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Electrocatalytic Activity of Organically Functionalized Silver Nanoparticles in Oxygen Reduction

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Silver nanoparticles capped by a variety of organic ligands (i.e., 1-hexanethiol, 1-octyne, and 4-trifluoromethylphenyl fragments) were synthesized by a chemical reduction route, with the resulting nanoparticles denoted as AgSC6, AgHC8, and AgPhCF3, respectively. The nanoparticle structures were characterized by using a variety of techniques including NMR, UV-vis, infrared, thermogravimetric analysis, and X-ray photoelectron spectroscopies, high-resolution transmission electron microscopy, and electrochemical methods; and their electrocatalytic activities in oxygen reduction in alkaline media were evaluated and compared within the context of metal-ligand interfacial bonding interactions by using “bare” Ag nanoparticles supported on carbon black (Ag/C) as the benchmark materials. The results demonstrated that the electrocatalytic activity increased in the order of AgSC6 < Ag/C < AgHC8 < AgPhCF3. Of these, the activity of the AgSC6 nanoparticles was even lower than that of Ag/C, whereas the AgPhCF3 nanoparticles exhibited a specific activity that was about 13 times that of Ag/C and an onset potential that was ca. 200 mV more positive than that of Ag/C. The observed discrepancy of the nanoparticle electrocatalytic performance was accounted for by the deliberate manipulation of the nanoparticle electronic energy by the metal-ligand interfacial bonding interactions that dictated the adsorption of oxygen and reaction intermediates and hence the electron-transfer dynamics of oxygen reduction.
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Keywords: ELECTROCATALYSIS; FUEL CELL; ORGANIC CAPPING LAYER; OXYGEN REDUCTION; SILVER NANOPARTICLE

Document Type: Research Article

Publication date: November 1, 2013

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  • Science of Advanced Materials (SAM) is an interdisciplinary peer-reviewed journal consolidating research activities in all aspects of advanced materials in the fields of science, engineering and medicine into a single and unique reference source. SAM provides the means for materials scientists, chemists, physicists, biologists, engineers, ceramicists, metallurgists, theoreticians and technocrats to publish original research articles as reviews with author's photo and short biography, full research articles and communications of important new scientific and technological findings, encompassing the fundamental and applied research in all latest aspects of advanced materials.
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