Low temperature synthesis of Co<Subscript>2</Subscript>SiO<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> nanocomposite using a modified sol–gel method

The paper presents a study on the preparation of Co₂SiO₄/SiO₂ nanocomposites by a new modified sol–gel method. We have prepared gels starting from tetraethylorthosilicate (Si(OC₂H₅)₄), cobalt nitrate Co(NO₃)₂·6H₂O and some diols: ethylene glycol (C₂H₆O₂), 1,2propanediol (C₃H₈O₂) and 1,3propanediol (C₃H₈O₂), for a final composition: 30% CoO/70% SiO₂. During the heating of the gels at 140 °C, a redox reaction takes place between NO₃ ⁻ ions and diol with formation of some carboxylate anions. These carboxylate anions react with the Co(II) ions to form coordination compounds embedded in silica matrix, as evidenced by FT-IR spectrometry and thermal analysis. These Co(II) coordinative compounds thermally decompose in the range 250–300 °C to the corresponding oxides: CoO and/or Co₃O₄ inside the matrices pores. When CoO results, it reacts with SiO₂ at low temperature leading to Co₂SiO₄, which crystallizes at 700 °C. XRD patterns of the samples annealed at temperatures lower than 700 °C were characteristic to amorphous phases. The samples annealed at temperatures ≥700 °C, contain Co₂SiO₄ (olivine) as unique crystalline phase inside the amorphous silica matrix, according to XRD patterns. As evidenced by TEM images, Co₂SiO₄ nanoparticles are homogenously dispersed inside the silica matrix.     

Preparation of CuCr<Subscript>2</Subscript>O<Subscript>4</Subscript> nanopowders using two different chromium sources

CuCr₂O₄ spinel powders were synthesized starting from different chromium sources, namely (i) chromium oxide (α-Cr₂O₃) and (ii) ammonium dichromate ((NH₄)₂Cr₂O₇). The copper source was a Cu(II) carboxylate-type complex. The Cu(II) carboxylate complex was obtained by the redox reaction between Cu(NO₃)₂·3H₂O and 1,3-propanediol (1,3PG) at 130 °C. In the first case (i), we have started from a mixture of α-Cr₂O₃, Cu(NO₃)₂·3H₂O and 1,3PG that upon heating formed the copper malonate complex, which decomposed around 220 °C forming an oxide mixture (CuO + α-Cr₂O₃). In the second case (ii), (NH₄)₂Cr₂O₇, Cu(NO₃)₂·3H₂O and 1,3PG were homogenously mixed. Heating this mixture at 130 °C resulted, in situ, in the Cu(II) complex. On controlled temperature increase, the violent decomposition of (NH₄)₂Cr₂O₇ took place at 180 °C along with the decomposition of the Cu(II) complex, leading to an amorphous oxide mixture of Cr₂O_3+x and CuO. By annealing the samples in the temperature range 400–1000 °C, the spinel phase (CuCr₂O₄) was obtained in both cases: (i) at 800 °C and (ii) at 600 °C as a result of the interactions between the precursors used, when the oxide system was amorphous and highly reactive. The presence of CuCr₂O₄ was highlighted by XRD and FTIR analyses.     

Preparation of CoxFe3?xO4 nanoparticles by thermal decomposition of some organo-metallic precursors

This paper presents a study for the preparation of Co_xFe_3−xO₄ (x = 0.02, 0.2, 0.5, 0.8, 1.0, 1.1, 1.5) nanoparticles, starting from metal nitrates: Co(NO₃)₂·6H₂O, Fe(NO₃)₃·9H₂O and ethylene glycol (C₂H₆O₂). By heating the solutions metal nitrates-ethylene glycol, the redox reaction took place between the anion NO₃ ⁻ and OH–(CH₂)₂–OH with formation of carboxylate anions. The resulted carboxylate anions reacted with Co(II) and Fe(III) cations to form coordinative compounds which are precursors for cobalt ferrite. XRD and magnetic measurements have evidenced the formation of cobalt ferrite for all studied molar ratios. The average diameter of the cobalt ferrite crystallites was estimated from XRD data and showed values in the range 10–20 nm. The crystallites size depends on the annealing temperature. The magnetization of the synthesized samples depends on the molar ratio Co/Fe and on the annealing temperature.     

Peculiarities of polythermic decomposition of iron,cobalt and nickel oxalates within pores of photonic crystals based on SiO<Subscript>2</Subscript> in atmosphere with oxygen lack

Iron(II), cobalt(II) and nickel(II) oxalates were synthesized as nanofractals inside the voids of the photonic crystals based on SiO₂. Guest substances undergone polythermic decomposition within the pores of the photonic crystals in helium atmosphere containing of oxygen traces (∼1 Pa) under static conditions. Pyrolysis of Fe(COO)₂·2H₂O, Co(COO)₂·2H₂O and Ni(COO)₂·2H₂O studied by TG and DSC techniques results in the formation of the metal oxides. The nanoparticles of Fe₂O₃, CoO (Co₃O₄) and NiO populated the interspheric voids of the photonic crystals exhibited no ferromagnetic effects indicating that no metallic inclusions were formed in helium in the presence of O₂ traces. The exothermic effect was observed by the thermal decomposition of the cobalt(II) oxalate only under oxygen lack.     

A new coordination mode of 6‐methylnicotinic acid in trans‐tetraaquabis(6‐methylpyridine‐3‐carboxylato‐κO)cobalt(II) tetrahydrate

The title compound, [Co(C₇H₆NO₂)₂(H₂O)₄]·4H₂O, contains a Co^II ion lying on a crystallographic inversion centre. The Co^II ion is octahedrally coordinated by two 6‐methylpyridine‐3‐carboxylate ligands in axial positions [Co—O = 2.0621 (9) Å] and by four water molecules in the equatorial plane [Co—O = 2.1169 (9) and 2.1223 (11) Å]. There are also four uncoordinated water molecules. The 6‐methylpyridine‐3‐carboxylate ligands are bound to the Co^II ion in a monodentate manner through a carboxylate O atom. There is one strong intramolecular O—H...O hydrogen bond, and six strong intermolecular hydrogen bonds of type O—H...O and one of type O—H...N in the packing, resulting in a complex three‐dimensional supramolecular structure.     

Synthesis of nanocrystalline nickel ferrite by thermal decomposition of organic precursors

Nickel ferrite powders were synthesized by thermal decomposition of the precursors obtained in the redox reaction between the mixture of Ni(NO₃)₂·6H₂O and Fe(NO₃)₃·9H₂O with polyalcohol: 1,4-butanediol, polyvinyl alcohol and also with their mixture. During this reaction the primary C?COH groups were oxidized at ?CCOOH, while secondary C?COH groups at C=O groups. The carboxylic groups formed coordinate to the present Ni(II) and Fe(III) cations leading to carboxylate type compounds, further used as precursors for NiFe₂O₄. These precursors were characterized by thermal analysis and FT-IR spectrometry. All precursors thermally decomposed up to 350?°C leading to nickel ferrite weakly crystallized. By annealing at higher temperatures, nanocrystalline nickel ferrite powders were obtained, as resulted from XRD. SEM images have evidenced the formation of nanoparticulate powders; these powders present magnetic properties characteristic to the oxidic system formed by magnetic nanoparticles.     

TG and DTA Evaluation of Cobalt Salts and Complexes Mixed with Activated Carbon

The thermal decomposition process of mixtures of CoC₂O₄⋅2H₂O (COD) or Co(HCOO)₂⋅2H₂O (CFD) or [Co(NH₃)₆]₂(C₂O₄)₃⋅4H₂O (HACOT) with activated carbon was studied with simultaneous TG–DTG–DTA measurements under non-isothermal conditions in argon and argon/oxygen admixtures. The results show that the thermal decomposition of the studied mixtures in Ar proceeds in the same manner. It begins with the salt decomposition to Co_met+CoO mixture followed by (T>680 K) the simultaneous reduction of CoO to Co_metand carbon degasification. The final product of the thermal decomposition of COD-C and CFD-C mixtures, identified by XRD, is β-Co. Cobalt contents determined in the final products fall in the range 71–78 mass%. The rest is amorphous residual carbon. In Ar/O₂ admixtures the end product is Co₃O₄ with ash admixture. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Carboxylate clusters with the M<Subscript>4</Subscript>O<Subscript>4</Subscript> cubane-like core: pivalate cocrystal containing Co<Superscript>II</Superscript> and Ni<Superscript>II</Superscript>

Joint thermolysis of the dinuclear pivalate complexes M₂(μ-H₂O)(μ-Piv)₂(Piv)₂(HPiv)₄ (M = Co (1) and Ni (2), Piv^- is the pivalate anion), in decane at 174 °C at the reactant ratio 1: 1 followed by treatment of the dry thermolysis product with methanol afforded crystals of a new cocrystallization product of the molecules containing the heterometallic cubane-like core M₄(Co,Ni)O₄. According to the X-ray diffraction data and the results of magnetic measurements, inductively coupled plasma atomic emission spectrometry (ICP-AES), and investigations of the solid-state thermal decomposition products, the isolated cocrystallization product has the general formula [Co_1.6Ni_2.4(μ₃-OMe)₄(μ₂-Piv)₂(pg² -Piv)₂(MeOH)₄] ·4MeOH (3·4MeOH). Thermolysis of the crystals of the solvate 3·4MeOH is a destructive process accompanied by the intramolecular redox reaction. A mixture of metallic Ni and cobalt oxide (CoO) are the final solid decomposition products of 3 · 4MeOH in an argon atmosphere, whereas a mixture of the phases NiO, Co₃O₄, and NiCo₂O₄ is formed in air.     

Synthesis and Thermal Decomposition of Cobalt(II) bis (Tartrato) Cobaltate(II) Trihydrate

The paper describes the synthesis and characterization of cobalt(II) bis (tartrato) cobaltate(II) trihydrate Co[Co[C₄O₆H₄)₂]·3H₂O. The complex was characterized on the basis of elemental analysis, infrared, electronic, e.s.r. spectra and X-ray powder diffraction studies. The thermal decomposition of the complex led to a mixture of Co₂O₃and Co₃O₄in air at about 400°C, whereas in nitrogen it was decomposed to a mixture of CoO and C at about 384°C. A tentative reaction mechanism is suggested for the thermal decomposition of the complex in air and nitrogen. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polythermic decomposition of Co(COO)2 · 2H2O compound synthesized within pores of photonic crystals based on SiO2

Polythermic decomposition of Co(COO)₂ · 2H₂O synthesized within pores of photonic crystals based on SiO2 was studied by thermogravimetry and differential scanning calorimetry techniques in helium and air in flow and under static conditions. Efficient activation energies and dehydratation enthalpies of the photonic crystals based on SiO₂ both in the absence and in the presence of Co(COO)₂ · 2H₂O phase (23.6, 41.5 and 77.6, 49.8 kJ mol^-1, respectively) were calculated. Polythermic Co(COO)₂ · 2H2O decomposition within pores of the photonic crystallites was found to yield CoO and Co₃O₄ nanoparticles in helium and air, respectively, exhibiting higher catalytic activity in CO oxidation by molecular oxygen. A conclusion was drawn that exothermic effect in the temperature range covering dehydrated oxalate decomposition is due to heterogeneously catalytic CO oxidation on the CoO and Co₃O₄ phases.     

Synthesis characterization and catalytic evaluation of Ni/ZrO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> aerogels catalysts

The Ni/ZrO₂/SiO₂ aerogels catalysts were synthesized via three different routes: (i) impregnation ZrO₂–SiO₂ composite aerogels with a aqueous solution of Ni(NO₃)₂, (ii) impregnation SiO₂ aerogels with a mixed aqueous solution of Ni(NO₃)₂ and ZrO(NO₃)₂ · 2H₂O, (iii) one-pot sol–gel procedure from precursors Ni(NO₃)₂/ZrO(NO₃)₂ · 2H₂O/Si(OC₂H₅)₄. These catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), ammonia temperature-programmed desorption (NH₃-TPD), N₂ adsorption–desorption isotherms and Fourier transform infrared (FT-IR). The Liquid-phase hydrogenation of maleic anhydride (MA) was performed over these catalysts. The results revealed that the different preparation routes result in a difference between the obtained samples, concerning the crystal structure and composition, surface acidity, mixed level of each component, texture, and catalytic selectivity.     

Thermal Analysis of Cobalt(II) Salts with some Carboxylic Acids

The thermal analysis of CoC₂O₄·2H₂O, Co(HCOO)₂·2H₂O and Co(CH₃COO)₂·4H₂O was carried out with simultaneous TG-DTG-DTA measurements under non-isothermal conditions in air and argon atmospheres. The intermediates and the end products of decomposition were characterised by X-ray diffraction and IR and UV-VIS spectroscopy. The decomposition of the studied compounds occur in several stages. The first stage of dissociation of each compound is dehydration both in air and argon. The next stages differ in air and argon. The final product of the decomposition of each compound in air is Co₃O₄. In argon it is a mixture of Co and CoO for cobalt(II) oxalate and cobalt(II) formate but CoO for cobalt(II) acetate. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nanostructured VOx/VO(PO<Subscript>4</Subscript>)<Subscript>n</Subscript> Using Solid-State Vanadium Containing Phosphazene Precursors: A Useful Potential Bi-Catalyst System

Pyrolysis of molecular precursors containing vanadium organometallic and cyclic phosphazene affords mixtures of nanostructured vanadium oxides and pyrophosphates. The products from the molecular precursor [N₃P₃(OC₆H₅)₅OC₅H₄N·Cp₂VCl][PF₆], and of the mixtures Cp₂VCl₂/N₃P₃(OC₆H₄CHO)₆ and Cp₂VCl₂/[NP(O₂C₁₂H₈)]₃ in several relationships 1:1, 1:3, 1:5 and 1:10, pyrolyzed under air and at 400 °C and 600 °C, give mixtures mainly V₂O₅ and VO(PO₃)₂. Varied morphologies depending on the molecular or mixture precursors and of the temperature used were observed. Nanowires with diameters of approximate 40 nm were observed for the 1:5 Cp₂VCl₂/[NP(O₂C₁₂H₈)]₃ mixture pyrolyzed at 400 °C, while the same mixture pyrolyzed at 600 °C, affords xerogels of V₂O₅. The products were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), infra-red (IR) spectroscopy and X-ray diffraction (XRD). The preparation method constitutes a novel one-pot solid-state way to nanostructured materials with potential applications both in oxidative dehydrogenation of light hydrocarbons with V₂O₅, as well as alkenes oxidations with VO(PO₃)₂.     

The effect of tin precursors on the formation of Zr<Subscript>0.8</Subscript>Sn<Subscript>0.2</Subscript>TiO<Subscript>4</Subscript> nano-powder by sol gel process

Different precursors can have different effects upon the properties of materials. In this paper, two different tin precursors, i.e., tin (IV) chloride pentahydrate (SnCl₄·5H₂O) and tin (IV) t-butoxide (Sn(OC₄H₉)₄) have been used to prepare Zr_0.8Sn_0.2TiO₄ powders. The dry gel and powder were characterized by Simultaneous DTA/TGA analysis (SDT), X-ray diffraction (XRD), Scanning electron microscopy (SEM), and Accelerated surface area and porosimetry analyzer (ASAP). The results show less weight loss for dry gel from precursor SnCl₄·5H₂O than that of Sn(OC₄H₉)₄. The onset of polycrystalline ZST nano powders occurred at 450 °C from precursor SnCl₄·5H₂O which is 50 °C lower than that of Sn(OC₄H₉)₄. Even though the powders from SnCl₄·5H₂O had a specific surface area of 30.4 m²/g which is higher than that of 28.7 m²/g from Sn(OC₄H₉)₄. The crystallite size of ZST powders were about the same around 15 nm. This may be due to the powders are more aggregated in Sn(OC₄H₉)₄ system. Two major mechanisms are proposed for above differences in morphology and the formation of powders.     

Synthesis,structural characterization and thermal analysis of the cobalt(II) oxalate obtained through the reaction of 1,2-ethanediol with Co(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O

The homopolynuclear coordination compound [CoL · 2.5H₂O]_n with L=C₂O₄ ²⁻ was synthesized by a new unconventional method. It consist in the redox reaction between 1,2-ethanediol and cobalt nitrate in presence of nitric acid. The coordination compound was characterized by chemical analysis, electronic and vibrational spectra respectively, thermal analysis. In the coordination compound the Co(II) ion exists in a high spin octahedral configuration and oxalate anion acts as double-bridge ligand, tetradentate, similar as in CoC₂O₄ · 2H₂O obtained by the classical method. Nonstoichiometric oxide, Co₃O_4+0.25 with deficit in cobalt and normal spinel Co₃O₄ where identified as thermal decomposition intermediates. As final product of decomposition, the oxide CoO was obtained.     

Phase formation in the ZrO(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-H<Subscript>3</Subscript>PO<Subscript>4</Subscript>-CsF-H<Subscript>2</Subscript>O system at low concentration of the phosphorus-containing component

The ZrO(NO₃)₂-H₃PO₄-CsF-H₂O system was studied at 20°C along the section at a molar ratio of PO₄³⁻/Zr = 0.5 (which is of the greatest interest in the context of phase formation) at ZrO₂ concentrations in the initial solutions of 2–14 wt % and molar ratios of CsF: Zr = 1−6. The following compounds were isolated for the first time: crystalline fluorophosphates CsZrF₂PO₄ · H₂O, amorphous oxofluorophosphate Cs₂Zr₃O₂F₄(PO₄)₂ · 3H₂O, and amorphous oxofluorophosphate nitrate CsZr₃O_1.25F₄(PO₄)₂(NO₃)_0.5 · 4.5H₂O. The compound Cs₃Zr₃O_1.5F₆(PO₄)₂ · 3H₂O was also isolated, which forms in a crystalline or glassy form, depending on conditions. The formation of the following new compounds was established: Cs₂Zr₃O_1.5F₅(PO₄)₂ · 2H₂O, Cs₂Zr₃F₂(PO₄)₄ · 4.5H₂O, and Zr₃O₄(PO₄)_1.33 · 6H₂O, which crystallize only in a mixture with known phases. All the compounds were studied by X-ray powder diffraction, crystal-optical, thermal, and IR spectroscopic analyses.     

Effect of cerium dioxide on the properties of monolithic CuO-ZnO-CeO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/cordierite catalysts in methanol decomposition

Cerium dioxide as a component of CuO-ZnO-CeO₂/Al₂O₃/cordierite catalysts stabilizes their action in the decomposition of methanol by preventing carbon deposition on the surface and facilitating hydrogen formation with selectivity and yield in the range 85–96%. The optimal indices for this reaction are obtained for a CeO₂-CuO/Al₂O₃/cordierite sample prepared using an ammonium precursor for cerium, (NH₄)₂Ce(NO₃)₆. This catalyst displays enhanced reductive capacity relative to the analogous CeO₂-CuO composition prepared using Ce(NO₃)₃·6H₂O.     

Synthesis and characterization of Co<Subscript>0.8</Subscript>Zn<Subscript>0.2</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles

Cobalt zinc ferrite, Co_0.8Zn_0.2Fe₂O₄, nanoparticles have been synthesized via autocatalytic decomposition of the precursor, cobalt zinc ferrous fumarato hydrazinate. The X-ray powder diffraction of the ‘as prepared’ oxide confirms the formation of single phase nanocrystalline cobalt zinc ferrite nanoparticles. The thermal decomposition of the precursor has been studied by isothermal, thermogravimetric and differential thermal analysis. The precursor has also been characterized by FTIR, and chemical analysis and its chemical composition has been determined as Co_0.8Zn_0.2Fe₂(C₄H₂O₄)₃·6N₂H_4. The Curie temperature of the ‘as-prepared oxide’ was determined by AC susceptibility measurements.     

Cobalt(II) and nickel(II) complexes of isoquinoline‐1‐carboxylate

trans‐Di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ²N,O)­cobalt(II) dihydrate, [Co(C₁₀H₆NO₂)₂(H₂O)₂]·2H₂O, and trans‐di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ²N,O)­nickel(II) dihydrate, [Ni(C₁₀H₆NO₂)₂(H₂O)₂]·2H₂O, contain the same isoquinoline ligand, with both metal atoms residing on a centre of symmetry and having the same distorted octahedral coordination. In the former complex, the Co—O(water) bond length in the axial direction is 2.167 (2) Å, which is longer than the Co—O(carboxylate) and Co—N bond lengths in the equatorial plane [2.055 (2) and 2.096 (2) Å, respectively]. In the latter complex, the corresponding bond lengths for Ni—O(water), Ni—O(carboxylate) and Ni—N are 2.127 (2), 2.036 (2) and 2.039 (3) Å, respectively. Both crystals are stabilized by similar stacking interactions of the ligand, and also by hydrogen bonds between the hydrate and coordinated water molecules.