Growing high-quality single crystals of transitional metal vanadates is of interest because of the applications of vanadates in different fields such as magnetism, optics, and batteries. Vanadium has very rich chemistry due to its ability to adopt various oxidation states (+2 to +5) and different geometries ranging from four to six-coordinate. Vanadate(V) is an excellent building block for magnetic structures because it is stable and magnetically silent. Vanadates can also adopt numerous structural arrangements via the corner-sharing of their tetrahedra, such as chains, rings, or layers reminiscent of poly silicates. The d0 vanadate building blocks are suitable magnetic coupling units for first-row transition metals as well.<br/>Our group has been able to grow high-quality crystals of different first-row transition metal ions with various vanadate building blocks using the hydrothermal technique. In this work, the reactions were designed by the inspiration of natural brine environments carrying out in high concentrations of carbonates, alkaline halides, and hydroxides as mineralizers. The concentrated alkali metal brines play a complicated role in the formation of novel metal vanadate phases. They sometimes incorporate into the structural lattice, or they sometimes act only as a mineralizer to solubilize the materials leading to good-quality crystals. Several novel first-row transitional metal vanadates are presented, including K2M(VO3)4 (M = Mn, Co) and CsMV2O6Cl (M = Mn, Co, Fe, Ni, Cu). The structures and preliminary magnetic properties of these new materials and the role of the brines in their formation will be discussed.

Growth novel metal vanadates in hydrothermal brines

ACS Fall 2021

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