Expanding negative thermal expansion range of ZrMnMo3O12 to cover room temperature by introducing V5+

Solid solutions of Zr1+xMn1-xMo3-2xV2xO12 (0 ≤ x ≤ 0.5) are developed with reduced phase transition temperature (from 362 to 160 K) by introducing V5+ into ZrMnMo3O12. Zr1+xMn1-xMo3-2xV2xO12 adopt monoclinic (P21/a) and orthorhombic (Pbcn) structure at room temperature (RT) for x ≤ 0.1 and x ≥ 0.2, respectively. The formation of bond V–O induces a larger average effective negative charge on oxygen to enhance the repulsive force between them and then strengthens the bond of Mo–O, which reduces the phase transition temperature due to the reduction in effective electronegativity and expands negative thermal expansion (NTE) range covering RT. NTE property in a wide temperature range (from 160 to 673 K) for Zr1.5Mn0.5Mo2VO12 is realized, implying great potential for applications. The NTE property of the materials is induced by low-frequency phonons.