High-efficiency and low-cost hybrid nanomaterial as enhancing electrocatalyst: Spongelike AWN core/shell nanomaterial with hollow cavity

A high-efficiency and low-cost spongelike Au/Pt core/shell electrocatalyst with hollow cavity has been facilely obtained via a simple two-step wet chemical process. Hollow gold nanospheres were first synthesized via a modified galvanic replacement reaction between Co nanoparticles in situ produced and HAUCl(4). The as-prepared gold hollow spheres were employed as seeds to further grow spongelike Pt shell. It is found that the surface of this hybrid nanomaterial owns many Pt nanospikes, which form a spongelike nanostructure. All experimental data including scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-vis-near-infrared spectroscopy have been employed to characterize the obtained Au/Pt hybrid nanomaterial. The rapid development of fuel cell has inspired us to investigate the electrocatalytic properties for dioxygen and methanol of this novel hybrid nanomaterial. Spongelike hybrid nanomaterial mentioned here exhibits much higher catalytic activity for dioxygen reduction and methanol oxidation than the common Pt electrode.

Molecular dynamics studies on dislocations in crystallites of nanocrystalline alpha-iron

Molecular dynamics simulations have been carried our to study the atomic structure of the crystalline component of nanocrystalline alpha-iron. A two-dimensional computational block is used to simulate the consolidation process. It is found that dislocations are generated in the crystallites during consolidation when the grain size is large enough. The critical value of the grain size for dislocation generation appears to be about 9 nm. This result agrees with experiment qualitatively. AN dislocations that are preset in the original grains glide out during consolidation. It shows that dislocations in the crystallites we generated in consolidation process, but not in the original grains. Higher consolidation pressure results in more dislocations. Furthermore, new interfaces are found within crystallites. These interfaces might result from the special environment of nanomaterial. (C) 1998 Acta Metallurgica Inc.

Magnetic coupling properties of mn-doped ZnO nanowires: First-principles calculations

Based on the density functional theory, we study the magnetic coupling properties of Mn-doped ZnO nanowires. For the nanowires with passivated surfaces, the antiferromagnetic state is found and the Mn atoms have a clustering tendency. When the distance between two Mn atoms is large, the system energetically favors the paramagnetic or spin-glass state. For the nanowires with unpassivated surfaces, the ferromagnetic (FM) coupling states appear between the two nearest Mn atoms, and the zinc vacancies can further stabilize the FM states between them. The electrons with enough concentration possibly mediate the FM coupling due to the negative exchange splitting of conduction band minimum induced by the s-d coupling, which could be useful in nanomaterial design for spintronics. (C) 2008 American Institute of Physics.

Structural phase transformations of ZnS nanocrystalline under high pressure

In-situ energy dispersive x-ray diffraction on ZnS nanocrystalline was carried out under high pressure by using a diamond anvil cell. Phase transition of wurtzite of 10 nm ZnS to rocksalt occurred at 16.0 GPa, which was higher than that of the bulk materials. The structures of ZnS nanocrystalline at different pressures were built by using materials studio and the bulk modulus, and the pressure derivative of ZnS nanocrystalline were derived by fitting the equation of Birch-Murnaghan. The resulting modulus was higher than that of the corresponding bulk material, which indicates that the nanomaterial has higher hardness than its bulk materials.

An investigation on the pressure-induced phase transition of nanocrystalline ZnS

An in situ energy dispersive x-ray diffraction study on nanocrystalline ZnS was carried out under high pressure up to 30.8 GPa by using a diamond anvil cell. The phase transition from the wurtzite to the zinc-blende structure occurred at 11.5 GPa, and another obvious transition to a new phase with rock-salt structure also appeared at 16.0 GPa-which was higher than the value for the bulk material. The bulk modulus and the pressure derivative of nanocrystalline ZnS were derived by fitting the Birch-Murnaghan equation. The resulting modulus was higher than that of the corresponding bulk material, indicating that the nanomaterial has higher hardness than the bulk material.

磁靶向给药体系及磁性纳米材料的制备与表征

磁靶向给药体系能有效减小化疗药物的毒副作用，提高药效，减少用药量，为癌症肿瘤的靶向治疗提供了一个新的途径。磁性靶向抗癌药物体系主要由纳米级磁性材料、骨架材料、化疗药物组成。其结构可以分为包埋型和偶联型：前者是将药物和磁性纳米材料包埋、分散在高分子基质中；后者是将药物通过某种作用力偶联在磁性高分子微球的表面。尽管磁靶向药物的研究已经取得了很大的进展，但是目前还存在着诸如药物载体的生物相容性、靶向功能单一和药物释放缺乏控制等一系列的问题，并且主要集中在包埋型的制备和研究，药物在输送到病灶的过程中会产生一系列的副反应，在将来的临床应用中受到很大的限制。而偶联型磁靶向给药体系的药物释放既可以达到空间控制的效果，也可以起到一定的时间控制的作用。磁性纳米材料不仅是磁靶向给药体系制备的基础，并且在细胞分离，固定化酶，核酸杂交等生物领域和磁记录、吸波材料等方面有广泛的应用。本论文以此为立题依据，共分为七个部分。第一至第四部分以共沉淀法制备的具有超顺磁性的Fe3O4纳米粒子为磁核，选择能生物降解且无毒的无机材料二氧化硅、天然高分子壳聚糖和人工合成的高分子聚乳酸为包覆材料，常用的抗癌药阿霉素、甲氨喋呤为模型药物，制备了三个偶联型磁靶向给药体系，对其体外药物释放行为及磁学性质进行了测定；第五部分结合生物医药对Fe3O4纳米粒子的应用要求，提出了一种简单制备粒径可控的单分散性的亲油/亲水性Fe3O4纳米粒子的新方法, 同时还探讨了亲油/亲水性Fe3O4纳米粒子的可能形成过程；第六部分将阿霉素以酰胺键接枝在可降解高分子材料P3HB4HB上，将得到的P3HBP4HB－DOX偶联物和第五部分所制备的亲油性Fe3O4纳米粒子共混于氯仿中进行静电纺丝，成功地制备了载有DOX的磁性纤维，改变了以往磁靶向给药体系的单一微球形貌；第七部分以EDTA和FeCl2为原料，采用水热法制备了十二面体四氧化三铁纳米粒子，探讨了EDTA和FeCl2的摩尔比、反应温度、反应时间和反应介质对产物形貌的影响，并提出了这一新颖形貌的可能形成机理。

Nanoporous In2O3 nanocrystal clusters: One-step synthesis, thermal stability and optical property

Nanoporous In2O3 nanocrystal clusters with high surface areas have been synthesized by a one-step solvent-thermal method at a relatively low temperature. On the basis of our experimental data and nanomaterial growth mechanism, a template-assistant dehydration accompanied by aggregation mechanism was proposed to explain their formation. Besides, the influence of the high-temperature treatment on their porous structure and optical properties were studied and compared by various technologies.

Pt Nanoparticles Supported on TiO2 Colloidal Spheres with Nanoporous Surface: Preparation and Use as an Enhancing Material for Biosensing Applications

An easy surface-modified method has been developed to link -NH2 groups to the TiO2 colloidal spheres with nanoporous surface (f-TiO2). It was found that the as-prepared f-TiO2 is positively charged in neutral conditions and could act as an electrostatic anchor for nanosructures with opposite charge, Furthermore, platinum nanoparticles (Pt NPs) are successfully assembled on the f-TiO2 mainly via electrostatic interaction to fabricate a new kind of Pt NPs/TiO2 hybrid nanomaterial (f-TiO2-Pt NPs). The morphology, structure, and composition of the hybrids were characterized by the means of diverse techniques such as transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction, and Raman spectra. Electrochemical experiments indicate the electrode modified with f-TiO2-Pt NPs shows prominent electrocatalytic activity toward the oxidation of hydrogen peroxide.

Nanoelectrocatalyst based on high-density Au/Pt hybrid nanoparticles supported on a silica nanosphere

A high-efficiency nanoelectrocatalyst based on high-density Au/Pt hybrid nanoparticles supported on a silica nanosphere (Au-Pt/SiO2) has been prepared by a facile wet chemical method. Scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy are employed to characterize the obtained Au-Pt/SiO2. It was found that each hybrid nanosphere is composed of high-density small Au/Pt hybrid nanoparticles with rough surfaces. These small Au/Pt hybrid nanoparticles interconnect and form a porous nanostructure, which provides highly accessible activity sites, as required for high electrocatalytic activity. We suggest that the particular morphology of the AuPt/SiO2 may be the reason for the high catalytic activity. Thus, this hybrid nanomaterial may find a potential application in fuel cells.

High-density gold nanoparticles supported on a [Ru(bpy)(3)](2+)-doped silica/Fe3O4 nanocomposite: Facile preparation, magnetically induced immobilization, and applications in ECL detection

A large-scale process combined sonication with self-assembly techniques for the preparation of high-density gold nanoparticles supported on a [Ru(bpy)(3)](2+)-doped silica/Fe3O4 nanocomposite (GNRSF) is provided. The obtained hybrid nanomaterials containing Fe3O4 spheres have high saturation magnetization, which leads to their effective immobilization on the surface of an ITO electrode through simple manipulation by an external magnetic field (without the need of a special immobilization apparatus). Furthermore, this hybrid nanomaterial film exhibits a good and very stable electrochemiluminescence (ECL) behavior, which gives a linear response for tripropylamine (TPA) concentrations between 5 mu m and 0.21 mM, with a detection limit in the micromolar range. The sensitivity of this ECL sensor can be easily controlled by the amount of [Ru(bpy)(3)](2+) immobilized on the hybrid nanomaterials (that is, varying the amount of [Ru(bpy)(3)](2+) during GNRSF synthesis).

Gold/platinum hybrid nanoparticles supported on multiwalled carbon nanotube/silica coaxial nanocables: Preparation and application as electrocatalysts for oxygen reduction

A simple approach combining sonication and sol-gel chemistry was employed to synthesize silica coated carbon nanotube (CNTs) coaxial nanocables. It was found that a homogeneous silica layer can be coated on the surface of the CNTs. This method is simple, rapid, and reproducible. Furthermore, gold nanoparticle supported coaxial nanocables were facilely obtained using amino-functionalized silica as the interlinker. Furthermore, to reduce the cost of Pt in fuel cells, designing a Pt shell on the surface of a noble metal such as gold or silver is necessary. High-density gold/platinum hybrid nanoparticles were located on the surface of I-D coaxial nanocables with high surface-to-volume ratios. It was found that this hybrid nanomaterial exhibits a high electrocatalytic activity for enhancing oxygen reduction (low overpotential associated with the oxygen reduction reaction and almost four-electron electroreduction of dioxygen to water).