High-Temperature Behavior of Laser Electrodispersion-Prepared Pd/ZSM-5 Hydrocarbon Traps under CO Oxidation Conditions.

Zeolites and metal-doped zeolites are now widely considered as low-temperature hydrocarbon traps to be a part of emission control systems in automobiles. However, due to the high temperature of exhaust gases, the thermal stability of such sorbent materials is of great concern. To avoid the thermal instability problem, in the present work, laser electrodispersion was used to deposit Pd particles on the surface of ZSM-5 zeolite grains (SiO2/Al2O3 = 55 and SiO2/Al2O3 = 30) to obtain Pd/ZSM-5 materials with a Pd loading as low as 0.03 wt.%. The thermal stability was evaluated in a prompt thermal aging regime involving thermal treatment at temperatures up to 1000 °C in a real reaction mixture (CO, hydrocarbons, NO, an excess of O2, and balance N2) and a model mixture of the same composition with the exception of hydrocarbons. Low-temperature nitrogen adsorption and X-ray diffraction analysis were used to examine the stability of the zeolite framework. Special attention was paid to the state of Pd after thermal aging at varied temperatures. By means of transmission electron microscopy, X-ray photoelectron spectroscopy, and diffuse reflectance UV-Vis spectroscopy, it was shown that palladium, having been initially located on the surface of zeolite, undergoes oxidation and migrates into the zeolite's channels. This enhances the trapping of hydrocarbons and their subsequent oxidation at lower temperatures.

Studies on High-Temperature Evolution of Low-Loaded Pd Three-Way Catalysts Prepared by Laser Electrodispersion.

Pd/Al2O3 catalyst of the "crust" type with Pd loading of 0.03 wt.% was prepared by the deposition of 2 nm Pd particles on the outer surface of the alumina support using laser electrodispersion (LED). This technique differs from a standard laser ablation into a liquid in that the formation of monodisperse nanoparticles occurs in the laser torch plasma in a vacuum. As is found, the LED-prepared catalyst surpasses Pd-containing three-way catalysts, obtained by conventional chemical synthesis, in activity and stability in CO oxidation under prompt thermal aging conditions. Thus, the LED-prepared Pd/Al2O3 catalyst showed the best thermal stability up to 1000 °C. The present research is focused on the study of the high-temperature evolution of the Pd/Al2O3 catalyst in two reaction mixtures by a set of physicochemical methods (transmission electron microscopy, X-ray photoelectron spectroscopy, and diffuse reflectance UV-vis spectroscopy). In order to follow the dispersion of the Pd nanoparticles during the thermal aging procedure, the testing reaction of ethane hydrogenolysis was also applied. The possible reasons for the high stability of LED-prepared catalysts are suggested.

Efficient Production of Segmented Carbon Nanofibers via Catalytic Decomposition of Trichloroethylene over Ni-W Catalyst.

The catalytic utilization of chlorine-organic wastes remains of extreme importance from an ecological point of view. Depending on the molecular structure of the chlorine-substituted hydrocarbon (presence of unsaturated bonds, intermolecular chlorine-to-hydrogen ratio), the features of its catalytic decomposition can be significantly different. Often, 1,2-dichloroethane is used as a model substrate. In the present work, the catalytic decomposition of trichloroethylene (C2HCl3) over microdispersed 100Ni and 96Ni-4W with the formation of carbon nanofibers (CNF) was studied. Catalysts were obtained by a co-precipitation of complex salts followed by reductive thermolysis. The disintegration of the initial bulk alloy driven by its interaction with the reaction mixture C2HCl3/H2/Ar entails the formation of submicron active particles. It has been established that the optimal activity of the pristine Ni catalyst and the 96Ni-4W alloy is provided in temperature ranges of 500-650 °C and 475-725 °C, respectively. The maximum yield of CNF for 2 h of reaction was 63 g/gcat for 100Ni and 112 g/gcat for 96Ni-4W catalyst. Longevity tests showed that nickel undergoes fast deactivation (after 3 h), whereas the 96Ni-4W catalyst remains active for 7 h of interaction. The effects of the catalyst's composition and the reaction temperature upon the structural and morphological characteristics of synthesized carbon nanofibers were investigated by X-ray diffraction analysis, Raman spectroscopy, and electron microscopies. The initial stages of the carbon erosion process were precisely examined by transmission electron microscopy coupled with elemental mapping. The segmented structure of CNF was found to be prevailing in a range of 500-650 °C. The textural parameters of carbon product (SBET and Vpore) were shown to reach maximum values (374 m2/g and 0.71 cm3/g, respectively) at the reaction temperature of 550 °C.

Comparative Study of Pd-Mayenite Catalysts Prepared via Aerogel Approaches.

Pd-containing catalysts based on highly dispersed aerogel-derived mayenite were prepared via two approaches. The Pd@C12A7 sample was obtained through the addition of Pd nitrate solution to a fresh Ca(OH)2-Al(OH)3 gel. Pd/C12A7 was synthesized through conventional wet impregnation of the aerogel-derived mayenite. The evolution of the textural characteristics of the support (C12A7) depending on the calcination temperature was investigated. Pd-containing samples were explored using transmission electron microscopy and spin probe EPR spectroscopy. Using the latter method, the presence of active oxygen species capable of producing nitroxyl radicals from diphenylamine was observed. The activity of these species and the reproducibility of their redox behavior were studied in three cycles of temperature-programmed reduction in both hydrogen and CO atmospheres. A prompt thermal aging technique was used to access and compare the activity of the samples towards CO oxidation. The state of Pd species before and after the aging procedure was studied via UV-Vis spectroscopy. It was found that the dispersion of PdO was higher in the case of the Pd/C12A7 catalysts compared to the Pd@C12A7 sample. This is why the Pd/C12A7 catalyst demonstrated higher activity in CO oxidation and better reducibility in TPR cycles.

Effect of Pretreatment with Acids on the N-Functionalization of Carbon Nanofibers Using Melamine.

Nowadays, N-functionalized carbon nanomaterials attract a growing interest. The use of melamine as a functionalizing agent looks prospective from environmental and cost points of view. Moreover, the melamine molecule contains a high amount of nitrogen with an atomic ratio C/N of 1/2. In present work, the initial carbon nanofibers (CNFs) were synthesized via catalytic pyrolysis of ethylene over microdispersed Ni-Cu alloy. The CNF materials were pretreated with 12% hydrochloric acid or with a mixture of concentrated nitric and sulfuric acids, which allowed etching of the metals from the fibers and oxidizing of the fibers' surface. Finally, the CNFs were N-functionalized via their impregnation with a melamine solution and thermolysis in an inert atmosphere. According to the microscopic data, the initial structure of the CNFs remained the same after the pretreatment and post-functionalization procedures. At the same time, the surface of the N-functionalized CNFs became more defective. The textural properties of the materials were also affected. In the case of the oxidative treatment with a mixture of acids, the highest content of the surface oxygen of 11.8% was registered by X-ray photoelectron spectroscopy. The amount of nitrogen introduced during the post-functionalization of CNFs with melamine increased from 1.4 to 4.3%. Along with this, the surface oxygen concentration diminished to 6.4%.

Preparation of the Nanostructured Ni-Mg-O Oxide System by a Sol-Gel Technique at Varied pH.

In the present work, a series of two-component Ni-Mg-O oxide systems were prepared using a sol-gel technique at varied pH of hydrolysis procedure. The aqueous solutions of nitric acid or ammonia were added to control the pH values. The xerogel samples obtained after drying were analysed using a thermogravimetric approach. The oxide systems were characterized by a set of physicochemical methods (low-temperature nitrogen adsorption, X-ray diffraction analysis, scanning electron microscopy, UV-vis spectroscopy, and temperature-programmed reduction method). The thermal stability of the samples was examined in a testing reaction of CO oxidation in a prompt thermal aging regime. It was revealed that the pH value during the magnesium methoxide hydrolysis stage significantly affects the properties of the intermediate hydroxide and final oxide nanomaterials. The thermal decomposition of nitric acid or ammonia is accompanied by exothermal effects, which noticeably influence the textural characteristics. Moreover, the pH of the hydrolysing solution defines the strength of the nickel interaction with the MgO matrix. An increase in pH facilitates the formation of the NixMg1-xO solid solution with a higher amount of incorporated nickel, which is characterized by the reproducible broad temperature range of the hydrogen uptake and the enhanced thermal stability.

Comparative analysis of the characteristics of carbonaceous material obtained via single-staged steam pyrolysis of waste tires.

The two-stage technology of porous carbonaceous material obtained via pyrolysis in inert medium with subsequent activation by steam is well known. While steam could be a suitable substance for pyrolysis as well, single-staged technology for waste tire recycling is yet to be developed. A comparative analysis of the characteristics of the carbonaceous materials obtained by the single-staged steam pyrolysis of waste tires was carried out, which could provide a theoretical background for the development of such technology. The steam pyrolysis was performed in a tubular reactor in an overheated steam medium (500°C with 5 kg/h mass flow rate). The technical characteristics of the obtained samples were evaluated in the context of their potential for further application as absorbent and raw material for rubber production according to Chemical Abstracts Service No. 1333-86-4. The composition and physico-chemical properties of the obtained samples were studied using BET and thermogravimetric analysis, atomic emission, transmission and scanning electron microscopies, Raman, X-ray diffraction, and photoelectron spectroscopies. The results revealed that the structure and properties of all obtained carbonaceous material samples were similar. The samples consisted of amorphous carbon (with a disordered graphite lattice) and contained a significant amount of metal oxides. According to experimental data, zinc was present in the form of ZnO with a binding energy of 1022.4 eV, while sulfur was observed in the form of sulfide and oxysulfide with binding energies of 161.8 and 163.2 eV, respectively. According to electron microscopy, the morphology of samples was represented by a set of spherical agglomerates comprising nanosized particles. According to the BET analysis of the samples, the specific surface area varied in the range between 52.0 and 66.0 m2/g and the pore volume values were within a range of 0.53-0.87 cm3/g, while the average pore size varied from 412 to 527 Å.Implications: Our paper presents original research in the field of characterization of solid material obtained by single-staged steam gasification of waste tires, which were produced and exploited in conditions of Russia. Modern technology allows thermal utilization of waste tires by obtaining powders of carbonaceous material, which could be used as fuel, adsorbent, etc., but this process usually consists of two stages - pyrolysis in inert medium and activation in steam or carbon dioxide. One of the most promising directions of technological development is simplifying this process into single step, ensuring that the obtained material could be used as carbon black or adsorbent for gas steam cleansing. No data on suitability of carbonaceous material obtained by single-step steam pyrolysis of all-season waste tires to be adsorbent and/or carbon black is present in the literature. In order to evaluate the suitability of the obtained material to be adsorbent, the high specific surface area should be determined, while CAS technical standards specify many chemical and physical properties of industrial carbon black.The aim of the current article is to study the properties of carbonaceous material obtained during single-staged steam gasification of four different all-season tires (due to their widespread application worldwide) and evaluate its fitness as industrial-scale carbon black or adsorbent. The additional problem addressed was the evaluation of the variation in characteristics of carbonaceous material obtained due to different origins of tires. Experiments were conducted in a tubular lab reactor in order to simplify the experimental procedure while ensuring the applicability of the obtained results to practical conditions.The obtained results could be used for the development of the technology for closed-cycle tire processing (because black carbon is used for tire production) and adsorbent production. The characteristics of the materials obtained allow us to choose optimal parameters for such treatment and develop special policies and programs, which will integrate and regulate waste tire utilization via steam gasification.

Effect of Mo on the catalytic activity of Ni-based self-organizing catalysts for processing of dichloroethane into segmented carbon nanomaterials.

A series of micro-disperse Ni-Mo alloys with the sponge-like structure was prepared by a simultaneous precipitation method followed by sintering of the sediment in H2 atmosphere at 800 °C. According to XRD data, the formation of single-phase solid solution Ni1-xMox took place for the samples with Mo content of 0.6-8.3 wt.%. Synthesized samples were studied in a process of the catalytic CVD of C2H4Cl2 at 550-700 °C. In situ kinetic studies of carbon deposition process were carried out in a flow gravimetric setup equipped with McBain balances. An interaction of Ni-Mo alloys with C2H4Cl2 is accompanied by their rapid disintegration with formation of disperse active particles catalyzing the growth of carbon nanomaterials (CNM). The strong boosting effect of Mo on the catalytic performance of Ni was revealed. The maximum yield of CNM product (8.3 wt.% Mo, 600 °C, 120 min) was as high as 45 g/gM. The study on effect of the reaction temperature on the CNM yield allowed one to define an optimal temperature regime. The impact of Mo concentration upon the morphology, structural features and textural properties of the produced carbon fibers was investigated by means of SEM, TEM, Raman spectroscopy and low-temperature nitrogen adsorption. The role of chemisorbed chlorine species in a pulse-to-pulse regime of the segmented carbon filaments formation was discussed.