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A Lacunary Polyoxovanadate Precursor and Transition‐Metal‐Sandwiched Derivatives for Catalytic Oxidation of Sulfides
Author(s) -
Wan Rong,
He Peipei,
Liu Zhen,
Ma Xinyi,
Ma Pengtao,
Singh Vikram,
Zhang Chao,
Niu Jingyang,
Wang Jingping
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905741
Subject(s) - lacunary function , x ray photoelectron spectroscopy , transition metal , catalysis , electron paramagnetic resonance , chemistry , crystallography , ion , single crystal , metal , inorganic chemistry , nuclear magnetic resonance , organic chemistry , mathematics , pure mathematics , physics
A SeO 3 ‐centered lacunary Keggin‐type heteropolyoxovanadate (hetero‐POV) K 6 H 2 [SeV 10 O 28 (SeO 3 ) 3 ] ⋅ 14 H 2 O ( 1 ) was isolated by one‐pot reaction of KVO 3 and SeO 2 under acidic conditions. X‐ray studies revealed that it comprised a single {VO 5 }‐capped trivacant B‐α‐type Keggin ion [SeV 9 O 33 (VO)] 14− with its lacunary sites decorated by three {SeO 3 } pyramids. Interestingly, this new basic hetero‐POV building block was further used as a precursor to assemble with different transition‐metal (TM) ions, yielding a series of TM‐sandwiched POVs K 6 H 8 [(SeV 10 O 28 (SeO 3 ) 3 ) 2 (M(H 2 O) 4 )] ⋅ 24 H 2 O (M 2+ =Mn 2+ ( 2 ), Co 2+ ( 3 ), Zn 2+ ( 4 )). All four compounds were characterized by single‐crystal X‐ray structure analysis, IR, X‐ray photoelectron spectroscopy (XPS), EPR, and 51 V NMR spectroscopy. Importantly, three TM‐sandwiched derivatives exhibited effective catalytic activity for the heterogeneous oxidative desulfurization of sulfides at room temperature.