在线性或交联的聚氨酯粒子内原位还原制备纳米银粒子

纳米金属粒子有特异性质 ,可用作高效催化剂、非线性光学材料等 .为防止其聚集 ,不少研究者采用表面活性剂 [1]、配位体 [2 ]和高分子等以阻止纳米金属粒子的聚集 .近年来高分子金属复合纳米粒子引起人们广泛的兴趣 [3～ 9] .文献上大多采用线性或嵌段双亲高分子作纳米金属的分散稳定剂[6 ] 或在高分子粒子表面沉积纳米金属粒子[5] ,也有人采用多孔交联高分子微球的孔洞作为微反应器形成纳米金属粒子[7] .这些方法均不能有效地控制金属粒子的粒径 ,特别难以合成粒径小于 3 0 nm的银粒子 .本文首次报道了在常温处于粘弹态 ,线性或交联的高分…     

在线性或交联的聚氨酯粒子内原位还原制备的纳米银粒子

纳米金属粒子有特异性质，可用作高效催化剂、非线性光学材料等，为防止其聚集，不少研究者采用表面活性剂、配位体和高分子等以阻止纳米金属粒子的聚集，近年来高分子金属复合纳米粒子引起人们广泛的兴趣。     

溶液体系中的纳米金属粒子形状控制合成*

纳米尺度的金属粒子由于量子尺寸效应等原因而表现出不同于宏观金属块体的电学、磁学、光学和热学等性质.纳米金属粒子的性质不仅受到尺寸的影响,还与粒子的形状密切相关.不同形状的纳米金属粒子通常具有不同的表面结构和性质.近年来,纳米金属粒子的形状控制合成正受到越来越多的关注;其中,Ⅷ族和IB族金属的研究已取得一定进展.本文评述了纳米金属粒子的合成以及尺寸和形状控制的方法,分别介绍了铂、钯、镍、金、银、铜以及钴等金属的形状控制合成的近期研究进展.     

Pt/Al_2O_3和Pt-Sn/Al_2O_3模型催化剂烧结的电镜研究

对利用溅射技术制备的Pt/Al_2O_3和Pt-Sn/Al_2O_3模型催化剂,以透射电子显微镜研究了金属粒子在H_2气中加热过程的烧结情况。实验结果表明,随着加热温度的升高,催化剂品粒逐渐长大,但加热到700℃经2h后,Pt/Al_2O_3的晶粒比Pt-Sn/Al_2O_3的大,这可能是Sn对Pt晶粒烧结起抑制作用。如将晶粒已经长大的样品再在空气中于500℃加热2h,则晶粒发生再分散。另外,在H_2气中加热后的催化剂的电子衍射花样,在Pt/Al_2O_3样品中仍表现Pt的特征;而在Pt-Sn/Al_3O_3样品中则形成几种不同组成的合金,我们推测可能是在还原过程中Pt与Sn之间发生强相互作用。     

基于单原子催化剂研究金属-载体相互作用

正金属-载体相互作用是负载型金属催化剂的基本结构特征,也是影响催化性能的关键因素。长期以来,对金属-载体相互作用机制的研究大都集中在氧化还原性氧化物负载的贵金属纳米粒子催化剂体系;但是由于金属粒子尺寸分布的不均匀性和氧化物载体表面的各向异性,很难从原子尺度上形成对催化活性位点和反应机理明确认知,也难以定量描述和理解金属-载体相互作用的化学本质~1。基于单原子催化剂研究金属-载体相互作用能够排除金属颗粒在金属-载体界面上尺寸、形貌和取向的影响,因此,单原子催化剂被     

纳米金属催化在偶联反应中的应用*

在过去的一二十年里,纳米材料科学的发展主要集中在纳米材料的合成,结构的修饰与表征以及相应的物理性质,而纳米材料在有机反应中的催化还未受到应用的重视。最近具有大的表面积和高反应活性的纳米形态受到广泛的关注。利用晶型的纳米金属粒子作为催化剂在有机合成领域得到了越来越多的应用,本综述主要概括了各种金属纳米粒子在偶联反应中的应用,包括C-C键、C-N键、C-O键和C-S键的形成。     

高分散度Pt-Ir疏水催化剂制备及氢-水液相交换催化性能研究

用乙二醇作为碳黑分散溶剂，微波辐射快速加热，1～2 MPa压力下制备了Pt/C及不同Pt、Ir比例的Pt-Ir/C催化剂，用浸渍还原法制备了Pt-Ir/C催化剂，并用XRD，TEM和XPS对催化剂进行了表征。将两种方法制备的Pt/C，Pt-Ir/C催化剂与聚四氟乙烯(PTFE)一起负载于多孔金属载体，得到疏水催化剂，考查了其对氢-水液相交换反应的催化活性。微波辐射加热法制备的Pt/C和Pt-Ir/C催化剂活性金属粒子在碳载体上分布均匀，平均粒径大小分别为2.1 nm和2.2 nm，Ir的加入改变了活性金属粒子的形状和晶相结构，Pt-Ir/C中Pt以Pt(0)，Pt(Ⅱ)和Pt(Ⅳ)形式存在，Ir以Ir(0)和Ir(Ⅳ)形式存在。浸渍还原法制备的Pt-Ir/C催化剂活性金属粒子有明显团聚，晶粒平均大小为4.8 nm。微波辐射法所得催化剂对氢-水液相交换反应有更高催化活性；Pt中掺入适量Ir，可提高单一Pt催化剂活性，Pt、Ir原子比例为4∶1时，催化剂活性最高。     

金属蒸气合成制备有机硅化合物包裹的金属微粒催化剂

用金属蒸气合成法制备了三种有机硅包裹的金属催化剂Ni/D_4,Ni-Mn/D_4,Ni-Mn-La/D_4。用XRD,TEM,XPS,FMR,静磁对它们进行了性质表征。催化剂中金属粒子小于3.5 nm。XPS结果表明催化剂中金属以零价和氧化态多种形式存在,金属被有机硅包裹着,阻止了内层金属被氧化,FMR和静磁结果表明金属微粒呈球形,具有超顺磁性。在催化糠醛合成糠醇加氢反应中,Ni-Mn-La/D_4活性最高。     

碳包裹软磁金属纳米粒子的绿色合成及热稳定性研究

本文报道了一种制备碳包裹软磁金属纳米粒子的绿色合成方法:将金属醋酸盐溶液与可溶性淀粉均匀混合,蒸发、烘干后在N2保护下热处理,得到金属纳米复合粒子(C@Ni,C@Co,C@Fe,C@CoNi,C@CoFe,C@FeNi)。TEM结果表明金属粒子均匀分散在碳介质中,粒径为3~5 nm。样品在室温下具有良好的抗氧化性、热稳定性和软磁性能。     

相转移法制备金属纳米粒子研究进展

相转移法是可控合成纳米金属粒子的一种简便、有效而重要的方法。通过相转移试剂的作用,水相中制备得到的大量金属纳米粒子在稳定剂的包裹下能够几乎完全转移到有机相当中。所得到的金属纳米粒子尺度均匀,形貌独特,结构稳定。本文综述了相转移方法制备金属纳米粒子的发展、动向以及相转移剂和稳定剂的应用情况。     

Synthesis of narrowly size-distributed metal salt/poly(HEMA) hybrid particles in inverse miniemulsion: versatility and mechanism

Hybrid particles containing different hydrophilic metal salts such as tetrafluoroborates of iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), and nitrates of cobalt(II), nickel(II), copper(II), zinc(II), and iron(III), and cobalt(II) chloride were synthesized via inverse miniemulsion polymerization of 2-hydroxyethyl methacrylate (HEMA). All salts delivered narrowly size-distributed hybrid particles with the exception of iron(III), where only the nitrate salt could be successfully employed. The size and size distribution of the hybrid particles were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The particle morphology and the distribution of salt in the dried particles were observed by TEM. The influences of the type of metal salts and salt content on the particle size distribution were extensively investigated.     

Study of support effects on the reduction of Ni2+ ions in aqueous hydrazine

We have studied the effect of silica of quartz-type on the reducibility of nickel acetate in aqueous hydrazine (80 degrees C, pH = 10-12) and metal particle formation. The obtained materials were characterized by X-ray diffraction, transmission electron microscopy, and thermodesorption experiments. With nickel acetate alone, the reduction was partial (45%) and a metal film at the liquid-gas interface or a powdered metal precipitate with an average particle size of 120 nm was obtained. In the presence of silica as the surfactant, the reduction of nickel acetate was total and the nickel phase deposited as a film on the support with an average particle size of 25 nm. Supported nickel acetate was also totally reduced. Crystallites of a mean particle size of about 3 nm were obtained. Decreasing the nickel content or increasing the hydrazine/nickel ratio decreased the metal particle size. Whiskers were formed for low nickel loadings. Hydrogen thermal treatment of the reduced phase showed that the organic acetate fragment, belonging to the precursor salt, still remained strongly attached to the nickel phase. The amount of the retained organic matrix depended on the metal particle size. Surface defects are suggested as active sites, which enhanced nickel ion reduction in the presence of silica as the surfactant or support. Metal-support interactions and the nucleation/ growth rate were the main factors determining the size and morphology of the supported metal particles formed. The organic matrix covered the reduced nickel phase.     

自催化还原制备微米和纳米级空心镍球的研究

提出了一种新型的制备超细空心金属镍粉的方法.通过FESEM,TEM和XRD衍射对该制备方法进行了研究,并考察了有关工艺参数对产物粒径和粒度分布的影响.研究认为,通过在胶核表面发生自催化还原反应,形成金属镍壳,同时胶核发生自分解,最后可得到空心金属镍球.控制反应物浓度和NaOH的配比可得到粒径均匀的镍球;通过调整这两个参数可得到粒度在微米或纳米尺度的空心镍球.     

多相体系中Ni-PMMA纳米复合材料的γ辐射制备

在多相体系中,运用γ射线辐射法, 在常温常压下成功地一步合成了镍-聚甲基丙烯酸甲酯(Ni-PMMA)纳米复合材料.XRD、 TEM分析和IR光谱表明,在此实验条件下,镍离子和甲基丙烯酸甲酯已成功地被还原或聚合,镍粒子为面心立方,尺寸为7.33 nm.研究显示,用醋酸钠代替氢氧化钠或氨水作为碱性试剂,可以有效地控制体系的pH,同时不影响单体的聚合.     

Electrodeposition of mesoporous semimetal and magnetic metal films from lyotropic liquid crystalline phases

Mesoporous semimetal bismuth film and magnetic metal nickel and cobalt thin films have been electrodeposited from hexagonal or lamellar structured lyotropic liquid crystalline phases with polyoxyethylene surfactant. The liquid crystalline templates are characterized by low-angle X-ray diffraction (XRD) and polarized-light optical microscopy (POM). The metal films are characterized by low-angle and wide-angle XRD, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The magnetic measurements on the mesoporous nickel and cobalt films are shown to have higher coercivity (Hc) than the nonporous polycrystalline films.     

Nanoparticles of nickel oxide and nickel hydroxide using lyophilisomes of fibrinogen as template

Stable lyophilisomes of fibrinogen at pH 7.5 have been prepared by the method of a rapid freezing–heating and annealing sequence. Reduction of the lyophilisomes of the nickel–fibrinogen complex coated on solid substrates and subsequent heating showed formation of nickel hydroxide and finally nickel oxide. Ultraviolet–visible spectroscopy has been used to monitor the thin films of pure fibrinogen microcapsules, as well as the subsequent nucleation and growth of nanoparticles within the supramolecular structure. Transmission electron microscopy showed initially a thread-like structure which disappeared on continued heating, resulting in nanoparticles ranging from 10 to 50 nm. Particle-size distribution of product was analyzed by using X-ray diffraction (XRD), transmission electron microscopy (TEM) and the corresponding selected area electron diffraction (SAED), and Brunauer–Emmett–Teller (BET) N₂ adsorption. The results suggest that the NiO particles have a body-centered cubic structure and are well dispersed. The particle-size distribution ranges from 10 to 50 nm with an average particle size about 28 nm, and the specific surface area is 34 m²/g. Magnetic study carried out on the prepared nanoparticles showed a ferromagnetic behavior.     

Production and structural characterization of crystalline silver nanoparticles from Bacillus cereus isolate

To date, biosynthesis of metal nanoparticles has been intensively studied using bacteria and fungi. We have isolated and identified metal resistant bacterial strains from electroplating industries, they produce silver nanoparticles. The reduction reaction of aqueous silver nitrate with bacterial biomass was carried out for 120 h. Bacteria produced metallic nanoparticles showed a strong absorbance at surface plasmon resonance wavelength around 420 nm. The size and morphology of these nanoparticles were typically imaged using high resolution transmission electron microscopy, the particles size ranges between 4 and 5 nm and are spherical in shape. The crystal structure of the particles was characterized by X-ray diffraction pattern. The full width half maxima from X-ray diffraction measurements indicated that the particles exhibited face-centered cubic phase.     

水性体系中超细镍粉的液相还原制备

采用快捷、温和的液相还原法,在水溶液中,以氢氧化钠为pH值调节剂,利用水合肼的还原作用将氯化镍还原得到超细镍粉．利用扫描电镜（SEM）及X射线衍射（XRD）的表征手段研究了反应条件对超细镍粉微观结构的影响．结果表明,所得到的产物是纯的面心立方结构的镍材料,颗粒的尺寸介于200～500nm之间,且分布较为均匀．     

Synthesis of CoOOH nanorods and application as coating materials of nickel hydroxide for high temperature Ni-MH cells

Studies on nanoscale materials have received great interest in both fundamental and applied aspects in recent years. In this letter, we report the synthesis of CoOOH nanorods and their possible applications as coating materials on nickel hydroxide for high-temperature nickel-metal hydride (Ni-MH) cells. The morphology and structure of CoOOH nanorods and coated nickel hydroxide particles are investigated by transmission electron microscopy, X-ray diffraction, and scanning electron microscopy, respectively. The electrochemical properties in the cylindrical AA size Ni-MH cells are evaluated. Our results show that the Ni-MH cells, where the positive electrodes are composed of such nanometer sized CoOOH coatings, have a higher capacity available and good performance at elevated temperatures of >50 degrees C.     

Characterization of Hydrocarbon Soluble Metal Oxides. Precursors to Supported Catalysts

Abstract

The metal oxide carboxylate complexes described in the previous chapter have been characterized by infrared spectroscopy, x-ray diffraction, electron microscopy, and analytical ultracentrifugation. The molecular weights and solution particle diameters have been determined for a number of the hydrocarbon soluble particles by analytical ultracentrifugation methods, and the use of a spherical model consistent with the particulate shape observed by electron microscopy. The size of the soluble complexes has been studied as a function of: metal, metal/acid ratio, acid composition, and solvent. The molecular weights for the ultimate particles are reasonably independent of the metal employed in the synthesis and are relatively constant for materials with similar metal/acid equivalents ratios. The single particle molecular weights for the complexes studied ranged from approximately 5×10⁴ to 1.5×10⁶g mole^?1. The solution size distribution was polydisperse in all cases, with aggregates of the ultimate particles prevalent. Weight average molecular weights in excess of 10⁹g mole^?1 have been observed. The aggregation is dependent on the surface acid composition and on the solvent in which the soluble complex is dispersed. Solubility and stability of these materials have been examined in a number of solvents. The metal oxide particles are initially soluble in octane, isooctane, cyclohexane, mineral spirits, carbon tetrachloride, benzene, and tetrahydrofuran. However, most of the complexes eventually precipitate from dilute solutions in carbon tetrachloride, benzene, and tetrahydrofuran. The stability of the particles is decreased in the presence of oxygen, or when carboxylic acids, alcohols, or ketones are present even in small amounts, and is decreased even further at temperatures above 100°C. Heterogeneous catalysts have been prepared by deposition of several of the soluble metal oxides onto supports such as alumina, silica, or kieselguhr followed by oxidation to yield supported metal oxides or reduction to yield supported metal. The application of few supported metals and metal oxides in hydrogenations of olefins, benzene, and naphthalene is described.