Design of a new nanocomposite based on Keggin-type [ZnW12O40]6- anionic cluster anchored on NiZn2O4 ceramics as a promising material towards the electrocatalytic hydrogen storage.

Extensive research efforts have been dedicated to developing electrode materials with high capacity to address the increasing complexities arising from the energy crisis. Herein, a new nanocomposite was synthesized via the sol-gel method by immobilizing K6ZnW12O40 within the surface of NiZn2O4. ZnW12O40@NiZn2O4 was characterized by FT-IR, UV-Vis, XRD, SEM, EDX, BET, and TGA-DTG methods. The electrochemical characteristics of the materials were examined using cyclic voltammogram (CV) and charge-discharge chronopotentiometry (CHP) techniques. Multiple factors affecting the hydrogen storage capacity, including current density (j), surface area of the copper foam, and the consequences of repeated cycles of hydrogen adsorption-desorption were evaluated. The initial cycle led to an impressive hydrogen discharge capability of 340 mAh/g, which subsequently increased to 900 mAh/g after 20 cycles with a current density of 2 mA in 6.0 M KOH medium. The surface area and the electrocatalytic characteristics of the nanoparticles contribute to facilitate the formation of electrons and provide good diffusion channels for the movement of electrolyte ions throughout the charge-discharge procedure.

Deep oxidative desulfurization of gas oil by iron(III)-substituted polyoxometalate immobilized on nickel(II) oxide, ((n-C4H9)4N)4H[PW11FeO39]@NiO, as an efficient nanocatalyst.

Sulfur compounds are among the most unfavorable constituents of petroleum derivatives, so stringent regulations have been established to curb their atmospheric emissions. In this regard, a new nanocomposite ((n-C4H9)4N)4H[PW11FeO39]@NiO) was synthesized composed of quaternary ammonium bromide salt of ironIII-substituted Keggin-type polyoxometalate immobilized on nickel(II) oxide nanoceramics via sol-gel method. The assembled (n-C4H9)4N)4H[PW11FeO39]@NiO nanocomposite was identified by FT-IR, UV-Vis, XRD, SEM, EDX, and TGA-DTG methods. The characterization results exhibited that ((n-C4H9)4N)4H[PW11FeO39] dispersed uniformly over the surface of the NiO nanoceramics. The ((n-C4H9)4N)4H[PW11FeO39]@NiO nanocomposite was employed as a heterogeneous nanocatalyst in the extractive coupled oxidation desulfurization (ECOD) of real gas oil and dibenzothiophene (DBT) as a model compound. Under relatively moderate conditions, the catalytic performance of the ((n-C4H9)4N)4H[PW11FeO39]@NiO in the ECOD procedure was studied by incorporating acetic acid/hydrogen peroxide as an oxidant system at a volume ratio of 1:2. According to the ECOD results, the ((n-C4H9)4N)4H[PW11FeO39]@NiO demonstrated the effectiveness of up to 95% with 0.1 g at 60 °C under optimal operating conditions. Moreover, the ((n-C4H9)4N)4H[PW11FeO39]@NiO nanocatalyst could be separated and reused for five runs without a noticeable decrease in the ECOD process. This study provides a promising way to meet the target of ultra-low sulfur as an essential process in oil refineries.

High Oxidation Desulfurization of Fuels Catalyzed by Vanadium-Substituted Phosphomolybdate@Polyaniline@Chitosan as an Inorganic-Organic Hybrid Nanocatalyst.

From the environmental protection and human health perspectives, the design and synthesis of efficient and reusable oxidative desulfurization nanocatalysts has always been sought after by scientists and industries. In this regard, a new heterogeneous nanocatalyst (V-SPM@PANI@CH) was synthesized by immobilizing Keggin-type vanadium-substituted phosphomolybdate ([PVMo11O39]4-) (named V-SPM) clusters on the surface of polyaniline (PANI) and chitosan (CH) polymers. The features of the assembled nanocatalyst were detected by Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, X-ray diffraction (XRD), scanning electron microscopy, and energy-dispersive X-ray spectroscopy techniques in detail. The XRD studies indicated that the average crystallite size of V-SPM@PANI@CH was estimated to be about 36 nm. The catalytic performance of V-SPM@PANI@CH was investigated in the extractive and catalytic oxidation desulfurization (ECOD) procedure of real and thiophenic model gasoline by H2O2/AcOH (volume proportion of 2:1) as an oxidizing system. The optimal desulfurization conditions for ECOD reactions were as follows: 50 mL of model/real gasoline, 0.1 g of V-SPM@PANI@CH, reaction time of 60 min, and reaction temperature of 35 °C. Under the experimental conditions outlined above and the designed ECOD system, the content of sulfur in real gasoline could decline from 0.4985 to 0.0193 wt %, which corresponds to an efficiency of 96%. Moreover, the removal percentage of aromatic hydrocarbons, including thiophene (Th), benzothiophene (BT), and di-benzothiophene (DBT) as model fuels decreases in the order of DBT ≥ BT > Th under identical operating conditions. High catalytic activity was maintained with only a slight loss during five cycles. This work offers the ECOD system (V-SPM@PANI@CH/AcOH/H2O2) for the desulfurization of liquid fuels, which had a great repercussion on the ECOD efficiency.

Catalytic oxidative desulphurization of gasoline using amphiphilic polyoxometalate@polymer nanocomposite as an efficient, reusable, and green organic-inorganic hybrid catalyst.

To preparation of ultra-clean gasoline fuel, a new amphiphilic nanocomposite (TBA-SiWMn@PVA) has been successfully synthesized by supporting sandwich-type silicotungstate polyoxometalate ((n-C4H9)4N)7H5Si2W18Mn4O68 (TBA-SiWMn) on polyvinylalcohol (PVA) as an efficient catalyst for catalytic oxidative desulphurization (CODS) of gasoline. The synthesized materials were characterized by means of elemental analysis, 113Mn NMR, 29Si NMR, XRD, SEM, FT-IR and UV-vis techniques. The catalytic activity of TBA-SiWMn@PVA nanocomposite was tested on real gasoline in the presence of CH3COOH/H2O2 as an oxidant and the results were compared with model sulphur compounds at the same conditions. The TBA-SiWMn@PVA nanocomposite was shown excellent catalytic performance and recoverability for ODS of gasoline with high yield. The effects of the reaction time, reaction temperature, dosage and nature of catalyst were investigated. The reaction mechanism and the kinetic parameters of sulphur compounds oxidation were also discussed. The probable mechanism was proposed via the electrophilic mechanism through the formation of a peroxometalate intermediate complex with phase transfer properties. Results were indicated that the kinetics of sulphur oxidation fitted the pseudo-first-order kinetic model. After 5 oxidation runs, the heterogeneous nanocatalyst was separated and recovered easily.