Evaluation of physicochemical properties of citric acid crosslinked starch elastomers reinforced with silicon dioxide.

Thermoplastic starch (TPS), derived from renewable resources, offers advantages such as biodegradability and lower production costs compared to petroleum-based plastics. However, its limited mechanical properties pose a challenge for broader applications. This research aims to explore the potential of enhancing the mechanical and barrier properties of TPS films through the incorporation of silicon dioxide as a reinforcement filler and citric acid as a crosslinking agent. By introducing silicon dioxide as a reinforcement filler, the mechanical strength of the TPS films is expected to be improved. Additionally, the incorporation of citric acid as a crosslinking agent is anticipated to enhance the barrier properties of the films. The combination of these additives holds promise for creating TPS films with improved performance, contributing to the development of sustainable and environmentally friendly materials in various industries. The results reveal that SiO2 improves the stiffness of the films at lower concentrations but causes brittleness at higher concentrations. In contrast, citric acid crosslinked films exhibit improved flexibility and density. Scanning electron microscopy demonstrates the morphological changes in the films, with SiO2 affecting surface roughness and aggregate formation. SiO2 reduces film thickness and transparency, while citric acid enhances water resistance and barrier properties. X-ray diffraction analysis shows a reduction in crystallinity due to the plasticization process. Fourier-transform infrared spectroscopy highlights chemical changes and antimicrobial activity is observed with citric acid against specific bacteria. The soil burial test reveals that citric acid crosslinked films exhibit slower degradation due to antimicrobial properties. The combination of SiO2 reinforcement and citric acid crosslinking enhances the overall performance of the films, promising sustainable and environmentally friendly materials for various applications.

High-performance hybrid supercapacitor-immobilized Wells-Dawson polyoxometalates on activated carbon electrodes.

The nanofabrication of electroactive hybrid materials for next-generation energy storage devices is becoming increasingly significant as supercapacitor (SC) technology develops rapidly. The present study utilizes activated carbon (AC) templates reinforced with Wells-Dawson polyoxotungstates (POMs) to produce nanohybrid electrodes for high-performance supercapacitors. This study analyzes Wells-Dawson polyoxotungstates (P2W18) for the first time integrated with AC, and its structural and electrochemical performances are discussed. First, the electrochemical performances of symmetric supercapacitors were characterized in an acidic aqueous electrolyte (0.5 M H2SO4). It was observed that a supercapacitor cell containing the 5 wt% AC-P2W18 hybrid symmetric displayed a noteworthy specific capacitance of 289 F g-1 and a remarkable energy density of 40 W h kg-1. Moreover, 5% AC-P2W18 symmetric supercapacitor cells showed 89% cyclic stability over 4000 cycles. Three LED lights were charged onto the electrode. The LEDs continued to illuminate continuously for red until 160 seconds, yellow until 20 seconds, and blue until 10 seconds after removing the electrode from the electrochemical workstation, demonstrating the device's power and energy density.

Waste dry cell derived photo-reduced graphene oxide and polyoxometalate composite for solid-state supercapacitor applications.

In the modern era, realizing highly efficient supercapacitors (SCs) derived through green routes is paramount to reducing environmental impact. This study demonstrates ways to recycle and reuse used waste dry cell anodes to synthesize nanohybrid electrodes for SCs. Instead of contributing to landfill and the emission of toxic gas to the environment, dry cells are collected and converted into a resource for improved SC cells. The high performance of the electrode was achieved by exploiting battery-type polyoxometalate (POM) clusters infused on a reduced graphene oxide (rGO) surface. Polyoxometalate (K5[α-SiMo2VW9O40]) assisted in the precise bottom-up reduction of graphene oxide (GO) under UV irradiation at room temperature to produce vanadosilicate embedded photo-reduced graphene oxide (prGO-Mo2VW9O40). Additionally, a chemical reduction route for GO (crGO) was trialed to relate to the prGO, followed by the integration of a faradaic monolayer (crGO-Mo2VW9O40). Both composite frameworks exhibit unique hierarchical heterostructures that offer synergic effects between the dual components. As a result, the hybrid material's ion transport kinetics and electrical conductivity enhance the critical electrochemical process at the electrode's interface. The simple co-participation method delivers a remarkable specific capacity (capacitance) of 405 mA h g-1 (1622 F g-1) and 117 mA h g-1 (470 F g-1) for prGO-Mo2VW9O40 and crGO-Mo2VW9O40 nanocomposites alongside high capacitance retentions of 94.5% and 82%, respectively, at a current density of 0.3 A g-1. Furthermore, the asymmetric electrochromic supercapacitor crGO//crGO-Mo2VW9O40 was designed, manifesting a broad operating potential (1.2 V). Finally, the asymmetric electrode material resulted in an enhanced specific capacity, energy, and power of 276.8 C g-1, 46.16 W h kg-1, and 1195 W kg-1, respectively, at a current density of 0.5 A g-1. The electrode materials were tested in the operating of a DC motor.

Revealing the Structural Organization of Gamma-irradiated Starch Granules Using Polarization-resolved Second Harmonic Generation Microscopy.

Starch is a semi-crystalline macromolecule with the presence of amorphous and crystalline components. The amorphous amylose and crystalline amylopectin regions in starch granules are susceptible to certain physical modifications, such as gamma irradiation. Polarization-resolved second harmonic generation (P-SHG) microscopy in conjunction with SHG-circular dichroism (CD) was used to assess the three-dimensional molecular order and inherent chirality of starch granules and their reaction to different dosages of gamma irradiation. For the first time, the relationship between starch achirality (χ21/χ16 and χ22/χ16) and chirality (χ14/χ16) determining susceptibility tensor ratios has been elucidated. The results showed that changes in the structure and orientation of long-chain amylopectin were supported by the decrease in the SHG anisotropy factor and the χ22/χ16 ratio. Furthermore, SHG-CD illustrated the molecular tilt angle by revealing the arrangement of amylopectin molecules pointing either upward or downward owing to molecular polarity.

Preparation of 5-(Acyloxymethyl)furfurals from Carbohydrates Using Zinc Chloride/Acetic Acid Catalyst System and Their Synthetic Value Addition.

5-(Acyloxymethyl)furfurals (AMFs) have received considerable attention as hydrophobic, stable, and halogen-free congeners of 5-(hydroxymethyl)furfural (HMF) for synthesizing biofuels and biochemicals. In this work, AMFs have been prepared directly from carbohydrates in satisfactory yields using the combination of ZnCl2 as the Lewis acid catalyst and carboxylic acid as the Brønsted acid catalyst. The process was initially optimized for 5-(acetoxymethyl)furfural (AcMF) and then extended to producing other AMFs. The effects of reaction temperature, duration, loading of the substrate, and dosage of ZnCl2 on AcMF yield were explored. Fructose and glucose provided AcMF in 80% and 60% isolated yield, respectively, under optimized parameters (5 wt % substrate, AcOH, 4 equiv ZnCl2, 100 °C, 6 h). Finally, AcMF was converted into high-value chemicals, such as 5-(hydroxymethyl)furfural, 2,5-bis(hydroxymethyl)furan, 2,5-diformylfuran, levulinic acid, and 2,5-furandicarboxylic acid in satisfactory yields to demonstrate the synthetic versatility of AMFs as carbohydrate-derived renewable chemical platforms.

Spectroscopic methods for assessment of hand sanitizers.

Sanitization of inanimate objects or body surfaces using disinfectant is essential for eliminating disease-causing pathogens and maintaining personal hygiene. With the advent of health emergencies, the importance and high demand for hand sanitizers (HS) are observed in everyday life. It is also important to know the constituent added to formulate HS, as the presence of harsh chemicals can cause skin irritation. In this study, different spectroscopic techniques were used to assess several commercially available HS along with the in-house prepared HS as per the WHO protocol. Fourier transform infrared spectroscopy and Raman spectroscopy identified the different HS chemical bonds and quantified the amount of alcohol and water in the HS. Varying amount of alcohols in HS, calibration profile was generated to identify its amount in commercial samples. Further, the commercial samples were also checked for contaminants whose presence in the HS might bring down its sanitization efficacy. Supplementary Information: The online version contains supplementary material available at 10.1007/s11696-022-02208-x.

An insight into microscopy and analytical techniques for morphological, structural, chemical, and thermal characterization of cellulose.

Cellulose obtained from plants is a bio-polysaccharide and the most abundant organic polymer on earth that has immense household and industrial applications. Hence, the characterization of cellulose is important for determining its appropriate applications. In this article, we review the characterization of cellulose morphology, surface topography using microscopic techniques including optical microscopy, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Other physicochemical characteristics like crystallinity, chemical composition, and thermal properties are studied using techniques including X-ray diffraction, Fourier transform infrared, Raman spectroscopy, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. This review may contribute to the development of using cellulose as a low-cost raw material with anticipated physicochemical properties. HIGHLIGHTS: Morphology and surface topography of cellulose structure is characterized using microscopy techniques including optical microscopy, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Analytical techniques used for physicochemical characterization of cellulose include X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and thermogravimetric analysis.

One-Pot Synthesis of Polyoxometalate Decorated Polyindole for Energy Storage Supercapacitors.

The demand for energy storage supercapacitor devices has increased interest in completing all innovative technologies and renewable energy requirements. Here, we report a simple method of two polyoxomolybdate (H4[PVMo11O40] and H5[PV2Mo10O40]) doped polyindole (PIn) composites for electrochemical supercapacitors. The interactions between polyoxomolybdates and PIn were measured by Fourier transform infrared spectroscopy (FTIR), and powder XRD, and stability was measured by thermogravimetry. The field emission scanning microscopy (FESEM) was employed to investigate the morphology of the materials. The electrochemical measurements show that the PIn/PV2Mo10 electrode exhibits a higher capacitance of 198.09 F/g with an energy density of 10.19 Wh/kg and a power density of 198.54 W/kg at 0.2 A/g current density than the PIn/PVMo11 electrode. Both electrodes show a pseudocapacitance behavior due to the doping of redox-active polyoxomolybdates on the PIn surface and enhance the electrochemical properties. The electrodes' capacitive nature was measured by electrochemical impedance spectroscopy (EIS), which shows that the PIn/PVMo11 electrode has a resistive nature within the electrode-electrode interface. Moreover, the PIn/PV2Mo10 electrode offers remarkable cycle stability, retaining ∼84% of its capacitance after 10,000 cycles (∼83% for the PIn/PVMo11 electrode). The higher specific capacitance, faster charge/discharge rates, and higher cycle stability make them promising electrodes in supercapacitors.

Microscopic and spectroscopic characterization of rice and corn starch.

Starch granules from rice and corn were isolated, and their molecular mechanism on interaction with α-amylase was characterized through biochemical test, microscopic imaging, and spectroscopic measurements. The micro-scale structure of starch granules were observed under an optical microscope and their average size was in the range 1-100 µm. The surface topological structures of starch with micro-holes due to the effect of α- amylase were also visualized under scanning electron microscope. The crystallinity was confirmed by X-ray diffraction patterns as well as second-harmonic generation microscopy. The change in chemical bonds before and after hydrolysis of the starch granules by α- amylase was determined by Fourier transform infrared spectroscopy. Combination of microscopy and spectroscopy techniques relates structural and chemical features that explain starch enzymatic hydrolysis which will provide a valid basis for future studies in food science and insights into the energy transformation dynamics.

Width dependence of the 0.5 × (2e2/h) conductance plateau in InAs quantum point contacts in presence of lateral spin-orbit coupling.

The evolution of the 0.5Go (Go = 2e2/h) conductance plateau and the accompanying hysteresis loop in a series of asymmetrically biased InAs based quantum point contacts (QPCs) in the presence of lateral spin-orbit coupling (LSOC) is studied using a number of QPCs with varying lithographic channel width but fixed channel length. It is found that the size of the hysteresis loops is larger for QPCs of smaller aspect ratio (QPC channel width/length) and gradually disappears as their aspect ratio increases. The physical mechanisms responsible for a decrease in size of the hysteresis loops for QPCs with increasing aspect ratio are: (1) multimode transport in QPCs with larger channel width leading to spin-flip scattering events due to both remote impurities in the doping layer of the heterostructure and surface roughness and impurity (dangling bond) scattering on the sidewalls of the narrow portion of the QPC, and (2) an increase in carrier density resulting in a screening of the electron-electron interactions in the QPC channel. Both effects lead to a progressive disappearance of the net spin polarization in the QPC channel and an accompanying reduction in the size of the hysteresis loops as the lithographic width of the QPC channel increases.

Inhibition of Na+/K+- and Ca2+-ATPase activities by phosphotetradecavanadate.

Polyoxometalates (POMs) are promising inorganic inhibitors for P-type ATPases. The experimental models used to study the effects of POMs on these ATPases are usually in vitro models using vesicles from several membrane sources. Very recently, some polyoxotungstates, such as the Dawson anion [P2W18O62]6-, were shown to be potent P-type ATPase inhibitors; being active in vitro as well as in ex-vivo. In the present study we broaden the spectrum of highly active inhibitors of Na+/K+-ATPase from basal membrane of epithelial skin to the bi-capped Keggin-type anion phosphotetradecavanadate Cs5.6H3.4PV14O42 (PV14) and we confront the data with activity of other commonly encountered polyoxovanadates, decavanadate (V10) and monovanadate (V1). The X-ray crystal structure of PV14 was solved and contains two trans-bicapped α-Keggin anions HxPV14O42(9-x)-. The anion is built up from the classical Keggin structure [(PO4)@(V12O36)] capped by two [VO] units. PV14 (10 µM) exhibited higher ex-vivo inhibitory effect on Na+/K+-ATPase (78%) than was observed at the same concentrations of V10 (66%) or V1 (33%). Moreover, PV14 is also a potent in vitro inhibitor of the Ca2+-ATPase activity (IC50 5 µM) exhibiting stronger inhibition than the previously reported activities for V10 (15 µM) and V1 (80 µM). Putting it all together, when compared both P-typye ATPases it is suggested that PV14 exibited a high potential to act as an in vivo inhibitor of the Na+/K+-ATPase associated with chloride secretion.

Redox switching of polyoxometalate-methylene blue-based layer-by-layer films.

Iron-substituted crown-type polyoxometalate (POM) [P(8)W(48)O(184)Fe(16)(OH)(28)(H(2)O)(4)](20-) has been successfully immobilized onto glassy carbon electrode surfaces by means of the layer-by-layer (LBL) technique employing the cationic redox active dye, methylene blue (MB). The constructed multilayers exhibit pH-dependent redox activity for both the anionic POM and the cationic dye moieties, which is in good agreement with their solution behavior. The films have been characterized by alternating current impedance, atomic force microscopy, and X-ray photoelectron spectroscopy, whereby the nature of the outer layer within the assemblies was found to have an effect upon the film's behavior. Preliminary investigations show that the POM dye-based films show electrocatalytic ability toward the reduction of hydrogen peroxide, however, only when there is an outer anionic POM layer.

Reactive Zr(IV) and Hf(IV) butterfly peroxides on polyoxometalate surfaces: bridging the gap between homogeneous and heterogeneous catalysis.

At variance with previously known coordination compounds, the polyoxometalate (POM)-embedded Zr(IV) and Hf(IV) peroxides with formula: [M(2)(O(2))(2)(α-XW(11)O(39))(2)](12-) (M=Zr(IV), X=Si (1), Ge (2); M=Hf(IV), X=Si (3)) and [M(6)(O(2))(6)(OH)(6)(γ-SiW(10)O(36))(3)](18-) (M=Zr(IV) (4) or Hf(IV) (5)) are capable of oxygen transfer to suitable acceptors including sulfides and sulfoxides in water. Combined (1)H NMR and electrochemical studies allow monitoring of the reaction under both stoichiometric and catalytic conditions. The reactivity of peroxo-POMs 1-5 is compared on the basis of substrate conversion and kinetic. The results show that the reactivity of POMs 1-3 outperforms that of the trimeric derivatives 4 and 5 by two orders of magnitude. Reversible peroxidation of 1-3 occurs by H(2)O(2) addition to the spent catalysts, restoring oxidation rates and performance of the pristine system. The stability of 1-3 under catalytic regime has been confirmed by FT-IR, UV/Vis, and resonance Raman spectroscopy. The reaction scope has been extended to alcohols, leading to the corresponding carbonyl compounds with yields up to 99% under microwave (MW) irradiation. DFT calculations revealed that polyanions 1-3 have high-energy peroxo HOMOs, and a remarkable electron density localized on the peroxo sites as indicated by the calculated map of the electrostatic potential (MEP). This evidence suggests that the overall description of the oxygen-transfer mechanism should include possible protonation equilibria in water, favored for peroxo-POMs 1-3.

Alpha and beta isomers of tetrahafnium(IV) containing decatungstosilicates, [Hf4(OH)6(CH3COO)2(x-SiW10O37)2]12- (x = α, ß).

The two dimeric, Hf-containing tungstosilicates [Hf(4)(OH)(6)(CH(3)COO)(2)(α-SiW(10)O(37))(2)](12-) (1) and [Hf(4)(OH)(6)(CH(3)COO)(2)(ß-SiW(10)O(37))(2)](12-) (2) have been synthesized by reacting HfCl(4) with [γ-SiW(10)O(36)](8-) in potassium acetate solutions at pH = 3.6 and 4.8, respectively. Polyanions 1 and 2 comprise a tetrahafnium(iv) assembly {Hf(4)(OH)(6)(CH(3)COO)(2)} sandwiched between two dilacunary [α-SiW(10)O(36)](8-) (in 1) or {ß-SiW(10)} (in 2) Keggin type decatungstosilicates. This implies that the starting precursor {γ-SiW(10)} isomerizes in situ to [ß-SiW(10)O(37)](10-) and then to [α-SiW(10)O(37)](10-) by controlled variation of pH and temperature. The hydrated potassium salts of 1 and 2 were investigated in the solid state by single-crystal XRD, FT-IR, thermogravimetric and elemental analyses, and in solution by UV-Vis and (183)W NMR spectroscopy, and electrochemistry.

Transition metal catalysed dehydrogenation of amine-borane fuel blends.

Mixtures containing ammonia-borane and sec-butylamine-borane remain liquid throughout the hydrogen release process that affords tri(N-sec-butyl)borazine and polyborazylene. Concentrated solutions with metal catalysts afford >5 wt% H(2) in 1 h at 80 °C and addition of (EMIM)EtSO(4) ionic liquid co-solvent eliminates competing formation of insoluble linear poly(aminoborane) (EMIM = 1-ethyl-3-methyl-imidazolium).

Yttrium(III)-containing tungstoantimonate(III) stabilized by tetrahedral WO4(2-) capping unit, [{Y(α-SbW9O31(OH)2)(CH3COO)(H2O)}3(WO4)]17-.

The yttrium(III)-containing tungstoantimonate(III) [{Y(α-SbW(9)O(31)(OH)(2))(CH(3)COO)(H(2)O)}(3)(WO(4))](17-) (1) has been synthesized in a simple one-pot reaction of Y(3+) ions with [α-SbW(9)O(33)](9-) and WO(4)(2-) in a 3:3:1 molar ratio in 1 M LiOAc/AcOH buffer at pH 5.3. Polyanion 1 is composed of three (α-SbW(9)O(33)) units linked by three Y(3+) ions and a capping, tetrahedral WO(4)(2-) capping unit, resulting in an assembly with C(3v) symmetry. The hydrated ammonium-sodium salt of 1 was investigated in the solid state by single-crystal XRD, FT-IR spectroscopy, thermogravimetric and elemental analyses, and in solution by multinuclear NMR spectroscopy.

Cobalt, manganese, nickel, and vanadium derivatives of the cyclic 48-tungsto-8-phosphate [H(7)P(8)W(48)O(184)](33-).

The cobalt(II) containing tungstophosphate [Co(4)(H(2)O)(16)P(8)W(48)O(184)](32-) (1) has been synthesized by addition of Co(2+) ions to an aqueous solution of [H(7)P(8)W(48)O(184)](33-) (P(8)W(48)) and characterized by single-crystal XRD, IR, and UV-vis spectroscopy, elemental analysis, electrochemistry, and magnetochemistry. The novel polyanion 1 is a derivative of the superlacunary P(8)W(48) with four cobalt(II) ions coordinated to the rim of the central cavity and two additional cobalt(II) ions linked on the outside bridging neighboring polyanions. Using similar synthetic procedures, but adding a few drops of H(2)O(2), we isolated the manganese(II) derivative [Mn(4)(H(2)O)(16)(P(8)W(48)O(184))(WO(2)(H(2)O)(2))(2)](28-) (2) and its nickel(II) analogue [Ni(4)(H(2)O)(16)(P(8)W(48)O(184))(WO(2)(H(2)O)(2))(2)](28-) (3). Both polyanions have picked up two equivalents of tungsten resulting in the unprecedented {P(8)W(50)} host framework. We also made the vanadium(V) derivative [(VO(2))(4)(P(8)W(48)O(184))](36-) (4), with four tetrahedral vanadate groups grafted to the P(8)W(48) host. The voltammetric patterns associated with the W-centers in polyanions 1, 2, and 4 display enough distinct features allowing for a qualitative classification according to relative basicity of the reduced polyanions: 2 > P(8)W(48) > 1 > 4. The electrochemistry of 1 offers a new example for detection of the Co(2+) centers in a multicobalt containing polyanion. During a study of the Mn(2+) centers of 2 at pH 5, a film deposition is observed. The vanadium(V) centers of 4 are well-behaved in a pH 0.33 medium. Temperature and magnetic field dependence of the magnetic moment of 1-3 were performed on a SQUID magnetometer over the temperature range 1.8-250 K and field range 0-7 T. The results are consistent with the model of noninteracting 3d metal ions. Variable temperature (4-295 K) and variable frequency (34-413 GHz) EPR measurements support the magnetic susceptibility results. The zero-field splitting D and g values obtained for 1-3 are in agreement with those reported for high-spin Co(2+), Mn(2+), and Ni(2+) ions in axially distorted octahedral environments.

Peroxo-Zr/Hf-containing undecatungstosilicates and -germanates.

A family of dimeric, peroxo-containing heteropolytungstates, [M(2)(O(2))(2)(XW(11)O(39))(2)](12-) [M = Zr(4+), X = Si (1), Ge (2); M = Hf(4+), X = Si (3)], have been synthesized by reacting ZrCl(4)/HfCl(4) with the respective monolacunary Keggin precursor [XW(11)O(39)](8-) (X = Si, Ge) in an aqueous acidic medium (pH 4.8). The isostructural polyanions 1-3 are composed of two (XW(11)O(39)) Keggin units encapsulating a central diperoxo-dimetal fragment {M(2)(O(2))(2)}(4+) (M = Zr(4+), Hf(4+)). Cyclic voltammetry and exhaustive electrolysis studies indicate fast reductive release of the peroxo ligands upon reduction of 1-3. Stoichiometric oxo-transfer studies from 1-3 to the substrate l-methionine were performed, and the reactions were monitored by (1)H NMR.

Wheel-shaped Cu(20)-tungstophosphate [Cu(20)X(OH)(24)(H(2)O)(12)(P(8)W(48)O(184))](25-) ion (X = Cl, Br, I) and the role of the halide guest.

We have synthesized the known [Cu(20)Cl(OH)(24)(H(2)O)(12)(P(8)W(48)O(184))](25-) (1) and report here its bromide and iodide analogues, [Cu(20)Br(OH)(24)(H(2)O)(12)(P(8)W(48)O(184))](25-) (2) and [Cu(20)I(OH)(24)(H(2)O)(12)(P(8)W(48)O(184))](25-) (3). These polyanions were characterized in the solid state by IR spectroscopy and single-crystal X-ray diffraction. Magnetic susceptibility and magnetization data over 1.8-300 K show that the Cu(2+) ions in 1-2 are antiferromagnetically coupled, leading to a diamagnetic ground state. The effective exchange coupling constant J(eff) was estimated as approximately -3 K for both 1 and 2. Electron paramagnetic resonance measurements were made on 1 and 2 over 5-295 K at microwave frequencies of 9.5, 34, and 220 GHz. The observed (weak) signals were characteristic of randomly distributed Cu(2+) ions only, with g values and hyperfine constants typical of the unpaired electron in a 3d(x(2)-y(2)) orbital of Cu(2+). No signals attributable to the copper-hydroxo cluster were detected, supporting the conclusions from the magnetization measurements. DFT calculations were performed as well to obtain additional information on the anionic guest inside the cavity created by the copper-hydroxo cage related to electronic structure and energies of encapsulation. The polyanions 2 and 3 were also characterized by cyclic voltammetry (CV) in a pH 5 medium. Their CVs are composed by an initial two-step reduction of the Cu(2+) centers to Cu(0) through Cu(+), followed at more negative potential by the redox processes of the W centers. A comparison with the CV characteristics of the previously studied compound 1 indicates that the potential locations of the Cu or W waves of the three analogues do not depend significantly upon the identity of the central halide X. This observation is in accordance with conclusions of DFT calculations. The modified electrodes based on 2 and the room-temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate triggers an efficient reduction of nitrate. To our knowledge, this is the first example of electrocatalytic nitrate reduction by a polyanion entrapped in room-temperature ionic liquid films.