二维金纳米微粒有序阵列的制备

对于用十二烷基硫醇包覆的金纳米微粒，用Langmuir-Blodgett(LB)技术制备了二维金纳米微粒有序阵列．在单纯的硫醇包覆的金纳米微粒形成的LB膜中，由于硫醇分子之间的疏水相互作用，容易导致金纳米微粒的自组织而在LB膜中形成缺陷．为了改善金纳米微粒的成膜性能和提高金纳米微粒阵列的有序性，正十二醇作为添加剂和润滑剂加入到金纳米微粒的氯仿溶液中与金纳米微粒一起形成LB膜．用透射电子显微镜对金纳米微粒的二维阵列进行了表征．结果表明，正十二醇的加入可以有效地减少用LB技术制备的二维金纳米微粒阵列中的缺陷，提高金纳米微粒阵列的有序性．     

Shape control technology during electrochemical synthesis of gold nanoparticles

Gold nanoparticles with different shapes and sizes were prepared by adding gold precursor (HAuCl₄) to an electrolyzed aqueous solution of poly(N-vinylpyrrolidone) (PVP) and KNO₃, which indicates the good reducing capacity of the PVP-containing solution after being treated by electrolysis. Using a catholyte and an anolyte as the reducing agents for HAuCl₄, respectively, most gold nanoparticles were spherical particles in the former case but plate-like particles in the latter case. The change in the pH value of electrolytes caused by the electrolysis of water would be the origin of the differences in shape and morphology of gold nanoparticles. A hypothesis of the H+ or OH? catalyzed PVP degradation mechanism was proposed to interpret why the pH value played a key role in determining the shape or morphology of gold nanoparticles. These experiments open up a new method for effectively controlling the shape and morphology of metal nanoparticles by using electrochemical methods.     

One-step and high-density protein immobilization on epoxysilane-modified silica nanoparticles

Silica nanoparticles are most commonly modified with amino-silanes, followed by post-modification activation for protein immobilization. In this work, epoxy-functionalized silica nanoparticles were prepared by modification with glycidyloxypropyl trimethoxysilane （GPTMS） for direct protein immobilization. Silica nanoparticles possessed an average size of 46 nm, but increased to 63 nm after GPTMS modification. Reaction time, reaction temperature and GPTMS content had no significant effect on par- ticle size. Zeta potential of SiO2 changed from -26mV to ＋38mV after modification. Fourier-transformed infrared spectroscopy revealed alkyl C--H bending and stretching bands at 2944 cm-1, 1343 cm-1 and 1465 cm-1, respectively, for the modified nanoparticles. Fluorescein cadaverine was found to bind to GPTMS-modified SiO2, but not to bare SiO2, indicating the chemical reactivity of epoxy groups on the modified nanoparticle with amines. Finally, fluorescenUy labeled bovine serum albumin （BSA） was used as a model protein to investigate the capacity of epoxy-SiO2 nanoparticles for protein immobilization. The results showed that more proteins were immobilized on the particle with longer reaction time, higher NaCI concentration, lower pH, and less GPTMS content. More importantly, proteins bound to epoxy-SiO2 nanoparticle were highly stable. Under optimized reaction conditions, as much as 25 mg BSA/g nanoparticle was covalentiy attached to the nanoparticle. The epoxy silane modification of silica nanoparticles offers a reactive surface for one-step and high-density protein immobilization.     

3D TEM study on hollow α-Fe_2O_3 nanostructures and nanorings

Controlled synthesis of hollow structures with non-spherical holes is significant in fabricating nanomaterials with well-defined geometries and specific catalytic and electrochemical properties. Here we report the synthesis of uniform hexagonal bipyramid hematite(α-Fe_2O_3) nanoparticles with hollow and faceted interior via directional etching process in solution. The delicate hollow structures were investigated by electron tomography and growth mechanism was revealed unambiguously. The three-dimensional visualization demonstrates the outside surfaces of hematite particles are enclosed by six {104} and twelve {113} planes, due to the stabilizing effect of the F-anions on the exposed surfaces. The concurrent etching process is a reverse process of crystal growth and leads to the dissolution occurring at the edges and tips of the hexagonal bipyramid particles, resulting in the perforated crystals with exposed {102} internal facets or overetched nanorings with hexagonal cross-sections.This nanoscale growth and etching process still strictly follows the bulk crystal growth mechanism, thus shedding light on the synthesis of other nanoparticle with controlled morphologies and porous structures.     

PVP-assisted laser ablation growth of Ag nanocubes anchored on reduced graphene oxide(rGO) for efficient photocatalytic CO_2 reduction

Metallic nanoparticles loaded graphene nanocomposites have been widely studied for various scientific and technological applications. In this study, a facile method was reported to realize a straightforward growth of shape and size-controllable of metallic nanoparticles, and the subsequent hybridization with graphene in solution by strategically coupling wet-chemical route and laser ablation. By mixing graphene oxide(GO) with a tunable concentration level of polyvinylpyrrolidone(PVP) in aqueous solution, Ag nanocubes with a face-centered cubic crystal structure were generated by pulsed laser ablation and then mounted on GO nanosheets with the assistance of PVP. The preferential adsorption of PVP to Ag(100) crystal face led to the production of Ag nanocubes with exposed(100) facet. The result showed that the morphological yield of spherical particles decreased with the increase in PVP concentration. X-ray diffraction(XRD) and UV–visible spectroscopy analyses confirmed that GO was partially reduced. In the reduction of CO_2 gas, the photocatalytic conversion rate could achieve 133.1 μmol g~(-1) h~(-1) in 6 hrs for cubic Ag-loaded reduced GO composites.     

ZnO及其掺杂纳米粒子的反相微乳液法合成及表征

 分别以OP/正庚烷/正己醇/水溶液和吐温60/溴代十六烷基吡啶/二甲苯/正戊醇/水溶液反相微乳液体系,合成了ZnO及ZnO-Cr₂O₃,ZnO-Cr₂O₃-NiO,ZnO-Cr₂O₃-NiO-MnO掺杂纳米粒子.研究了前驱物、反应物浓度和后处理对粒子制备和粒径的影响.结果表明:所给微乳液体系适合ZnO及其掺杂纳米粒子的制备;通过选择反应途径及控制反应物浓度可实现对粒径的控制;ZnO纳米粒子的粒径为10～200nm,二元、三元、四元掺杂型纳米粒子的粒径均约为20nm.     

Competing crystallite size and zinc concentration in silica coated cobalt ferrite nanoparticles

Silica coated(30 wt%) cobalt zinc ferrite(Co1 xZnxFe2O4, x?0, 0.2, 0.3, 0.4, 0.5 and 1) nanoparticles were synthesized by using sol–gel method. Silica acts as a spacer among the nanoparticles to avoid the agglomeration. X-ray diffraction(XRD) reveals the cubic spinel ferrite structure of nanoparticles with crystallite size in the range 37–45 nm. Fourier transform infrared(FTIR) spectroscopy confirmed the formation of spinel ferrite and SiO2. Scanning electron microscopy(SEM) images show that the nanoparticles are nearly spherical and non-agglomerated due to presence of non-magnetic SiO2 surface coating. All these measurements signify that the structural and magnetic properties of Co1 xZnxFe2O4 ferrite nanoparticles strongly depend on Zn concentration and nanoparticle average crystallite size in different Zn concentration regimes.& 2014 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.     

同步辐射XANES方法对FeCl3 水溶液的研究

利用X 射线近边吸收谱学(X-ray Absorption Near Edge Structure, XANES)方法研究了不同浓度的FeCl₃ 水溶液中Fe³⁺离子的电子结构和近邻结构. 在不同浓度的FeCl₃ 水溶液的XANES 谱中, XANES 谱的形状随着FeCl₃ 浓度的不同而发生改变. 在XANES 谱的边前结构中观测到边前锋的分裂, 其分裂的能量差约为1.6 eV, 随着浓度的降低约有0.2 eV 的高能方向的位移, 此边前结构由1s-3d 轨道的电子跃迁引起, 双峰分裂来源于配位体配位引起的3d 轨道分裂. 随着FeCl₃ 浓度的改变, XANES 谱的主峰也发生变化, 此变化来源于溶液中Fe—Cl 配位与Fe—O 配位的比例变化. 另外, 利用量子化学计算的方法对于Fe³⁺与不同数目的H₂O 和Cl^?配位体络合时的构型进行了计算, 得到了Fe³⁺在水溶液中近邻结构的信息, 从另一方面解释了FeCl₃ 溶液中Fe³⁺离子3d 轨道分裂能的变化     

Preparation of porous chitosan-poly（acrylic acid）- calcium phosphate hybrid nanoparticles via mineralization

In this work, the preparation of chitosan-poly（acrylic acid）-calcium phosphate hybrid nanoparticles （CS-PAA-CaP NP） based on the mineralization of calcium phosphate （CAP） on the surface of chitosan-poly （acrylic acid） nanoparticles （CS-PAA NPs） was reported. CS-PAA-CaP NPs were achieved by directly adding ammonia to the aqueous solution of CS-PAA nanoparticles or by thermal decomposition of urea in the aqueous solution of CS-PAA nanoparticles, resulting in the mineralization of CaP on the surface of CS-PAA NPs. Through these two routes, especially using urea as a pH-regulator, the precipitation of CS-PAA NPs, a common occurrence in basic environment, was avoided. The size, morphology and ingredient of CS-PAA-CaP hybrid nanoparticles were characterized by dynamic light scattering （DLS）, transmission electron microscope （TEM）, scanning electron microscope （SEM）, thermogravimetry analysis （TGA） and X-ray diffractometer （XRD）. When urea was used as the pH regulator to facilitate the mineralization during the thermal urea decomposition procedure, regular CS-PAA-CaP hybrid nanoparticles with a porosity-structural CaP shells and 400-600 nm size were obtained. TGA result revealed that the hybrid NPs contained approximately 23% inorganic component, which was consistent with the ratio of starting materials. The XRD spectra of hybrid nanoparticles in- dicated that dicalcium phosphate （DCP： CaHPO4） crystal was a dominant component of mineralization. The porous structure of the CS-PAA-CaP hybrid NPs might be greatly useful in pharmaceutical and other medical applications.     

Two-dimensional array of nanoparticles intermitted by long chain molecules

It is an important theme in nanoscience to control the interval of the ordered array of nanoparticles through modifying the chain length of the passivating molecules of the nanoparticles. The theme runs through most of the applications of the ordered array of nanoparticles. Though the Langmuir-Blodgett (LB) technique is one of the most important ways to prepare the two- dimensional ordered array of nanoparticles, it has only been used in case that the passivating molecules are short enough (相似文献   

微流体反应器制备金纳米粒子的研究

利用全聚合物微流体反应器,在紫外光照射下制备了金纳米粒子。采用紫外-可见吸收光谱、激光粒度分析仪、高分辨透射电镜等对柠檬酸钠-氯金酸微流体光化学反应体系进行了表征,并考察了注射泵的流速、柠檬酸钠与氯金酸的浓度比、紫外辐射强度对金纳米粒子产率和粒径大小的影响。结果表明,得到的金纳米粒子最小粒径约20nm;金纳米粒子的产率随注射泵流速的增大而上升,但是随柠檬酸钠与氯金酸浓度比的增大和紫外辐射强度的增强而减弱;金纳米粒子的粒径随注射泵流速的增大和紫外辐射强度的增强而减小,但是在柠檬酸钠与氯金酸浓度比小于16时,粒径变化不大,当柠檬酸钠与氯金酸浓度比大于16时,粒径迅速增大。     

Synthesis of Silver Nanoparticle and Its Morphological Control

Silver nanoparticles with different morphologies were prepared in AgNO3 aqueous solution using nanocarbon as template medium and polymer surfactant as protecting agent in an ultrasonic field. The polymer surfactant polyvinylpyrrolidone ( PVP) was self-prepared and used directly in aqueous solution form. The molecular weight of PVP was measured by viscosimeter. The crystalline phase,component, size, and morphology of the as-synthesized silver naoparticles were characterized by XRD, TEM,FTIR, and Laser Granularity Instrument. The results indicated that ultrasonic was the key factor to deoxidize Ag+to be Ag°nanocarbon and polymer surfactants accelerated the deoxidization reaction course and controlled the agglomeration of freshly formed silver nanoparticles, the category of polymer surfactant had decisive effect on the morphology of as-synthesized nanoparticle. Well-defined dendrites silver nanoparticle could be attained when choosing PVP as surfactant in AgNO3 aqueous solution,while regular sphere silver nanoparticle could be synthesized in the presence of polyvinyl alcohol (PVA) surfactant.Moreover, the concentration of AgNO3 and ultrasonic action time also had obvious effect on the morphology of silver nanoparticle, low concentration of AgNO3 and long time of ultrasonic were not in favor of forming dendrite silver.     

Synthesis and properties of ultrahigh molecular weight polyethylene/WS2 nanoparticle fiber for bullet-proof materials

Ultrahigh molecular weight polyethylene (UHMWPE)/WS2 nanoparticle fibers were prepared by adding WS2 nanoparticles treated by coupling agent in the precursor solution of UHMWPE. The influence of WS2 nanoparticles on the microstructure and properties of UHMWPE fibers was characterized by SEM, TGA, mechanical property measurement and bullet-shock test. The results showed that WS2 nanoparticles can be uniformly dispersed in the UHMWPE fiber. After incorporating of WS2 nanoparticles, UHMWPE fibers became stiffer and tougher than the pristine ones. Particularly, the modulus of the fiber increased from 1203 to 1326cN/dtex. Furthermore, UHMWPE/WSfibers showed an improved thermal stability.     

Uniform composition film of hydrophilic colloidal gold nanoparticles and hydrophobic carbazole functionalized fluorene trimers for enhanced fluorescence and stability

Compositing gold nanoparticles into conjugated molecules have been developed to be one of the most important approaches to increase stability, since degradation of conjugated materials is now one of the biggest bottle-necks to be conquered before industrialization application. Big-size colloidal gold nanoparticles with strong surface plasma resonance are designed to composite with conjugated molecules, in order to realize effective fluorescence enhancement and stabilization. The uniform composition film of hydrophilic colloidal gold nanoparticles (particle diameter of 30 nm) and hydrophobic carbazole functionalized fluorene trimers has been obtained by direct mixing of their aqueous and THF solutions, which is determined by AFM. By the comparison of composition based on fluorene trimers with similar structures, we have found that peripheral carbazole group and molecular size of fluorene trimers play an important role in the balance of incompatible solubility, which is regarded as increasing solubility of fluorene trimers in mixed solvent, connecting AuNP and peripheral carbazole groups, and restraining aggregate of gold nanoparticle. This allows facile hydrophilic gold nanoparticle to disperse uniformly in hydrophobic-conjugated host. Our investigations show that fluorescence intensity of composition film is enhanced by 4 folds, and heat treatment (200°C for 4h) for the composition film does not induce the degradation of conjugated backbone without the appearance of low-energy emission band, demonstrating the prominent potency of gold nanoparticles in enhanced fluorescence and stability of conjugated molecules and polymers.     

DNA-guided crystallization of colloidal nanoparticles

Many nanometre-sized building blocks will readily assemble into macroscopic structures. If the process is accompanied by effective control over the interactions between the blocks and all entropic effects, then the resultant structures will be ordered with a precision hard to achieve with other fabrication methods. But it remains challenging to use self-assembly to design systems comprised of different types of building blocks-to realize novel magnetic, plasmonic and photonic metamaterials, for example. A conceptually simple idea for overcoming this problem is the use of 'encodable' interactions between building blocks; this can in principle be straightforwardly implemented using biomolecules. Strategies that use DNA programmability to control the placement of nanoparticles in one and two dimensions have indeed been demonstrated. However, our theoretical understanding of how to extend this approach to three dimensions is limited, and most experiments have yielded amorphous aggregates and only occasionally crystallites of close-packed micrometre-sized particles. Here, we report the formation of three-dimensional crystalline assemblies of gold nanoparticles mediated by interactions between complementary DNA molecules attached to the nanoparticles' surface. We find that the nanoparticle crystals form reversibly during heating and cooling cycles. Moreover, the body-centred-cubic lattice structure is temperature-tuneable and structurally open, with particles occupying only approximately 4% of the unit cell volume. We expect that our DNA-mediated crystallization approach, and the insight into DNA design requirements it has provided, will facilitate both the creation of new classes of ordered multicomponent metamaterials and the exploration of the phase behaviour of hybrid systems with addressable interactions.     

Nanotribological behaviors of in situ nanoparticles doped molecular deposition films

The molecular deposition films of poly （diallyl dimethylammonium chloride） （PDDA） and poly （acrylicacid） （PAA） with Cu2＋ on quartz and glass substrates were prepared in laboratory first, then different bilayers films were dipped into fresh Na2S aqueous solution. As a result, CuS nanoparticles were fabricated in multilayer molecular deposition films in situ. The structure and nanotribological properties of the composite films were analyzed by ultraviolet-visible （UV-visible） spectroscopy, XPS and atomic force microscope （AFM）. It was found that the CuS nanoparticles were homogeneously distributed throughout the whole film. And these films had a much smaller friction force than their substrates and higher antiwear life than pristine PDDA/PAA molecular deposition films. The fluctuation and variation trend of the topography, hardness, and friction with the AFM indentation length were also investigated.     

Nickel-introduced structurally ordered PtCuNi/C as high performance electrocatalyst for oxygen reduction reaction

Designing highly active and durable oxygen reduction reaction (ORR) electrocatalysts is essential for developing efficient proton-exchange membrane fuel cells (PEMFCs). In this work, ordered PtCuNi/C nanoparticles (NPs) were synthesized using an impregnation reduction method. This study shows that the incorporation of Ni in ordered PtCu/C can effectively adjust the electronic structure of Pt, thereby optimizing oxygen binding energy for the ORR. The obtained intermetallic ordered PtCuNi/C NPs significantly improved ORR activity and durability compared to ordered PtCu/C. Specifically, PtCu_0·5Ni_0·5/C-700 shows a mass activity of 1.29 ​A ​mg _Pt⁻¹ ​at 0.9 ​V vs. reversible hydrogen electrode (RHE), which is about 9.2 times higher than that of commercial Pt/C. PtCu_0.5Ni_0.5/C-700 is also shown to be competent cathode catalyst for a single-cell system exhibiting high power density (461 ​mW ​cm⁻²). This work demonstrates that ordered PtCu_0·5Ni_0·5/C-700 can be used as a highly active and durable ORR catalyst in PEMFCs.     

Influence of particle size and temperature on the dielectric properties of CoFe2O4 nanoparticles

The objective of this study was to establish the dielectric properties of CoFe2O4 nanoparticles with particle sizes that varied from 28.6 to 5.8 nm. CoFe2O4 nanoparticles were synthesized using a chemical coprecipitation method. The particle sizes were calculated accord-ing to the Scherrer formula using X-ray diffraction （XRD） peaks, and the particle size distribution curves were constructed by using field-emission scanning electron microscopy （FESEM） images. The dielectric permittivity and loss tangents of the samples were determined in the frequency range of 1 kHz to 1 MHz and in the temperature range of 300 to 10 K. Both the dielectric permittivity and the loss tangent were found to decrease with increasing frequency and decreasing temperature. For the smallest CoFe2O4 nanoparticle size, the dielectric per-mittivity and loss tangent exhibited their highest and lowest values, respectively. This behavior is very useful for materials used in devices that operate in the microwave or radio frequency ranges.     

Synthesis and application of bilayer-surfactant-enveloped Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: water-based bilayer-surfactant-enveloped ferrofluids

Superparamagnetic carbon-coated Fe₃O₄ nanoparticles with high magnetization (85 emu·g-1) and high crystallinity were synthesized using polyethylene glycol-4000 (PEG (4000)) as a carbon source. Fe₃O₄ water-based bilayer-surfactant-enveloped ferrofluids were subsequently prepared using sodium oleate and PEG (4000) as dispersants. Analyses using X-ray photoelectron spectroscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy indicate that the Fe₃O₄ nanoparticles with a bilayer surfactant coating retain the inverse spinel-type structure and are successfully coated with sodium oleate and PEG (4000). Transmission electron microscopy, vibrating sample magnetometry, and particle-size analysis results indicate that the coated Fe₃O₄ nanoparticles also retain the good saturation magnetization of Fe₃O₄ (79.6 emu·g-1) and that the particle size of the bilayer-surfactant-enveloped Fe₃O₄ nanoparticles is 42.97 nm, which is substantially smaller than that of the unmodified Fe₃O₄ nanoparticles (486.2 nm). UV–vis and zeta-potential analyses reveal that the ferrofluids does not agglomerate for 120 h at a concentration of 4 g·L-1, which indicates that the ferrofluids are highly stable.     

钆基无机纳米粒子磁共振造影剂设计的研究进展

磁共振成像（MRI）技术是常见的临床医学影像学的检测手段之一.在临床诊断中使用最多的是纵向弛豫（T₁）造影剂：马根维显（Gd-DTPA）.自其正式商用化后,人们对钆基造影剂进行了大量研究.文章介绍了钆基无机纳米粒子（Gd IONPs）造影剂的作用原理,阐述了无机纳米粒子的形貌、尺寸、表面修饰、氧空位等因素的影响,并对Gd IONPs造影剂的设计做了展望.