Topics in Catalysis

, Volume 55, Issue 5–6, pp 376–390 | Cite as

Electronic Structure Engineering in Heterogeneous Catalysis: Identifying Novel Alloy Catalysts Based on Rapid Screening for Materials with Desired Electronic Properties

  • Hongliang Xin
  • Adam Holewinski
  • Neil Schweitzer
  • Eranda Nikolla
  • Suljo Linic
Original Paper


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.


Structure–reactivity relationships Alloy Density functional theory X-ray absorption spectroscopy Oxygen reduction reaction Platinum Rapid screening 



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.


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Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Hongliang Xin
    • 1
  • Adam Holewinski
    • 1
  • Neil Schweitzer
    • 2
  • Eranda Nikolla
    • 3
  • Suljo Linic
    • 1
  1. 1.Department of Chemical EngineeringUniversity of MichiganAnn ArborUSA
  2. 2.Argonne National LaboratoryArgonneUSA
  3. 3.Department of Chemical EngineeringWayne State UniversityDetroitUSA

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