Varied roles of Pb in transition-metal PbMO3 perovskites (M=Ti, V, Cr, Mn, Fe, Ni, Ru)

被引：26

作者：

Goodenough, John B. ^{[1
]}

Zhou, Jianshi

机构：

[1] Univ Texas Austin, Mat Sci & Engn Program, Austin, TX 78712 USA

来源：

SCIENCE AND TECHNOLOGY OF ADVANCED MATERIALS | 2015年 / 16卷 / 03期

关键词：

perovskites; lone pair electrons; crystal structure; HIGH-PRESSURE SYNTHESIS; SPECTRAL-FUNCTION; PBCRO3; 0-LESS-THAN-OR-EQUAL-TO-X-LESS-THAN-OR-EQUAL-TO-1; MICROSTRUCTURE; FERROMAGNETISM; TRANSFORMATION; BATTERIES; EVOLUTION; CRYSTAL;

D O I：

10.1088/1468-6996/16/3/036003

中图分类号：

T [工业技术];

学科分类号：

08 ;

摘要：

Different structural chemistries resulting from the Pb2+ lone-pair electrons in the PbMO3 perovskites are reviewed. The Pb2+ lone-pair electrons enhance the ferroelectric transition temperature in PbTiO3, stabilize vanadyl formation in PbVO3, and induce a disproportionation reaction of CrIV in PbCrO3. A Pb2+ + Ni-IV= Pb4++ Ni-II reaction in PbNiO3 stabilizes the LiNbO3 structure at ambient pressure, but an A-site Pb4+ in an orthorhombic perovskite PbNiO3 is stabilized at modest pressures at room temperature. In PbMnO3, a ferroelectric displacement due to the lone pair electron effect is minimized by the spin-spin exchange interaction and the strong octahedral site preference of the Mn-IV/III cation. PbRuO3 is converted under pressure from the defective pyrochlore to the orthorhombic (Pbnm) perovskite structure where Pb-Ru interactions via a common O -2p orbital stabilize at low temperature a metallic Imma phase at ambient pressure. Above P-c similar or equal to 32GPa, a covalent Pb-Ru bond is formed by Pb2++ Ru-IV= Pb4+ + Ru-II electron sharing.

引用

页数：11

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