Abstract

Precisely tailoring the structure and fully making use of the components of nanoparticles are effective to enhance their catalytic performance for a given reaction. We herein demonstrate the design of cage-bell structured Pt-Pd nanoparticles, where a Pd shell is deliberately selected to enhance the catalytic property and methanol tolerance of Pt for oxygen reduction reaction. This strategy starts with the synthesis of core-shell Pt@Ag nanoparticles, followed by galvanic replacement reaction between the Ag shell and Pd2+ ions to form core-shell-shell Pt@Ag@Ag-Pd nanoparticles with a Pt core and double shells composed of Ag at inner and alloy Ag-Pd at outer, respectively. Then, the core-shell-shell templates are agitated with saturated NaCl solution to eliminate the Ag component from the double shells, leading to the formation of bimetallic Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell, which show enhanced catalytic activity for oxygen reduction compared with that of the Pt seeds due to the additional catalysis from Pd shell. In addition, owing to the different diffusion behavior of methanol and oxygen molecules in the porous Pd shell, the Pt-Pd cage-bell nanostructures also exhibit superior methanol tolerant property in catalyzing the oxygen reduction.

Highlights

  • Core-shell-shell Pt@Ag@Ag-Pd templates are agitated with NaCl solution to eliminate the Ag component from the inner and outer shells for the formation of final Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell

  • Analogous to the synthesis of CBS Pt-M (M = Ru, Os, or Ir) nanoparticles we reported earlier[4,6], the protocol in this study begins with the preparation of Pt seed particles by oleylamine reduction of Pt(II) acetylacetonate (Pt(acac)2)

  • The X-ray diffraction (XRD) patterns of monometallic Ag and Pd nanoparticles prepared in oleylamine were presented, as shown by Supplementary Information (SI) Figure S1b,c, respectively

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Summary

Introduction

Core-shell-shell Pt@Ag@Ag-Pd templates are agitated with NaCl solution to eliminate the Ag component from the inner and outer shells for the formation of final Pt-Pd nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a porous Pd shell. As we will display later, the CBS Pt-Pd nanoparticles show superior activity, durability, and selectivity for the ORR in the presence of high concentration of methanol in comparison with those of the staring Pt seed particles. The concept in this work might be extended to generate other CBS nanoparticles with enhanced activity and desired selectivity for a given chemical reaction

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