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1.
Ni/SiO2 materials with identical composition (SiO2/Ni = 1.0) have been synthesized by precipitation of Ni(NO3)2 · 6H2O solution with Na2CO3 solution on the silica gel, obtained at three different pH values. The present investigation was undertaken in an endeavor to study the effects of the silica gel support type and the reduction temperature on the formation and dispersion of the metallic nickel phase in the reduced Ni/SiO2 precursors of the vegetable oil hydrogenation catalyst. The physicochemical characterization of the unreduced and reduced precursors has been accomplished appropriately by powder X-ray diffraction, infrared spectroscopy, temperature programmed reduction and H2-chemisorption techniques. It can be stated that the texture peculiarities of the silica gels used as supports influence on the crystalline state and distribution of the deposited Ni-containing phases during the preparation of the precursors, on the reduction temperature of the investigated solids as well as on the bulk size and surface dispersion of the arising metallic nickel particles. It was shown that two types of Ni2+-species are formed during the synthesis procedure, namely basic nickel carbonate-like and Ni-phyllosilicate with different extent of presence, location and strength of interaction. The different location of these species is supposed to result in various strength of Ni-O and Ni-O-Si interaction, thus determining the overall reducibility of the precursors. It was specified that the Ni2+-species are strongly bonded to the surface of the silica gel obtained at neutral pH value and weakly bonded to the surface of those prepared in acidic and alkaline conditions. It was established that the precursor, derivates from the silica gel obtained at alkaline conditions, demonstrates both significant reduction of the Ni2+ ions at 430°C and finely dispersed metallic nickel particles on its surface. High dispersion of the metallic nickel might be the crucial reason for achieving of high activity in the vegetable oil hydrogenation.  相似文献   

2.
CuO/SiO2 and NiO/SiO2 with bimodal pore structure were prepared by sol-gel reactions of Tetra-methoxysilane (TMOS) and the respective metal nitrate in the presence of poly (ethylene oxide) (PEO) with an average molecular weight of 10 000 and the catalyst of acetic acid. In this process, the interconnected macroporous morphology was formed when transitional structures of spinodal decomposition were frozen by the sol-gel transition of silica. The addition of copper and nickel into the silica-PEO system had a negligible effect on the morphology formation. In gel formation, it was found that NiO crystalline sizes in the samples increased with decreasing Si/Ni molar ratio. It was considered that PEO interacted with both silica and nickel cations. In the CuO/SiO2 with the presence of PEO, CuO crystalline sizes were larger than those of NiO/SiO2. It was considered that there was no obvious interaction between the Cu cation and PEO, most of the copper ions in wet silica gel were present in the outer solution. They easily aggregated as copper salts in the drying process of wet gel and decomposed into CuO particles in heating. While in the CuO/SiO2 with the absence of PEO, the Cu was selectively entrapped as small particles in the gel skeleton due to the interaction between Cu aqua complex and silica gel network.  相似文献   

3.
Two series of silver modified Ni-Mg materials were synthesized by precipitation-deposition on SiO2 support derived from two silica sources: diatomite activated at 800°C (Series a; Mg/Ni = 0.1 and SiO2/Ni = 1.07) and synthetic water glass (Series b; Mg/Ni = 0.1 and SiO2/Ni = 1.15). The modification with silver was made at three molar Ag/Ni ratios, namely 0.0025, 0.025, and 0.1. The effects of the source of the silica support and the silver presence and content on the nickel state in the silver modified reduced-passivated NiMg/SiO2 precursors of the vegetable oil hydrogenation catalyst were established by X-ray diffraction and X-ray photoelectron spectroscopy techniques. The passivation procedure was applied in order to protect the metallic nickel particles from further oxidation. The crystallization of the formed nickel hydrosilicate phases depends on the source of the silica support, more expressed in the diatomite supported samples. It was shown that the silver modification of the NiMg/SiO2 precursors enhances the reduction of the nickel hydrosilicates accompanied by formation of relatively smaller metallic nickel particles, more pronounced in the water glass supported precursors. The increase of the silver content in the water glass deposited samples is responsible for the metallic nickel dispersion increase. The higher content of the Ni0 particles on the surface of the diatomite deposited samples is in accordance with the higher stability of the larger metallic nickel crystallites to oxidation during the passivation step. On contrary, higher dispersed Ni0 particles on the surface of the water glass supported samples are more susceptible to the oxida The article is published in the original.  相似文献   

4.
Structural formation process of Ni/SiO2 and Cu/SiO2 catalysts prepared by solution exchange of wet silica gel was investigated. Microstructures of Cu/SiO2 and Ni/SiO2 were quite different from each other. In the case of Cu/SiO2, Cu particles with diameter of ca. 3–5 nm dispersed homogeneously at less Cu content, and the particle size of Cu as well as pore size of silica gel support increased with increasing Cu content. In the Ni/SiO2, the Ni particles with diameter of ca. 6–10 nm gathered densely to form aggregates in silica matrix resulting in sea-island structure, whereas the size of Ni particle slightly increased with increasing Ni content. The difference in the structure of the metal-silica composites is probably caused by the difference in interaction between silica gel network and metal ions during drying and heating processes.  相似文献   

5.
This work continues a series of our studies on the synthesis of nanostructured carbon (NSC) by the pyrolysis of H2 + C3–C4 alkane mixtures on nickel and cobalt metal catalysts supported on chemically diverse inorganic materials (aluminosilicates, alumina, carbon) having different textural characteristics (mesoporous and macroporous supports) and shapes (granules, foamed materials, and honeycomb monoliths). Here, we consider Ni catalysts supported on granular mesoporous silica (SiO2). It has been elucidated how the yield of synthesized carbon depends on the Ni/SiO2 catalyst preparation method (homogeneous precipitation or impregnation) and on the composition of the impregnating solution, including the molar ratio of its components—nickel nitrate and urea. The morphology of catalytic NSC and Ni distribution in the silica granule have been investigated using a scanning electron microscope with an EDX analyzer. Carbon-containing composite supports (NSC/SiO2) have been employed as adsorbents for immobilizing microbial lipase. The enzymatic activity and stability of the resulting biocatalysts have been estimated in transesterification reactions of vegetable (sunflower and linseed) oils involving methyl or ethyl acetate, esterification, and synthesis of capric acid–isoamyl alcohol esters in nonaqueous media.  相似文献   

6.
NiO/SiO2 catalysts were prepared with Ni contents ranging from 2–15% using a microporous silica support at pH ~11.5. The role of the method of preparation on the resulting catalyst is also investigated. Structural and textural changes were followed using X-ray diffraction, TG and DTA techniques—the surface area measurements were carried out on the parent catalysts and those produced in the temperature range 250–1000°C.Impregnation of the silica gel in the nickel ammine complex solution (catalyst series 1N–4N) with subsequent drying at 80°C overnight produced crystalline catalysts with two distinct peaks at d-spacings of 2.035 and 2.349 Å resulting from a surface silicate. This is easily destroyed by thermal treatment at 250°C for Ni contents ? 10% but is stable to this temperature for the higher Ni content. Drying the catalyst at room temperature (3Nb) gives rise to an amorphous product. A non-crystalline catalyst is also obtained when concentrated ammonia solution is added to the adsorbed nickel salt (3Nc). At high Ni content, the hydroxo ligand becomes significant and results in a surface compound in which one silanol group is attacked. This gives rise to a crystalline product at 500°C with characteristic d-spacings at 2.201 and 2.049 Å which, subsequently, produces a poorly crystalline NiO product at 1000°C. The presence of this hydroxo ligand is manifested by a small endotherm at 260°C.At Ni contents below 15% but greater than 2% a small exotherm is observed at ~ 500°C resulting from a reduction process. Entrained SO42? ions present as an impurity are evolved at temperatures & > 750°C and can be estimated by TG analysis.The specific surface area decreases with Ni contents ? 5% but increases for higher Ni contents. Catalyst samples containing 15% Ni possess the highest specific area at all temperatures.Pore structure analysis showed that microporosity increased with increase in Ni content for the catalyst series 1N–4N. Samples from preparations 3Nb and 3Nc showed more mesoporosity than that of 3N. Thermal treatment causes widening of the pores for catalysts 1N–3N becoming predominantly mesoporous, co-existing with some micropores. Catalyst samples with 15% Ni remained predominantly microporous-mesoporosity increasing only at 1000°C.  相似文献   

7.
A significant effect of pore size has been found on the yield of photolysis of water to hydrogen, ozone (oxidising product) and methane (decomposing product of catalyst or solvent) using [pol-Ti(OBu)4 + CH3OH]-complex/SiO2. The pore structure of silica gel has been found to provide good conditions for forming this type of catalyst.  相似文献   

8.
In spite of great commercial importance of the Phillips CrOx/SiO2 catalyst and long term research efforts, the precise physicochemical nature of active sites and polymerization mechanisms still remains unclear. The difficulties in a clear mechanistic understanding of this catalyst mainly come from the complexity of the surface chemistry of the amorphous silica gel support. In this work, novel silsesquioxane-supported Phillips Cr catalysts are utilized as realistic models of the industrial catalyst for theoretical investigation using the density functional theory (DFT) method in order to elucidate the effects of surface chemistry of silica gel in terms of supporting of chromium compounds and fluorination of the silica surface on the catalytic properties of the Phillips catalyst. Both qualitative and quantitative aspects with respect to various electronic properties and thermodynamic characteristics of the model catalysts were achieved. The future prospects of a state-of-the-art catalyst design and mechanistic approaches for the heterogeneous SiO2-supported Phillips catalyst has been demonstrated. The text was submitted by the authors in English.  相似文献   

9.
CH4与CO2干重整反应对于环境保护和天然气资源的合理利用具有重要意义。SiO2和Al2O3是适用于甲烷干重整反应的两种典型的催化剂载体。为了阐明这两种载体对催化剂性能的影响,本研究采用等体积浸渍法制备了Ni/Al2O3和Ni/SiO2催化剂,并利用BET、TEM、H2-TPR、XRD、TG和Raman等技术对还原和反应后的催化剂进行了表征。结果表明,由于载体的性质不同,Ni基催化剂在甲烷干重整中的催化性能也不同。Ni/SiO2催化剂的初始活性较高,但由于其金属-载体相互作用较弱,催化稳定性较差,在800℃下反应15h其催化活性急剧下降;较弱的金属-载体相互作用使得Ni/SiO2催化剂上的Ni颗粒较大,有利于积炭前驱物种的生成,导致催化剂快速失活。而对于Ni/Al2O3催化剂,金属-载体相互作用较强,Ni颗粒较小,但由于Ni与Al2O3生成了NiAlxOy物种,有效活性位减少,其催化活性相对较低,但催化稳定性较好,干重整反应进行50h其活性保持稳定;Ni与Al2O3之间较强的相互作用有利于形成小且稳定的Ni粒子,能减少积炭,因而具有优异的催化稳定性。  相似文献   

10.
Song  Qi  Ran  Rui  Li  Dongyang  Zhao  Baohuai  Weng  Duan 《Catalysis Surveys from Asia》2021,25(3):312-323

Mesoporous silica was used in conjunction with the ammonia evaporation method to prepare highly dispersed Ni catalysts for the dry reforming of methane (DRM). The effect of Ni dispersion on the catalytic performance was investigated by applying different Ni loadings. The pore structure, morphology, Ni dispersion, catalytic activity for DRM as well as the coke resistance were investigated. During the reaction at a relatively low temperature of 600 °C, all the three catalysts exhibited high stability in CH4 and CO2 conversion and excellent coke resistance, in comparison to Ni/SiO2 catalyst prepared by the incipient wetness method. Among them, 10% Ni–SiO2 exhibited the best catalytic performance with the maximum steady conversions of 62% and 69% for CH4 and CO2 at 600 °C, which was beneficial from its optimal Ni content and the presence of highly-dispersed metal nanoparticles confined in the mesopores.

  相似文献   

11.
A new variant of the sol–gel method for synthesising silica glasses and optical composites containing nanoparticles of chromium oxide has been designed. Monolithic gels are produced by mixing preformed silica modified with chromium oxide (Cr2O3/SiO2), with a sol–gel solution containing Si(OC2H5)4, and gelation catalyst ((CH2)6N4 or NH3). Highly dispersed Cr2O3/SiO2 samples were synthesised through a step-by-step controlled adsorption of vapours of CrO2Cl2 and C6H14 on the surface of fumed silica (A-300) and a subsequent thermal decomposition. With increasing chromium concentration in samples from 0.9 to 5.1 wt.%, the size of chromium oxide nanoparticles increases from 10 to 46 nm. XRD, DTA, TG, IR-spectroscopy and measurements of specific surface area have been used to investigate structural and physico-chemical properties of Cr2O3/SiO2 and xerogels during the course of their thermal transformations up to formation of glasses. A study has also been carried out of optical properties of transparent samples (distribution of refractive index values through cross section of a preform). The glasses synthesised with the aid of Cr2O3/SiO2 have a more uniform distribution of doping constituents and exhibit a larger refractive index in comparison to glasses synthesised through impregnation of silica matrices with a solution of (NH4)2Cr2O7.  相似文献   

12.
Aluminum was doped into amorphous silica gel to modify its surface structure. The obtained SiO2-Al2O3 support was used to prepare the CuCl/SiO2-Al2O3 catalyst by solid-state ion exchange, and the catalyst activity for liquid-phase oxidative carbonylation of methanol to dimethyl carbonate was investigated. The results showed that the prepared SiO2-Al2O3 support kept the amorphous structure of the silica gel. The BET specific surface area of the silica gel was decreased to 200 m2/g, and the surface acid sites (including Brønsted acid sites) were increased. In the CuCl/SiO2-Al2O3 catalyst, CuCl was not only dispersed on surface but also was ion exchanged with surface Brønsted acid sites of the SiO2-Al2O3 support to form Cu+ species, which resulted in a decrease in BET specific surface area to 148 m2/g. These two kinds of Cu+ species on the catalyst surface were both active centers for the oxidative carbonylation of methanol to dimethyl carbonate. When the catalyst was prepared with Si/Al molar ratio of 5 and was calcined at 500 °C, the selectivity and space-time yield of dimethyl carbonate reached 74% and 1.27 g/(g·h), respectively.  相似文献   

13.
Summary: Supported catalyst system for the slurry phase polymerization of styrene in toluene was prepared by the immobilization of 2-methylindenyltrichlorotitanium(2-MeIndTiCl3) on silica and activation of this catalyst was performed by methylaluminoxane(MAO) in polymerization media. Homogeneous polymerization of styrene with 2-methylindenyltrichlorotitanium activated by MAO was performed in toluene. The morphology of obtained syndiotactic polystyrene (sPS) via heterogeneous and homhgeneous catalyst system was compared. Polymerization of styrene by homogeneous catalyst lead to formation of gel and resultant polymers presented a compact and dense texture while the global gelation do not occur with silica supported catalyst at different Ti/SiO2 mol ratios and sPS was obtained as separated particles. Unlike to the homogeneous catalyst, obtained polymers showed a porous texture. Highly porous texture of sPS was obtained with Ti/SiO2 = 0.5% mol ratio.  相似文献   

14.
The activity of NiCu-SiO2 catalysts with a metal content of 90% and different Ni/Cu ratios has been investigated in the hydrodeoxygenation of anisole, a model compound of bio-oil, at 280°C and 6 MPa. A homogeneous phase composition of the active component has been synthesized by the co-decomposition of nickel and copper nitrates followed by the introduction of SiO2 as a stabilizer. The resulting catalysts have been characterized by temperature-programmed reduction, X-ray powder diffraction, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy combined with energy-dispersive microanalysis. The bulk and surface composition of active-component particles has been determined by XPS and X-ray diffraction. In all of the catalysts containing 15–85 wt % Ni, there are two types of solid solutions. One has a constant composition, Cu0.95Ni0.05, which is independent of the Ni/Cu ratio in the catalyst; in the other, the nickel stoichiometry increases with an increasing Ni content of the active component. A correlation has been established between the Ni/Cu ratio and the rate constants of the reaction examined and between the Ni/Cu ratio and the degree of hydrodeoxygenation for all samples. The most active catalyst is Ni85Cu5-SiO2.  相似文献   

15.
This review paper reports the recent progress concerning the application of nickel–alumina–zirconia based catalysts to the ethanol steam reforming for hydrogen production. Several series of mesoporous nickel–alumina–zirconia based catalysts were prepared by an epoxide-initiated sol–gel method. The first series comprised Ni–Al2O3–ZrO2 xerogel catalysts with diverse Zr/Al molar ratios. Chemical species maintained a well-dispersed state, while catalyst acidity decreased with increasing Zr/Al molar ratio. An optimal amount of Zr (Zr/Al molar ratio of 0.2) was required to achieve the highest hydrogen yield. In the second series, Ni–Al2O3–ZrO2 xerogel catalysts with different Ni content were examined. Reducibility and nickel surface area of the catalysts could be modulated by changing nickel content. Ni–Al2O3–ZrO2 catalyst with 15 wt% of nickel content showed the highest nickel surface area and the best catalytic performance. In the catalysts where copper was introduced as an additive (Cu–Ni–Al2O3–ZrO2), it was found that nickel dispersion, nickel surface area, and ethanol adsorption capacity were enhanced at an appropriate amount of copper introduction, leading to a promising catalytic activity. Ni–Sr–Al2O3–ZrO2 catalysts prepared by changing drying method were tested as well. Textural properties of Ni–Sr–Al2O3–ZrO2 aerogel catalyst produced from supercritical drying were enhanced when compared to those of xerogel catalyst produced from conventional drying. Nickel dispersion and nickel surface area were higher on Ni–Sr–Al2O3–ZrO2 aerogel catalyst, which led to higher hydrogen yield and catalyst stability over Ni–Sr–Al2O3–ZrO2 aerogel catalyst.  相似文献   

16.
The organic–inorganic composite materials based on mesoporous silica were synthesized using sol–gel method. The surface area of silicas was modified by bovine serum albumin (BSA) and guanidine polymers: polyacrylate guanidine (PAG) and polymethacrylate guanidine. The mesoporous silicas were characterized by nitrogen adsorption–desorption analysis, Fourier transform infrared spectroscopy, transmission electron microscopy. The obtained materials were used as adsorbents for selective bilirubin removal. It was shown that the structural properties and surface area of modified materials depend on the nature of polymers. Incorporation of polymers in silica gel matrix during sol–gel process leads to the formation of mesoporous structure with high pore diameter and a BET surface area equals to 346 m2/g for SiO2/BSA and 160 m2/g for SiO2/PAG. Analysis of adsorption isotherms showed that modification of silica by BSA and guanidine polymers increases its adsorption ability to bilirubin molecules. According to Langmuir model, the maximum bilirubin adsorption capacity was 1.18 mg/g.  相似文献   

17.
An effective way of trapping phthalocyanines inside porous silica has been achieved when an aqueous solution of these macrocyclic species is reacted in situ with silicon alkoxide. The resultant porous gel network can encapsulate a myriad of metal phthalocyanine molecules at relatively high concentrations and, most importantly, in a disaggregated way. By employing this method metal sulfophthalocyanines of Fe, Co, Ni, Cu, Al, Eu or Sm can be encapsulated within SiO2 xerogels. Here, the chemical entrapment of phthalocyanines inside silica gel pore networks is accomplished by the attachment of bifunctional groups to the walls of these substrates; while one of these moieties is directly linked to the macrocycle end groups, the other one is covalently bonded to the silanol groups resting on the SiO2 walls. Furthermore, when the proper concentrations of phthalocyanine species, H2O, silicon alkoxide, and HCl are reacted together, it is possible to obtain monolithic translucent silica xerogels. This latter property provides straightforward evidence of the innate fluorescence of the trapped macrocycles. The average size of the cavities encapsulating the macrocyclic molecules range from 2.0 to 3.6 nm; the precise size depends on the cation present in the complex and on the identity and position of the substituent groups at the periphery of the macrocycle. When the silica network is prepared from standard and/or organo-substituted alkoxides, the aggregation, degradation or stability of the macrocyclic species trapped in silica cavities depends on the nature of the alkyl group attached to the pore walls.  相似文献   

18.
Abstract

Tunisian industrial phosphoric acid H3PO4 was supported on silica gel SiO2 (SIPA) to catalyze the hydrolysis reaction of aqueous alkaline sodium borohydride (NaBH4). The SiO2 was produced from purified quartz sand using alkali fusion-acidification chemical process. The BET surface area results indicate that the prepared silica gel could reach a specific surface area up to 585 m2/g. The addition of PO3H2 functional groups resulted in an increase of surface acidity of SiO2 catalyst as shown by FT-IR and DTA-DTG spectra. The total acidity of SIPA catalyst was determined by titration to be 2.8?mmol H+/g. SEM/EDS maps reveal the distribution of heavy metals on the silica surface. The effect of supported PO3H2 functional groups and heavy metals on the NaBH4 hydrolysis reaction was studied for different ratios of SIPA catalyst to NaBH4. The sample 12SIPA/NaBH4 leads to a very high hydrogen generation rate (up to 90%). The activation energy of hydrogen generation by NaBH4 hydrolysis was 25.7?kJ mol?1.  相似文献   

19.
A novel and simple method for the synthesis of monodispersed microporous SiO2 microspheres with high specific surface area was developed by hydrolysis of tetraethoxysilane (TEOS) in a water-ethanol mixed solution and using dodecylamine (DDA) as hydrolysis catalyst and template. The as-prepared products were characterized with differential thermal analysis-thermogravimetry, scanning electron microscopy, high-resolution transmission electron microscopy, small angle X-ray diffraction and nitrogen adsorption. The effects of experimental conditions including hydrolysis temperatures, calcination temperature and concentrations of TEOS and DDA on the morphology and pore parameters of the as-prepared SiO2 microspheres were investigated and discussed. The results showed that hydrolysis temperature and concentrations of TEOS and DDA are important parameters for the control of size and morphology of particles. The specific surface area and specific pore volume of the as-prepared SiO2 microspheres increased with increasing DDA concentration and calcination temperature. DDA may act not only as a good hydrolysis catalyst but also as a template for the formation of monodispersed SiO2 microspheres with high specific surface area. This research may provide new insight into the synthesis of monodispersed microporous SiO2 microspheres.  相似文献   

20.
The effect of a cerium additive on the catalytic activity of a 2 wt % Ni/SiO2 catalyst is studied. It found that under both flow and static conditions the activity of (2 wt % Ni + 0.2 wt % Ce)/SiO2 catalyst is higher than that of the original sample; the increase in activity results from a sharp increase in the number of active sites. A change in the composition of the surface layer of the catalysts is analyzed by X-ray photoelectron spectroscopy. It was found that the fraction of nickel decreases and the fraction of carbon increases in cerium-containing catalyst. An explanation of the change in the elemental composition of the catalytic active sites of a nickel catalyst in the presence of cerium is proposed on the basis of XPS data and previous quantum chemical calculations.  相似文献   

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