Facet-Selective Platinum Electrodeposition at Free-standing Polycrystalline Boron-Doped Diamond Films
Center for Advanced Nanoscale Materials and Department of Chemistry, University of Puerto Rico, Rio Piedras Campus, P.O. Box 23346, San Juan, Puerto Rico 00931-3346.Langmuir (Impact Factor: 4.46). 08/2009; 25(17):10329-36. DOI: 10.1021/la8035055
In the present investigation, electrochemical deposition of platinum particles was carried out on boron doped diamond (BDD) films by using cyclic voltammetry at different potential sweep rates while maintaining the Pt concentration and number of potential cycles during the deposition as constant for all samples. The BDD film surfaces were studied using Raman spectroscopy, X-ray diffraction, and scanning electrochemical microscopy. The deposited particles were characterized by scanning electron microscopy/X-ray energy dispersive analysis, X-ray photoelectron spectroscopy, and cyclic voltammetry before and after methanol oxidation. The platinum nanoparticles are found to be selectively electrodeposited on the (111) facets of the BDD. In addition, the location of the Pt particles on the diamond facets was affected by the potential sweep rate. For higher sweep rates, the particle size was dependent on the facet on which the particles are electrodeposited with smooth (110) facets exhibiting a smaller number of particles but with a larger particle diameter. After methanol oxidation studies using cyclic voltammetry and controlled potential electrolysis for several hours, the platinum particles remained attached to the (111) facets of the BDD, while the particles on the (110) facets of the BDD became agglomerated along grain boundaries. Functional groups present on the (111) facet of the diamond surface play an important role on the stability of the particles attached to the diamond surface. After methanol oxidation, the particles deposited on other facets appeared to lose their adhesion leading to agglomeration on the grain boundaries. BDD appears to be a promising electrocatalyst support material that can help to resist platinum nanoparticle agglomeration in direct methanol and other low temperature fuel cell applications.
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ABSTRACT: The catalytic performance of nanoparticles can be tuned either by their composition, which mediates electronic structure, or by shape. The shape of a particle is determined by the surface atomic arrangement and coordination. This is affected by the chosen route to synthesize the particle. The route we employed for treating Pt nanoparticles through the application of a square-wave potential is presented. This treatment enhanced the ammonia oxidation stability at platinum modified boron-doped diamond electrodes. Starting from Pt nanoparticles electrodeposited on diamond substrate instead of bulk Pt, we obtained tetrahexahedral Pt nanoparticles. SEM images showed platinum particles with an irregular shape, close to it several regular sharp shaped platinum particles with a size regime of tenths (100-10 nm) of nanometers. Skeleton type particles appear to be the remains of the precursor platinum particles after the square wave treatment breaks down the platinum particles. Platinum features were not shown on the cyclic voltammograms for treatments longer than 30 minutes. This treatment debilitates the C-O-Pt interaction that provides the stability of the platinum particles on the diamond (111) surface. Non-treated particles show a higher current density for the oxidation of ammonia, than the treated particles. The decay of the current after the potential cycling was greater with the non-treated particles than on the particles, which were subjected to the square wave treatment. The chronoamperometry traces reflects similar behaviors.218th ECS Meeting; 01/2010
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ABSTRACT: Environmental compatibility, high flammability, richest in energy per mass unit, and easy conversion into thermal, mechanical and electrical energy are the key advantages of hydrogen fuel, which makes it an idealized vision for future energy as a promising alternative to the diminishing fossil fuels. Unlike the methods very well known in the literature, we used environmental benign photoelectrochemical (PEC) hydrogen production method. Pt is one of the promising electrode materials for PEC method, but high cost makes it impractical for commercialization. A methodology for low Pt loading (7.22 × 10−5 g cm−2) based on electrospray technique is explained for the preparation of hydrogen evolution electrode. The resulted films are annealed at different temperatures and investigated by different characterization techniques that showed surface morphological and compositional changes with annealing temperature. The pores-type structure is transformed to vertically aligned plate-like structure with annealing temperature. After annealing at 400 °C, Pt film is more oxidized and enriching about ∼30% of film surface area with oxidized Pt. The solar to hydrogen conversion efficiency in water splitting was raised from an initial value of 8.4–10.6% and Pt loading was reduced by approximately 1000-fold (from 0.07 to 7.22 × 10−5 g cm−2). Thus, present high efficient hydrogen electrode preparation method utilized less Pt material than the conventional Pt electrode and the efficiency was increased by 26%. This can be scaled up for becoming a volume production low-cost method.International Journal of Hydrogen Energy 07/2010; 35(13-35):6541-6548. DOI:10.1016/j.ijhydene.2010.02.028 · 3.31 Impact Factor
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ABSTRACT: Sequential electrodeposition of Pt and Ru on boron-doped diamond (BDD) films, in 0.5 M H2SO4 by cyclic voltammetry, has been prepared. The potential cycling, in the aqueous solutions of the respective metals, was between 0.00 and 1.00 V versus Ag/AgCl. The catalyst composites, Pt and PtRu, deposited on BDD film substrates, were tested for methanol oxidation. The modified diamond surfaces were also characterized by scanning electron microscopy-X-ray fluorescence-energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The scanning Auger electron spectroscopy mapping showed the ruthenium signal only in areas where platinum was electrodeposited. Ruthenium does not deposit on the oxidized diamond surface of the boron-doped diamond. Particles with 5–10% of ruthenium with respect to platinum exhibited better performance for methanol oxidation in terms of methanol oxidation peak current and chronoamperometric current stability. The electrogenerated •OH radicals on BDD may interact with Pt surface, participating in the methanol oxidation as shown in oxidation current and the shift in the peak position. The conductive diamond surface is a good candidate as the support for the platinum electrocatalyst, because it ensures catalytic activity, which compares with the used carbon, and higher stability under severe anodic and cathodic conditions.Advances in Physical Chemistry 01/2011; 2011(5). DOI:10.1155/2011/679246
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