Study of the state of nickel in ion-exchanged NiNaY zeolite by IR spectroscopy using molecular hydrogen adsorbed at low temperatures

The state of nickel cations in NiNaY zeolite subjected to thermal vacuum and oxidative-reductive treatment was analyzed using diffuse reflectance IR spectra of molecular hydrogen, CO, and hydroxy groups. In a sample dehydrated at 570 K, nickel forms oxide particles, which are presumably located in big cavities of a zeolite. Heating of the sample at 670 K results in decomposition of the oxide with the participation of hydroxy groups followed by the formation of stabilized Ni²⁺ cations in large cavities of the zeolite. Calcination of NiNaY zeolite in a hydrogen atmosphere at 730 K leads to Ni²⁺ cation reduction to the metal state and to the formation of acidic hydroxy groups. Nevertheless, Ni²⁺ cations can be regenerated by reoxidation of the reduced sample with oxygen at 670 K and further evacuation at 870 K. Thermal destruction of NiO in the reoxidized sample also proceeds on acidic hydroxy groups, but the temperature of this process is higher than the temperature of oxide decomposition in the initial NiNaY zeolite. The IR spectra of molecular hydrogen complexes with Ni²⁺ cations were observed for the first time. A considerable decrease in the H-H stretching vibration frequency for the coordinated molecules (up to 210 cm’1) can be explained by electron density redistribution between a hydrogen molecule and the cation in the complex     

Untersuchungen an oxidischen Katalysatoren. XLI. Redoxverhalten des Nickels in NiNa–Y-Zeolithen 3. Reduzierbarkeit von Ni2+ -Ionen und Eigenschaften des reduzierten Nickels in aciden NiNa–Y-Zeolithen

Studies on Oxide Catalysts. XLI. Redox Behavior of Nickel in Zeolites NiNa? Y. 3. Reducibility of Ni²⁺ Ions and Properties of the Reduced Nickel in Acidic Zeolites NiNa? Y The reducibility of nickel ions in zeolites NiNa? Y and the properties of metallic nickel were evaluated by tpr measurements, oxygen chemisorption and conversion of cyclohexane. In NiNa? Y samples which contain NH₄⁺(H⁺) and/or Al³⁺(H⁺) ions the reducibility of Ni²⁺ ions is decreased caused by increasing acidity and the metal dispersion is improved. The electronic interaction between the acidic support and the metallic nickel leads to a decrease of both dehydrogenation and hydrogenolysis activity whereas the dehydrogenation selectivity increases.     

Untersuchungen an oxidischen Katalysatoren. XXXIV. Redoxverhalten des Nickels in NiNaY-Zeolithen 1. Reduzierbarkeit und Reoxydierbarkeit von Nickel in NiNaY-Zeolithen

Studies on Oxide Catalysts. XXXIV. Redoxbehaviour of Nickel in Zeolite NiNaY. 1. Reducibility and Reoxidizability of Nickel in Zeolites NiNaY The properties of metallic nickel in reduced (470–870 K) and reoxidized (470, 670 K) samples were studied by chemical analysis (reaction with K₂Cr₂O₇) and spectroscopic methods (FMR, IR after CO adsorption, UV/VIS). The reduction of Ni²⁺ cations from oxidic clusters proceeds in an onestep reaction. Contrary to this, isolated Ni²⁺ cations are reduced stepwise to Ni⁺ cations and subsequently to metallic nickel. The reduction degree depends in characteristic manner on the reduction temperature. Metallic nickel which was reduced at temperatures < 620 K, can be completely reoxidized at 470 K. Higher temperatures result in metallic aggregations which are not completely reoxidized even at 670 K.     

Untersuchungen an Nickeloxid-Mischkatalysatoren. I. Strukturelle Eigenschaften von NiO/SiO2-Katalysatoren

Studies on Nickel Oxide Mixed Catalysts. I. Structural Properties of NiO/SiO₂ Catalysts Structural properties of NiO/SiO₂ catalysts prepared by precipitation-deposition and impregnation have been investigated. A nickel-layer-silicate like structure is formed only in the precipitated catalysts showed infrared spectroscopic measurements. After thermal treatment at 723 K by means of magnetic measurements and reflectance spectroscopy besides Ni²⁺ ions in octahedral environment tetrahedral coordinated Ni²⁺ions were found. The part of tetrahedral coordinated Ni²⁺ ions is independent of the NiO-content up to 40 mole % NiO. Nickel oxide is formed above a content of 40 mole %. In the case of the impregnated catalysts nickel oxide cluster are formed on the surface after annealing at 723 K.     

Untersuchungen an Nickeloxid-Mischkatalysatoren. XI. Oberflächenchemische Eigenschaften von NiO/SiO2-Katalysatoren

Studies on Nickel Oxide Mixed Catalysts. XI. Surface Chemical Properties of NiO/SiO₂ Catalysts NiO/SiO₂ catalysts with different composition prepared by precipitation have been investigated which are characterized by a nickel layersilicate-like structure. The determination of the surface chemical properties was carried out by infrared spectroscopy (before and after pyridine adsorption), ¹H-NMR-measurements, chemisorption of ammonia, and titration with n-butylamine. It has been found three kinds of hydroxid groups which are assigned to Ni? OH and Si? OH groups with respect to investigations on definite nickel layersilicates. Furthermore, coordinatively unsaturated Ni^II surface sites were indicated. The number of the OH groups as well as the centers determined by chemisorption of bases increase with increasing NiO content. The obtained results allow the conclusion that the OH groups and the coordinatively unsaturated Ni^II surface sites are weakly acid.     

Enhanced NiO Dispersion on a High Surface Area Pillared Heterostructure Covered by Niobium Leads to Optimal Behaviour in the Oxidative Dehydrogenation of Ethane

A Nb-containing siliceous porous clay heterostructure (PCH) with Nb contents from 0 to 30 wt %) was prepared from a bentonite and used as support in the preparation of supported NiO catalysts with NiO loading from 15 to 80 wt %. Supports and NiO-containing catalysts were characterised by several physicochemical techniques and tested in the oxidative dehydrogenation (ODH) of ethane. The characterisation studies on Nb-containing supports showed the presence of well-anchored Nb⁵⁺ species without the formation of Nb₂O₅ crystals. High dispersion of nickel oxide with low crystallinity was observed for the Nb-containing PCH supports. In addition, when NiO is supported on these Nb-containing porous clays, it is more effective in the ODH of ethane (ethylene selectivity of ca. 90 %) than NiO supported on the corresponding Nb-free siliceous PCH or on Nb₂O₅ (ethylene selectivities of ca. 30 and 60 %, respectively). Factors such as the NiO–Nb⁵⁺ interaction, the NiO particle size and the properties of surface Niⁿ⁺ species were shown to determine the catalytic performance.     

Untersuchungen an Nickeloxid-Mischkatalysatoren. XVI. Reduktionsverhalten amorpher NiO?Al2O3/SiO2-Katalysatoren

Studies on Nickel Oxide Mixed Catalysts. XVI. Reduction Behaviour of Amorphous NiO? Al₂O₃/SiO₂ Catalysts The reduction behaviour of NiO? Al₂O₃/SiO₂ catalysts prepared by precipitationdeposition is influenced by the phase composition (amorphous nickel layersilicates and nickel alumino layersilicates, nickel spinels, nickel oxide) and the differences of the composition between surface and bulk. TPR measurements, determinations of the reduction degree, and the nickel particle sizes by static magnetic measurements showed that the reducibility of the NiO? Al₂O₃/SiO₂ catalysts is enhanced and the nickel dispersity is decreased at low Al₂O₃ contents. The decrease of the reducibility at Al₂O₃ contents >5 mole% is caused by the formation of nickel spinels and the decrease of the Ni^II ion surface concentration.     

Untersuchungen an oxidischen Katalysatoren. XXXV. Redoxverhalten des Nickels in NiNaY-Zeolithen 2. Untersuchungen zur Dispersität von Ni- und Ni/NiO-Teilchen in reduzierten und reoxydierten NiNaY-Proben

Studies on Oxide Catalysts. XXXV. Redoxbehaviour of Nickel in Zeolite NiNaY. 2. Investigation on the Dispersion of Ni- und Ni/NiO-Species in Reduced and Reoxidized NiNaY Samples Oxygen chemisorption and electronmicroscopic measurements (ultramicrotome technique) correspondingly show a decrease of the metal dispersion with increasing reduction temperature (470–870 K) and exchange degree (10, 29, 54 equ.-% resp.). Contrary to this results electronmicroscopic measurements with replica technique don't reflect such a dependence. Increase of particle size after reoxidation (470 K) and reduction at 470 to 870 K (regeneration) of the NiNaY samples are attributed on the one hand to the aggregation of oxidic particles and on the other hand to metal sintering by the subsequent reduction step. A decrease of dispersion after a reoxidation process at 670 K is caused by formation and relocalisation of isolated nickel ions.     

Untersuchungen an oxidischen Katalysatoren. XLII. Redoxverhalten des Nickels in NiNa?Y-Zeolithen 4. Einfluß der Zusammensetzung auf die Reduzierbarkeit von Nickel in NiNa?Y-Zeolithen

Studies on Oxide Catalysts. XLii. Redox Behaviour of Nickel in Zeolites NiNa? Y. 4. Influence of Composition on the Reducibility of Nickel in Zeolites NiNa? Y By chemical analysis (reaction with K₂Cr₂O₇) and ESCA investigations we determined the degree of reduction in reduced samples NiNa-Y as function of the mole ratio SiO₂/Al₂O₃ (module), of the Ni²⁺ degree of exchange and the kind of the second cations. (NH₄₊, Ca²+, Co²+, and Nd³+) in the temperature region of 620–770 K. The degree of nickel reduction increases with increasing module, decreasing degree of exchange and decreasing number of Brönsted acidic centres. This behaviour is caused by the influence of the interaction between cations Ni²⁺ and zeolite lattice on the reduction equilibrium.     

Chemical composition optimization and characterization of the NiO/B<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system as a catalyst for ethylene oligomerization

The samples of the NiO/B₂O₃-Al₂O₃ system with NiO contents from 0.48 to 38.30 wt % were synthesized by the impregnation of borate-containing alumina (20 wt % B₂O₃). It was found that nickel oxide occurred in an X-ray amorphous state in the samples containing to 23.20 wt % NiO. At a NiO content of 4.86 wt % or higher, the support was blocked by the modifier to cause a decrease in the specific surface area from 234 to 176 m²/g and in the amount of acid sites from 409–424 to 333 μmol/g. An extremal character of the dependence of catalyst activity in ethylene oligomerization on NiO content was found with a maximum in the range of 4.86–9.31 wt %. Based on spectroscopic data, it was found that ethylene activation on the NiO/B₂O₃-Al₂O₃ catalyst can be associated with the presence of Ni²⁺ cations, which chemically interact with the support. The catalyst containing 4.86 wt % NiO at 200°C, a pressure of 4 MPa, and an ethylene supply rate of 1.1 h⁻¹ provided almost complete ethylene conversion at the yield of liquid oligomerization products to 90.0 wt %; the total concentration of C⁸⁺ alkenes in these products was 89.0 wt %.     

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.     

Untersuchungen an Nickeloxid-Mischkatalysatoren. XV. Oberflächenchemische Eigenschaften von NiO/Al2O3?SiO2-Katalysatoren

Studies on Nickel Oxide Mixed Catalysts. XV. Surface Chemical Properties of NiO/Al₂O₃-SiO₂ Catalysts Surface chemical properties of precipitated NiO/Al₂O₃? SiO₂ catalysts different compositions and the corresponding Al₂O₃? SiO₂ carriers have been investigated. Infrared spectroscopic measurements (before and after adsorption of pyridine and ammonia), ¹H-n.m.r. and ammonia adsorption measurements showed that the number of the Lewis-acidic sites are increased mainly by incorporation of the nickel component on the X-ray amorphous Al₂O₃? SiO₂ carriers, whereas the number of the hydroxide groups do not change significantly. With growing alumina content the number and the strength of the Lewis-acidic sites are increased where the part of the Ni^II surface sites decreases and those of the Al^III surface sites increases. Brönsted-acidic sites are detectable at high alumina contents.     

以水滑石及类水滑石为前体制备的Ni、Mg、Al混合氧化物的合成和表征

采用了BET、XRD、TG-DSC、TPR、FTIR、微量量热吸附和异丙醇催化反应等测试方法，对以共沉淀法合成的水滑石(HT)和类水滑石(HTLcs)为前体制备的4Mg/Al、3Ni/Mg/Al、3.5Ni/0.5Mg/Al和4Ni/Al混合氧化物和前体进行了研究。测定表明：制备的混合氧化物的比表面积较大、随着镍含量的增大而降低。由于Ni²⁺离子的氧化还原属性，Ni²⁺离子进入后，削弱了HT层对阴离子的键合能力，从而使得样品的热分解温度及热稳定性降低，导致焙烧后     

Electrolytic Nickel Oxides in the Electrodes of Lithium Secondary Batteries

A nickel oxide is synthesized for lithium secondary batteries using the suggested technology of electrolysis of aqueous solutions containing Ni²⁺. These oxides are studied by methods of x-ray structure analysis, thermal analysis, and atomic force microscopy in parallel with the determination of electrochemical characteristics. Electrolytic NiO has better specific discharge characteristics and cycle life as compared with other electrolytic nickel oxide compounds. It may be used as cathodic and anodic material in thin-layer lithium batteries.     

High selective ethylbenzene obtainment through alkylation of dilute ethene with gas phase-liquid phase benzene and transalkylation feed

A novel industrial process was designed for the highly selective production of ethylbenzene. It comprised of a reactor vessel, vapor phase ethylene feed stream, benzene and transalkylation feed stream. Especially the product stream containing ethylbenzene was used to heat the reactor vessel, which consisted of an alkylation section, an upper heat exchange section, and a bottom heat exchange section. In such a novel reactor, vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section. The process was demonstrated by the thermodynamic analysis and experimental results. In fact, during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction, the ethene conversion was above 95%, and the ethylbenzene selectivity was above 83% (only benzene feed) and even higher than 99% (benzene plus transalkylation feed). At the same time, the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140–185 °C of temperature, 1.6–2.1 MPa of pressure, 3.0–5.5 of benzene/ethylene mole ratio, 4–6 v% of transalkylation feed/(benzene+transalkylation feed), 0.19–0.27 h^?1 of ethene space velocity, and 1000 g of 3998 catalyst loaded. Thus, compared with the conventional ethylbenzene synthesis route, the transalkylation reactor could be omitted in this novel industrial process.     

EPR Studies of Photoreduction of Ni/TiO2 Catalysts

Irradiations of Ni/TiO₂ catalyst by UV in hydrogen at 77 K produced not only Ni⁺ ions on the catalyst surface, but also Ni³⁺ and Ti³⁺ species in bulk or near the interface between nickel and titania. These photo-generated species were detected and characterized by low temperature electron paramagnetic resonance (EPR) spectroscopy. Relative spin concentrations of the photogenerated paramagnetic species (Niⁿ⁺ and Ti³⁺) varied with the nickel content in titania. A high nickel content in the sample resulted in a high peak intensity ratio of Niⁿ⁺ to Ti³⁺. It was found that the photoinduced self-redox reaction of Ni²⁺ ions to form Ni⁺ and Ni³⁺ ions has a priority over the photoreduction of Ti⁴⁺ to Ti³⁺ ions. The characteristic EPR spectrum of the Ni³⁺ (3d⁷) ions with g₁ = 2.268, g₂ = 2.237, and g₃ = 2.045 indicates that the Ni³⁺ ions are most likely located in the substitutional sites of TiO₂, possibly near the surface rutile phase. The Ni⁺ species (3d⁹) with g₄ = 2.130 and g₁ = 2.063 are on the surface of TiO₂. Both Ni⁺ and Ni³⁺ ions are quite stable in hydrogen. The Ni³⁺ ions seem to be responsible for anchoring the nickel ions onto titania and stablizing the Ni⁺ species on the surface. The Ni⁺ ions are thus free from oxygen poisoning and still show a high activity toward olefin oligomerization.     

Untersuchungen an oxidischen Katalysatoren. XXIX. Spektroskopische und katalytische Untersuchungen an Ni2+-, Co2+-, Cr3+- und Cu2+-ausgetauschten Mordeniten

Studies on Oxide Catalysts. XXIX. Spectroscopic and Catalytic Investigations on Ni²⁺-, Co²⁺-, Cr³⁺-, and Cu²⁺-exchanged Mordenites NiNaM, CoNaM, CrNaM und CuNaM (M = Mordenite) have been characterized by UV-VIS, EPR and i.r. spectroscopy and the results were compared with the catalytic activity and the activity-time-dependence in the cracking of n-octane and with the shape selectivity in the cracking of a n-octane and isooctane mixture. Water molecules acting as ligands of the exchanged cations are able to dissociate yielding Brönsted acidity. Brönsted sites may be regarded as catalytic active centers in the cracking reaction. Unreduced transition metal cations facilitate the “coking” of the mordenite. The unreduced chromium and cobalt cations for which a position within the main channel is expected, affect the diffusion of the branched paraffin molecule thus increasing shape selectivity.     

Synthesis and selective recognition property of Ni2+‐imprinted microporous polymer beads

Nickel ion‐imprinted polymer (IIP) was synthesized from dimethylglyoxime and 4‐vinyl pyridine monomers. These functional monomers were self assembled with the Ni²⁺ template and then copolymerized with divinylbenzene and ethylene glycol dimethacrylate crosslinkers in toluene porogen via suspension polymerization. Imprinting was achieved by removing the template ion from the copolymers by extensive washing. The IIP particles produced were 300–700 µm in diameter and were spherical. The chemical and physical structures were characterized by Fourier transform infrared spectroscopy, energy dispersive X‐ray spectroscopy, and Brunauer–Emmett–Teller analysis. The adsorption capacity and kinetics, and separation selectivity were investigated using atomic adsorption spectroscopy in batch adsorption operation mode. The Ni²⁺‐imprinted polymers showed excellent adsorption ability and selective separation property. The adsorption capacity for Ni²⁺ was 320 µmol/g, and the selectivity factors (α) for Cu²⁺, Zn²⁺, Fe²⁺, and Cd²⁺ were 6, 11, 12, and 27, respectively. The adsorption capacity and separation selectivity were affected by the environmental pH, as the protonation easily took place in acidic condition. Copyright © 2013 John Wiley & Sons, Ltd.     

The effect of the precursor structure on the catalytic properties of the nickel—chromium catalysts of hydrogenation reactions

The influence of the Ni²⁺/Cr³⁺ ratio in the precursor compound on the formation of the catalyst structure and its transformation upon the thermal treatment and reductive activation in hydrogen was studied. The precursors with the cation ratio Ni²⁺/Cr³⁺ = (2.3–3)/1 represent a homogeneous system of the stichtite-type structure. The treatment of the precursors at T ～400 °C in an inert atmosphere forms a nanosized phase of the NiO-type structure with the lattice parameter a = 4.186±0.005 Å. At 600 °C the lattice parameter of this phase decreases to the tabulated value (a = 4.177±0.005 Å). The phase of nickel chromite of the cubic spinel structure with the lattice parameter a = 8.320±0.005 Å is also observed. Hydrogen activation of the catalyst preheated at 300 °C in an inert gas leads to the formation of Ni⁰ crystallites with a size of ～5.5 nm and a specific surface area of ～7.0 m² g^?1. This catalyst exhibits high activity and selectivity in benzene hydrogenation and preferential CO hydrogenation in the presence of CO₂. The catalysts with the ratio Ni²⁺/Cr³⁺ = 1/(2?3) containing nickel and chromium hydroxocarbonates as precursors are less active in the hydrogenation of benzene to cyclohexane.     

Simultaneous determination of copper, nickel, cobalt and zinc using zincon as a metallochromic indicator with partial least squares

The partial least squares (PLS) applied to the simultaneous determination of the divalent ions of copper, nickel, cobalt and zinc based on the formation of their complexes with 2-carboxy-2′-hydroxy-5′-sulfoformazyl benzene (zincon). The absorption spectra were recorded from 515 through 750 nm. The effect of pH on sensitivity and the selectivity was studied in the range 3.0-10.0 and the pH 8.0 was choused according to net analyte signal (NAS) as a function of pH. The concentration range for Cu²⁺, Ni²⁺, Co²⁺and Zn²⁺ in solution calibration sets were 0-2.6, 0-4.6, 0-3.0 and 0-4.92 ppm, respectively. The root mean squares differences (RMSD) for copper, nickel, cobalt and zinc were 0.0181, 0.0488, 0.0309 and 0.0463, respectively.