Structure and electronic properties of new rutile-like rhenium (IV) dioxide ReO2

Ivanovskiĭ, A. L.; Чупахина, Т. И.; Зубков, В. Г.; Tyutyunnik, A. P.; Красильников, В. Н.; Базуев, Г. В.; Okatov, S. V.; Lichtenstein, A. I.

doi:10.1016/j.physleta.2005.08.025

Cited by 36 publications

(29 citation statements)

References 24 publications

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“…Electron, neutron, and x-ray diffraction experiments have detected a large number of transition-metal dioxides to possess very stable ␤Ј rutile crystal phases. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] In addition, some theoretical studies, at different levels of theory, have confirmed the structural results of the experiments, showing enhanced stability of the rutile phase for most metal dioxides. [20][21][22][23] Rutile oxides are interesting in connection with electrochemical and photoelectrochemical water splitting, [24][25][26][27] and recently the surface redox processes on, e.g., RuO 2 and TiO 2 have been treated using density functional theory ͑DFT͒.…”

Section: Introductionmentioning

confidence: 95%

Formation energies of rutile metal dioxides using density functional theory

et al. 2009

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We apply standard density functional theory at the generalized gradient approximation ͑GGA͒ level to study the stability of rutile metal oxides. It is well known that standard GGA exchange and correlation in some cases is not sufficient to address reduction and oxidation reactions. Especially the formation energy of the oxygen molecule and the electron self-interaction for localized d and f electrons are known shortcomings. In this paper we show that despite the known problems, it is possible to calculate the stability of a wide range of rutile oxides MO 2 , with M being Pt, Ru, Ir, Os, Pb, Re, Mn, Se, Ge, Ti, Cr, Nb, W, Mo, and V, using the electrochemical series as reference. The mean absolute error of the formation energy is 0.29 eV using the revised Perdew-Burke-Ernzerhof ͑PBE͒ GGA functional. We believe that the reason for the success is due to the reference level being H 2 and H 2 O and not O 2 and due to a more accurate description of exchange for this particular GGA functional compared to PBE. Furthermore, we would expect the self-interaction problem to be largest for the most localized d orbitals; that means the late 3d metals and since Co, Fe, Ni, and Cu do not form rutile oxides they are not included in this study. We show that the variations in formation energy can be understood in terms of a previously suggested model separating the formation energy into a metal deformation contribution and an oxygen binding contribution. The latter is found to scale with the filling of the d band.

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Section: Introductionmentioning

confidence: 95%

Formation energies of rutile metal dioxides using density functional theory

et al. 2009

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“…Above T c , a lower measured paramagnetic moment of Cr +4 compared with the theoretically calculated one was registered for CrO 2 [32]. According to our structural data, Cr x Re 1Àx O 2 phases do not show this kind of distortion of MO 6 octahedra, but rather the one of ReO 2 [15]: two shorter and four longer M-O distances ( …”

Section: Discussionmentioning

confidence: 48%

“…Fig. 10 shows the dependence of ''a'' and ''c'' lattice parameters on Cr-content x in Cr x Re 1Àx O 2 together with the tetragonal modification of ReO 2 [15] and CrO 2 [13] as the end members and Cr 2 ReO 6 with trirutile structure. Both dependences are fitted by exponential functions in the composition region from x ¼ 0 (ReO 2 ) to x ¼ 0.67 (Cr 2 ReO 6 ) and these fits are shown as guides for the eyes in Fig.…”

Section: Discussionmentioning

confidence: 99%

“…Both end members, CrO 2 [13] and the monoclinic modification of ReO 2 [14], have a rutile-like structure. A new modification of ReO 2 with rutile structure was also recently reported [15]. Sleight [16] has reported on Cr 2 ReO 6 , prepared under high-pressure high-temperature conditions, and proposed for this compound a trirutile structure.…”

Section: Introductionmentioning

confidence: 90%

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Cr_xRe_1−xO₂oxides with different rutile-like structures: changes in the electronic configuration and resulting physical properties

Mikhailova¹,

Ehrenberg²,

Trots³

et al. 2009

Acta Cryst Sect A

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a b s t r a c tMixed chromium-rhenium oxides, Cr x Re 1Àx O 2 with 0.31pxp0.66, have been synthesized for the first time by high-pressure high-temperature synthesis and in evacuated quartz tubes. The crystal structures of the compounds have been determined by single crystal and powder X-ray diffraction. Depending on synthesis conditions (pressure and temperature) these phases crystallize either in a tetragonal structure (P4 2 /mnm) with statistical distribution of metal ions on one site (rutile-type), with cation ordering along c-axis (trirutile-type), or in a monoclinic rutile-like structure (C2/m) with ordering of Cr-and Re-cations and metallic Re-Re bonds.

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“…Assuming that the oxidation takes place at the surface of the Re NPs, the Re À O bond in the nanoparticles (2.05 ) is longer than that in bulk ReO 2 (1.98 ). [27] The fraction of oxidized Re in the nanoparticles can be estimated from the number of ReÀO bonds, which are 6 in bulk ReO 2 and 2.8 in Re NPs. Thus the percentage of ReO 2 in Re NPs is 2.8/6 = 0.47 (i.e.…”

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confidence: 99%

A Reusable Unsupported Rhenium Nanocrystalline Catalyst for Acceptorless Dehydrogenation of Alcohols through γ‐C–H Activation

Miller

Zemlyanov

et al. 2013

Angew Chem Int Ed

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Rhenium nanocrystalline particles (Re NPs), of 2 nm size, were prepared from NH4ReO4 under mild conditions in neat alcohol. The unsupported Re NPs convert secondary and benzylic alcohols to ketones and aldehydes, respectively, through catalytic acceptorless dehydrogenation (AD). The oxidant- and acceptor-free neat dehydrogenation of alcohols to obtain dihydrogen gas is a green and atom-economical process for making carbonyl compounds. Secondary aliphatic alcohols give quantitative conversion and yield. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Re K-edge X-ray absorption near-edge structure (XANES), and X-ray absorption fine structure (EXAFS) data confirmed the characterization of the Re NPs as metallic rhenium with surface oxidation to rhenium(IV) oxide (ReO2). Isotope labeling experiments revealed a novel γ-CH activation mechanism for AD of alcohols.

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Structure and electronic properties of new rutile-like rhenium (IV) dioxide ReO2

Cited by 36 publications

References 24 publications

Formation energies of rutile metal dioxides using density functional theory

Formation energies of rutile metal dioxides using density functional theory

Cr_xRe_1−xO₂oxides with different rutile-like structures: changes in the electronic configuration and resulting physical properties

A Reusable Unsupported Rhenium Nanocrystalline Catalyst for Acceptorless Dehydrogenation of Alcohols through γ‐C–H Activation

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Structure and electronic properties of new rutile-like rhenium (IV) dioxide ReO2

Cited by 36 publications

References 24 publications

Formation energies of rutile metal dioxides using density functional theory

Formation energies of rutile metal dioxides using density functional theory

CrxRe1−xO2oxides with different rutile-like structures: changes in the electronic configuration and resulting physical properties

A Reusable Unsupported Rhenium Nanocrystalline Catalyst for Acceptorless Dehydrogenation of Alcohols through γ‐C–H Activation

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Cr_xRe_1−xO₂oxides with different rutile-like structures: changes in the electronic configuration and resulting physical properties