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

IF 5.1 3区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Nanoscale Pub Date : 2024-11-14 DOI:10.1039/D4NR03785E

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 and Seiji Yamazoe

{"title":"In situ QXAFS study of CO and H2 adsorption on Pt in [PtAu8(PPh3)8]-H[PMo12O40] solid†","authors":"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 and Seiji Yamazoe","doi":"10.1039/D4NR03785E","DOIUrl":null,"url":null,"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.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":" 5","pages":" 2480-2487"},"PeriodicalIF":5.1000,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nanoscale","FirstCategoryId":"88","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/nr/d4nr03785e","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

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.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

固体[PtAu8(PPh3)8]-H[PMo12O40]中 CO 和 H2 在铂上吸附的原位 QXAFS 研究

通过时间分辨率为 0.1 秒的原位快速扫描 X 射线吸收精细结构（QXAFS）测量，研究了 H2 和 CO 分子在冠型 [PtAu8(PPh3)8]-H[PMo12O40]（PtAu8-PMo12）固体中的吸附行为。由于 Pt-H2/Pt-CO 相互作用的形成，PtAu8-PMo12 中铂的电子状态因 H2 和 CO 分子的吸附而发生了急剧变化。与 CO（约 2.5 秒）相比，H2 在铂上的吸附速度更快（< 0.5 秒），并且在 PtAu8-PMo12 中的铂原子上表现出可逆的吸附/解吸行为。H2 的快速吸附是由于 H2 在 PtAu8-PMo12 闭合空隙之间的狭窄通道中的快速扩散，而 H2 的动力学直径比 CO 小。同时，通过 XAFS 分析和密度泛函理论计算，CO 不可逆地吸附在铂上，导致结构异构化为稳定的 "茶色基团 "PtAu8。由于冠型 PtAu8-PMo12 中铂附近的空隙尺寸比 CO 的动力学直径窄，因此结构异构化是通过将配体推向一边来为 CO 的吸附腾出空间。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

Nanoscale CHEMISTRY, MULTIDISCIPLINARY-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

12.10

自引率

3.00%

发文量

1628

审稿时长

1.6 months

期刊介绍： Nanoscale is a high-impact international journal, publishing high-quality research across nanoscience and nanotechnology. Nanoscale publishes a full mix of research articles on experimental and theoretical work, including reviews, communications, and full papers.Highly interdisciplinary, this journal appeals to scientists, researchers and professionals interested in nanoscience and nanotechnology, quantum materials and quantum technology, including the areas of physics, chemistry, biology, medicine, materials, energy/environment, information technology, detection science, healthcare and drug discovery, and electronics.