Tungsten Promoted Ni／Al2O3 Catalysts for Carbon Dioxide Reforming of Methane to Synthesis Gas

A series of tungsten promoted alumina supported nickel catalysts has been prepared for the carbon diox-ide reforming of methane to synthesis gas. The catalysts have been characterized by means of XRD, TEM,and Laser Raman spectroscopy. It is shown that the addition of tungsten to the nickel catalyst can stabilize the catalyst and increase the resistance to carbon deposition. Adding a suitable amount of tungsten can also increase the catalyst activity to be close to that of supported noble metal catalysts. The carburisation of the tungsten modified nickel catalyst decreases the catalyst activity at lower reaction temperatures (＜1123K),but has no effect on the catalyst performance at higher reaction temperatures. The alumina supported nickel catalyst modified by 0. 67% (mass fraction) WO3 has the equivalent equilibrium constant of the dry reforming reaction to that of alumina supported 5% (mass fraction) Ru at 873 K, and also has a lower activation energy for dry reforming than the latter.     

On the synthesis of chlorine pentafluoride

The reaction between chlorine trifluoride and elemental fluorine was studied in order to find the optimal reaction conditions for the synthesis of chlorine pantafluoride. It has been found that nickel difluoride is a very effective catalyst for the mentioned reaction. The obtained results are expressed as space-time-yield of chlorine pentafluoride.     

Raney镍催化松香加氢反应的机理

催化加氢;反应机理;氢化松香;Raney镍催化松香加氢反应的机理     

Perfluorinated membranes as catalyst supports

The perfluorinated polymer Nafion and porous PTFE/Nafion composite membranes have been employed as supports for nickel complexes or for platinum and palladium metal particles. The resultant materials have been employed as catalysts in various olefin conversion processes. Supported platinum and palladium metal systems were evaluated as catalysts for the hydrogenation of cyclohexene. Rates of reaction are better than those of commercially available catalysts; turnover numbers in excess of 6000 have been obtained with no poisoning apparent. Catalysts may be regenerated many times. The reduction rate approaches a limit at high pressures of hydrogen and has an activation energy of 13 kJ mol^?1 in neat cyclohexene. Nafion was employed as a strong acid cocatalyst to activate and then support a nickel complex catalyst. The resultant catalyst was active for double-bond-shift isomerization.     

1,2-二氯丙烷加氢脱氯制丙烯Ni/活化炭化树脂催化剂

镍催化剂;1;2-二氯丙烷加氢脱氯制丙烯Ni/活化炭化树脂催化剂     

Immobilization of nickel ions onto the magnetic nanocomposite based on cross‐linked melamine groups: Effective heterogeneous catalyst for N‐Arylation of Arylboronic acids

A new magnetic heterogeneous catalyst was synthesized by immobilization of nickel ions onto a cross‐linked polymeric nanocomposite composed of cyanuric chloride, ethylenediamine and functionalized magnetic nanoparticles. The resulting nitrogen rich support was capable of adsorbing large amounts of nickel ions (1.20 mmol g^?1). The synthesized catalyst was characterized using AAS, TEM, FT‐IR, EDX, TGA, SEM, BET and XRD techniques. The performance of the prepared catalyst was investigated in the C‐N coupling of arylamines with aryl boronic acids. The reaction was carried out under a mild condition and good to moderate to good yields of products was obtained using only 5.0 mol% of the catalyst. The catalyst was easily recovered and reused for at least 7 times without any significant loss of its activity.     

Carbon nitride with encapsulated nickel for semi-hydrogenation of acetylene: pyridinic nitrogen is responsible for hydrogen dissociative adsorption

A new mechanism of catalyst has been demonstrated in this article. With the interaction between carbon nitride (CN) and encapsulated nickel, the CN in the catalyst has been endowed with new active sites for the adsorption and activation of hydrogen while nickel itself is physically isolated from the contact with reactive molecules. For the selective hydrogenation of acetylene in large amount of ethylene, the catalyst shows excellent ethylene selectivity than the nickel catalyst itself, which is almost totally unselective. Meanwhile, the CN itself is inactive for the reaction. The results of characterization demonstrate that pyridinic nitrogen doped in the carbon matrix should be the active sites for hydrogen dissociative adsorption. The theoretical calculations further confirm the results and provide with the detail in the electron transfer between nickel and CN in the catalyst. The current results supply a new concept for design of high performance catalyst.     

Studies on a vapour-phase process for the manufacture of chlorofluoroethanes

Fluorination of hexachloroethane or of tetrachloroethylene + chlorine by hydrogen fluoride at ca. 400°C in the presence of an aluminium fluoride catalyst gives the unsymmetrical isomers of dichlorotetrafluoroethane and of trichlorotrifluoroethane as the major products. Under similar conditions but using a catalyst of aluminium fluoride containing small amounts of iron, chromium and nickel, symmetrical trichlorotrifluoroethane is the major product. Analogous fluorinations of various intermediates over these catalyst systems have been studied and detailed information about the reaction pathways obtained. Under suitable conditions, s-trichlorotrifluoroethane or s-dichlorotetrafluoroethane can be prepared in a high state of purity.     

Simultaneous Production of Hydrogen and Carbon Nano-Materials from Decomposition of Methane

From the decomposition of methane, hydrogen without carbon oxides can be produced with a high energy-efficiency, which is attractive for its suitability of utilization in the fuel cells. At a same time carbon nano-materials with attractive texture and structure can be produced in a large amount. Toward a simultaneous bulk production of hydrogen and nanocarbon, catalysts based on nanometer scale nickel particles prepared from a hydrotalcite-like anionic clay precursor have been designed and tested to fit the process goals. For hydrogen production, as the equilibrium methane conversion of the reaction increases with the increase of the reaction temperature, the process is commercially more attractive if it can be operated at a temperature higher than 1073 K. However, a nickel catalyst has a maximum activity for nanocarbon production at 923 K. Modification of the catalyst with doping of copper increased the activation temperature and leads to a production of nanocarbon with an tubular structure. The feasibility and the challenges met for the coupling of the two process goals is discussed, and some promising results are presented in this work.     

Catalytic performance of Ni-Al layered double hydroxides in CO purification processes

Ni-Al layered double hydroxides with Ni²⁺/Al³⁺ molar ratios of 1.5 and 3.0 have been synthesized by co-precipitation and studied as catalyst precursors for purification of CO-containing gas-mixtures by means of CO oxidation to CO₂ and conversion of CO by water vapor (water-gas shift reaction). The influence of the alkali additives (K⁺ ions) on the water-gas shift activity has been also examined. It was established that the catalytic activity of both reactions increases with the temperature and the nickel content. Hypothetic schemes are proposed about activation of the catalysts in the WGSR and CO oxidation including redox Ni²⁺ ? Ni³⁺ transition on the catalyst surface. The activity in WGSR is positively affected by the presence of potassium promoter, depending on its amount. The sample with higher nickel loading is the most effective catalyst as for CO oxidation as well as for WGSR at intermediate temperatures after potassium promotion.     

Solid-supported cross-coupling catalysts derived from homogeneous nickel and palladium coordination complexes

Solid-supported catalysts derived from homogeneous nickel(II) and palladium(II) non-symmetrical salen-type coordination complexes have been prepared and shown to be effective in the heterogeneous catalysis of carbon-carbon cross-coupling reactions. The nickel catalyst has been used in room-temperature Tamao-Kumada-Corriu reactions and the palladium catalyst in the Heck reaction at elevated temperatures. The complexes were prepared by improved methods and characterised by spectroscopic techniques. Comparisons between the solid-supported catalysts and their homogeneous analogues are reported. The single-crystal structure determination of the nickel and palladium complexes [M(salenac-OH)][M = Ni, Pd; salenac-OH = 9-(2',4'-dihydroxyphenyl)-5,8-diaza-4-methylnona-2,4,8-trienato](2-)] is reported.     

Linear dimerization of propylene and 1-butene catalyzed by (η3-4-cyclooctene-1-yl)- (1,1,1,5,5-hexafluoro-2,4-pentanedionato)nickel

The dimerization and oligomerization of propylene and 1-butene in the presence of homogeneous Group VIII transition metal catalysts has been extensively studied. In most cases the products obtained are mixtures of isomers in which branched species predominate, in accordance with preferred anti-Markownikov addition pathways.In what is perhaps the most well-defined catalyst system to date, a family of substituted fluoroacetylacetonate cyclooctenyl nickel complexes, 1-butene is oligomerized to up to 82% linear octenes. Propylene and 1-butene are dimerized to predominantly normal alkenes using homogeneous hydrocarbon solutions of (η³-4-cyclooctene-1-yl)(1,1,1,5,5,5-hexafluoro)-2,4-pentanedionato)nickel. Two disadvantages of this catalyst system are its relatively low activity and rapid deactivation on storage.In this paper, an improved synthesis of the catalyst is reported, in addition to a method of catalyst storage which virtually eliminates deactivation A comprehensive olefin dimerization reaction scheme is formulated on the basis of detailed gas chromatographic analyses of propylene and 1-butene dimers. The relative amounts of the materials identified allow conclusions to be drawn on relative rates for the competing olefin insertion, β-elimination pathways.     

Mechanism of dehydrohydrolysis of cyclohexylamine with water vapor on a nickel-chromium catalyst

The mechanism of the dehydrohydrolysis of cyclohexaylamine by water vapor on a nickel-chromium catalyst has been studied by IR spectroscopy of the adsorbed molecules and the response method. It has been shown that the reaction proceeds via the formation of a nickel oxide complex and its interaction with an adsorbed cyclohexylamine molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2732–2739, December, 1991.     

New mechanistic aspects and structure activity relationships in the allyl nickel complex catalysed butadiene polymerization

The present state of knowledge of the mechanism of the allyl nickel complex catalysed stereoselective butadiene polymerization is outlined. On the basis of the reaction model, which has been worked out more thoroughly and comprehensively by our systematic experimental investigations during the last years, the thermodynamic and kinetic control of the catalytic activity and selectivity in dependence on the structure of the allylnickel complexes will be discussed. Finally, it will be shown how the structure of the technical nickel catalyst could be elucidated for the first time and how its catalytic properties can be explained in the framework of the derived structure-activity relationships.     

Tandem Difluoroalkylation‐Arylation of Enamides Catalyzed by Nickel

A nickel‐catalyzed three‐component reaction for the synthesis of difluoroalkylated compounds through tandem difluoroalkylation‐arylation of enamides has been developed. The reaction tolerates a variety of arylboronic acids and widely available difluoroalkyl bromides, and even the relatively inert substrate chlorodifluoroacetate. The significant advantages of this protocol are the low‐cost nickel catalyst, synthetic convenience, excellent functional‐group compatibility and high reaction efficiency.     

Effect of group VIII elements on the behavior of Li/CaO catalyst in the oxidative dehydrogenation of ethane

The effect of addition of group VIII elements to Li/CaO on the oxidative dehydrogenation of ethane has been investigated in the range of 550–650°c. Iron, cobalt and nickel promote the reaction. The experiments show that iron and cobalt additives in Li/CaO catalysts mainly increase the catalytic activity. Li/Ni/CaO catalyst gives a high ethane conversion and excellent ethylene selectivity. The results on the catalyst are probably due to coordinative interaction between lithium and nickel. The characteristics of the catalysts revealed by XRD also give evidence that the promotion for both catalytic activity and ethylene selectivity is directly related to the formation of favorable crystal phases.     

How does the nickel pincer complex catalyze the conversion of CO2 to a methanol derivative? A computational mechanistic study

The mechanistic details of nickel-catalyzed reduction of CO(2) with catecholborane (HBcat) have been studied by DFT calculations. The nickel pincer hydride complex ({2,6-C(6)H(3)(OP(t)Bu(2))(2)}NiH = [Ni]H) has been shown to catalyze the sequential reduction from CO(2) to HCOOBcat, then to CH(2)O, and finally to CH(3)OBcat. Each process is accomplished by a two-step sequence at the nickel center: the insertion of a C═O bond into [Ni]H, followed by the reaction of the insertion product with HBcat. Calculations have predicted the difficulties of observing the possible intermediates such as [Ni]OCH(2)OBcat, [Ni]OBcat, and [Ni]OCH(3), based on the low kinetic barriers and favorable thermodynamics for the decomposition of [Ni]OCH(2)OBcat, as well as the reactions of [Ni]OBcat and [Ni]OCH(3) with HBcat. Compared to the uncatalyzed reactions of HBcat with CO(2), HCOOBcat, and CH(2)O, the nickel hydride catalyst accelerates the H(δ-) transfer by lowering the barriers by 30.1, 12.4, and 19.6 kcal/mol, respectively. In general, the catalytic role of the nickel hydride is similar to that of N-heterocyclic carbene (NHC) catalyst in the hydrosilylation of CO(2). However, the H(δ-) transfer mechanisms used by the two catalysts are completely different. The H(δ-) transfer catalyzed by [Ni]H can be described as hydrogen being shuttled from HBcat to nickel center and then to the C═O bond, and the catalyst changes its integrity during catalysis. In contrast, the NHC catalyst simply exerts an electronic influence to activate either the silane or CO(2), and the integrity of the catalyst remains intact throughout the catalytic cycle. The comparison between [Ni]H and Cp(2)Zr(H)Cl in the stoichiometric reduction of CO(2) has suggested that ligand sterics and metal electronic properties play critical roles in controlling the outcome of the reaction. A bridging methylene diolate complex has been previously observed in the zirconium system, whereas the analogous [Ni]OCH(2)O[Ni] is not a viable intermediate, both kinetically and thermodynamically. Replacing HBcat with PhSiH(3) in the nickel-catalyzed reduction of CO(2) results in a high kinetic barrier for the reaction of [Ni]OOCH with PhSiH(3). Switching silanes to HBcat in NHC-catalyzed reduction of CO(2) generates a very stable NHC adduct of HCOOBcat, which makes the release of NHC less favorable.     

Ni/sepiolite hydrogenation catalysts: Part 1: Precursor–support interaction and nature of exposed metal surfaces

A 10% loaded nickel on sepiolite catalyst has been prepared by a precipitation method and the characteristics of the resultant material compared with a similarly prepared Ni/silica catalyst and a sample in which only ion exchanged nickel was present in the sepiolite. Samples have been characterised by infrared (IR) and X-ray photoelectron spectroscopies, ²⁹Si MAS–NMR and X-ray diffraction in an attempt to determine the nature of the nickel species present in the precursor stage. Nickel silicate species have been identified for both supports but this precursor is more resistant to reduction for the sepiolite which leads to the formation of catalysts with lower metal areas than the silica support. The nature of the reduced nickel particles has been determined by hydrogen chemisorption, IR of adsorbed CO and temperature programmed desorption of hydrogen.     

CO2化学利用的一条新途径

C02开发利用一直是世界各国大型化工企业异常关注的研究课题，但是，由于C02结构稳定，化学活性差，因而决定了该领域的研究课题难度较大，进展比较缓慢．本文报道了一种利用天然气还原C02制备会成气的最新研究结果，该过程不仅可以为破一化学工业提供廉价原料，从而开辟一条极重要的非石油原料的化学工业路线，而且对减缓全球性温室效应也具有一定的社会意义．1实验日分1·1催化剂制备按表1所列组成，以7－AI。0。、硝酸镍、硝酸镁和稀土硝酸盐为原料，采用常规浸渍法参照文献［‘］制备催化剂．1·Zfffe反应评价催化反应评价采用双套管…     

Neutral nickel oligo- and polymerization catalysts: the importance of alkyl phosphine intermediates in chain termination

An unconventional chain termination reaction has been explored for the SHOP (Shell higher olefin process)-type, anilinotropone, and salicylaldiminato nickel-based oligo- and polymerization catalysts by using density functional theory (DFT). Starting from the tetracoordinate alkyl phosphine complex, the termination reaction was found to involve a rearrangement of the alkyl chain to form a pentacoordinate β-agostic complex, β-hydride elimination, and olefinic chain dissociation and to compete with propagation at sufficiently high phosphine concentration and/or basicity. It provides the first complete and convincing mechanistic rationale for the decreasing chain lengths observed upon increasing phosphine concentration and basicity. The unconventional reaction was found to be a major termination pathway for the SHOP-type catalyst and is very unlikely to lead to branching and olefin isomerization, which is critical for explaining why the SHOP catalyst, in contrast to the anilinotropone and salicylaldiminato catalysts, tends to lead to the oligomerization of ethylene to form linear α-olefins. Based on our results we have proposed a new and extended catalytic cycle for the SHOP-type ethylene oligomerization catalyst. Finally, the importance of the new termination reaction for the SHOP-type catalyst suggests that this reaction may also operate with other ethylene oligomerization nickel catalysts. This prediction was confirmed for a pyrazolonatophosphine catalyst, for which the new termination route was found to be even more facile, which explains the short oligomers produced by this catalyst.