CuO-CeO2 binary oxide nanoplates: Synthesis, characterization, and catalytic performance for benzene oxidation

This work reports the first synthesis of CuO-CeO₂ binary oxides with a plate-like morphology by a solvothermal method. The as-prepared CuO-CeO₂ nanoplates calcined at 400 °C were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectrum, and tested for catalytic oxidation of dilute benzene in air. Various structural characterizations showed that large amounts of copper species were exposed on the CuO-CeO₂ nanoplate surface. The effect of the synthesis conditions on the structure of the product, as well as the growth process of the nanoplates, has been studied and discussed. The CuO-CeO₂ nanoplates exhibited an excellent catalytic activity for benzene oxidation despite its relatively low surface area and could catalyze the complete oxidation of benzene at a temperature as low as 240 °C.     

Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO₃H-MCM-41-NH₂. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state ¹³C CP/MAS NMR and solid-state ²⁹Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO₃H-MCM-41-NH₂) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.     

Control over the morphology and structure of manganese oxide by tuning reaction conditions and catalytic performance for formaldehyde oxidation

Flower-like manganese oxide nanospheres as assembled by layered MnO₂ sheets have been successfully fabricated via a facile route using a hydrothermal treatment at 120 °C for 12 h. XRD, FE-SEM, TEM and BET were used to investigate the crystalline structure, morphology, specific surface area, and porosity of the products. The products have a BET surface area of ca. 94.6 m²/g. Effects of preparation conditions including hydrothermal temperature, reaction time, pH value and kinds of anion were investigated on the morphology, structure and crystalline phase. It was found that control over the morphology and structure of product can be achieved by tuning reaction conditions. On the basis of experimental results, the formation mechanism of the products was investigated and discussed. The manganese oxide nanomaterials showed high catalytic activities for oxidative decomposition of formaldehyde. The crystallographic structure of the products had great influence on the catalytic performance in formaldehyde oxidation. Thereinto, the catalytic activity of the cryptomelane-type MnO₂ was higher than other crystalline manganese oxides below 120 °C.     

Catalytic behavior of AMoOx (A = Ba, Sr) in oxidation of 2-propanol

Perovskite-type oxides, BaMoO₃ and SrMoO₃, were prepared by reduction of scheelite-type oxides, BaMoO₄ and SrMoO₄, in H₂ flow at 873 K and characterized by XRD, TG, SEM, TPR, NH₃-TPD, UV-vis DRS and BET measurement. The catalytic activity of these alkaline-earth molybdenum oxide catalysts was tested for oxidation of 2-propanol with gaseous oxygen under atmospheric pressure. Dehydration to propylene was mainly promoted over the scheelite-type with Mo⁶⁺, while oxidative dehydrogenation to acetone was mainly promoted over the perovskite-type with Mo⁴⁺, and selectivity to acetone was much higher over BaMoO₃ than over SrMoO₃. Both perovskite-type oxide catalysts underwent oxidation to some degree during the catalytic reaction, so that they also contained some Mo⁶⁺. We concluded that the high selectivity to acetone resulting from oxidative dehydrogenation during 2-propanol conversion is related to the constantly changing oxidation state of the catalyst, resulting in coexistence of Mo⁶⁺ octahedra and Mo⁴⁺ octahedra on the AMoO₃ oxides.     

TiO2 supported on rod-like mesoporous silica SBA-15: Preparation, characterization and photocatalytic behaviour

TiO₂ nanoparticles have been successfully incorporated in the pores of mesoporous silica SBA-15 with different morphologies by a wet impregnation method. The composites were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) emission spectroscopy, transmission electron microscopy (TEM), N₂-sorption and UV-Vis diffuse reflectance spectroscopy. The photodegradation of methyl orange (MO) was used to study their photocatalytic property. It is indicated that the morphology of SBA-15 had a great influence on the photocatalytic activity of the composites. When TiO₂/SBA-15 composite was prepared by loading TiO₂ nanoparticles on uniform rod-like SBA-15 of 1 μm length, it showed higher photocatalytic degradation rate than that on less regular but much larger SBA-15 support. This difference was rationalized in terms of the homogeneously distributed and shorter channels of rod-like SBA-15, which favored mass transport and improved the efficient utilization of the pore surface.     

FTIR study of the photocatalytic degradation of gaseous benzene over UV-irradiated TiO2 nanoballs synthesized by hydrothermal treatment in alkaline solution

In this study, photocatalysts of TiO₂ nanoballs were obtained via a hydrothermal treating of commercial P25 in alkaline solution, and then characterized with SEM, XRD, BET and surface photovoltage spectroscopy techniques. The UV-assisted photodegradation of gaseous benzene over P25 and the prepared TiO₂ nanoballs was monitored by an in situ infrared technique. The results demonstrated that the prepared TiO₂ nanoballs in anatase form were more active than commercial P25 in photocatalytic oxidation of gaseous benzene. The promoted activity of the hydrothermal-treated TiO₂ is attributed to the increasing specific surface area and larger band gap induced by the reduced crystallite size. The spectra of FTIR indicated that weakly adsorbed phenol was formed as the reaction progress. Hydroxyl groups on the surface of TiO₂ nanoballs are able to react with photo-produced phenol, which is then retained on the catalyst surface leading to the progressive deactivation of the catalyst in the gas-solid system.     

Co-electrospinning fabrication and photocatalytic performance of TiO2/SiO2 core/sheath nanofibers with tunable sheath thickness

In this paper, core/sheath TiO₂/SiO₂ nanofibers with tunable sheath thickness were directly fabricated via a facile co-electrospinning technique with subsequent calcination at 500 °C. The morphologies and structures of core/sheath TiO₂/SiO₂ nanofibers were characterized by TGA, FESEM, TEM, FTIR, XPS and BET. It was found that the 1D core/sheath nanofibers are made up of anatase–rutile TiO₂ core and amorphous SiO₂ sheath. The influences of SiO₂ sheath and its thickness on the photoreactivity were evaluated by observing photo-degradation of methylene blue aqueous solution under the irradiation of UV light. Compared with pure TiO₂ nanofibers, the core/sheath TiO₂/SiO₂ nanofibers performed a better catalytic performance. That was attributed to not only efficient separation of hole–electron pairs resulting from the formation of heterojunction but also larger surface area and surface silanol group which will be useful to provide higher capacity for oxygen adsorption to generate more hydroxyl radicals. And the optimized core/sheath TiO₂/SiO₂ nanofibers with a sheath thickness of 37 nm exhibited the best photocatalytic performance.     

Preparation of Fe-doped TiO2 nanotube arrays and their photocatalytic activities under visible light

Fe-doped TiO₂ nanotube arrays have been prepared by the template-based liquid phase deposition method. Their morphologies, structures and optical properties were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and UV-vis absorption spectroscopy. Their photocatalytic activities were evaluated by the degradation of methylene blue under visible light. The UV-vis absorption spectra of the Fe-doped TiO₂ nanotube arrays showed a red shift and an enhancement of the absorption in the visible region compared to the undoped sample. The Fe-doped TiO₂ nanotube arrays exhibited good photocatalytic activities under visible light irradiation, and the optimum dopant amount was found to be 5.9 at% in our experiments.     

Factors affecting CO oxidation over nanosized Fe2O3

Nanocrystallite iron oxide powders with different crystallite sizes were prepared by co-precipitation route. The prepared powders with crystallite size 75, 100 and 150 nm together with commercial iron oxide (250 nm) were tested for the catalytic oxidation of CO to CO₂. The influence of different factors as crystallite size, catalytic temperature and weight of catalyst on the rate of catalytic reaction was investigated using advanced quadrupole mass gas analyzer system. It can be reported that the rate of conversion of CO to CO₂ increased by increasing catalytic temperature and decreasing crystallite size of the prepared powders. The experimental results show that nanocrystallite iron oxide powders with crystallite size 75 nm can be recommended as a promising catalyst for CO oxidation at 500 °C where 98% of CO is converted to CO₂. The mechanism of the catalytic oxidation reaction was investigated by comparing the CO catalytic oxidation data in the absence and presence of oxygen. The reaction which was found to be first order with respect to CO is probably proceeded by adsorption mechanism where the reactants are adsorbed on the surface of the catalyst with breaking OO bonds, then CO pick up the dissociated O atom forming CO₂.     

Sonochemical preparation of bimetallic Co/Cu nanoparticles in aqueous solution

Co/Cu bimetallic nanocrystallites, with average diameter of 50 nm, were prepared by a sonochemical method in the hydrazine solution of copper chloride and cobalt chloride. Cobalt was face-centered cubic phase when synthesized and remained fcc phase throughout the annealing process. X-ray diffractometer (XRD), transmission electron microscope (TEM), differential scanning calorimetry (DSC), vibrating sample magnetometry (VSM), inductively coupled plasma-atomic emission spectrometer (ICP-AES) measurements were carried out to investigate their structural and magnetic properties. It was found that the magnetic properties of bimetallic nanocrystallites were close to that of the sputtered alloys.     

Ligand-assisted hydrothermal synthesis of ZnWO4 rods and their photocatalytic activities

ZnWO₄ rods were prepared using a ligand-assisted hydrothermal method with ZnCl₂ and Na₂WO₄ in the presence of various amines as ligands for zinc ions. The choice of ligand was found to play an important role in the formation of ZnWO₄ rods. The aspect ratio of the ZnWO₄ rods increased with increasing ligand strength. XRD and HRTEM confirmed that the ZnWO₄ rods grow along the [1 0 0] direction. The photochemical activities of the ZnWO₄ rods for the decomposition of Rhodamine 6G were examined. The photocatalytic activity was found to depend on the aspect ratio of the ZnWO₄ rods.     

Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

The CaFe₂O₄ spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 °C which was lower than that of ferrite prepared by other methods. CaFe₂O₄ catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H₂O₂ (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H₂O₂ molar ratio and solvents on the conversion and product distribution were studied.     

Porous manganese oxide synthesized through organic-electrolyte templates and their catalytic applications

We report a facile approach to the preparation of porous manganese oxide materials by the organic-electrolyte templates based on strategy. The final products are thoroughly characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field-emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and Brunauer–Emmett–Teller (BET) techniques. The results reveal that porosity (pore size and distribution, surface area) of these manganese oxides has strong relationship with the templates used, which implies a simple way to obtain a series of porous materials. By comparing the catalytic effects of these manganese oxides in oxidation of indene and benzyl alcohol, we find that the pore size and distribution are also crucial to the catalytic properties of these porous materials.     

Preparation, characterization, and electrochemical application of mesoporous copper oxide

Mesoporous CuO was successfully synthesized via thermal decomposition of CuC₂O₄ precursors. These products had ring-like morphology, which was made up of nanoparticles with the average diameter of 40 nm. The electrochemical experiments showed that the mesoporous CuO decreased the overvoltage of the electrode and increased electron transference in the measurement of dopamine.     

A novel route to the synthesis of nanosized metallic molybdenum at moderate temperature and its catalytic properties

Nanosized metallic molybdenum could be synthesized from MoO₃ and KBH₄ by solid-state reaction at moderate temperature. The crystallinity, morphology, surface properties of as-synthesized metallic molybdenum were investigated by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectral (XPS). The results of its catalytic activity test show that the as-synthesized nanosized metallic molybdenum is superior to the noble metal catalyst 0.3% Pd/Al₂O₃ for the selective hydrogenation of alkadienes at higher temperature and pressure.     

Visible-light-driven NaTaO3−xNx catalyst prepared by a hydrothermal process

NaTaO_3−xN_x catalyst has been successfully synthesized from N-doped Ta₂O₅ precursors by a simple hydrothermal process. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and diffuse reflectance spectroscopy. Density functional theory calculations suggested that the valence band of the catalysts was composed of the hybrid O 2p and N 2p orbitals, and the visible-light sensitivity is due to the narrowing of the band gap by mixing N 2p and O 2p states. NaTaO_3−xN_x catalyst could decompose the gaseous formaldehyde under the visible-light irradiation (λ > 400 nm), and its photocatalytic activity depended on N dopant concentration. NaTaO_2.943N_0.047 showed the highest photoactivity for the formaldehyde photodegradation.     

Microwave irradiation assisted rapid synthesis of Fe-Ru bimetallic nanoparticles and their catalytic properties in water-gas shift reaction

Fe-Ru bimetallic nanoparticles were prepared by a microwave irradiation assisted glycol reduction method using poly-N-vinyl-2-pyrrolidone (PVP) as protective agent. The structure and morphology of the nanoparticles were characterized by X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDXA) and high-resolution transmission electron microscopy (HRTEM). EDXA and XRD analysis confirmed the presence of Fe and Ru. The bimetallic nanoparticles were subsequently loaded onto an MgAl₂O₄ supporter with K₂O as promoters and used as catalyst for water-gas shift reaction. The results indicated that the FeRu bimetallic nanoparticles exhibit high catalytic activity for water-gas shift reaction due to the synergistic effect between iron and ruthenium. Potassium oxide can enhance the CO selectivity of the catalyst significantly besides increasing the catalyst activity.     

Pd-porphyrin functionalized ionic liquid-modified mesoporous SBA-15: An efficient and recyclable catalyst for solvent-free Heck reaction

The Pd-porphyrin functionalized ionic liquid could be covalently anchored in the channels of mesoporous SBA-15 through ion-pair electrostatic interaction between imidazolium-cationic and Pd-porphyrin-anionic moieties. Such modified SBA-15 materials were prepared successfully via a post-synthesis (surface sol-gel polymerization) or a one-pot sol-gel procedure, which were characterized by powder X-ray diffraction, UV-visible spectroscopy, Fourier transform infrared spectroscopy, N₂ sorption, elemental analysis, and transmission electron microscopy. The modified SBA-15 materials are efficient and recyclable catalysts for cross-coupling of aryl iodides or activated aryl bromides with ethyl acrylate without activity loss and Pd leaching even after 9 runs.     

Synthesis of perovskite-type (La1−xCax)FeO3 (0 ≤ x ≤ 0.2) at low temperature

Gel formation was realized by adding citric acid to a solution of La(NO₃)₃·5H₂O, Ca(NO₃)₂·4H₂O, and Fe(NO₃)₂·9H₂O. Perovskite-type (La_1−xCa_x)FeO₃ (0 ≤ x ≤ 0.2) was synthesized by firing the gel at 500 °C in air for 1 h. The crystallite size (D_1 2 1) decreased with increasing x, while the specific surface area was 6.8-9.4 m²/g and independent of x. The XPS measurement of the (La_1−xCa_x)FeO₃ surface indicated that the Ca²⁺ ion content increased with increasing x, while the Fe ion content was independent of x. Catalytic activity for CO oxidation increased with increasing x.     

Hybrid catalyst containing nano-sized LaMnO3 and carbon black for high yield and selective ketonization of n-butanol

An attempt has been made to synthesize a two-component hybrid material for highly selective catalytic ketonization of n-butanol. The perovskite-type oxide nano-crystallites were synthesized in the presence of carbon black particles by thermal transformation of equimolar mixture of lanthanum and manganese hydroxides into the perovskite-type oxide. The two-component material was tested as a catalyst for unconventional conversion of n-butanol to heptanone-4. The catalyst exhibited very high selectivity and yield towards the products, despite low content of LaMnO₃ in the two-component material (less than 10% by weight). The low oxide content led to the reduction of the cost of catalyst fabrication and is compensated by its high dispersion (grains ca. 20-30 nm in diameter) providing high conversion and yield comparable to pure-oxide catalysts. Catalyst fabrication is simple and environment friendly since it does not require organic solvents and excess amount of heavy metals (La and Mn).