Niobium-containing catalysts—the state of the art

This review article is devoted to the materials containing niobium, which have been discovered or developed in the past few years and exhibit the potential application in heterogeneous catalysis. Niobium oxides and mixed oxides as well as sulfides, nitrides (oxynitrides), carbides (oxycarbides), and phosphates are considered. Among the catalytic processes in which Nb-containing materials were tested, liquid and gas phase oxidation is described in details, and the role of niobium in the prevention of the catalyst from SO₂ poisoning is mentioned.     

A study of the large strain deformation and failure behaviour of mixed biopolymer gels via in situ ESEM

A mixed biopolymer gel, consisting of a protein (gelatin) and polysaccharide (maltodextrin) mixture has been investigated. By controlling the composition it was possible to construct an ‘emulsion-like’ structure, with included spherical particles of one phase (maltodextrin) within a continuous matrix of the second (gelatin). Large strain deformation and failure behaviour of this system has been examined via in situ environmental scanning electron microscopy (ESEM). ESEM has been employed to explore the changes in the structure of the material, whilst allowing the sample to stay hydrated as it was subjected to tensile strain, thereby allowing simultaneous imaging and determination of stress-strain data of the native sample. Ductile behaviour was observed, which has been attributed to the stretching, tearing and fracture of gelatin ligaments and debonding at the interface between the maltodextrin particles and continuous gelatin matrix. Deformation and fracture of the maltodextrin particles during tensile testing was also observed. The interfacial fracture energy of the composite has been calculated following an elastomer composite-debonding model, although there are several limitations to this approach for the mixed gel. It was found in samples tested after different ageing times that the debonding stress and strain was decreasing with ageing leading to a lower interfacial fracture energy. Samples were also tested after successive loading cycles, which resulted in a mechanical strength decrease after each cycle.     

Self-reorganization of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica substrates in response to combined selective solvent treatments and thermal annealing

This article reports reversible changes in surface morphology and surface wettability of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes with PS M_n slightly lower than that of PMMA in response to combined selective solvent treatments and thermal annealing. The mixed brushes were synthesized from asymmetric difunctional initiator-terminated monolayers by controlled radical polymerizations. Two sets of experiments were performed. The first set involved treating the samples with glacial acetic acid (AA), a selective solvent for PMMA, followed by treatment with cyclohexane, a selective solvent for PS, or thermal annealing. The surfaces were rough and composed of relatively ordered nanodomains after AA treatment. Subsequent cyclohexane treatment or thermal annealing made the surfaces flattened and surface analysis indicated that the outermost layers were occupied by PS. The second set of experiments involved treating the samples with cyclohexane or thermal annealing, followed by AA treatment. The surfaces were smooth after cyclohexane treatment or thermal annealing and became very rough in the subsequent AA treatment. The nanodomains formed in AA treatment were speculated to be micelles with PS forming the core shielded by PMMA chains.     

Determination of heavy metal ions in mixed solution by imprinted SAMs

Specific selectivity toward different heavy metal ions could be introduced into self-assembled monolayers (SAMs) by ion imprinting. In the mixed solution, good response toward mercury ions could be obtained on mercury ions imprinted SAMs, the copper ions imprinted SAMs presented good selectivity toward copper ions, while on lead ions imprinted SAMs, significantly higher insertion of lead ions than mercury and copper ions were observed. Linear calibration plots were obtained for each heavy metal ion and the regression equations were: [Hg(II)]/(10⁻⁶ M), [Cu(II)]/(10⁻⁶ M) and [Pb(II)]/(10⁻⁶ M) for mercury, copper and lead ions, respectively. The detection limits were determined to be: 1.46×10⁻⁸ M for Hg(II), 3.73×10⁻⁸ M for Cu(II) and 4.34×10⁻⁸ M Pb(II). The decreases in current response for mercury, copper and lead ions in the presence of 100-fold interferential ions were: 3.37%, 9.16% and 7.60%, respectively. Acceptable recoveries were obtained in mixed solutions at both high and low concentrations.     

Synthesis,Characterization and Application of Co–MgO Mixed Oxides in Oxidation of Carbon Monoxide

The present work deals with the synthesis of nanostructured Co–MgO mixed oxides with different weight ratios of cobalt by a facile co-precipitation method as a catalyst for low-temperature CO oxidation. The prepared samples were characterized by X-ray diffraction (XRD), N₂ adsorption/desorption (BET), Fourier transform infrared spectroscopy (FTIR), and transmission and scanning electron microscopies (TEM and SEM) techniques. The results revealed that inexpensive cobalt–magnesium mixed metal oxide nanoparticles have a high potential as catalyst in low-temperature CO oxidation. The Co–MgO mixed oxide with 30 wt.% cobalt had the highest activity. The results showed that the catalysts pretreated under O₂-containing atmosphere possessed higher activity compared to the catalyst pretreated under H₂ atmosphere. Co–MgO catalyst showed a good repeatability in reaction condition. The stability test exhibited that the Co–MgO mixed oxides were highly stable for CO oxidation over a 30 h time on stream in the feed gas containing a high amount of moisture and CO₂.     

Local structure and photocatalytic activity of B2O3–SiO2/TiO2 ternary mixed oxides prepared by sol–gel method

The local structure and the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides (SiO₂ content was fixed as 30 at.% with respect to TiO₂) was investigated by using XRD, FT-IR, BET, UV-vis spectra, and electron paramagnetic resonance (EPR) measurement. In FT-IR analysis, boron was incorporated into the framework of titania matrix with replacing Ti---O---Si with Si---O---B or Ti---O---B bonds. Also, paramagnetic species such as O⁻ and Ti³⁺ defects were formed by the boron incorporation. In SiO₂/TiO₂ mixed oxides, a blue shift in the light absorption band was observed due to the quantization of band structure. All B₂O₃–SiO₂/TiO₂ samples had pure anatase phase and no rutile phase was formed even though the calcination temperature was over 900 °C. Incorporating boron oxides of more than 10% enlarges the grain size of anatase phase and causes a red shift of the light absorption spectrum. The surface area was monotonically decreased with increasing the content of boron content. As a result, the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides was greatly influenced by the content of boron oxide. The highest photoactivity (g moles/min l) was obtained when the boron content was 5% and seven times higher than that of silica/titania binary mixed oxide. In addition, the specific photoactivity (g moles/m² l) was maximum still at 5%. It was concluded that the large reduction of surface area, the change of band structure, and more formation of bulk Ti³⁺ sites are responsible for the deterioration in the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides when the content of boron is over 10%, although their crystallinity was enhanced by increasing the calcination temperature with keeping anatase phase.     

Infiltrated La0.5Ba0.5CoO3-δ in La0.8Sr0.2Ga0.8Mg0.2O2.8 scaffolds as cathode material for IT-SOFC

The electrochemical response of infiltrated La_0.5Ba_0.5CoO_3-δ (LBC) in porous La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (LSGM) has been investigated. The thermal expansion coefficient (TEC) of the resulting electrode was measured, obtaining α?=?12.5?×?10^?6 K^?1, a value similar to that of LSGM. The polarization resistance (Rp) and the processes involved in the oxygen reduction reaction (ORR) for the new electrode were studied and analyzed through complex impedance spectroscopy measurements as a function of temperature and oxygen partial pressure (pO₂), using a symmetrical cell. The value of Rp for the infiltrated LBC turned out to be lower than that measured for an electrode prepared with a composite LBC-LSGM (1:1?wt%) by an order of magnitude, for the temperature range 750?°C ≤ T?≤?900?°C, and about 5 times lower for the temperature range 450?°C≤ T?≤?650?°C. At 600?°C, the LBC infiltrated cathode exhibits a polarization resistance R_p =?0.22?Ω?cm², in air. The complex impedance spectra show two processes, one identified as low frequency (LF),with a characteristic frequency of 10?Hz, and the other as intermediate frequency (IF), with a range between 0.05 and 2000?Hz. The LF process could be associated to the diffusion of oxygen in the gas phase through the pores of the electrode. Its resistance, R_LF =?0.01?Ωc?m²_, was found to be independent of the temperature and half of that obtained for the LBC composite cathode. On the other hand, the IF process is related to charge transfer at the electrode surface and the electrode-electrolyte interface. The LBC cobaltite infiltrated in the LSGM scaffolds offers an adequate thermal expansion coefficient and good electrocatalytic activity for the ORR.     

Selectivity of high surface area Ce0.68Zr0.32O2 for the new generation of TWC under environments with different redox character

A number of experiments were carried out with fresh and aged high surface area Ce_0.68Zr_0.32O₂ mixed oxide samples with complex feed-streams in order to determine their performance as three way catalyst (TWC). The results confirmed the oxygen storage capacity (OSC) of these samples, which favour NO conversion in cycled versus stationary stoichiometric operation. Several experiments carried out with different feed-streams have shown that a pre-reducing treatment can significantly improve both NO reduction at low-temperature and selectivity to N₂, which can be very useful to reduce the emission of nitrogen oxides immediately after starting the automobile. Although a significant reduction of the specific surface area of the mixed oxide takes place during ageing at 1173 K, it has been shown that the performance of the sample remains similar or even better than when fresh, due to an increased OSC. Thus, the reduction of CO and hydrocarbon emissions during start could be achieved by situating the catalytic converter nearer the exhaust to the engine, where the catalyst will be heated faster.     

Effect of cobalt promoter on Co–Mo–K/C catalysts used for mixed alcohol synthesis

The structures of sulfided Co–Mo–K/C catalysts were studied by means of X-ray diffraction (XRD), laser Raman spectra (LRS), and X-ray absorption fine structure (XAFS). Activities for alcohol synthesis via CO hydrogenation were used to characterize the catalytic performance of these catalysts. On the activated carbon support, molybdenum is mainly present as MoS₂ species which shrinks with the cobalt loading, while cobalt is mainly present in the form of “Co–Mo–S” phase at the low Co loading and partly in a Co₉S₈-like structure at higher Co loading. The catalysts exhibit outstanding performance for higher alcohol synthesis due to the addition of the promotion of cobalt. The activity for alcohol formation is optimized at a Co/Mo atomic ratio of 0.5. Co species operate as a synergistic system, rather than independently from the MoS₂ phase.     

Geometrical Optimization of the Overlap in Mixed Adhesive Lap Joints

The aim of this research is to optimize the geometry of the overlap in mixed adhesive single- and double-lap joints using a modified version of Bees and Genetic Algorithms (BA and GA). Accounting for adherends Poisson's ratio in the deduced equilibrium equations, the proposed shear lag model gives a more accurate approximation of joint failure load in comparison with Volkersen's solution. The objective functions used in this work are used separately to maximize the load bearing capacity f and the specific strength (f/w) of the joint. This procedure is applied to optimize aeronautical adhesively bonded assemblies, while taking manufacturing constraints into account. The employed constraints are the application of yield criterion on adherends as well as geometrical constraint on the overlap length. The proposed straightforward procedure provides 18 optimal configurations amid a wide range of changes for optimization variables, among which the designer can take a choice, depending on his/her goal. The efficiency of the two employed algorithms, BA and GA, in searching for the optimum geometrical design of the mixed adhesive joints have also been investigated. The results show the more robust and efficient performance of the modified version of BA over GA in such kinds of engineering problems.