Chen Xingxing, Eckhard Kathrin, Zhou Min, Bron Michael, Schuhmann Wolfgang
Analytische Chemie, Elektroanalytik & Sensorik, Ruhr-Universität Bochum, D-44780 Bochum, Germany.
Anal Chem. 2009 Sep 15;81(18):7597-603. doi: 10.1021/ac900937k.
A strategy for the screening of the electrocatalytic activity of electrocatalysts for possible application in fuel cells and other devices is presented. In this approach, metal nanoclusters (Pt, Au, Ru, and Rh and their codeposits) were prepared using a capillary-based droplet-cell by pulsed electrodeposition in a diffusion-restricted viscous solution. A glassy carbon surface was modified with carbon nanotubes (CNTs) by electrophoretic accumulation and was used as substrate for metal nanoparticle deposition. The formed catalyst spots on the CNT-modified glassy carbon surface were investigated toward their catalytic activity for oxygen reduction as a test reaction employing the redox competition mode of scanning electrochemical microscopy (RC-SECM). Qualitative information on the electrocatalytic activity of the catalysts was obtained by varying the potential applied to the substrate; semiquantitative evaluation was based on the determination of the electrochemically deposited catalyst loading by means of the charge transferred during the metal nanoparticle deposition. Qualitatively, Au showed the highest electrocatalytic activity toward the oxygen reduction reaction (ORR) in phosphate buffer among all investigated single metal catalysts which was attributed to the much higher loading of Au achieved during electrodeposition. Coelectrodeposited Au-Pt catalysts showed a more positive onset potential (-150 mV in RC-SECM experiments) of the ORR in phosphate buffer at pH 6.7. After normalizing the SECM image by the charge during the metal nanocluster deposition which represents the mass loading of the catalyst, Ru showed a higher electrocatalytic activity toward the ORR than Au.
本文提出了一种筛选电催化剂电催化活性的策略,该策略可用于燃料电池及其他器件。在这种方法中,通过在扩散受限的粘性溶液中脉冲电沉积,利用基于毛细管的液滴池制备了金属纳米团簇(Pt、Au、Ru、Rh及其共沉积物)。通过电泳富集用碳纳米管(CNT)修饰玻碳表面,并将其用作金属纳米颗粒沉积的基底。采用扫描电化学显微镜(RC-SECM)的氧化还原竞争模式,研究了在CNT修饰的玻碳表面形成的催化剂斑点对氧还原反应的催化活性,以此作为测试反应。通过改变施加在基底上的电势,获得了关于催化剂电催化活性的定性信息;半定量评估基于通过金属纳米颗粒沉积过程中转移的电荷来确定电化学沉积的催化剂负载量。定性地说,在所有研究的单金属催化剂中,Au在磷酸盐缓冲液中对氧还原反应(ORR)表现出最高的电催化活性,这归因于电沉积过程中实现的更高的Au负载量。在pH 6.7的磷酸盐缓冲液中,共沉积的Au-Pt催化剂显示出ORR的起始电势更正(在RC-SECM实验中为-150 mV)。在用代表催化剂质量负载的金属纳米团簇沉积过程中的电荷对SECM图像进行归一化后,Ru对ORR的电催化活性高于Au。