Abstract
The grafting of the triangular 1,3,5-benzene tricarboxylate linkers (denoted trim) on tetrahedral e-Keggin polyoxometalates (POMs) capped by Zn(II) ions, formed in situ under hydrothermal conditions, has generated three novel POM-based metal organic frameworks (POMOFs). (TBA)(3)[(PMo8Mo4O36)-Mo-V-O-VI(OH)(4)Zn-4][C6H3(COO)(3)](4/3)center dot 6H(2)O (epsilon(trim)(4/3)) is a 3D open-framework built of molecular Keggin units connected by trim linkers, with channels occupied by tetrabutylammonium (TBA) counterions. epsilon(trim)(4/3) is a novel (3,4)-connected net, named ofp for open-framework polyoxometalate, and computer simulations have been used to evaluate its relative stability in comparison with ctn- and bor-like polymorphs, showing the stability of this novel phase directly related to its greatest density. A computational study was also undertaken with the aim of locating TBA molecules, the positions of which could not be deduced from single crystal X-ray diffraction, and further rationalizes their structure directing role. In (TBA)(3)[(PMo8Mo4O37)-Mo-V-O-VI(OH)(3)Zn-4][C6H3(COO)(3)] (epsilon(2)(trim)(2)), the building unit is not the molecular Keggin but a dimerized form of this POM. Their connection via trim linkers generates a 3D framework with channels filled by TBA cations. In (TBA)(3)[(PMo8Mo4O37)-Mo-V-O-VI(OH)(3)Zn-4][C6H3(COO)(3)]center dot 8H(2)O ([epsilon(trim)](infinity)), zigzag chains are connected via the organic linkers, forming 2D grids. Modified electrodes were fabricated by direct adsorption of the POMOFs on glassy carbon or entrapment in carbon paste (CPE). A remarkable electrocatalytic hydrogen evolution reaction (HER) was detected with a yield greater than 95%, and a turnover number as high as 1.2 x 10(5) was obtained after 5 h. The reported POMOF-based electrodes are more active than platinum, with a roughly 260 mV anodic shift. Finally, the electrocatalytic activities of epsilon(trim)(4/3)/CPE electrodes in various XCl (X = Li, Na, K, Cs) media have been studied. This allowed us to detect a cation effect and propose an electrocatalytic mechanistic pathway for the HER.