Rational design, synthesis, and applications of carbon-assisted dispersive Ni-based composites

The unique structural characteristics of carbon-assisted metallic nickel-based composites endow intriguing physicochemical properties and wide applications, especially for catalysis and protein adsorption. In this minireview, we review the recent developments...

Development of Ni-Sr(V,Ti)O3-δ Fuel Electrodes for Solid Oxide Fuel Cells

A series of strontium titanates-vanadates (STVN) with nominal cation composition Sr1-xTi1-y-zVyNizO3-δ (x = 0–0.04, y = 0.20–0.40 and z = 0.02–0.12) were prepared by a solid-state reaction route in 10% H2–N2 atmosphere and characterized under reducing conditions as potential fuel electrode materials for solid oxide fuel cells. Detailed phase evolution studies using XRD and SEM/EDS demonstrated that firing at temperatures as high as 1200 °C is required to eliminate undesirable secondary phases. Under such conditions, nickel tends to segregate as a metallic phase and is unlikely to incorporate into the perovskite lattice. Ceramic samples sintered at 1500 °C exhibited temperature-activated electrical conductivity that showed a weak p(O2) dependence and increased with vanadium content, reaching a maximum of ~17 S/cm at 1000 °C. STVN ceramics showed moderate thermal expansion coefficients (12.5–14.3 ppm/K at 25–1100 °C) compatible with that of yttria-stabilized zirconia (8YSZ). Porous STVN electrodes on 8YSZ solid electrolytes were fabricated at 1100 °C and studied using electrochemical impedance spectroscopy at 700–900 °C in an atmosphere of diluted humidified H2 under zero DC conditions. As-prepared STVN electrodes demonstrated comparatively poor electrochemical performance, which was attributed to insufficient intrinsic electrocatalytic activity and agglomeration of metallic nickel during the high-temperature synthetic procedure. Incorporation of an oxygen-ion-conducting Ce0.9Gd0.1O2-δ phase (20–30 wt.%) and nano-sized Ni as electrocatalyst (≥1 wt.%) into the porous electrode structure via infiltration resulted in a substantial improvement in electrochemical activity and reduction of electrode polarization resistance by 6–8 times at 900 °C and ≥ one order of magnitude at 800 °C.

Determining the influence of the microstructure and phase composition of glass-metal-ceramic coatings on their basic physical-technical properties

Given the development of new heat-resistant nickel alloys that operate at temperatures up to 1,250 °C, as well as the introduction of additive technologies for the production of various parts, it is a relevant task to devise new compositions of highly heat-resistant coatings. Determining the influence of the phase composition of glass-metal-ceramic coatings on its basic properties could improve the effectiveness of protecting those parts that operate under extreme conditions. Therefore, it is promising to conduct a study aimed at establishing the relationship between the microstructure and phase composition of glass-metal-ceramic coatings and the main physical-technical characteristics. This study's results have established that the most high-quality coatings were obtained on the basis of non-crystallizing glass. Such glass is characterized by a temperature coefficient of linear expansion of 92·10-7 degrees-1, a glass transition temperature of 625 °C, and surface tension of 260·10-3 N/m at 850 °C. These properties contribute to the formation of a defect-free coating, providing uniform spreading and high-quality adhesion to the substrate. The resulting optimal coating is characterized by the adhesion strength of 98 %, the thermal resistance (mode 950↔20 °C) of 50 cycles, and the high heat resistance (a weight gain after 100 h in the temperature range of 1,000‒1,050 °C) of 0.03 g/m2·h. Coatings with a minimum amount of glass bonding are distinguished by uniformity and high quality. The optimal ratio of phases "glass:metal-ceramic composition" is 10:90. The structure of the recommended coating is uniform, characterized by the homogeneous distribution of components, the absence of cracks, visible defects, and high quality. The phase composition of the coating after firing is represented by crystals of metallic nickel and silicon, as well as a small amount of residual glass phase.

Synthesis and Catalytic Properties of New Polymeric Monometallic Composites Based on Copolymers of Polypropylene Glycol Maleate Phthalate with Acrylic Acid

Metal-polymer composites based on copolymers of polypropylene glycol maleate phthalate with acrylic acid and metallic nickel and silver were synthesized for the first time. The objects obtained were characterized by infrared (IR) and Raman spectroscopies, thermogravimetry, a scanning electron microscope with energy dispersive spectroscopy, and atomic emission spectrometry. The catalytic activity of new metal-polymer composites that exhibited a rather high efficiency in the reactions of electrocatalytic hydrogenation of pyridine was studied. It is shown that nanoparticles of metals are evenly distributed in the volume of the polymer matrix; more than 80% of nanoparticles are in the range from 25 to 40 nm and have spherical and rhombic shapes. The reusability of the obtained composites is shown.

Elucidating the Role and Interplay of Nickel and Molybdenum Carbide Particles Supported on Zeolite Y in Methane-Steam Reforming

Methane steam reforming (MSR) reaction is a mature industrial process that has been applied for large-scale hydrogen production. Here, we report the synthesis and characterization, reaction kinetics, and deactivation mechanism of a series of catalysts with metallic nickel (Ni) clusters and molybdenum carbide (Mo2C) particles supported on zeolite Y (Ni-Mo2C/FAU) in MSR reaction at 850 oC. Despite low Ni loading less than 2.4 wt%, MSR on Ni-Mo2C/FAU exhibits high activity and stability, yet deactivation of Ni-FAU (the sample without Mo2C) is significant. Further investigations elucidate that the catalyst deactivation is caused by Ni particle sintering via Ostwald ripening instead of coking, and steam induces hydroxylated Ni surface that accelerates sintering. Moreover, encapsulated Mo2C boosts the activity and stability of Ni on zeolite Y by enhancing CH4 activation rather than activating H2O. The interplays among Mo2C and Ni particles dynamically balance the carbon formation and consumption rates, and inhibit Ni sintering. This study enables insights into an alternative design principle of transition metal carbide – Ni catalysts with high activity and stability for effective MSR by tuning the compositional, structural, and interfacial factors.

Carbon Microsphere-Supported Metallic Nickel Nanoparticles as Novel Heterogeneous Catalysts and Their Application for the Reduction of Nitrophenol

Nickel nanoparticles are gaining increasing attention in catalysis due to their versatile catalytic action. A novel, low-cost and facile method was developed in this work to synthesize carbon microsphere-supported metallic nickel nanoparticles (Ni-NP/C) for heterogeneous catalysis. The synthesis was based on carbonizing a polystyrene-based cation exchange resin loaded with nickel ions at temperatures between 500 and 1000 °C. The decomposition of the nickel-organic framework resulted in both Ni-NP and carbon microsphere formation. The phase composition, morphology and surface area of these Ni-NP/C microspheres were characterized by powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy and BET analysis. Elemental nickel was found to be the only metal containing phase; fcc-Ni coexisted with hcp-Ni at carbonization temperatures between 500 and 700 °C, and fcc-Ni was the only metallic phase at 800–1000 °C. Graphitization and carbon nanotube formation were observed at high temperatures. The catalytic activity of Ni-NP/C was tested in the reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride, and Ni-NP/C was proved to be an efficient catalyst in this reaction. The relatively easy and scalable synthetic method, as well as the easy separation and catalytic activity of Ni-NP/C, provide a viable alternative to existing nickel nanocatalysts in future applications.