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1.
Electronic metal-support interactions (EMSIs) of oxide-supported metal catalysts strongly modifies the electronic structures of the supported metal nanoparticles. The strong influence of EMSIs on the electronic structures of oxide overlayers on metal nanoparticles employing cerium oxides/Ag inverse catalysts is reported herein. Ce2O3 overlayers were observed to exclusively form on Ag nanocrystals at low cerium loadings and be resistant to oxidation treatments up to 250 °C, whereas CeO2 overlayers gradually developed as the cerium loading increased. Ag cubes enclosed by {001} facets with a smaller work function exert a stronger EMSI effect on the CeOx overlayers than Ag cubes enclosed by {111} facets. Only the CeO2 overlayers with a fully developed bulk CeO2 electronic structure significantly promote the catalytic activity of Ag nanocrystals in CO oxidation, whereas cerium oxide overlayers with other electronic structures do not. These results successfully extend the concept of EMSIs from oxide-supported metal catalysts to metal-supported oxide catalysts.  相似文献   

2.
Nanosized iron oxides stabilized on the surface of ultradispersed poly(tetrafluoroethylene) (UPTFE) granules were synthesized by the thermal destruction of iron formate in boiling bed of UPTFE on the surface of heated mineral oil. The particle size of nanoparticles (∼6 nm) containing 5, 10, and 16 wt.% Fe depends weakly on the temperature of synthesis and iron to polymer ratio. The metal state is determined by the synthesis conditions. The nanoparticles synthesized at 280 °C consist mainly of the Fe3O4 and Fe2O3 phases. The samples obtained at 320 °C also contain iron(II) oxide. The catalytic properties of the obtained samples were tested in dichlorobutene isomerization. Unlike isomerization on the iron oxide nanoparticles supported on silica gel, reaction over the UPTFE supports proceeds without an induction period. The sample with 10 wt.% Fe containing magnetically ordered γ-Fe2O3 nanoparticles possesses the highest catalytic activity. Fast electron exchange between the iron ions in different oxidation states and high defectiveness of the nanoparticles contribute, most likely, to the catalytic activity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1383–1390, June, 2005.  相似文献   

3.
Three different forms of carbon, i.e., multi-walled carbon nanotubes (CNTs), single-walled CNTs, and soot, were decorated with gold nanoparticles by a new method. In this method C10H8 ions transfer electrons to the CNTs or soot. These electrons on the carbon surface can then reduce Au3+ species to form supported Au nanoparticles with a narrow particle size distribution. Thermogravimetric/differential thermal analyses (TG/DTA), XRD, Raman, and TEM show that naphthalene molecules remain trapped inside the Au nanoparticles and can only be removed by treatment at ca. 300 °C. Remarkable effect of the Au nanoparticles on the oxidation of carbon by O2 is also observed by TG/DTA, i.e., on-set oxidation temperature and activation energy (E a). It is shown that as the Au particle size decreases from 25 to 2 nm a linear decrease of the oxidation temperature is observed. Au particles larger than 25 nm do not produce any significant effect on carbon oxidation. These results are discussed in terms of spillover catalytic effect where Au nanoparticles activate O2 molecules to produce active oxygen species which oxidize the different carbon supports.  相似文献   

4.
This work represents a first systematic approach to the size-based elemental quantification and size estimation of metal(loid) oxide nanoparticles such as silica (SiO2) in a real food matrix using asymmetric flow field-flow fractionation coupled online with inductively coupled plasma mass spectrometry (ICP-MS) and multi-angle light scattering (MALS) and offline with transmission electron microscopy (TEM) with energy-dispersive X-ray analysis (EDAX). Coffee creamer was selected as the model sample since it is known to contain silica as well as metal oxides such as titania at the milligramme per kilogramme levels. Optimisation of sample preparation conditions such as matrix-to-solvent ratio, defatting with organic solvents and sonication time that may affect nanoparticle size and size distribution in suspensions was investigated. Special attention was paid to the selection of conditions that minimise particle transformation during sample preparation and analysis. The coffee creamer matrix components were found to stabilise food grade SiO2 particles in comparison with water suspensions whilst no significant effect of defatting using hexane was found. The use of sample preparation procedures that mimic food cooking in real life was also investigated regarding their effect on particle size and particle size distribution of silica nanoparticles in the investigated food matrix; no significant effect of the water temperature ranging from ambient temperature to 60 °C was observed. Field-flow fractionation coupled to inductively coupled plasma-mass spectrometry (FFF-ICP-MS) analysis of extracts of both unspiked coffee creamer and coffee creamer spiked with food grade silicon dioxide, using different approaches for size estimation, enabled determination of SiO2 size-based speciation. Element-specific detection by ICP-MS and post-FFF calibration with elemental calibration standards was used to determine the elemental composition of size fractions separated online by FFF. Quantitative data on mass balance is provided for the size-based speciation of the investigated inorganic nano-objects in the complex matrix. The combination of FFF with offline fractionation by filtration and with detection by ICP-MS and TEM/EDAX has been proven essential to provide reliable information of nanoparticle size in the complex food matrix.
Figure
Characterisation of silica nanoparticles in a coffee creamer matrix using FFF-based methodology  相似文献   

5.
The morphology, particle size, and thermochemical properties of the surface of oxides Al2O3, NiO, TiO2, ZnO, and ZrO2 obtained by the wire electroexplosion method were studied. The nanoparticles are spherical, with a mean diameter of 54–86 nm depending on the nature of the oxide. The hydrophilicity of the surface of metal oxide nanopowders was found to change in the series NiO-ZrO2-TiO2-ZnO-Al2O3. Nanocomposites with widely varied compositions were obtained from butyl methacrylate copolymer with 5 wt % methacrylic acid and the oxides under study. The enthalpies of dissolution of the composites in chloroform were determined by Calvet calorimetry. The enthalpies of copolymer mixing with oxides were calculated using the thermochemical cycle. The limiting enthalpies of copolymer adhesion to the oxide surface were calculated from the thermochemical data. The limiting adhesion enthalpy was shown to be negative for all oxides under study; these values decreased in magnitude as the surface hydrophilicity increased. The results were analyzed from the viewpoint of balance between the specific and dispersion interactions at the interface.  相似文献   

6.
Metal ferrites nanocrystallites, MFe2O4 (M = Mn, Co, Ni, Zn) were prepared by coprecipitation method and characterized by a combination of physico‐chemical and spectroscopic techniques. MFe2O4 nanoparticles having particle size in the range 10–35 nm were tested as catalysts in the oxidation of o‐phenylenediamine (OPD) to 2,3–diaminophenazine (DAP) using hydrogen peroxide as oxidant at room temperature. Kinetic data was collected for the catalytic oxidation of OPD to DAP by monitoring the UV–vis absorbance at 415 nm and fit well to the Michaelis–Menten model yielding kinetic parameters Km (Michaelis–Menten constant) and Vmax (maximum rate of reaction). MnFe2O4 nanoparticles provide the highest catalytic activity in the oxidation of OPD to DAP at room temperature. A colorimetric method was developed based on the MnFe2O4/OPD system for the detection of H2O2 in reaction solution. The method has a detection limit of 30 μM for H2O2 and wide linear range.  相似文献   

7.
Nickel nanoparticles supported on silica were prepared by hydrazine reduction in aqueous medium. The obtained solids were characterized by X-ray diffraction (XRD), Transmission Electronic Microscopy (TEM), Electron Diffraction (ED), hydrogen chemisorption, and Temperature Programmed Desorption of hydrogen (H2-TPD). The catalytic properties were evaluated for benzene hydrogenation in the temperature range 75–230 °C. XRD patterns reveal presence of the metallic nickel particles with fcc structure. Metal dispersion and hydrogen storage increase with decreasing metal particle size. The H2-TPD profiles exhibit two domains, one due to desorption of hydrogen from Ni metal and another due to spillover from metal to the support. The catalytic activity strongly depends on the metal loading. It increases with decreasing metal loading. This is attributed to metal surface area, which also increases with decreasing metal loading. Kinetic studies of benzene hydrogenation on the Ni catalysts showed that the benzene partial order is around −2. This significant negative value is ascribed to a strong adsorption of benzene on the catalyst surface.  相似文献   

8.
We have synthesized colloidal Pt nanoparticles with a mean particle size of 2.6±0.4 nm by reducing PtCl2 dissolved in N,N-dimethylacetamide with t-BuMe2SiH. The latter compound acted both as a reducing agent and a stabilizer of the Pt nanoparticles. Pt nanoparticles were deposited onto the Au substrate and IR reflectance absorption spectroscopy (IRRAS) was applied to investigate CO adsorption and oxidation at the surface of the catalyst. The reactivity of the catalyst covered with Nafion was compared with the reactivity of the catalyst without Nafion. In addition, the reactivity of the colloidal Pt was compared with the reactivity of bulk polycrystalline Pt. We found that CO oxidation proceeds at lower over-potentials at nanoparticles than at polycrystalline Pt. The IRRAS data indicate that the difference in the reactivity may be explained by a different mechanism of the oxidation reaction; Langmuir–Hinshelwood at Pt nanoparticles and island formation and growth at polycrystalline Pt. We have also observed that a film of Nafion slows down the CO oxidation reaction. The IRRAS spectra for CO adsorbed at Pt nanoparticles covered by Nafion were significantly different from the spectra recorded for the nanoparticles in the absence of Nafion. The spectroscopic features suggest that in the presence of Nafion the nanoparticles experience regions of lower and higher proton concentration.This paper is dedicated to Prof. G. Horanyi on the occasion of his 70th birthday and in recognition of his contribution to electrochemistry.  相似文献   

9.
Activated carbon (AC) supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation (PROX) in excess H2 was evaluated. Ag/AC catalysts, after reduction in H2 at low temperatures (≤200 °C) following heat treatment in He at 200 °C (He200H200), exhibited the best catalytic properties. Temperature-programmed desorption (TPD), X-ray diffraction (XRD) and temperature-programmed reduction (TPR) results indicated that silver oxides were produced during heat treatment in He at 200 °C which were reduced to metal silver nanoparticles in H2 at low temperatures (≤200 °C), simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 °C. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H200 treatment displayed similar PROX of CO reaction properties to Ag/SiO2. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.  相似文献   

10.
Oxidation of sodium succinate in aqueous solution by potassium ferricyanide was investigated. The effects of different reaction parameters such as initial concentration of succinate, concentration of ferricyanide, and influence of metal ions (Zn+2, Ni+2, Cu+2, Cd+2) on the oxidation of succinate were investigated at 25 ± 0.05 °C. Large rate enhancements were observed in the redox reaction between succinate and ferricyanide with increasing concentrations of both oxidant and reductant. The kinetics results indicated that the succinate oxidation was significantly inhibited in the presence of metal ions. Pseudo first order rate constants values were found decreased with increase in concentrations of metal ions which reflected that inhibition rate was directly influenced with the metal ions concentration.  相似文献   

11.
The effect of the size distribution of metal particles on the process kinetics was studied for the oxidation and reduction of cobalt nanoparticles (6–10 nm) in the Co/SiO2, Co/Al2O3, and Co/ZrO2 systems in both isothermic and temperature-programmed regimes in the temperature range from 280 to 500 K. The average size of the cobalt particles was estimated by measurements of the coercive force and residual magnetization using a vibration magnetometer. It was found that the average particle size increases upon cobalt oxidation and decreases upon cobalt reduction due to changes in the fraction of nonsuperparamagnetic particles with sizes of at least 6.5 nm.  相似文献   

12.
Electrocatalytic systems utilizing carbon (Vulcan)-supported PtRh nanoparticles (PtRh/Vulcan) admixed with either molybdenum oxide or tungsten oxide were tested and compared during electrooxidation of ethanol. The systems' performance was diagnosed using electrochemical techniques such as voltammetry and chronoamperometry. The proposed electrocatalytic materials were also characterized with X-ray diffraction (XRD), transmission and scanning electron microscopies (TEM and SEM), as well as SEM-coupled energy dispersive X-ray spectroscopy (SEM-EDX). For both systems containing molybdenum and tungsten oxides, enhancements in catalytic activities (relative to the behavior observed at bare PtRh/Vulcan nanoparticles) were found during ethanol electrooxidation at room temperature (22?°C). Further, it was from chronoamperometric current (density)–time responses that anodic electrocatalytic currents measured at 0.3?V (vs. RHE) were more than 20% higher in the case of the MoO3-containing PtRh/Vulcan system relative to that utilizing WO3. The diagnostic “CO-stripping” experiments were consistent with the view that addition of molybdenum oxide or tungsten oxide to PtRh/Vulcan tended to shift potential for the oxidation of inhibiting CO-adsorbate ca. 80 or 40?mV towards less negative values in comparison to the analogous but oxide-free system. The fact that carbon (Vulcan)-supported PtRu nanoparticles exhibited higher electrocatalytic reactivity observed phenomena may be attributed to specific interactions between noble metal centers and the oxides in addition to chemical reactivity of metal oxo groups in the vicinity of PtRh/Vulcan at the electrocatalytic interface.  相似文献   

13.
A series of mixed metal hydroxide (Ni x Mn x Co(1–2x)(OH)2) precursors for the preparation of lithiated mixed metal oxides (LiNi x Mn x Co(1–2x)O2) were prepared using a novel coprecipitation approach based on the thermal decomposition of urea. Three different methods were used to achieve the temperature required to decompose urea and subsequently precipitate the hydroxides. The first two methods consisted of either a hydrothermal or microwave-assisted hydrothermal synthesis at 180 °C and elevated pressures. The final method was an aqueous reflux at 100 °C. A complete series (x = 0.00–0.50) was prepared for each method and fully characterized before and after converting the materials to lithiated metal oxides (LiNi x Mn x Co(1–2x)O2). We observed the formation of a complex structure after the coprecipitation of the hydroxides. Scanning electron micrographs images demonstrate that the morphology and particle size of the hydroxide particles varied significantly from x = 0.00–0.50 under hydrothermal synthesis conditions. There is also a significant change in particle morphology as the urea decomposition method is varied. The X-ray diffraction profiles of the oxides synthesized from these hydroxide precursors all demonstrated phase pure oxides that provided good electrochemical performance.  相似文献   

14.
采用气相催化沉积法催化合成纳米碳管,比较了不同金属氧化物和金属负载型沸石催化剂以及不同分子筛载体对合成纳米碳管的影响,并用TEM,XRD表征其形貌和结晶度,用DTA-TG考察了纳米碳管的热和稳定性。实验结果表明纳米碳管的形成除了与金属种类有关外,还直接与催化剂的颗粒大小和分散状态有关。粒径在20nm左右的不规则形状的纳米粒子是形成纳米碳管的活性组分,非负载和负载型的催化剂均表明活性组分的粒径与纳米碳管的管径有一定的对应关系。化学提纯后能得到高纯度的纳米碳管;其管壁具有较好的石墨化结构,在空气中的热稳定性大于400℃,而在氮气中能维持到1200℃以上。  相似文献   

15.
A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.  相似文献   

16.
Poly(butadiene‐co‐acrylonitrile) (NBR) nanoparticles were synthesized in a semibatch emulsion polymerization system using Gemini surfactant trimethylene‐1,3‐bis (dodecyldimethylammonium bromide), referred to as Gemini‐type surfactant (GS) 12‐3‐12, as the emulsifier. In this polymerization system, an enhanced decomposition rate of initiator ammonium persulfate was achieved even under the low temperature of 50 °C which is attributed to the acidic initiation environment provided using GS 12‐3‐12. The microstructure and copolymer composition of the polymer nanoparticles were characterized by Fourier‐transformed infrared and 1H nuclear magnetic resonance spectroscopy. The effects of the surfactant concentration on the particle size, zeta potential, polymerization conversion, copolymer composition, molecular weight, and glass transition temperature (Tg) were investigated. It was found that the particle diameter can be controlled by the surfactant concentration and monomer/water ratio and particle sizes below 20 nm can be reached. The obtained latex particles exhibit a spherical morphology. A kinetic study of the copolymerization reaction was carried out, which indicated that an azeotropic composition was produced. The synthesized fine NBR nanoparticles can be employed as the nano substrate for a subsequent hydrogenation process so as to overcome the challenge involved in the field of latex hydrogenation of polymers, which can be found in a related report: Organic Solvent‐Free Catalytic Hydrogenation of Diene‐based Polymer Nanoparticles in Latex Form: Part II. Kinetic Analysis and Mechanistic Study. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

17.
Non-Stoichiometric CoFe2O4 nanoparticles dispersed in an silica matrix with a silica content of 87 wt% and Co/Fe molar ratio of 1:1, were prepared by the sol-gel method using an ethanolic solution of tetraethoxysilane and either iron(III) and cobalt(II) nitrates or iron(II) and cobalt(II) acetates. The influence of different metal precursors on the xerogels were examined by X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and N2 physisorption measurements at 77 K. Magnetic properties of the samples were investigated by field cooled FC and zero field cooled ZFC measurements.Depending on the metal precursor, different spinel oxides of a few nanometers were observed in the samples treated at 350°C. After heating at 900°C non-stoichiometric CoFe2O4 was formed in both samples, whose average particle size was only slightly larger than in samples treated at 350°C.  相似文献   

18.
This paper reports the chitosan-mediated synthesis of porous hematite nanoparticles with FeCl3 as the precursor via a hydrothermal approach at 160 °C. A series of porous chitosan/iron oxide hybrid nanoparticles were obtained via changing the ratio of chitosan to FeCl3, FeCl3 concentration and pH value of the reaction solution, and producing porous iron oxide nanoparticles after calcination. The as-prepared samples were characterized by means of X-ray diffraction, transmission electron microscopy, thermal gravimetric analysis, Fourier transform infrared, and N2 sorption. The particle sizes of these metal oxides were less than 100 nm, and the pore sizes were in the range of 2–16 nm. It was demonstrated that chitosan played a key role in the formation of the porous structures. The resultant α-Fe2O3 nanoparticles were used as the support to immobilize Au or Pd nanoparticles, producing Au/α-Fe2O3 or Pd/α-Fe2O3 nanoparticles. The as-prepared α-Fe2O3 nanocatalyst exhibited high selectivity towards cyclohexanone and cyclohexanol for catalyzing cyclohexane oxidation with O2 at 150°C.  相似文献   

19.
碱-乙二醇法制备的"非保护型"金属及合金纳米簇由表面吸附的溶剂分子和简单离子实现稳定化,它们被广泛用于制备高性能复相催化剂和研究复相催化剂中的尺寸、组成、载体表面基团以及修饰剂对催化性能的影响。关于此类非保护金属纳米簇的形成过程及机理的认识尚有待进一步深化。本文采用原位快速扫描X射线吸收精细结构谱(QXAFS)、原位紫外-可见(UV-Vis)吸收光谱、透射电子显微镜和动态光散射技术研究了碱-乙二醇法合成中非保护型金属胶体纳米簇的形成过程与机理。结果表明,在碱-乙二醇法合成非保护型Pt金属纳米簇的过程中,室温下即有部分Pt(IV)被还原至Pt(II)。随着反应温度的升高,OH-逐渐取代与Pt离子配位的Cl-,在Pt―Pt键形成之前,反应体系的UV-Vis吸收光谱中可观察到明显的纳米粒子的散射信号,原位QXAFS分析表明Pt纳米簇是由Pt氧化物纳米粒子还原所形成的;在Ru金属纳米簇的形成过程中,OH-首先取代了Ru Cl_3中的Cl~-,形成羟基配合物Ru(OH) _6~(3-),后者进一步缩合形成氧化钌纳米粒子,最终Ru金属纳米簇由乙二醇还原氧化钌纳米粒子形成。由于先形成了氧化物纳米粒子,后续的还原反应被限制在氧化物纳米粒子内,使最终得到的非保护型金属纳米簇具有尺寸小、分布窄的特点。本工作所获得的知识对发展高性能能源转化催化剂、精细化学合成催化剂、传感器等功能体系具有重要意义。  相似文献   

20.
Catalysts based on Mn-substituted cordierite 2MnO · 2Al2O3 · 5SiO2 have been synthesized using different manganese oxides (MnO, Mn2O3, and MnO2) at a calcination temperature of 1100°C. The catalysts differ in their physicochemical properties, namely, phase composition (cordierite content and crystallinity), manganese oxide distribution and dispersion, texture, and activity in high-temperature ammonia oxidation. The synthesis involving MnO yields Mn-substituted cordierite with a defective structure, because greater part of the manganese cations is not incorporated in this structure and is encapsulated and the surface contains a small amount of manganese oxides. This catalyst shows the lowest ammonia oxidation activity. The catalysts prepared using Mn2O3 or MnO2 are well-crystallized Mn-substituted cordierite whose surface contains different amounts of manganese oxides differing in their particle size. They ensure a high nitrogen oxides yield in a wide temperature range. The product yield increases with an increasing surface concentration of Mn3+ cations. The highest NOx yield (about 76% at 800–850°C) is observed for the MnO2-based catalyst, whose surface contains the largest amount of manganese oxides.  相似文献   

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