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Single-crystal structure determination of two new ternary bismuthides: Rh₆Mn₅Bi₁₈ and RhMnBi₃.

ABSTRACT: A study of the ternary Rh-Mn-Bi phase diagram revealed the existence of two new ternary bismuthides, viz. hexarhodium pentamanganese octadecabismuthide (Rh₆Mn₅Bi₁₈) and rhodium manganese tribismuthide (RhMnBi₃). Their crystal structures represent new structure types. Rh₆Mn₅Bi₁₈, with a Wyckoff sequence a f2 g2 i5, crystallizes in the tetragonal system (space group P4₂/mnm; Pearson symbol tP58), and RhMnBi₃, with a Wyckoff sequence a c g i q, crystallizes in the orthorhombic system (Cmmm; oS20). In the Rh₆Mn₅Bi₁₈ structure, the transition metal atoms are linked into ribbon-like structural units aligned along the [001] direction, whereas planar sheets are formed in RhMnBi₃. In both crystal structures, the units formed by the transition metal atoms are enveloped by Bi atoms, which themselves form a loosely bound network. The linkage results in a layer structure for RhMnBi₃, while in the case of Rh₆Mn₅Bi₁₈, a three-dimensional network is formed; the latter, however, contains several areas where Bi...Bi distances suggest van der Waals interactions. Both phases under discussion have analogous structural motifs.

SUBMITTER: Kainzbauer P

PROVIDER: S-EPMC6038359 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Single-crystal structure determination of two new ternary bismuthides: Rh6Mn5Bi18 and RhMnBi3.

Kainzbauer Peter P Richter Klaus W KW Effenberger Herta Silvia HS Marker Martin C J MCJ Ipser Herbert H

Acta crystallographica. Section C, Structural chemistry 20180628 Pt 7

A study of the ternary Rh-Mn-Bi phase diagram revealed the existence of two new ternary bismuthides, viz. hexarhodium pentamanganese octadecabismuthide (Rh6Mn5Bi18) and rhodium manganese tribismuthide (RhMnBi3). Their crystal structures represent new structure types. Rh6Mn5Bi18, with a Wyckoff sequence a f2 g2 i5, crystallizes in the tetragonal system (space group P42/mnm; Pearson symbol tP58), and RhMnBi<sub ...[more]

PMID: 29973426

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Project description:Recently, photo-electrooxidation of fuel using a noble metal-semiconductor junction has been one of the most promising approaches in fuel cell systems. Herein, we report the development of a Pd-supported Bi2MoO6-Bi2O2CO3-CuO novel ternary heterojunction for ethanol oxidation in alkali in the presence and absence of visible light. Various spectroscopic and microscopic characterization techniques confirm strong coupling between palladium nanoparticles and Bi2MoO6-Bi2O2CO3-CuO ternary heterojunction supports. The photo-electrocatalytic efficacy of the synthesized catalysts was inspected by cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). The CV study reveals that the forward peak current density (in mA mg-1 of Pd) of the synthesized quaternary heterojunction was about 1482.5, which is 2.4, 4, and 4.6 times higher than that of Pd/CuO (608.3), Pd/Bi2MoO6-Bi2O2CO3 (368.3), and similarly synthesized Pd catalyst (321.5) under visible light radiation. The best heterojunction catalyst shows 2.21-fold higher peak current density in visible light compared to that in dark. CA study reveals that after operation for 6000 s, the current density of the quaternary electrode is 1.5 and 3.4 times greater than that of Pd/CuO and Pd/C catalysts, respectively. The greater photocurrent response, lower photoluminescence (PL) emission intensity, and smaller semicircle arc in the Nyquist plot of the quaternary catalyst demonstrate the efficient segregation and higher charge transfer conductance of photogenerated charges to facilitate the photo-electrooxidation process of ethanol. The stability test shows that the quaternary catalyst loses only 9.8 and 7.7% of its maximum current density after 500 cycles of CV operation in the dark and light, respectively, indicating that light energy is more beneficial in establishing high stability. The dramatic enhancement of the photo-electrocatalytic activity of the quaternary electrode is owing to the lower band gap, high ECSA, enhanced charge separation of photogenerated carriers (e--h+), and all cocatalytic support of Bi2MoO6, Bi2O2CO3, and CuO in Pd/ Bi2MoO6-Bi2O2CO3-CuO under visible light radiation. The morphology and structure of the used quaternary catalyst are tested using FESEM and PXRD. Finally, ex situ FTIR spectroscopy and HPLC techniques help understand the ethanol electrooxidation reaction mechanism.

Dataset Information

Single-crystal structure determination of two new ternary bismuthides: Rh₆Mn₅Bi₁₈ and RhMnBi₃.

Publications

Single-crystal structure determination of two new ternary bismuthides: Rh<sub>6</sub>Mn<sub>5</sub>Bi<sub>18</sub> and RhMnBi<sub>3</sub>.

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