金刚石颗粒表面Cr金属化及薄膜间界面扩散反应的研究

运用直流磁控溅射法可在金刚石颗粒表面沉积150nm的金属Cr层.在超高真空条件下,经300-600℃的热退火处理,可促进Cr膜与金刚石基底间的界面扩散和反应.利用俄歇电子能谱研究了Cr/金刚石颗粒界面的结合状态,发现Cr与金刚石薄膜发生了强烈的界面扩散,Cr元素渗入金刚石层达90nm,并在界面上发生化学反应形成Cr的碳化物层.对界面扩散反应动力学的研究表明,Cr/金刚石界面扩散反应的表观活化能为38.4kJ/mol,界面扩散反应主要由碳的扩散过程控制.热处理温度越高,界面扩散及反应越显著,但不利于碳化物层生成的氧化反应速度也会有所增加,界面反应产物从Cr₂C₃转变为Cr₂C物种.延长热处理时间有利于金属碳化物的生成,同样导致界面反应产物从Cr₂C₃转变为Cr₂C物种.     

强磁场碳黑催化法制备纳米新金刚石粉

在直流恒稳强磁场(10T)作用下，以纳米铁为催化剂，碳黑为碳源，在常压和1100℃下保温100min成功地制备出了类金刚石和新金刚石，并用XRD，TEM和Raman对制备的样品粉末进行表征．结果表明，样品粉末是由纳米类金刚石粉和石墨包覆新金刚石纳米颗粒组成，纳米类金刚石粉的大小为20nm，石墨包覆新金刚石的大小为100nm．     

化学还原法制备纳米级Ag粉高分子保护机理研究

本文研究了化学还原法制备纳米级Ag粉的高分子保护机理, 实验结果显示聚乙烯基吡咯烷酮(PVP)能有效地阻止颗粒团聚并降低Ag晶粒尺寸, 得到近单分散200nm以下的Ag粉。PVP的保护机制为: 第一步, PVP与Ag^+形成配位键。第二步,配位键促进Ag颗粒成核。第三步, 形成大量小晶核使Ag颗粒平均尺寸减小, 而PVP吸附在Ag颗粒表面形成位阻效应阻止了颗粒团聚。     

纳米Sn-Co/石墨复合材料的制备、结构和电化学性能

以化学沉积法制备Sn-Co合金纳米粒子/石墨复合材料,XRD和Ram an光谱表征物相结构,SEM观察表面形貌.结果显示,500℃高温热处理的Sn-Co/石墨复合材料,其颗粒密集均匀地分散于石墨载体上.Sn-Co合金纳米粒子颗粒直径100 nm左右.Sn-Co/石墨电极具有较高的比容量和循环寿命,这可能是该合金纳米粒子与棒状石墨间的亲合能有效地阻止Sn的脱落,Sn-Co的颗粒间隙缓冲锂嵌脱过程的结构张力,防止合金的膨胀与粉化.     

原位限域合成介孔碳负载四氧化三铁纳米颗粒

利用废弃蟹壳做模板制备的具有均一孔道结构的介孔碳材料做载体,在孔道内限域原位合成四氧化三铁氧化物纳米颗粒。 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射(XRD)表征了材料的结构和性能。 结果表明,孔道结构呈整体式结构,孔直径在40~50 nm,长50~200 μm。 纳米颗粒为四氧化三铁,粒径在10 nm左右,尺寸单分散性好,可均匀分散在介孔孔道内。 该方法工艺路线简单,绿色环保。     

团聚纳米SiO_2在苯乙烯乳液聚合过程中的再分散过程及机理

用二氧化硅 (SiO2 )存在下的乳液聚合法制备了聚苯乙烯 (PSt) 纳米SiO2 复合材料 ,研究了苯乙烯(St)乳液聚合过程中团聚纳米SiO2 的解离与再分散过程及分散的机理 .发现商品纳米SiO2 粒子以团聚体形式存在 ,团聚体大小远超出纳米级范围 .随聚合时间的延长 ,St的转化率逐渐增加 ,而PSt SiO2 复合微胶囊的粒径逐渐减小 ,反应 12 0min后 ,转化率和复合微胶囊粒子的粒径趋于稳定 .透射电镜 (TEM)也显示PSt SiO2 复合微胶囊粒子具有海岛结构 ,而SiO2 粒子的粒径在纳米范围内 ,表明在乳液聚合过程中SiO2 团聚体被逐渐解离 ,并重新分散到纳米尺度 .红外光谱研究发现 ,在乳液聚合过程中 ,除生成PSt均聚物外 ,还在纳米SiO2 表面生成了PSt接枝共聚物 ,改善了无机纳米粒子与聚合物之间的界面相容性 .聚合过程中的反应热和剪切搅拌是团聚体被解离和重新分散的主要原因 ,而生成的聚合物起到隔离作用     

静电纺丝法制备SrTiO3多晶微纳米纤维

应用静电纺丝法并结合Sol-gel 技术制备了SrTiO3微纳米纤维. SEM, TEM及电子衍射分析结果显示, 于900 ℃煅烧获得的纤维直径分布在50~400 nm之间, 其典型直径约为280 nm. XRD分析结果表明, 纤维由立方结构的SrTiO3晶粒组成, 平均晶粒尺寸为33 nm.     

高能振动球磨法制备纳米钙钛矿粉体La_(0.8)Ca_(0.2)MnO_3

利用高能振动球磨法,以氧化镧、氧化钙和二氧化锰为原料,制备出纳米氧化物粉体La0.8Ca0.2MnO3。采用XRD分析了球磨过程中粉体的晶化过程;以TEM观察了制备出的粉体的颗粒尺寸和分散状况。结果表明,采用高能振动球磨法20 h就能制备出颗粒尺寸在50~100 nm,属正交晶系的纳米钙钛矿粉体La0.8Ca0.2MnO3;在该反应体系的球磨过程中,产物晶粒经历了先长大后细化的过程。将球磨法制备出的粉体压成电极,进行放电分析。结果表明采用该方法制备出的纳米La0.8Ca0.2MnO3粉体具有很好的电催化活性。     

块状LaNi5基纳米合金的正电子湮灭研究

利用高温高压技术，在不同的压力和温度(-4．5GPa，-800℃)下将LaNi5基快淬合金粉直接压制成了块状纳米晶合金。X射线衍射分析表明，高压使其晶粒内部发生了明显的压致晶粒碎化，其平均晶粒尺寸在4．5GPa下从75．5nm降至24．6nm。利用正电子湮灭技术研究了这种晶粒碎化效应对纳米合金内部缺陷结构的影响。测试结果表明，在高温高压的作用下，由于界面上原子的迁移和弛豫加剧，导致晶界上尺寸较大的微孔隙缺陷逐渐转化为尺寸较小的自由体积缺陷，使得纳米合金的致密度逐渐增强，显微硬度逐渐升高，从而在高温高压下得到致密的块状纳米合金材料。     

纳米电极上单个银纳米颗粒氧化电流分辨能力的研究

在单体电化学的研究中,提高信号分辨能力是一项挑战.缩小电极尺寸有利于对体系噪音电流的控制,有望提高电流的分辨能力.本研究制备了直径为480 nm的铂纳米圆盘电极,选用银纳米颗粒碰撞电极产生银电化学氧化行为作为模型,考察了纳米电极相对于微米电极在单体电化学信号分辨能力上的优化作用.研究表明,不同尺寸电极上观察到的银纳米颗粒的碰撞频率符合扩散控制的碰撞规律.说明单个电流信号对应于单个纳米颗粒的电化学氧化过程.同时,当电极尺寸缩小至纳米尺度后,噪音电流下降50%左右,提高了对银纳米颗粒碰撞电极过程中氧化电流的分辨能力.研究结果表明使用纳米电极能进一步提高对单体电化学中微小电流的检测能力.     

Graphitic encapsulation of catalyst particles in carbon nanotube production

A new model is proposed for the encapsulation of catalyst metal particles by graphite layers that are obtained, for example, in low-temperature chemical vapor deposition production of carbon nanotubes (CNTs). In this model graphite layers are primarily formed from the dissolved carbon atoms in the metal-carbide particle when the particle cools. This mechanism is in good agreement with molecular dynamics simulations (which show that precipitated carbon atoms preferentially form graphite sheets instead of CNTs at low temperatures) and experimental results (e.g., encapsulated metal particles are found in low-temperature zones and CNTs in high-temperature regions of production apparatus, very small catalyst particles are generally not encapsulated, and the ratio of the number of graphitic layers to the diameter of the catalyst particle is typically 0.25 nm(-1)).     

洋葱状富勒烯的提纯研究

以石墨粉为碳源, Al为催化剂, 采用真空热处理法制备了平均粒径为15～35 nm的洋葱状富勒烯(OLFs).并用CS₂分离和空气氧化法对得到的OLFs初产品进行了提纯处理.高分辨透射电镜(HRTEM)、X射线衍射(XRD)、热重分析(TGA)对提纯前后样品的分析表明, CS₂分离处理可有效去除初产品中裸露的金属催化剂微粒,然后在空气中610 ℃焙烧200 min,可基本去除无定型碳,并大量去除了石墨状碎片等碳杂质, OLFs的纯度在50％(体积分数)以上.     

Preparation of Ag/HOPG model catalysts with a variable particle size and an in situ xps study of their catalytic properties in ethylene oxidation

The preparation of model silver catalysts supported on highly oriented pyrolytic graphite is described, and the effect of the Ag particle size on the catalytic ethylene oxidation into ethylene oxide, studied by in situ XPS and mass spectrometry, is considered. For a mean particle diameter of 8 nm, the adsorbed oxygen species characterized by an O 1s binding energy of 530.8 ± 0.2 eV (electrophilic oxygen) forms on the silver surface exposed to the ethylene-oxygen reaction mixture. Larger silver particles with a mean diameter of 40 nm additionally contain the adsorbed oxygen species characterized by an O 1s binding energy of 529.2 ± 0.2 eV (nucleophilic oxygen). The presence of both oxygen species on the surface of the larger particles ensures the formation of ethylene oxide, while the sample with the smaller silver particles is inactive in the epoxidation reaction. The O 1s signal at 530.8 eV is partly due to oxygen dissolved in the subsurface layers of silver.     

A comparative analysis of self-assembly in poly(methacrylates) with bulky side substituents of different molecular masses in the solid state and in solutions

A comparative investigation of self-assembly in poly(methacrylates) with bulky substituents based on gallic acid both in the condensed state and in hexane solutions has been performed by using the methods of SAXS and DSC. The size and shape of the formed supramolecular aggregates have been analyzed for the polymers of two different degrees of polymerization (150 and 21). In fresh solutions of a low-molecular-mass polymer, extended piles composed of several molecules are formed. Each molecule from a disk with a diameter of ～4.4 nm, which is similar to the diameter of columnar phase cylinders in the solid state. In solutions of a highmolecular-mass polymer, several molecules form a wormlike particle. The observed supramolecular aggregates are unstable: within several months, their order breaks down and particles are dissolved.     

焙烧温度对Au/Fe2O3选择性氧化富氢气体中CO催化性能的影响

甲醇重整在线制氢作为质子交换膜燃料电池的燃料成为当前研究的热点。受重整反应动力学及热力学的限制，使得甲醇重整气(富氢气体)中除含有大量的氢气外还含有少量的CO，CO极易吸附在燃料电池阳极催化剂表面，使电池性能下降，因而必须去除重整气中的CO，选择性氧化脱除富氢气     

多壁碳纳米管的制备及改性处理

用自制的镍 硅二元气凝胶作催化剂,合成了多壁碳纳米管.甲烷在680℃催化裂解120min,再升温至800℃继续裂解20min,得到多壁碳纳米管.TEM、HRTEM和Raman光谱分析表明,所得多壁碳纳米管与高定向石墨具有相似的层状结构,其管径分布均匀,约15～30nm左右,长径比大,管端封闭,并含有金属催化剂粒子;采用不同方法改性处理,发现经过稀硝酸浸泡和空气氧化处理后,能去除碳管中金属催化剂,同时碳纳米管管长变短,端帽开口,能有效利用内表面,比表面积增大.     

过渡金属氧化物和金属负载型沸石催化剂上合成 纳米碳管及其表征

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。     

Redox properties of undoped 5 nm diamond nanoparticles

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH(3))(6)(3+/2+) and Fe(CN)(6)(4-/3-) was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction. Surface modification of the ND powders by heating in air or in a hydrogen flow resulted in oxygenated and hydrogenated forms of the ND, respectively. Oxygenated ND was found to exhibit the greatest electrochemical activity and hydrogenated ND the least. Differential pulse voltammetry of electrode-immobilised ND layers in the absence of solution redox species revealed oxidation and reduction peaks that could be attributed to direct electron transfer (ET) reactions of the ND particles themselves. It is hypothesised that ND consists of an insulating sp(3) diamond core with a surface that has significant delocalised pi character due to unsatisfied surface atoms and C[double bond, length as m-dash]O bond formation. At the nanoscale surface properties of the particles dominate over those of the bulk, allowing ET to occur between these essentially insulating particles and a redox species in solution or an underlying electrode. We speculate that reversible reduction of the ND may occur via electron injection into available surface states at well-defined reduction potentials and allow the ND particles to act as a source and sink of electrons for the promotion of solution redox reactions.     

Platinum Nanosheets Intercalated into Natural and Artificial Graphite Powders

Insertion of sheet-type platinum particles (platinum nanosheets) between graphite layers was achieved by a thermal treatment of a mixture of platinum chloride (IV) and graphite powder (natural graphite or artificial graphite) under 0.3 MPa of chlorine at 723 K, followed by the treatment under 40 kPa of hydrogen pressure. Similar platinum nanosheets, which were 1–3 nm in thickness and 100–500 nm in width and had a number of hexagonal holes and edges with 120° angle, were formed between the layers of both natural graphite or artificial graphite; however, their location in the graphite layers depended on the type of graphite used. A number of platinum nanosheets were observed in the edge region of natural graphite particles which have flat surface. On the other hand, a number of platinum nanosheets were found inside and away from the edge of the artificial graphite particles especially in the vicinity of the cracks. Both the platinum nanosheet-containing artificial and natural graphite samples showed high selectivity to cinnamyl alcohol in cinnamaldehyde hydrogenation under supercritical carbon dioxide conditions, while spherical platinum particles, which were located on the surface of natural and artificial graphite, showed lower selectivity.     

Particle restabilization in silica/PEG/ethanol suspensions: how strongly do polymers need to adsorb to stabilize against aggregation?

We study the effects of increasing the concentration of a low molecular weight polyethylene glycol on the stability of 44 nm diameter silica nanoparticles suspended in ethanol. Polymer concentration, c(p), is increased from zero to that characterizing the polymer melt. Particle stability is accessed through measurement of the particle second-virial coefficient, B(2), performed by light scattering and ultrasmall angle X-ray scattering (USAXS). The results show that at low polymer concentration, c(p) < 3 wt %, B(2) values are positive, indicating repulsive interactions between particles. B(2) decreases at intermediate concentrations (3 wt % < c(p) < 50 wt %), and particles aggregates are formed. At high concentrations (50 wt % < c(p)) B(2) increases and stabilizes at a value expected for hard spheres with a diameter near 44 nm, indicating the particles are thermodynamically stable. At intermediate polymer concentrations, rates of aggregation are determined by measuring time-dependent changes in the suspension turbidity, revealing that aggregation is slowed by the necessity of the particles diffusing over a repulsive barrier in the pair potential. The magnitude of the barrier passes through a minimum at c(p) ≈ 12 wt % where it has a value of ～12 kT. These results are understood in terms of a reduction of electrostatic repulsion and van der Waals attractions with increasing c(p). Depletion attractions are found to play a minor role in particle stability. A model is presented suggesting displacement of weakly adsorbed polymer leads to slow aggregation at intermediate concentration, and we conclude that a general model of depletion restabilization may involve increased strength of polymer adsorption with increasing polymer concentration.