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Relating the Composition of Pt x Ru 100− x /C Nanoparticles to Their Structural Aspects and Electrocatalytic Activities in the Methanol Oxidation Reaction
Author(s) -
Taufany Fadlilatul,
Pan ChunJern,
Lai FengJu,
Chou HungLung,
Sarma Loka Subramanyam,
Rick John,
Lin JhihMin,
Lee JyhFu,
Tang MauTsu,
Hwang BingJoe
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202473
Subject(s) - bimetallic strip , vacancy defect , x ray absorption spectroscopy , catalysis , alloy , nanoparticle , band gap , materials science , absorption spectroscopy , transmission electron microscopy , methanol , ethylene glycol , density functional theory , analytical chemistry (journal) , crystallography , chemistry , nanotechnology , computational chemistry , metallurgy , biochemistry , chromatography , physics , optoelectronics , organic chemistry , quantum mechanics
A controlled composition‐based method—that is, the microwave‐assisted ethylene glycol (MEG) method—was successfully developed to prepare bimetallic Pt x Ru 100− x /C nanoparticles (NPs) with different alloy compositions. This study highlights the impact of the variation in alloy composition of Pt x Ru 100− x /C NPs on their alloying extent (structure) and subsequently their catalytic activity towards the methanol oxidation reaction (MOR). The alloying extent of these Pt x Ru 100− x /C NPs has a strong influence on their Pt d‐band vacancy and Pt electroactive surface area (Pt ECSA); this relationship was systematically evaluated by using X‐ray absorption (XAS), scanning electron microscopy (SEM) coupled with energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), density functional theory (DFT) calculations, and electrochemical analyses. The MOR activity depends on two effects that act in cooperation, namely, the number of active Pt sites and their activity. Here the number of active Pt sites is associated with the Pt ECSA value, whereas the Pt‐site activity is associated with the alloying extent and Pt d‐band vacancy (electronic) effects. Among the Pt x Ru 100− x /C NPs with various Pt:Ru atomic ratios ( x =25, 50, and 75), the Pt 75 Ru 25 /C NPs were shown to be superior in MOR activity on account of their favorable alloying extent, Pt d‐band vacancy, and Pt ECSA. This short study brings new insight into probing the synergistic effect on the surface reactivity of the Pt x Ru 100− x /C NPs, and possibly other bimetallic Pt‐based alloy NPs.