Effect of vanadium valence state on the solution chemistry and the stability of vanadium substituted polyoxometalates

Chang Liu; Jie Cao; Qian Qian Wang; Jie Chao Zang; Cheng Gang Ci

doi:10.1039/C6RA24432G

Effect of vanadium valence state on the solution chemistry and the stability of vanadium substituted polyoxometalates

Chang Liu
, Jie Cao^*
, Qian Qian Wang
, Jie Chao Zang
, Cheng Gang Ci

^*Corresponding author for this work

Ministry of Education in China
Qiannan Normal College for Nationalities
Northeast Normal University
Daqing Normal University

Research output: Contribution to journal › Article › peer-review

5 Citations (Scopus)

Abstract

The reactions of lacunary Keggin-type silicotungstates ({SiW_12x}, x = 1-3) with vanadyl sulfate (V^IVOSO₄) as the tetravalent vanadium source were monitored in real-time by ESI-MS in conjunction with DPV. Different phenomena from the pentavalent vanadium counterpart (NaV^VO₃) 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.

Original language	English
Pages (from-to)	110922-110927
Number of pages	6
Journal	RSC Advances
Volume	6
Issue number	112
DOIs	https://doi.org/10.1039/C6RA24432G
Publication status	Published - 2016
Externally published	Yes

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title = "Effect of vanadium valence state on the solution chemistry and the stability of vanadium substituted polyoxometalates",

abstract = "The reactions of lacunary Keggin-type silicotungstates (\{SiW12x\}, 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.",

author = "Chang Liu and Jie Cao and Wang, \{Qian Qian\} and Zang, \{Jie Chao\} and Ci, \{Cheng Gang\}",

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year = "2016",

doi = "10.1039/C6RA24432G",

language = "English",

volume = "6",

pages = "110922--110927",

journal = "RSC Advances",

issn = "2046-2069",

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TY - JOUR

T1 - Effect of vanadium valence state on the solution chemistry and the stability of vanadium substituted polyoxometalates

AU - Liu, Chang

AU - Cao, Jie

AU - Wang, Qian Qian

AU - Zang, Jie Chao

AU - Ci, Cheng Gang

PY - 2016

Y1 - 2016

N2 - The reactions of lacunary Keggin-type silicotungstates ({SiW12x}, 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.

AB - The reactions of lacunary Keggin-type silicotungstates ({SiW12x}, 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.

UR - https://www.scopus.com/pages/publications/84997638356

U2 - 10.1039/C6RA24432G

DO - 10.1039/C6RA24432G

M3 - Article

AN - SCOPUS:84997638356

SN - 2046-2069

VL - 6

SP - 110922

EP - 110927

JO - RSC Advances

JF - RSC Advances

IS - 112

ER -

Effect of vanadium valence state on the solution chemistry and the stability of vanadium substituted polyoxometalates

Abstract

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