Search Results (6)

New energy storage materials are an object of study within the framework of the global energy transition. The development of renewable sources is being boosted thanks to stationary energy storage systems such as redox flow batteries (RFBs). This work reports the synthesis of the cobalt-containing Keggin-type polyoxometalates [CoW₁₂O₄₀]⁶⁻ (CoW₁₂) and [Co(H₂O)SiW₁₁O₃₉]⁶⁻ (CoSiW₁₁), which have previously been shown to have applicability in RFBs. These procedures were reassessed to meet the strict requirements associated with the further implementation of RFBs, including fast and affordable synthetic procedures with high reaction yields. In contrast to the lengthy and complicated synthetic approaches published to date, the optimized synthesis reported in this work enables the isolation of the pure crystalline salt of the CoW₁₂ anion with a 75% reduction of the time of the whole reaction procedure, eliminating tedious steps such as the recrystallization and including a 20% increased yield. The control of the stoichiometry, fine-tuning of reaction conditions, and the identification of intermediate species, as well as the acidic equilibria taking place during the process, were monitored via thermal, spectroscopic, and structural analyses. In the case of the CoSiW₁₁ anion, its preparation was based on a simple and highly efficient procedure. Moreover, promising electrochemical properties were observed with the use of the one-pot synthetic approach, in which the stoichiometric amounts of the starting reagents are dissolved in the supporting electrolyte to be directly implemented as the electrolyte for a RFB. Full article

Microbial fuel cells (MFCs) are a promising technology that can be applied in a bifunctional process in which wastewater treatment is used for renewable electric power generation. In this study, novel transition metal-modified Keggin-type lacunar polyoxometalate salts (L-POMs) Cs₅PMo₁₁M(H₂O)O₃₉ (M = Fe, Co), were synthesized and characterized by X-ray diffraction, SEM, EDX, IR, TGA/DSC, and UV-Vis/DSR spectroscopies to be tested, for the first time, as a cathode component in wastewater-fed air chamber MFCs. Both materials were tested in the presence and absence of light to evaluate their photocatalytic behavior. The best performance in terms of electricity production was obtained for the MFC containing the Co-modified POM-based cathode, which showed a maximum power of 418.15 mW/m² equivalent to 331 mW per cubic meter of treated wastewater, and a maximum COD removal percentage of 97% after 96 h of MFC operation. Co- and Fe-modified POMs had outstanding optical behavior with lower energy gap values, 1.71 and 2.68 eV, respectively. The newly developed materials can be considered as promising alternative cathode catalysts in a new generation of MFC devices integrating full carbon removal from wastewater and a fast reduction of oxygen. Full article

A series of tetrabutyl ammonium (TBA) salts of V-included Keggin-type polyoxoanions with W (TBA₄PW₁₁V₁O₄₀ and TBA₅PW₁₀V₂O₄₀) and Mo (TBA₄PMo₁₁V₁O₄₀ and TBA₅PMo₁₀V₂O₄₀) as addenda atoms were prepared using a hydrothermal method. These synthesized materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance (DRS UV-Vis), thermogravimetric analysis (TGA), CHN elemental analysis (EA), inductively coupled plasma spectrometry (ICP-MS), and N₂ physisorption techniques to assess their physicochemical/textural properties and correlate them with their catalytic performances. According to FT-IR and DRS UV-Vis, (PV_XW(Mo)_12−XO₄₀)^(3+X)− anions are the main species present in the TBA salts. Additionally, CHN-EA and ICP-MS revealed that the desired stoichiometry was obtained. Their catalytic activities in the liquid-phase aerobic oxidation of benzyl alcohol to benzaldehyde were studied at 5 bar of O₂ at 170 °C. Independently of the addenda atom nature, the catalytic activity increased with the number of V in the Keggin anion structure. For both series of catalysts, TBA salts of polyoxometalates with the highest V-substitution degree (TBA₅PMo₁₀V₂O₄₀ and TBA₅PW₁₀V₂O₄₀) showed higher activity. The maximum benzyl alcohol conversions obtained were 93% and 97% using (TBA)₅PMo₁₀V₂O₄₀ and (TBA)₅PW₁₀V₂O₄₀ as catalysts, respectively. In all the cases, the selectivity toward benzaldehyde was higher than 99%. Full article

Adipic acid (AA) was obtained by catalyzed oxidation of cyclohexene, epoxycyclohexane, or cyclohexanediol under organic solvent-free conditions using aqueous hydrogen peroxide (30%) as an oxidizing agent and molybdenum- or tungsten-based Keggin polyoxometalates (POMs) surrounded by organic cations or ionically supported on functionalized Merrifield resins. Operating under these environmentally friendly, greener conditions and with low catalyst loading (0.025% for the molecular salts and 0.001–0.007% for the supported POMs), AA could be produced in interesting yields. Full article

A new hybrid inorganic-organometallic salt has been obtained from the reaction of the Keggin-type silicotungstate anion with ferrocene in a water/methanol mixture as a result of the partial oxidation of ferrocene molecules to ferrocenium cations. Single-crystal X-ray diffraction analysis reveals the presence of four ferrocenium (Fe^III) cations and one ferrocene (Fe^II) molecule per plenary Keggin anion in the crystal structure of [Fe^III (Cp)₂]₄[SiW₁₂O₄₀]·[Fe^II(Cp)₂]·2CH₃OH (1). Compound 1 thus constitutes the first example in the literature in which ferrocenium and ferrocene species coexist in the structure of a polyoxometalate-based salt. The two crystallographically independent ferrocenium species in the asymmetric unit of 1 exhibit different configurations: One displays an eclipsed conformation with ideal D_5h symmetry, whereas the conformation in the other one is staggered D_5d. The crystal packing of 1 can be best described as an organometallic sub-lattice of ferrocenium and ferrocene species linked by a network of π-π interactions that generates rectangular cavities of about 14 × 10 Å in which strings of Keggin anions and methanol molecules are hosted, further connected to each other via weak O_POM···C_MeOH-O_MeOH···O_POM type hydrogen bonds. The charge-transfer nature of the salt has been studied by solid-state diffuse reflectance UV-Vis spectroscopy and the presence of magnetically isolated Fe^III/Fe^II centres has been confirmed by Mössbauer spectroscopy. A topological study carried out on all of the pristine ferrocenyl species deposited in the Cambridge Structural Database (CSD) has allowed two main conclusions to be drawn: (1) these species tend to adopt extreme conformations (either eclipsed or staggered) with less than a 15% of examples showing intermediate states and (2) the oxidation state of the iron centres can be unequivocally assigned on the basis of a close inspection of the Fe···Cp distances, which allows ferrocene neutral molecules and ferrocenium cations to be easily distinguished. Full article

The β,β-isomer of open-Wells–Dawson polyoxometalate (POM) containing a tetra-iron(III) cluster, K₉[{Fe₄(H₂O)(OH)₅}(β,β-Si₂W₁₈O₆₆)]·17H₂O (potassium salt of β,β-Fe₄-open), was synthesized by reacting Na₉H[A-β-SiW₉O₃₄]·23H₂O with FeCl₃·6H₂O at pH 3, and characterized by X-ray crystallography, FTIR, elemental analysis, TG/DTA, UV–Vis, and cyclic voltammetry. X-ray crystallography revealed that the {Fe³⁺₄(H₂O)(OH)₅}⁷⁺ cluster was included in the open pocket of the β,β-type open-Wells–Dawson polyanion [β,β-Si₂W₁₈O₆₆]¹⁶⁻ formed by the fusion of two trilacunary β-Keggin POMs, [A-β-SiW₉O₃₄]¹⁰⁻, via two W–O–W bonds. The β,β-open-Wells–Dawson polyanion corresponds to an open structure of the standard γ-Wells–Dawson POM. β,β-Fe₄-open is the first example of the compound containing a geometrical isomer of α,α-open-Wells–Dawson structural POM. Full article