Tunable model promoters in DFT simulations of catalysts

Andrew Mahler, Kassidy Panno, Benjamin G. Janesko, Salvador Moncho Escriva, Edward Brothers

Research output: Contribution to journalArticle

Abstract

Promoter atoms can tune a catalyst's activity and selectivity by transferring charge to and from the active site. Rational design of promoted catalysts, using density functional theory calculations, is today limited by the need to simulate many catalyst and promoter configurations. We present a simple approximation that rapidly captures some trends in promoter effects, at a cost of complexity comparable with simulating unpromoted catalysts. Negative (positive) noninteger point charges introduced into the catalyst simulate how electropositive (electronegative) promoters might affect each predicted intermediate. Calculations return Sabatier plots, relating promoters' predicted efficacy to readily measured properties such as catalyst work functions. We illustrate our approach for two reactions associated with the Fischer–Tropsch process, hydrogen–deuterium scrambling, and carbon monoxide dissociation over ruthenium. Consistent with experiment, electropositive promoters are predicted to accelerate hydrogen scrambling and unassisted CO dissociation. Simulations also provide a new prediction: electronegative promoters accelerate hydrogen-assisted CO dissociation over hydrogen-precovered surfaces by stabilizing the initial CO adsorption.

Original languageEnglish
JournalJournal of Computational Chemistry
DOIs
Publication statusPublished - 1 Jan 2019

Fingerprint

Carbon Monoxide
Catalyst
Promoter
Discrete Fourier transforms
Hydrogen
Catalysts
Simulation
Ruthenium
Accelerate
Model
Catalyst selectivity
Adsorption
Catalytic Domain
Charge
Carbon monoxide
Density functional theory
Catalyst activity
Costs and Cost Analysis
Selectivity
Density Functional

Keywords

  • catalyst promoter
  • density functional theory
  • heterogeneous catalyst
  • rational design
  • Sabatier plot

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

Tunable model promoters in DFT simulations of catalysts. / Mahler, Andrew; Panno, Kassidy; Janesko, Benjamin G.; Moncho Escriva, Salvador; Brothers, Edward.

In: Journal of Computational Chemistry, 01.01.2019.

Research output: Contribution to journalArticle

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AU - Moncho Escriva, Salvador

AU - Brothers, Edward

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N2 - Promoter atoms can tune a catalyst's activity and selectivity by transferring charge to and from the active site. Rational design of promoted catalysts, using density functional theory calculations, is today limited by the need to simulate many catalyst and promoter configurations. We present a simple approximation that rapidly captures some trends in promoter effects, at a cost of complexity comparable with simulating unpromoted catalysts. Negative (positive) noninteger point charges introduced into the catalyst simulate how electropositive (electronegative) promoters might affect each predicted intermediate. Calculations return Sabatier plots, relating promoters' predicted efficacy to readily measured properties such as catalyst work functions. We illustrate our approach for two reactions associated with the Fischer–Tropsch process, hydrogen–deuterium scrambling, and carbon monoxide dissociation over ruthenium. Consistent with experiment, electropositive promoters are predicted to accelerate hydrogen scrambling and unassisted CO dissociation. Simulations also provide a new prediction: electronegative promoters accelerate hydrogen-assisted CO dissociation over hydrogen-precovered surfaces by stabilizing the initial CO adsorption.

AB - Promoter atoms can tune a catalyst's activity and selectivity by transferring charge to and from the active site. Rational design of promoted catalysts, using density functional theory calculations, is today limited by the need to simulate many catalyst and promoter configurations. We present a simple approximation that rapidly captures some trends in promoter effects, at a cost of complexity comparable with simulating unpromoted catalysts. Negative (positive) noninteger point charges introduced into the catalyst simulate how electropositive (electronegative) promoters might affect each predicted intermediate. Calculations return Sabatier plots, relating promoters' predicted efficacy to readily measured properties such as catalyst work functions. We illustrate our approach for two reactions associated with the Fischer–Tropsch process, hydrogen–deuterium scrambling, and carbon monoxide dissociation over ruthenium. Consistent with experiment, electropositive promoters are predicted to accelerate hydrogen scrambling and unassisted CO dissociation. Simulations also provide a new prediction: electronegative promoters accelerate hydrogen-assisted CO dissociation over hydrogen-precovered surfaces by stabilizing the initial CO adsorption.

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