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, 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^*

^*Corresponding author for this work

Program of Physics

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

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.

Original language	English
Pages (from-to)	2480-2487
Number of pages	8
Journal	Nanoscale
Volume	17
Issue number	5
DOIs	https://doi.org/10.1039/d4nr03785e
State	Published - 2024/11/14

ASJC Scopus subject areas

General Materials Science

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10.1039/d4nr03785e

Cite this

Matsuyama, T., Suzuki, T., Oba, Y., Kikkawa, S., Uchida, S., Ohyama, J., Higashi, K., Kaneko, T., Kato, K., Nitta, K., Uruga, T., Hatada, K., Yoshikawa, K., Heilmaier, A., Suzuki, K., Yonesato, K., Yamaguchi, K., Nakatani, N., Kawasoko, H., & Yamazoe, S. (2024). In situ QXAFS study of CO and H₂ adsorption on Pt in [PtAu₈(PPh₃)₈]-H[PMo₁₂O₄₀] solid. Nanoscale, 17(5), 2480-2487. https://doi.org/10.1039/d4nr03785e

@article{cf2f1dd6d84244eb98cab1c572cc6f3e,

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

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.",

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

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2025.",

year = "2024",

month = nov,

day = "14",

doi = "10.1039/d4nr03785e",

language = "英語",

volume = "17",

pages = "2480--2487",

journal = "Nanoscale",

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Matsuyama, T, Suzuki, T, Oba, Y, Kikkawa, S, Uchida, S, Ohyama, J, Higashi, K, Kaneko, T, Kato, K, Nitta, K, Uruga, T, Hatada, K, Yoshikawa, K, Heilmaier, A, Suzuki, K, Yonesato, K, Yamaguchi, K, Nakatani, N, Kawasoko, H & Yamazoe, S 2024, 'In situ QXAFS study of CO and H₂ adsorption on Pt in [PtAu₈(PPh₃)₈]-H[PMo₁₂O₄₀] solid', Nanoscale, vol. 17, no. 5, pp. 2480-2487. https://doi.org/10.1039/d4nr03785e

TY - JOUR

T1 - In situ QXAFS study of CO and H2 adsorption on Pt in [PtAu8(PPh3)8]-H[PMo12O40] solid

AU - Matsuyama, Tomoki

AU - Suzuki, Taishi

AU - Oba, Yuto

AU - Kikkawa, Soichi

AU - Uchida, Sayaka

AU - Ohyama, Junya

AU - Higashi, Kotaro

AU - Kaneko, Takuma

AU - Kato, Kazuo

AU - Nitta, Kiyofumi

AU - Uruga, Tomoya

AU - Hatada, Keisuke

AU - Yoshikawa, Kazuki

AU - Heilmaier, Amelie

AU - Suzuki, Kosuke

AU - Yonesato, Kentaro

AU - Yamaguchi, Kazuya

AU - Nakatani, Naoki

AU - Kawasoko, Hideyuki

AU - Yamazoe, Seiji

PY - 2024/11/14

Y1 - 2024/11/14

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85210929913&partnerID=8YFLogxK

U2 - 10.1039/d4nr03785e

DO - 10.1039/d4nr03785e

M3 - 学術論文

C2 - 39611297

AN - SCOPUS:85210929913

SN - 2040-3364

VL - 17

SP - 2480

EP - 2487

JO - Nanoscale

JF - Nanoscale

IS - 5