posted on 2023-11-20, 18:06authored byHui-Jie Lun, Sheng-Qiang Dai, Ya-Xin Li, Hui-Li Guo, Swetha Andra, Dong-Bin Dang, Yan Bai
Lanthanide-containing polyoxometalate-based
metal–organic
frameworks (POMOFs) not only enjoy intriguing architectures but also
have good application prospects as catalysts. Herein, three novel
three-dimensional (3D) POMOFs with the formulas of {H[Ln3(2,6-pydc)2(H2O)10(MnMo9O32)]·2H2O}n (Ln = La(1), Pr(2), Nd(3))
have been synthesized based on Waugh-type [MnMo9O32]6– anions and pyridine-2,6-dicarboxylate (2,6-H2pydc). Compounds 1–3 are
isomorphic, and there are two kinds of one-dimensional (1D) helical
chains with opposite handedness staggered into two-dimensional (2D)
layers. Interestingly, the coordinated L- and R-[MnMo9O32]6– anions
are encapsulated in 1D chains with the same chirality and are further
expanded into 3D structures. The catalytic tests indicate that compounds 1–3 exhibit high-efficiency heterogeneous
catalytic activity in the oxidative desulfurization reaction for catalyzing
the oxidation of sulfides to sulfoxides using tert-butyl hydrogen peroxide (TBHP) as the oxidant. Moreover, a series
of control experiments have been conducted to investigate the influence
of various parameters such as temperature, time, solvent, catalyst,
and substrate on the reaction. Significantly, compound 2, as an example, exhibits good reusability and structural stability
in the oxidative desulfurization reaction. It is worth noting that
investigations on the oxidative desulfurization of [MnMo9O32]6– anions are scarce. Moreover,
their electrochemical properties are also explored.