Hydrothermal Synthesis of Transition Metal Oxides

CHAPTER 5

CONCLUSIONS

Hydrothermal method has been used for the all reactions and it was proven to be a good procedure for synthesizing of new metal oxide crystals.

This research has focused on synthesis and structure solution of single crystals of a novel lead chlorovanadate compound, PbVO₃Cl, and of a known alkali-metal trivanadate compound, KV₃O₈. Most vital part of this thesis is the structure solution of crystals that were obtained.

The needle shaped yellow crystals of PbVO₃Cl compound have synthesized by hydrothermal method. This compound was prepared from the reaction of NaVO₃, and PbCl₂ in 1.66M of boric acid solution (with 1: 1: 7.5 mole ratios). These needle shaped yellow crystals were obtained at 170^o C for 3 days. The compound crystallizes in the space group Pnma of the orthorhombic system. Structure of the lead chlorovanadate, PbVO₃Cl, consists of a chain of VO₅ and [PbCl] _n sheets running along b-axis. The edge-sharing VO₅ pyramids with a trans configuration were formed by [VO₃] _n chains. Such chains have already been observed in the AV₃O₇ type of compounds [65], and this compound is isostructural to BaVO₃Cl and SrVO₃Cl reported by Borel et.al [58]. Each of the V centers has square pyramidal with the oxidation state of 5.00(2).

A known alkali metal trivanadate compound, KV₃O₈, have also synthesized. The compound KV₃O₈ has been prepared by hydrothermal synthesis at 170^o C for 3 days from KVO₃, and PbCl₂ in 1.66M of B(OH)₃ solution. This compound originally synthesized by through very complicated reaction process. We were able to obtain these crystals very easily after trying a number of different reaction conditions. At the end this compound was able to be obtained with only using KVO₃ in B(OH)₃ solution in 2 days.

The crystal structure was determined by single crystal X-ray diffraction and found to crystallize in monoclinic crystal system with space group P2(1)/m. The orange hexagonal plate-shaped crystal, KV₃O₈, is composed of a layered structure with V₃O₈ layers consisting of VO₆ octahedra and VO₅ square pyramids. The compound has two unique vanadium atoms (V1, V2) with different coordination environment. The V1 has a distorted octahedral environment and the V2 has a square pyramidal coordination environment. All V are pentavalent with approximately the oxidation state of +5.

Water has proven to be excellent medium to synthesize novel compounds under the hydrothermal conditions.

After all the experiments, one new and one known compound were able to be obtained and analyzed their some properties. By slightly varying the reaction conditions, good single crystals were able to be prepared.

In the future work, we should try to change V with other transition metals.

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