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Itti, R.; Izumi, Teruo; Ikeda, K.; Tai, Keishi; Koshizuka, N.; Tanaka, Shōji

doi:10.1103/physrevb.43.435

Cited by 23 publications

(8 citation statements)

References 25 publications

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“…As shown in Figure a, and according to our recent report, it is reasonably deduced that the potassium atoms of K 1 /HMO have electron DOS higher than that of K + , and the same results are also obtained from DFT calculations (Figure S5 in the Supporting Information). Likewise, the BE of the Rb 3 d 5/2 peak of RbOH is centered at 109.3 eV, which is characteristic of Rb + , whereas the BE of Rb 3 d 5/2 of Rb 1 /HMO decreases to about 108.2 eV through a downshift of about 1.1 eV with respect to that of RbOH (Figure b), indicative of the high electronic DOS of Rb ions. The results are in line with the above XANES data.…”

Section: Resultsmentioning

confidence: 98%

“…As shown in Figure 7a,a nd according to our recent report, [23] it is reasonably deduced that the potassium atoms of K 1 /HMO have electron DOS highert han that of K + ,a nd the same resultsa re also obtained from DFT calculations ( Figure S5 in the Supporting Information). Likewise, the BE of the Rb 3d 5/2 peak of RbOH is centered at 109.3 eV,w hich is characteristic of Rb + , [41] whereas high electronic DOS, are energetically favorable for the adsorption and subsequentd issociation of O 2 :1 )orbital hybridization of single alkali-metal adatomsb yl ocal transfer of sp electrons to an empty ds hell allows O 2 to approacha lkali-metal atoms until chemisorption occurs because of weakening of the Pauli repulsion;a nd 2) abundant electrons of single alkali-metal adatomsa re favorable for charge transfer to antibonding p*o rbitals of O 2 to weaken the OÀOb ond until dissociation occurs. [27] As ac onsequence, the high electronic DOS of the single alkalimetal adatoms is mainly responsible for the strong ability towards activating O 2 .…”

Section: Resultsmentioning

confidence: 99%

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Activating Inert Alkali‐Metal Ions by Electron Transfer from Manganese Oxide for Formaldehyde Abatement

Gao

Chen

Wan

et al. 2017

Chemistry A European J

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Alkali-metal ions often act as promoters rather than active components due to their stable outermost electronic configurations and their inert properties in heterogeneous catalysis. Herein, inert alkali-metal ions, such as K and Rb , are activated by electron transfer from a Hollandite-type manganese oxide (HMO) support for HCHO oxidation. Results from synchrotron X-ray diffraction, absorption, and photoelectron spectroscopies demonstrate that the electronic density of states of single alkali-metal adatoms is much higher than that of K or Rb , because electrons transfer from manganese to the alkali-metal adatoms through bridging lattice oxygen atoms. Electron transfer originates from the interactions of alkali metal d-sp frontier orbitals with lattice oxygen sp orbitals occupied by lone-pair electrons. Reaction kinetics data of HCHO oxidation reveal that the high electronic density of states of single alkali-metal adatoms is favorable for the activation of molecular oxygen. Mn L -edge and O K-edge soft-X-ray absorption spectra demonstrate that lattice oxygen partially gains electrons from the Mn e orbitals, which leads to the upshift in energy of lattice oxygen orbitals. Therefore, the facile activation of molecular oxygen by the electron-abundant alkali-metal adatoms and active lattice oxygen are responsible for the high catalytic activity in complete oxidation of HCHO. This work could assist the design of efficient and cheap catalysts by tuning the electronic states of active components.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Activating Inert Alkali‐Metal Ions by Electron Transfer from Manganese Oxide for Formaldehyde Abatement

Gao

Chen

Wan

et al. 2017

Chemistry A European J

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“…For instance, different interpretations have been proposed 9,11,14,15 for the Bi 4 f and O 1s core-level data in terms of the number of chemically shifted components corresponding to inequivalent sites and/or oxidation states. In the reported valenceband data there is a growing consensus that superconducting samples give a clear Fermi edge 9,11,13,15,16 which is lacking for the semiconducting compositions, 9,13,15,16 but in two studies 12,14 no clear Fermi edge was found for superconducting samples. All studies except one 16 were performed with polycrystalline samples and scraping was the most frequently used method to clean the surface.…”

Section: Introductionmentioning

confidence: 99%

Photoemission and x-ray absorption study of superconducting and semiconductingBa1−xKxBi

et al. 1996

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Semiconducting Ba 0.9 K 0.1 BiO 3 and superconducting Ba 0.6 K 0.4 BiO 3 single crystals cleaved in situ have been studied by core level and valence band photoelectron spectroscopy and O K edge x-ray absorption spectroscopy. It was found that the general shape of the valence band spectrum agrees with the shape predicted by band structure calculations, but the intensity near the Fermi level was lower in the experimental spectrum as compared to the calculated. The O K edge spectra showed that the metallic phase is not related to the presence of doping inducted O 2 p holes. This property of Ba 1Ϫx K x BiO 3 shows that the semiconductor-metal transition of this system is of a different nature than that of the hole doped cuprate high-T c superconductors. The core level photoemission spectra of the cations showed a small asymmetry for Ba 0.9 K 0.1 BiO 3 . Corresponding spectra for Ba 0.6 K 0.4 BiO 3 showed a larger asymmetry resulting in a resolved high binding energy shoulder in the Bi 4 f spectrum. The origin of this feature is discussed.

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“…This transition has been studied in a number of photoemission measurements, which show the disappearance of the DOS at the Fermi level as the transition is approached, with a corresponding shift in valence-band and core-level peaks (e.g. van Veenendaal, Sawatzky & Groen, 1994;van Veenendaal, Schlatmann, Sawatzky & Groen, 1993;Itti et al, 1991;Golden, Golden, Egdell & Flavell, 1991). The valence modulation caused by the addition of Y is accompanied by structural modifications, primarily contraction along the c axis of the structure, and expansion in the ab plane, which contains the Cu-O2 planes, with corresponding changes in Cu-O hybridization (Manthiram & Goodenough, 1988;Tamegai et al, 1989;Groen et al, 1990).…”

Section: Introductionmentioning

confidence: 99%

Resonant Photoemission from Complex Cuprates and Nickelates

Flavell¹,

Hollingworth²,

Howlett³

et al. 1995

J Synchrotron Radiat

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Synchrotron-excited resonant-photoemission measurements at rare-earth 4d ~ 4fand transition-metal 3p ~ 3d thresholds have been carried out using a variety of complex cuprates and nickelates on stations 6.1 (grazing-incidence monochromator) and 6.2 (toroidal-grating monochromator) at the SRS CLRC Daresbury Laboratory. The systems studied are Nd2Nil _xCuxO4, La2_xSrxNil _yFeyO4 + 6 and Bi2Sr/Cal_xYxCu208 + 6. A combination of EDC and constant-initial-state data is used to examine the 4f and 3d contributions to the valence-band density of states and their binding-energy positions relative to the Fermi energy. This allows the study of the valence states of the transitionmetal ions and their modulation on doping. For La2_ xSrxNii _ yFeyO4 + 6, this approach is used to infer a valence state of _> 3.0 for Fe. In the case of Bi2Sr2Cal _ xYxCuz08 + 6, the effect of Cu valence modulation on the 3p resonance is observed as x is varied. This is discussed in the light of controversy surrounding shifts in core-level photoemission with doping for this system.

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Photoelectron spectroscopic study ofBa1−xRb

Cited by 23 publications

References 25 publications

Activating Inert Alkali‐Metal Ions by Electron Transfer from Manganese Oxide for Formaldehyde Abatement

Activating Inert Alkali‐Metal Ions by Electron Transfer from Manganese Oxide for Formaldehyde Abatement

Photoemission and x-ray absorption study of superconducting and semiconductingBa1−xKxBi

Resonant Photoemission from Complex Cuprates and Nickelates

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