Cu (II)‐β‐cyclodextrin complex stabilized on magnetic nanoparticles: A retrievable hybrid promoter for green synthesis of spiropyrans

The magnetic core of manganese ferrite (MnFe₂O₄) nanoparticles has a significant stability in comparison with ferrite (Fe₃O₄) nanoparticles. The unique supramolecular properties of β‐cyclodextrin (β‐CD), such as hydrophobic cavity, hydrophilic exterior and ‐OH functional groups, make it a good candidate for functionalization and catalytic application. So, a surface‐modified magnetic solid support with the Cu (II)‐β‐CD complex was prepared. The structure of nanoparticles was characterized by Fourier transform‐infrared spectroscopy, X‐ray powder diffraction, thermogravimetric analysis, vibrating‐sample magnetometry, inductively coupled plasma‐optical emission spectrometry and scanning electron microscope analyses. The catalytic activity of these nanoparticles was investigated in the synthesis of spiropyrans and high yields of desired products obtained under green media. Some advantages of this novel catalyst for this reaction are high yields, short reaction times, green solvent and conditions, easy workup procedure, negligible copper leaching, reusability without a significant diminish in catalytic efficiency, and simple separation of nanocatalyst by using an external magnet alongside the environmental compatibility and sustainability.     

Synthesis of multielement ferrites and their silica composites

Ferrites of composition M_0.2Co_0.4Zn_0.4Fe₂O₄ with M = Cu²⁺, Mn²⁺ and Ni²⁺ were prepared by citrate complex method. Later, their composites with silica have also been obtained by a simple route. The citrate complex precursors of multielement ferrites were characterized by FTIR spectroscopy and thermal analysis, been found a similar behavior for the three systems. The thermal treatment (at 400, 600 and 800 °C) of precursors gives, as result, the spinel type cubic ferrite pure when the ions substituted were copper and nickel; when manganese was used an hematite phase was obtained as contaminant at 800 °C. The presence of all ions involved and the particle size was corroborated by EDX analysis and measured from a TEM micrograph, respectively. The magnetic parameters related to magnetic properties, magnetization and coercivity, were different depending of the chemical composition of the ferrite and the thermal treatment temperature, as it was expected. At room temperature, the values obtained were near to those reported for Co-ferrite in bulk. The synthesis route of the composites M_0.2Co_0.4Zn_0.4Fe₂O₄-SiO₂, proposed in this work, gives as result magnetic nanoparticles in an amorphous silica matrix. Their magnetic properties were depending on weight percentage of the magnetic phase in the composite.     

Effect of preparation conditions on the formation of the active phase of carbon fiber catalytic systems for the low-temperature oxidation of carbon monoxide

We studied the effects of the composition of impregnating solution and heat treatment conditions on the activity of catalytic systems for the low-temperature oxidation of CO obtained by the impregnation of Busofit carbon-fiber cloth with aqueous solutions of palladium, copper, and iron salts. The formation of an active phase in the synthesized catalysts at different stages of their preparation was examined with the use of differential thermal and thermogravimetric analyses, X-ray diffraction analysis, X-ray photoelectron spectroscopy, and elemental spectral analysis. The catalytic system prepared by the impregnation of electrochemically treated Busofit with the solutions of PdCl₂, FeCl₃, CuBr₂, and Cu(NO₃)₂ and activated under optimum conditions ensured 100% CO conversion under a respiratory regime at both low (0.03%) and high (0.5%) carbon monoxide contents of air. It was found that the activation of a catalytic system at elevated temperatures (170–180°C) leads to the conversion of Pd(II) into Pd(I), which was predominantly localized in a near-surface layer. The promoting action of copper nitrate consists in the formation of a crystalline phase of the rhombic atacamite Cu₂Cl(OH)₃. The catalyst surface is finally formed under the conditions of a catalytic reaction, when a joint Pd(I)-Cu(I) active site is formed.     

Spark plasma sintering synthesis of Ni1−xZnxFe2O4 ferrites: Mössbauer and catalytic study

Nickel-zinc ferrite nanoparticles, Ni_1−xZn_xFe₂O₄ (x = 0, 0.2, 0.5, 0.8, 1.0) were prepared by combination of chemical precipitation and spark plasma sintering (SPS) techniques and conventional thermal treatment of the obtained precursors. The phase composition and structural properties of the obtained materials were investigated by X-ray diffraction and Mössbauer spectroscopy and their catalytic activity in methanol decomposition was tested. A strong effect of reaction medium leading to the transformation of ferrites to a complex mixture of different iron containing phases was detected. A tendency of formation of Fe-carbide was found for the samples synthesized by SPS, while predominantly iron-nickel alloys ware registered in TS obtained samples. The catalytic activity and selectivity in methanol decomposition to CO and methane depended on the current phase composition of the obtained ferrites, which was formed by the influence of the reaction medium.     

Thermal stability and flammability of polyurethane foams chemically reinforced with POSS

Manganese ferrite nanopowder was prepared by a new solvothermal method, using 1,2 propanediol as solvent and KOH as precipitant. The as-synthesized powder, by solvothermal treatment in autoclave at 195 °C, for 12 h, consisted of fine manganese ferrite nanoparticles. The further thermal treatment of the initial manganese ferrite powder to higher temperature resulted in manganese ferrite decomposition due to Mn(II) oxidation to Mn(III), as observed by X-ray diffraction. FT-IR spectroscopy has evidenced that the oxidation takes place even at 400 °C. The oxidation of Mn(II) to Mn(III) was studied by TG/DSC simultaneous thermal analysis. It was shown that Mn(II) oxidation takes place in a very small extent up to 400 °C. The main oxidation step occurs around 600 °C, when a clear mass gain is registered on TG curve, associated with a sharp exothermic effect on DSC curve. The exothermic effect is smaller in case of the powder annealed at 400 °C, confirming the superficial oxidation of Mn(II) up to 400 °C. In order to avoid Mn(II) oxidation, the powder obtained at 400 °C was further annealed at 800 °C in argon atmosphere, without degassing, when manganese ferrite MnFe₂O₄ was obtained as major crystalline phase (69 %). All manganese ferrite powders showed a superparamagnetic behavior, with maximum magnetization of 51 emu g^?1 in case of the as-synthesized powder, characteristic of magnetic ferrite nanopowders.     

Fe2O3-Li2O Catalysts for Ammonia Oxidation

The catalytic properties of the Fe₂O₃-Li₂O system in ammonia oxidation were studied in the high-temperature region. The influence of the phase composition of the system on the physicochemical, catalyticproperties of the catalysts were revealed. The catalytic properties of lithium ferrite, which is the most activeand selective component of the Fe₂O₃-Li₂O system, were studied. The mechanism of lithium ferrite deactivation at 1273 K is considered.     

Ethanol dehydrogenation on copper catalysts with ytterbium stabilized tetragonal ZrO<Subscript>2</Subscript> support

The physicochemical and catalytic properties of Cu-containing crystalline zirconia, obtained via sol–gel synthesis in the presence of Yb³⁺ ions and polyvinylpyrrolidone, are studied. DTG/DSC, TEM, XRD and BET methods are used to analyze the crystallization, texture, phase uniformity, surface and porosity of ZrO₂ nanopowders. It is shown that increasing the copper content (1, 3, and 5 wt % from ZrO₂) raises the dehydrogenation activity in the temperature range of 100–400°C and lowers the activation energy of acetaldehyde formation. It is found that the activity of all Cu/t-ZrO₂ catalysts grows under the effects of the reaction medium, due to the migration and redispersion of copper.     

Mechanism of oxygen releasing of copper ferrite in the formation of the corresponding oxygen-deficient compound

Copper ferrite is a promising material for hydrogen production through thermochemical water splitting. In this work, the cation distribution of copper ferrite and the corresponding oxygen-deficient compound of spinel structure was analyzed based on the crystal structural chemistry theory. The mechanism of oxygen releasing of CuO, Fe₂O₃, CuFe₂O₄ and metal (M=Ni, Mn or Zn) doped copper ferrite in the process of temperature rising was investigated by differential thermal analysis-thermogravimetry (DTA-TG). By combining the theoretical analysis with experimental results, the mechanism of oxygen releasing of copper ferrite is proposed, which is different from that of other ferrites. For copper ferrite, the oxygen releasing caused by Cu(II)→Cu(I) plays a predominant role, while for other ferrites, the oxygen releasing resulting from Fe(III)·Fe(II) is dominant. Supported by the National Defense Fundamental Research Fund (Grant No. A1420080145)     

Evaluation of the catalytic effect of ZnO as a secondary phase in the Ni0.5Zn0.5Fe2O4 system and of the stirring mechanism on biodiesel production reaction

In search of efficient ways to produce biodiesel under environmentally friendly conditions, catalytic reactions have been explored with emphasis on replacing homogeneous by heterogeneous catalysis with the use of new catalyst types, such as the spinel ferrites, which are described as a viable option, since they are stable, highly active, inexpensive, reusable, and allow the easy recovery of the reaction medium through the application of magnetic fields. In this context, the present work proposes to contribute to the consolidation of the catalytic viability of the Ni_0.5Zn_0.5Fe₂O₄ system obtained by combustion reaction, because although previous studies indicate the catalytic effectiveness of this system in polyphasic form, the present work seeks as differential to evaluate the influence of the secondary phases and magnetization of the Ni-Zn system in the conversion to biodiesel, and for this purpose, it aims to evaluate the catalytic effect of ZnO formed as secondary phase and obtained concomitantly in the Ni-Zn ferrite synthesis, besides evaluating the effect of the stirring mechanism used in biodiesel production reaction by the ethyl transesterification of soybean oil. The synthesized Ni-Zn ferrites and ZnO sample were characterized by X-ray diffraction (XRD), nitrogen adsorption textural analysis (BET), particle size distribution, and then, tested in two reactor types, one with magnetic stirring, and another of mechanical stirring, to observe the magnetization effect of the material, and the characterization of the obtained biodiesels by gas chromatography (GC) and acidity index. The performed catalytic tests showed that the Ni-Zn ferrites promoted excellent ester conversions with values near and above 94%, thus confirming that although ZnO also promotes good ester conversion (83.9%), the catalytic effectiveness of the Ni-Zn ferrite is evident and independent of secondary phases. Moreover, the catalytic tests performed in the magnetic stirring reactor using the Ni-Zn ferrites as catalysts made it possible to realize that their magnetic properties may be interference in the catalytic effectiveness, being this, a more determining factor than the surface characteristics.     

Preparation of Mixed Co and Cu Oxides via Thermal Decomposition of Their Oxalates,and Study of Their Catalytic Properties

Mixed oxides were prepared by the thermal decomposition of the oxalates of cobalt(II) and copper(II) coprecipitated from aqueous solution or made by mechanical mixing. The compositions and structures of the oxides were confirmed by means of TG and X-ray powder diffraction spectroscopy. The catalytic behaviour of the oxides obtained was studied by using the decomposition of H₂O₂ as a model reaction. The results were compared with those on the oxides produced from the thermal decomposition of mechanically mixed oxalates. The catalytic activities of the mixed oxides were found to be lower than that of pure cobalt oxide, but higher than that of copper oxide. This result was interpreted in terms of the relative standard reduction potential of the catalyst as compared with that of H₂O₂. The catalytic activity of the mixed oxides obtained from the coprecipitate was found to be lower than that of the oxides obtained from the mechanical mixture at the same temperature. As the temperature of preparation was increased, the catalytic activities of the oxides obtained decreased. This was attributed to the solid-solid interactions, which gave a new phase with lower catalytic activity than those of the interacting phases. This revised version was published online in July 2006 with corrections to the Cover Date.     

A comparative study on the activity of metal exchanged MCM22 zeolite in the selective catalytic reduction of NOx

A series of MCM22 zeolites exchanged with copper and cobalt are studied for the selective catalytic reduction (SCR) of NO with C₃H₈ and the behavior compared with that of Cu and Co-beta and ZMS5 zeolites. The results show that Co and Cu-MCM22 samples are stable SCR catalysts. These zeolites give the maximum activity at 450°C. Their behavior towards oxygen content in the reactant phase and exchange level of the metal in the catalyst, is qualitatively similar to that of metal exchanged beta and ZSM5 zeolite, but the yields obtained with this zeolite are lower in any case. The infrared studies of adsorbed NO show, contrary to what is occurring in ZSM5 in which only Cu⁺ sites are observed at low NO partial pressure, that in this condition, Cu⁺ and Cu²⁺ species are formed on MCM22. The results indicate that in MCM22, the copper located in the 10 member ring (MR) circular channels behaves similarly to that present in ZSM5, while the Cu present in the 12 MR cavities has a strong tendency to agglomerate forming non active CuO clusters.     

Catalytic Properties of the Fe2O3–MnO System for Ammonia Oxidation

The effect of the chemical and phase composition of the Fe₂O₃–MnO catalytic system for ammonia oxidation on its activity and selectivity to NO at 873–1273 K is demonstrated. The optimal parameters of the process over manganese ferrite, the most active and highly selective component of the system, are determined. The combination of the factors of chemical and phase transformations of the catalyst results in the formation of an inactive component (Fe₃O₄) and in the structural changes (recrystallization and cationic redistribution of spinel) and is the reason for the deactivation of manganese ferrite at 1273 K.     

Low-temperature synthesis and characterization of the Mn–Zn ferrite

Nanocrystalline ferrite with the composition: Mn_0.6Zn_0.4Fe₂O₄ was synthesized by two-stage route: the precipitation of Zn, Mn and Fe hydroxides from sulphates solution and the synthesis of a precursor by the sol–gel auto-combustion method. The ferrite powder obtained from the gel by ashing was sintered under air at a temperature of 720, 1150 and 1300 °C. The composition and morphology of the as-obtained phases were examined by ICP-AES, TG/DTA, XRD, FTIR, SEM and low-temperature nitrogen adsorption (BET). It was found that the spinel phase forms after gel combustion. The nanometric ferrite powder obtained as a result of the combustion is soft-agglomerated. The zinc content in the ferrite during ashing and auto-combustion is lower by about 21 mol% than the assumed one and the final product turn out to be Mn_0.68Zn_0.32Fe₂O₄.     

Reductive amination of cyclohexanol/cyclohexanone to cyclohexylamine using SBA-15 supported copper catalysts

Amination of cyclohexanol was investigated in vapour phase over copper catalysts supported on mesoporous SBA-15. The different products identified during reductive amination of cyclohexanol reaction were cyclohexanone, cyclohexylamine, along with small amounts of N-Cyclohexylidinecyclohexylamine and dicyclohexylamine. Among several catalysts tested for the reductive amination, 5% Cu supported on SBA-15 exhibited better catalytic performance than other catalysts with 36% selectivity towards cylclohexylamine at 80% cyclohexanol conversion. The optimum reaction conditions employed to achieve the best catalyst performance were at 250 °C, 0.1 MPa of H₂/NH₃, TOS-10h. The active Cu sites, acidity of the catalyst, and effect of reaction parameters play a pivotal role in the reductive amination reaction. The prepared catalysts were characterized by XRD, BET, SEM, H₂-TPR and NH₃-TPD. The dispersion of Cu, particle size, and metal surface area (m²/g) calculated from pulse N₂O decomposition method. TPR findings reveal the presence of substantially dispersed copper oxide species at lower loadings which is easily reducible than the bulk copper oxide species found at higher Cu loadings. The acidity measurements by NH₃-TPD analysis suggest that the maximum acidic strength was obtained at 5 wt% copper on porous SBA-15, and decreased with Cu loadings. The catalytic properties are well in agreement with the findings of catalysts characterization.     

Mechanistic features of reduction of copper chromite and state of absorbed hydrogen in the structure of reduced copper chromite

The review discusses the experimental data on the unusual mechanism of the reduction of copper cations from the copper chromite, CuCr₂O₄, structure. Treatment of copper chromite in hydrogen at 180–370°C is not accompanied by water formation but leads to absorption of hydrogen by the oxide structure with simultaneous formation of metallic copper as small flat particles which are epitaxially bound to the oxide. This process is due to the redox reaction Cu²⁺ + H₂ → Cu⁰ + 2H⁺; the protons are stabilized in the oxide phase, which is confirmed by neutron diffraction studies. The reduced copper chromite which contains absorbed hydrogen in its oxidized state and the metallic copper particles epitaxially bound to the oxide phase structure exhibit catalytic activity in hydrogenation reactions.     

Stabilization of Copper Catalysts for Liquid‐Phase Reactions by Atomic Layer Deposition

Atomic layer deposition (ALD) of an alumina overcoat can stabilize a base metal catalyst (e.g., copper) for liquid‐phase catalytic reactions (e.g., hydrogenation of biomass‐derived furfural in alcoholic solvents or water), thereby eliminating the deactivation of conventional catalysts by sintering and leaching. This method of catalyst stabilization alleviates the need to employ precious metals (e.g., platinum) in liquid‐phase catalytic processing. The alumina overcoat initially covers the catalyst surface completely. By using solid state NMR spectroscopy, X‐ray diffraction, and electron microscopy, it was shown that high temperature treatment opens porosity in the overcoat by forming crystallites of γ‐Al₂O₃. Infrared spectroscopic measurements and scanning tunneling microscopy studies of trimethylaluminum ALD on copper show that the remarkable stability imparted to the nanoparticles arises from selective armoring of under‐coordinated copper atoms on the nanoparticle surface.     

Reactivity of nanoparticles; interaction between zinc and copper oxide nanoparticles and iron ions in an alkaline medium

The reactivity of zinc and copper oxide nanoparticles was investigated upon their interaction with iron oxides. It was ascertained that, depending on the reaction conditions, nanoparticles of zinc and copper ferrites (ZnFe₂O₄ and CuFe₂O₄) or core/shell nanoparticles (Fe₃O₄/ZnO) are produced. Size, composition, and structure of the resulting nanoparticles were determined by transmission electron microscopy and X-ray diffraction analysis. The average size of zinc and copper ferrite nanoparticles was ascertained to be 9–10 and 2–3 nm, respectively. For core/shell Fe₃O₄/ZnO nanoparticles, the average size is 20 nm. It was experimentally proved that the photoluminescence radiative characteristics of ZnO nanoparticles are retained in core/shell Fe₃O₄/ZnO nanoparticles.     

Methane catalytic combustion on La-based perovskite catalysts

Two series of La-based perovskites oxides (La_1–xSr_xMO_3–y with M=Fe or Co) have been used as methane total oxidation catalysts. The best catalytic performances, in isothermal, high temperature conditions (900 °C), in the presence of water and carbon dioxide, were obtained for both series when 20 % of lanthanum cations are replaced by strontium. The catalytic behavior of the two series of catalysts is quite similar, although the cobalt-containing samples are easily reducible by H₂ or CH₄, whereas the iron-containing ones are not reduced in the same conditions. It is proposed, to explain this apparent inconsistency, that the active sites reoxidation process occurs directly from the molecular oxygen of the gas phase, without participation of the bulk oxygen species mobility.     

Cu_xCo_(1-x)/Al_2O_3/FeCrAl整体式催化剂上甲苯催化燃烧(英文)

以FeCrAl合金薄片为基底,Al2O3浆料为过渡胶体,不同摩尔比的Cu、Co为催化活性组分,制备了一系列CuxCo1-x/Al2O3/FeCrAl(x=0-1)新型整体式催化剂.采用X射线粉末衍射(XRD),扫描电子显微镜(SEM),X光电子能谱(XPS)和程序升温还原(TPR)等手段对催化剂的结构进行了表征.在微型固定床反应器上评价了催化剂的催化甲苯燃烧性能.研究结果表明:在所制备的整体式催化剂上,当Cu含量比较低时,形成了Cu-Co-O固溶体;当Cu含量比较高时,可以测得CuO的衍射峰.催化剂表面颗粒大小和形貌与Cu、Co摩尔比密切相关.在催化剂表面,Co以Co2+和Co3+价态存在,而Cu主要以Cu2+价态存在.催化剂中的Cu可以改善Co的氧化还原性,从而有利于催化剂活性的提高.在所制备的催化剂中,Cu0.5Co0.5/Al2O3/FeCrAl催化剂具有最好的活性,甲苯在374oC可以完全催化燃烧消除.     

Characterisation of nickel–zinc ferrite/silica nanocomposites with low ferrite concentration obtained by an improved modified sol–gel method

The paper presents a study regarding the structure, morphology and magnetic behaviour of x% (Ni_0.65Zn_0.35Fe₂O₄)/(100 − x)% SiO₂ ferrimagnetic nanocomposites for low Ni–Zn ferrite concentration (x = 5, 10, 15, 20 and 30 mass percent) obtained by an improved modified sol–gel method. The obtained gels and nanocomposites have been characterized by fast Fourier transform-infrared (FT-IR) spectrometry, X-ray diffraction (XRD), transmission electron microscopy (TEM) and magnetic measurements (MM). The addition of a supplementary quantity of diol in the synthesis, corresponding to a molar ratio EG : TEOS = 1:1, and the control of the thermal treatment applied to the precursor xerogels tetraethylortosilicate (TEOS)–metal nitrates (MN)–ethylene glycol (EG) leads to fine (~2–9 nm), almost spherical Ni–Zn ferrite nanoparticles homogenously dispersed inside the amorphous SiO₂ matrix. TEM images reveal the fine nature and the narrow size distribution of the ferrite nanoparticles. Nanoparticles diameter increases with the ferrite concentration and with the annealing temperature. For all concentrations of ferrite in SiO₂ and all annealing temperature, we have obtained Ni_0.65Zn_0.35Fe₂O₄ ferrite as single phase (proven by XRD) in the amorphous silica matrix, only after a pre-treatment of synthesized gels, at 573 K, for 3 h. The magnetic behaviour of ferrite nanoparticles in quasi-static magnetic fields is very particular, depending on the annealing temperature and the ferrite content in silica matrix. We have obtained superparamagnetic behaviour for the nanocomposites, for a concentration of 30% ferrite in SiO₂ at high annealing temperature, of 1,273 K.