Polyoxovanadates Research Articles

Rational fabrication of two polyoxovanadate-based frameworks for efficient detoxifying mustard gas simulant

Two polyoxovanadates (POVs)-based cobalt–organic frameworks, namely [H2Co2(p-bix)4][V8O23] (1) and [Co(o-bix)][V2O6] (2) (where p-bix = 1,4-bis(imidazol-1-ylmethyl)benzene and o-bix = 1,2-bis(imidazol-1-ylmethyl)benzene), were synthesized via a hydrothermal process and thoroughly characterized structurally. Compound 1 features a three-dimensional framework where the inorganic layers {V8Co2}, containing circular [V4O12]4− ({V4}) dimers, are interconnected by p-bix ligands. While compound 2 forms a two-dimensional layer structure where the inorganic {V4} clusters are linked by four binuclear [Co2O3(o-bix)2]2− units through the sharing of O atoms from {V4} clusters. Given the catalytic prowess of POVs in oxidizing various organic substrates, we evaluated the catalytic performance of these two compounds as heterogeneous catalysts for detoxifying mustard gas simulant CEES (2-chloroethyl ethyl sulfide) into the non-toxic CEESO (2-chloroethyl ethyl sulfoxide). The catalytic tests revealed that both compounds effectively catalyze the oxidation of CEES, yielding solely CEESO. Particularly, catalyst 2 exhibited excellent catalytic properties, achieving nearly 100 % conversion and selectivity within just 40 min at room temperature. The prominent performance of 2 remains consistent through at least five recycling cycles, showcasing its durability and effectiveness. This exceptional performance of 2 was achieved due to the synergistic interaction between V and coordinatively unsaturated Co sites within the structure, as confirmed by detailed comparative studies of structure and catalytic activity as well as density functional theory (DFT) calculations.

Redox-active polyoxovanadates as cofactors in the development of functional protein assemblies

The interactions of polyoxovanadates (POVs) with proteins have increasingly attracted interest in recent years due to their potential biomedical applications. This is especially the case because of their redox and catalytic properties, which make them interesting for developing artificial metalloenzymes. Organic-inorganic hybrid hexavanadates in particular offer several advantages over all-inorganic POVs. However, they have been scarcely investigated in biological systems even though, as shown in this work, hybrid hexavanadates are highly stable in aqueous solutions up to relatively high pH. Therefore, a novel bis-biotinylated hexavanadate was synthesized and shown to selectively interact with two biotin-binding proteins, avidin and streptavidin. Bridging interactions between multiple proteins led to their self-assembly into supramolecular bio-inorganic hybrid systems that have potential as artificial enzymes with the hexavanadate core as a redox-active cofactor. Moreover, the structure and charge of the hexavanadate core were determined to enhance the binding affinity and slightly alter the secondary structure of the proteins, which affected the size and speed of formation of the assemblies. Hence, tuning the polyoxometalate (POM) core of hybrid POMs (HPOMs) with protein-binding ligands has been demonstrated to be a potential strategy for controlling the self-assembly process while also enabling the formation of novel POM-based biomaterials that could be of interest in biomedicine.

Hydrophobic Two-Dimensional Layered Superstructure of a Polyoxometalate Cluster as the Cathode Material for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries hold promise for sustainable energy storage, yet challenges in finding high-performance cathode materials persist. Polyoxovanadates (POVs) are emerging as potential candidates due to their structural diversity and robust redox activity. Despite their potential, issues like dissolution in electrolytes, structural degradation, and byproduct accumulation persist. This work introduces a POV-based hydrophobic two-dimensional (2D) layered superstructure that addresses these challenges. The hydrophobic nature minimizes POV dissolution, enhancing structural stability and inhibiting phase transitions during cycling. The 2D arrangement ensures a larger surface area and improved electronic conductivity, resulting in faster kinetics and higher specific capacity. The superstructure demonstrates improved cycle life and an increased operating voltage, marking a significant advancement in POV-based cathode materials for aqueous zinc-ion batteries.

Polyoxovanadate Li7[V15O36(CO3)] and its derivative γ-LiV2O5 as superior performance cathode materials for aqueous zinc-ion batteries

Recently, many reports have been published about polyoxovanadates (POVs) with multiple electrons redox activity for energy storage. However, they are easily transformed into solid-state oxides after calcination. We noted that although dehydrated Li7[V15O36(CO3)] (Li7V15) exhibited a high capacity for lithium-ion batteries (LIBs), it was reported that the electrochemical behavior of the dehydrated sample same as γ-LiV2O5 (γ-LVO) which prepared by annealing the cluster and undehydrated Li7V15 was not redox-active. Interestingly, we were surprised to find that undehydrated Li7V15 and its derivative γ-LVO showed better electrochemical performance than LIBs when first proposed as the cathode to store Zn2+. Both Li7V15 and γ-LVO electrodes provided excellent rate performance and satisfied cyclability (135.0 and 214.1 mAh g−1 at 3 A g−1 after 1000 cycles, respectively). The fast kinetics of Li7V15 and γ-LVO were verified by pseudocapacitive analysis, GITT and EIS tests. Moreover, the Zn2+ storage mechanism and redox behavior of Li7V15 and γ-LVO were examined by ex-situ measurements. First-principles calculations revealed that the Zn2+ was chemisorbed on the clusters and physisorbed between the clusters. This work enriches the POVs cathode chemistry in aqueous energy storage.

Two polyoxovanadates for visible light driven photocatalytic performance

The synthesis of the highest-nuclearity IPOV using PhPO3 as the only organic ligand.

Ni/Mn-Complex-Tethered Tetranuclear Polyoxovanadates: Crystal Structure and Inhibitory Activity on Human Hepatocellular Carcinoma (HepG-2).

Polyoxometalates (POMs) exhibit unique structural characteristics and excellent physical and chemical properties, which have attracted significant attention from scholars in the fields of anticancer research and chemotherapy. Herein, we successfully synthesized and structurally characterized two novel polyoxovanadates (POVs), denoted as POVs-1 and POVs-2, where [M(1-vIM)4]2[VV4O12]·H2O (M: NiII and MnII, 1-vinylimidazole abbreviated as 1-vIM) serve as ligands. The two POVs are isomeric and consist of fundamental structural units, each comprising one [V4O12]4- cluster, two [M(1-vIM)4]2+ cations, and one water molecule. Subsequently, we evaluated the cell viability of human hepatocellular carcinoma (HepG-2) cells treated with the synthesized POVs using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazoliumbromide) assay. And the changes in cell nucleus morphology, mitochondrial membrane potential (Δψm), and reactive oxygen species levels in HepG-2 exposed to POVs were monitored using specific fluorescent staining techniques. Both hybrid POVs showed potent inhibitory activities, induing apoptosis in HepG-2 cells along with significant mitochondria dysfunction and a burst of reactive oxygen species. Notably, the inhibitory effects of POVs-2 were more pronounced than those of POVs-1, which is primarily attributed to the different transition metal ions present. These findings underscore the intricate relationship between the metal components, structural characteristics, and the observed antitumor activities in HepG-2 cells.

In Vitro, Oral Acute, and Repeated 28-Day Oral Dose Toxicity of a Mixed-Valence Polyoxovanadate Cluster.

Polyoxovanadates (POV) are a subgroup of polyoxometalates (POM), which are nanosized clusters with reported biological activities. This manuscript describes the first toxicity evaluation of a mixed-valence polyoxovanadate, pentadecavanadate, (Me4N)6[V15O36Cl], abbreviated as V15. Cytotoxicity experiments using peripheral blood mononuclear cells (PBMC), larvae of Artemia salina Leach, and in vivo oral acute and repeated 28-day doses in mice was carried out. The LC50 values in PBMC cells and A. salina were 17.5 ± 5.8 μmol L-1, and 17.9 µg L-1, respectively, which indicates high cytotoxic activity. The toxicity in mice was not observed upon acute exposure in a single dose, however, the V15 repeated 28-day oral administration demonstrated high toxicity using 25 mg/kg, 50 mg/kg and, 300 mg/kg doses. The biochemical and hematological analyses during the 28-day administration of V15 showed significant alteration of the metabolic parameters related to the kidney and liver, suggesting moderate toxicity. The V15 toxicity was attributed to the oxidative stress and lipid peroxidation, once thiobarbituric acid (TBAR) levels significantly increased in both males and females treated with high doses of the POV and also in males treated with a lower dose of the POV. This is the first study reporting a treatment-related mortality in animals acutely administrated with a mixed-valence POV, contrasting with the well-known, less toxic decavanadate. These results document the toxicity of this mixed-valence POV, which may not be suitable for biomedical applications.

Multifunctional Aryl Sulfonium Decavanadates: Tuning the Photochromic and Heterogeneous Oxidative Desulfurization Catalytic Properties Using Salicylaldehyde-type Functional Moieties on Counterions.

Multifunctional materials based on polyoxovanadates (POVs) have rarely been reported. Herein, we used aryl sulfonium counterions (ASCIs) bearing a salicylaldehyde-type functionality to tune the properties of decavanadate ([V10O28]6-)-based hybrids for their application in photochromism and heterogeneous oxidative desulfurization (ODS) catalysis. The counterions FHPDS ((3-formyl-4-hydroxyphenyl)dimethylsulfonium), DFHPDS ((3,5-diformyl-4-hydroxyphenyl)dimethylsulfonium), and EFPDS ((4-ethoxy-3-formylphenyl)dimethylsulfonium) were clubbed with the decavanadate cluster to generate the hybrids (FHPDS)4[H2V10O28](H2O)4 (HY1), (DFHPDS)4[H2V10O28](H2O)3 (HY2), and (EFPDS)4[H2V10O28](H2O)6 (HY3). The photochromic properties of these hybrids were tested under 365 nm irradiation, which showed a color change from yellow to green. Different hybrids exhibited different photocoloration half-life (t1/2) values in the range of 0.77-28.38 min, suggesting the dependence of the photocoloration properties upon functional groups on the counterions. The hybrid HY2, having a 2,6-diformyl phenol moiety on the ASCI, exhibited an impressive t1/2 of 0.77 min. UP to 70% reversibility of photocoloration was achieved for the best photochromic hybrid HY2 in 48 h at 70 °C under an oxygen atmosphere. Theoretical and experimental data suggested that some of these aryl sulfonium POVs follow a different e--h+ stabilization mechanism than traditional sulfonium POM hybrids. Further, the salicylaldehyde-type ASCIs control the solubility of the decavanadate hybrids, which enables their application as heterogeneous catalysts for the selective oxidation of various sulfides. The nature of the substituents on the ASCIs also affected their catalytic activities; the counterion that facilitates the reversible V4+/V5+ switching enhances the catalytic ODS efficiency of the hybrids. Using HY2 as the catalyst, up to 99% conversion and 96% selectivity toward sulfones were achieved in dibenzothiophene (DBT) oxidation. The present study suggests a new promising approach for controlling POVs' photoresponsive and catalytic properties by using ASCIs bearing salicylaldehyde-type functional moieties.

Photochemical Ammonia Synthesis over Reduced Polyoxovanadate-Intercalated Defective ZnAl Layered Double Hydroxide Nanosheets.

The exploration of efficient and stable N2 fixation photocatalysts featuring a broad absorption spectrum and N2 fixation active sites has become specifically conspicuous. Herein, a series of reduced polyoxovanadates (POVs) were intercalated into copper-induced ZnAl layered double hydroxide (0.5%-ZnAl LDH) nanosheets with oxygen vacancies via an anion exchange strategy toward green ammonia production. The intervalence charge transfer arising from mixed-valence POV materials is responsible for its light-harvesting behavior, and the LDHs lay the foundation for the chemical adsorption and activation process of nitrogen molecules; both contributions facilitate the nitrogen photofixation performance of such composite materials. As predicted, the catalytic efficiency of V34/0.5%-ZnAl is 7.0 times higher than 0.5%-ZnAl LDH. Therefore, such an all-inorganic system exhibits an apparent quantum efficiency of 0.3137% at 500 nm. The strategy of "working in tandem" established by POV-based light-absorber species and oxygen vacancies as the sites for N2 activation is extremely vital for enhanced ammonia formation. This work opens up a versatile insight for the rational design of an efficient photo-driven nitrogen-reduction composite catalyst toward sustainable ammonia production compared to the industrial Haber-Bosch process.

Polyoxometalates Impact as Anticancer Agents.

Polyoxometalates (POMs) are oxoanions of transition metal ions, such as V, Mo, W, Nb, and Pd, forming a variety of structures with a wide range of applications. Herein, we analyzed recent studies on the effects of polyoxometalates as anticancer agents, particularly their effects on the cell cycle. To this end, a literature search was carried out between March and June 2022, using the keywords "polyoxometalates" and "cell cycle". The effects of POMs on selected cell lines can be diverse, such as their effects in the cell cycle, protein expression, mitochondrial effects, reactive oxygen species (ROS) production, cell death and cell viability. The present study focused on cell viability and cell cycle arrest. Cell viability was analyzed by dividing the POMs into sections according to the constituent compound, namely polyoxovanadates (POVs), polyoxomolybdates (POMos), polyoxopaladates (POPds) and polyoxotungstates (POTs). When comparing and sorting the IC50 values in ascending order, we obtained first POVs, then POTs, POPds and, finally, POMos. When comparing clinically approved drugs and POMs, better results of POMs in relation to drugs were observed in many cases, since the dose required to have an inhibitory concentration of 50% is 2 to 200 times less, depending on the POMs, highlighting that these compounds could become in the future an alternative to existing drugs in cancer therapy.

Recent advances in oxidative catalytic applications of polyoxovanadate-based inorganic-organic hybrids.

Polyoxovanadates (POVs) have received widespread attention in catalytic applications due to their various structures and remarkable redox properties. By introducing a second transition metal, POV-based inorganic-organic hybrid (POVH) catalysts show increasing stability and more catalytic active sites compared with pure POVs. In this perspective article, POVH materials as oxidative catalysts have been classified into two main categories according to the interactions between transition metal-complex units and POV clusters: (i) hybrids with metal-organic units act as isolated cations and (ii) hybrids with an organic ligand coordinate to the second transition metal, which is further linked to a POV cluster via oxygen bridges directly or indirectly to give zero-, one-, two- or three-dimensional supramolecular structures. The oxidative conversion of organic compounds, including thiophene derivatives, thioethers, alkanes, alcohols, and alkenes, and oxidative detoxification of a sulfur mustard simulant or degradation of lignin, along with the oxidative photo/electrocatalytic transformation of organic compounds catalyzed by POVH materials, are discussed in detail. Furthermore, the challenges and prospects toward the development of POVH catalysts are explored briefly from our perspectives.

Catalytic application of polyoxovanadates in the selective oxidation of organic molecules

The structural synthesis and catalytic application of polyoxovanadates (POVs), an important subfamily of polyoxometalates (POMs), have attracted significant attention, owing to their rich coordination chemistry and splendid redox properties. In this review, the advances in the past 10 years in the oxidative transformations catalyzed using all-inorganic POVs, organ functionalized POVs, and POV-based inorganic–organic hybrids have been summarized and are discussed in detail. In particular, we focus on the selective oxidation of organic molecules, including alkanes, alkenes, alcohols, sulfides, sulfur-mustard simulants, and organic dyes. For most oxidative transformations, the active V-peroxo species generated in the presence of hydrogen peroxide or tert-butyl hydroperoxide account for enhanced catalytic activities. In addition, the challenges and prospects in the development of POM-based catalysts are addressed.

Research on the electrochemical performance of polyoxovanadate material K4Na2V10O28 as a novel aqueous zinc-ion batteries cathode

The aqueous zinc-ion batteries (ZIBs) field has witnessed a tremendous advancement in the exploration of materials that can combine high energy density and short charge times. Nevertheless, these materials are primarily focused on manganese-based or vanadium-based oxides, and there are fewer reports on new materials. Herein, we proposed a new ZIBs cathode material based on polyoxovanadates (POVs) type K4Na2V10O28 (KNVO). It demonstrated the advantages of POVs, which could undergo multi-electron redox processes at each V center. The reversible capacity was maintained at 152.3 mAh g−1 after 100 cycles at 0.1 A g−1, and the capacity retention was close to 100% after 1000 cycles at 1 A g−1. Additionally, the kinetic properties of the KNVO/Zn cell were investigated by Trasatti research, pseudocapacitance analysis and GITT test, respectively, manifesting a strong capacitive behavior as well as a high Zn2+ diffusion coefficient (order of 10−10 cm2 s−1). Not only that, but we also analyzed the relevant characteristic parameters of EIS in-depth, aiming to systematically probe the changes in electrochemical behavior before and after cycling. The synthesis and investigation of KNVO cathode materials may provide directions for the development of electrode materials for a rising generation of aqueous ZIBs.

Reducing obesity and inflammation in mice with organically-derivatized polyoxovanadate clusters

Obesity, characterized by the dysregulation of energy balance in adipose tissue and other metabolic organs, is frequently accompanied by chronic low-grade inflammation. As long-acting insulin sensitizers, the organically-derivatized polyoxovanadates (POVs), can extend the dosing interval of antidiabetic drugs from hourly to almost daily. In this work, the protective activity of POVs is investigated by an eight-week in vivo experiment, in which a small amount of POVs was administrated orally to a mouse model of diet-induced obesity every day. The present study shows that administration of POVs significantly decreases the body weight of mice, reduces adipose tissue accumulation, and simultaneously reduces adipose tissue inflammation. In addition, the anti-obesogenic population of iNKT cells is protected potentially by POVs, which subsequently alleviates visceral adipose tissue inflammation in high-fat-diet (HFD)-fed mice against diet-induced obesity. By contrast, the change in body weight after POV treatment is the result of a substantial reduction in fat mass, with no obvious effects on lean body mass. These findings demonstrate that supplementary of POVs would be an effective way to combat obesity and metabolic disorders while lowering metabolic inflammation.

New Insight on K2 Zn2 V10 O28 as an Advanced Cathode for Rechargeable Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) have recently attracted people's extensive attention in their application in energy storage systems resulting from their exclusive characteristics of low cost and environmental compatibility. However, finding suitable cathode materials continues to be the major challenge. Polyoxovanadates (POVs), as an important branch of polyoxometalates (POMs), are considered as a promising electrode material for reversible aqueous ZIBs relying on the flexible valence state of V. Herein, POVs (K2 Zn2 V10 O28 : KZVO) are reported as an advanced cathode for storing Zn2+ , which delivers a high discharge capacity of 223.4mAhg-1 at 0.1Ag-1 , considerable energy density (182.9Whkg-1 ) and power density (40.38Wkg-1 ), and robust cyclic performance. In addition, the dynamic properties of the KZVO/Zn battery are revealed by pseudocapacitance analysis and GITT tests. Meanwhile, the storage mechanism of Zn2+ is further analyzed by ex situ XRD, XPS, TEM, and HRTEM. Overall, this work not only draws up a cathode material for the POMs system in aqueous ZIBs, but also demonstrates that POMs are the rising star in energy storage and electric energy applications.

Three Si-substituted polyoxovanadates as efficient catalysts for Knoevenagel condensation and selective oxidation of styrene to benzaldehyde.

Three new Si-substituted polyoxovanadates (POVs), [Cd2(dien)2][Cd(dien)][Cd(Hdien)2][V15Si6O46(OH)2(H2O)]·7H2O (1), [Co(enMe)2]3[Co2(enMe)2(H2O)2][V16Si4O44(OH)2(H2O)]·6H2O (2), and [Co(teta)]4[V16Si4O42(OH)4(H2O)]·10H2O (3) (dien = diethylenetriamine; enMe = 1,2-diaminopropane; teta = triethylenetetramine) were synthesized by the hydrothermal method and characterized. Structural analysis sheds light on the fact that the {V15Si6O48}/{V16Si4O46} clusters of compounds 1-3 were formed by replacing {VO5} square pyramids in the classical {V18O42} cluster with {Si2O7} units. Compound 1 is a 2D bilayer structure formed by the [V15Si6O46(OH)2(H2O)]10- cluster and two types of bridging Cd complexes containing binuclear groups [Cd2(dien)2]4+. Compound 2 is a 3D framework constructed from the [V16Si4O44(OH)2(H2O)]10- cluster and two types of Co complex fragments including binuclear [Co2(enMe)2(H2O)2]4+. In compound 3, the [V16Si4O42(OH)4(H2O)]8- cluster is connected with bridging [Co(teta)]2+ to expand into a 2D network. Compounds 1 and 3 represent the first 2D assemblies based on a vanadosilicate cluster. 1-3 served as heterogeneous catalysts and exhibited highly efficient catalytic activities for the Knoevenagel condensation under mild ambient conditions with low catalyst loading, featuring the open Lewis base {V15Si6O48}/{V16Si4O46} sites and Lewis acid Cd2+/Co2+ sites. The conversion of benzaldehyde was up to 99.3% in 80 min at room temperature using 1 as a heterogeneous catalyst with only 0.37% catalyst loading. Moreover, compounds 1-3 as catalysts for selective oxidation of styrene to benzaldehyde exhibited excellent catalytic performance, high selectivity and could be readily recycled. Most strikingly, compound 1 showed excellent catalytic performance with 97.6% conversion of styrene and 100% selectivity of benzaldehyde in 15 min. In addition, the catalytic activity of catalyst 1 was well maintained after five cycling reactions.

Polyoxovanadates as new P-glycoprotein inhibitors: insights into the mechanism of inhibition.

A promising strategy to overcome multidrug resistance is the use of inhibitors of ABC drug transporters. For this reason, we evaluated the polyoxovanadates (POVs) [V10 O28 ]6- (V10 ), [H6 V14 O38 (PO4 )]5- (V14 ), [V15 O36 Cl]6- (V15 ) and [V18 O42 I]7- (V18 ) as inhibitors of three major multidrug resistance-linked ABC transporters: P-glycoprotein (P-gp), ABCG2 and MRP1. All of the POVs selectively inhibited P-gp. V10 and V18 were the two most promising compounds, with IC50 values of transport inhibition of 25.4 and 22.7 µm, respectively. Both compounds inhibited P-gp ATPase activity, with the same IC50 value of 1.26 µm. V10 and V18 triggered different conformational changes in the P-gp protein with time-dependent inhibition, which was confirmed using the synthesized salt of V10 with rhodamine B, RhoB-V10 . The hydrophilic nature of POVs supports the hypothesis that these compounds target an unusual ligand-binding site, opening new possibilities in the development of potent modulators of ABC transporters.

Host-Guest Complexation Between Cyclodextrins and Hybrid Hexavanadates: What are the Driving Forces?

Host-guest complexes between native cyclodextrins (α-, β- and γ-CD) and hybrid Lindqvist-type polyoxovanadates (POVs) [V6 O13 ((OCH2 )3 C-R)2 ]2- with R = CH2 CH3 , NO2 , CH2 OH and NH(BOC) (BOC = N-tert-butoxycarbonyl) were studied in aqueous solution. Six crystal structures determined by single-crystal X-ray diffraction analysis revealed the nature of the functional R group strongly influences the host-guest conformation and also the crystal packing. In all systems isolated in the solid-state, the organic groups R are embedded within the cyclodextrin cavities, involving only a few weak supramolecular contacts. The interaction between hybrid POVs and the macrocyclic organic hosts have been deeply studied in solution using ITC, cyclic voltammetry and NMR methods (1D 1 H NMR, and 2D DOSY, and ROESY). This set of complementary techniques provides clear insights about the strength of interactions and the binding host-guest modes occurring in aqueous solution, highlighting a dramatic influence of the functional group R on the supramolecular properties of the hexavanadate polyoxoanions (association constant K1:1 vary from 0 to 2 000 M-1 ) while isolated functional organic groups exhibit only very weak intrinsic affinity with CDs. Electrochemical and calorimetric investigations suggest that the driving force of the host-guest association involving larger CDs (β- and γ-CD) is mainly related to the chaotropic effect. In contrast, the hydrophobic effect supported by weak attractive forces appears as the main contributor for the formation of α-CD-containing host-guest complexes. In any cases, the origin of driving forces is clearly related to the ability of the macrocyclic host to desolvate the exposed moieties of the hybrid POVs.

Self-assembly of three Ag-polyoxovanadates frameworks for their efficient construction of C[sbnd]N bond and detoxification of simulant sulfur mustard

Three imidazole-modified Ag-polyoxovanadates frameworks (APFs) with a controllable molar ratio of Ag+ to polyoxovanadates (POVs) [Ag(IM)2]2V4O12·2Ag(IM)2 (APF-1), [Ag2(1-eIM)4]2[Ag(1-eIM)2]3·2Ag(1-eIM)2·3(1-HeIM)[V10O28]2 (APF-2) and [Ag(1-pIM)2]3[HV10O28]·2Ag(1-pIM)2·2H2O (APF-3) (IM = imidazole; 1-eIM = 1-ethylimidazole and 1-pIM = 1-propylimidazole) have been successfully achieved by self-assembly of POVs, Ag+ cations, and three different imidazole derivatives. Interestingly, the molar ratios of Ag+ to POVs vary from 4:1, 4.5:1 to 5:1 by changing the vanadium resources and imidazole derivatives. Notably, the coordination environment of Ag+ cations and the structure of POVs in the APFs are also different. Specifically, for APF-1, the four Ag atoms adopt three-coordinated and four-coordinated geometries, respectively, and Ag-imidazole complexes and [V4O12]4− cluster form the one-dimensional polymeric chains. While Ag atoms in APF-2 and APF-3 exhibit two-, four- and five-coordinated geometries for APF-2, four-, five- and six-coordinated geometries for APF-3, respectively. These Ag+ cations and decavanadate clusters are assembled into the 2D supramolecular structure through the Ag-O bonds and Ag…Ag argentophilic interaction. Remarkably, thus-obtained APF-2 can serve as powerful efficient heterogeneous catalyst for construction of CN bond and detoxification of simulant sulfur mustard (yields up to 99%), which enable successful recycling for three cycles with remained catalytic activities and structure stability.

Decavanadate-graphene oxide nanocomposite as an electrode material for electrochemical capacitor

ABSTRACT We have synthesized new electrode material for the supercapacitor application. Polyoxovanadates (POVs) have been used for energy storage electrode materials due to their fast multi-electron redox properties. The formation of SDV/GO composites was confirmed using various analytical methods, e.g., Fourier transforms infrared spectroscopy (FTIR) and powder X-ray diffraction (XRD), followed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The composite electrode’s electrochemical behavior was studied using a neutral 1 M sodium sulphate (Na2SO4) solution in three-electrode cyclic voltammetry (CV) system. The SDV/GO composite electrode showed a specific capacitance of 306 F/g for a scan rate of 5 mV/s and a corresponding energy density of 42.4 Wh/Kg. Galvanostatic charge/discharge exhibits a specific capacitance of 310 F/g with energy densities of 43.08 Wh/kg. Electrochemical impedance spectroscopy (EIS), which was used to investigate interface property, yielded a considerably higher power density of 172.41 KW/kg with an equivalent series resistance of 5 Ω.