In situ QXAFS study of CO and H2 adsorption on Pt in [PtAu8(PPh3)8]-H[PMo12O40] solid

Tomoki Matsuyama; Taishi Suzuki; Yuto Oba; Soichi Kikkawa; Sayaka Uchida; Junya Ohyama; Kotaro Higashi; Takuma Kaneko; Kazuo Kato; Kiyofumi Nitta; Tomoya Uruga; Keisuke Hatada; Kazuki Yoshikawa; Amelie Heilmaier; Kosuke Suzuki; Kentaro Yonesato; Kazuya Yamaguchi; Naoki Nakatani; Hideyuki Kawasoko; Seiji Yamazoe

doi:10.1039/D4NR03785E

In situ QXAFS study of CO and H₂ adsorption on Pt in [PtAu₈(PPh₃)₈]-H[PMo₁₂O₄₀] solid†

Tomoki Matsuyama,^a Taishi Suzuki,^a Yuto Oba,^a Soichi Kikkawa,

^a Sayaka Uchida,

^b Junya Ohyama,

^c Kotaro Higashi,^d Takuma Kaneko,^d Kazuo Kato,^d Kiyofumi Nitta,^d Tomoya Uruga,^d Keisuke Hatada,^e Kazuki Yoshikawa,^e Amelie Heilmaier,

^ef Kosuke Suzuki,

^g Kentaro Yonesato,

^g Kazuya Yamaguchi,

^g Naoki Nakatani,

^a Hideyuki Kawasoko

^ah and Seiji Yamazoe

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji-shi, Tokyo 192-0397, Japan
E-mail: yamazoe@tmu.ac.jp

^b Department of Basic Science, School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan

^c Faculty of Advanced Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto-shi, Kumamoto 860-8555, Japan

^d Center for Synchrotron Radiation Research, Japan Synchrotron Radiation Research Institute (JASRI), 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan

^e Department of Physics, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan

^f Department of Chemistry, Ludwig-Maximilians-Universität (LMU), Butenandtstr. 5-13, 81377 Munich, Germany

^g Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

^h Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), 7, Gobancho, Chiyoda-ku, Tokyo 102-0076, Japan

Abstract

The adsorption behaviors of H₂ and CO molecules in crown-motif [PtAu₈(PPh₃)₈]-H[PMo₁₂O₄₀] (PtAu8-PMo12) solids were investigated by in situ quick-scan X-ray absorption fine structure (QXAFS) measurements with a time resolution of 0.1 s. The electronic state of Pt in PtAu8-PMo12 was drastically changed by the adsorption of H₂ and CO molecules because of the formation of Pt–H₂/Pt–CO interactions. H₂ was adsorbed more rapidly (<0.5 s) on Pt than CO (∼2.5 s) and showed reversible adsorption/desorption behavior on Pt atoms in PtAu8-PMo12. The rapid adsorption of H₂ is due to the fast diffusion of H₂, which has a smaller kinetic diameter than CO, in the narrow channels between the closed voids in PtAu8-PMo12. Meanwhile, CO was irreversibly adsorbed on Pt, resulting in structural isomerization to the stable “chalice-motif” PtAu8, which was determined by XAFS analysis and density functional theory calculations. Structural isomerization was involved by pushing ligands aside to make space for CO adsorption as the void size near Pt in the crown-motif PtAu8-PMo12 was narrower than the kinetic diameter of CO.

This article is part of the themed collection: Metal nanoclusters

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In situ QXAFS study of CO and H₂ adsorption on Pt in [PtAu₈(PPh₃)₈]-H[PMo₁₂O₄₀] solid†

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In situ QXAFS study of CO and H₂ adsorption on Pt in [PtAu₈(PPh₃)₈]-H[PMo₁₂O₄₀] solid

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