A3A'3Zn6Te4O24 (A = Na, A' = Rare Earth) Garnets: A-Site Ordered Noncentrosymmetric Structure, Photoluminescence, and Na-Ion Conductivity.

A large number of oxides that adopt the centrosymmetric (CS) garnet-type structure (space group Ia3̅d) have been widely studied as promising magnetic and host materials. Hitherto, no noncentrosymmetric (NCS) garnet has been reported yet, and a strategy to NCS garnet design is therefore significant for expanding the application scope. Herein, for the series A3A'3Zn6Te4O24 (A = Na, A' = La, Eu, Nd, Y, and Lu), we demonstrated that the structural symmetry evolution from CS Ia3̅d (A' = La) to NCS I4122 (A' = Eu, Nd, Y, and Lu) could be achieved due to the A-site cationic ordering-driven inversion symmetry breaking. Na3A'3Zn6Te4O24 (A' = rare earth) are the first garnets that possess NCS structures with A-site cationic ordering. Diffuse reflectance spectra and theoretic calculations demonstrated that all these NCS garnets are indirect semiconductors. Moreover, their potential applications as host materials for red phosphors and Na-ion conductors were also investigated in detail, which firmly confirmed the NCS structure and A-site cationic ordering. Our findings have paved the way to design NCS or even polar garnets that show intriguing functional properties, such as ferroelectricity, multiferroicity, and second harmonic generation.

Titania-Samarium-Manganese Composite Oxide for the Low-Temperature Selective Catalytic Reduction of NO with NH3.

A novel Ti-doped Sm-Mn mixed oxide (TiSmMnOx) was first designed for the selective catalytic reduction (SCR) of NOx with NH3 at a low temperature. The TiSmMnOx catalyst exhibited a superior catalytic performance, in which NOx conversion higher than 80% and N2 selectivity above 90% could be achieved in a wide-operating temperature window (60-225 °C). Specially, the catalyst also showed high durability against the large space velocity and excellent SO2/H2O resistance. Ti incorporation can efficiently inhibit MnOx crystallization and tune the MnOx phase during calcination at a high temperature. Subsequently, a high specific surface area as well as an increased amount of acid sites on the TiSmMnOx catalysts were produced. Further, the reducibility of the Sm-doped MnOx catalyst was modulated, facilitating NO oxidation and inhibiting NH3 nonselective oxidation. Consequently, a superior SCR activity was achieved at a low temperature and the operating temperature window of the TiSmMnOx catalyst was significantly widened. These findings may provide new insights into the reasonable design and development of the new non-vanadium catalysts with a high NH3-SCR activity for industrial application.

The impact of A-site cations on the crystal structure and magnetism of the new double perovskites ALaCoTeO6 (A = Na and K).

In this work, we report the structural and magnetic characterization of two new B-site rock-salt ordered double perovskites ALaCoTeO6 (A = K+ and Na+) with mixed A-site cations. KLaCoTeO6 crystallizes in the space group P4/nmm with a long-range ordering degree of 84.8% for the A-site K+/La3+ cations, whereas NaLaCoTeO6 adopts an unexpected triclinically distorted I1̄-structure with Na/La3+ disordering, validated by combined Rietveld refinements against high-resolution neutron diffraction data and Cu Kα1 X-ray powder diffraction data. Magnetic susceptibility at low temperatures shows clear antiferromagnetic (AFM) transitions for both compounds. KLaCoTeO6 exhibits the highest AFM transition temperature of 20 K amongst all the Co/Te-ordered 3C-type A2CoTeO6 (A = Pb2+, Sr2+, and Ca2+) and ALaCoTeO6 double perovskites due to its larger Co2+-O-Te6+ bond angle and A-site cationic ordering-induced larger distortion of the Co2+-based face-centered cubic sublattice. Moreover, we found that the average radius of the A-site cations plays a decisive role in the AFM transition temperatures of all these ordered double perovskites, that is, a larger A-site cation always results in a higher AFM transition temperature. This provides a strategy to subtly manipulate the magnetic properties of ordered double perovskites.