González-González Ileana, Fachini Estevão Rosim, Scibioh M Aulice, Tryk Donald A, Tague Michele, Abruña Héctor D, Cabrera Carlos R
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. 2009 Sep 1;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.
在本研究中,通过循环伏安法在不同的电位扫描速率下,在硼掺杂金刚石(BDD)薄膜上进行铂颗粒的电化学沉积,同时在沉积过程中保持所有样品的铂浓度和电位循环次数恒定。使用拉曼光谱、X射线衍射和扫描电化学显微镜对BDD薄膜表面进行了研究。通过扫描电子显微镜/X射线能量色散分析、X射线光电子能谱以及甲醇氧化前后的循环伏安法对沉积颗粒进行了表征。发现铂纳米颗粒选择性地电沉积在BDD的(111)晶面上。此外,铂颗粒在金刚石晶面上的位置受电位扫描速率的影响。对于较高的扫描速率,颗粒尺寸取决于颗粒电沉积所在的晶面,光滑的(110)晶面上颗粒数量较少,但颗粒直径较大。在使用循环伏安法和恒电位电解进行数小时的甲醇氧化研究后,铂颗粒仍附着在BDD的(111)晶面上,而BDD的(110)晶面上的颗粒则沿晶界团聚。金刚石表面(111)晶面上存在的官能团对附着在金刚石表面的颗粒的稳定性起着重要作用。甲醇氧化后,沉积在其他晶面上的颗粒似乎失去了附着力,导致在晶界上团聚。BDD似乎是一种很有前景的电催化剂载体材料,可有助于在直接甲醇和其他低温燃料电池应用中抵抗铂纳米颗粒的团聚。