Single‐Molecule Nanocatalysis Shows In Situ Deactivation of Pt/C Electrocatalysts during the Hydrogen‐Oxidation Reaction

Abstract

By coupling a Pt-catalyzed fluorogenic reaction with the Pt-electrocatalyzed hydrogen-oxidation reaction (HOR), we combine single-molecule fluorescence microscopy with traditional electrochemical methods to study the real-time deactivation kinetics of a Pt/C electrocatalyst at single-particle level during electrocatalytic hydrogen-oxidation reaction. The decay of the catalytic performance of Pt/C could be mainly attributed to the electrocatalysis-induced etching or dissolution of Pt nanoparticles. Spontaneous regeneration of activity and incubation period of the Pt electrocatalyst were also observed at single-particle level. All these new insights are practically useful for the understanding and rational design of highly efficient electrocatalysts for application in fuel cells.

Imaging the electrochemistry of single nanoparticles with optical microscopy

“…TIRFM是目前单分子荧光技术中最常用的成像 方法之一 [27] 示催化反应的异相动力学行为. Zhang等 [36] 通过将Pt 催化的荧光反应和Pt电催化的氢氧化反应相结合, 实 时研究了单个Pt/C电催化剂在电催化氢氧化反应中的 图 1 (A)单层石墨烯片的异相电化学氧化和还原过程研究 [31] . (B)缺陷驱动的石墨烯-电极界面异相电子转移动力学研究 [35] .…”

“…(B)缺陷驱动的石墨烯-电极界面异相电子转移动力学研究 [35] . (C)Pt/C电催化剂在电催化氢氧化过程中的原位失活研究 [36] . (D)单分子水平上两电子氧还原动力学的选择性研究 [37] (网络版 彩图)…”

Recent progress on single-molecule nanocatalysis based on single-molecule fluorescence microscopy

“…For the design and development of highly efficient electrocatalysts, the deactivation mechanism of these Pt-based electrocatalysts need to be understood deeply. In our recent work [44], by coupling a Pt-catalyzed fluorogenic reaction [45] with Pt-electrocatalyzed HOR tandemly [46] (Fig. 5), we studied the deactivation process of individual Pt nanocatalysts.…”

Adsorption and desorption mechanisms on graphene oxide nanosheets: Kinetics and tuning

“…Currently, total internal reflection fluorescence microscopy (TIRFM) has attracted worldwide interest due to the important role in unraveling the kinetics and dynamics of catalysis at the single-nanoparticle level. 21 , 22 , 23 , 24 , 25 , 26 For instance, TIRFM was used to resolve the active site distribution and the position-related kinetics mechanism of Au nanoparticles. 27 It was also used to study the differences of catalytic kinetics between the plane and edge atoms on shaped Pd nanocrystals.…”