The grafting of the triangular 1,3,5-benzene tricarboxylate linkers (denoted trim) on tetrahedral ε-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)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)][C(6)H(3)(COO)(3)](4/3)·6H(2)O (ε(trim)(4/3)) is a 3D open-framework built of molecular Keggin units connected by trim linkers, with channels occupied by tetrabutylammonium (TBA) counterions. ε(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)[PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)][C(6)H(3)(COO)(3)] (ε(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)[PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)][C(6)H(3)(COO)(3)]·8H(2)O ([ε(trim)](∞)), 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 × 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 ε(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.

The targeted design and simulation of a new family of zeolitic metal-organic frameworks (MOFs) based on benzenedicarboxylate (BDC) as the ligand and epsilon-type Keggin polyoxometalates (POMs) as building units, named here Z-POMOFs, have been performed. A key feature is the use of the analogy between the connectivity of silicon in dense minerals and zeolites with that of the epsilon-type Keggin POMs capped with Zn(II) ions. Handling the epsilon-Keggin as a building block, a selection of 21 zeotype structures, together with a series of dense minerals were constructed and their relative stabilities computed. Among these Z-POMOFs, the cristobalite-like structure was predicted to be the most stable structure. This prediction has been experimentally validated by the targeted synthesis of the first experimental Z-POMOF structure, which was strikingly found to possess the cristobalite topology, with three interpenetrated networks. Crystals of [NBu(4)](3)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)(BDC)(2)].2H(2)O (Z-POMOF1) have been isolated under hydrothermal conditions from the reduction of ammonium heptamolybdate in the presence of phosphorous acid and Zn(II) ions. Tetrabutylammonium cations play the role of counterions and space-filling agents in this tridimensional interpenetrated framework. Moreover, the electrochemistry of the epsilon-Keggin POM is maintained and can be exploited in the insoluble Z-POMOF1 framework, as demonstrated by the electrocatalytic reduction of bromate.