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1.
The synthesis of MoVNbTe(Sb)O(x)() composite oxide catalysts based on the self-organization of polyoxometalates (POMs) was investigated. The catalysts which were synthesized via reduction of POMs by using reducing agents under mild conditions and/followed by calcination in an O(2)-excluded atmosphere which superior performance for propane (amm)oxidation. It was suggested that the metastable phase formed at an elevated temperature with a specific oxidation state corresponds to the catalytic activity. 相似文献
2.
Atobe J Koyasu K Furuse S Nakajima A 《Physical chemistry chemical physics : PCCP》2012,14(26):9403-9410
The electronic properties of germanium and tin clusters containing a transition- or lanthanide-metal atom from group 3, 4, or 5, MGe(n) (M = Sc, Ti, V, Y, Zr, Nb, Lu, Hf, and Ta) and MSn(n) (M = Sc, Ti, Y. Zr, and Hf), were investigated by anion photoelectron spectroscopy at 213 nm. In the case of the group 3 elements Sc, Y, and Lu, the threshold energy of electron detachment of MGe(n)(-) exhibits local maxima at n = 10 and 16, while in the case of the group 4 elements Ti, Zr, and Hf, it exhibits a local minimum only at n = 16, associated with the presence of a small bump in the spectrum. A similar behavior is observed for MSn(n)(-) around n = 16, and these electronic characteristics of MGe(n) and MSn(n) are closely related to those of MSi(n). Compared to MSi(n), however, the larger cavity size of a Ge(n) cage allows metal atom encapsulation at a smaller size n. A cooperative effect between the electronic and geometric structures of clusters with a large cavity of Ge(16) or Sn(16) is discussed together with the results of experiments that probe their geometric stability via their reactivity to H(2)O adsorption. 相似文献
3.
Kiichirou Koyasu Christian Braun Sebastian Proch Gerd Gantef?r 《Applied Physics A: Materials Science & Processing》2010,100(2):431-436
The lifetimes of electronically excited states of Al4O
m
− clusters are measured for m=1,3,4,5, and 6 using time-resolved photoelectron spectroscopy. With increasing number of oxygen atoms the lifetimes increase.
This can be explained qualitatively by a metal-semiconductor transition occurring between the metal-like Al4
− cluster and the fully oxidized semiconductor-like Al4O6
− cluster. Long lifetimes of electron-hole excitations are characteristic for semiconductors, while in metals the strong interaction
between the delocalized electrons causes short lifetimes. 相似文献
4.
Akutsu M Koyasu K Atobe J Hosoya N Miyajima K Mitsui M Nakajima A 《The journal of physical chemistry. A》2006,110(44):12073-12076
The geometric and electronic structures of aluminum binary clusters, AlnX (X = Si and P), have been investigated, using mass spectrometry, anion photoelectron spectroscopy, photoionization spectroscopy, and theoretical calculations. Both experimental and theoretical results show that Al12Si has a high ionization energy and low electron affinity and Al12P has a low ionization energy, both with the icosahedral structure having a central Si or P atom, revealing that Al12Si and Al12P exhibit rare-gas-like and alkali superatoms, respectively. Experiments confirmed the possibility that the change in the total number of valence electrons on substitution could produce ionically bound binary superatom complexes, the binary cluster salts Al12P+ F- and Al12B- Cs+. 相似文献
5.
Silicon (Si), germanium (Ge), tin (Sn), and lead (Pb) clusters mixed with a group-4 transition metal atom [M = titanium (Ti), zirconium (Zr), and hafnium (Hf)] were generated by a dual-laser vaporization method, and their properties were analyzed by means of time-of-flight mass spectroscopy and anion photoelectron spectroscopy together with theoretical calculations. In the mass spectra, mixed neutral clusters of MSi(16), MGe(16), and MSn(16) were produced specifically, but the yield of MPb(16) was low. The anion photoelectron spectra revealed that MSi(16), MGe(16), and MSn(16) neutrals have large highest occupied molecular orbital-lowest unoccupied molecular orbital gaps of 1.5-1.9 eV compared to those of MPb(16) (0.8-0.9 eV), implying that MSi(16), MGe(16), and MSn(16) are evidently electronically stable clusters. Cage aromaticity appears to be an important determinant of the electronic stability of these clusters: Calculations of nucleus-independent chemical shifts (NICSs) show that Si(16)(4-), Ge(16)(4-), and Sn(16)(4-) have aromatic characters with negative NICS values, while Pb(16)(4-) has an antiaromatic character with a positive NICS value. 相似文献
6.
Kiichirou Koyasu Christian Braun Sebastian Proch Gerd Ganteför 《Applied Physics A: Materials Science & Processing》2011,102(3):615-620
In general, clusters are unstable and in many cases several metastable isomers exist even at low temperature. Therefore, a
cluster may react with a dramatic geometry change to a small disturbance such as a weak field or to the absorption of a low-energy
photon. Here, we study the response of Al3O3-\mathrm{Al}_{3}\mathrm{O}_{3}^{-} to photoexcitation using time-resolved photoelectron spectroscopy. Earlier experimental and theoretical studies suggested
that this cluster anion undergoes a geometry change after photoexcitation. In contrast, our time-resolved spectra indicate
that photoexcitation triggers ultra-fast fragmentation. This example demonstrates that ultra-fast processes in clusters are
not well understood and that it is still difficult to gain reliable experimental data about such processes. 相似文献
7.
Kiichirou?Koyasu Wilko?Westh?user Marco?Niemietz Jan?Heinen Gerd?Gantef?r 《Applied Physics A: Materials Science & Processing》2009,96(3):679-684
Using time-resolved photoelectron spectroscopy, the decay channels of AuO2− and Au2O2− following photoexcitation with 3.1-eV photons have been studied. For AuO2−, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption
can be excluded. For Au2O2−, the spectra indicate O2 desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au
n
O2− with analogous data on Ag
n
O2− clusters, a discernible pattern emerges: for dissociatively bound O2(AuO2−, Ag3O2−), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au2O2−, Ag2O2−, Ag4O2−, Ag8O2−), the 3.1-eV photoexcitation triggers fast O2 desorption with a high quantum yield. 相似文献
8.
Kaname Kanai Kouki Akaike Kiichirou Koyasu Kentaro Sakai Toshio Nishi Yasunori Kamizuru Tatsuhiko Nishi Yukio Ouchi Kazuhiko Seki 《Applied Physics A: Materials Science & Processing》2009,95(1):309-313
The unoccupied π
* states of the solid film of electron accepting organic molecules, 7,7,8,8-tetracyanoquinodimethane (TCNQ), fluorinated TCNQ
derivatives, 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (TNAP), C60, and 6,6-phenyl-C61-butyric acid methyl ester (PCBM) have been studied by inverse photoemission spectroscopy. The assignment of the π
* affinity levels of these typical electron accepting molecules provides the basic information for the organic electronics
and the new electronic functional molecular design. The comparison with density functional theory calculations enables understanding
how the electron affinity evolves in terms of molecular orbitals. The correlation between the film morphology and the irradiation
damage on the TCNQ derivative samples by electron impact during the inverse photoemission measurements is also discussed. 相似文献
9.
Controlled Synthesis of Diphosphine-Protected Gold Cluster Cations Using Magnetron Sputtering Method
Lewei Wang Tsubasa Omoda Kiichirou Koyasu Tatsuya Tsukuda 《Molecules (Basel, Switzerland)》2022,27(4)
We demonstrated, for the first time, atomically precise synthesis of gold cluster cations by magnetron sputtering of a gold target onto a polyethylene glycol (PEG) solution of 1,3-bis(diphenylphosphino)propane (Ph2PCH2CH2CH2PPh2, dppp). UV-vis absorption spectroscopy and electrospray ionization mass spectrometry revealed the formation of cationic species, such as [Au(dppp)n]+ (n = 1, 2), [Au2(dppp)n]2+ (n = 3, 4), [Au6(dppp)n]2+ (n = 3, 4), and [Au11(dppp)5]3+. The formation of [Au(dppp)2]+ was ascribed to ionization of Au(dppp)2 by the reaction with PEG, based on its low ionization energy, theoretically predicted, mass spectrometric detection of deprotonated anions of PEG. We proposed that [Au(dppp)2]+ cations thus formed are involved as key components in the formation of the cluster cations. 相似文献
10.
Haru Hirai Shun Ito Shinjiro Takano Kiichirou Koyasu Tatsuya Tsukuda 《Chemical science》2020,11(45):12233
Monolayer-protected gold/silver clusters have attracted much interest as nano-scale building units for novel functional materials owing to their nonbulk-like structures and size-specific properties. They can be viewed as ligand-protected superatoms because their magic stabilities and fundamental properties are well explained in the framework of the jellium model. In the last decade, the number of ligand-protected superatoms with atomically-defined structures has been increasing rapidly thanks to the well-established synthesis and structural determination by X-ray crystallography. This perspective summarizes the current status and emerging trends in synthesis and characterization of superatoms. The topics related to synthesis include (1) development of targeted synthesis based on transformation, (2) enhancement of robustness and synthetic yield for practical applications, and (3) development of controlled fusion and assembly of well-defined superatoms to create new properties. New characterization approaches are also introduced such as (1) mass spectrometry and laser spectroscopies in the gas phase, (2) determination of static and dynamic structures, and (3) computational analysis by machine learning. Finally, future challenges and prospects are discussed for further promotion and development of materials science of superatoms.This perspective summarizes the current status and emerging trends in synthesis and characterization of ligand-protected gold/silver superatoms. 相似文献