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1.
J Phys Condens Matter ; 32(26): 265402, 2020 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-32249759

RESUMO

The oxygen ion conductivity of polycrystalline samples of Lu doped ceria is studied using impedance spectroscopy. Lutetium doped ceria is of particular interest as Lu has a similar ionic radius as the host cation Ce. The change of the ionic conductivity as a function of the Lu dopant fraction is investigated in detail revealing a similar behavior as Sm doped ceria that has one of the highest ionic conductivity in ternary cerium oxides. In comparison with simulations, the experimental dependence of the conductivity on the dopant fraction reveals that migration barriers for oxygen vacancy jumps around Lu ions are slightly higher than for jumps in pure ceria. The absolute conductivity is small due to the strong trapping of oxygen vacancies near Lu dopants.

2.
Inorg Chem ; 55(12): 6161-8, 2016 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-27248288

RESUMO

We report the oxidation-controlled synthesis of the ytterbium amides Yb(NH2)2 and Yb(NH2)3 and the first rare-earth-metal guanidinates YbC(NH)3 and Yb(CN3H4)3 from liquid ammonia. For Yb(NH2)2, we present experimental atomic displacement parameters from powder X-ray diffraction (PXRD) and density functional theory (DFT)-derived hydrogen positions for the first time. For Yb(NH2)3, the indexing proposal based on PXRD arrives at R3̅, a = 6.2477(2) Å, c = 17.132(1) Å, V = 579.15(4) Å(3), and Z = 6. The oxidation-controlled synthesis was also applied to make the first rare-earth guanidinates, namely, the doubly deprotonated YbC(NH)3 and the singly deprotonated Yb(CN3H4)3. YbC(NH)3 is isostructural with SrC(NH)3, as derived from PXRD (P63/m, a = 5.2596(2) Å, c = 6.6704(2) Å, V = 159.81(1) Å(3), and Z = 2). Yb(CN3H4)3 crystallizes in a structure derived from the [ReO3] type, as studied by powder neutron diffraction (Pn3̅, a = 13.5307(3) Å, V = 2477.22(8) Å(3), and Z = 8 at 10 K). Electrostatic and hydrogen-bonding interactions cooperate to stabilize the structure with wide and empty channels. The IR spectra of the guanidinates are compared with DFT-calculated phonon spectra to identify the vibrational modes. SQUID magnetometry shows that Yb(CN3H4)3 is a paramagnet with isolated Yb(3+) (4f(13)) ions. A CONDON 2.0 fit was used to extract all relevant parameters.

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