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In this work, synthesized 12-tungstenphosphoric acid (H3PW12O40 × nH2O; PWA) was further ionically exchanged with Fe3+ ions, which led to the formation of the 12- tungstophosporic acid iron salt, (FePW12O40 × nH2O; Fe-PWA). Fe-PWA was then subjected to thermal analysis (TGA/DTA), determining the phase transition temperature of 576°C from Fe-PWA to its corresponding phosphate tungsten bronze doped with iron, Fe-PWB. Using the X-ray powder diffraction (XRPD), Fourier-transform infrared spectroscopy (FTIR), and Scanning electron microscopy with an energy dispersive X-ray spectroscopy (SEM-EDS) method, the obtained Fe-PWA and Fe-PWB were additionally characterized, and compared. Due to channels and cavities in their structures, Fe-PWA and Fe-PWB were next examined as electrode materials for aqueous rechargeable batteries. Electrochemical measurements were done in aqueous solutions of 6 M LiNO3 by cyclic voltammetry. Fe-PWA and Fe-PWB exhibit different redox processes, which are discussed thoroughly in this work. Electrochemical results are showing that within the Fe-PWA structure, more Li+ ions can be intercalated in the first discharge cycle, but consecutive cycling leads to a fast capacity fade. While the Fe- PWB redox process was stable during cycling, its specific capacity is limited by the material's poor electrical conductivity. Improvements in Fe-PWB conductivity must be addressed in future studies in order to boost material’s electrochemical performance.

The calcium phosphate tungsten bronze (Ca-PWB) has been synthesized and characterized (TGA, DSC, XRPD, FTIR, SEM). The influence of solid insoluble materials Ca- PWB, as well as lithium doped (Li-PWB) and cation free phosphate tungsten (PWB) bronzes on the oscillatory Briggs-Rauscher (BR) reaction dynamics, is compared. The results show that doping with Li and Ca reduces sensitivity of the BR reaction towards bronzes addition. These findings suggest the usage of the BR reaction as an innovative method for testing of different properties of bronze material. The behavior of PWB in the BR reaction is significantly changed with divalent cation (Ca2+) doping. The reasons for the different bronzes behavior were found in their calculated unit cell volumes. Namely, the compressed Ca-PWB unit cell volume indicates the difficult availability of the active site for heterogeneous catalysis. Hence, the linear correlation (slope) of the BR oscillogram’s length (τosc) vs. mass of bronze in BR reaction might be considered as a new parameter for the evaluation of the bronzes catalytic activity.

Phosphate tungsten bronzes, obtained by thermal treatment, are insufficiently investigated bronzes and there is scarce literature data on their chemical behavior and structure. Due to high-sensitivity of the Briggs-Rauscher (BR) reaction to addition of different analytes, this oscillatory reaction presents a potentially important chemical system for investigation and characterization of phosphate-tungsten bronzes, doped and undoped. The reaction mixture for the oscillatory BR reaction typically consists of H2O2, HClO4, KIO3, Mn(II) (catalyst), and CH2(COOH)2 (malonic acid, as an organic substrate). This paper deals with phosphate tungsten bronzes (PWB) and lithium doped phosphate tungsten bronzes (LiPWB) and their effects on the Briggs-Rauscher reaction dynamics. It is shown that the addition of phosphate tungsten bronzes decreases the oscillatory period length in this reaction. Furthermore, the obtained results show that PWB has a stronger influence on the BR reaction dynamics then LiPWB. In both cases, the oscillatory period is a linear function of the added bronze mass. The obtained linear functions can be successfully used for determination of the unknown bronze mass. Furthermore, due to different slopes of these functions, the Briggs-Rauscher reaction can be used as a system-detector for lithium doped and undoped phosphate tungsten bronzes. In order to elucidate the mechanism of bronze action, the inductively coupled plasma optical emission spectrometry (ICP-OES) was used to measure the total contents of K, Mn, W, Li. The aliquots of the above solution (i.e. CH2(COOH)2, MnSO4, HClO4, KIO3 but without H2O2) with the identical masses of PWB and LiPWB were examined. For the sake of comparison, contents of the metals in the solution without the bronze addition were measured, as well. Results obtained by the ICP-OES analysis show that the bronze structure is disturbed in the strong oxidizing environment (iodate in acidic solution) so that both, tungsten and lithium, leach into the BR solution. Accordingly, the proposed mechanism of the bronze action is probably by the reaction of tungsten ion with hydrogen-peroxide resulting in formation of a tungsten-peroxo complex. This complex is a stronger oxidizing agent then hydrogen peroxide itself. Thus, formation of the tungsten-peroxo complex potentially affects the kinetics of the Briggs-Rauscher reaction. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172015, Grant no. III45001 and Grant no. III45014]

The influence of additives (alkyl polyglucoside, Glucopon 600 CS UP and alcohol ethoxylate C18E100) on the behavior of the water/toluene/Lutensol ON 50 (technical oxoalcohol, i-C10E5) microemulsion system as a function of temperature and composition has been investigated. The phase behavior of the microemulsions was determined by vertical sections through the Gibbs phase prism (fish-like phase diagrams). Alkyl polyglucoside shifts the one phase region to lower temperatures compared with water/toluene/Lutensol ON 50 mixtures. This is contrary to the expectation, considering the extreme hydrophilic nature of the sugar headgroup. The addition of hydrophilic alcohol ethoxylate (C18E100) to the water/toluene/Lutensol ON 50 system increases the solubilization capacity of the surfactant, even if the co-surfactant is used in small quantities, and shifts the one-phase region to higher temperature by a few degrees Celsius. [Projekat Ministarstva nauke Republike Srbije, br. 172051]

Experimental adsorption isotherms were used to evaluate the specific surface area and the surface fractal dimensions of acid-activated bentonite samples modified with a heteropoly acid (HPW). The aim of the investigations was to search for correlations between the specific surface area and the geometric heterogeneity, as characterized by the surface fractal dimension and the content of added acid. In addition, mercury intrusion was employed to evaluate the porous microstructures of these materials. The results from the Frankel-Halsey-Hill method showed that, in the p/p0 region from 0.75 to 0.96, surface fractal dimension increased with increasing content of heteropoly acid. The results from mercury intrusion porosimetry (MIP) data showed the generation of mesoporous structures with important topographical modifications, indicating an increase in the roughness (fractal geometry) of the surface of the solids as a consequence of the modification with the heteropoly acid. By comparison, MIP is preferable for the characterization because of its wide effective probing range.

The possibility of modifying polyethylene and many other polymers with high energy radiation has led to many useful applications. Due to their new combination of properties and the shortage of experimental data, the radiolysis of a new class of materials, cyclo-olefin copolymers (COC), polymerised from norbornene and ethylene using metallocene catalysts, is of great interest to the study of radiation chemistry and the physics of polymeric systems. Ethylenenorbornene copolymer, pristine and containing an antioxidant were subjected to gamma irradiation in the presence of air and in water. The irradiated copolymer was studied using IR and UV-vis spectrophotometric analysis. The radiation-induced changes in the molecular structure were correlated to changes in the glass transition temperature measured by the DSC method.

A series of silica-supported Ni-catalyst precursors was synthesized, with different SiO2/Nimole ratios between 0.2 and 1.15. The reduction of all the prepared samples was studied by thermogravimetry (TG) in a hydrogen flow. The results of the TG analysis were analyzed by the multi-thermal history model-fitting method, with non-linear regression. The activation energies for the reduction of each sample were determined. The statistical F-test was performed to discriminate between various models. It was found that increasing the SiO2/Ni mole ratio leads to a change in the reaction mechanism of the nickel reduction, resulting finally in a change from second order reaction kinetics to three halves order reaction kinetics.

The infrared spectra of the copigments of malvin with several organic acids: caffeic, ferulic, sinapic, chlorogenic, and tannic, were analyzed in order to elucidate the bonding of the molecules in the copigments. It was established that copigmentation is realized through hydrogen bonding between malvin molecules and the acids under study. The infrared spectra reveal that two groups of hydrogen bonds are formed, which include interactions of different molecular structures: hydroxy groups (bands around 3500 cm-1) and oxonium ions of the molecules (bands below 3000 cm-1). The formed hydrogen bonds were found to be of different strengths. The strengths of the hydrogen bonds were tentatively correlated with thermodynamic properties of the corresponding copigmentation reactions.

In this paper local processes and structural phase transformations of the copper salt of 12-tungstophosphoric acid are investigated. The structural phase transformations were followed through bands, characteristic for the host lattice, in the IR and Raman spectra. The results of these investigations, as well as those of XRPD analysis and impedance measurements as a function of temperature show that some local processes provoke the change in the secondary structure of the Keggin anions.

In this paper the latest results of our continuing investigation of heteropoly acids and their salts are reported. Specially attention was paid to the influence of cations on the dynamic equilibrium of protonic species, as well as on the structure of the host lattice itself, i.e., the Keggin anions. The investigations were done by IR and Raman spectroscopy within the range of 1200.40 cm-1.

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Experimental adsorption isotherms were used to evaluate the specific surface area and the surface fractal dimensions of acid-activated bentonite samples modified with a heteropoly acid (HPW). The aim of the investigations was to search for correlations between the specific surface area and the geometric heterogeneity, as characterized by the surface fractal dimension and the content of added acid. In addition, mercury intrusion was employed to evaluate the porous microstructures of these materials. The results from the Frankel--Halsey--Hill method showed that, in the p/p0 region from 0.75 to 0.96, surface fractal dimension increased with increasing content of heteropoly acid. The results from mercury intrusion porosimetry (MIP) data showed the generation of mesoporous structures with important topographical modifications, indicating an increase in the roughness (fractal geometry) of the surface of the solids as a consequence of the modification with the heteropoly acid. By comparison, MIP is preferable for the characterization because of its wide effective probing range. [ABSTRACT FROM AUTHOR]