Search Results (15)

Redox Flow Batteries (RFBs) are promising large-scale Energy Storage Systems, which support the integration of renewable energies into the current electric grid. Emerging chemistries for electrolytes, such as Polyoxometalates (POMs), are being studied. POMs have attracted great interest because of their reversible multi-electron transfers and the possibility of tuning their electrochemical properties. Recently, the cobalt-containing Keggin-type species [CoW₁₂O₄₀]⁶⁻ (CoW₁₂) has been successfully implemented in a symmetric RFB, and its further implementation calls for new materials for the membrane to enhance its cell performance. In this work, different types of ion exchange membranes (Nafion™-NR212, FAPQ-330 and Amphion™) were tested. The electrolyte uptake, swelling, conductivity and permeability of the membranes in the CoW₁₂ electrolyte, as well as a detailed cell performance study, are reported herein. Better performance results ascribed to the robustness, efficiency and energy density of the system were found for Nafion™-NR212, with 88.5% energy efficiency, 98.9% capacity retention and 3.1 Wh L⁻¹ over 100 cycles at 20 mA cm⁻². FAPQ-330 and Amphion membranes showed large capacity fade (up to 0.2%/cycle). Crossover and the low conductivity of these membranes in the mild pH conditions of the electrolyte were revealed to be responsible for the reduced cell performance. Full article

The coordination of rare-earth metal ions (Ln³⁺) to polyoxometalates (POM) is regarded as a way of modifying and controlling their properties, such as single-molecular magnetism or luminescent behavior. The half-sandwich complexes of Ln³⁺ with monolacunary Keggin POMs (Ln³⁺/POM = 1:1) are of particular interest, since the Ln³⁺ retains its ability to coordinate extra ligands. Thus, the knowledge of the exact structures of 1:1 Ln/POM complexes is important for the development of reliable synthetic protocols for hybrid complexes. In this work, we isolated three 1:1 Gd³⁺/POM complexes of the general formula Cat₄Gd(PW₁₁O₃₉)·xH₂O (Cat = K⁺ or Me₄N⁺). Complex (Me₄N)₂K₂[Gd(H₂O)₂PW₁₁O₃₉]·5H₂O (1) is polymeric, revealing a layered structural motif via bridging Gd³⁺ and K⁺ ions. Complexes (Me₄N)₆K₂[Gd(H₂O)₃PW₁₁O₃₉]₂·20H₂O (2) and (Me₄N)₇K[Gd(H₂O)₃PW₁₁O₃₉]₂·12H₂O (3) are classified as dimeric; the difference between them consists of the different crystal packing of the polyoxometalates, which is induced by a variation in the cationic composition. Isostructural complexes have also been characterized for praseodymium, europium, terbium and dysprosium. The coordination number of Ln³⁺ (8) persists in all the compounds, while the binding mode of the POM varies, giving rise to different architectures with two or three H₂O co-ligands per Ln³⁺. However, whatever the particular structure and exact composition, the {Ln(PW₁₁O₃₉)} moieties are always involved in bonding with each other with the formation either of polymeric chains or dimeric units. In water, these aggregates can dissociate with the formation of [Ln(H₂O)₄PW₁₁O₃₉]^4-. This behavior must be taken into account when choosing L for the design of hybrid {Ln(L)POM} complexes. Full article

Surfactants are functional molecules utilized in various situations. The self-assembling property of surfactants enables several molecular arrangements that can be employed to build up nanometer-sized architectures. This is beneficial in the construction of functional inorganic–organic hybrids holding the merits of both inorganic and organic components. Among several surfactants, bolaamphiphile surfactants with two hydrophilic heads are effective, as they have multiple connecting or coordinating sites in one molecule. Here, a functional polyoxotungstate inorganic anion was successfully hybridized with a bolaamphiphile to form single crystals with anisotropic one-dimensional alignment of polyoxotungstate. Keggin-type metatungstate ([H₂W₁₂O₄₀]⁶⁻, H₂W₁₂) was employed as an inorganic anion, and 1,12-dodecamethylenediammonium (C₁₂N₂) derived from 1,12-dodecanediamine was combined as an organic counterpart. A simple and general ion-exchange reaction provided a hybrid crystal consisting of H₂W₁₂ and C₁₂N₂ (C₁₂N₂-H₂W₁₂). Single crystal X-ray structure analyses revealed a characteristic honeycomb structure in the C₁₂N₂-H₂W₁₂ hybrid crystal, which is possibly effective for the emergence of conductivity due to the dissociative protons of C₁₂N₂. Full article

In the present investigation, a one-step hydrothermal approach is proposed to synthesize Li⁺, Rb⁺, and In³⁺intercalated PW₁₂O₄₀ (PTA) thin films. The photoelectrochemical performance of the deposited Li₃PW₁₂O₄₀ (Li−PTA), Rb₃PW₁₂O₄₀ (Rb−PTA), and In₃PW₁₂O₄₀ (In−PTA) photocathodes were investigated using a two-electrode cell configuration of FTO/Li₃PW₁₂O₄₀/(0.1 M I⁻/I³⁻)_aq./Graphite. The energy band gaps of 2.24, 2.11, and 2.13 eV were observed for the Li−PTA, Rb−PTA, and In−PTA films, respectively, as a function of Li⁺, Rb⁺, and In³⁺. The evolution of the spinal cubic crystal structure with increased crystallite size was observed for Rb⁺ intercalation within the PTA Keggin structure, which was confirmed by X-ray diffraction (XRD). Scanning electron microscopy (SEM) revealed a modification in the surface morphology from a rod-like structure to a densely packed, uniform, and interconnected microsphere to small and large-sized microspheres for Li−PTA, Rb−PTA, and In−PTA, respectively. Compositional studies confirmed that the composing elements of Li, Rb, In, P, W, and O ions are well in accordance with their arrangement for Li⁺, Rb⁺, In³⁺, P⁵⁺, W⁶⁺, and O²⁻ valence states. Furthermore, the J-V performance of the deposited photocathode shows power conversion efficiencies (PCE) of 1.25%, 3.03%, and 1.62%, as a function of the incorporation of Li⁺, Rb⁺, and In³⁺ ions. This work offers a one-step hydrothermal approach that is a prominent way to develop Li⁺, Rb⁺, and In³⁺ ions intercalated PTA, i.e., Li₃PW₁₂O_40, Rb₃PW₁₂O₄₀, and In₃PW₁₂O₄₀ photocathodes for competent solar energy harvesting. Full article

Reactive oxygen species (ROS) can be used as an effective method to treat tumors. Artificial oxidase has received increasing attention as a catalyst for ROS generation in fields ranging from bioinorganic chemistry to pharmaceutical chemistry. In this study, an artificial oxidase based on a binuclear zinc complex and Keggin-type silicotungstate [Zn₂(4,4′-bpy)(Phen)₂][SiW₁₂O₄₀] (ZSW) (4,4′-bpy = 4,4′-bipyridine; Phen = 1,10-phenanthroline) was synthesized and structurally featured in terms of its X-ray photoelectron spectrum (XPS), bond valence sum (Σs) calculation, IR spectra, and single-crystal X-ray diffraction (SXRD). ZSW is an ionic compound in which the cation is a binuclear zinc complex [Zn₂(4,4′-bpy)(Phen)₂]⁴⁺ and the anion is a α-Keggin-type silicotungstate [SiW₁₂O₄₀]^4– cluster. Notably, the Zn ions in the [Zn₂(4,4′-bpy)(Phen)₂] exist in tri-coordination, which was first obtained in polyoxometalate (POM) chemistry. It was also demonstrated that ZSW is capable of efficiently catalyzing the production of ROS, which, according to the computational calculations, may be due to the synergistic action of zinc complexes and POM building blocks. Furthermore, ZSW exhibited inhibition ability toward ROS-sensitive tumor cells, such as PC12 cells. Full article

Accurately characterizing the conformational variation of novel molecular assemblies is important but often ignored due to limited characterization methods. Herein, we reported the use of ion-mobility mass spectrometry (IMS/MS) to investigate the conformational changes of four azobenzene covalently functionalized Keggin hybrids (azo-Keggins, compounds 1–4). The as-prepared azo-Keggins showed the general molecular formula of [C₁₆H₃₆N]₄[SiW₁₁O₄₀(Si(CH₂)₃NH–CO(CH₂)_nO–C₆H₄N=NC₆H₄–R)₂] (R = H, n = 0 (1); R = NO₂, n = 0 (2); R = H, n = 5 (3); R = H, n = 10 (4)). The resultant azo-Keggins maintained stable monomeric states in the gas phase with intact molecular structures. Furthermore, the subtle photo-responsive trans-cis conformational variations of azo-Keggins were clearly revealed by the molecular shape-related collision cross-section value difference ranging from 2.44 Ų to 6.91 Ų. The longer the alkyl chains linkers were, the larger the conformational variation was. Moreover, for compounds 1 and 2, higher stability in trans-conformation can be observed, while for compounds 3 and 4, bistability can be achieved for both of them. Full article

Lacunary polyoxometalates (LPOMs) are key precursors for the synthesis of functional POMs. To date, reviews dedicated to behavioral studies of LPOMs often comprise the role of metal ions, including transition metal (TM) and rare earth (RE) ions, in extending and stability of high-nuclearity clusters. In contrast, the role of organic ligands in the structures and properties of lacunary-based hybrids has remained less explored. In this review, we focus on the role of organic fragments in the self-assembling process of POM-based architectures and discuss relationships between the nature and structure of organic ligand and properties such as the topology of hybrid inorganic–organic material in RE and TM-RE heterometallic derivatives of lacunary Keggin-type POMs. The effects of organic fragment in mixed ligand hybrids are also briefly reviewed. Full article

A series of K_xH_1.1-xCu_0.2Cs₁(NH₄)_1.5PVMo₁₁O₄₀ (KxCuCsNH₄PVA) catalysts with different x values were synthesized to catalyze the selective oxidation of methacrolein (MAL) to methacrylic acid (MAA). The effects of potassium (K) ions on both the structure and catalytic activity were studied in detail. The optimum K_0.6CuCsNH₄PVA exhibited a large surface area, more acid sites, and abundant active species (V⁴⁺/VO²⁺) in the secondary structure of the Keggin structure, consequently offering good catalytic performance. Furthermore, K ions increased the MAA selectivity at the expense of carbon monoxide and carbon dioxide (together defined as CO_X). Additionally, several process parameters for MAL oxidation were evaluated in the processing experiments. The effects of aldehyde impurities (formaldehyde and propanal) on the catalytic performance were investigated. Possible detrimental effects (catalyst poisoning and structural damage) of aldehyde impurities were excluded. A light decrease in MAL conversion could be attributed to the competitive adsorption of aldehyde impurities and MAL on the catalyst. Hopefully, this work contributes to the design of stable and feasible catalysts for the industrial production of MAA. Full article

The present study investigates modified Mo/V/W mixed oxides as a possible alternative for state of the art heteropoly acid catalysts (HPA) in the partial oxidation of methacrolein (MAC) to methacrylic acid (MAA). Even though HPAs show an excellent activity and MAA selectivity, their long-term stability is unsatisfying, rendering the catalyst inoperable after runtimes of roughly 6 months. Mo/V/W mixed oxides consisting of M1 and a hexagonal (Mo,V,W)O_x-phase (h-phase) in varying proportions were modified by impregnation with aqueous solutions containing cesium and phosphate ions. All samples were characterized with respect to specific surface area, crystallinity, elemental and phase composition. The catalytic performance in the oxidation of MAC to MAA was investigated using a continuously operated reaction unit with tubular fixed bed reactor. Impregnation with cesium and phosphate ions and subsequent heating triggers the transformation of the mixed oxide into a Keggin-type HPA, whereby the h-phase is more reactive than M1. The transformation into HPA is accompanied by a change in the catalytic properties, i.e., the selectivity to MAA is considerably improved. Compared to HPA synthesized directly, however, the HPA samples obtained by transformation of mixed oxides exhibit no advantages, be it with respect to activity, MAA selectivity or stability. Full article

The sorption of Cu²⁺ onto bentonite modified with Al Keggin cations and humic acid from CuCl₂ solutions at pH 4.5 was studied. Modification of Na-bentonite with Al Keggin cations was found to result in an increase in the basal spacing of montmorillonite from 1.29 nm for N-form to 1.85 and 1.78 nm for HAl₁₃ and Al₁₃ forms respectively, in a reduction of CEC (cation exchange capacity) and in the formation of additional sites with a variable charge with pH_PZC 4.2. Al₁₃-bentonite is not affected by heat. Under the conditions of the experiments at pH of 4.5 Na-bentonite adsorbs more Cu²⁺ from CuCl₂ solutions then Al₁₃ forms of bentonites. The main mechanism of copper sorption on Na-bentonite is the cation exchange Cu²⁺–Na⁺. The reduction of CEC of Na-bentonite after modification with Al Keggin cations leads to a decrease in the Cu²⁺ sorption. pH-dependent sorption sites on Al₁₃-bentonites have a pH_PZC of 4.2 and, therefore, under conditions of the experiment have positive charge which prevents Cu²⁺ sorption. Na-bentonite adsorbs more humic acid solution (HA) then Al₁₃-bentonite and the proportion of adsorbed HA remains constant over the entire concentration range. Treatment of the Al₁₃-bentonite with HA leads to the formation of the additional sorption sites. The amount of sorbed Cu²⁺ and the percentage of their extraction from solutions by HAAl₁₃-bentonite is similar to those values for Na-bentonite. Full article

Phosphotungstic and silicotungstic acid salt catalysts (CuPW, CuSiW, FePW, FeSiW) were synthesized by substitution of protons with ferric and copper ions through a simple replacement reaction. The structure and thermal stability were characterized by IR, XRD and TG, and the salts showed a keggin structure and a thermal tolerance near 450 °C. Temperature programmed reactions indicated that the four catalysts showed similar trends in the change of methanol conversion, DME selectivity, and light olefins selectivity at 100–400 °C. Copper salt catalysts showed a 100% DME selectivity at temperatures ranging from 100–250 °C, while FeSiW and FePW catalysts had a 100% DME selectivity near 250 °C. Moreover, the heteropolyacid salt catalysts also produced a certain number of light olefins at the temperature ranging from 250–350 °C, and the CuSiW catalyst exhibited the highest ethylene and propylene selectivity of 44%. In the stability test evaluated at 200 °C, the catalysts showed different tendencies during the induction period and the same trends during the reduction period for the methanol conversion to DME, due to the differences in the strengths of the strong acid sites. Finally, the silicotungstic acid salt catalysts showed the longest lifetime of 120 h, much longer than the heteropolyacids. This approach provides an effective way to synthesize hydrocarbons through methanol, especially DME, at different temperatures using one catalyst. Full article

Heteropoly acids (HPAs) with the Keggin structure have been widely used in NO_x removal. Two kinds of catalysts (those with and without the Keggin structure) are prepared for studying the effect of the Keggin structure on the NH₃-SCR reaction. A series of in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) analyses are conducted to investigate the surface-adsorbed species on the catalysts during the SCR reaction. The mechanism for enhancing low-temperature activity of the catalysts is proposed. Furthermore, the effect of NH₄⁺ in the Keggin structure is also investigated. Results indicate that both the Langmuir–Hinshelwood (L-H) and Eley–Rideal (E-R) mechanisms occurred in the NH₃-SCR reaction over the catalyst with the Keggin structure (Cat-A); in addition, when more acid sites are provided, NO_x species activity is improved and more NH₄⁺ ions participate in reaction over Cat-A, thus promoting SCR activity. Full article

This work describes the synthesis and characterization of pillared clays using a new pillaring method: the reuse of the pillaring solution. First, an Al pillared clay (PILC) was synthesized, and after filtration, the pillaring agent was stored and reused for an additional three pillaring procedures (P1, P2, and P3). The filtered pillaring solution was stored for one year and then reused for one additional pillaring procedure (P4). The samples were analyzed using XRD, N₂ physisorption measurements and chemical analysis (EDX). All of the samples exhibited basal spacings larger than 17 Å and BET surface areas greater than 160 m²/g. After the P4 pillaring, the pillaring agent was precipitated with a Na₂SO₄ solution, and the resulting solid was analyzed using XRD and SEM. The results indicated that even after a total of five pillaring procedures, Al₁₃ ions were still present in solution. Therefore, it is possible to reuse the pillaring solution four times and to even store the solution for one year, which is important from an industrial perspective. Full article

A new 30-center Ga(III)-oxy-hydroxide cation cluster was synthesized by hydrolysis of an aqueous GaCl₃ solution near pH = 2.5 and crystallized using 2,6-napthalene disulfonate (NDS). The cluster has 30 metal centers and a nominal stoichiometry: [Ga₃₀(μ₄-O)₁₂(μ₃-O)₄(μ₃-OH)₄(μ₂-OH)₄₂(H₂O)₁₆](2,6-NDS)₆, where 2,6-NDS = 2,6-napthalene disulfonate This cluster augments the very small library of Group 13 clusters that have been isolated from aqueous solution and closely resembles one other Ga(III) cluster with 32 metal centers that had been isolated using curcurbit ligands. These clusters have uncommon linked Ga(O)₄ centers and sets of both protonated and unprotonated μ₃-oxo. Full article

Reaction products of titanium(IV) sulfate in HCl-acidic aqueous solution with the dimeric species linked through three intermolecular Ti-O-Ti bonds of the two tri-titanium(IV)-substituted α-Keggin polyoxometalate (POM) subunits are described. Two novel titanium(IV)-containing α-Keggin POMs were obtained under different conditions. One product was a dimeric species through two intermolecular Ti-O-Ti bonds of the two tetra-titanium(IV)-substituted α-Keggin POM subunits, i.e., [[{Ti(H₂O)₃}₂(μ-O)](α-PW₉Ti₂O₃₈)]₂^6- (1). The other product was a monomeric α-Keggin species containing the tetra-titanium(IV) oxide cluster and two coordinated sulfate ions, i.e., [{Ti₄(μ-O)₃(SO₄)₂(H₂O)₈}(α-PW₉O₃₄)]^3- (2). Molecular structures of 1 and 2 were also discussed based on host (lacunary site)-guest (titanium atom) chemistry. Full article