Watanabe Kengo, Okamoto Keisuke, Kawakami Hiroki, Yoshida Shohei, Kurioka Tomoyuki, Chen Chun-Yi, Yu Chi-Hua, Hsu Yung-Jung, Nakamoto Takamichi, Sone Masato, Chang Tso-Fu Mark
Institute of Integrated Research, Institute of Science Tokyo, Yokohama 226-8501, Japan.
Department of Engineering Science, National Cheng Kung University, Tainan 70101, Taiwan.
Materials (Basel). 2025 Jun 2;18(11):2594. doi: 10.3390/ma18112594.
Noble metals are widely recognized for their ability to catalyze the electro-oxidation of organic compounds, with smaller particle sizes significantly enhancing electrocatalytic activity. In this study, catalytic electrodes decorated with atomic-level platinum and Pt-Au clusters were fabricated using cyclic atomic-metal electrodeposition. The interactions between the iminium (protonated imine) groups in emeraldine salt polyaniline (PANI) and metal chloride complexes in the electrolyte enabled precise control over the cluster size and composition. The electrocatalytic activity of these electrodes for propanol oxidation was systematically evaluated using cyclic voltammetry (CV). Notably, PANI electrodes decorated with odd-numbered atomic-level Pt clusters exhibited higher peak oxidation currents compared to even-numbered clusters, revealing a unique even-odd effect. For atomic-level Pt-Au clusters, the catalytic activity was significantly influenced by the sequence of Pt and Au deposition, with PANI-AuPt achieving the highest catalytic activity (35.34 mA/cm). Bi-metallic clusters consistently outperformed mono-metallic clusters, and clusters containing only one Pt atom demonstrated superior catalytic activity. These findings provide valuable insights into the design of high-performance catalytic electrodes by leveraging atomic-level control of the cluster size, composition, and deposition sequence, paving the way for advanced applications in electrochemical sensors.
贵金属因其催化有机化合物电氧化的能力而被广泛认可,较小的粒径可显著提高电催化活性。在本研究中,使用循环原子金属电沉积法制备了装饰有原子级铂和铂 - 金团簇的催化电极。翠绿盐聚苯胺(PANI)中的亚胺鎓(质子化亚胺)基团与电解质中的金属氯化物配合物之间的相互作用能够精确控制团簇的尺寸和组成。使用循环伏安法(CV)系统地评估了这些电极对丙醇氧化的电催化活性。值得注意的是,与偶数团簇相比,装饰有奇数原子级铂团簇的聚苯胺电极表现出更高的氧化峰电流,揭示了独特的奇偶效应。对于原子级铂 - 金团簇,催化活性受铂和金沉积顺序的显著影响,聚苯胺 - 金铂实现了最高的催化活性(35.34 mA/cm)。双金属团簇始终优于单金属团簇,并且仅含有一个铂原子的团簇表现出优异的催化活性。这些发现通过利用对团簇尺寸、组成和沉积顺序的原子级控制,为高性能催化电极的设计提供了有价值的见解,为电化学传感器的先进应用铺平了道路。