Platinum-monolayer shell on AuNi(0.5)Fe nanoparticle core electrocatalyst with high activity and stability for the oxygen reduction reaction.
ABSTRACT We describe a simple method for preparing multimetallic nanoparticles by in situ decomposition of the corresponding Prussian blue analogue, which is adsorbed on carbon black. The example involves the AuNi(0.5)Fe core of the Pt(ML)/Au(1)Ni(0.5)Fe core-shell electrocatalyst for the oxygen reduction reaction. The core contains 3-5 surface atomic layers of Au, which play an essential role in determining the activity and stability of the catalyst. The Pt(ML)/AuNi(0.5)Fe electrocatalyst exhibited Pt mass and specific activities of 1.38 A/mg(Pt) and 1.12 × 10(-3) A/cm(2)(Pt), respectively, both of which are several times higher than those of commercial Pt/C catalysts. Its all-noble-metal mass activity (0.18 A/mg(Pt,Au)) is higher than or comparable to those of commercial samples. Stability tests showed an insignificant loss in activity after 15,000 triangular-potential cycles. We ascribe the high activity and stability of the Pt(ML)/AuNi(0.5)Fe electrocatalyst to its hierarchical structural properties, the Pt-core interaction, and the high electrochemical stability of the gold shell that precludes exposure to the electrolyte of the relatively active inner-core materials.
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ABSTRACT: Platinum is a widely used precious metal in many catalytic nanostructures. Engineering the surface electronic structure of Pt-containing bi- or multimetallic nanostructure to enhance both the intrinsic activity and dispersion of Pt has remained a challenge. By constructing Pt-on-Au (Pt^Au) nanostructures using a series of monodisperse Au nanoparticles in the size range of 2-14 nm, we disclose herein a new approach to steadily change both properties of Pt in electrocatalysis with downsizing of the Au nanoparticles. A combined tuning of Pt dispersion and its surface electronic structure is shown as a consequence of the changes in the size and valence-band structure of Au, which leads to significantly enhanced Pt mass-activity on the small Au nanoparticles. Fully dispersed Pt entities on the smallest Au nanoparticles (2 nm) exhibit the highest mass-activity to date towards formic acid electrooxidation, being 2 orders of magnitude (75-300 folds) higher than conventional Pt/C catalyst. Fundamental relationships correlating the Pt intrinsic activity in Pt^Au nanostructures with the experimentally determined surface electronic structures (d-band center energies) of the Pt entities and their underlying Au nanoparticles are established.ACS Nano 02/2012; 6(3):2226-36. · 10.77 Impact Factor
Article: Structurally ordered intermetallic platinum-cobalt core-shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts.[show abstract] [hide abstract]
ABSTRACT: To enhance and optimize nanocatalyst performance and durability for the oxygen reduction reaction in fuel-cell applications, we look beyond Pt-metal disordered alloys and describe a new class of Pt-Co nanocatalysts composed of ordered Pt(3)Co intermetallic cores with a 2-3 atomic-layer-thick platinum shell. These nanocatalysts exhibited over 200% increase in mass activity and over 300% increase in specific activity when compared with the disordered Pt(3)Co alloy nanoparticles as well as Pt/C. So far, this mass activity for the oxygen reduction reaction is the highest among the Pt-Co systems reported in the literature under similar testing conditions. Stability tests showed a minimal loss of activity after 5,000 potential cycles and the ordered core-shell structure was maintained virtually intact, as established by atomic-scale elemental mapping. The high activity and stability are attributed to the Pt-rich shell and the stable intermetallic Pt(3)Co core arrangement. These ordered nanoparticles provide a new direction for catalyst performance optimization for next-generation fuel cells.Nature Material 10/2012; · 32.84 Impact Factor