Fine dispersion of Pt subnanoclusters and Pt single atoms over porous carbon supports and their structural analyses with X-ray absorption spectroscopy

Itoi, Hiroyuki*; Nishihara, Hirotomo*; Kobayashi, Shunsuke*; Ittisanronnachai, S.*; Ishii, Takafumi*; Berenguer, R.*; Ito, Masashi*; Matsumura, Daiju   ; Kyotani, Takashi*

We demonstrate the fine dispersion of Pt subnanoclusters or Pt single atoms on two types of porous carbon supports, Ketjen black (KB) and zeolite-templated carbon (ZTC). For the fine dispersion of Pt subnanoclusters, simply filling an organoplatinum complex, (COD)PtMe, as a Pt precursor into the micropores is found to be crucial to prevent agglomeration or sintering of Pt subnanoclusters. Moreover, it is possible to disperse Pt single atoms on ZTC, simply by decreasing the Pt loading amount down to ca. 0.9 wt%, owing to some stabilization effect by oxygen-containing functional groups. Extended X-ray absorption fine structure (EXAFS) analysis for Pt subnanoclusters reveals that the Pt-Pt bond is contracting to a large extent (2.8%) relative to balk values, and upon hydrogen chemisorption, the bond elongates more than the reported values for the 1.0 nm sized Pt nanoparticles.