以天然椰壳为碳源制备硼碳氮微米线

首次以天然椰壳为碳源,高温下在流动氨气中用氯化铁(FeCl3)对无定型硼粉和椰壳进行退火,大规模合成了硼碳氮(BCN)微纳米结构,即由纳米片包覆竹节状纳米管组装而成的微米线.利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光(FTIR)、X射线光电子能谱仪(XPS)以及荧光光谱仪(PL)等手段对所得微米线进行了表征.结果显示,微米线的直径约为200～600 nm,纳米片的平均厚度小于20 nm.纳米片大多是以弯曲和皱折的形态分离的.微米线由B、C、N元素组成,计算出B、C、N的原子比为11.4:1:9.2.提出了汽液固(VLS)和汽固(VS)相结合的生长机理并对B11.4 CN9.2微米线的形成进行了研究.初步讨论了反应温度对微米线的影响.     

硫化铋纳米管的制备及性能研究

以NaBiS2为前驱物采用水热法合成了硫化铋纳米管,运用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)、紫外-可见-近红外分光光度计(UV-Vis-NIR)、荧光分光光度计(PL)等检测手段对样品进行表征.结果表明制备的Bi2S3为正交相纳米晶,产物形貌受到反应物比例、温度、时间等因素影响,Bi2S3纳米管的形成是固体-溶液-固体转化过程.紫外-可见-近红外吸收光谱表明Bi2S3纳米管对900nm以下的光有较强的吸收,当激发波长为519 nm时,Bi2S3纳米管在778 nm处有一个较强的荧光发射峰.     

金属纳米线填充氮硼碳纳米管电子结构与光学性质的研究

基于第一性原理、密度泛函理论,通过CASTEP模块对填充金,银,铜纳米线的氮硼碳纳米管进行计算,研究其电子结构及光学性质.发现填充不同金属,稳定性由高到低分别为铜填充氮硼纳米管,银填充氮硼纳米管,金填充氮硼纳米管;体系能带图中带隙为零,即金属填充的氮硼纳米管使得本征(8,0)碳纳米管由半导体性转变为金属性;态密度分布中,价带处态密度主要由金属元素的d轨道和氮硼纳米管的s,p轨道贡献,导带处的态密度主要为氮硼纳米管的p轨道贡献;通过差分电荷密度图得知,填充金属的氮硼纳米管中共价键,离子键,金属键共存,光学性能中吸收系数峰值均增大,反射系数均出现红移.     

SnO2负载TiO2纳米管的制备与光催化活性

结合阳极氧化法和脉冲沉积法合成SnO2/TiO2纳米管光催化剂,实现了SnO2纳米颗粒在TiO2纳米管表面的均匀负载.利用场发射扫描电子显微镜(FE-SEM)、能谱仪(EDS)、X射线衍射仪(XRD)以及紫外-可见漫反射光谱(UV-Vis DRS)对样品进行表征,以甲基橙为模拟污染物,评价了纳米管的光催化活性.结果表明,SnO2/TiO2纳米管经750℃煅烧后主晶相为锐钛矿相TiO2,含少量金红石相TiO2和SnO2,三者两两之间形成三元异质结,促进光生电子-空穴对的分离,此时SnO2/TiO2纳米管表现出最佳的光催化活性,紫外光下对甲基橙1 h分解比例由32.4;提升至96.5;.     

碳掺杂(9,0)型闭口硼氮纳米管场发射第一性原理研究

本文运用第一性原理研究了(9,0)型闭口硼氮纳米管及其两种C掺杂体系的场发射性能.对三种纳米管体系的态密度、局域态密度、赝能隙、最高占据分子轨道/最低未占据分子轨道能隙和Mulliken电荷的分析结果表明,C替代顶层六元环中硼与氮原子的场发射性能分别最优和最差.由此可见,C掺杂改善硼氮纳米管场发射性能的关键在于被置换原子的种类.     

超声辅助法控制合成三方相硒纳米管

通过将水热反应制备的非晶态硒(a-Se)球形纳米粒子分散在无水乙醇中进行超声,成功地合成了三方相硒(t-Se)纳米管.分别用扫描电子显微镜(SEM)和X射线粉末衍射仪(XRD)对样品的形貌和晶体结构进行了表征.SEM观察发现纳米管外径约为150～300 nm,管壁厚约30～60 nm,管长几微米.XRD分析证明纳米管是三方相硒.进一步研究了超声时间对样品形貌的影响,并分析了t-Se纳米管的生长机制.     

硼碳氮纳米管的溶剂热法制备及其表征

以无水CH3CN*BCl3和Li3N为原料,以苯为溶剂,在温度为330℃,压力为8～9MPa条件下,利用溶剂热合成方法成功地制备出了BCN三元化合物.X射线粉末衍射(XRD)分析表明,产物为类石墨态结构,透射电子显微镜(TEM)观测到产物中含有B-C-N纳米管.X射线能谱(XPS)和Fourier变换红外光谱(FTIR)分析表明硼碳氮是以原子级化合的形式存在.     

SiW12、CsPbI3协同提高TiO2纳米管光电转换效率的研究

为克服TiO₂纳米管在光电转换时电子-空穴复合率高和吸收光谱范围窄的缺陷,利用多酸H₄SiW₁₂O₄₀(SiW₁₂)和CsPbI₃量子点对其协同修饰,采用电沉积法将SiW₁₂沉积在TiO₂纳米管上,制备了SiW₁₂/TiO₂纳米管复合薄膜;使用高温热注射法合成出CsPbI₃量子点,再通过化学浴沉积法沉积CsPbI₃量子点到复合薄膜上,得到SiW₁₂/CsPbI₃/TiO₂纳米管复合薄膜,探究SiW₁₂沉积时间、CsPbI₃沉积次数对TiO₂纳米管光电性能的影响。利用扫描电子显微镜(SEM)、能谱仪(EDS)、透射电子显微镜(TEM)、X射线衍射(XRD)仪、红外分光光度计(FT-IR)、紫外-可见分光光度计(UV-Vis)对薄膜进行表征,使用电化学工作站测试薄膜的光电化学性能。结果表明:TiO₂纳米管沉积多酸SiW₁₂和CsPbI₃量子点后,光吸收范围扩大、电荷转移电阻降低,光电转换效率得到显著提升,最高达到0.52%。说明SiW₁₂和CsPbI₃的协同作用很好地抑制了TiO₂纳米管电子-空穴的复合,并拓宽了吸收光谱范围,提高了TiO₂纳米管的光电转换效率。     

电解液温度对二氧化钛纳米管阵列结构及光电性能的影响

以氟化铵(NH4F)、乙二醇溶液为电解液,在不同的电解液温度(0～50℃)条件下,采用电化学阳极氧化法制备二氧化钛(TiO2)纳米管阵列.采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、紫外-可见分光光度计(UV-Vis)对TiO2纳米管阵列的形貌、结构和光学性能进行表征.结果表明,电解液温度高于20℃均能制备出纳米管阵列.光照下电解液温度40℃时制备的TiO2纳米管阵列具有最高光电流密度(Iph)0.2408 mA/cm2.以活性艳红X-3B为目标降解物,在室温、紫外光照射条件下考察了电解液温度对光催化活性的影响,结果显示电解液温度40℃时制备的TiO2纳米管阵列具有最高的光催化活性.     

熔盐辅助碳热还原氮化法制备氮化钽晶须

本文以五氧化二钽、活性炭为主要原料,氟化钾为熔盐介质,通过碳热还原氮化法在氨气气氛下成功制备了氮化钽(Ta5N6)晶须.运用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)对合成产物的组成、结构和形貌进行了表征.研究了升温方式、氮化气氛、氮化时间和催化剂含量对产物形成的影响.当Ni与Ta2O5的摩尔比为0.1、氮化气氛为氨气(流量为300 mL/min)、氮化时间为6h时制备的晶须形貌最佳,晶须直径80～250 nm,长为1～5μm,晶须的生长机制为气-液-固(VLS)和气-固(VS)两种机理的混合机制.     

A facile route to prepare boron nitride hollow particles at 450 °C

Hexagonal boron nitride (h-BN) particles including hollow spheres (with a proportion of ~30–40%) and nanotubes (10%) have been synthesized by using sodium fluoroborate and sodium azide at 450 °C for 20 h. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) studies show that the as-obtained BN hollow particles are crystalline. The total specific surface area of the product calculated from Brunauer–Emmentt–Teller (BET) absorption measurement is 89.79 m²/g, indicating that it may be utilized as a promising candidate for hydrogen storage container or catalyst. Thermal gravimetric analysis (TGA) result reveals its excellent thermal stability below 800 °C. Its possible growth mechanism and the effects of reaction parameters were also briefly discussed.     

Fenton试剂对碳纳米管表面改性研究

利用Fenton试剂对碳纳米管进行表面改性,研究了Fenton, Fenton/超声波(US)以及Fenton/紫外线(UV)对碳纳米管表面的影响,并探讨了Fenton试剂与碳纳米管的作用机理.用热重分析(TGA)来观察纯化前后碳纳米管的纯度,用红外光谱(FTIR)分析碳纳米管表面官能团的变化,用透射电镜(TEM)对碳纳米管微观结构进行分析.结果表明:Fenton/UV反应能够在碳纳米管表面引入大量羟基以及少量的羧基,且不会较大程度地损坏碳纳米管的结构;机理分析表明, Fenton试剂主要是利用Fenton反应产生的羟基自由基(HO·)对碳纳米管的不饱和键进行羟基化加成.     

Preparation of amorphous carbon nanotubes using attapulgite as template and furfuryl alcohol as carbon source

Amorphous carbon nanotubes were synthesized by vapor deposition polymerization (VDP) method using attapulgite as template and furfuryl alcohol as carbon source. The morphology and microstructure analysis of the as-prepared samples showed that highly pure amorphous carbon nanotubes were obtained, and determined by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SEAD) and energy dispersive X-ray (EDX) spectrum. The Brunauer–Emmett–Teller (BET) surface area analysis indicated that the specific surface area of the as-prepared amorphous carbon nanotubes reaches up to 503.1 m²/g. A hypothesis about the formation mechanism of the amorphous carbon nanotubes was also proposed accordingly.     

Synthesis of highly ordered hBN in presence of group I/IIA carbonates by solid state reaction

This comprehensive study declares experimentally the effects of IA/IIA metal carbonates on the formation of hexagonal boron nitride (hBN) with the aid of the available experimental methods as regards Fourier transform infrared spectroscopy (FT‐IR), powder X‐ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (TEM). hBN is synthesized in the existence of the metal carbonates at the low temperature by modified O'Connor method. The experimental findings of FT‐IR and XRD investigations show that the addition of metal carbonates affects considerably the crystallization of hBN powder during the synthesis process. The presence of the high concentration level of the additions improves harshly the crystallinity. In this respect, the graphitization index deduced from the XRD patterns reduces with the enhancement in the amount of the dopant content. At the same time, the differentiation between the products is analyzed by the SEM surveys. According to the results, the materials synthesized by the Li₂CO₃ powder exhibit both the tubular form and rod‐like while the other samples prepared by the CaCO₃ chemical dopant display the homogeneous plates. Even, the TEM images confirm the nanowires and nanotubes structures such as multi‐walled cylindrical, bamboo nanotubes in all the materials studied in this work.     

碳纳米管负载氧化铋的制备及催化二硝酰胺铵热分解的研究

采用微波辐射法制备了沉积于碳纳米管(CNTs)表面的氧化铋(Bi2O3)纳米粒子(Bi2O3/CNTs),用扫描电子显微镜(SEM)、光电子能谱(XPS)和X射线衍射(XRD)对制备的Bi2O3/CNTs纳米粒子进行了表征。研究了Bi2O3/CNTs纳米粒子对二硝酰胺铵(ADN)的催化热分解。结果表明,纳米Bi2O3均匀沉积在CNTs表面,平均粒径为8nm;添加3%Bi2O3/CNTs纳米粒子的ADN的初始热分解温度降低了12.8℃,热分解终止温度降低了29.3℃;NH4N(NO2)2→NH4NO3 N2O为ADN初始热分解的主导反应。     

对Fe-Ni-B催化剂合成的金刚石中含硼包裹物的研究

本文以自制的Fe基含硼合金作催化剂,石墨片作碳源,压力和温度分别为5.3GPa和1570K条件下,在六面顶压机上合成了0.6mm左右的含硼金刚石晶体.利用X射线衍射仪(XRD)分析了金刚石晶体的结构,证明金刚石是六方结构的.在光学显微镜下观察了金刚石的晶形,利用透射电子显微镜(TEM)和能谱仪(EDS)对金刚石晶体进行了微观分析,发现了多种含硼包裹物,包括(Fe,Ni)23(C,B)6,(Fe,Ni)3(C,B),(Fe,Ni)B,(Fe,Ni)2B,Ni3B,B4C等.研究了它们的化学组成与微观结构,并分析了含硼包裹物的来源与形成过程.结合金刚石的生长过程分析认为,合金触媒是金刚石中包裹物元素的主要来源,通过调整触媒的成份和含量可以控制金刚石内杂质元素的种类.硼元素在金刚石中既可以以化合物的形式存在,也可以替代碳原子存在于金刚石内.     

ZnO-SiO2的制备及其光催化降解罗丹明B

采用溶胶-凝胶法制备负载型ZnO-SiO2光催化材料,研究升温速率及负载量对ZnO结构、形貌及光催化活性的影响.通过X射线衍射、N2物理吸附-脱附、扫描电子显微镜、光致发光光谱和紫外-可见漫反射光谱等手段对催化剂进行表征,并以罗丹明B为模拟污染物,紫外光为光源,评价催化剂活性.结果表明,升温速率对ZnO-SiO2光催化剂结晶度和光催化活性影响显著.当ZnO与SiO2的质量比为1∶1时,ZnO-SiO2具有均匀、平滑的球形形貌,并且ZnO光催化活性明显改善.     

Different copper oxide nanostructures: Synthesis,characterization, and application for C‐N cross‐coupling catalysis

Cupric oxide and cuprous oxide micro‐/nanomaterials with well‐controlled sizes and morphologies have been synthesized via different crystal growth techniques. Structural and morphological characterizations of these copper oxide micro‐/nanomaterials were performed by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). After that, these copper oxide micro‐/nanomaterials were used as catalysts for a typical C‐N cross‐coupling reaction directly. The catalytic results showed that different copper oxide micro‐/nanomaterials had different catalytic activities in C‐N cross‐coupling reaction. The particle size of cupric oxide and the oxidation state of copper played vital roles in the catalytic process. Cupric oxide with small particle size has the best catalytic activity, while cupric oxide with different morphologies has almost the same yields and cuprous oxide has very poor yields. Further, the possible catalytic mechanism for copper oxide nanomaterials catalyzed cross‐coupling reaction was proposed. And the influence of particle size and oxidation state was carefully discussed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

均相沉淀法制备γ-La2S3粉体及球形形貌控制研究

以La2O3和尿素为原料,丙三醇为分散剂,采用均相沉淀方法制备镧盐前驱体,并通过H2S硫化得到γ-La2S3粉体。采用X射线衍射仪和扫描电子显微镜对镧盐前驱体和γ-La2S3粉末的结构和形貌进行表征。结果表明,当加热温度为95℃,尿素和La2O3的物质的量比为15∶1,V(丙三醇)/V(水)=1∶1,反应时间为3 h时,可制备出高纯、分散性好、球形γ-La2S3纳米粉体。     

Effect of Boron Doping in Bi-based 2223 Superconductors

Samples with the stoichiometric composition Bi_2−xPb_xSr₂Ca₂Cu_3−yB_yO_z (x = 0.3, y = 0.2, 0.25, 0.3, 0.4) ceramics were prepared by a solid state reaction method. The samples were annealed at 850 °C for 100 hours (treatment A), and the other at 850 °C for 200 hours (treatment B). From the X-ray diffraction data of a ceramic sample it is revealed that all the samples were mixed phases of 2212 and 2223. The variation of the lattice parameters with the dopant level are represented. From the D.C. four-probe electrical resistivity data it was found that for the samples subjected to treatment B the T_c(0) values were higher than those with treatment A. The A.C. susceptibility data were collected by change in the inductance method. The effect of boron doping on the phase formation and T_c(0) is presented and the volume fraction of the phases estimated from the X-ray data. The presence of boron in the samples was confirmed by the inductive coupled plasma method. The microstructure of the samples was studied by scanning electron microscopy.