Preparation and investigation of rare earth magnesium hexaaluminate solid solutions

Conditions of preparation, by the method of solid state reactions, of rare-earth hexaaluminates RE_1?x?yM_xM’_yMgAl₁₁O₁₉ (RE = La, Sm; M, Mt’ = Gd, Yb, Lu, Y, Sc; x, y = 0, 0.15, 0.3), were investigated. For a number of compositions, high-degree single-phase products were obtained applying multi-step heat treatments in Ar/H₂ atmosphere at 1650–1690°C. Intense (107) and (114) diffraction lines typical for the hexaaluminate phase have been observed in X-ray diffraction patterns. Studies of microstructure and of elemental composition showed that magnesium deficiency on the sample surface may reach some 20%, while composition in the bulk is more homogeneous and close to stoichiometric. Our estimations of structural homogeneity and thermal conductivity show that lanthanum hexaaluminates La_1?x?yM_xM’_yMgAl₁₁O₁₉ with pair additives Gd-Yb, Gd-Y, Y-Yb, Y-Lu, Y-Sc (x = y = 0.15) and samarium hexaaluminates Sm_1?x?yM_xM’_yMgAl₁₁O₁₉ with pair additives Gd-Yb, Y-Yb (x = y = 0.15), as well as Sm_0.7Yb_0.3MgAl₁₁O₁₉, may present interest as thermal barrier coatings.     

Prediction of optimum catalysts and cocatalysts for chemical growth of carbon nanotubes

A practically important problem of growth of different kinds of carbon nanotubes from nanodrops of a metal catalyst oversaturated by carbon is solved by finding cocatalysts that provide a minimum nucleation energy for the critical nucleus of a nanotube. For pure catalysts, it turns out that the optimum is achieved using atoms of well-known elements of the iron group, which have a minimum energy of the van-der-Waals interaction with graphene islands and a certain energy E _Me-C of the interaction with a carbon atom. It is also possible to obtain even more effective catalysts by finding an appropriate ratio of the components by the trial and error method. In particular, the experimentally found combinations nickel-yttrium and cobalt-molybdenum are among the most effective ones.     

Characterization of ZrO2-promoted Cu/ZnO/nano-Al2O3 methanol steam reforming catalysts

Three Cu/ZnO/ZrO₂/Al₂O₃ methanol reforming catalysts were investigated using X-ray photoelectron spectroscopy (XPS). The catalysts which contained ZrO₂ from a monoclinic nanoparticle ZrO₂ precursor exhibit both a higher activity toward the methanol steam reforming reaction and a lower CO production rate compared to catalysts composed of an XRD-amorphous ZrO₂ produced by impregnation using a Zr(NO₃)₂ precursor. The presence of a monoclinic phase appears to result in an increased charge transfer between the Zr and Cu species, as evidenced by a relatively electron-rich ZrO₂ phase and a partially oxidized Cu species on reduced catalysts. This electron deficient Cu species is more reactive toward the methanol reforming reaction and partially suppresses CO formation through the reverse water gas shift or methanol decomposition reactions.     

Study of selective Fischer-Tropsch catalysts synthesized by the destruction of bimetallic carbonyl complexes on activated γ-Al2O3 support

The bimetallic catalysts obtained by the deposition of a Fe?Co binuclear cluster on the dehydroxylated γ-Al₂O₃ are studied and compared to some other relative systems. These bimetallic catalysts are found to be active and selective in olefin synthesis. This is connected with the formation of Fe?Co contact which is detectable by Mössbauer spectroscopy.     

Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts

Al₂O₃-SiO₂-based Co(Ni)-Mo(W)-S catalysts are widely investigated hydrodesulfurization (HDS) catalysts in recent decades. XPS is a suitable technique to detect the surface properties of HDS catalysts. Typical overlapping spectra in the XPS analysis of HDS catalysts, such as Mo3d and S2s, Si2p and bremsstrahlung-induced Al KL₂₃L₂₃ using nonmonochromatic AlKα source, W4f and W5p_3/2, as well as the disturbance of Auger lines on Ni2p and Co2p, are carefully studied in the present paper. Besides, effective methods to overcome the influence of peak overlaps are illustrated. These results would provide basic and important information in interpreting XPS results of HDS catalysts.     

A study of propylene polymerization over bimetallic titanium–vanadium catalysts

New bimetallic catalysts based on microspherical TiCl₃ modified with vanadium trichloride to obtain its different concentrations on the TiCl₃ surface were synthesized. The presence of a VCl₃ crystalline phase in the catalyst was confirmed by X-ray analysis. The synthesized catalysts were applied to studying propylene polymerization in a liquid monomer medium. The kinetics of the polymerization process was determined, and the structure and properties of the synthesized isotactic polypropylene (IPP) were established. It was demonstrated that the PPI samples synthesized over the developed titanium–vanadium catalysts has enhanced freeze resistance as compared to IPP sample obtained over conventional titanium catalysts.     

The synthesis and regeneration of palladium catalysts with the use of supercritical carbon dioxide

The solubility of palladium chloride complexes with organic ligands in supercritical carbon dioxide (SC-CO₂) was measured. The possibility of using SC-CO₂ as a working medium for the preparation and regeneration of deposited palladium catalysts was studied. The active catalyst component was deposited from solutions of palladium chloride complexes with organic ligands in SC-CO₂. The regeneration of catalysts deactivated during the hydrogenation of acetylene in an ethane-ethylene mixture was also performed in SC-CO₂ with varying process conditions. A comparison of the specific surface areas and activities of freshly prepared and regenerated samples showed that the methods suggested were highly competitive compared with the traditional regeneration techniques.     

Alkylation of imidazole under ultrasound irradiation over alkaline carbons

N-Alkyl-imidazole has been synthesized by sonochemical irradiation of imidazole and 1-bromobutane using alkaline-promoted carbons (exchanged with the binary combinations of Na, K and Cs). The catalysts were characterized by X-ray photoelectron spectroscopy, thermal analysis and N₂ adsorption isotherms. Under the experimental conditions, N-alkyl-imidazoles can be prepared with a high activity and selectivity. It is observed that imidazole conversion increases in parallel with increasing the basicity of the catalyst. The influence of the alkaline promoter, the reaction temperature, and the amount of catalyst on the catalytic activity has been studied. For comparison, the alkylation of imidazole has also been performed in a batch reactor system under thermal activation.     

Photocatalytic activity of multielement doped TiO2 in the degradation of congo red

TiO₂ although considered a promising photocatalyst for the degradation of aqueous pollutants, it suffers from poor absorption in the visible region and hence requires ultraviolet (UV) light for activation. To make TiO₂ a visible active photocatalyst, multielement (C, N, B, and F) doping has been done. The synthesised CNBF/TiO₂ catalysts were calcined at different temperatures and characterized by XRD, BET surface area, UV DRS, XPS, HRSEM-EDAX, and TEM techniques. These catalysts found to show less band gap values when compared to bare TiO₂. These catalysts were tested for their catalytic activity towards the degradation of a textile dye - congo red (CR) under different reaction conditions. It was found that the photocatalytic activity was dependent on both doping of multielement and the calcination temperature of CNBF/TiO₂. The co-doped catalysts which were calcined at 400 °C and 600 °C (100% intensity in anatase phase) were found to be the best catalysts (100% decolourisation of CR in 21/2 h and 2 h respectively). TOC analysis carried out for the samples at the reaction time of 5 h showed very high percentage (83%) degradation of CR over CNBF/TiO₂ catalysts calcined at 600 °C when compared to the other catalysts calcined at different temperatures. CNBF/TiO₂ (1000 °C) showed very less photocatalytic activity due to the formation of rutile phase.     

Physicochemical characteristics of ZSM-5/SAPO-34 composite catalyst for MTO reaction

SAPO-34 and ZSM-5 are the most well-known catalyst for MTO reaction. A combination of ZSM-5 and SAPO-34 might give rise to optimal catalyst to meet a change of market demand for ethylene, propylene and butadiene. In this study, we have developed ZSM-5/SAPO-34 composite catalysts to control the composition of light olefins in MTO reaction. ZSM-5/SAPO-34 composite catalysts showed very different physicochemical and catalytic properties with respect to ZSM-5 and SAPO-34 synthetic procedure. The physicochemical properties of the composite catalysts have been compared by XRD, SEM, N₂ isotherm, FT-IR and NH₃-TPD. Their catalytic performances were also evaluated for MTO reaction. The series composite catalyst synthesized by successive crystallization of SAPO-34 synthetic gel after ZSM-5 crystallization exhibited relatively high catalytic performance.     

Evaluation of semiconducting sensor materials on the basis of catalytic test reaction

Oxidative-reductive properties on the acid-base surfaces of the oxide compositions Sn-Ce-Rh-O and Zr-Mg-Y-O, active as catalysts in the ketonization of secondary alcohols were determined based on the isopropanol conversion selectivity. The kinetics of isopropanol conversion was measured in the oxygen-free atmosphere. Activation energies for both directions of conversion (dehydration to propylene and dehydrogenation to acetone) were calculated. The results were compared with the kinetics over SnO₂ and ZrO₂. Both oxide compositions, Sn-Ce-Rh-O and Zr-Mg-Y-O are oxidative-reductive catalysts containing Lewis acid centers.     

Surface chemistry and catalysis of oxide model catalysts from single crystals to nanocrystals

Fundamental understandings of surface chemistry and catalysis of solid catalysts are of great importance for the developments of efficient catalysts and corresponding catalytic processes, but have been remaining as a challenge due to the complex nature of heterogeneous catalysis. Model catalysts approach based on catalytic materials with uniform and well-defined surface structures is an effective strategy. Single crystals-based model catalysts have been successfully used for surface chemistry studies of solid catalysts, but encounter the so-called “materials gap” and “pressure gap” when applied for catalysis studies of solid catalysts. Recently catalytic nanocrystals with uniform and well-defined surface structures have emerged as a novel type of model catalysts whose surface chemistry and catalysis can be studied under the same operational reaction condition as working powder catalysts, and they are recognized as a novel type of model catalysts that can bridge the “materials gap” and “pressure gap” between single crystals-based model catalysts and powder catalysts. Herein we review recent progress of surface chemistry and catalysis of important oxide catalysts including CeO₂, TiO₂ and Cu₂O acquired by model catalysts from single crystals to nanocrystals with an aim at summarizing the commonalities and discussing the differences among model catalysts with complexities at different levels. Firstly, the complex nature of surface chemistry and catalysis of solid catalysts is briefly introduced. In the following sections, the model catalysts approach is described and surface chemistry and catalysis of CeO₂, TiO₂ and Cu₂O single crystal and nanocrystal model catalysts are reviewed. Finally, concluding remarks and future prospects are given on a comprehensive approach of model catalysts from single crystals to nanocrystals for the investigations of surface chemistry and catalysis of powder catalysts approaching the working conditions as closely as possible.     

A versatile sonication-assisted deposition–reduction method for preparing supported metal catalysts for catalytic applications

This work aims to develop a rapid and efficient strategy for preparing supported metal catalysts for catalytic applications. The sonication-assisted reduction–precipitation method was employed to prepare the heterogeneous mono- and bi-metallic catalysts for photocatalytic degradation of methyl orange (MO) and preferential oxidation (PROX) of CO in H₂-rich gas. In general, there are three advantages for the sonication-assisted method as compared with the conventional methods, including high dispersion of metal nanoparticles on the catalyst support, the much higher deposition efficiency (DE) than those of the deposition–precipitation (DP) and co-precipitation (CP) methods, and the very fast preparation, which only lasts 10–20 s for the deposition. In the AuPd/TiO₂ catalysts series, the AuPd(3:1)/TiO₂ catalyst is the most active for MO photocatalytic degradation; while for PROX reaction, Ru/TiO₂, Au–Cu/SBA-15 and Pt/γ-Al₂O₃ catalysts are very active, and the last one showed high stability in the lifetime test. The structural characterization revealed that in the AuPd(3:1)/TiO₂ catalyst, Au–Pd alloy particles were formed and a high percentage of Au atoms was located at the surface. Therefore, this sonication-assisted method is efficient and rapid in the preparation of supported metal catalysts with obvious structural characteristics for various catalytic applications.     

Characterization of K2CO3/Co–MoS2 catalyst by XRD,XPS, SEM,and EDS

MoS₂, Co–MoS₂ and K₂CO₃/Co–MoS₂ catalysts have been characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). XRD analysis indicates that Co–MoS₂ is a primary phase in K₂CO₃/Co–MoS₂ catalyst and the diffraction lines of Co–MoS₂ are not changed by the addition of K₂CO₃. Co₉S₈ phase is not present at Co/Mo mole ratio of 0.5 using a co-precipitation method for preparation of cobalt–molybdenum catalyst. The binding energies (BEs) of chemical species present on the surface of the catalysts are compared through the course of catalyst preparation. K₂CO₃/Co–MoS₂ catalyst has been investigated as a function of dispersion of K on the surface and exposure to a mixture of carbon monoxide and hydrogen (syngas) by scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). The distribution of potassium on the surface of the K-promoted catalyst is not uniform.     

Hydrogenation of p-chloronitrobenzene on Ni–B Nanometal Catalysts

A series of Ni–B catalysts were prepared by mixing nickel acetate in 50% ethanol/water or methanol/water solution. The solution of sodium borohydride (1 M) in excess amount to nickel was then added dropwise into the mixture to ensure full reduction of nickel cations. The mol ratio of boron to nickel in mother solution was 3 to 1. The effects of preparation conditions such as temperature, stirring speed, and sheltering gas on the particle size, surface compositions, electronic states of surface atoms and catalytic activities of the Ni–B catalysts were studied. Ranel nickel catalyst was included for comparison. These catalysts were characterized by N₂ sorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalysts were tested for liquid phase hydrogenation of p-chloronitrobenzene. All of the catalysts prepared in this study had nanosized particles. The preparation condition has significant influence on the particle size and surface compositions of the catalyst. The Ni–B catalyst was passivated by boron; therefore it was more stable than Raney nickel and did not catch fire after exposure to air. The catalysts prepared under N₂ flow could suppress the oxidation of Ni by the dissolved oxygen in water and had metallic state of nickel. The catalyst prepared with vigorous stirring at 25°C under N₂ stream yielded the smallest particles and resulted in the highest activity. It was much more active than the Raney nickel catalyst. The reaction condition also has pronounced effect on the hydrogenation activity. Using methanol as the reaction solvent increased p-chloronitrobenzene conversion to a large extent, compared to that using ethanol as the reaction medium. The selectivity of main product (p-chloroaniline) was greater than 99% on all of the Ni–B catalysts.     

A Mössbauer Effect Study on the Structural Components in Potassium-Promoted Iron Oxide Catalysts for Dehydrogenation of Ethylbenzene

Potassium-promoted iron oxide catalysts for dehydrogenation of ethylbenzene to styrene belong to one kind of complex oxide catalysts with a spinel structure and they exhibit good catalytic properties. In this work, two series of potassium-promoted catalysts were prepared with different potassium-to-iron ratios and using different calcining temperatures. Mössbauer spectroscopy has been used to determine the optimal potassium amount and the lowest calcining temperature for spinel structure formation, and to detect other structural components in the catalysts. Information was obtained for K₂CO₃-promoted iron oxides which may prove useful for industrial applications of this type of catalysts.     

Mössbauer spectroscopy and nuclear inelastic scattering studies on polynuclear oxo-bridged iron catalyst—first results

Polynuclear iron catalysts are interesting materials because of their novel properties. In the future they may help to replace high cost and hazardous heavy metal catalysts by efficient, non toxic and economic iron compounds. In this work, we present some preliminary results on a novel polynuclear oxo-bridged iron catalyst. The chemical environment of the metal species (Fe) was studied under Gif-type conditions (Fe catalyst/Zn/O₂ in pyridine/acetic acid) with cyclohexene as substrate. Such Gif-type catalysts are able to catalyse the selective oxidation of alkanes and alkenes. The characterization was done by Mössbauer spectroscopy and nuclear inelastic scattering. In order to identify the intermediate species during the reaction (selective oxidation using molecular O₂), a freeze-quench technique was used. This also helps to understand the kinetics of the chemical reaction.     

利用生物质合成气在钼基催化剂上制备混合醇

采用柠檬酸作络合剂的溶胶凝胶法制备了一系列的钼基催化剂,并应用到从生物质气化合成气有效合成低碳混合醇的实际过程中. 在钼基催化剂中,Cu₁Co₁Fe₁Mo₁Zn_0.5-6%K催化剂具有相对较高的混合醇时空产率. 通过实验发现, 反应温度在340 oC以下时,碳转化率随着反应温度的增加而不断上升,总醇的选择性却逐渐下降. 在试验测试的条件内,从生物质气化合成气合成的混合醇最大产率为494.8 g/(kg_catal·h),其中C2⁺醇(C2-C6高碳醇)占总醇含量的80.4%. 在不同的钼基催化剂上合成的混合醇,其醇分布除甲醇以外均符合Schulz-Flory方程. 在醇类产物中,C2以上的高级醇含量占总醇重量的百分比为70%-85%. 同时,利用X射线衍射和BET等表征手段对钼基催化剂的形态和结构进行了表征. 从生物质合成气生产的洁净生物质燃料混合醇具有较高的辛烷值,可以用作运输燃料或汽油的添加剂.     

Effect of Ni, Pd and Ni-Pd nano-islands on morphology and structure of multi-wall carbon nanotubes

In this research, the effect of Ni, Pd and Ni-Pd catalysts have studied on morphology and structure of synthesized multi-wall carbon nanotubes (MWCNTs). Initially, thin films of Ni (with two thicknesses of 10 and 20 nm), Pd/Ni (5/10 nm) and Pd (10 nm) were deposited as catalysts on SiO₂ (60 nm)/Si(1 0 0) substrates, using dc magnetron sputtering technique. The deposited films were annealed at 900 °C in ammonia environment for 45 min, in order to obtain nano-structured catalyst on the surface. Using scanning electron microscopy (SEM), the average size of Ni nano-islands (synthesized by the 10 and 20 nm Ni films), Pd and Ni-Pd nano-islands were measured about 55, 110, 45 and 50 nm, respectively. According to X-ray photoelectron spectroscopy analysis (XPS), the ratio of Ni/Pd on the surface was about 3 for the bilayer sample. The CNTs were synthesized on the nano-island catalysts at 940 °C in CH₄ ambient using a thermal chemical vapor deposition method. The results revealed that average diameter of the CNTs were about 70, 110, 120 nm for Ni, Ni-Pd and Pd catalysts, respectively. Raman spectra of the MWCNTs showed that intensity ratio of two main peaks located in the range of 1550-1600 and 1250-1450 cm⁻¹ (as a quality factor for the CNTs) for Ni, Pd and Ni-Pd catalysts were 1.42, 0.91 and 0.85, respectively. Therefore, based on our data analysis, although addition of Pd to Ni catalyst caused a considerable reduction in the quality of the grown MWCNTs as compared to the pure Ni catalyst, but it resulted in an enhancement in the methane decomposition rate. For the pure Pd catalyst samples, both a slow methane decomposition rate as compared with Ni-Pd catalyst samples and a poor quality of CNTs were observed as compared with the Ni catalyst, under similar experimental conditions.     

Nd- or Zr-modified CuO-CeO2/Al2O3/FeCrAl monolithic catalysts for preferential oxidation of carbon monoxide in hydrogen-rich gases

This work presents a study on the role of the additives over CuO-CeO₂/Al₂O₃/FeCrAl monolithic catalysts for the preferential oxidation of CO. The monolithic catalysts were prepared by in situ combustion method and characterized using SEM, XRD and TPR techniques. The results show that the addition of neodymium or zirconium in the CuO-CeO₂/Al₂O₃/FeCrAl catalysts influences the dispersion state of copper oxide and ceria, lowers the activity of hydrogen oxidation and broadens the temperature window for total CO-conversion.