Synthesis and Characterization of Pt–Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction

Yang, Xuan; Roling, Luke T.; Vara, Madeline; Elnabawy, Ahmed O.; Zhao, Ming; Hood, Zachary D.; Bao, Shixiong; Mavrikakis, Manos; Xia, Younan

doi:10.1021/acs.nanolett.6b03395

Synthesis and Characterization of Pt–Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction

Journal Article · Fri Sep 23 00:00:00 EDT 2016 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.6b03395· OSTI ID:1398266

Yang, Xuan ^[1]; Roling, Luke T. ^[2]; Vara, Madeline ^[3]; Elnabawy, Ahmed O. ^[2]; Zhao, Ming ^[3]; Hood, Zachary D. ^[4]; Bao, Shixiong ^[5]; Mavrikakis, Manos ^[2]; Xia, Younan ^[5]

Georgia Institute of Technology and Emory Univ., Atlanta, GA (United States); Department of Chemical and Biological Engineering, University of Wisconsin—Madison
Univ. of Wisconsin-Madison, Madison, WI (United States)
Georgia Inst. of Technology, Atlanta, GA (United States)
Georgia Inst. of Technology, Atlanta, GA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Georgia Institute of Technology and Emory Univ., Atlanta, GA (United States)

Engineering the elemental composition of metal nanocrystals offers an effective strategy for the development of catalysts or electrocatalysts with greatly enhanced activity. Herein, we report the synthesis of Pt–Ag alloy nanocages with an outer edge length of 18 nm and a wall thickness of about 3 nm. Such nanocages with a composition of Pt₁₉Ag₈₁ could be readily prepared in one step through the galvanic replacement reaction between Ag nanocubes and a Pt(II) precursor. Here, after 10 000 cycles of potential cycling in the range of 0.60–1.0 V as in an accelerated durability test, the composition of the nanocages changed to Pt₅₆Ag₄₄, together with a specific activity of 1.23 mA cm^–2 toward oxygen reduction, which was 3.3 times that of a state-of-the-art commercial Pt/C catalyst (0.37 mA cm^–2) prior to durability testing. Density functional theory calculations attributed the increased activity to the stabilization of the transition state for breaking the O–O bond in molecular oxygen. Even after 30 000 cycles of potential cycling, the mass activity of the nanocages only dropped from 0.64 to 0.33 A mg^–1_Pt, which was still about two times that of the pristine Pt/C catalyst (0.19 A mg^–1_Pt).

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin-Madison, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Contributing Organization:: Environmental Molecular Sciences Laboratory; and the UW-Madison Center for High Throughput Computing (CHTC); the Center for Nanoscale Materials at Argonne National Laboratory; the National Energy Research Scientific Computing Center (NERSC)

Grant/Contract Number:: FG02-05ER15731

OSTI ID:: 1398266

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 10 Vol. 16; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Pt−Ag alloy
density functional theory
nanocage
oxygen reduction reaction
platinum-based catalyst

Synthesis and Characterization of Pt–Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction

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