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Monodisperse ordered indium-palladium nanoparticles: synthesis and the role of indium boosting superior electrocatalytic activity for ethanol oxidation reaction

Abstract

The slow kinetics of ethanol oxidation reaction (EOR) limits its widespread use on fuel cells. Bimetallic catalysts with optimized surface compositions can greatly fasten or govern rate-determining steps through better selectivity for CH3COOH formation or facilitating the adsorption of OHads via a bifunctional effect of alloy, so as to increase the EOR’s kinetic rates. Here, we show monodisperse ordered In-Pd nanoparticles as new bimetalic high-performane catalysts for EOR. In-Pd nanoparticles, i.e., In3Pd2 and In3Pd5, were prepare by arrested precipitation in solution, and their composition, structures, phase and crystallinity were confirmed by a variety of analyses, including TEM, XPS, EDS and XRD. In-Pd nanoparticles were loaded on carbon black (Vulcan XC-72) as electrocatalysts for EOR in alkaline media. In3Pd2 and In3Pd5 nanoparticles have respectively 5.8 times and 4.0 times higher mass activity than that of commercial Pd/C, which shows that the presence of indium greatly boost eletrocatalytic reactivity for EOR of Pd-catalysts. This performance ranks the best among bimetallic nanoparticles reported up to date. Such high performance of In-Pd nanoparticles may be attributed to the following two reasons. First, In-Pd nanoparticles can exhibit excellent CO anti-poison ability as confirmed by CO striping experiments. Second, as revealed by DFT calculation of metals with OHads adsorption, In atoms on In3Pd2 surface has the lowest energy (-1.659 eV) for OHads adsoprtion as compared to other common oxophilic metals, including Sn, SnPt, Ag, Ge, Co, Pb, Cu, which proposes the presence of indium sites promote efficienet free OH radicals adsorption on indium sites and results in faster reaction rate of acetate formation from acetaldehydre (the rate dterming step for the EOR on Pd sites). Finally, single direct ethanol fuel cell (DEFC) with Pd/C anode was prepared. Compared to a commerical Pd/C anode, the open circuit voltage (OCV) of In3Pd2/C was improved by 0.25 V (from 0.64 to 0.89 V), and the power density was improved by ~80% (from 3.7 to 6.7 mW cm-2), demonstrating its practical uses as Pt or Pd catalyst alternatives for DEFC.

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Supplementary files

Publication details

The article was received on 10 Sep 2018, accepted on 02 Jan 2019 and first published on 04 Jan 2019


Article type: Paper
DOI: 10.1039/C8NR07342B
Citation: Nanoscale, 2019, Accepted Manuscript
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    Monodisperse ordered indium-palladium nanoparticles: synthesis and the role of indium boosting superior electrocatalytic activity for ethanol oxidation reaction

    Y. Chen, Y. Chen, C. Chiang, K. Tung, T. Yeh and H. Tuan, Nanoscale, 2019, Accepted Manuscript , DOI: 10.1039/C8NR07342B

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