In-situ heating study on the structural change of surfactant-templated germanium oxide mesostructure

Mesostructured germanium oxide has been well-synthesized by using a surfactant-templated approach under basic hydrothermal conditions. The cationic surfactant cetyltrimethylammonium bromide (CTAB) has formed nanotubes with uniform diameter of about 3.2 nm. Blanket-like morphology of the as-prepared sample has been observed with transmission electron microscopy (TEM). High-resolution TEM image reveals that the nanotubes are connected with inorganic germanium oxide and have self-assembled into periodic mesostructure. In-situ heating X-ray diffraction (XRD) patterns confirm that the germanium oxide is in amorphous phase in the temperature range from room temperature (RT) to 700 degrees C. In-situ heating small-angle X-ray scattering (SAXS) presents the mesostructural change with temperature. The local atomic structures around germanium atom have been obtained with in-situ heating X-ray adsorption fine structure (XAFS) techniques. The stability of this mesostructure has been determined to be correlated with the cationic surfactant CTAB. The structural evolution from the GeO 2/NaOH aqueous solution, the as-prepared sample to the sample heated at 700 degrees C, has been described, and the formation mechanism of mesostructured germanium oxide has been discussed.     

原子层沉积制备掺氮碳膜修饰的 Pt/CNTs 实现甲醇高效电催化氧化

甲醇燃料电池作为一种清洁、高效的能源转化形式广受关注. 贵金属 Pt 是甲醇燃料电池阳极催化剂不可缺少的活性组分, 但 Pt 价格昂贵, 易与 CO 等中间体强相互作用而中毒失活, 从而限制了甲醇燃料电池的广泛应用. 因此, 如何提高Pt 的利用率成为一个关键问题. 研究表明, 在碳材料载体中掺杂氮元素, 改变了载体本身的表面结构和电子性质, 有利于Pt 颗粒的成核和生长, 可获得尺寸小、分布均匀的 Pt 纳米颗粒, 能显著提升催化反应活性和 Pt 利用率. 然而, 传统的氮掺杂方法需要在高温、高压及氨气条件下进行, 增加了催化剂制备难度和成本.原子层沉积技术是逐层超薄沉积技术, 能够在原子级别精确控制膜的厚度, 既可制备尺度均一、高度可控的纳米粒子,也能实现材料表面的可控超薄修饰. 本课题组利用原子层沉积技术优势, 首先在碳纳米管表面沉积了直径 2 nm 左右的 Pt纳米颗粒, 然后在 Pt 纳米颗粒外表面超薄修饰聚酰亚胺膜, 通过后处理得到多孔掺氮碳膜修饰的 Pt/CNTs 催化剂. 碳膜的厚度可简单通过调控聚酰亚胺膜的沉积厚度来控制. 结果表明, 适当厚度的碳膜修饰 Pt/CNTs 催化剂可显著提升其甲醇电氧化性能, 电流密度可达商业 20% Pt/C 的 2.7 倍, 催化剂稳定性也显著改善. 然而碳膜修饰过厚会导致催化剂活性降低.通过计算催化剂电化学活性表面积发现, 超薄修饰碳膜后催化剂活性表面积有所降低, 这是由于碳膜的覆盖导致表面 Pt原子数减少. 修饰前后催化剂颗粒尺度变化不大, 推测催化剂活性的提高与形成了有利于催化反应的 Pt-碳膜界面有关.然而, 当碳膜修饰层过厚时, 会导致反应物分子难以扩散到 Pt 颗粒表面, 使催化剂活性降低. 预吸附单层 CO 溶出实验结果表明, 多孔掺氮碳膜超薄修饰 Pt/CNTs 催化剂后, CO 氧化峰的起始电位和峰值电位都向低电位处偏移, 这表明 Pt 表面吸附的 CO 在较低电位下即可被氧化, CO 更容易从 Pt 表面移除, 从而提高了催化剂的抗 CO 毒化能力. X 射线光电子能谱实验结果进一步表明, 经多孔掺氮碳膜修饰后, Pt 的 4f 电子向高结合能处偏移, 表明 Pt 原子周围的电子密度减小, 从而弱化了 Pt 对 CO 吸附的σ-π键反馈作用, 即减弱了 Pt 原子对 CO 的吸附, 这是导致掺氮碳膜修饰后催化剂活性及稳定性都大幅提高的原因.     

Carbonization of electrospun poly(acrylonitrile) nanofibers containing multiwalled carbon nanotubes observed by transmission electron microscope with in situ heating

Composite nanofibers with 5% w/w multiwalled carbon nanotubes (MWCNTs) in polyacrylonitrile (PAN) were fabricated using the electrospinning technique. Morphological development during the carbonization process was characterized by transmission electron microscopy (TEM) with in situ heating. It was found that the orientation of graphitic layers increases with temperature and does not change significantly with time during our TEM measurement, except the 750 °C. In the heating stage at 750 °C noticeable enhancement of orientation with time was observed. The presence of embedded CNTs enhances the order of the formed graphitic structures even when the CNTs are irregular or entangled. The results indicate that embedded MWCNTs in the PAN nanofibers nucleate the growth of carbon crystals during PAN carbonization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

原位缩聚制备聚氨酯/碳纳米管复合泡沫材料

采用球磨方法制备了均匀分散的碳纳米管(CNTs)/聚丙二醇分散体系,解决了碳纳米管在高黏滞聚醚醇中的分散问题,进一步以水为发泡剂,采用两步的原位缩聚法制备了碳纳米管均匀分散的聚氨酯(PU)/碳纳米管复合泡沫材料.通过FTIR、SEM、压缩实验、亲水性实验等表征了材料的结构和性能.结果表明碳纳米管的加入使聚氨酯材料的压缩强度和保水率得到显著提高.     

Effect of nanosized carbon black on thermal stability and flame retardancy of polypropylene/carbon nanotubes nanocomposites

Nanosized carbon black (CB) was introduced into polypropylene/carbon nanotubes (PP/CNTs) nanocomposites to investigate the effect of multi‐component nanofillers on the thermal stability and flammability properties of PP. The obtained ternary nanocomposites displayed dramatically improved thermal stability compared with neat PP and PP/CNTs nanocomposites. Moreover, the flame retardancy of resultant nanocomposites was greatly improved with a significant reduction in peak heat release rate and increase of limited oxygen index value, and it was strongly dependent on the content of CB. This enhanced effect was attributed mainly to the formation of good carbon protective layers by CB and CNTs during combustion. Rheological properties further confirmed that CB played an important role on promoting the formation of crosslink network on the base of PP/CNTs system, which were also responsible for the improved thermal stability and flame retardancy of PP. Copyright © 2013 John Wiley & Sons, Ltd.     

新型聚乙烯醇缩甲醛基凝胶聚合物电解质的热稳定性简

采用原位热聚合法制备了聚乙烯醇缩甲醛(PVFM)基凝胶聚合物电解质,通过差示扫描量热法(DSC)研究了PVFM基凝胶聚合物电解质的热稳定性,并利用热重-红外/质谱(TGA-FTIR/MS)联用技术比较研究了液态电解质和PVFM基凝胶聚合物电解质升温过程中逸出气体的成分及变化. 结果表明,相比于液态电解质,凝胶聚合物电解质中PVFM热聚合产生的三维网络结构可以有效抑制有机溶剂的挥发,降低体系中HF的含量,从而改善电解质体系的热稳定性,提高其应用于锂离子电池的安全性能.     

Pt 纳米颗粒在聚二甲基二烯丙基氯化铵功能化碳纳米管上的自发沉积及其对甲醇的电氧化性能

利用聚二甲基二烯丙基氯化铵(PDDA)非共价修饰的碳纳米管(CNTs)与PtCl₆^2-之间的自发氧化还原作用, 制备了Pt 纳米颗粒(Pt NPs)/CNTs-PDDA复合催化剂. PDDA在该催化剂中具有三种作用: (1) 作为金属前驱体PtCl₆^2-还原为Pt NPs 的还原剂; (2) 作为原位产生的Pt NPs 的稳定剂; (3) 在CNTs 表面形成保护膜抑制CNTs 在甲醇电催化氧化过程中的腐蚀. 采用傅里叶变换红外(FTIR)光谱、热重分析和拉曼光谱对CNTs-PDDA进行了表征, 表明PDDA通过π-π作用已成功覆盖在CNTs 表面, 并且修饰过程没有导致CNTs 结构的破坏. 采用透射电子显微镜(TEM)对Pt NPs/CNTs-PDDA 催化剂进行了表征, 结果表明, Pt NPs 均匀地分散在CNTs上, 平均粒径约2 nm, 且粒径分布范围窄. 用循环伏安法、计时电流法进一步考察了Pt NPs/CNTs-PDDA催化剂在酸性介质中对甲醇的电催化氧化的性能. 电化学测试结果表明, 与原始CNTs 负载的Pt NPs催化剂相比,Pt NPs/CNTs-PDDA催化剂具有更高的电化学活性表面积、电催化质量比活性和稳定性.     

Iron-doped carbon aerogels: novel porous substrates for direct growth of carbon nanotubes

We present the synthesis and characterization of Fe-doped carbon aerogels (CAs) and demonstrate the ability to grow carbon nanotubes directly on monoliths of these materials to afford novel carbon aerogel-carbon nanotube composites. Preparation of the Fe-doped CAs begins with the sol-gel polymerization of the potassium salt of 2,4-dihydroxybenzoic acid with formaldehyde, affording K+-doped gels that can then be converted to Fe2+- or Fe3+-doped gels through an ion exchange process, dried with supercritical CO2, and subsequently carbonized under an inert atmosphere. Analysis of the Fe-doped CAs by TEM, XRD, and XPS revealed that the doped iron species are reduced during carbonization to form metallic iron and iron carbide nanoparticles. The sizes and chemical composition of the reduced Fe species were related to pyrolysis temperature as well as the type of iron salt used in the ion exchange process. Raman spectroscopy and XRD analysis further reveal that, despite the presence of the Fe species, the CA framework is not significantly graphitized during pyrolysis. The Fe-doped CAs were subsequently placed in a thermal CVD reactor and exposed to a mixture of CH4 (1000 sccm), H2 (500 sccm), and C2H4 (20 sccm) at temperatures ranging from 600 to 800 degrees C for 10 min, resulting in direct growth of carbon nanotubes on the aerogel monoliths. Carbon nanotubes grown by this method appear to be multiwalled (approximately 25 nm in diameter and up to 4 microm long) and grow through a tip-growth mechanism that pushes catalytic iron particles out of the aerogel framework. The highest yield of CNTs was grown on Fe-doped CAs pyrolyzed at 800 degrees C treated at CVD temperatures of 700 degrees C.     

Pt/C和Pt/CNTs电极的电化学稳定性研究

采用恒电位氧化法研究了Pt/C和Pt/CNTs电极的电化学稳定性. 相同条件下, Pt/C电极的氧化电流大约为Pt/CNTs电极的2倍; 120 h氧化后, Pt/C电极Pt的电化学表面积下降了21.3%, 而Pt/CNTs电极仅下降了7.6%, 表明Pt/CNTs电极性能衰减较慢. X射线光电子能谱(XPS)分析表明, Pt/C的载体碳黑表面氧增加量大于Pt/CNTs中碳纳米管(CNTs)表面氧的增加量, 说明碳黑的被氧化程度较高, 电化学稳定性差; Pt的表面化学状态没有发生变化; 碳纳米管本身的抗电化学氧化性也大于碳黑. 所以, 载体的被氧化程度不同是两种电极性能衰减不同的主要原因之一, 并且排除了Pt表面状态的影响.     

In-situ preparation and the characterization of Pt/SnO2

To enhance the cycling stability of Pt-based catalysts,the anti-corrosion property of support and the attachment of Pt with support should both get improved.For this purpose,a novel method is presented for in situ preparing Pt/SnO₂.The structure of Pt/ SnO₂ is characterized by X-ray diffraction（XRD） and transmission electron microscopy（TEM）,confirming the homogeneous deposition of Pt on SnO₂.The high resolution TEM（HRTEM） shows the large interfaces between Pt and SnO₂.The TEM photos recorded after accelerated durability tests with Pt/SnO₂ show that the agglomeration and size increment of Pt particles is not severe, indicating the good stability of Pt/SnO₂.The electrochemical active surface area（EAS） of Pt/SnO₂ keeps increasing during the 1000 cycles of cyclic voltammetric（CV） sweeping in H₂SO₄,while the EAS decayed by 35%when mixing Pt/SnO₂ with carbon nanotubes（CNTs）,indicating the superior anti-corrosion property of SnO₂ in contrast to CNTs.     

Thermodynamics of Chitinase Partitioning in Soy Lecithin Liposomes and Their Storage Stability

The goal of this study was to define the partitioning behavior of chitinase from Trichoderma spp. in soy lecithin liposomes, using a thermodynamic approach based on the partitioning variation with temperature. An effort has been made to define the liposomes, as well as free and immobilized enzyme stability during storage at 4 and 25 °C. The partition coefficients (K (o/w)) were greater than 1; therefore, the standard free energies of the enzyme transfer were negative, indicating an affinity of the enzymes for encapsulation in liposomes. The enthalpy calculation led to the conclusion that the process is exothermic. The presence of enzyme decreased the liposome storage stability from 70 days to an approximately 20 days at 25 °C and 30 days at 4 °C. Monitoring of the liposome's diameter demonstrated that their size and concentration decreased during storage. The liposome's diameters ranged from 1.06 to 3.30 μm. The higher percentage of liposome corresponded to a diameter range from 1.06 to 1.34 μm. This percentage increased during storage. There were no evidences for liposome fusion process. The stability of immobilized enzyme was increased in comparison with free chitinase.     

Development of novel synthetic method of carbon nanotubes from electrospun polystyrene fibers by using microwave heating

We have developed a novel synthetic method that enables us to easily synthesize metal‐capsulated carbon nanotubes (CNTs) in a laboratory by using a combined technology of electrospinning‐metallization and microwave heating. These techniques greatly shorten the time for the synthesis of the CNTs in comparison with the conventional methods. TEM analysis confirmed a successful formation of the CNTs, and the resulting CNTs were multi‐walled and found to be about 25–100 nm in diameters. The products prepared by heating at 600 and 900°C exhibited less‐developed and strongly curved CNTs, whereas the products prepared by heating at 700 and 800°C relatively well‐developed long CNTs. Copyright © 2010 John Wiley & Sons, Ltd.     

Electronic structure and field emission of multiwalled carbon nanotubes depending on growth temperature

The electronic structure of multiwalled carbon nanotubes (CNTs) has been investigated, depending on the growth temperature, using synchrotron X-ray photoelectron spectroscopy (XPS) and field emission measurements. The vertically aligned CNTs are grown via pyrolysis of ferrocene and acetylene in a broad temperature range 600-1000 degrees C. The CNTs have a cylindrical structure with a uniform diameter of 20 nm. As growth temperature increases, due to an improved crystallinity of the graphitic sheets, the width of the XPS C 1s peak becomes narrower and the intensity of the valence band increases. Field emission from the as-grown CNTs exhibits a large enhancement of current density with growth temperature, strongly correlated with the electronic structure revealed by XPS.     

Influence of MWCNT morphology on dispersion and thermal properties of polyethylene nanocomposites

In this study a series of multi-walled carbon nanotube (MWCNT)/Polyethylene (PE) composites with different kinds and several concentrations of carbon nanotubes (CNTs) were investigated. The morphology and degree of dispersion of the fillers in the polymer matrix at different length scales was investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Both individual and agglomerated MWCNTs were evident but a good dispersion was observed for some of them. TGA measurements were performed on nanocomposites in order to understand if CNTs affect the stabilization mechanism during thermal and oxidative degradation. The analysis demonstrates that MWCNTs presence slightly delays thermal volatilisation (15-20 °C) without modification of thermal degradation mechanism. In contrast, thermal oxidative degradation in air is delayed up to about 100 °C dependently from MWCNTs concentration, in the range used here (0.1-2.0 wt%), and degree of dispersion. The stabilization is due to the formation of a thin protective layer of entangled MWCNTs kept together by carbon char generated on the surface of the nanocomposites as shown by SEM images taken on degradation residues.     

The noble effect of aging on the thermal conductivity of modified CNTs-ethylene glycol nanofluids

In order to improve the heat transfer process by using nanofluids, different nanoparticles and base fluids have been studied. In this work, stability and effect of aging and temperature on the thermal conductivity of CNTs-ethylene glycol (EG) nanofluids were investigated. Chemical functionalisation was used to oxidise the surface of CNTs. The functionalised CNTs were used to prepare the nanofluids by a two-step method. The stability of nanofluids was measured by UV-vis spectroscopy and the results showed that the nanofluids had a good stability over several days. Immediately after nanofluid preparation not too much increase was observed for thermal conductivity but the nanofluid aging had a great influence on the improvement of the thermal conductivity, as after 65 days, about 50% increase was observed. The increase has been attributed to forming an ordered nanolayer of EG molecules around the CNTs. Also no significant temperature dependence of thermal conductivity was observed up to 50°C possibly due to the lack of temperature dependence of CNTs Brownian motions.     

NiSe2 nanoparticles encapsulated in CNTs covered and N-doped TiN/carbon nanofibers as a binder-free anode for advanced sodium-ion batteries

Metal selenides are promising anodes for sodium-ion batteries (SIBs) due to the high theoretical capacity through conversion reaction mechanism. However, developing metal selenides with superior electrochemical sodium-ion storage performance is still a great challenge. In this work, a novel composite material of free-standing NiSe₂ nanoparticles encapsulated in N-doped TiN/carbon composite nanofibers with carbon nanotubes (CNTs) in-situ grown on the surface (NiSe₂@N-TCF/CNTs) is prepared by electrospinning and pyrolysis technique. In this composite materials, NiSe₂ nanoparticles on the surface of carbon nanofibers were encapsulated into CNTs, thus avoiding aggregation. The in-situ grown CNTs not only improve the conductivity but also act as a buffer to accommodate the volume expansion. TiN inside the nanofibers further enhances the conductivity and structural stability of carbon-based nanofibers. When directly used as anode for SIBs, the NiSe₂@N-TCF/CNT electrode delivered a reversible capacity of 392.1 mAh/g after 1000 cycles and still maintained 334.4 mAh/g even at a high rate of 2 A/g. The excellent sodium-ion storage performance can be attributed to the fast Na⁺ diffusion and transfer rate and the pseudocapacitance dominated charge storage mechanism, as is evidenced by kinetic analysis. The work provides a novel approach to the fabrication of high-performance anode materials for other batteries.     

Degradation of Fatty Acid Phase-Change Materials (PCM): New Approach for Its Characterization

The use of adequate thermal energy storage (TES) systems is an efficient way to achieve thermal comfort in buildings reducing the cooling and heating demand. Besides, deploy phase change materials (PCM) to meet and enhance the TES needs is highly effective and widely studied. In this paper, a study of the degradation of two fatty acids is presented, capric and myristic acids, in order to evaluate whether their thermo-physical properties are affected throughout time during service. This was carried out by means of two different types of thermal treatments: degradation at constant temperature (thermal stability test), 60 °C during 100 h and 500 h, and degradation with heating and cooling cycling (thermal cycling stability), between a temperature range from 15 °C to 70 °C with 0.5 °C/min ramp during 500 and 1000 cycles. Despite no significant changes were measured for myristic acid, experimental results revealed a decrease of melting enthalpy of 6.6% in capric acid thermally treated for 500 h. Evidences of chemical degradation were found that might explain the decrease in thermophysical properties during use.     

Thermal stability of carbon nanotubes

Heat capacities of the carbon nanotubes (CNTs) with different sizes have been measured by modulated temperature differential scanning calorimetry (MDSC) and reported for the first time. The results indicated the values of C _p increased with shortening length of CNTs when the diameters of CNTs were between 60 and 100 nm. However, the values of C _p of CNTs were not affected by their diameter when the lengths of CNTs were 1–2 um, or not affected by the length of CNTs when their diameters were below 10 nm. The thermal stabilities of the CNTs have been studied by TG-DTG-DSC. The results of TG-DTG showed that thermal stabilities of CNTs were enhanced with their diameters increase. With lengths increase, the thermal stabilities of CNTs increased when their diameters were between 60 and 100 nm, but there is a slight decrease when their diameters were less than 60 nm. The further DSC analyses showed both released heat and T _onset increased with the increase of CNTs diameters, which confirms the consistency of the results from both TG-DTG and DSC on CNTs thermal stability.     

Growth of Aligned Carbon Nanotubes on Large Scale by Methane Decomposition with Deactivation Inhibitor

The effects of additives containing iron or nickel during chemical vapor deposition(CVD)on the growth of carbon nanotubes(CNTs)by methane decomposition on Mo/MgO catalyst were investigated. Ferrocene and nickel nitrate were introduced as deactivation inhibitors by in-situ evaporation during CVD. The precisely controlled in-situ introduction of these inhibitors increased the surface renewal of catalyst, and therefore prevented the catalyst from deactivation.Using this method,aligned multi-walled CNTs with parallel mesopores can be produced on a large scale.     

How a Zigzag Carbon Nanotube Grows

Owing to the unique structure of zigzag (ZZ) carbon nanotubes (CNTs), their ring‐by‐ring growth behavior is different from that of chiral or armchair (AC) CNTs, on the rims of which kinks serve as active sites for carbon attachment. Through first‐principle calculations, we found that, because of the high energy barrier of initiating a new carbon ring at the rim of a ZZ CNT, the growth rate of a ZZ CNT is proportional to its diameter and significantly (10–1000 times) slower than that of other CNTs. This study successfully explained the broad experimental observation of the lacking of ZZ CNTs in CNT samples and completed the theory of CNT growth.