carbon monoxide even at 250 °C. Furthermore, these results clearly show that the ALD nanocavities provide a basis for future design of single-atom catalysts that are highly efficient and stable.

Authors:
 [1];  [1];  [1];  [2];  [3];  [4];  [5];  [1]
  1. Univ. of Alabama in Huntsville, Huntsville, AL (United States). Dept. of Chemical and Materials Engineering
  2. Univ. of Illinois, Chicago, IL (United States). Research Resources Center
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Energy Systems Division
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); ORAU; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22) - National Science Foundation (NSF)
OSTI Identifier:
1319206
Alternate Identifier(s):
OSTI ID: 1337161
Grant/Contract Number:  
AC05-00OR22725; CBET-1511820; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 8; Journal Issue: 33; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Piernavieja-Hermida, Mar, Lu, Zheng, White, Anderson, Low, Ke-Bin, Wu, Tianpin, Elam, Jeffrey W., Wu, Zili, and Lei, Yu. Towards ALD thin film stabilized single-atom Pd 1 catalysts. United States: N. p., 2016. Web. https://doi.org/10.1039/c6nr04403d.
Piernavieja-Hermida, Mar, Lu, Zheng, White, Anderson, Low, Ke-Bin, Wu, Tianpin, Elam, Jeffrey W., Wu, Zili, & Lei, Yu. Towards ALD thin film stabilized single-atom Pd 1 catalysts. United States. https://doi.org/10.1039/c6nr04403d
Piernavieja-Hermida, Mar, Lu, Zheng, White, Anderson, Low, Ke-Bin, Wu, Tianpin, Elam, Jeffrey W., Wu, Zili, and Lei, Yu. Wed . "Towards ALD thin film stabilized single-atom Pd 1 catalysts". United States. https://doi.org/10.1039/c6nr04403d. https://www.osti.gov/servlets/purl/1319206.
@article{osti_1319206,
title = {Towards ALD thin film stabilized single-atom Pd 1 catalysts},
author = {Piernavieja-Hermida, Mar and Lu, Zheng and White, Anderson and Low, Ke-Bin and Wu, Tianpin and Elam, Jeffrey W. and Wu, Zili and Lei, Yu},
abstractNote = {Supported precious metal single-atom catalysts have shown interesting activity and selectivity in recent studies. However, agglomeration of these highly mobile mononuclear surface species can eliminate their unique catalytic properties. Here we study a strategy for synthesizing thin film stabilized single-atom Pd1 catalysts using atomic layer deposition (ALD). The thermal stability of the Pd1 catalysts is significantly enhanced by creating a nanocavity thin film structure. In situ infrared spectroscopy and Pd K-edge X-ray absorption spectroscopy (XAS) revealed that the Pd1 was anchored on the surface through chlorine sites. The thin film stabilized Pd1 catalysts were thermally stable under both oxidation and reduction conditions. The catalytic performance in the methanol decomposition reaction is found to depend on the thickness of protecting layers. While Pd1 catalysts showed promising activity at low temperature in a methanol decomposition reaction, 14 cycle TiO2 protected Pd1 was less active at high temperature. Pd L3 edge XAS indicated that the low reactivity compared with Pd nanoparticles is due to the strong adsorption of carbon monoxide even at 250 °C. Furthermore, these results clearly show that the ALD nanocavities provide a basis for future design of single-atom catalysts that are highly efficient and stable.},
doi = {10.1039/c6nr04403d},
journal = {Nanoscale},
number = 33,
volume = 8,
place = {United States},
year = {2016},
month = {7}
}

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Works referenced in this record:

Atomic layer deposition of titanium dioxide from TiCl4 and H2O: investigation of growth mechanism
journal, March 2001


Surface poisoning in the nucleation and growth of palladium atomic layer deposition with Pd(hfac)2 and formalin
journal, June 2011


Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation
journal, April 2009

  • Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu
  • Journal of the American Chemical Society, Vol. 131, Issue 16
  • DOI: 10.1021/ja809936n

Isolated Metal Active Site Concentration and Stability Control Catalytic CO 2 Reduction Selectivity
journal, February 2015

  • Matsubu, John C.; Yang, Vanessa N.; Christopher, Phillip
  • Journal of the American Chemical Society, Vol. 137, Issue 8
  • DOI: 10.1021/ja5128133

Acetylene Cyclotrimerization on Supported Size-Selected Pd n Clusters (1 ≤ n ≤ 30): One Atom Is Enough!
journal, April 2000

  • Abbet, S.; Sanchez, A.; Heiz, U.
  • Journal of the American Chemical Society, Vol. 122, Issue 14
  • DOI: 10.1021/ja9922476

CO Oxidation on Au n /TiO 2 Catalysts Produced by Size-Selected Cluster Deposition
journal, May 2004

  • Lee, Sungsik; Fan, Chaoyang; Wu, Tianpin
  • Journal of the American Chemical Society, Vol. 126, Issue 18
  • DOI: 10.1021/ja049436v

Direct propylene epoxidation over barium-promoted Au/Ti-TUD catalysts with H2 and O2: Effect of Au particle size
journal, September 2007


Effects of Chlorine in Titanium Oxide on Palladium Atomic Layer Deposition
journal, September 2014

  • Lei, Yu; Liu, Bin; Lu, Junling
  • The Journal of Physical Chemistry C, Vol. 118, Issue 39
  • DOI: 10.1021/jp5067567

Role of Cluster Size in Catalysis:  Spectroscopic Investigation of γ-Al 2 O 3 -Supported Ir 4 and Ir 6 during Ethene Hydrogenation
journal, June 2003

  • Argo, Andrew M.; Odzak, Josip F.; Gates, Bruce C.
  • Journal of the American Chemical Society, Vol. 125, Issue 23
  • DOI: 10.1021/ja027741f

Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects
journal, April 2010


In situ surface characterization of the intermetallic compound PdGa – A highly selective hydrogenation catalyst
journal, June 2009


Electronic Structure Controls Reactivity of Size-Selected Pd Clusters Adsorbed on TiO2 Surfaces
journal, November 2009


CO Adsorption on Monometallic and Bimetallic Au−Pd Nanoparticles Supported on Oxide Thin Films
journal, July 2010

  • Abbott, H. L.; Aumer, A.; Lei, Y.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 40
  • DOI: 10.1021/jp1038333

Isolated Metal Atom Geometries as a Strategy for Selective Heterogeneous Hydrogenations
journal, March 2012

  • Kyriakou, Georgios; Boucher, Matthew B.; Jewell, April D.
  • Science, Vol. 335, Issue 6073
  • DOI: 10.1126/science.1215864

Catalysis and In Situ Studies of Rh 1 /Co 3 O 4 Nanorods in Reduction of NO with H 2
journal, April 2013

  • Wang, Lei; Zhang, Shiran; Zhu, Yuan
  • ACS Catalysis, Vol. 3, Issue 5
  • DOI: 10.1021/cs300816u

Effect of Particle Size and Adsorbates on the L3, L2 and L1 X-ray Absorption Near Edge Structure of Supported Pt Nanoparticles
journal, February 2011


Catalytically active Au-O(OH) x - species stabilized by alkali ions on zeolites and mesoporous oxides
journal, November 2014


Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis
journal, June 2016


A View from the Inside:  Complexity in the Atomic Scale Ordering of Supported Metal Nanoparticles
journal, December 2001

  • Frenkel, Anatoly I.; Hills, Charles W.; Nuzzo, Ralph G.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 51
  • DOI: 10.1021/jp012769j

Reactivity and stability of Au in and on TS-1 for epoxidation of propylene with H2 and O2
journal, August 2004


Size- and support-dependency in the catalysis of gold
journal, April 1997


Catalyst Design with Atomic Layer Deposition
journal, February 2015

  • O’Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs501862h

CO Oxidation Catalyzed by Supported Gold: Cooperation between Gold and Nanocrystalline Rare-Earth Supports Forms Reactive Surface Superoxide and Peroxide Species
journal, July 2005

  • Guzman, Javier; Carrettin, Silvio; Fierro-Gonzalez, Juan C.
  • Angewandte Chemie International Edition, Vol. 44, Issue 30
  • DOI: 10.1002/anie.200500659

Intact Size-Selected Au n Clusters on a TiO 2 (110)-(1 × 1) Surface at Room Temperature
journal, October 2005

  • Tong, Xiao; Benz, Lauren; Kemper, Paul
  • Journal of the American Chemical Society, Vol. 127, Issue 39
  • DOI: 10.1021/ja052778w

Alumina Over-coating on Pd Nanoparticle Catalysts by Atomic Layer Deposition: Enhanced Stability and Reactivity
journal, January 2011


The Production of Propene Oxide:  Catalytic Processes and Recent Developments
journal, May 2006

  • Nijhuis, T. Alexander; Makkee, Michiel; Moulijn, Jacob A.
  • Industrial & Engineering Chemistry Research, Vol. 45, Issue 10
  • DOI: 10.1021/ie0513090

Catalytic Oxidation of Carbon Monoxide on Monodispersed Platinum Clusters:  Each Atom Counts
journal, April 1999

  • Heiz, U.; Sanchez, A.; Abbet, S.
  • Journal of the American Chemical Society, Vol. 121, Issue 13
  • DOI: 10.1021/ja983616l

Imaging Isolated Gold Atom Catalytic Sites in Zeolite NaY
journal, March 2012

  • Lu, Jing; Aydin, Ceren; Browning, Nigel D.
  • Angewandte Chemie International Edition, Vol. 51, Issue 24
  • DOI: 10.1002/anie.201107391

Carbon monoxide-induced adatom sintering in a Pd–Fe3O4 model catalyst
journal, June 2013

  • Parkinson, Gareth S.; Novotny, Zbynek; Argentero, Giacomo
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3667

Atomically Dispersed Au–(OH) x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction
journal, March 2013

  • Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria
  • Journal of the American Chemical Society, Vol. 135, Issue 10
  • DOI: 10.1021/ja312646d

Spectroscopic study of the interaction of carbon monoxide with cationic and metallic palladium in palladium–alumina catalysts
journal, January 1992

  • Tessier, Didier; Rakai, Ahmed; Bozon-Verduraz, François
  • J. Chem. Soc., Faraday Trans., Vol. 88, Issue 5
  • DOI: 10.1039/FT9928800741

Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013

  • Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300361m

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition
journal, May 2013

  • Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep01775

Palladium Nanoparticle Formation on TiO 2 (110) by Thermal Decomposition of Palladium(II) Hexafluoroacetylacetonate
journal, August 2014

  • Gharachorlou, Amir; Detwiler, Michael D.; Nartova, Anna V.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 16
  • DOI: 10.1021/am504127k

Resolving Precursor Deligation, Surface Species Evolution, and Nanoparticle Nucleation during Palladium Atomic Layer Deposition
journal, May 2013

  • Lei, Yu; Lu, Junling; Zhao, Haiyan
  • The Journal of Physical Chemistry C, Vol. 117, Issue 21
  • DOI: 10.1021/jp401196f

Atomic Layer Deposition: An Overview
journal, January 2010

  • George, Steven M.
  • Chemical Reviews, Vol. 110, Issue 1, p. 111-131
  • DOI: 10.1021/cr900056b

Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011

  • Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
  • Nature Chemistry, Vol. 3, Issue 8
  • DOI: 10.1038/nchem.1095

The Surface Chemistry of Atomic Layer Depositions of Solid Thin Films
journal, May 2012

  • Zaera, Francisco
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 10
  • DOI: 10.1021/jz300125f

The adsorption and oxidation of methanol on thin palladium films
journal, August 1996


Titanium isopropoxide as a precursor for atomic layer deposition: characterization of titanium dioxide growth process
journal, July 2000


Adsorbate-Induced Structural Changes in 1–3 nm Platinum Nanoparticles
journal, June 2014

  • Lei, Yu; Zhao, Haiyan; Rivas, Rosa Diaz
  • Journal of the American Chemical Society, Vol. 136, Issue 26
  • DOI: 10.1021/ja4126998

Design and synthesis of model and practical palladium catalysts using atomic layer deposition
journal, January 2016

  • Lu, Zheng; Kizilkaya, Orhan; Kropf, A. Jeremy
  • Catalysis Science & Technology, Vol. 6, Issue 18
  • DOI: 10.1039/C6CY00682E

Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts
journal, September 2015


Cluster Chemistry:  Size-Dependent Reactivity Induced by Reverse Spill-Over
journal, August 2007

  • Röttgen, Martin A.; Abbet, Stephane; Judai, Ken
  • Journal of the American Chemical Society, Vol. 129, Issue 31
  • DOI: 10.1021/ja068437f

Selective Vapor-Phase Epoxidation of Propylene over Au/TiO2Catalysts in the Presence of Oxygen and Hydrogen
journal, September 1998

  • Hayashi, Toshio; Tanaka, Koji; Haruta, Masatake
  • Journal of Catalysis, Vol. 178, Issue 2
  • DOI: 10.1006/jcat.1998.2157

CO Oxidation Catalyzed by Supported Gold: Cooperation between Gold and Nanocrystalline Rare-Earth Supports Forms Reactive Surface Superoxide and Peroxide Species
journal, July 2005

  • Guzman, Javier; Carrettin, Silvio; Fierro-Gonzalez, Juan C.
  • Angewandte Chemie, Vol. 117, Issue 30
  • DOI: 10.1002/ange.200500659

Imaging Isolated Gold Atom Catalytic Sites in Zeolite NaY
journal, March 2012

  • Lu, Jing; Aydin, Ceren; Browning, Nigel D.
  • Angewandte Chemie, Vol. 124, Issue 24
  • DOI: 10.1002/ange.201107391

A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries
journal, August 2013

  • Lu, Jun; Lei, Yu; Lau, Kah Chun
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3383

    Works referencing / citing this record:

    Recent Advances in Atomic Metal Doping of Carbon-based Nanomaterials for Energy Conversion
    journal, April 2017


    Strategies for Stabilizing Atomically Dispersed Metal Catalysts
    journal, December 2017


    Recent Advances for MOF‐Derived Carbon‐Supported Single‐Atom Catalysts
    journal, February 2019


    Palladium single atoms supported by interwoven carbon nanotube and manganese oxide nanowire networks for enhanced electrocatalysis
    journal, January 2018

    • Xiang, Weikai; Zhao, Yonghui; Jiang, Zheng
    • Journal of Materials Chemistry A, Vol. 6, Issue 46
    • DOI: 10.1039/c8ta09034c

    Atomically dispersed metal catalysts for the oxygen reduction reaction: synthesis, characterization, reaction mechanisms and electrochemical energy applications
    journal, January 2019

    • Liu, Minmin; Wang, Linlin; Zhao, Kangning
    • Energy & Environmental Science, Vol. 12, Issue 10
    • DOI: 10.1039/c9ee01722d

    Atmosphere-dependent stability and mobility of catalytic Pt single atoms and clusters on γ-Al 2 O 3
    journal, January 2019

    • Dessal, Caroline; Sangnier, Alexis; Chizallet, Céline
    • Nanoscale, Vol. 11, Issue 14
    • DOI: 10.1039/c9nr01641d