Nikolay Cherkasov

Ultrasound‐ and Microwave‐Assisted Preparation of Lead‐Free Palladium Catalysts: Effects on the Kinetics of Diphenylacetylene Semi‐Hydrogenation

The effect of environmentally benign enabling technologies such as ultrasound and microwaves on the preparation of the lead‐free Pd catalyst has been studied. A one‐pot method of the catalyst preparation using ultrasound‐assisted dispersion of palladium acetate in the presence of the surfactant/capping agent and boehmite support produced the catalyst containing Pd nanoparticles and reduced the number of pores larger than 4 nm in the boehmite support. This catalyst demonstrated higher activity and selectivity. The comparison of kinetic parameters for diphenylacetylene hydrogenation showed that the catalyst obtained by using the one‐pot method was seven times as active as a commercial Lindlar catalyst and selectivity towards Z‐stilbene was high. Our work also illustrated that highly selective Pd/boehmite catalysts can be prepared through ultrasound‐assisted dispersion and microwave‐assisted reduction in water under hydrogen pressure without any surfactant.

Ultrasound-assisted selective hydrogenation of C-5 acetylene alcohols with Lindlar catalysts

The selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) was performed in the presence of Lindlar catalyst, comparing conventional stirring with sonication at different frequencies of 40, 380 and 850 kHz. Under conventional stirring, the reaction rates were limited by intrinsic kinetics, while in the case of sonication, the reaction rates were 50-90% slower. However, the apparent reaction rates were found to be significantly frequency dependent with the highest rate observed at 40 kHz. The original and the recovered catalysts after the hydrogenation reaction were compared using bulk elemental analysis, powder X-ray diffraction and scanning and transmission electron microscopy coupled with energy-dispersive X-ray analysis. The studies showed that sonication led to the frequency-dependent fracturing of polycrystalline support particles with the highest impact caused by 40 kHz sonication, while monocrystals were undamaged. In contrast, the leaching of Pd/Pb particles did not depend on the frequency, which suggests that sonication removed only loosely-bound catalyst particles.

Kinetic characteristics of the synthesis of multiwall carbon nanotubes by aerosol pyrolysis of a ferrocene solution in benzene

Approximating the experimental data on the mass distribution of multiwall carbon nanotubes (MCNT) along a reactor, a three-step kinetic model of their synthesis in the aerosol pyrolysis of a ferrocene solution in benzene is proposed. The values of effective rate constants upon the introduction of a catalyst in situ for the reactions that are the basis for synthesizing MCNT via the pyrolysis of hydrocarbons are obtained for the first time.

Metal oxide–zeolite composites in transformation of methanol to hydrocarbons : do iron oxide and nickel oxide matter?

The methanol-to-hydrocarbon (MTH) reaction has received considerable attention as utilizing renewable sources of both value-added chemicals and fuels becomes a number one priority for society. Here, for the first time we report the development of hierarchical zeolites (ZSM-5) containing both iron oxide and nickel oxide nanoparticles. By modifying the iron oxide (magnetite, Fe3O4) amounts, we are able to control the catalyst activity and the product distribution in the MTH process. At the medium Fe3O4 loading, the major fraction is composed of C9–C11 hydrocarbons (gasoline fraction). At the higher Fe3O4 loading, C1–C4 hydrocarbons prevail in the reaction mixture, while at the lowest magnetite loading the major component is the C5–C8 hydrocarbons. Addition of Ni species to Fe3O4–ZSM-5 leads to the formation of mixed Ni oxides (NiO/Ni2O3) positioned either on top of or next to Fe3O4 nanoparticles. This modification allowed us to significantly improve the catalyst stability due to diminishing coke formation and disordering of the coke formed. The incorporation of Ni oxide species also leads to a higher catalyst activity (up to 9.3 g(methanol)/(g(ZSM-5) × h)) and an improved selectivity (11.3% of the C5–C8 hydrocarbons and 23.6% of the C9–C11 hydrocarbons), making these zeolites highly promising for industrial applications.

Sulphur-free synthesis of helical carbon nanotubes

Unique three-dimensional structure of helical carbon nanotubes renders them important in polymer composites, electrode materials of electrochemical devices and microwave absorbers. The most thoroughly studied synthetic method involves hydrocarbon pyrolysis in the presence of sulphur-containing compounds which provide coiling effect. However, sulphur compounds are toxic and are usually undesirable in the coils obtained. The present work describes a novel method for the synthesis of coiled nanotubes by the aerosol pyrolysis of ferrocene solution in methanol, which is easily scalable for high-quantity production and uses no sulphur. The results of systematic investigation of the synthetic procedure with the use of other metal nanoparticle precursors and oxygen sources as well as oxygen role are discussed in details.

Direct amide synthesis over core–shell TiO2@NiFe2O4 catalysts in a continuous flow radiofrequency-heated reactor

Core-shell composite magnetic catalysts TiO2@NiFe2O4 with a titania loading of 9–32 wt. % have been synthesised by sol-gel method for direct amide synthesis in a radiofrequency (RF)-heated continuous flow reactor. The catalyst calcination temperature was optimised in the range of 350-500 oC and the highest activity was observed for the catalyst calcined at 500 oC due to conversion of titania into catalytically active anatase phase. No reaction between the magnetic core and the titania shell was observed up to the calcination temperature of 1000 oC and no sintering of titania shell was observed after calcination at 500 oC. The comparison of direct amide synthesis in a continuous flow fixed bed reactor under conventional and RF heating demonstrated that the RF heating mode increased the apparent reaction rate by 60 % and decreased the deactivation rate due to a better temperature uniformity. The titania weight normalised reaction rate in the RF-heated reactor was constant for titania loadings above 17 wt. %, while it decreased by a factor of 3 at lower titania loadings because of interactions between the ferrite core on the thin layer of the catalyst. The catalyst deactivation study showed that the deactivation rate could be accurately described by a first order kinetics and that the main reason of deactivation was coking. The catalyst regeneration via calcination at 400 oC resulted in the catalyst sintering, while a treatment with a hydrogen peroxide solution at 90 oC fully recovered catalytic activity.

Mathematical modeling of the multi-walled carbon nanotube growth by the pyrolysis of a ferrocene solution in benzene

The possibility of scaling up the growth of multi-walled carbon nanotubes (MWCNTs) synthesized by the pyrolysis of aerosol of a ferrocene solution in benzene was experimentally and theoretically studied. The morphology and yields of the reaction products and the influence of the volume of the introduced solution and ferrocene concentration on the duration of the process were investigated. A quantitative mathematical model of the nanotube growth process was proposed, and the possibility of using the model in scaling up the synthesis was analyzed. The experimental and model curves of the distribution of sample weights over the reactor length were compared and showed that the proposed model is correct.

The Composition of Iron-Containing Microphases in the Structure of Multiwalled Carbon Nanotubes

The phase composition of carbon nanotubes (CNTs) with encapsulated iron atoms was studied by 57Fe Mössbauer spectroscopy. The synthesis of CNTs was shown to stabilize iron atoms as both thermodynamically stable iron carbide and oxide phases and phases not characteristic under synthesis conditions (γ-Fe and γ-Fe2O3). In addition, an analysis of the data obtained led us to suggest the existence of Fe-CNT atomic complexes in interlayer positions. CNTs and iron-containing phases were shown to be stable when subjected to prolonged annealing in air at temperatures up to 670 K.