摘要
Platinum clusters(Pt_(n))are extensively used as electrocatalysts for oxygen reduction reaction(ORR)because they provide excellent performance together with a reduced Pt requirement.However,the precise synthesis and atomic-level insights into the structure-activity relationship of Pt_(n) remain a great challenge.Here,we present a combinatorial synthesis and analysis method to investigate the atomicity-activity relationships of Pt_(n) at the individual level.We employ single nanoparticle collision electrochemistry to facilitate the in-situ electrodeposition of a single precisely tunable Pt_(n) on the graphene quantum dot support,followed by instantaneous measurement of the intrinsic ORR activity of the resulting Pt_(n).By relying on highly sensitive electrochemical measurements,our investigations clarify the atomicity-specific ORR activity of Pt_(n),which is attributed to their distinct geometric and electronic structures at varying cluster sizes.Significantly,Pt_(n) with low atomicity,especially below 20,can reach extraordinarily high ORR activities due to atom-by-atom arrangement.Our work provides a simple and efficient method for investigating the atomicity-activity relationships of other nanoclusters under real reaction conditions,enabling a better design of the electrocatalysts at the atomic level.
铂团簇(Pt_(n))由于具有优异催化性能和低Pt用量而被广泛用作氧还原反应电催化剂.然而,精确合成Pt_(n)以及从原子尺度探讨其构效关系仍然是领域内巨大的挑战.为此,我们提出了一种兼具合成和分析的组合方法在单个水平上深入探究了Pt_(n)原子数-活性之间的关系.本研究采用单颗粒碰撞电化学方法实现了在石墨烯量子点载体上原位电沉积单个原子数精确可控的Pt_(n),并即时测量其本征氧还原反应活性.通过高灵敏的电化学测量,我们的研究阐明了氧还原反应条件下Pt_(n)比活性与原子数之间的明确关系,这归因于不同原子数下团簇所呈现的独特几何和电子结构.值得注意的是,低原子数的Pt_(n),尤其是n<20时,通过逐个原子排列的方式表现出极高的氧还原反应活性.该研究为在真实反应条件下研究其他团簇的原子数-活性关系提供了一种简便有效的方法,为从原子尺度优化电催化剂的设计提供了新思路.
基金
financially supported by the National Natural Science Foundation of China(22272052)
the Major Research Project(92061108)
the Science and Technology Commission of Shanghai Municipality(24DX1400200)。
