Abstract
Tetrahedral units can transport oxide anions via interstitial or vacancy defects owing to their great deformation and rotation flexibility. Compared with interstitial defects, vacancy-mediated oxide-ion conduction in tetrahedra-based structures is more difficult and occurs rarely. The isolated tetrahedral anion Scheelite structure has showed the advantage of conducting oxygen interstitials but oxygen vacancies can hardly be introduced into Scheelite to promote the oxide ion migration. Here we demonstrate that oxygen vacancies can be stabilized in the BiVO(4) Scheelite structure through Sr(2+) for Bi(3+) substitution, leading to corner-sharing V(2)O(7) tetrahedral dimers, and migrate via a cooperative mechanism involving V(2)O(7)-dimer breaking and reforming assisted by synergic rotation and deformation of neighboring VO(4) tetrahedra. This finding reveals the ability of Scheelite structure to transport oxide ion through vacancies or interstitials, emphasizing the possibility to develop oxide-ion conductors with parallel vacancy and interstitial doping strategies within the same tetrahedra-based structure type.