Oscillatory mass transport in vapor-liquid-solid growth of sapphire nanowires

In vapor-liquid-solid (VLS) growth, the liquid phase plays a pivotal role in mediating mass transport from the vapor source to the growth front of a nanowire. Such transport often takes place through the liquid phase. However, we observed by in situ transmission electron microscopy a different behavior for self-catalytic VLS growth of sapphire nanowires. The growth occurs in a layer-by-layer fashion and is accomplished by interfacial diffusion of oxygen through the ordered liquid aluminum atoms. Oscillatory growth and dissolution reactions at the top rim of the nanowires occur and supply the oxygen required to grow a new (0006) sapphire layer. A periodic modulation of the VLS triple-junction configuration accompanies these oscillatory reactions.     

Experimental realization of the covalent solid carbon nitride

Pulsed laser ablation of graphite targets combined with an intense, atomic nitrogen source has been used to prepare C-N thin film materials. The average nitrogen content in the films was systematically varied by controlling atomic nitrogen flux. Rutherford backscattering measurements show that up to 40 percent nitrogen can be incorporated on average into these solids under the present reaction conditions. Photoelectron spectroscopy further indicates that carbon and nitrogen form an unpolarized covalent bond in these C-N materials. Qualitative tests indicate that the C-N solids are thermally robust and hard. In addition, strong electron diffraction is observed from crystallites within the films. Notably, analysis of these diffraction data show that the only viable structure for the C-N crystallites is that of beta-C(3)N(4), a material predicted theoretically to exhibit superhardness. The experimental synthesis of this new C-N material offers exciting prospects for both basic research and engineering applications.     

苯甲酸钠微波催化合成乙酰水杨酸的研究

[目的]利用微波辐射法制备乙酰水杨酸。[方法]以水杨酸和乙酸酐为原料,以苯甲酸钠作为催化剂,微波辐射合成乙酰水杨酸。采用正交试验优化微波辐射苯甲酸钠催化合成乙酰水杨酸的工艺条件,并探讨合成工艺的影响因素。[结果]乙酰水杨酸的最佳合成工艺为:6.3 g水杨酸,9 ml乙酸酐,催化剂苯甲酸钠用量0.4 g,微波功率240 W,辐射时间90 s。在此优化条件下,乙酰水杨酸产率达67.07%。[结论]与传统合成工艺相比,微波辐射合成乙酰水杨酸反应时间短,产品收率高。     

Laser ablation and the production of polymer films

The formation of high-quality thin films of polytetrafluoroethylene (PTFE) is important in many applications ranging from material reinforcement to molecular electronics. Laser ablation, a technique widely used to deposit a variety of inorganic materials, can also be used as a simple and highly versatile method for forming thin polymer films. The data presented show that PTFE films can be produced on various supports by the evaporation of a solid PTFE target with a pulsed ultraviolet laser. The composition of the ablation plume suggests that PTFE ablation and subsequent film formation occur by way of a laser-induced pyrolitic decomposition with subsequent repolymerization. The polymer films produced by this method are composed of amorphous and highly crystalline regions, the latter being predominantly in a chain-folded configuration with the molecular axis aligned parallel to the substrate surface.     

Germanium nanowire growth below the eutectic temperature

Nanowires are conventionally assumed to grow via the vapor-liquid-solid process, in which material from the vapor is incorporated into the growing nanowire via a liquid catalyst, commonly a low-melting point eutectic alloy. However, nanowires have been observed to grow below the eutectic temperature, and the state of the catalyst remains controversial. Using in situ microscopy, we showed that, for the classic Ge/Au system, nanowire growth can occur below the eutectic temperature with either liquid or solid catalysts at the same temperature. We found, unexpectedly, that the catalyst state depends on the growth pressure and thermal history. We suggest that these phenomena may be due to kinetic enrichment of the eutectic alloy composition and expect these results to be relevant for other nanowire systems.     

Fe3 O4／TiO2复合物的制备

[目的]以钛铁矿为原料,制备包覆性Fe_3O_4/TiO_2磁性光催化剂。[方法]研究不同温度、反应时间、钛铁矿颗粒大小、是否冷凝回流等条件下钛铁矿的溶解情况以及TiO_2、Fe_3O_4/TiO_2的产率和催化效果,并采用X射线粉末衍射仪(XRD)、红外光谱(FT-IR)、扫描电镜(SEM)、透射电镜(TEM)等对催化剂产物进行表征,且验证催化剂的磁性能。[结果]该方法可以制备出磁性良好、包覆效果好、较纯净的Fe_3O_4/TiO_2包覆性光催化材料。[结论]制备出的Fe_3O_4/TiO_2复合物保持了Fe_3O_4的磁性,是一种性能优良的包覆性光催化材料。     

化学催化制备鱼油三甘酯

[目的]用化学催化方法制备鱼油三甘酯。[方法]采用酯交换反应,以鱼油乙酯和醋酸三甘酯为原料,制备三甘酯型鱼油,同时研究催化剂种类及用量(基于醋酸三甘酯的质量)、反应温度、物料比(油乙酯和醋酸三甘酯的摩尔比)、反应时间对鱼油三甘酯制备的影响,并通过液相色谱对鱼油三甘酯产物的成分进行定量分析。[结果]制备鱼油三甘酯的最佳条件为:催化剂为甲醇钠,用量为三甘酯质量的3.0%,反应温度为100℃,物料比为鱼油乙酯过量5%(相对于醋酸三甘酯),反应时间为2 h。在此最佳条件下制备产物三甘酯含量大于80%。[结论]通过此方法可实现鱼油乙酯向鱼油三甘酯的转化,成本较低,扩大了鱼油类产品在医药和保健品中的应用。     

Virus-based toolkit for the directed synthesis of magnetic and semiconducting nanowires

We report a virus-based scaffold for the synthesis of single-crystal ZnS, CdS, and freestanding chemically ordered CoPt and FePt nanowires, with the means of modifying substrate specificity through standard biological methods. Peptides (selected through an evolutionary screening process) that exhibit control of composition, size, and phase during nanoparticle nucleation have been expressed on the highly ordered filamentous capsid of the M13 bacteriophage. The incorporation of specific, nucleating peptides into the generic scaffold of the M13 coat structure provides a viable template for the directed synthesis of semiconducting and magnetic materials. Removal of the viral template by means of annealing promoted oriented aggregation-based crystal growth, forming individual crystalline nanowires. The unique ability to interchange substrate-specific peptides into the linear self-assembled filamentous construct of the M13 virus introduces a material tunability that has not been seen in previous synthetic routes. Therefore, this system provides a genetic toolkit for growing and organizing nanowires from semiconducting and magnetic materials.     

Dislocation-driven nanowire growth and Eshelby twist

Hierarchical nanostructures of lead sulfide nanowires resembling pine trees were synthesized by chemical vapor deposition. Structural characterization revealed a screwlike dislocation in the nanowire trunks with helically rotating epitaxial branch nanowires. It is suggested that the screw component of an axial dislocation provides the self-perpetuating steps to enable one-dimensional crystal growth, in contrast to mechanisms that require metal catalysts. The rotating trunks and branches are the consequence of the Eshelby twist of screw dislocations with a dislocation Burgers vector along the 110 directions having an estimated magnitude of 6 +/- 2 angstroms for the screw component. The results confirm the Eshelby theory of dislocations, and the proposed nanowire growth mechanism could be general to many materials.     

分子筛改性催化乳酸丁酯制备农药中间体丙烯酸酯的合成研究

[目的]在改性分子筛的作用下,研究了以乳酸丁酯为原料催化制备农药中间体丙烯酸酯的工艺。[方法]考察了K、Ca、La等金属离子改性的NaX、NaY、ZSM-6、ZSM-8等沸石分子筛对乳酸丁酯脱水制备丙烯酸酯的影响。[结果]K/ZSM-6改性分子筛对该脱水过程具有较高的选择性和转化率。最佳反应温度为380℃,空速为3h-1,甲醇与乳酸丁酯的摩尔比为2.0,转化率达到100%,丙烯酸及其酯的总选择性达到了64.3%。     

相转移催化法制备高取代度羧甲基壳聚糖

[目的]探讨制备水溶性羧甲基壳聚糖(CMC)的方法,确定制备CMC的反应条件。[方法]以醇水溶液为反应介质,采用相转移催化法制备了水溶性CMC,考察了催化剂种类、催化剂用量、反应温度、反应时间和溶剂中水醇比对CMC取代度的影响,探讨了工艺条件对CMC取代度的影响规律。[结果]在醇水反应介质中,采用相转移催化法在碱性条件下用氯乙酸对壳聚糖进行化学改性,合成了水溶性的高取代度的CMC。该方法降低了有机溶剂异丙醇的使用量,提高了CMC的取代度。制备CMC的较好反应条件为:以6%的十六烷基三甲基氯化铵作催化剂,反应温度60℃,反应时间4.0 h,溶剂中水醇比1∶4(V/V)。在此条件下,CMC的取代度为1.53。[结论]该研究为制备不同取代度的CMC提供参考。     

CrCl3催化果糖制备5-羟甲基糠醛的研究

以CrCl3.6H2O为催化剂,考察溶剂种类、反应温度、反应时间、催化剂用量等条件对果糖制备5-羟甲基糠醛(HMF)产率的影响。结果表明,二甲基亚砜(DMSO)是果糖制备HMF的优良溶剂;以DMSO为溶剂,当反应温度为180℃、反应时间140 min、CrCl3.6H2O催化剂用量为果糖质量5%时,果糖制备HMF的产率可达49.2%。     

CrCl3催化果糖制备5-羟甲基糠醛的研究

以CrCl3·6H2O为催化剂,考察溶剂种类、反应温度、反应时间、催化剂用量等条件对果糖制备5-羟甲基糠醛（HMF）产率的影响。结果表明,二甲基亚砜（DMSO）是果糖制备HMF的优良溶剂;以DMSO为溶剂,当反应温度为180℃、反应时间140min、CrCl3·6H2O催化剂用量为果糖质量5％时,果糖制备HMF的产率可达49．2％。     

非均相UV/Fenton光催化降解土霉异味研究

[目的]探索非均相UV/Fenton光催化降解土霉异味的效果。[方法]利用离子交换方法将Fe2+负载在NaY分子筛载体上,制得催化剂FeY。在不同紫外波长照射下,利用Fenton反应降解2种土霉异味物质2-甲基异莰醇(MIB)和土腥素(Geosmin),优化pH和H2O2等降解条件,并将MIB和Geosmin添加到东湖本底湖水中进行降解。[结果]FeY的负载量为352.8 mg/g,Fe2+脱附率为5.7%。在FeY为28 mg/L,pH 6.5,H2O220 mg/L和反应60min的试验条件下,非均相UVB/Fenton体系对MIB和Geosmin的降解率分别为80.2%和84.9%。在UVA、UVB和UVC紫外光(波长分别为365、312和256 nm)条件下Photo-Fenton体系对MIB和Geosmin的降解率,随着紫外波长的降低而增大,且Geosmin降解速率常数高于MIB。湖泊水样中加入MIB和Geosmin降解表明,降解效率明显低于纯水样品。[结论]该研究制得的催化剂应用于非均相光催化体系,不仅可循环使用,而且还可扩大反应体系的pH应用范围。     

工业级茶油制备生物柴油及其结构表征

[目的]研究工业级茶油制备生物柴油的适宜条件。[方法]以茶油精炼副产物提取的工业级油脂为原料,采用碱催化酯交换法制备生物柴油,研究了工艺条件对工业级茶油转化率的影响。[结果]选择酸度不大于1、酸值小于2的工业级茶油,在甲醇用量为原料油重量的20%,KOH用量为原料油重量的0.8%的条件下,于60℃反应1.5 h,茶油转化率可达94.33%。利用红外光谱和气相色谱-质谱联用对生物柴油的结构进行了分析和表征,其主要成分为棕榈酸甲酯、亚油酸甲酯、油酸甲酯。[结论]该研究确定了工业级茶油制备生物柴油的适宜条件。     

Room-temperature ultraviolet nanowire nanolasers

Room-temperature ultraviolet lasing in semiconductor nanowire arrays has been demonstrated. The self-organized, <0001> oriented zinc oxide nanowires grown on sapphire substrates were synthesized with a simple vapor transport and condensation process. These wide band-gap semiconductor nanowires form natural laser cavities with diameters varying from 20 to 150 nanometers and lengths up to 10 micrometers. Under optical excitation, surface-emitting lasing action was observed at 385 nanometers, with an emission linewidth less than 0.3 nanometer. The chemical flexibility and the one-dimensionality of the nanowires make them ideal miniaturized laser light sources. These short-wavelength nanolasers could have myriad applications, including optical computing, information storage, and microanalysis.     

Assembling materials with DNA as the guide

DNA's remarkable molecular recognition properties and structural features make it one of the most promising templates to pattern materials with nanoscale precision. The emerging field of DNA nanotechnology strips this molecule from any preconceived biological role and exploits its simple code to generate addressable nanostructures in one, two, and three dimensions. These structures have been used to precisely position proteins, nanoparticles, transition metals, and other functional components into deliberately designed patterns. They can also act as templates for the growth of nanowires, aid in the structural determination of proteins, and provide new platforms for genomics applications. The field of DNA nanotechnology is growing in a number of directions, carrying with it the promise to substantially affect materials science and biology.     

杨木木粉在酸性氯化胆碱/丙三醇中的快速液化研究

将可再生的木质纤维生物质进行液化转化制备高分子化合物可减少化石资源的消耗。以氯化胆碱/丙三醇低共熔溶剂为液化试剂,硫酸为催化剂,研究不同的反应条件包括液化温度、液化时间、催化剂浓度、液固比等对杨木木粉液化率的影响,并借助傅里叶变换红外（FTIR）、凝胶渗透色谱（GPC）和气相色谱-质谱（GC-MS）对水溶性、丙酮溶和丙酮不溶（液化残渣）3个组分液化产物进行分析。结果表明,反应条件为240℃、15 min、硫酸质量浓度8%、液固比10∶1时,木材液化率达到最大值78.13%。在液化剂氯化胆碱/丙三醇作用下,木质素和半纤维素可以快速发生液化,水溶性液化产物组分主要包括醛、酮、酸、酯以及芳香衍生物等,丙酮溶组分液化产物主要为木质素降解产物,液化残渣主要为不溶的纤维素。研究表明氯化胆碱/丙三醇是一种高效的木材液化试剂,且液化组分主要为木质素和半纤维素。     

柚子皮制备多孔碳材料处理聚氯乙烯微塑料废水实验研究

柚子皮是福建漳州常见的农业废弃物,作为垃圾处理对环境造成一定压力,急需开展资源化利用。本论文以柚子皮为原料,碱活化和高温碳化制备多孔碳材料,并将其应用于聚氯乙烯微塑料的处理。实验结果表明,制备的多孔碳材料对聚氯乙烯微塑料具有较好的吸附处理效果。聚氯乙烯微塑料去除率随着吸附时间和多孔碳材料投加量的增加而逐渐增大。多孔柚子皮碳材料适宜在弱酸或弱碱性条件下处理聚氯乙烯微塑料废水。这为柚子皮资源化利用提供了新方向和技术。     

强酸性阳离子交换树脂催化制备乳酸乙酯研究

[目的]研究强酸性阳离子交换树脂NKC-9催化制备乳酸乙酯。[方法]以乙醇、乳酸为原料,以强酸性阳离子交换树脂为催化剂,间歇催化合成乳酸乙酯;通过正交试验,考察了反应温度、催化剂用量、酸醇摩尔比对合成乳酸乙酯的影响;并通过重复试验考察了该催化剂的活性。[结果]在不分离产物情况下,制备乳酸乙酯的优化条件为：反应温度为85℃,酸醇摩尔比为0.5∶1,催化剂用量（以乳酸加入质量计）为5%,反应时间为1h,乳酸的转化率达42.48%。[结论]该研究为乳酸乙酯的生产工艺研究提供了理论依据。