Abstract
The immense phase space of multimetallic materials spanned by structural and compositional degrees of freedom precludes thorough screening for efficient alloy catalysts, even with combinatorial high-throughput experiments or quantum-chemical calculations. Based on X-ray absorption spectroscopy measurements and density functional theory calculations, we have identified critical electronic structure descriptors that govern local chemical reactivity of different sites in metal alloys. These descriptors were used to develop a model that allows us to predict variations in the adsorption energy of various adsorbates on alloy surfaces based on easily accessible physical characteristics of the constituent elements in alloys, mainly their electronegativity, atomic radius, and the spatial extent of valence orbitals. We show that this model, which is grounded on validated theories of chemisorption on metal surfaces, can be used to rapidly screen through a large phase space of alloy catalysts and identify optimal alloys for targeted catalytic transformations. We underline the potential of the electronic structure engineering, relating alloy geometry to its catalytic performance using simple electronic structure descriptors, in catalysis.
Original language | English (US) |
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Pages (from-to) | 376-390 |
Number of pages | 15 |
Journal | Topics in Catalysis |
Volume | 55 |
Issue number | 5-6 |
DOIs | |
State | Published - Jun 2012 |
Funding
Acknowledgments We gratefully acknowledge the support of the US Department of Energy DOE-BES, Division of Chemical Sciences (FG-02-05ER15686) and the National Science Foundation (CBET 1132777). S. Linic also acknowledges the DuPont Young Professor grant by DuPont Corporation and the Camille Dreyfus Teacher– Scholar Award from the Camille & Henry Dreyfus Foundation.
Keywords
- Alloy
- Density functional theory
- Oxygen reduction reaction
- Platinum
- Rapid screening
- Structure-reactivity relationships
- X-ray absorption spectroscopy
ASJC Scopus subject areas
- Catalysis
- General Chemistry