New synthesis method for M(II) chromites/silica nanocomposites by thermal decomposition of some precursors formed inside the silica gels

In this article, we present a new method for the obtaining of ZnCr₂O₄ and MgCr₂O₄ embedded in silica matrix. This method consists in the formation of Cr(III), Zn(II) and Cr(III), Mg(II) hydroxycarboxylate/carboxylate compounds, during the redox reaction between the nitrate ion and diol (1,3-propanediol), uniformly dispersed in the pores of hybrid gels. The thermal decomposition of these precursors leads to a mixture of corresponding metal oxides. The gels were synthesized starting from mixtures of Cr(NO₃)₃·9H₂O, Zn(NO₃)₂·6H₂O and Cr(NO₃)₃·9H₂O, Mg(NO₃)₂·6H₂O with tetraethyl orthosilicate and 1,3-propanediol for final compositions 50% ZnCr₂O₄/50% SiO₂ and 50% MgCr₂O₄/50% SiO₂. The obtained gels have been thermally treated at 140?°C, when the redox reaction nitrates-diol took place with formation of the precursors within the xerogels pores. The thermal decomposition of all precursors took place up to 300?°C, with formation of oxides mixtures (Cr₂O_3?+?x and ZnO) and (Cr₂O_3?+?x and MgO), respectively. At 400?°C, Cr₂O_3?+?x turn to Cr₂O₃ which reacts with ZnO forming ZnCr₂O₄/SiO₂. Starting with 400?°C, Cr₂O₃ reacts with MgO to an intermediary phase MgCrO₄, which decomposes with the formation of MgCr₂O₄/SiO₂. The formation of the precursors inside the silica matrix and the evolution of the crystalline phases were studied by thermal analysis, FT-IR spectrometry, XRD, and TEM.     

Catalytic properties of spinel-type complex oxides in oxidation reactions

The catalytic activity of M^IM^II ₂O₃ spinel-type complex oxides (M^I = Cu, Ni, Mn, Zn, Mg, Co, M^II = Co, Cr, Al) in the oxidation of CO and ethylbenzene has been investigated. The Co-containing catalysts were more active than the Cr- and Al-containing catalysts. The nature of the cation influenced the catalytic activity. Higher activities were observed for the catalysts containing two transition elements. A correlation between the catalytic and adsorption properties was established.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1730–1732, October, 1994.     

Thermodynamics of Cr2O3, FeCr2O4, ZnCr2O4, and CoCr2O4

High-temperature heat capacity measurements were obtained for Cr₂O₃, FeCr₂O₄, ZnCr₂O₄, and CoCr₂O₄ using a differential scanning calorimeter. These data were combined with previously available, overlapping heat capacity data at temperatures up to 400 K and fitted to 5-parameter Maier–Kelley C_p(T) equations. Expressions for molar entropy were then derived by suitable integration of the Maier–Kelley equations in combination with recent S^∘(298) evaluations. Finally, a database of high-temperature equilibrium measurements on the formation of these oxides was constructed and critically evaluated. Gibbs free energies of Cr₂O₃, FeCr₂O₄, and CoCr₂O₄ were referenced by averaging the most reliable results at reference temperatures of (1100, 1400, and 1373) K, respectively, while Gibbs free energies for ZnCr₂O₄ were referenced to the results of Jacob [K.T. Jacob, Thermochim. Acta 15 (1976) 79–87] at T = 1100 K. Thermodynamic extrapolations from the high-temperature reference points to T = 298.15 K by application of the heat capacity correlations gave Δ_fG^∘(298) = (−1049.96, −1339.40, −1428.35, and −1326.75) kJ · mol⁻¹ for Cr₂O₃, FeCr₂O₄, ZnCr₂O₄, and CoCr₂O₄, respectively.     

Adsorption characteristics of Titan yellow and Congo red on CoFe2O4 magnetic nanoparticles

This paper assesses the adsorption characteristics of Titan yellow and Congo red on CoFe₂O₄ magnetic nanoparticles. The adsorption behavior of Titan yellow and Congo red from aqueous solution onto CoFe₂O₄ magnetic nanoparticles has been determined by investigating the effects of pH, concentration of the dye, amount of adsorbent, contact time, ionic strength and temperature. Experimental results indicated that CoFe₂O₄ nanoparticles can remove more than 98 % of each dye under optimum operational conditions of a dosage of 15.0 mg CoFe₂O₄, pH 3.0, initial dye concentration of 22–140 mg L^?1, and contact times of 2.0 and 15.0 min for Congo red and Titan yellow, respectively. Langmuir and Freundlich isotherm models have been used to evaluate the ongoing adsorption kinetic equations. Regeneration of the saturated adsorbent was possible by NaCl/acetone solution as eluent. The maximum adsorption capacities were 200.0 and 212.8 mg dye per gram adsorbent for Congo red and Titan yellow, respectively. With the help of adsorption isotherm, thermodynamic parameters such as free energy, enthalpy and entropy have been calculated. On the basis of pseudo-first-order and pseudo-second-order kinetic equations, different kinetic parameters have been obtained.     

The effects of thermal treatment of ZnO–ZnCr<Subscript>2</Subscript>O<Subscript>4</Subscript> catalyst on the particle size and product selectivity in dehydrocyclization of crude glycerol and ethylenediamine

The ZnO–ZnCr₂O₄ (Zn–Cr–O) sample obtained by decomposition of Zn-Cr hydrotalcite precursor was subjected to the thermal treatment at different temperatures and the physico-chemical properties of the Zn–Cr–O system were compared with its catalytic behavior in dehydrocyclization of crude glycerol and ethylenediamine (EDA). Upon high temperature treatment of Zn–Cr–O the Cr⁶⁺ ions underwent autoreduction to form stable Cr³⁺ species and the particle size of both ZnO and ZnCr₂O₄ increased dramatically. Thermal effect did not influence the intermolecular cyclisation of EDA to form pyrazine. By contrast, an inversely proportional dependence was found between the rate of formation of 2-methylpyrazine and the particle size of Zn–Cr–O whereas the rate of 2-pyrazinylmethanol was directly proportional to the particle size.     

Rapid removal of anionic organic dye from contaminated water using a poly(3-aminobenzoic acid/graphene oxide/cobalt ferrite) nanocomposite low-cost adsorbent via adsorption techniques

This research study aims to remove hazardous anionic azo dyes (Congo red (CR)) from aqueous solutions via a simple adsorption method using a poly(3-aminobenzoic acid/graphene oxide/cobalt ferrite) nanocomposite (P3ABA/GO/CoFe₂O₄) as a novel and low-cost nanoadsorbent, as synthesized by a simple and straightforward polymerization method. Typically, 3-aminobenzoic acid (3ABA), as monomer, was chemically polymerized with graphene oxide (GO) and cobalt ferrite (CoFe₂O₄) in an aqueous acidic medium containing an ammonium persulfate initiator. The adsorbent P3ABA/GO/CoFe₂O₄ nanocomposite was characterized using various techniques such as Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, energy-dispersive analysis by X-ray and Brunauer–Emmett–Teller, vibrating sample magnetometer, and zeta potential techniques. These techniques confirmed the interaction between the poly(3-aminobenzoic acid) with GO and CoFe₂O₄ due to the presence of π-π interactions, hydrogen bonding, and electrostatic forces. Herein, the removal efficiency of dye from aqueous solution by the adsorbent was studied according to several parameters such as the pH of the solution, dye concentration, dosage of adsorbent, contact time, and temperature. The adsorption of the dye was fitted using a Langmuir model (R² between 0.9980 and 0.9995) at different temperatures, and a kinetic model that was pseudo-second order (R² = between 0.9993 and 0.9929) at various initial concentrations of CR dye. In addition, the data revealed that the P3ABA/GO/CoFe₂O₄ nanocomposite exhibited a high adsorption capacity (153.92 mg/g) and removal for CR dye (98 %) at pH 5. Thermodynamic results showed the adsorption process was an endothermic and spontaneous reaction. It was found that, in terms of reusability, the P3ABA/GO/CoFe₂O₄ adsorbent can be used for up to six cycles. In this study, P3ABA/GO/CoFe₂O₄ nanocomposites were found to be low cost, and have an excellent removal capability and fast adsorption rate for CR from wastewater via a simple adsorption method. Moreover, this adsorbent nanocomposite could be simply separated from the resultant solution and recycled.     

Photogenic MnO2/Ag metal nanocomposites and their dye adsorbing activities

• Manganese dioxide/silver (MnO₂/Ag) nanoparticles were fabricated by using KMnO₄-NaBH₄ redox reaction at room temperature. The optical and structural properties of MnO₂/Ag were determined using UV–visible and Fourier transform infrared spectroscopies. The morphology was established with scanning and transmission electron microcopies, and X-ray diffraction. MnO₂/Ag showed excellent adsorbing activity to the removal of Congo red. The various kinetic models were used to determine the rate of dye removal. Congo red adsorption onto MnO₂Ag proceeds through the pseudo-second-order kinetic model. Langmuir adsorption capacity (Q⁰_max = 97.1 mg/g), and sorption intensity (n = 1.6) were estimated with Langmuir and Freundlich adsorption isotherm models for 250 mg/L Congo red. Elovich model suggest the adsorption of Congo red with the MnO₂Ag proceeds through the film diffusion. The positive values of enthalpy changes (ΔH⁰), entropy changes (ΔS⁰), and negative Gibbs free energy changes (ΔG⁰) showed that the Congo red adsorption process was endothermic, spontaneous, and chemisorption process followed with physical mechanism. The results showed that the removal efficiency decreases from 98% to 89% after the six consecutive experiments.

     

Effect of Ca,Mg-ions on the properties of LiCo0.9M0.1PO4/graphitic carbon composites

LiCo_0.9M_0.1PO₄ (M = Co²⁺, Mg²⁺, Ca²⁺)/graphitic carbon composites are synthesized by Pechini-assisted sol–gel process and annealed by the 2-steps annealing process (300 °C for 5 min in air, then at 730 °C for 12 h in nitrogen). The structural investigation, performed on powders, reveals the presence of LiCoPO₄ as the major crystalline phase and of CoP₂O₇ (M = Co), of Co₂P (M = Mg), of Co₂P, Li₃PO₄, (Ca,Co)₃(PO₄)₂ (M = Ca) as impurities. The morphological investigation of the composites shows the formation of crystalline “islands-like” structures with acicular crystallites with different dimensions (typically 5–50 μm) on the top of them. The voltammetric analysis shows a very good reversibility of the (de)intercalation processes and the presence of two mean peak maxima in the cathodic region at ∼5.01 V and ∼5.05 V respectively. The discharge specific capacities, at a discharge rate of C/10 and room temperature, were 100 mAh g⁻¹ for M = Co, 68 mAh g⁻¹ for M = Mg and 104 mAh g⁻¹ for M = Ca respectively. The electrochemical impedance spectroscopy data reveal a decrease of the electrical resistance and the improvement of the Li-ion conductivity in the Ca and Mg ions containing composites.     

Spectral, thermal and X-ray studies on some new bis-hydrazine metal glyoxylates and bis-hydrazine mixed metal glyoxylates

Bis-hydrazine complexes of metal glyoxylates and mixed metal glyoxylates of 3d-metal ions of the formula M(OOCCHO)₂(N₂H₄)₂, where M = Mg, Mn, Co, Ni, Cu, Zn or Cd and M_1/3Co_2/3(OOCCHO)₂(N₂H₄)₂, where M = Mg, Mn, Ni, Zn or Cd, respectively, have been prepared and studied. The compositions of the complexes have been determined by chemical analyses. The magnetic moments and electronic spectra suggest a high-spin octahedral geometry for the metal complexes. Infrared spectral data indicate the bidentate bridging by hydrazine molecules and monodentate coordination by glyoxylate ions in both the metal and mixed metal compounds. Thermogravimetry and differential thermal analyses in air have been used to study the thermal behaviour of the complexes. The simultaneous TG-DTA traces of all the complexes show multi-step degradation and the final products are found to be the respective metal oxides in the case of metal complexes and metal cobaltites in the case of mixed metal complexes. The final residues were identified by their X-ray powder diffraction patterns. X-ray powder diffraction patterns of the complexes including mixed metal complexes are almost superimposable with in each of the series indicating isomorphism. The metal cobaltites MCo₂O₄, where M = Mg, Mn, Ni, Zn or Cd were also prepared by decomposing the respective mixed metal complex in a pre-heated silica crucible at about 300 °C, and their identities were confirmed by chemical analyses, infrared spectra and X-ray powder diffraction.     

Evaluation of cation influence on the formation of M(II)Cr2O4 during the thermal decomposition of mixed carboxylate type precursors

This paper reports an investigation regarding the influence of the cation M(II) (M = Zn, Ni, Mg) on the formation of MCr₂O₄ by thermal decomposition of the corresponding M(II),Cr(III)-carboxylates (precursors) obtained by redox reaction between the corresponding metal nitrates and 1,3-propanediol. The decomposition products at different temperatures have been characterized by FT-IR spectroscopy and thermal analysis. Thus, we have evidenced that by thermal decomposition of the studied precursors in the range 250–300 °C, different amorphous oxidic phases mixtures form depending on the nature of metalic cation: (Cr₂O_3+x + ZnO) (Cr₂O_3+x + Ni/NiO) and (Cr₂O_3+x+MgO). In case of M = Zn, around 400 °C when the transition Cr₂O_3+x to Cr₂O₃ takes place, zinc chromite nuclei form by the interaction ZnO with Cr₂O₃. In case of M = Ni, due to the partial reduction of Ni(II) at Ni(0) during the thermal decomposition of the precursor the formation of nickel chromite by the reaction NiO + Cr₂O₃ is shifted toward 500 °C, when Ni is oxidized at NiO. The thermal evolution of the mixture (MgO + CrO₃) is different due to the formation as intermediary phase of MgCrO₄, which decomposes to MgCr₂O₄ around 560 °C. In order to investigate the chromites formation mechanism, we have studied the mechanical mixtures of single oxides obtained from the corresponding carboxylates. These mixtures (MO + Cr₂O₃) have been annealed at 400, 500, and 600 °C to study the evolution of the crystalline phases. It results in the prepared mixture behaving different from the mixtures obtained by thermal decomposition of the binary M(II),Cr(III)-carboxylates, recommending our synthesis method for obtaining binary oxides.     

The effect of active oxygen species in nano-ZnCr2O4 spinel oxides for methane catalytic combustion

The nano-ZnCr₂O₄ spinel oxides was synthesized by a ethylene glycol mediated solvothermal method. Catalytic combustion of methane test showed that an excellent activity over nano-ZnCr₂O₄ with T_10% = 300 °C and T_90% = 400 °C. The results of X-ray diffraction (XRD), scanning electron microscopy (SEM), N₂ adsorption-desorption measurements (BET) indicated that a uniform nano-ZnCr₂O₄ spinel oxides particles with the high surface area (96.2 m²g⁻¹) was successfully synthesized. Oxygen temperature programmed desorption (O₂-TPD) profile revealed there were two obvious desorption of oxygen species from nano-ZnCr₂O₄ in the range of 300–400 °C and 500–700 °C. It was clear that the desorption temperature range of the first oxygen species coincided with the methane catalytic combustion temperature. X-ray photoelectron spectroscopy (XPS) analysis exhibited that Cr⁶⁺ was present in the lattice of ZnCr₂O₄ apart from Cr³⁺. High valence cations of chromium in crystal lattice probable caused the presence of interstitial oxygen species in the structure to maintain the electroneutrality. Additionally, Raman spectra proved that there is the interstitial oxygen species in the crystal lattice of ZnCr₂O₄. Therefore, the excellent catalytic activity for methane combustion was contributed to the flexible interstitial oxygen in the ZnCr₂O₄.     

Thermal characterization and compatibility studies of perovskite-type Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) oxide with Cr2O3 at high temperature

The chemical compatibility of perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) oxides with Cr₂O₃ has been examined between room temperature and 1,100 °C. Differential thermal analysis and thermogravimetric analysis were used to analyze the thermal behavior of BSCF–Cr₂O₃ binary mixtures in all composition ranges (0–100 mass% BSCF). The reaction products were identified by X-ray analysis after heating at 700–1,100 °C. As we expected, it was found that perovskite-type BSCF oxide had a poor chemical compatibility with the Cr₂O₃ oxide. In particular, the decomposition process of the BSCF–Cr₂O₃ binary mixture is quite complex and it starts at about 700–750 °C. The mixtures of BSCF and Cr₂O₃ oxides reacted forming mixed complex oxides based on (Ba/Sr)FeO₃, (Co/Fe)CrO₄, and (Ba/Sr)CrO₄ mixtures.     

Synthesis,characterization and photocatalytic activity of a new type of high-efficiency polyacid composite

In order to achieve the degradation of Congo red dye in wastewater, a new type of three-dimensional porous composite catalyst PW₇Mo₃Cu₂/PANI/MnO₂ was prepared by using heteropoly acid [TBA]₄H₃[PW₇Mo₃Cu₂O₃₈(H₂O)₂] doped intermediate PANI/MnO₂. Using IR, UV, SEM, XPS and other characterization techniques, it was confirmed that the heteropoly acid [TBA]₄H₃[PW₇Mo₃Cu₂O₃₈(H₂O)₂] was successfully doped into the intermediate PANI/MnO₂ to form a three-dimensional porous structure. The results of N₂ adsorption–desorption experiment indicated that the composite catalyst belongs to the type IV (a) mesoporous structure material and has a large pore size and specific surface area. Then, the composite catalyst PW₇Mo₃Cu₂/PANI/MnO₂ was used to photocatalyze the degradation of Congo red dye. Under the best photocatalytic conditions, the decolorization rate of Congo red dye reached 93.84%. After recovering and repeating the photocatalysis experiment three times, the decolorization rate of Congo red dye was 73.18%. The experimental results proved that the novel composite catalyst has a strong ability to degrade Congo red dye and reusability, and has potential application value.

     

Gibbs free energies of formation of ZnAl2O4 and ZnCr2O4

The standard free energies of formation of zinc aluminate and chromite were determined by measuring the oxygen potential over a solid CuZn alloy, containing 10 at.?% Zn, in equilibrium with ZnO, ZnAl₂O₄+Al₂O₃(χ) and ZnCr₂O₄+Cr₂O₃, in the temperature range 700–900°C. The oxygen potential was monitored by means of a solid oxide galvanic cell in which a Y₂O₃ThO₂ pellet was sandwiched between a CaOZrO₂ crucible and tube. The temperature dependence of the free energies of formation of the interoxidic compounds can be represented by the equations,

The heat of formation of the spinels calculated from the measurements by the “Second Law method” is found to be in good agreement with calorimetrically determined values. Using an empirical correlation for the entropy of formation of cubic spinel phases from oxides with rock-salt and corundum structures and the measured high temperature cation distribution in ZnAl₂O₄, the entropy of transformation of ZnO from wurtzite to rock-salt structure is evaluated.     

Catalytic properties of chromites with a spinel structure in the oxidation of CO and hydrocarbons and reduction of nitrogen oxides

The catalytic activity of supported chromites MCr₂O₄/-Al₂O₃ (M = Cu, Co, Mn, Zn, Mg) in the oxidation of CO, C₃H₆, and o-xylene and NO_x reduction was studied. The catalytic activity depends on the calcination temperature and cation nature. The features of the formation of the catalysts were studied by the UV-Vis diffuse reflectance and IR spectroscopies.     

Surface Reorganization on Electrochemically-Induced Zn–Ni–Co Spinel Oxides for Enhanced Oxygen Electrocatalysis

Herein, we highlight redox-inert Zn²⁺ in spinel-type oxide (Zn_XNi_1−XCo₂O₄) to synergistically optimize physical pore structure and increase the formation of active species on the catalyst surface. The presence of Zn²⁺ segregation has been identified experimentally and theoretically under oxygen-evolving condition, the newly formed V_Zn−O−Co allows more suitable binding interaction between the active center Co and the oxygenated species, resulting in superior ORR performance. Moreover, a liquid flow Zn–air battery is constituted employing the structurally optimized Zn_0.4Ni_0.6Co₂O₄ nanoparticles supported on N-doped carbon nanotube (ZNCO/NCNTs) as an efficient air cathode, which presents remarkable power density (109.1 mW cm⁻²), high open circuit potential (1.48 V vs. Zn), excellent durability, and high-rate performance. This finding could elucidate the experimentally observed enhancement in the ORR activity of Zn_XNi_1−XCo₂O₄ oxides after the OER test.     

Catalytic properties of ferrites in oxidation reactions

Catalytic activities of ferrites MFe₂O₄ (M = Cu, Co, Ni, Mg, and Zn) and M¹ _0.5M² _{0 .5}Fe₂O₄ (M¹ = CU; M² = Co, Zn, and Mg) in oxidation of CO and ethylbenzene were investigated, and their dependences on the cation nature were established. Higher activities were observed for catalysts containing ions with variable valence (Cu, Co, and Ni). A correlation between catalytic and adsorption properties of ferrites was found.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 49–52, January, 1996.     

Studies on InFeMO4 (M=Mg, Co, Ni, Cu and Zn) compounds: Crystal structure and cation distribution

The crystal structure and the cation distribution in a series of InFeMO₄ compounds (M=Mg, Co, Ni, Cu and Zn) have been studied by means of X-ray powder diffraction and ⁵⁷Fe Mössbauer spectroscopy. The M=Mg, Co and Ni samples were confirmed to crystallize with the cubic spinel structure (space group Fd-3m), whereas the M=Cu and Zn samples adopted a hexagonal structure. For all the phases, the cation stoichiometry was found to deviate from the ideal molecular formula, InFeMO₄. The paramagnetic Mössbauer spectra of the samples were analyzed using a four-component fitting model suggested by a statistical simulation with point-charge calculation. The Mössbauer data confirmed the trivalent state for iron at both cation sites in all samples. The results from the fitting of the Mössbauer spectra were also employed in Rietveld refinement of the X-ray diffraction data for the determination of exact cation distribution. It was seen that the distribution of Fe at the A and B sites follows very closely the 1:2 ratio of the ideal formula AB₂O₄ for all samples, whereas trivalent indium was clearly seen to favor the A site and divalent M cation the B site.     

Facile synthesis of ZnO and Co3O4 nanoparticles by thermal decomposition of novel Schiff base complexes: Studying biological and catalytic properties

In this paper, a novel Zn(II) and Co(II) Schiff base complexes were synthesized by template method via refluxing 2,3-Naphthalenedicarboxaldehyde, Metal(II) chloride (Metal = Zn or Co), and L-phenylalanine. ZnO and Co₃O₄ nanoparticles were synthesized by thermal decomposition of Zn(II) and Co(II) complexes, respectively. The products were characterized using different instruments such as CHN, Conductivity, FT-IR, XRD, HR-TEM, and UV–Vis spectrophotometer. The experimental results of elemental analysis for Zn(II) and Co(II) complexes, agree with the calculated results, indicating that the Zn(II) and Co(II) complexes have 1:1 ligand/metal ratios. The molar conductance of the Zn(II) and Co(II) complexes, is less than 5 Ω^?1cm^?1mol^?1, confirming the non-electrolytic nature of the synthesized complexes. The average crystallite diameter of the ZnO and Co₃O₄ samples is 39.64 and 30.38 nm, respectively. The optical energy gap of the ZnO and Co₃O₄ samples are 2.75 and 3.25 eV, respectively. Methylene blue dye was utilized to examine the photocatalytic properties of the synthesized nanoparticles using UV irradiations in the absence and presence of hydrogen peroxide. The % degradation of the methylene blue dye in the presence of hydrogen peroxide using ZnO and Co₃O₄ samples after 40 min is 94.55 and 98.98, respectively. Six pathogenic microbes were utilized to examine the antimicrobial properties of the synthesized Schiff base complexes and their nanoparticles: Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Streptococcus species, Aspergillus species, and Candida species. Zn(II) and Co(II) complexes display inhibition towards all the studied microbes. Besides, ZnO and Co₃O₄ nanoparticles exhibit less inhibition towards Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Streptococcus species. Moreover, ZnO and Co₃O₄ nanoparticles have no activity towards Aspergillus and Candida species.