In situ molecular transformation under
hydrothermal
conditions is a feasible method to introduce distinct organic ligands
and suppress competitive reactions between different synthons. However,
this strategy has not yet been explored for the preparation of polyoxometalate
(POM)-encapsulated metal–organic frameworks (MOFs). In this
work, we designed and prepared a new compound, [Co2(3,3′-bpy)(3,5′-bpp)(4,3′-bpy)](H2O)3[SiW12O40] (1) (4,3′-bpy = 4,3′-dipyridine, 3,5′-bpp = 3,5′-bis(pyrid-4-yl)pyridine,
and 3,3′-bpy = 3,3′-bis(pyrid-4-yl) dipyridine), via an in situ ligand synthesis route.
The compound shows a novel POM-encapsulated MOF structure with two
pairs of left- and right-handed double helixes. These left- and right-handed
helical chains further lead to triangular and rhombus-like channels,
respectively. Moreover, the as-synthesized title compound shows superior
electrocatalytic activity toward the hydrogen evolution reaction (HER)
in 1 M KOH aqueous solution with a low overpotential and Tafel slope
of 92 mV and 92.1 mV dec–1, respectively, under
a current density of 10 cm–2. Also, the compound
exhibits a high activity for the photocatalytic degradation of the
dye rhodamine B. The excellent performance of the compound may be
attributed to the synergistic effect between W and Co elements and
the presence of encapsulated POMs. The title compound proves that
it is possible to prepare multifunctional MOFs with POMs and transition
metals showing HER activity and dye degradation activity.