Nitric oxide oxidation of a Ta encapsulating Si cage nanocluster superatom (Ta@Si16) deposited on an organic substrate; A Si cage collapse indicator

Masahiro Shibuta, Toshiki Niikura, Toshiaki Kamoshida, Hironori Tsunoyama, Atsushi Nakajima

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The chemical reaction kinetics of an alkali-like superatom comprising a tantalum encapsulating Si16 cage nanocluster (Ta@Si16) deposited on an n-type organic substrate composed of overlayered C60 fullerene upon exposure to nitric oxide (NO) as a reactive gas are investigated. Core level X-ray photoelectron spectroscopy reveals that Ta@Si16 oxidation with NO proceeds stepwise from the outer Si16 cage to the central Ta atom; during the initial stage, NO is dissociatively chemisorbed by the cage surface of Ta@Si16 without penetrating the cage, while under extreme reaction conditions, the collapse of the Si16 cage leads to NO oxidation of the central Ta atom. In particular, molecular NO adsorption is associated with Ta oxidation only after the collapse of the Si16 cage of Ta@Si16. The reaction kinetics of M@Si16 with NO in the earlier stages of oxidation are discussed in conjunction with density functional theory calculations. Due to the superatomic nature of the shell closure with valence electrons coupled with metal encapsulation, surface oxidation of the caged Si in Ta@Si16 takes place gently compared to that of a naked Si surface, with molecularly physisorbed NO functioning as an indicator of Si cage collapse.

Original languageEnglish
Pages (from-to)26273-26279
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number41
DOIs
Publication statusPublished - 2018 Jan 1

Fingerprint

encapsulating
Nanoclusters
nitric oxide
nanoclusters
Nitric Oxide
Oxidation
oxidation
Substrates
reaction kinetics
Reaction kinetics
Tantalum
Atoms
Core levels
Alkalies
tantalum
Encapsulation
closures
fullerenes
metal surfaces
Density functional theory

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Nitric oxide oxidation of a Ta encapsulating Si cage nanocluster superatom (Ta@Si16) deposited on an organic substrate; A Si cage collapse indicator. / Shibuta, Masahiro; Niikura, Toshiki; Kamoshida, Toshiaki; Tsunoyama, Hironori; Nakajima, Atsushi.

In: Physical Chemistry Chemical Physics, Vol. 20, No. 41, 01.01.2018, p. 26273-26279.

Research output: Contribution to journalArticle

@article{7fc50be7729c4d9ab8b45e70247e631a,
title = "Nitric oxide oxidation of a Ta encapsulating Si cage nanocluster superatom (Ta@Si16) deposited on an organic substrate; A Si cage collapse indicator",
abstract = "The chemical reaction kinetics of an alkali-like superatom comprising a tantalum encapsulating Si16 cage nanocluster (Ta@Si16) deposited on an n-type organic substrate composed of overlayered C60 fullerene upon exposure to nitric oxide (NO) as a reactive gas are investigated. Core level X-ray photoelectron spectroscopy reveals that Ta@Si16 oxidation with NO proceeds stepwise from the outer Si16 cage to the central Ta atom; during the initial stage, NO is dissociatively chemisorbed by the cage surface of Ta@Si16 without penetrating the cage, while under extreme reaction conditions, the collapse of the Si16 cage leads to NO oxidation of the central Ta atom. In particular, molecular NO adsorption is associated with Ta oxidation only after the collapse of the Si16 cage of Ta@Si16. The reaction kinetics of M@Si16 with NO in the earlier stages of oxidation are discussed in conjunction with density functional theory calculations. Due to the superatomic nature of the shell closure with valence electrons coupled with metal encapsulation, surface oxidation of the caged Si in Ta@Si16 takes place gently compared to that of a naked Si surface, with molecularly physisorbed NO functioning as an indicator of Si cage collapse.",
author = "Masahiro Shibuta and Toshiki Niikura and Toshiaki Kamoshida and Hironori Tsunoyama and Atsushi Nakajima",
year = "2018",
month = "1",
day = "1",
doi = "10.1039/c8cp05580g",
language = "English",
volume = "20",
pages = "26273--26279",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "41",

}

TY - JOUR

T1 - Nitric oxide oxidation of a Ta encapsulating Si cage nanocluster superatom (Ta@Si16) deposited on an organic substrate; A Si cage collapse indicator

AU - Shibuta, Masahiro

AU - Niikura, Toshiki

AU - Kamoshida, Toshiaki

AU - Tsunoyama, Hironori

AU - Nakajima, Atsushi

PY - 2018/1/1

Y1 - 2018/1/1

N2 - The chemical reaction kinetics of an alkali-like superatom comprising a tantalum encapsulating Si16 cage nanocluster (Ta@Si16) deposited on an n-type organic substrate composed of overlayered C60 fullerene upon exposure to nitric oxide (NO) as a reactive gas are investigated. Core level X-ray photoelectron spectroscopy reveals that Ta@Si16 oxidation with NO proceeds stepwise from the outer Si16 cage to the central Ta atom; during the initial stage, NO is dissociatively chemisorbed by the cage surface of Ta@Si16 without penetrating the cage, while under extreme reaction conditions, the collapse of the Si16 cage leads to NO oxidation of the central Ta atom. In particular, molecular NO adsorption is associated with Ta oxidation only after the collapse of the Si16 cage of Ta@Si16. The reaction kinetics of M@Si16 with NO in the earlier stages of oxidation are discussed in conjunction with density functional theory calculations. Due to the superatomic nature of the shell closure with valence electrons coupled with metal encapsulation, surface oxidation of the caged Si in Ta@Si16 takes place gently compared to that of a naked Si surface, with molecularly physisorbed NO functioning as an indicator of Si cage collapse.

AB - The chemical reaction kinetics of an alkali-like superatom comprising a tantalum encapsulating Si16 cage nanocluster (Ta@Si16) deposited on an n-type organic substrate composed of overlayered C60 fullerene upon exposure to nitric oxide (NO) as a reactive gas are investigated. Core level X-ray photoelectron spectroscopy reveals that Ta@Si16 oxidation with NO proceeds stepwise from the outer Si16 cage to the central Ta atom; during the initial stage, NO is dissociatively chemisorbed by the cage surface of Ta@Si16 without penetrating the cage, while under extreme reaction conditions, the collapse of the Si16 cage leads to NO oxidation of the central Ta atom. In particular, molecular NO adsorption is associated with Ta oxidation only after the collapse of the Si16 cage of Ta@Si16. The reaction kinetics of M@Si16 with NO in the earlier stages of oxidation are discussed in conjunction with density functional theory calculations. Due to the superatomic nature of the shell closure with valence electrons coupled with metal encapsulation, surface oxidation of the caged Si in Ta@Si16 takes place gently compared to that of a naked Si surface, with molecularly physisorbed NO functioning as an indicator of Si cage collapse.

UR - http://www.scopus.com/inward/record.url?scp=85055607805&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85055607805&partnerID=8YFLogxK

U2 - 10.1039/c8cp05580g

DO - 10.1039/c8cp05580g

M3 - Article

VL - 20

SP - 26273

EP - 26279

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 41

ER -