title: Assembly of a basket-like {Sr ⊂ P6Mo18O73} cage from 0D dimmer to 2D network and its photo-/electro-catalytic properties.
abstract: A series of basket-like heteropoly blues, formulated as (H4bth)[{Cu(H2O)}2{Sr ⊂ P6MoV2MoVI16O73}]·4H2O (1), {H2bih}3[{FeII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (2), (H2bih)3[{CoII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (3), (H2bih)3[{NiII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (4), (H2bih)2(H2bip)[{Zn (H2O)0.5}{Sr ⊂ P6MoV2MoVI16O73}]·5.5H2O (5), (bth = 1,6-bis(triazole)hexane; bih = 1,6-bis(imidazol)hexane; bip = 1,5-bis(imidazol)pentane) have been synthesized hydrothermally and fully characterized. The structural analysis shows that all the compounds contain two electron reduced polyanions [Sr ⊂ P6MoV2MoVI16O73]8− (abbreviated as {P6Mo18O73}), which consists of a tetra vacant γ-Dawson-type{P2Mo14} unit and a “handle”-shaped {P4Mo4} segment encapsulating a Sr2+ cation in the central cavity. Compound 1 is a 6-connected two-dimensional (2D) layer, which represents the first 2D assembly of basket-type polyoxometalates. Compounds 2–4 are isostructural one-dimensional zigzag chains linked by an M(H2O)2 linker (M = iron for 2, cobalt for 3, and nickel for 4). Compound 5 is a dimeric cluster supported by a binuclear {Zn2(H2O)} unit. The optical band gaps of 1–5 reveal their semiconductive natures. The compounds if used as photocatalysts exhibit a universal high efficiency degradation ability for dyes such as methylene blue, Rhodamine B, and Azon phloxine. The lifetime and reaction mechanism of the catalysts were investigated with a series of experiments. The compounds also show good bifunctional electrocatalytic behavior for the oxidation of ascorbic acid (AA) and reduction of nitrite ions.
authors.affiliation: Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin 150025, People's Republic of China. hlyukai188@163.com zhou_bai_bin@163.com.
authors.forename: He
authors.initials: H
authors.lastname: Zhang
authors.forename: Jing-Hua
authors.initials: JH
authors.lastname: Lv
authors.forename: Kai
authors.initials: K
authors.lastname: Yu
authors.forename: Chun-mei
authors.initials: CM
authors.lastname: Wang
authors.forename: Chun-xiao
authors.initials: CX
authors.lastname: Wang
authors.forename: Di
authors.initials: D
authors.lastname: Sun
authors.forename: Bai-bin
authors.initials: BB
authors.lastname: Zhou