skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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. 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]
  1. Davidson School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive West Lafayette IN 47906 USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1543475
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 57; Journal Issue: 47; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
Chemistry

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.
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. doi:10.1002/anie.201808246.
Choksi, Tej, Majumdar, Paulami, and Greeley, Jeffrey P. Tue . "Electrostatic Origins of Linear Scaling Relationships at Bifunctional Metal/Oxide Interfaces: A Case Study of Au Nanoparticles on Doped MgO Substrates". United States. doi:10.1002/anie.201808246.
@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. 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)},
issn = {1433-7851},
number = 47,
volume = 57,
place = {United States},
year = {2018},
month = {10}
}

Works referenced in this record:

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

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

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


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


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


Projector augmented-wave method
journal, December 1994


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