Pt17 nanocluster electrocatalysts: preparation and origin of high oxygen reduction reaction activity

Tokuhisa Kawawaki; Yusuke Mitomi; Naoki Nishi; Ryuki Kurosaki; Kazutaka Oiwa; Tomoya Tanaka; Hinoki Hirase; Sayuri Miyajima; Yoshiki Niihori; D J Osborn; Takanori Koitaya; Gregory F Metha; Toshihiko Yokoyama; Kenji Iida; Yuichi Negishi

doi:10.1039/d3nr01152f

Pt₁₇ nanocluster electrocatalysts: preparation and origin of high oxygen reduction reaction activity

Nanoscale. 2023 Apr 27;15(16):7272-7279. doi: 10.1039/d3nr01152f.

Authors

Tokuhisa Kawawaki^{1

2

3}, Yusuke Mitomi¹, Naoki Nishi¹, Ryuki Kurosaki¹, Kazutaka Oiwa¹, Tomoya Tanaka¹, Hinoki Hirase⁴, Sayuri Miyajima¹, Yoshiki Niihori², D J Osborn⁵, Takanori Koitaya^{3

6}, Gregory F Metha⁵, Toshihiko Yokoyama^{3

6}, Kenji Iida⁴, Yuichi Negishi^{1

2}

Affiliations

¹ Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. Kawawaki@rs.tus.ac.jp.
² Research Institute for Science & Technology, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
³ Physical and Chemical Research Infrastructure Group, RIKEN SPring-8 Center, RIKEN, Sayo, Hyogo 679-5198, Japan.
⁴ Institute for Catalysis, Hokkaido University, Sapporo, Hokkaido 001-0021, Japan.
⁵ Department of Chemistry, University of Adelaide, Adelaide, South Australia, 5005, Australia.
⁶ Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan.

PMID: 36987742
DOI: 10.1039/d3nr01152f

Abstract

We recently found that [Pt₁₇(CO)₁₂(PPh₃)₈]^z (Pt = platinum; CO = carbon monoxide; PPh₃ = triphenylphosphine; z = 1+ or 2+) is a Pt nanocluster (Pt NC) that can be synthesized with atomic precision in air. The present study demonstrates that it is possible to prepare a Pt₁₇-supported carbon black (CB) catalyst (Pt₁₇/CB) with 2.1 times higher oxygen reduction reaction (ORR) activity than commercial Pt nanoparticles/CB by the adsorption of [Pt₁₇(CO)₁₂(PPh₃)₈]^z onto CB and subsequent calcination of the catalyst. Density functional theory calculation strongly suggests that the high ORR activity of Pt₁₇/CB originates from the surface Pt atoms that have an electronic structure appropriate for the progress of ORR. These results are expected to provide design guidelines for the fabrication of highly active ORR catalysts using Pt NCs with a diameter of about 1 nm and thereby enabling the use of reduced amounts of Pt in polymer electrolyte fuel cells.