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

Title: Electrostatic Origins of Linear Scaling Relationships at Bifunctional Metal/Oxide Interfaces: A Case Study of Au Nanoparticles on Doped MgO Substrates

Abstract

Linear scaling relationships (SRs), which relate binding energies of adsorbates across a space of catalyst surfaces, have been extensively explored for metal and oxide surfaces, but little is known about their properties at interfaces between metal nanoparticles and oxide supports, which are ubiquitous in heterogeneous catalysis. Using periodic DFT calculations, scaling principles are extended to bifunctional Au/oxide interfaces. Adopting a Au nanorod on doped MgO (100) as a model, SRs for species participating in water gas shift, methanol synthesis, and oxidation reactions are reported. SR slopes are not constrained by the bond order conservation rule postulated for metals, oxides, and zeolites, potentially permitting greater flexibility in catalyst design strategies. Finally, the deviation from bond counting, along with the physical origin of scaling behavior at interfaces, are explored using a conceptual framework involving electrostatic interactions at the Au/oxide interface.

Authors:
 [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Purdue Univ., West Lafayette, IN (United States). School of Chemical Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1543475
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 47; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; catalyst screening; computational chemistry; doping; scaling relations; supported catalysts

Citation Formats

Choksi, Tej, Majumdar, Paulami, and Greeley, Jeffrey P. Electrostatic Origins of Linear Scaling Relationships at Bifunctional Metal/Oxide Interfaces: A Case Study of Au Nanoparticles on Doped MgO Substrates. United States: N. p., 2018. Web. doi:10.1002/anie.201808246.
Copy to clipboard
Choksi, Tej, Majumdar, Paulami, & Greeley, Jeffrey P. Electrostatic Origins of Linear Scaling Relationships at Bifunctional Metal/Oxide Interfaces: A Case Study of Au Nanoparticles on Doped MgO Substrates. United States. https://doi.org/10.1002/anie.201808246
Copy to clipboard
Choksi, Tej, Majumdar, Paulami, and Greeley, Jeffrey P. Wed . "Electrostatic Origins of Linear Scaling Relationships at Bifunctional Metal/Oxide Interfaces: A Case Study of Au Nanoparticles on Doped MgO Substrates". United States. https://doi.org/10.1002/anie.201808246. https://www.osti.gov/servlets/purl/1543475.
Copy to clipboard
@article{osti_1543475,
title = {Electrostatic Origins of Linear Scaling Relationships at Bifunctional Metal/Oxide Interfaces: A Case Study of Au Nanoparticles on Doped MgO Substrates},
author = {Choksi, Tej and Majumdar, Paulami and Greeley, Jeffrey P.},
abstractNote = {Linear scaling relationships (SRs), which relate binding energies of adsorbates across a space of catalyst surfaces, have been extensively explored for metal and oxide surfaces, but little is known about their properties at interfaces between metal nanoparticles and oxide supports, which are ubiquitous in heterogeneous catalysis. Using periodic DFT calculations, scaling principles are extended to bifunctional Au/oxide interfaces. Adopting a Au nanorod on doped MgO (100) as a model, SRs for species participating in water gas shift, methanol synthesis, and oxidation reactions are reported. SR slopes are not constrained by the bond order conservation rule postulated for metals, oxides, and zeolites, potentially permitting greater flexibility in catalyst design strategies. Finally, the deviation from bond counting, along with the physical origin of scaling behavior at interfaces, are explored using a conceptual framework involving electrostatic interactions at the Au/oxide interface.},
doi = {10.1002/anie.201808246},
journal = {Angewandte Chemie (International Edition)},
number = 47,
volume = 57,
place = {United States},
year = {Wed Sep 12 00:00:00 EDT 2018},
month = {Wed Sep 12 00:00:00 EDT 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/anie.201808246
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: SRs at doped Au/MgO interfaces. (a) Side view of an Au nanorod on MgO (100). (b) – (f): Top views for OH*, NH2*, COOH*, CH2O* and CHO*. (g), (h): SRs for OH*, NH* and NH2*, which show slopes deviating from BOC. (i), (j): SRs for COOH*, CH2O* andmore » CHO*. Dopant colors range from blue (LVDs) to red (HVDs). All adsorbate BE’s are referenced to corresponding gas phase energies.« less
All figures and tables (4 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:

O 2 activation at the Au/MgO(001) interface boundary facilitates CO oxidation
journal, January 2016

  • Duan, Zhiyao; Henkelman, Graeme
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 7
  • DOI: 10.1039/C5CP05558J

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride Surfaces
journal, June 2008

  • Fernández, Eva M.; Moses, Poul G.; Toftelund, Anja
  • Angewandte Chemie, Vol. 120, Issue 25
  • DOI: 10.1002/ange.200705739

Projector augmented-wave method
journal, December 1994

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Methanol–Alkene Reactions in Zeotype Acid Catalysts: Insights from a Descriptor-Based Approach and Microkinetic Modeling
journal, November 2014

  • Brogaard, Rasmus Y.; Wang, Chuan-Ming; Studt, Felix
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs5014267

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Catalysis by Doped Oxides
journal, December 2012

  • McFarland, Eric W.; Metiu, Horia
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr300418s

Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
journal, July 2014

Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design
journal, June 2016

Universality in Heterogeneous Catalysis
journal, July 2002

  • Nørskov, J. K.; Bligaard, T.; Logadottir, A.
  • Journal of Catalysis, Vol. 209, Issue 2
  • DOI: 10.1006/jcat.2002.3615

Computational catalyst screening: Scaling, bond-order and catalysis
journal, September 2016

Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO 2 Reduction to CO
journal, January 2013

  • Hansen, Heine A.; Varley, Joel B.; Peterson, Andrew A.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 3
  • DOI: 10.1021/jz3021155

Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol
journal, March 2014

  • Studt, Felix; Sharafutdinov, Irek; Abild-Pedersen, Frank
  • Nature Chemistry, Vol. 6, Issue 4
  • DOI: 10.1038/nchem.1873

Scaling Relationships for Molecular Adsorption and Dissociation in Lewis Acid Zeolites
journal, March 2016

  • Bukowski, Brandon C.; Greeley, Jeffrey
  • The Journal of Physical Chemistry C, Vol. 120, Issue 12
  • DOI: 10.1021/acs.jpcc.6b01157

Adsorption Energy Correlations at the Metal–Support Boundary
journal, June 2017

Ab initio molecular dynamics for open-shell transition metals
journal, November 1993

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

Relaxed core projector-augmented-wave method
journal, September 2006

  • Marsman, M.; Kresse, G.
  • The Journal of Chemical Physics, Vol. 125, Issue 10
  • DOI: 10.1063/1.2338035

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces
journal, July 2007

Trends in methanol decomposition on transition metal alloy clusters from scaling and Brønsted–Evans–Polanyi relationships
journal, January 2012

  • Mehmood, Faisal; Rankin, Rees B.; Greeley, Jeffrey
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 24
  • DOI: 10.1039/c2cp00052k

A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006

How Doped MoS 2 Breaks Transition-Metal Scaling Relations for CO 2 Electrochemical Reduction
journal, June 2016

Scaling Relationships for Binding Energies of Transition Metal Complexes
journal, December 2015

Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride Surfaces
journal, June 2008

  • Fernández, Eva M.; Moses, Poul G.; Toftelund, Anja
  • Angewandte Chemie International Edition, Vol. 47, Issue 25
  • DOI: 10.1002/anie.200705739

Analyzing the Case for Bifunctional Catalysis
journal, March 2016

  • Andersen, Mie; Medford, Andrew J.; Nørskov, Jens K.
  • Angewandte Chemie International Edition, Vol. 55, Issue 17
  • DOI: 10.1002/anie.201601049

New design paradigm for heterogeneous catalysts
journal, April 2015

  • Vojvodic, Aleksandra; Nørskov, Jens K.
  • National Science Review, Vol. 2, Issue 2
  • DOI: 10.1093/nsr/nwv023

Tuning the surface metal work function by deposition of ultrathin oxide films: Density functional calculations
journal, January 2006

The Theory of Intermolecular Forces
book, January 2013

Towards the computational design of solid catalysts
journal, April 2009

  • Nørskov, J.; Bligaard, T.; Rossmeisl, J.
  • Nature Chemistry, Vol. 1, Issue 1, p. 37-46
  • DOI: 10.1038/nchem.121

Nature of Lone-Pair–Surface Bonds and Their Scaling Relations
journal, June 2018

Analyzing the Case for Bifunctional Catalysis
journal, March 2016

  • Andersen, Mie; Medford, Andrew J.; Nørskov, Jens K.
  • Angewandte Chemie, Vol. 128, Issue 17
  • DOI: 10.1002/ange.201601049

Active Role of Oxide Support during CO Oxidation at A u / M g O
journal, May 2003

Surface Dipoles and Electron Transfer at the Metal Oxide–Metal Interface: A 2PPE Study of Size-Selected Metal Oxide Clusters Supported on Cu(111)
journal, June 2014

  • Yang, Yixiong; Zhou, Jia; Nakayama, Miki
  • The Journal of Physical Chemistry C, Vol. 118, Issue 25
  • DOI: 10.1021/jp503646u

Scaling relations between adsorption energies for computational screening and design of catalysts
journal, January 2014

  • Montemore, Matthew M.; Medlin, J. Will
  • Catal. Sci. Technol., Vol. 4, Issue 11
  • DOI: 10.1039/C4CY00335G

Breaking scaling relations to achieve low-temperature ammonia synthesis through LiH-mediated nitrogen transfer and hydrogenation
journal, August 2016

  • Wang, Peikun; Chang, Fei; Gao, Wenbo
  • Nature Chemistry, Vol. 9, Issue 1
  • DOI: 10.1038/nchem.2595

Establishing and Understanding Adsorption–Energy Scaling Relations with Negative Slopes
journal, November 2016

How covalence breaks adsorption-energy scaling relations and solvation restores them
journal, January 2017

  • Calle-Vallejo, Federico; Krabbe, Alexander; García-Lastra, Juan M.
  • Chemical Science, Vol. 8, Issue 1
  • DOI: 10.1039/C6SC02123A

Size and Support Effects for the Water–Gas Shift Catalysis over Gold Nanoparticles Supported on Model Al 2 O 3 and TiO 2
journal, February 2012

  • Shekhar, Mayank; Wang, Jun; Lee, Wen-Sheng
  • Journal of the American Chemical Society, Vol. 134, Issue 10
  • DOI: 10.1021/ja210083d

Alloys of platinum and early transition metals as oxygen reduction electrocatalysts
journal, September 2009

  • Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.
  • Nature Chemistry, Vol. 1, Issue 7, p. 552-556
  • DOI: 10.1038/nchem.367

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

High-resolution X-ray luminescence extension imaging
journal, February 2021

Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Transition‐Metal–Boron Intermetallics with Strong Interatomic d–sp Orbital Hybridization for High‐Performance Electrocatalysis
    journal, January 2020

    • Ai, Xuan; Zou, Xu; Chen, Hui
    • Angewandte Chemie International Edition, Vol. 59, Issue 10
    • DOI: 10.1002/anie.201915663

    Strategies to break linear scaling relationships
    journal, October 2019

    Enhancing electrostatic interactions to activate polar molecules: ammonia borane methanolysis on a Cu/Co(OH) 2 nanohybrid
    journal, January 2019

    • Chen, Qian-Qian; Li, Qiang; Hou, Chun-Chao
    • Catalysis Science & Technology, Vol. 9, Issue 11
    • DOI: 10.1039/c9cy00584f

    Predicting metal–metal interactions. II. Accelerating generalized schemes through physical insights
    journal, March 2020

    • Choksi, Tej S.; Streibel, Verena; Abild-Pedersen, Frank
    • The Journal of Chemical Physics, Vol. 152, Issue 9
    • DOI: 10.1063/1.5141378
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1 (p. 3)figure
      Table 1 (p. 3)table
      Figure 2 (p. 4)figure
      Figure 3 (p. 5)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: