Hydrothermal Synthesis and Crystal Structure of a Novel Bismuth Oxide: (K_0.2Sr_0.8)(Na_0.01Ca_0.25Bi_0.74)O₃

A novel distorted perovskite-type (K0.2Sr0.8)(Na0.01Ca0.25Bi0.74)O3 was prepared by a hydrothermal method using the starting materials NaBiO3·nH2O, Sr(OH)2·8H2O, Ca(OH)2, and KOH. Single-crystal X-ray diffraction of the novel compound revealed a GdFeO3-related structure belonging to the monoclinic system of the space group Cc with the following cell parameters: a = 11.8927 (17) Å, b = 11.8962 (15) Å, c = 8.4002 (10) Å, and β = 90.116 (9)°. The final R-factors were obtained as R1 = 0.0354 and wR2 = 0.0880 (using all the data). K+ and Sr2+ ions were distributed at four types of A-sites. On the other hand, four Bi5+-sites (Bi1, Bi2, Bi3, and Bi4) were occupied by four Ca2+ ions (Ca1, Ca2, Ca3, and Ca4), and the first three B-sites were occupied predominantly by Bi5+ with Na+ ions. The forth B-site was occupied predominantly by the Ca2+ ion with Bi5+ ions. Two types of B-sites, thus forming tilted distorted (Na/Ca/Bi)O6 and (Bi/Ca)O6 octahedra, have an ordering of 3:1 represented as (K/Sr)4(Na/Ca/Bi)3(Bi/Ca)O12. The distorted (Na/Ca/Bi)O6 and (Ca/Bi)O6 octahedra formed a perovskite-type network by corner sharing with features closely matching those of a GdFeO3-type structure. The novel compound is the first example of a perovskite-type bismuth oxide containing only Bi5+ in a system without a Ba atom and has a unique ordering (3:1) of the B site. The compound showed photocatalytic activity for phenol degradation under visible light irradiation.