Applying Topological and Economical Principles in Catalyst Design: New Alumina–Cobalt Core–Shell Catalysts

Designing new and effective catalysts may be an art, but its consequences are very real and pragmatic. That said, chemists often build designs on ideal systems, whereas the manufacturing of chemicals requires catalysts that withstand varied feeds, harsh conditions and long exposure times. Moreover, economical considerations are often underestimated at the catalyst design stage. Here we discuss the inclusion of economical and topological considerations early on in the catalyst design process, giving as an example the synthesis and testing of a new type of alumina/cobalt Fischer–Tropsch catalysts.

     

Alumina and Alumina–Baria Supported Cobalt Catalysts for DeNO x : Influence of the Support and Cobalt Content on the Catalytic Performance

Co/Al₂O₃ and Co/Al₂O₃–BaO catalysts with low cobalt loading (0.1, 0.3 and 1 wt%) for the selective catalytic reduction (SCR) of NO _x by C₃H₆ were prepared. The distribution of cobalt species was investigated by UV–vis diffuse reflectance spectroscopy and by H₂-TPR in order to identify the active cobalt species in hydrocarbons (HC)-selective catalytic reduction (SCR). It was found that the nature of cobalt species strongly depends on the cobalt loading as well as on the properties of the support. The barium addition to the alumina slows down solid state diffusion processes, improving the thermal stability of the support and preventing diffusion of cobalt into the bulk. Highly dispersed surface Co²⁺ species over alumina were identified as active sites in the NO-SCR process. Accordingly, a high concentration of surface Co²⁺ sites in Co 1 wt%/Al₂O₃ improves the catalytic performance in NO-SCR, the long term stability as well as the water tolerance. On the contrary, the formation of Co₃O₄ particles in Co 1 wt%/Al₂O₃–BaO promotes the propylene oxidation by oxygen, decreasing the activity and selectivity of the catalyst in NO reduction.     

Biomagnetic of Apatite-Coated Cobalt Ferrite: A Core–Shell Particle for Protein Adsorption and pH-Controlled Release

Magnetic nanoparticle composite with a cobalt ferrite (CoFe₂O₄, (CF)) core and an apatite (Ap) coating was synthesized using a biomineralization process in which a modified simulated body fluid (1.5SBF) solution is the source of the calcium phosphate for the apatite formation. The core–shell structure formed after the citric acid–stabilized cobalt ferrite (CFCA) particles were incubated in the 1.5 SBF solution for 1 week. The mean particle size of CFCA-Ap is about 750 nm. A saturation magnetization of 15.56 emug^-1 and a coercivity of 1808.5 Oe were observed for the CFCA-Ap obtained. Bovine serum albumin (BSA) was used as the model protein to study the adsorption and release of the proteins by the CFCA-Ap particles. The protein adsorption by the CFCA-Ap particles followed a more typical Freundlich than Langmuir adsorption isotherm. The BSA release as a function of time became less rapid as the CFCA-Ap particles were immersed in higher pH solution, thus indicating that the BSA release is dependent on the local pH.     

Synthesis of High Coercivity Core–Shell Nanorods Based on Nickel and Cobalt and Their Magnetic Properties

Hybrid magnetic nanostructures with high coercivity have immense application potential in various fields. Nickel (Ni) electrodeposited inside Cobalt (Co) nanotubes (a new system named Ni @ Co nanorods) were fabricated using a two-step potentiostatic electrodeposition method. Ni @ Co nanorods were crystalline, and they have an average diameter of 150 nm and length of ~15 μm. The X-ray diffraction studies revealed the existence of two separate phases corresponding to Ni and Co. Ni @ Co nanorods exhibited a very high longitudinal coercivity. The general mobility-assisted growth mechanism proposed for the growth of one-dimensional nanostructures inside nano porous alumina during potentiostatic electrodeposition is found to be valid in this case too.     

Synthesis of Polystyrene Microsphere-Supported Ag–Ni-Alloyed Catalysts with Core–Shell Structures for Electrocatalytic Performance

Rationally designed synthesis strategy for well-defined morphology which can endow the catalysts with unexpectedly enhanced catalytic properties remains a significant challenge in heterogeneous catalytic reactions. Hence, here we report a facile and controllable synthesis of polystyrene microsphere-supported Ag–Ni-alloyed catalysts (PS@Ag–Ni) with uniform core–shell structures through sulfonated treatment coupled with the subsequent liquid-phase reduction strategy. In this typical synthesis, sulfuric acid acts as the bifunctional roles in directing the core–shell morphology and the linker between the polystyrene microspheres and Ag–Ni alloy. The as-obtained PS@Ag–Ni optimized by tuning in a mass ratio of 1:1 shows superior oxygen reduction reaction activity and electrocatalytic performance toward the degradation of p-nitrophenol in comparison with other range of polystyrene microspheres and Ag–Ni alloy feeding ratios. The superior electrocatalytic and oxygen reduction reaction activity are attributed to its highly uniform core–shell morphology and exposure of much more active sites. Moreover, our as-prepared core–shell electrocatalysts will enable further investigation in other catalytic reactions.     

Fabrication and Optical Behaviors of Core–Shell ZnS Nanostructures

Novel core–shell nanostructures comprised of cubic sphalerite and hexagonal wurtzite ZnS have been synthesized at 150°C by a simple hydrothermal method. The results of HR-TEM and SAED investigation reveal that the cores of hexagonal wurtzite ZnS (ca. 200 nm in average diameter) are encapsulated by a shell of cubic sphalerite ZnS. The FE-SEM image of the nanomaterials shows a surface tightly packed with nanoparticles (<10 nm in size). The optical properties of the fabricated material have been studied in terms of ultraviolet–visible absorption and photoluminescence. Furthermore, a possible mechanism for the fabrication of the core–shell nanostructures has been presented.     

Mn3O4@ZnO Core–Shell Nanocomposite: Synthesis and Characterization

Nano-sized single-phase Mn₃O₄@ZnO core–shell nanocomposite was prepared via a simple one-pot sequential polyol using triethylene glycol as a high boiling point solvent as well as a reducing agent. The presence of both Mn₃O₄ and ZnO was confirmed with X-ray diffractometry. Infrared measurements proved the presence of triethylene glycol on the surface of Mn₃O₄@ZnO core–shell. The average particle size is between 8 and 13 nm. Reference intensity ratios method calculations showed that the weight percentage of phases were found as 54.7 % ZnO and 45.3 % Mn₃O₄. The lower Tc maybe explained by interface effects and dominant ZnO shell in magnetic properties of core–shell nanocomposite.     

Synthesis and Characterization of FePt/NiO Core–Shell Nanoparticles

Monodisperse FePt nanoparticles were successfully synthesized using the chemical polyol process. Annealing at the high temperatures is required to achieve the hard ferromagnetic behavior with L1₀ phase. Annealing causes the surfactant surrounding particles to be decomposed. Under such circumstances, FePt particles are agglomerated, and their size increases. In this research, NiO oxide particle with a high melting point was used for the first time as the shell around FePt core particles to prevent agglomeration. As a result, coercivity, H_c, of FePt and FePt/NiO nanoparticles after annealing at 750?°C are equal to 10 and 7?kOe, respectively.     

Highly Selective and Active Niobia-Supported Cobalt Catalysts for Fischer–Tropsch Synthesis

The performance of Co/Nb₂O₅ was compared to that of Co/γ-Al₂O₃ for the Fischer–Tropsch synthesis at 20 bar and over the temperature range of 220–260 °C. The C₅₊ selectivity of Nb₂O₅-supported cobalt catalysts was found to be very high, i.e. up to 90 wt% C₅₊ at 220 °C. The activity per unit weight cobalt was found to be similar for Nb₂O₅ and γ-Al₂O₃-supported catalysts at identical reaction temperature. However, due to the low porosity of crystalline Nb₂O₅, the cobalt loading was limited to 5 wt% and consequently the activity per unit weight of catalyst was lower than of Co/γ-Al₂O₃ catalysts with higher cobalt loadings. This low activity was largely compensated by increasing the reaction temperature, although the C₅₊ selectivity decreased upon increasing reaction temperature. Due to the high intrinsic C₅₊ selectivity, Nb₂O₅-supported catalysts could be operated up to ~250 °C at a target C₅₊ selectivity of 80 wt%, whereas γ-Al₂O₃-supported catalysts called for an operation temperature of ~210 °C. At this target C₅₊ selectivity, the activity per unit weight of catalyst was found to be identical for 5 wt% Co/Nb₂O₅ and 25 wt% Co/Al₂O₃, while the activity per unit weight of cobalt was a factor of four higher for the niobia-supported catalyst.     

Selective Catalytic Reduction of NO x Over Nano-Sized Gold Catalysts Supported on Alumina and Titania and Over Bimetallic Gold–Silver Catalysts Supported on Alumina

The reduction of NO with octane under lean conditions was examined over gold supported on alumina and titania and over alumina supported bimetallic gold–silver catalysts. The silver loading was either 1.2 or 1.9 wt% whereas 0.3, 1 or 5 wt% gold was used. The catalysts were characterized by means of EDXS, N₂-adsortion, UV–Vis and TEM to correlate recorded results with different preparation methods. UV–Vis measurements indicated that gold was present in the form of fine Au particles, single Au ions and small (Au)_n ^δ+ clusters on the catalysts and silver was mainly present in the form of single Ag ions. The highest NO to N₂ reduction activity was recorded over the 0.3Au–Al₂O₃ catalyst. The Au–TiO₂ catalysts did not result in significant NO to N₂ reduction.     

Novel Linear Piezo-resistive Auxetic Meta-Sensors with Low Young's Modulus by a Core–Shell Conceptual Design and Electromechanical Modelling

Production of piezo-resistive auxetic sensors is usually carried out through mixing and coating methods. Although these methods are beneficial, Young's modulus of mixed sensors becomes high because of using a high percentage of sensing elements while the durability of coated sensors gets low due to the separation of sensing elements from the sensor surface. This article presents a new core–shell metamaterial model to address the mentioned problems. The shell and the core are produced of polydimethylsiloxane (PDMS) rubber and a mixture of PDMS/graphite powders (73.45 wt% graphite powders), respectively. A finite element model is developed via COMSOL software to predict the electromechanical behaviors of the created sensor and verified by an experimental study. Scanning electron microscope imaging is conducted to detect the separations of the graphite particles. The main important feature of this meta-sensor is to possess a linear sensitivity due to having zero Poisson's ratio. The advantage of this method is that Young's modulus of the sensor does not decrease (unlike the mixing method), and the sensor-coated particles do not separate from the sensor after a while (unlike the coating method). The introduced model has advantages that promote potential applications such as using sensory gloves to detect, for instance, human hand movements.     

UV-Absorption and Silica/Titania Colloids Using a Core–Shell Approach

Metal-oxo-colloids have been prepared using tetraethoxysilane (TEOS) oligomers with titanium tetra-i-propoxide (TIP) or titanium (di-i-propoxide) bis(acetylacetonate) (TIA) precursors. Transmission electron microscopy (TEM), FTIR, UV-Vis, and photoluminescence spectroscopy were used to investigate the composition, the size, and optical properties of the Si/Ti core–shell colloids. The presence of hetero-bonded silicate structure (Si–O–Ti) was indicated by FTIR spectroscopy. The size of Si/TIP system ranged from 55 to 120 nm and Si/TIA system ranged from 220 to 250 nm. The TEM data indicated that the size of colloids can be controlled by the TIP or TIA content. The Si/Ti system exhibited strong absorption in the UV-range, yet had excellent optical transmittance in the visible range. The Si/Ti systems exhibited a photoluminescence emission at 329 nm.