Original Paper

Topics in Catalysis

, Volume 46, Issue 3, pp 276-284

First online:

Bimetallic and Ternary Alloys for Improved Oxygen Reduction Catalysis

  • Anand Udaykumar NilekarAffiliated withDepartment of Chemical and Biological Engineering, University of Wisconsin-Madison
  • , Ye XuAffiliated withCenter for Nanophase Materials Sciences and Chemical Sciences Division, Oak Ridge National Laboratory
  • , Junliang ZhangAffiliated withMaterials Science Department, Brookhaven National Laboratory
  • , Miomir B. VukmirovicAffiliated withMaterials Science Department, Brookhaven National Laboratory
  • , Kotaro SasakiAffiliated withMaterials Science Department, Brookhaven National Laboratory
  • , Radoslav R. AdzicAffiliated withMaterials Science Department, Brookhaven National Laboratory Email author 
  • , Manos MavrikakisAffiliated withDepartment of Chemical and Biological Engineering, University of Wisconsin-Madison Email author 

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Abstract

Using a combination of density functional theory (DFT) calculations and an array of experimental techniques including in situ X-ray absorption spectroscopy, we identified, synthesized, and tested successfully a new class of electrocatalysts for the oxygen reduction reaction (ORR) that were based on monolayers of Pt deposited on different late transition metals (Au, Pd, Ir, Rh, or Ru), of which the Pd-supported Pt monolayer had the highest ORR activity. The amount of Pt used was further decreased by replacing part of the Pt monolayer with a third late transition metal (Au, Pd, Ir, Rh, Ru, Re, or Os). Several of these mixed Pt monolayers deposited on Pd single crystal or on carbon-supported Pd nanoparticles exhibited up to a 20-fold increase in ORR activity on a Pt-mass basis when compared with conventional all-Pt electrocatalysts. DFT calculations showed that their superior activity originated from the interaction between the Pt monolayer and the Pd substrate and from a reduced OH coverage on Pt sites, the result of enhanced destabilization of Pt–OH induced by the oxygenated third metal. This new class of electrocatalysts promises to alleviate the major problems of existing fuel cell technology by simultaneously decreasing materials cost and enhancing performance.

Keywords

Density functional theory calculations Oxygen reduction reaction Platinum monolayer Fuel cells Electrocatalysis Cathode