Effect of vanadium valence state on the solution chemistry and the stability of vanadium substituted polyoxometalates
- Resource Type
- Authors
- Jie Cao; Chang Liu; Jie-Chao Zang; QianQian Wang; Cheng-Gang Ci
- Source
- RSC Advances. 6:110922-110927
- Subject
- Valence (chemistry)
010405 organic chemistry
Vanadyl sulfate
General Chemical Engineering
Inorganic chemistry
Vanadium
chemistry.chemical_element
General Chemistry
Solution chemistry
010402 general chemistry
01 natural sciences
0104 chemical sciences
chemistry.chemical_compound
Crystallography
chemistry
Lacunary function
- Language
- ISSN
- 2046-2069
The reactions of lacunary Keggin-type silicotungstates ({SiW12−x}, x = 1–3) with vanadyl sulfate (VIVOSO4) as the tetravalent vanadium source were monitored in real-time by ESI-MS in conjunction with DPV. Different phenomena from the pentavalent vanadium counterpart (NaVVO3) were found: the substitution products are unexpectedly stable whereas spontaneous transformations from mono- into di- and eventually tri-vanadium substituted products ({SiW11V} → {SiW10V2} → {SiW9V3}) were observed when the substituted vanadium is of +5 valence state. DFT calculations were utilized to interpret the intrinsic structural reasons for distinctive stability of the vanadium-substituted POMs with different valences and with different substitution degrees. The effect of the vanadium valence states on the solution chemistry and stability of the substituted POMs were thereby unraveled.