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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]
  1. Purdue Univ., West Lafayette, IN (United States). School of Chemical Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). 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)
OSTI Identifier:
1543475
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
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:
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.
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
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.
@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},
url = {https://www.osti.gov/biblio/1543475}, journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 47,
volume = 57,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
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Cited by: 9 works
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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*, NH 2*, COOH*, CH 2O* and CHO*. (g), (h): SRs for OH*, NH* and NH 2*, which show slopes deviating from BOC. (i), (j): SRs formore » COOH*, CH 2O* and CHO*. Dopant colors range from blue (LVDs) to red (HVDs). All adsorbate BE’s are referenced to corresponding gas phase energies.« less

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    Works referencing / citing this record:

    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


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


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.