Hydrocracking of vacuum gas oil in the presence of catalysts NiMo/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–amorphous aluminosilicates and NiW/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–amorphous aluminosilicates

Supported nickel–molybdenum and nickel–tungsten hydrocracking catalysts prepared using a support that consists of 70% Al₂O₃ and 30% amorphous aluminosilicate were characterized by nitrogen and mercury porosimetry, IR spectroscopy of adsorbed CO, and high-resolution electron microscopy. The catalytic tests in hydrocracking of vacuum gas oil containing 3.39% sulfur showed that the nature of the hydrogenating component (NiMo or NiW) only slightly influences the vacuum gas oil conversion and the diesel fraction yield, but noticeable influences the properties of the diesel fraction obtained. The catalyst NiMo/Al₂O₃–amorphous aluminosilicates, compared to NiW/Al₂O₃–amorphous aluminosilicates, ensures lower sulfur content in the diesel fraction obtained, whereas the catalyst NiW/Al₂O₃–amorphous aluminosilicates allows obtaining a diesel fraction with lower content of polyaromatic compounds.     

Selective oxidation of ethylbenzene by dioxygen. The effect of chelate center on catalysis by bicyclic nickel complexes

The effect of the nature of the chelate center in Ni^II complexes on their catalytic activity in the selective oxidation of ethylbenzene by dioxygen to α-phenylethyl hydroperoxide in the presence of nickel bis(acetylacetonate) (chelate center Ni(O,O)₂) and nickel bis(enaminoacetonate) (chelate center Ni(O,NH)₂) was studied. The efficiency of selective oxidation of ethylbenzene increases substantially in the presence of the chelate with the Ni(O,NH)₂ active center as a catalyst, which is mainly due to the transformation of the catalyst into more active species during the oxidation process. The mechanism of transformation of nickel bis(enaminoacetonate) under the action of dioxygen was suggested. The sequence of formation of the reaction products at different stages of the catalytic process was determined. The activity of the nickel complex with the Ni(O,NH)₂ chelate center and the products of its transformation in the elementary stages of chain oxidation of ethylbenzene is discussed. Translated fromIzvestiya Akedemii Nauk. Seriya Khimicheskaya, No. 1, pp. 55–60, January, 1999.     

Influence of the nature of molybdenum compounds on the activity of Mo/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and NiMo/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> hydrotreating catalysts

The influence of the nature of molybdenum compounds on the catalytic activity of sulfided NiMo/γ-Al₂O₃ catalysts was studied. The samples were prepared by impregnating the support with mixed aqueous solutions of nickel nitrate and molybdenum-containing compounds: ammonium paramolybdate and the 6-series heteropoly compounds (HPCs) ammonium 6-molybdonickelate (NiMo₆-HPC) and ammonium 6-molybdoaluminate (AlMo₆-HPC). Complexing agents (tartaric acid or a solution of NH₃) were used for stabilizing mixed aqueous ammonium paramolybdate and nickel nitrate solutions and for simultaneously producing an acidic or alkaline medium. The starting molybdenum compounds and catalysts in the oxide form were characterized using IR spectroscopy and x-ray diffraction analysis. The activity of catalysts based on NiMo₆-HPC in the hydrogenolysis of thiophene and in the hydrotreating of the diesel fraction was higher than that of catalysts based on ammonium paramolybdate: at 320°C, the degree of sulfur removal from the diesel fraction was higher by 13–16% and the average degree of hydrogenation of polycyclic aromatic hydrocarbons was higher by 14–15%. It was also found that the use of AlMo₆-HPC does not cause such an effect.     

Combustion synthesis of fine particle Zn–Ni ferrichromite by sol–gel method and their electrical properties

Oxides with the spinel structure are some of the most studied compounds in solid-state science due to their wide range of applications. In this, the system Zn_1−xNi_xFeCrO₄ was prepared by sol–gel auto-combustion method. The formation of spinel phase was identified using X-ray diffraction technique. All the compounds exhibited cubic spinel symmetry and lattice constant shows the decreasing trend with substitution of nickel. The morphology and size of the particles were studied by scanning electron microscope while an elemental composition of the metals in system is found to be equal to the relative compositions of the metals used for synthesis by stoichiometric calculations. Electrical properties of the system investigated for the compounds in the form of pellets indicate the semi-conducting nature of all the spinels which show the n to p-type conduction with nickel content.     

Hydrogenation catalysts based on palladium bisacetylacetonate and lithium tetrahydroaluminate: Formation mechanism and reasons for modified effect of water

Mechanism of formation, nature of activity, and properties of species active in hydrogenation catalysis in systems based on Pd(acac)₂ and LiAlH₄ were studied. The effect consisting in activation of catalytic systems was observed and reasons for the modifying action of water were considered.     

Über die Wirkungsweise löslicher Nickel-/Aluminium-Bimetallkatalysatoren auf der Basis von π-Cyclobutadien-Nickel-(II)-Verbindungen beider Niederdruck-Oligomerisation von Mono-Olefinen

Mixtures of π-cyclobutadiene-nickeldihalides and LEWIS acids such as Al(R)_nCl_3-n,, n = 1–2, represent very active homogeneous catalysts for dimerization of mono-olefins. As active cocatalyst may be used LEWIS bases, in particular compounds containing three-coordinated phosselectivity of the catalytic system has been investigated. The kinetics of the dimerization-reaction is outlined. The mechanisms of the olefin-dimerization is best characterized as a «double-cis-insertionreaction». The main catalytic activity is thought to be connected either to free positively charged nickel cations or to bimetallic nickel-aluminium-complexes, depending on theconditions of reaction, in particular the amount and chemical nature of the cocatalyst.     

Effects of the preparation methods on the properties of Ni-La2O3-SiO2 catalysts for m -dinitrobenzene hydrogenation

Ni-La₂O₃-SiO₂ catalysts were prepared by wetness impregnation and sol-gel method followed by conventional drying and supercritical drying, respectively. Their physico-chemical properties and activity for the hydrogenation of m-dinitrobenzene to m-phenylenediamine were investigated by BET, XRD, TPR, H₂-TPD and activity tests. The results showed that the structural and catalytic properties of the Ni-La₂O₃-SiO₂ catalysts obviously depended on the preparation method and the drying mode. The catalyst prepared by the sol-gel method in combination with conventional drying exhibited the highest catalytic activity among the catalysts tested, attributable to its well-dispersed nickel particles and larger active nickel surface area.     

E-Selective Hydrothiolation of Terminal Arylallenes with Arylthiols Catalyzed by Ni (PMe3)4

A catalytic system of regioselective synthesis of allyl sulfides via hydrothiolation of terminal arylallenes with arylthiols has been developed using nickel(0) complex Ni (PMe₃)₄ as a catalyst. In most cases the excellent to moderate yields were obtained under mild conditions. A catalytic mechanism was suggested and partially-experimentally verified. To the best of our knowledge, this is the first example of regioselective addition of thiophenols to terminal arylallenes catalyzed by nickel(0) complex. It was noteworthy that this catalytic system was only applicable to thiophenol compounds with terminal arylallenes.     

Fullerene compounds with transition metals MnC60: Preparation, structure, and properties

This review summarizes the results of studies on complexation of fullerene C₆₀ with transition metals. The structural background for metal-fullerene interaction is discussed. Much attention is focused on the compounds M_nC₆₀. Methods of their preparation, structure, and properties are considered in detail. The nature of their catalytic activity is discussed. Translated from Zhumal Struktumoi Khimii, Vol. 41, No. I, pp. 164-181, January–February, 2000.     

Nickel complexes with cyclic ligands containing P and N atoms as coordination sites: novel biomimetic catalysts for hydrogen oxidation

Nickel complexes with new cyclic ligands containing phosphorus and nitrogen atoms as coordination sites are novel efficient catalysts for hydrogen oxidation. A systematic study of their electrochemical properties made it possible to classify the nickel systems in question into four groups according to the sequence of electron transfer processes in the reduction (M^II-M^I-M⁰) and to the nature of solvents and counterions. Regularities of catalytic transformations involving nickel complexes with P,N-cyclic ligands in the H₂ oxidation reaction in the coordination sphere of the catalyst and a correlation between the structure of the complex and its redox properties were established. The most efficient catalysts contain phenyl and 2-pyridyl substituents at the phosphorus atom and benzyl or 2-pyridyl substituents at the nitrogen atom.     

Bridged bis-pyridinylimino dinickel(II) complexes: Syntheses, characterization, ethylene oligomerization and polymerization

A series of bridged bis(pyridinylimino) ligands were efficiently synthesized through the condensation reaction of 4,4′-methylene-bis(2,6-disubstituted aniline) with 2-pyridinecarboxaldehyde or 2-benzoylpyridine. They reacted with (DME)NiBr₂ to form dinuclear Ni(II) complexes. All resultant compounds were characterized by elemental analysis, IR spectra as well as the single-crystal X-ray diffraction to confirm the structures of ligands and complexes. Activated with methylaluminoxane (MAO), these nickel complexes showed considerably good activities for ethylene oligomerization and polymerization. Their catalytic activities and the properties of PEs obtained were depended on the arched environment of ligand and reaction conditions.     

New catalysts and adsorbents on the basis of the InSb-CdTe semiconducting system

The acid-base properties of solid solutions and binary components of the InSb-CdTe system were studied by IR spectroscopy, pH isoelectric point measurements, and conductometric titration; adsorption properties with respect to CO, O₂, NO₂, NH₃, CO + O₂, and NO₂ + NH₃, by piezoquartz microweighing; and catalytic properties in the oxidation of carbon(II) oxide and reduction of nitrogen(IV) oxide with ammonia, by the pulsed and circulation flow methods. The nature, strength, and concentration of acid centers were determined. Changes in the concentration of acid centers under the action of gases (NO₂ and NH₃), gamma irradiation, and composition variations were estimated. The experimental dependences, thermodynamic and kinetic adsorption characteristics, the electrophysical, acid-base, and other physicochemical characteristics of the adsorbents, and adsorption characteristic-composition phase diagrams were analyzed taking into account the electronic nature of adsorbate molecules to determine the mechanism and characteristics of adsorption processes depending on the conditions of adsorption and the composition of the system. The results of adsorption studies were used to preliminarily determine the temperature regions of the occurrence and the mechanism of the reactions studied. A shock mechanism was suggested. Separate components (predominantly, solid solutions) of the InSb-CdTe system showed high catalytic activity at comparatively low temperatures. Along with behavior common to the system and its binary compounds (InSb and CdTe), solid solutions exhibited features characteristic of multi-component systems. These were the presence of extrema in the pH_iso-composition, adsorption characteristic-composition, and catalytic activity-composition diagrams. The use of these diagrams allowed us to discover system components most active with respect to the gases and reactions studied and create high-sensitivity and selective sensors and high-activity and selective catalysts on the basis of these components.     

Formation and properties of nickel catalysts for hydrogenation under the action of lithium Di- and tris(<Emphasis Type="Italic">tert</Emphasis>-butoxy)hydroaluminates

It was demonstrated that systems based on Ni(II) compounds and the alkoxyhydride derivatives LiAlH(tert-BuO)₃ and LiAlH₂(tert-BuO)₂, in contrast to LiAlH₄, exhibit high catalytic activity in the reaction of styrene hydrogenation in the absence of activators. The inhibiting effect of an excess of LiAlH₂(tert-BuO)₂ was found. The analysis of the composition of reaction mixtures by NMR, EPR, and UV spectroscopy and TEM showed that side reactions of the conversion of aluminum-containing components occurred together with the formation of nickel nanoclusters. The most probable reaction schemes of LiAlH(tert-BuO)₃ and LiAlH₂(tert-BuO)₂ disproportionation were proposed. The nature of the stabilizers of nickel nanoparticles was considered.     

Influence of the support on the state of nickel in the Ni/SiO2, Ni/ZrO2, and Ni/SO4/ZrO2 oxide systems studied by diffuse-reflectance IR spectroscopy

The Ni/SiO₂, Ni/ZrO₂, and Ni/SO₄/ZrO₂ systems were studied by diffuse-reflectance IR spectroscopy using CO as a probe molecule. The Ni/SiO₂ and Ni/ZrO₂ systems are similar in properties, and the state of nickel in the Ni/ZrO₂ system is determined by the specific surface area. In the Ni/SO₄/ZrO₂ system, the surface sulfur compounds affect substantially the state of nickel: Ni^δ+ species with a partial positive charge are formed due to the strong electron-acceptor properties of the sulfur compounds. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 409–413, March, 1998.     

Hydrolysis of the uranyl ion in sodium nitrate medium

Studies on Nickel Oxide Mixed Catalysts. VIII. Catalytic Properties of NiO? Al₂O₃/SiO₂ Catalysts Catalytic properties of NiO? Al₂O₃/SiO₂ catalysts prepared by precipitation-deposition and impregnation have been investigated in dimerization of ethene and isomerization of but-1-ene. It was found that the catalytic activity is mainly determined by the interaction between the catalyst components where a X-ray amorphous nickel alumolayersilicate is formed. The dimerization of ethene proceeds by participation of coordinatively unsaturated nickel ions with aluminum ions in the neighbourhood. The catalytic activity in the isomerization of but-1-ene depends on the surface acidic properties of the catalyst.     

Ni-Co@C-N催化剂的制备及其催化硝基芳烃还原偶联反应

以ZIF-67为前驱体,通过高温热解和乙二醇还原的方法制备了低成本的负载镍纳米粒子催化剂Ni-Co@C-N。研究了催化剂对硝基芳烃化合物合成相应氧化偶氮苯类化合物的催化性能,并讨论了碱及分散剂种类对催化剂结构与性能的影响。结果表明,碱性增强可以加快纳米粒子的成核速率,分散剂分子量增加则会限制纳米粒子的粒径增长。其中,由弱碱与低分子量分散剂制备的Ni-Co@C-N-4对硝基芳烃还原具有良好的催化活性,原料的转化率和产率在反应30 min后分别达到92.8%和89.3%,且循环实验表明Ni-Co@C-N-4具有良好的稳定性。     

Ni-Co@C-N催化剂的制备及其催化硝基芳烃还原偶联反应

以ZIF-67为前驱体,通过高温热解和乙二醇还原的方法制备了低成本的负载镍纳米粒子催化剂Ni-Co@C-N。研究了催化剂对硝基芳烃化合物合成相应氧化偶氮苯类化合物的催化性能,并讨论了碱及分散剂种类对催化剂结构与性能的影响。结果表明,碱性增强可以加快纳米粒子的成核速率,分散剂分子量增加则会限制纳米粒子的粒径增长。其中,由弱碱与低分子量分散剂制备的Ni-Co@C-N-4 对硝基芳烃还原具有良好的催化活性,原料的转化率和产率在反应30 min 后分别达到92.8%和89.3%,且循环实验表明Ni-Co@C-N-4具有良好的稳定性。     

Catalytic properties of aluminum/nickel-, copper-containing oxide film compositions

The possibility of the single-step formation of nickel- and copper-containing thin-film oxide systems on aluminum by plasma electrolytic oxidation was demonstrated. The resulting structures were found to be active in the reaction of CO oxidation to CO₂ in the temperature region 300–500°C. However, the resulting structures exhibited stable catalytic activity only in the simultaneous presence of nickel and copper compounds. The films were studied using X-ray diffraction, X-ray spectroscopic analysis, X-ray photoelectron spectroscopy, and electron microscopy. The resulting films exhibited an essentially inhomogeneous composition through the thickness. Electrolyte elements such as nickel, copper, sodium, and phosphorus were concentrated at the surface. Nickel occurred as Ni²⁺, and copper occurred as Cu⁺ and Cu²⁺. The surface contained carbon in detectable amounts.     

Coordination behaviours of new (bidentate <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">O</Emphasis>-chelating) Schiff bases towards copper(II) and nickel(II) metal ions: synthesis,characterization, antimicrobial,antioxidant, and DFT studies

Two Schiff bases, HL₁ and HL₂, were synthesized in two different reactions involving 2-hydroxynaphthaldehyde with 2-amino-6-methylbenzothiazole and 2-amino-6-florobenzothiazole respectively. Copper(II) and nickel(II) complexes of the Schiff bases were subsequently prepared in 1:1 metal-to-ligand stoichiometric reactions. The compounds were characterized extensively by ¹H NMR, ¹³C NMR, Dept-90, UV–Vis, and IR spectroscopic techniques, magnetic susceptibility, TGA, DTG, and molar conductivity analysis. The spectroscopic results confirm bidentate nature of the Schiff bases and a four coordinate geometry for all the complexes: [CuL₁ClH₂O], [NiL₁ClH₂O], [Cu(L₂)₂], and [NiL₂ClH₂O]. Quantum chemical studies gave fully optimized geometries of the Schiff bases and metal complexes using the 6-31+g(d,p) basis set. The compounds were studied for their in vitro antibacterial activities against some selected Gram-positive and Gram-negative bacteria, using agar well diffusion. The metal complexes exhibited better antibacterial activities compared to the free ligand due to the effects of chelation, which improved the lipophilicity. Furthermore, the antioxidant potentials of the compounds were ascertained using DPPH radical scavenging and ferrous chelating assay. The copper complexes had the best antioxidant properties of all the tested compounds. The results of the biological analysis were in agreement with the theoretical data from quantum chemical calculations. The study presented biologically active coordination compounds with benzothiazole moiety that could be used as compounds of interest in the drug discovery processes.     

Liquid Nickel Salts: Synthesis,Crystal Structure Determination,and Electrochemical Synthesis of Nickel Nanoparticles

New nickel‐containing ionic liquids were synthesized, characterized and their electrochemistry was investigated. In addition, a mechanism for the electrochemical synthesis of nanoparticles from these compounds is proposed. In these so‐called liquid metal salts, the nickel(II) cation is octahedrally coordinated by six N‐alkylimidazole ligands. The different counter anions that were used are bis(trifluoromethanesulfonyl)imide (Tf₂N^?), trifluoromethanesulfonate (OTf^?) and methanesulfonate (OMs^?). Several different N‐alkylimidazoles were considered, with the alkyl sidechain ranging in length from methyl to dodecyl. The newly synthesized liquid metal salts were characterized by CHN analysis, FTIR, DSC, TGA and viscosity measurements. An odd‐even effect was observed for the melting temperatures and viscosities of the ionic liquids, with the complexes with an even number of carbon atoms in the alkyl chain of the imidazole having a higher melting temperature and a lower viscosity than the complexes with an odd number of carbons. The crystal structures of several of the nickel(II) complexes that are not liquid at room temperature were determined. The electrochemistry of the compounds with the lowest viscosities was investigated. The nickel(II) cation could be reduced but surprisingly no nickel deposits were obtained on the electrode. Instead, nickel nanoparticles were formed at 100 % selectivity, as confirmed by TEM. The magnetic properties of these nanoparticles were investigated by SQUID measurements.