Finding the Most Catalytically Active Platinum Clusters With Low Atomicity

Abstract

On a subnanometer scale, an only one‐atom difference in a metal cluster may cause significant transitions in the catalytic activity due to the electronic and geometric configurations. We now report the atomicity‐specific catalytic activity of platinum clusters with significantly small atomicity, especially below 20. The atomic coordination structure is completely different from that of the larger face‐centered cubic (fcc) nanocrystals. Here, an electrochemical study on such small clusters, in which the atomicity ranged between 12 and 20, revealed Pt19 as the most catalytically active species. In combination with a theoretical study, a common structure that leads to a high catalytic performance is proposed.

Kinetic Monte Carlo approach to Schottky defects in noble metal nanoclusters

“…Stable metal particles with enhanced catalytic activity strongly depend on the presence of single atoms or, vice-versa, of single vacancies. Investigations of nonmagic-number clusters in noble metals with 'with low atomicity' have just begun, i.e., by exploiting new synthesis methods promising the required single-atom precision in platinum clusters [24]. The results presented here substantially augment the ability to simulate the stability of such low-N metallic nanosystems.…”

In situ thermolysis of Pt-carbonyl complex to form supported clean Pt nanoclusters with enhanced catalytic performance

“…Nanoclusters with a high volume/surface ratio and quantum effect have been proven to be efficient catalysts in various useful reactions. To date, several synthetic approaches have been developed to fabricate these small nanoparticles, including solution-phase reduction, gas-phase synthesis, and the ligand-assisted approach [25][26][27][28][29]. However, the fabrication of small nanoparticles is still challenging because of their severe aggregation, wide size distribution, low output, and low activity.…”

Origin of high oxygen reduction reaction activity of Pt12 and strategy to obtain better catalyst using sub-nanosized Pt-alloy clusters

“…2 nm until Yamamoto, Imaoka et al . found that sub-nanosized Pt clusters showed extremely high ORR activities 6789…”

“…However, the geometries of sub-nanosized Pt clusters have not been observed directly. Scanning transmission electron microscopy, for example, can measure only two-dimensional geometries of sub-nanosized clusters7. Therefore, their electronic structures and the relationship between their structures and catalytic activities are unclear.…”

“…Among the sub-nanosized Pt clusters, we focused on Pt 12 , as the atomicity can be controlled precisely using the method developed by Yamamoto, Imaoka et al 6789…”