Is a 2D Nanostructured Surface Capable of Changing the Corrosion and Magnetic Properties of an Amorphous Alloy?

In this work, an attempt was made to reveal and explain the influence of the process of formation of 2D nanostructures at the surface of an amorphous alloy (an alloy with the composition Co75Si15Fe5Cr4.5Al0.5 (in at.%) was used for this purpose) on the corrosion and magnetic properties of such an alloy. Two-dimensional nanostructures (nanocells of 100-150 nm in size, which were obtained by anodizing the initial sample in an ionic liquid) are essentially a pattern on the surface of the sample, and they cannot completely cover and block the surface from external effects. It was postulated that the presence of these nanostructures during corrosion and magnetic tests has no significant effect. However, a noticeable inhibition effect was observed during corrosion tests and a less noticeable (but still detectable) effect was observed during magnetic tests. The authors believe that the effect obtained, with a detailed study, can be used to increase the corrosion resistance and to improve the properties of traditional magnetic materials.

CO2-Assisted Sugar Cane Gasification Using Transition Metal Catalysis: An Impact of Metal Loading on the Catalytic Behavior.

To meet the increasing needs of fuels, especially non-fossil fuels, the production of "bio-oil" is proposed and many efforts have been undertaken to find effective ways to transform bio-wastes into valuable substances to obtain the fuels and simultaneously reduce carbon wastes, including CO2. This work is devoted to the gasification of sugar cane bagasse to produce CO in the process assisted by CO2. The metals were varied (Fe, Co, or Ni), along with their amounts, in order to find the optimal catalyst composition. The materials were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), and electron diffraction, and were tested in the process of CO2-assisted gasification. The catalysts based on Co and Ni demonstrate the best activity among the investigated systems: the conversion of CO2 reached 88% at ~800 °C (vs. 20% for the pure sugarcane bagasse). These samples contain metallic Co or Ni, while Fe is in oxide form.

Liquid-Phase Partial Hydrogenation of Phenylacetylene at Ambient Conditions Catalyzed by Pd-Fe-O Nanoparticles Supported on Silica.

Catalysts with no hazardous or toxic components are required for the selective hydrogenation of acetylenic bonds in the synthesis of pharmaceuticals, vitamins, nutraceuticals, and fragrances. The present work demonstrates that a high selectivity to alkene can be reached over a Pd-Fe-O/SiO2 system prepared by the co-impregnation of a silica support with a solution of the metal precursors (NH4)3[Fe(C2O4)3] and [Pd(NH3)4]Cl2 followed by thermal treatment in hydrogen or in air at 400 °C. A DRIFT spectroscopic study of CO adsorption revealed large shifts in the position of the Pdn+-CO bands for this system, indicating the strong effect of Fen+ on the Pd electronic state, resulting in a decreased rate of double C=C bond hydrogenation and an increased selectivity of alkyne hydrogenation to alkene. The prepared catalysts consisted of mono- and bimetallic nanoparticles on an SiO2 carrier and exhibited a selectivity as high as that of the commonly used Lindlar catalyst (which contains such hazardous components as lead and barium), while the activity of the Fe-Pd-O/SiO2 catalyst was an order of magnitude higher. The hydrogenation of a triple bond over the proposed Pd-Fe catalyst opens the way to selective hydrogenation over nontoxic catalysts with a high yield and productivity. Taking into account a simple procedure of catalyst preparation, this direction provides a rationale for the large-scale implementation of these catalysts.

Recent Studies on the Application of Microwave-Assisted Method for the Preparation of Heterogeneous Catalysts and Catalytic Hydrogenation Processes.

Currently, microwave radiation is widely used in various chemical processes in order to intensify them and carry out processes within the framework of "green" chemistry approaches. In the last 10 years, there has been a significant increase in the number of scientific publications on the application of microwaves in catalytic reactions and synthesis of nanomaterials. It is known that heterogeneous catalysts obtained under microwave activation conditions have many advantages, such as improved catalytic characteristics and stability, and the synthesis of nanomaterials is accelerated several times compared to traditional methods used to produce catalysts. The present review article is to summarize the results of modern research on the use of microwave radiation for the synthesis of heterogeneous catalytic nanomaterials and discusses the prospects for research in the field of microwave-induced liquid-phase heterogeneous catalysis in hydrogenation.

Rhodium-Based Catalysts: An Impact of the Support Nature on the Catalytic Cyclohexane Ring Opening.

Because of the growing demand for high-quality fuels, the light cycle oil fraction improvement including cetane number improvement is important. The main way to reach this improvement is the ring opening of cyclic hydrocarbons, and a highly effective catalyst should be found. Cyclohexane ring openings are a possible option to investigate the catalyst activity. In this work, we investigated rhodium-loaded catalysts prepared using the commercially available industrial supports: single-component ones, SiO2 and Al2O3; and mixed oxides CaO + MgO + Al2O3 and Na2O + SiO2 + Al2O3. The catalysts were prepared by incipient wetness impregnation and investigated by N2 low-temperature adsorption-desorption, XRD, XPS, DRS UV-Vis and DRIFT spectroscopy, SEM, and TEM with EDX. The catalytic tests were performed in cyclohexane ring opening in the range of 275-325 °C. The best result was demonstrated by the sample 1Rh/CaMgAlO: the selectivity to n-hexane was about 75% while the cyclohexane conversion was about 25% at 275 °C. The space-time yield was up to 12 mmoln-hexane gcat-1h-1.

Influence of the Method of Fe Deposition on the Surface of Hydrolytic Lignin on the Activity in the Process of Its Conversion in the Presence of CO2.

Hydrolytic lignin is one of the non-demanded carbon materials. Its CO2-assisted conversion is an important way to utilize it. The use of the catalysts prepared by metal deposition on the surface of hydrolytic lignin makes it possible to apply milder conditions of the conversion process with CO2 and to improve the economic indicators. The development of methods of deposition of the active phase is a problem of high importance for any heterogeneous catalytic processes. This work aimed at investigating the influence of the conditions of iron deposition on the surface of hydrolytic lignin on the process of CO2-assisted conversion of lignin. Different Fe precursors (Fe(NO3)3, FeSO4, Fe2(SO4)3), solvents (water, isopropanol, acetone, and ethanol), and concentrations of the solution were used; the properties of Fe/lignin composites were estimated by SEM, EDX, TEM, XRD methods and catalytic tests. All the prepared samples demonstrate a higher conversion compared to starting lignin itself in the carbon dioxide-assisted conversion process. The carbon dioxide conversion was up to 66% at 800 °C for the sample prepared from Fe(NO3)3 using a twofold water volume compared to incipient wetness water volume as a solvent (vs. 39% for pure lignin).

IR-spectroscopic study of complex formation of nitrogen oxides (NO, N2O) with strong Lewis acid sites and the reactivity of adsorbed species in CO and CH4 oxidation.

The formation of complexes and transformations of nitrogen oxides (NO, N2O) on strong Lewis acid sites of HZSM-5, H[Ga]ZSM-5, ZnO/HZSM-5 zeolites and dealuminated mordenites was investigated by diffuse-reflectance IR spectroscopy. Adsorbed N2O that is formed by disproportionation of NO is capable of oxidizing CO and CH4 molecules to CO2. The behaviour of strong Lewis acid sites in zeolites and cationic forms of zeolites in the NO disproportionation and CO or CH4 oxidation was comparatively studied.

Synthesis and the Crystal Structure of a New Chiral 1D Metal-Organic Coordination Polymer Based on L-Prolineamide-Substituted Diarylacetylenedicarboxylic Acid Derivative.

The new homochiral 1D metal-organic coordination polymer [Cu2(EDPB)•H2O]n was synthesized starting from the original 3,3'-ethyne-1,2-diylbis[6-(L-prolylamino)benzoic acid] (H4EDPB). The unique crystal structure of the new compound was established by powder X-ray diffraction. The [Cu2(EDPB)•H2O]n system shows catalytic activity and enantioselectivity in a Henry reaction of p-nitrobenzaldehyde with nitromethane.

Activity of Mono-, Bi-, and Trimetallic Catalysts Pt-Ni-Cr/C in the Bicyclohexyl Dehydrogenation Reaction.

The influence of metals with different redox properties and a carbon carrier on the activity of mono-, bi- and trimetallic Pt-Ni-Cr/C catalysts has been studied in the bicyclohexyl dehydrogenation reaction as the hydrogen release stage in hydrogen storage. An increase in the conversion (X > 62%) of bicyclohexyl and selectivity for biphenyl (S > 84%) was observed on trimetallic catalysts Pt-Ni-Cr/C compared with the monometallic catalyst Rt/C (X > 55%; S > 68%). It has been established that the increase in the conversion of bicyclohexyl and selectivity for biphenyl in the dehydrogenation reaction on trimetallic catalysts is due to an increase in the activity of Pt nanoparticles in the vicinity of local Cr-Ni clusters of solid substitution solutions.

The formation of active phases in Pt-containing catalysts for bicyclohexyl dehydrogenation in hydrogen storage.

The fundamental role of the carbon carrier Sibunit® in the formation of active and selective phases in low-percentage Pt-containing catalysts Pt/C, Pt/Ni/C, Pt/Ni-Cr/C for the complete dehydrogenation of bicyclohexyl into biphenyl (320 °C, 1 atm) is shown. The Pt/Ni-Cr/C catalyst showed the greatest activity and selectivity in the complete dehydrogenation of bicyclohexyl into biphenyl. Detailed analysis of the catalyst surface by XPS, TEM-HR and EDX methods revealed two main processes associated with the high activity and successful course of the reaction of bicyclohexyl dehydrogenation: the formation of an active carbide Pt1-xCx phase and graphitization of the carbon carrier. Both these processes are realized equally in the Pt/Ni-Cr/C catalyst demonstrating the highest activity. The formation of the Pt1-xCx carbide phase at a low extent of graphitization of the catalyst surface is predominant for the Pt/C catalyst. Graphitization of the carbon carrier is most pronounced for Pt/Ni/C, where the yield of biphenyl is significantly reduced. The formation of graphite for the Pt/Ni/C catalyst at the metal-carrier interface leads to the encapsulation of a metal particle in a graphite shell, which apparently determines its low activity in the conversion of bicyclohexyl.

Microwave Heating of the Catalyst Bed as a Way of Energy-Saving Oxidative Dehydrogenation of Ethane on a Mo-V-Te-Nb-Ox Catalyst.

In search of a more effective process of ethane oxidative hydrogenation, different operation modes (thermal and microwave heating) are compared. The catalyst Mo1-V0.3-Te0.13-Nb0.11-Ox was prepared by hydrothermal synthesis and characterized by a set of physicochemical methods (XRD, N2 adsorption, SEM, EDX). The direct microwave heating of the catalyst layer is proposed as an alternative way of energy-saving ethane-to-ethylene oxidation by a Mo-V-Te-Nb-Ox system. A substantial decrease in the reactor temperature upon the microwave-assisted process is accompanied by extremely high catalyst selectivity, which remains at a very high level of 98+%.

The Toxicity of Coated Silver Nanoparticles and Their Stabilizers towards Paracentrotus lividus Sea Urchin Embryos.

Surface modification of nanoparticles with different stabilizers is one of the most widely used methods to improve their stability and applicability. Silver nanoparticle (AgNPs) dispersions with biologically active stabilizers have great potential as plant protection products with synergetic antimicrobial properties and sufficient stability in terms of field application. The obtained AgNPs dispersions have the ability to enhance growth, increase yield and give better protection to various crops. At the same time, it is important to determine the fate, stability, and ecotoxicity of the applied nanosized products. The toxic effects of AgNPs dispersions and their constituents, organic stabilizers and additives, were evaluated using a phenotypic sea urchin embryo assay. Certain AgNPs dispersions with organic stabilizers demonstrated sufficient stability, even in seawater. The toxicity of the AgNPs decreased with the increasing tendency to agglomerate in seawater. Furthermore, the applied stabilizers were hazardous towards sea urchin embryos. They caused pronounced embryo abnormalities at 0.25-2.6 mg/L concentrations. AgNPs exhibited a lethal effect at concentrations that were equal to the MLC or exceeded the MEC of their stabilizers. Silver ions were more toxic towards sea urchin embryos than AgNPs.

Facile Synthesis of Micro-Mesoporous Copper Phyllosilicate Supported on a Commercial Carrier and Its Application for Catalytic Hydrogenation of Nitro-Group in Trinitrobenzene.

Development of novel Cu-based catalysts has become one of the frontiers in the catalytic production of platform chemicals and in environment protection. However, the known methods of their synthesis are too complicated and result in materials that cannot be used instantly as commercial catalysts. In the present work, a novel material has been synthesized by the facile method of deposition-precipitation using thermal hydrolysis of urea. The conditions for Cu phyllosilicate formation have been revealed (molar ratio urea:copper = 10, 92 °C, 8-11 h). The prepared Cu-based materials were studied by TG-DTA, SEM, TEM, XRD, N2 adsorption and TPR-H2 methods, and it was found that the material involves nanoparticles of micro-mesoporous copper phyllosilicate phase with a chrysocolla-like structure inside the pores of a commercial meso-macroporous silica carrier. The chrysocolla-like phase is first shown to be catalytically active in the selective reduction of the nitro-group in trinitrobenzene to an amino-group with molecular hydrogen. Complete conversion of trinitrobenzene with a high yield of amines has been achieved in short time under relatively mild conditions (170 °C, 1.3 MPa) of nitroarene hydrogenation over a copper catalyst.

Understanding the Working Mechanism of the Novel HKUST-1@BPS Composite Materials as Stationary Phases for Liquid Chromatography.

Composite materials have been used based on coordination polymers or microporous metal-organic frameworks (MOFs) combined with mesoporous matrices for adsorption-related techniques, which enable outflanking some adverse phenomena manifested during pristine components operation and enhance the performance and selectivity of the resulting materials. In this work, for the first time, the novel HKUST-1@BPS composites synthesized by the microwave-assisted (MW) technique starting from microporous HKUST-1 (Cu3(btc)2) MOF and biporous silica matrix (BPS) with bimodal mesopore size distribution were comparatively studied as materials for liquid-phase adsorption techniques utilizing the high-performance liquid chromatography (HPLC) method and benzene as a model adsorbate. It was established that the studied HKUST-1@BPS composites can function as stationary phases for HPLC, unlike the pristine HKUST-1 and bare BPS materials, due to the synergetic effect of both components based on the preliminary enhanced adsorbate mass transfer throughout the silica mesopores and, subsequently, its penetrating into HKUST-1 micropores. The suggested mechanism involves the initial deactivation of open metal Cu2+ sites in the HKUST-1 framework structure by isopropanol molecules upon adding this polar component into the mobile phase in the region of the isopropanol concentration of 0.0 to 0.2 vol.%. Thereafter, at the medium range of varying the isopropanol concentration in the eluent of 0.2 to 0.3 vol.%, there is an expansion of the previously inaccessible adsorption centers in the HKUST-1@BPS composites. Subsequently, while further increasing the isopropanol volume fraction in the eluent in the region of 0.3 to 5.0 vol.%, the observed behavior of the studied chromatographic systems is similar to the quasi-normal-phase HPLC pattern. According to the obtained thermodynamic data, benzene adsorption into HKUST-1 micropores from solutions with a vol.% of isopropanol in the range of 0.4 to 5.0 follows the unique entropy-driven mechanism previously described for the MIL-53(Al) framework. It was found that HKUST-1 loading in the composites and their preparation conditions have pronounced effects on their physicochemical properties and adsorption performance, including the adsorption mechanism.

Kinetic Modeling of Hydrogen Production by Dehydrogenation of Polycyclic Naphthenes with Varying Degrees of Condensation.

The kinetics of reactions of dehydrogenation of polycyclic naphthenes (cyclohexane, decalin, bicyclohexyl, ortho-, meta-, and para-isomers of perhydroterphenyl) is modeled on the basis of a formal comparison of kinetic equations of the 1st and 2nd orders based on real experimental data. It is shown that the reaction of the 1st order is predominating in the series of cyclohexane-bicyclohexyl-perhydroparatherphenyl. For all other substrates, the probability of describing the reaction in accordance with the equation of the 2nd order increases markedly, and for trans-decalin it becomes the predominant form of describing the kinetics of the reaction.

Microwave-Assisted Conversion of Carbohydrates.

Catalytic conversion of carbohydrates into value-added products and platform chemicals became a trend in recent years. Microwave activation used in the processes of carbohydrate conversion coupled with the proper choice of catalysts makes it possible to enhance dramatically the efficiency and sometimes the selectivity of catalysts. This mini-review presents a brief literature survey related to state-of-the-art methods developed recently by the world research community to solve the problem of rational conversion of carbohydrates, mostly produced from natural resources and wastes (forestry and agriculture wastes) including production of hydrogen, synthesis gas, furanics, and alcohols. The focus is made on microwave technologies used for processing carbohydrates. Of particular interest is the use of heterogeneous catalysts and hybrid materials in processing carbohydrates.

Impact of composition and structural parameters on the catalytic activity of MFI type titanosilicalites.

Titanosilicalite of the MFI type was obtained via a hydrothermal method. Its initial and annealed at 75 °C (TS-1P(75)) and 500 °C (TS-1P(500)) forms were studied by X-ray powder diffraction (PXRD), X-ray absorption spectroscopy (XAS-method), Fourier-transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), temperature-programmed ammonia desorption (TPD NH3), and pyridine adsorption (Py). The full-profile Rietveld method allowed us to observe the presence of the organic template tetrapropylammonium hydroxide (TPAOH) in the framework voids, as well as to determine the silicate module (Si/Ti = 73.5) and the distribution of Ti4+ ions over the MFI-type structure sites (Ti atoms replace Si ones in two positions: T1 and T6). The coordination numbers of titanium (CNTi = 4.6 for TS-1P and TS-1P(75), CNTi = 3.8 for TS-1P(500)) were established by the XAS-method. The catalytic activity of titanosilicalites was found in the reactions of nitrous oxide decomposition (the maximal decomposition rate is demonstrated for the TS-1P(75) sample), allyl chloride epoxidation to epichlorohydrin (the best combination of all indicators was exhibited for the TS-1P sample) and propane conversion (maximum propane conversion, and butadiene and propylene selectivity were observed in both TS-1P(75) and TS-1P(500) samples). Mechanisms for the catalytic processes are proposed. The relationship between the catalytic properties and the composition (Si/Ti), Ti4+ ion distribution over the MFI-type structure sites, the local environment of titanium ions, and the number of acid sites in the titanosilicalites are discussed.

Nitrous Oxide Adsorption and Decomposition on Zeolites and Zeolite-like Materials.

Decomposition of N2O on modified zeolites, crystalline titanosilicalites, and related amorphous systems is studied by the catalytic and spectroscopic methods. Zinc-containing HZSM-5 zeolites and titanosilicalites with moderate Ti/Si ratios are shown to exhibit a better catalytic performance in N2O decomposition as compared with conventionally used Cu/HZSM-5 zeolites and amorphous Cu-containing catalysts. Dehydroxylation of the HZSM-5 zeolite by calcination at 1120 K results in an enhancement of the N2O conversion. The mechanism of the reaction and the role of coordinatively unsaturated cations and Lewis acid sites in N2O decomposition are discussed on the basis of the spectroscopic data.

Hydroamination of Phenylacetylene with Aniline over Gold Nanoparticles Embedded in the Boron Imidazolate Framework BIF-66 and Zeolitic Imidazolate Framework ZIF-67.

The hydroamination of alkynes is an atom-economy process in the organic synthesis for the C-N bond formation, thereby allowing the production of fine chemicals and intermediates. However, direct interaction between alkynes and amines is complicated due to the electron enrichment of both compounds. Therefore, efficient hydroamination catalysts, especially heterogeneous ones, are in great demand. This work aimed at the development of novel heterogeneous catalysts based on zeolite-like metal-organic frameworks for phenylacetylene hydroamination. The sodalite (SOD) type zeolitic imidazolate framework ZIF-67 (Co(meim)2, meim = 2-methylimidazolate) and boron imidazolate framework BIF-66 ({Co[B(im)4]2}n, im = imidazolate) were studied as the carriers for the gold nanoparticles (Au-NPs). Au-NPs were embedded in the ZIF-67 and BIF-66 matrices by incipient wetness impregnation. Au@ZIF-67 and Au@BIF-66 hybrids were studied for the first time in the liquid phase hydroamination of phenylacetylene with aniline in an air atmosphere and have shown high activity and selectivity in respect to imine in this process. The pronounced impact of the nature of the metal-organic carrier, Au source, and reducing agent on the catalytic performance of the synthesized nanomaterials was found. To the best of our knowledge, it is the first example of using the zeolitic imidazolate framework and boron-imidazolate framework as the components of the gold-containing catalytic systems for the alkyne hydroamination.

Electrochemical Synthesis of Unique Nanomaterials in Ionic Liquids.

The review considers the features of the processes of the electrochemical synthesis of nanostructures in ionic liquids (ILs), including the production of carbon nanomaterials, silicon and germanium nanoparticles, metallic nanoparticles, nanomaterials and surface nanostructures based on oxides. In addition, the analysis of works on the synthesis of nanoscale polymer films of conductive polymers prepared using ionic liquids by electrochemical methods is given. The purpose of the review is to dwell upon an aspect of the applicability of ILs that is usually not fully reflected in modern literature, the synthesis of nanostructures (including unique ones that cannot be obtained in other electrolytes). The current underestimation of ILs as an electrochemical medium for the synthesis of nanomaterials may limit our understanding and the scope of their potential application. Another purpose of our review is to expand their possible application and to show the relative simplicity of the experimental part of the work.