Aggregation and self-assembly of amphiphilic block copolymers in aqueous dispersions of carbon nanotubes

The self-assembly (SA) of amphiphilic block copolymers (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) was investigated in dispersions of single-walled and multiwalled carbon nanotubes (SWNT and MWNT, respectively) as a function of temperature. Differential scanning calorimetry (DSC) was used for characterization of the thermal behavior of the combined polymers-nanostructures system, and spin-probe electron paramagnetic resonance (EPR) was employed for probing the local dynamic and polarity of the polymer chains in the presence of nanostructures. It was found that SWNT and MWNT modify the temperature, enthalpy, and dynamic behavior of polymer SA. In particular, SWNT were found to increase the cooperativity of aggregating chains and dominate aggregate dynamics. MWNT reduced the cooperativity, while colloidal carbon black additives, studied for comparison, did not show similar effects. The experimental observations are consistent with the suggestion that dimensional matching between the characteristic radius of the solvated polymer chains and the dimensions of additives dominate polymer SA in the hybrid system.     

含聚浓度对轴向动态反冲洗法过滤和反冲洗效能影响*

利用轴向动态反冲洗法处理含聚污水,研究考察了聚合物浓度对滤层阻力损失、油和悬浮物去除效能、反冲洗强度、反冲洗历时、及滤料反洗再生效能的影响规律。结果表明,聚合物浓度可以减少滤层成熟时间,过滤后期滤层阻力增长率大。含聚浓度对过滤效能影响较小,油和悬浮物去除率达到95.67 %和80.87%以上。聚合物浓度对反冲洗过程影响较大,通过提高反冲洗强度和增加反冲洗历时可以消除聚合物浓度对反冲洗过程的影响,反冲洗强度为10.5L/s.m₂和反冲洗历时22.0~25.0min时滤料可以获得较好的反洗再生效果,反冲洗后核桃壳滤料油量为0.21~1.34 mg(油)/g(干核桃壳)。     

Effect of water electrolysis catalysts on carbon corrosion in polymer electrolyte membrane fuel cells

A new approach to preventing electrochemical carbon corrosion in the cathode of polymer electrolyte membrane fuel cells (PEMFCs) was developed. The addition of 2 wt % IrO(2) (0.016 mg cm(-2)) to the catalyst layer of the cathode was demonstrated to reduce the electrochemical corrosion of carbon by 76% at 1.6 V(NHE) and 70 °C compared with a commercial Pt/C catalyst of the same Pt loading of 0.4 mg cm(-2) and under the same test conditions. The IrO(2) was shown to behave as a catalyst for water electrolysis, thereby removing water from the catalyst layer, which promoted electrochemical carbon corrosion.     

聚苯乙烯修饰碳纳米管表面的研究

利用原子转移自由基聚合方法合成了端基具有一个卤素的聚苯乙烯, 并通过叠氮化反应得到端基为叠氮基团的聚苯乙烯. 利用叠氮基与单壁或复壁碳纳米管的反应， 将聚苯乙烯接到碳纳米管的表面上, 实现了碳纳米管的化学修饰. 通过FTIR, XPS, TEM, UV和Raman光谱等技术证明了聚苯乙烯以共价键形式结合到碳纳米管表面上. 利用TGA估算出连接在碳纳米管上的聚苯乙烯的含量, 并推测出复壁碳纳米管中较多的结构缺陷更有利于聚合物的接枝.     

CNT-CdTe versatile donor-acceptor nanohybrids

Single wall carbon nanotubes (SWNT) and multiwall carbon nanotubes (MWNT) were linked to thioglycolic acid (TGA)-capped CdTe nanoparticles (NP) through electrostatic interactions producing photoactive superstructures. The novel nanohybrids were characterized both in the ground and excited states with specific accent on electron-transfer chemistry. In fact, both assays provide kinetic and spectroscopic evidence that support a partial transfer of charge density, with rapid formation of microsecond-lived radical ion pair states. Since nanotubes provide a quick transportation route of charge carriers to the electrode, we took this remarkable finding further and constructed photoelectrochemical cells. Photocurrents were generated through the implementation of CdTe and SWNT or MWNT, which serve as excited-state electron donor components and electron acceptors, respectively.     

Pt-Ru supported on double-walled carbon nanotubes as high-performance anode catalysts for direct methanol fuel cells

Pt-Ru supported on carbon nanotubes (CNTs) (single-walled nanotubes, double-walled nanotubes (DWNTs), and multi-walled nanotubes) catalysts are prepared by an ethylene glycol reduction method. Pt-Ru nanoparticles with a diameter of 2-3 nm and narrow particle size distributions are uniformly deposited onto the CNTs. A simple and fast filtration method followed by a hot-press film transfer is employed to prepare the anode catalyst layer on a Nafion membrane. The Pt-Ru/DWNTs catalyst shows the highest specific activity for methanol oxidation reaction in rotating disk electrode experiments and the highest performance as an anode catalyst in direct methanol fuel cell (DMFC) single cell tests. The DMFC single cell with Pt-Ru/DWNTs (50 wt %, 0.34 mg Pt-Ru/cm(2)) produces a 68% enhancement of power density, and at the same time, an 83% reduction of Pt-Ru electrode loading when compared to Pt-Ru/C (40 wt %, 2.0 mg Pt-Ru/cm(2)).     

Efficient Synthesis of Dimethyl Ether from Methanol in a Bifunctional Zeolite Membrane Reactor

A sandwich FAU–LTA zeolite dual‐layer membrane has been developed and used as a catalytic membrane reactor for the synthesis of dimethyl ether (DME). In the top H‐FAU layer with mild acidity, methanol is dehydrated to DME. The other reaction product, water, is removed in situ through a hydrophilic Na‐LTA layer, which is located between the porous alumina support and the H‐FAU top layer. The combination of mild acidity with the continuous removal of water results in high methanol conversion (90.9 % at 310 °C) and essentially 100 % DME selectivity. Furthermore, owing to the selective and continuous removal of water through the Na‐LTA membrane, catalyst deactivation can be effectively suppressed.     

Bacteria capture, concentration and detection by alternating current dielectrophoresis and self-assembly of dispersed single-wall carbon nanotubes

The high polarizability and dielectrophoretic mobility of single-walled carbon nanotubes (SWNT) are utilized to capture and detect low numbers of bacteria and submicron particles in milliliter-sized samples. Concentrated SWNT solutions are mixed with the sample and a high-frequency (>100 kHz) alternating current (AC) field is applied by a microelectrode array to enhance bulk absorption of the particles (bacteria and nanoparticle substitutes) by the SWNTs via dipole-dipole interaction. The same AC field then drives the SWNT-bacteria aggregates to the microelectrode array by positive-AC dielectrophoresis (DEP), with enhanced and reversed bacteria DEP mobility due to the attached SWNTs. Since the field frequency exceeds the inverse RC time of the electrode double layer, the AC field penetrates deeply into the bulk and across the electrode gap. Consequently, the SWNTs and absorbed bacteria assemble rapidly (<5 min) into conducting linear aggregates between the electrodes. Measured AC impedance spectra by the same trapping electrodes and fields show a detection threshold of 10(4) bacteria/mL with this pathogen trapping and concentration technique.     

Processable hybrids of ferrocene-containing poly(phenylacetylene)s and carbon nanotubes: fabrication and properties

A group of ferrocene-containing poly(phenylacetylene)s (PPAs) with different alkyl spacers were synthesized by using organorhodium complexes [Rh(diene)Cl](2) and Rh (+)(nbd)[C(6)H(5)B (-)(C(6)H(5))(3)] as catalysts. With the aid of pi-pi interactions between the walls of carbon nanotubes (CNTs) and the PPA skeleton together with the ferrocene pendants, the polymer (P 1, P2(5) and P2(10)) chains effectively wrapped round the shells of both single-walled carbon nanotubes (SWNTs) and multiwalled carbon nanotubes (MWNTs). The "additive effect" of the PPA skeleton and the ferrocene pendants in dispersing the SWNTs and MWNTs resulted in the generation of highly soluble hybrids. The solubilities of P 1-functionalized SWNTs and MWNTs in tetrahydrofuran (THF) are up to 633 mg/L and 967 mg/L, respectively. They are much higher than the solubilities of M 1-modified SWNTs and MWNTs, which are only 167 mg/L and 133 mg/L in THF. The results indicate the existence of a powerful polymer effect on dispersing CNTs. The high solubilities of the hybrids in organic solvents allowed us to fabricate high-quality and large-area films. Meanwhile, the desirable loading of ferrocene-containing PPAs onto the CNTs offered polymer/CNTs hybrids with multiple redox centers and ferrocene-featured electrochemical properties. The P 1/MWNT hybrid exhibits evident optical-limiting properties. At high incident laser fluence, the optical-limiting power of P 1/MWNT is higher than that of C(60), a well-known optical limiter. Thermal analyses indicate that the decomposition temperatures ( T(d), the temperature at which a sample loses its 5% weight) for P1 and P1/MWNT are 342 and 346 degrees C, respectively, much higher than that for PPA (225 degrees C). Thus the attachment of a ferrocene pendant to a PPA backbone, followed by hybridization with CNTs, improved the thermal stability. Upon pyrolysis, both the polymer and the polymer/CNTs hybrid gave rise to superparamagnetic ceramics; the saturation magnetizations ( M(s)) of the ceramics derived from P1 and P1/MWNT are 29.9 and 26.9 emu/g, respectively. The latter datum is in the list of the best results reported for the magnetic nanocomposites obtained by the attachment of magnetic nanoparticles onto CNTs.     

Controlled functionalization of multiwalled carbon nanotubes with various molecular-weight poly(L-lactic acid)

Multiwalled carbon nanotubes (MWNT) were functionalized with poly(L-lactic acid) (PLLA) with different molecular weights using a "grafting to" technique. The oxidized MWNT (MWNT-COOH) were converted to the acyl-chloride-functionalized MWNT (MWNT-COCl) by treating them with thionyl chloride (SOCl2) and reacting them with PLLA to prepare the MWNT-g-PLLA. FTIR and Raman spectroscopy revealed that the PLLA was covalently attached to the MWNT, and the weight gain due to the functionalization was determined by thermogravimetric analyses (TGA). The Raman signals of the MWNT were greatly weakened as a result of the PLLA grafting. The morphology of the grafted PLLA was examined by using SEM and TEM. The amount of grafted PLLA depended on the molecular weight of the PLLA. The PLLA coated on the MWNT became thicker and more uniform with increasing PLLA molecular weight from 1000 to 3000. However, the amount of grafted PLLA became lower when the molecular weight of PLLA was further increased to 11,000 and 15,000, and the PLLA attached to the MWNT showed a squid leglike morphology forming blobs and leaving much of the MWNT surface bare.     

Adsorption of CO and O2 on W2C(0001)

CO, O(2), and H(2) adsorption on a clean W(2)C(0001)√13×√13 R ± 13.9° reconstructed surface at room temperature (RT) were investigated using high-resolution electron energy loss spectroscopy (HREELS). The W(2)C(0001) adsorbs CO molecularly and adsorbs O(2) dissociatively, but does not adsorb H(2) at RT. In the CO adsorption system, two C-O stretching (antisymmetric CCO stretching) modes were found at 242.3 meV (1954 cm(-1)) and at 253.0 meV (2041 cm(-1)). The low-frequency site is occupied at first with subsequent conversion to the high-frequency site with increasing coverage. Additionally, a small peak was apparent at 104.5 meV (843 cm(-1)), and a middle peak at 50-51 meV (400-410 cm(-1)), which are assignable to a symmetric stretching mode and a hindered translational mode, respectively, of a CCO (ketenylidene) species. These observations are consistent with the CO adsorption model on top of the surface carbon. For oxygen adsorption, two adsorption states were found at 65.2-68.1 meV (526-549 cm(-1)) and 73.6 meV (594 cm(-1)): typical frequencies to oxygen adsorption on metal surfaces. Results suggest that atomic oxygen adsorption occurred on a threefold hollow site of the second W layer.     

Water as buffer material for gold nanocluster growth

Water molecules adsorbed on SiO2/Si(100) at 140 K to form amorphous solid water (ASW) layers were utilized as a buffer for assisting the growth of gold nanoclusters. It was shown that the average height and diameter of the clusters deposited on the silicon oxide substrate following the buffer annealing/desorption increase as the buffer layer becomes thicker and as more gold is deposited. The clusters' height and diameter were determined by tapping mode AFM and high-resolution SEM imaging, respectively. Typical heights were between 0.5 and 4.5 nm, and the diameters were in the range of 3-9 nm for ASW layer thickness of 7-100 ML and gold deposition in the range of 0.2-1.2 A. The density of the clusters decreased from 65 x 10(10) to 8 x 10(10) cm (-2) in the same buffer layer thickness range. Significantly different morphology of the clusters is obtained when compared to those formed by direct deposition of gold on the silicon oxide surface and to those grown on top of Xe as buffer material.     

基于钼酸盐光度法测定总磷的浊度去除方法

采取新的浊度去除方法,改进了测定总磷的钼酸盐光度法。测定过程中,消解液的浊度会对测定结果产生干扰。通过比较机械过滤法和试剂补偿法的浊度校正效果,建立了中速定性滤纸单次机械过滤的浊度去除方法,确定了最佳去除条件:控制待滤液温度不高于30℃,清洗纯水的体积不少于20 m L。选择消解液具有浊度干扰项的6种代表性水样,分别进行平行测定和加标回收试验,方法检出限为0.008 mg/L,测定结果的相对标准偏差为2.8%~7.9%(n=6),加标回收率为92.0%~106%。该方法灵敏度、准确度高,精密度良好,与现行国标法相比,试剂消耗量少,分析效率高,能够满足多种水环境样品中总磷的测定要求。     

Effect of Bacteria‐Virus Interaction on Mechanism of Virus Removal Using Microfiltration Membranes

In this study, 0.22 μm hydrophobic GVHP membrane was challenged with host bacteria, Escherichia coli (ED 8656) and bacteriophage (λ wild type). For investigation of filtration mechanism, we employed blocking laws, which are based on the profiles of t/v versus time (t) and t/v versus volume (v). For prominent demonstrating the linearity, the profiles were reconstructed. When feed contained bacteriophage or a mixture of bacteriophages and host bacteria, the profiles indicated that at the beginning of the filtration, standard blocking (pore plugging) was the dominant mechanism. Over time the bacteriophages filled the pores and formed a cake layer on the membrane surface. The presence of bacteria facilitated the cake layer build up. Nevertheless the filtration mechanism started with pore blockage and ended with cake formation. The comparison of the present study with another research project carried out by the authors indicates that the removal mechanisms do not rely upon the interactions between microorganisms. However the details of cake layer specifications depend on the nature of the microorganisms and operating conditions.     

Surfactant-free nanofluids containing double- and single-walled carbon nanotubes functionalized by a wet-mechanochemical reaction

Single-walled carbon nanotubes (SWNTs) and double-walled carbon nanotubes (DWNTs) have been functionalized through the wet-mechanochemical reaction method. Results from the infrared spectrum and zeta potential measurements show that the hydroxyl groups have been introduced onto the treated SWNT and DWNT surfaces. Transmission electron microscope observations revealed that the SWNTs and DWNTs were cut short after being milled. SWNTs and DWNTs with optimized aspect ratio can be obtained by adjusting the ball milling parameters. Thermal conductivity enhancement of water-based nanofluids containing treated carbon nanotubes (CNTs) shows augmentation with the increase of temperature mainly due to the effects of an ordering liquid layer forming around the chemical surfaces of CNTs. Moreover, the thicker interfacial layer of water molecules on the surfaces of CNTs with smaller diameter, such as SWNTs, is in favor of greater thermal conductivity enhancement compared with the thinner one on the surfaces of DWNTs or MWNTs with larger diameter.     

Bacteria and bacteriophage inactivation by silver and zinc oxide nanoparticles

Microbial contaminants such as bacteria and viruses are of great concern in water. As nanotechnology continues to grow, understanding the interactions of nanoparticles with bacteria and viruses is important to protect public health and the environment. In this study, the effect of two commonly used nanoparticles, silver nanoparticles (AgNPs, average particle size=21 nm) and zinc oxide nanoparticles (ZnO NPs, average particle size=39 nm), on the growth of bacteria (Eschericia coli) and bacteriophages (MS2) were evaluated using a standard double agar layer (DAL) method and a turbidimetric microtiter assay. A 1-h prior exposure of MS2 to nanoparticles did not inactivate MS2 at the highest nanoparticle concentrations tested (5mg/L total Ag and 20 mg/L ZnO). No bacteriophage inactivation was observed in the presence of AgNPs, Ag(+)/AgNPs (50:50 in mass ratio) or Ag(+) ions, all at the total Ag concentration of 5mg/L. In a binary (bacteria-phages) system where the E. coli host was exposed to MS2 and nanoparticles simultaneously, the dynamic changes of active bacteria and MS2 phages during incubation demonstrated that exposure of AgNPs (5mg/L Ag) and ZnO NPs (20mg/L ZnO) increased the number of phages by 2-6 orders of magnitude. These results suggested that exposure of nanoparticles could greatly facilitate bacterial viruses like MS2 to infect the E. coli host.     

单层碳纳米管的化学修饰

单层碳纳米管 (SWNT)是 Iijima博士 [1]于 1 993年首次发现的 .它具有非常独特的物理和化学性质 ,因而成为近年来研究的热点问题 .随着单层碳纳米管的合成技术和纯化研究的不断完善 [2～ 5] ,关于它的研究方向开始转向化学反应和应用研究 .由于单层碳纳米管不溶于水或有机溶剂而限制了对其化学性质的研究 .单层碳纳米管的端头是由碳的五元环和六元环组成的半球形 .氧化作用可将该端头打开并转化为羧基 ,从而与其它的化学试剂发生反应 .Liu Jie等 [6] 用浓硫酸和浓硝酸的混合物氧化单层碳纳米管 ,将之裁剪成 1 50～ 80 0 nm的“短管”.在…     

Determination of trace phosphate ion in water by visual method after preconcentration on a membrane filter for field work

A sensitive visual method based on comparing the color intensity of precipitate as phosphomolybdenum blue on a membrane filter, has been developed for the determination of trace phosphate ion in water for field work. A sample solution containing 0.05-5.0 mug of phosphate was treated in a 25-ml polypropylene syringe, and the resulting precipitate was filtered through a membrane filter attached to the syringe. The color intensity of the precipitate on the membrane filter was measured visually following the standard series method. The coefficient of variation for five measurements at 0.5 mug of phosphate is 11%. The detection limit is 0.02 mug of phosphate ion in 22.5 ml (0.9 mug PO(3-)(4)/l) of water sample when the effective filtration area is 0.78 cm(2). The interference of various ions was studied and optimum conditions were developed for the determination of phosphate ion in natural water.     

两种固定化金属螯合复合亲和膜色谱介质制备

以纤维素滤纸为基质,通过碱处理、环氧活化、偶联亚氨基二乙酸二钠、固定化Ｃｕ＾２＋后制得了大孔纤维素亲和膜。另外,在活化后的膜上通过共价交联覆盖上琼脂糖,制得了具有类似“三明治”结构且性能优于的复合亲和膜,装柱后分别制得固定化金属螯合亲和膜色谱柱。对两种亲和膜进行牛血清白蛋白等温吸附测定显示,两者的最大吸附量分别为１．１７ｍｇ／ｃｍ＾２和１．３０ｍｇ／ｃｍ＾２,与传统的琼脂糖凝胶类介质吸附量相当,表     

Different methods of preparing electrode from single-wall carbon nanotubes and their effect on the Li ion insertion process

Single-wall carbon nanotube (SWNT) is processed in three different ways: (1) coating a film out of a slurry of SWNT with poly (vinilydene difluoride) (PVDF) binder on to a Cu substrate, (2) evaporating SWNT dispersion in methanol on to a Cu substrate, and (3) transferring a film on to a Cu substrate from the water–ethanol interface, to prepare the working electrode for studying the Li ion insertion process. The use of binder enhances irreversible capacity restricting the Coulomb efficiency to only 18% in the initial cycle. The electrode prepared by deposition of SWNT powder from a dispersion of methanol on the Cu substrate gives the best reversible capacity of 445 mA h g⁻¹ and Coulomb efficiency of 25% in the initial cycle. Use of the PVDF binder favors the formation of thicker solid electrolyte interface, which counts the large irreversible capacity.