生物油中固体颗粒物的特性分析

利用电感耦合等离子体发射光谱、红外光谱分析和X射线衍射对不同固体颗粒物样品的特性进行了研究。结果表明,生物油中的固体颗粒物主要由焦炭颗粒、灰分和少量高分子有机物组成,其中,灰分主要包括多种金属元素和一定量SiO₂,有机物主要是具有木质素结构的低聚物。不同热解工艺的固体颗粒物样品特性也不同。循环流化床工艺制取的生物油中固体颗粒物含量较高。此外,固体颗粒物样品中的金属元素含量受到热解原料种类的影响。     

In situ metal particle preparation in cross-linked poly(2-acrylamido-2-methyl-1-propansulfonic acid) hydrogel networks

Anionic hydrogels of poly(2-acrylamido-2-methyl-1-propansulfonic acid) (p(AMPS)) were prepared with a different amount of cross-linker extent and used for in situ preparation of magnetic and metal particles. The metal particles with various sizes were obtained inside the three-dimensional polymer matrixes by absorption of the corresponding metal ions from their aqueous solutions followed by the reduction in the presence of strong reducing agent. In addition to iron particles, cobalt, nickel, copper nanoparticles, and CdS, quantum dot has been prepared by utilizing hydrogel matrix as a template for inorganic/organic composite synthesis. It was observed that the amount of cross-linkers (0.5%, 0.75%, and 1% with respect to monomer mole ratio) used in this study for bare p(AMPS) has not significantly influenced the morphology of the hydrogels or the size of the iron particles while having great effect on swelling of p(AMPS) hydrogels in water. Copolymeric hydrogels of AMPS with acrylamide in different composition were also prepared. Thermogravimetric analysis and transmission electron microscopy results showed that the AMPS content of the copolymeric hydrogel has great impact on both the metal ion loading capacity and the size of the resultant metal particles.     

Mechanism of electric spark dispersion of aluminum in aqueous solutions

Aluminum electroerosion was continued to be studied. The obtained experimental data confirmed the validity of the previously proposed mechanism of electric spark dispersion of aluminum. The composition of the oxide film forming on the surface of dispersed metal particles depends on the amount of atomic oxygen produced during electroerosion.     

The inverse problem of the kinetics of redox sorption taking into account the size of ultradisperse metal particles in an electron-ion exchanger

The inverse kinetic problem of reducing sorption of molecular oxygen by a copper-containing electron-ion exchanger was formulated and solved taking into account the influence of the size of ultradisperse metal particles on the total rate of the process. These results were used to determine the inside diffusion coefficient of oxygen and rate constants for its interaction with disperse copper from the experimental kinetic curves. The diffusion coefficient obtained was compared with the result of an independent experiment. The kinetic parameters found were used to perform a theoretical analysis of the contributions of various factors influencing the rate of the process under consideration. The reason for the experimentally observed acceleration of the reducing sorption of oxygen by a high-dispersity electron-ion exchanger sample was shown to be an increase in the surface area of metal because of a decrease in the size of its particles and a comparatively high copper content in the surface layer of grains.     

Evolution of the passive film and organic constituents at the surface of stainless steel immersed in fresh water

The evolution of the surface of a conventional stainless steel (AISI 316L) immersed in aqueous medium simulating fresh water (pH approximately 8) was studied using XPS and AFM. A detailed analysis of XPS spectra allowed a distinction to be made between oxygen of organic and inorganic nature. During the first 48 h, the main changes concern the inorganic phase: the oxygen concentration in the passive layer increases, owing both to oxidation of metal elements, including conversion of Fe(II) to Fe(III), and to hydration; the molar ratio of oxidized species Fe(ox)/Cr(ox) decreases slightly; the formation of colloidal particles, presumably made of ferric hydroxide, is observed by AFM. After longer periods of immersion, the Fe(ox)/Cr(ox) is higher, while the coating of colloidal particles reaches a full surface coverage. The amount of organic compounds increases further and the XPS spectra reveal the accumulation of polysaccharides and proteins, which indicate that these organic compounds are of biological origin.     

Regard for particle size distribution in a model of the macrokinetics of the reduction of oxygen dissolved in water by a metal-ion-exchanger nanocomposite

The function of granulometric size distribution of metal particles is introduced into the equations of a mathematical model that describes the reduction of molecular oxygen from water by metal-ionexchanger nanocomposites. It is shown that the pattern and parameters of the distribution function have an effect on the behavior of the kinetic curve. It is noted that this is particularly important for systems in which small particles dominate. The calculation and analysis of changes in the metal particle size distribution curve during the process are performed using the example of a silver-sulfocation exchanger nanocomposite.     

Adsorption of aqueous metal ions on oxygen and nitrogen functionalized nanoporous activated carbons

In this study, the adsorption characteristics of two series of oxygen and nitrogen functionalized activated carbons were investigated. These series were a low nitrogen content (approximately 1 wt % daf) carbon series derived from coconut shell and a high nitrogen content (approximately 8 wt % daf) carbon series derived from polyacrylonitrile. In both series, the oxygen contents were varied over the range approximately 2-22 wt % daf. The porous structures of the functionalized activated carbons were characterized using N(2) (77 K) and CO(2) (273 K) adsorption. Only minor changes in the porous structure were observed in both series. This allowed the effect of changes in functional group concentrations on metal ion adsorption to be studied without major influences due to differences in porous structure characteristics. The surface group characteristics were examined by Fourier transform infrared (FTIR) spectroscopy, acid/base titrations, and measurement of the point of zero charge (pH(PZC)). The adsorption of aqueous metal ion species, M(2+)(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M(2+)(aq) metal species adsorbed have a linear relationship for the carbons with pH(PZC) < or = 4.15. Hydrolysis of metal species in solution may affect the adsorption of metal ion species and displacement of protons. In the case of basic carbons, both protons and metal ions are adsorbed on the carbons. The complex nature of competitive adsorption between the proton and metal ion species and the amphoteric character of carbon surfaces are discussed in relation to the mechanism of adsorption.     

紫外辐照法制备金属钴包覆苯乙烯-甲基丙烯酸共聚物复合粒子

紫外辐照法;钴;包覆;复合粒子;导电高分子;表面活性剂     

Space localization of the electrode reaction in copper-ion-exchanger nanocomposites

The formation of copper nanoparticles in a KU-23 15/100 sulfocation-exchanger was studied. It was demonstrated that the formation of copper as assemblies from nanoparticles with sizes of 3 to 10 nm during chemical synthesis is determined by the nature of the polymer and does not depend on the amount of metal precipitated. The percolation threshold of electron conductivity, which determines the formation of electrochemical activity of nanocomposites, was discovered. It was determined that the electroreduction of molecular oxygen takes place on the surface and in the subsurface zone of a nanocomposite grain, the size of which is determined by the local concentration of metal particles in the ion-exchanger phase.     

Deep deoxygenation of water with a metal-ion exchanger nanocomposite in closed system

Kinetics and dynamics of the reduction of oxygen dissolved in water by metal-ion exchanger nanocomposites differing in the nature (Ag, Cu, Bi, Ni), quantitative content of the introduced metal, and ionic form of the matrix were studied. It is shown that the process of oxygen absorption occurs to the fullest extent with the copper-containing nanocomposite. As the content of the metal increases, the amount of oxygen reduced by a single grain and granular bed grows and reaches the limiting values. It was found on this basis that the material with a copper capacity of 5.0 ± 0.5 mequiv cm^?3 in the H⁺ form is the most efficient for deep removal of molecular oxygen from water. The advisability of using the nanocomposite with the suggested parameters for deep deoxygenation of water in a closed system was confirmed by experiments and calculations.     

Microcalorimetric studies of the structure of supported bimetallic catalyst particles

Microcalorimetric studies of oxygen and hydrogen chemisorption during the last decade improved the understanding of the structure and structural dynamics of supported bimetallic catalyst particles. For example, it was found that on graphitic supports two different reduced surface compositions/structures can be created for base metal/noble metal particles. Appropriate treatments switch the surface from almost pure reduced base metal to true alloy. Calorimetric studies also indicate support interactions play a major role in controlling bimetallic particle surface structure. In contrast to behaviour found on graphitic supports, iron/noble metal particles supported on refractory oxides apparently do not form alloy surfaces. The reduced surface is dominated by the noble metal. Several studies indicate the value of the models of surface composition/structure developed using microcalorimetry for predicting the activity/selectivity of bimetallic particles.     

DFT Study of Metal Atoms Adsorbed at Low-coordinated Sites of MgO （001） Surface

1 INTRODUCTION The interfaces between metals and oxide play a vital role in many industrial applications: hetero- geneous catalysis, microelectronics, thermal barriers, corrosion protection, metal processing and so on[1]. In catalysis, the choice of metal and oxide support is critical in order to obtain a desired reactivity and selectivity[2]. This is due in part to the inherent reac- tivity of the two components. Also the size and shape of the metal particle, which depend on the choice…     

碳纳米纤维在浓硝酸-浓硫酸溶液中表面氧化对其负载的Pd-Pt催化剂颗粒分散状态的影响

摘要用混合的浓硝酸和浓硫酸在不同温度下氧化处理催化生长的碳纳米纤维. 利用X射线衍射、 N2物理吸附、 FTIR和离子交换研究了氧化处理对碳纳米纤维织构性质和表面含氧基团生成的影响. 采用等体积浸渍法制备碳纳米纤维负载Pd-Pt催化剂, 并利用高分辨电镜和脉冲H₂化学吸附对Pd-Pt金属颗粒的分散状况进行了研究. 结果表明, 经过氧化处理的碳纳米纤维表面生成了含氧基团, 生成量随着处理温度的升高而升高, 负载的Pd-Pt催化剂的分散程度也随着表面含氧基团浓度的增大而提高, 同时对后者的作用机理进行了讨论.     

Quantum chemical investigation of the interaction of the Pt<Subscript>6</Subscript> cluster with oxides of different nature

The interaction of a Pt₆ nanoparticle with different oxide supports, viz., γ-Al₂O₃, FAU and MFI zeolites, was investigated using the density functional theory. The interaction with the basic oxygen anions of the lattice and with hydroxyl groups of the support affects the electronic structure of the metal particles. The transfer of H atoms of the hydroxyl groups to the metal particle suppresses the Brönsted acidity of the support, and the activation energy of proton transfer decreases with an increase in the acidity of the support. The potential energy profiles were calculated for the transfer processes, and changes in the electronic structures and charge distribution of the supported particles were outlined. The H atom transfer results in positive charging by the metal particles, whereas the interaction with basic sites leads to the appearance of electron-enriched metal clusters.     

Nickel-supported metal-carbon nanocomposites: New catalysts of hydrogenation of phenylacetylene

Nickel-containing metal-carbon nanocomposites (Ni@C) synthesized by levitation melting in a flow of an inert gas-hydrocarbon mixture were used as catalysts of the hydrogenation of phenylacetylene (PA). The nanocomposites were characterized by X-ray photoelectron spectroscopy, simultaneous thermal analysis, and temperature-programmed reduction. The nickel-carbon nanocomposites were stable on storage in air, with only 13% of the total amount of nickel oxidized after 3.5 years of storage. In addition to nanoparticles completely covered with carbon, the composites contained partially coated metal particles, which are readily oxidized in air. Both types of particles exhibited the catalytic activity in phenylacetylene hydrogenation. At higher contents of nickel partially coated with carbon, the activity increased and the selectivity of styrene formation decreased. The minimum half-conversion temperature (75°C) was determined for a specially prepared Ni@C sample with an increased content of oxidized nickel (28%). The maximum selectivity of styrene formation (～75% at 150°C) was recorded in the presence of the sample with the smallest amount of oxidized nickel (less than 4%).     

Electrodeposited noble metal particles in polyelectrolyte multilayer matrix as electrocatalyst for oxygen reduction studied using SECM

Taking the advantage of the stability and penetrability of polyelectrolyte films formed by layer-by-layer (LbL) deposition, noble metal particles of Pd and Pt were fabricated in a preformed polyeletrolyte multilayer film by galvanic deposition. The metal deposition occurred as metal particles and they were tested for their properties as electrocatalyst for oxygen reduction. Atomic force microscopy (AFM) was used to characterize the morphology of the particle films. The noble metal particles were investigated by cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM) with respect to oxygen reduction. The results show that the electrocatalytic properties of the Pd particle film can be adjusted by the electrodeposition time. The hydrogen peroxide formed as an intermediate during electroreduction of dioxygen was conveniently measured in the SECM using the substrate-generation/tip-collection mode. The relevance of the main reduction pathways could be extracted from fitting the current transients to an analytical model.     

氧化铈形貌对Pd纳米粒子分散的影响

氧化铈由于在氧化和还原气氛下具有快速Ce4+/Ce3+氧化还原循环作用,使其具有优异的储放氧能力,不仅可以分散和稳定金属粒子,还可在界面处与金属物种发生化学键合,并形成活性位点,因此已被广泛应用于多个催化反应体系,且表现出显著的形貌效应.通过对氧化铈形貌进行调控,使其暴露特定(111)、(110)和(100)晶面,已成为调节金属-氧化铈相互作用强度及金属物种电子、几何结构,提高催化性能的有效策略,但对其机制及活性位结构还没有清晰的认识.我们以氧化铈纳米粒子和纳米立方体为载体,其中氧化铈立方体平均尺寸为23 nm,主要暴露6个{100}晶面,边缘和截角暴露少量{110}及{111}晶面;球形氧化铈纳米粒子平均尺寸为11 nm,主要暴露{111}晶面;并进一步将2.0 wt％Pd物种分散在氧化铈立方体和球形纳米粒子上,通过扫描透射电子显微镜(STEM)和X射线光电子能谱(XPS)等研究了钯物种在氧化铈球形粒子和立方体上的原子结构和化学环境,进而分析了纳米结构氧化铈形貌对钯物种分散的影响.在球形氧化铈纳米粒子上主要形成了平均尺寸为2.0 nm的非晶态Pd纳米粒子以及极小的Pd物种,这主要是因为球形氧化铈纳米粒子上丰富的表面氧空位可通过Pd-CeO2强相互作用和Pd物种紧密键合.氧化铈立方体上的晶态Pd粒子尺寸为2.9 nm,金属与载体之间具有明显的界面,且Pd原子嵌入到氧化铈晶格中.同时,CO化学吸附测试也证明了氧化铈球形粒子上的钯分散度(70％)高于氧化铈立方体(52％).对于甲烷燃烧反应,主要涉及发生在金属粒子表面的PdO/Pd氧化还原循环,即Pd被O2氧化,PdO被CH4还原,富氧条件下决速步骤是PdO对CH4中C?H的活化,因此氧化铈立方体表面大尺寸的晶态Pd粒子被氧化后更容易被CH4还原,有利于PdO/Pd氧化还原循环,从而具有更高的活性和稳定性;然而在CO氧化反应中Pd/CeO2却呈现了相反的形貌效应,这是由于该反应遵循Mars-van Krevelen机理:CO吸附在金属Pd上,化学吸附的CO移动到钯-氧化铈界面,被氧化铈晶格氧氧化成CO2,产生的氧空位被表面氧补充,最后表面氧空位被气相氧补充;由于氧化铈球形粒子上的较小尺寸Pd具有更大的钯-氧化铈界面周长和更强的氧物种移动性,更易完成界面处的氧化还原循环,因此具有更高的CO氧化活性.     

Catalyzed Nonhydrolytic Sol-Gel Route to Organosilsesquioxane Gels

Methyl-, vinyl- and octadecylsilsesquioxane gels have been prepared by the solvent-free nonhydrolytic condensation of organotrichlorosilane with oxygen donors in the presence of a catalytic amount of various metal chlorides. Pure phenylsilsesquioxane gels could not be obtained by this route owing to the partial ipso-cleavage of phenylsilicon bonds by the alkyl chloride formed during the condensation process. The rate of condensation depends on the nature of both the oxygen donor and the catalyst. For highly condensed methylsilsesquioxane gels, the extent of silicon loss by Si–O/Si–O and Si–C/Si–O redistribution reactions during pyrolysis depends mainly on the nature of the oxygen donor, whilst the composition of the volatile silicon species, and consequently that of the residue, depends on the nature of the metal chloride initially introduced. This process allows the formation of a rather well-condensed octadecylsilsesquioxane gel which is constituted of small particles assembled by crystallization of the long C18 chain.     

Charge state and activity of Pt/C catalysts in oxygen reduction reaction

Electrochemical experiments with a rotating disk electrode are used to measure specific catalytic activity of Pt/C structures in the oxygen reduction reaction at the density of Pt nanoparticles on the glassy carbon support surface below one monolayer. The specific activity maximum is found at the coverage of about 0.4 monolayer. An explanation of the observed dependence is suggested that is based on consideration of the relationship between the surface density and charge state of the system of metallic catalyst particles. A numeric model is developed that describes charge transfer in the catalyst structure due to the difference in the work functions between the metal nanoparticles and support with account for the discrete nature of the nanoparticle charging and their mutual polarization. Calculations show that the carbon support coverage by Pt particles of about 0.4 monolayer corresponds to the largest amount of charged particles with the maximum energy of electrons, which provides the maximum catalyst activity and explains the dependence observed in the experiment.     

含氧空位缺陷钨酸铋光催化产氢性能研究

新型半导体光催化剂钨酸铋是目前研究广泛的光催化剂,但因其电子空穴对易复合的问题,限制了光催化产氢性能。为解决这一问题,采用锂-乙二胺溶液在钨酸铋表面构筑可控氧空位缺陷和金属缺陷。通过材料表征对比了钨酸铋经锂-乙二胺处理前后的变化,并对两者进行了产氢速率测试。钨酸铋在经过锂-乙二胺处理过后产生了氧空位缺陷和降价的金属中心,材料颜色从原先的黄白色转变为黄棕色,增强了光吸收能力。颗粒的主体结构以及物质成分并未发生变化,仍保持花球状颗粒结构,但处理后钨酸铋颗粒表面原先的光滑的片状结构变得粗糙,且方形纳米薄片锋利边缘变光滑,提高了光催化反应面积。这些变化使锂-乙二胺处理后的钨酸铋光催化产氢性能相比未处理之前得到了一定的提升。