Institut National de la Recherche Scientifique, Energie, Materiaux & Telecommunications, 1650 Bd Lionel Boulet, Varennes, Quebec J3X 1S2, Canada.
ACS Appl Mater Interfaces. 2009 Aug;1(8):1623-39. doi: 10.1021/am900219g.
Nine non-noble-metal catalysts (NNMCs) from five different laboratories were investigated for the catalysis of O(2) electroreduction in an acidic medium. The catalyst precursors were synthesized by wet impregnation, planetary ball milling, a foaming-agent technique, or a templating method. All catalyst precursors were subjected to one or more heat treatments at 700-1050 degrees C in an inert or reactive atmosphere. These catalysts underwent an identical set of electrochemical characterizations, including rotating-disk-electrode and polymer-electrolyte membrane fuel cell (PEMFC) tests and voltammetry under N(2). Ex situ characterization was comprised of X-ray photoelectron spectroscopy, neutron activation analysis, scanning electron microscopy, and N(2) adsorption and its analysis with an advanced model for carbonaceous powders. In PEMFC, several NNMCs display mass activities of 10-20 A g(-1) at 0.8 V versus a reversible hydrogen electrode, and one shows 80 A g(-1). The latter value corresponds to a volumetric activity of 19 A cm(-3) under reference conditions and represents one-seventh of the target defined by the U.S. Department of Energy for 2010 (130 A cm(-3)). The activity of all NNMCs is mainly governed by the microporous surface area, and active sites seem to be hosted in pore sizes of 5-15 A. The nitrogen and metal (iron or cobalt) seem to be present in sufficient amounts in the NNMCs and do not limit activity. The paper discusses probable directions for synthesizing more active NNMCs. This could be achieved through multiple pyrolysis steps, ball-milling steps, and control of the powder morphology by the addition of foaming agents and/or sulfur.
来自五个不同实验室的九种非贵金属催化剂(NNMCs)被用于研究在酸性介质中 O(2)电还原的催化作用。催化剂前体通过湿浸渍、行星球磨、发泡剂技术或模板法合成。所有催化剂前体都在惰性或反应性气氛中在 700-1050°C 下进行一次或多次热处理。这些催化剂经历了相同的电化学特性测试,包括旋转圆盘电极和聚合物电解质膜燃料电池(PEMFC)测试以及在 N(2)下的伏安法测试。非原位表征包括 X 射线光电子能谱、中子活化分析、扫描电子显微镜以及 N(2)吸附及其与先进的碳质粉末模型的分析。在 PEMFC 中,几种 NNMC 在 0.8 V 对可逆氢电极的质量活性为 10-20 A g(-1),其中一种为 80 A g(-1)。后者的值对应于参考条件下 19 A cm(-3)的体积活性,是美国能源部为 2010 年设定目标(130 A cm(-3))的七分之一。所有 NNMC 的活性主要受微孔表面积控制,活性位似乎位于 5-15 A 的孔径中。氮和金属(铁或钴)似乎在 NNMC 中以足够的量存在,不会限制活性。本文讨论了合成更活性 NNMC 的可能方向。这可以通过多次热解步骤、球磨步骤以及通过添加发泡剂和/或硫来控制粉末形态来实现。