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Programming ORR Activity of Ni/NiO _x @Pd Electrocatalysts via Controlling Depth of Surface-Decorated Atomic Pt Clusters.

ABSTRACT: Carbon nanotube supported ternary metallic nanocatalysts (NCs) comprising Ni_core-Pd_shell structure and Pt atomic scale clusters in shell (namely, Ni@Pd/Pt) are synthesized by using wet chemical reduction method with reaction time control. Effects of Pt⁴⁺ adsorption time and Pt/Pd composition ratios on atomic structure with respect to electrochemical performances of experimental NCs are systematically investigated. By cross-referencing results of high-resolution transmission electron microscopy, X-ray diffraction, X-ray absorption, density functional theoretical calculations, and electrochemical analysis, we demonstrate that oxygen reduction reaction (ORR) activity is dominated by depth and distribution of Pt clusters in a Ni@Pd/Pt NC. For the optimum case (Pt⁴⁺ adsorption time = 2 h), specific activity of Ni@Pd/Pt is 0.732 mA cm^-2 in ORR. Such a value is 2.8-fold higher as compared to that of commercial J.M.-Pt/C at 0.85 V (vs reversible hydrogen electrode). Such improvement is attributed to the protection of defect sites from oxide reaction in the presence of Pt clusters in NC surface. When adsorption time is 10 s, Pt clusters tends to adsorb in the Ni@Pd surface. A substantially increased galvanic replacement between Pt⁴⁺ ion and Pd/Ni metal is found to result in the formation of Ni@Pd shell with Pt cluster in the interface when adsorption time is 24 h. Both structures increase the surface defect density and delocalize charge density around Pt clusters, thereby suppressing the ORR activity of Ni@Pd/Pt NCs.

SUBMITTER: Bhalothia D

PROVIDER: S-EPMC6645242 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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Programming ORR Activity of Ni/NiO x @Pd Electrocatalysts via Controlling Depth of Surface-Decorated Atomic Pt Clusters.

Bhalothia Dinesh D Chou Jyh-Pin JP Yan Che C Hu Alice A Yang Ya-Tang YT Chen Tsan-Yao TY

ACS omega 20180807 8

Carbon nanotube supported ternary metallic nanocatalysts (NCs) comprising Nicore-Pdshell structure and Pt atomic scale clusters in shell (namely, Ni@Pd/Pt) are synthesized by using wet chemical reduction method with reaction time control. Effects of Pt4+ adsorption time and Pt/Pd composition ratios on atomic structure with respect to electrochemical performances of experimental NCs are systematically investigated. By cross-referencing results of high-resolution t ...[more]

PMID: 31459005

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Project description:Crystalline platinum nanoparticles supported on carbon nanofibers were synthesized for use as an electrocatalyst for polymer electrolyte membrane fuel cells. The nanofibers were prepared by a method of electrospinning from polymer solution with subsequent pyrolysis. Pt nanoneedles supported on polyacrylonitrile pyrolyzed electrospun nanofibers were synthesized by chemical reduction of H2[PtCl6] in aqueous solution. The synthesized electrocatalysts were investigated using scanning, high resolution transmission and scanning transmission electron microscopies, EDX analysis and electron diffraction. The shape and the size of the electrocatalyst crystal Pt nanoparticles were controled and found to depend on the method of H2[PtCl6] reduction type and on conditions of subsequent thermal treatment. Soft Pt reduction by formic acid followed by 100 °C thermal treatment produced needle-shape Pt nanoparticles with a needle length up to 25 nm and diameter up to 5 nm. Thermal treatment of these nanoparticles at 500 °C resulted in partial sintering of the Pt needles. When formic acid was added after 24 h from the beginning of platinization, Pt reduction resulted in small-size spherical Pt nanoparticle of less than 10 nm in diameter. Reduction of H2[PtCl6], preadsorbed on electrospun nanofibers in formic acid with further treatment in H2 flow at 500 °C, resulted in intensive sintering of platinum particles, with formation of conglomerates of 50 nm in size, however, individual particles still retain a size of less than 10 nm. Electrochemically active surface area (ECSA) of Pt/C catalyst was measured by electrochemical hydrogen adsorption/desorption measurements in 0.5 M H2SO4. ECSA of needle-shape Pt nanoparticles was 25 m2 g-1. It increased up to 31 m2 g-1 after thermal treatment at 500 °C, likely, due to amorphous structures removal from carbon nanofibers and retaining of Pt nanoneedle morphology. ECSA of small-size spherical Pt nanoparticles was 26 m2 g-1. Further thermal treatment at 500 °C in vacuum decreased ECSA down to 20 m2 g-1 due to Pt sintering and Pt active sites deactivation. The thermal treatment of small-size spherical Pt nanoparticles in H2 flow at 500 °C produced agglomerates of Pt nanoparticles with ECSA of 14 m2 g-1.

Dataset Information

Programming ORR Activity of Ni/NiO _x @Pd Electrocatalysts via Controlling Depth of Surface-Decorated Atomic Pt Clusters.

Publications

Programming ORR Activity of Ni/NiO <i><sub>x</sub></i> @Pd Electrocatalysts via Controlling Depth of Surface-Decorated Atomic Pt Clusters.

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