过氧化苯甲酰对多壁碳纳米管衍生化的研究

近年来,利用化学修饰制备可溶性的碳纳米管进行了很多研究,使得碳纳米管（CNTs）的衍生化成为一个热点。本文通过在苯溶剂中加热回流的方法实现了碳纳米管和过氧化苯甲酰氧自由基的加成反应。一方面通过红外光谱证明了过氧化苯甲酰氧自由基和多壁碳纳米管之间的类烯加成反应,另一方面通过热重分析研究了反应产物与反应时间和反应物比例之间关系,说明了过氧化苯甲酰对碳纳米管衍生化的影响。     

碳纳米管负载纳米Fe2O3的研究

本文研究了用液相化学沉积法制备的碳纳米管负载Fe₂O₃。首先用浓HCl、浓HNO₃和浓HNO₃ / H₂SO₄(混酸)三种酸对碳纳米管进行改性处理，对样品进行了TEM形貌观察和FTIR光谱分析，FTIR分析表明浓HCl处理后不能在碳纳米管表面引入官能团，而浓HNO₃能在碳纳米管表面引入-OH和-C=O，浓HNOO₃ / H₂SO₄能在碳纳米管表面引入大量的-OH、-C=O、COOH。制备了以上三种碳纳米管分别负载Fe₂O₃。TEM分析表明，负载效果：混酸>浓HNO₃>浓HCl。经混酸处理后的碳纳米管所负载的Fe₂O₃的XRD分析，表明所负载的是α-Fe₂O₃。机理分析表明碳纳米管上的含氧基团能增强其在水溶液中的分散性，同时能增强其对Fe³⁺吸附和离子交换能力，使吸附在碳纳米管表面的Fe³⁺成为结晶成核中心，调节溶液pH值后，使Fe₂O₃沉积在碳纳米管表面。     

磷化钴/多壁碳纳米管的制备及电催化性能研究

不断增加的能源需求和环境污染危机推动了替代高效能源转换和储存技术的广泛研究。电催化分解水具有潜在的应用前景,其可以利用电能获得清洁无污染的氢能。鉴于此,本论文通过不同浓度KOH浸泡超声的多壁碳纳米管(MWNT_S)作为基底,CoCl₂溶液为反应液,运用水热与固体磷化法得到负载有CoP的多壁碳纳米管材料。通过X-射线粉末衍射仪(XRD)、冷场发射扫描电子显微镜(SEM)、比表面及孔隙度分析(BET)对复合材料的晶型、形貌和比表面积进行了分析;通过电化学工作站对其相关电学性能进行了测试。实验结果表明在浓度为1 mol·L^-1 KOH浸泡的碳纳米管吸附的CoP含量最高(CoP-MWNTS-1.0),且电催化性能最佳,其在10 mA·cm²的电流密度下过电势为196 mV,Tafel斜率为231.07 mV/dec。     

改性多壁碳纳米管/聚乳酸复合材料的研究

制备了改性多壁碳纳米管/聚乳酸复合材料,研究了改性多壁碳纳米管对聚乳酸的增强作用.通过拉曼光谱分析、热重分析证实了多壁碳纳米管酸化酯化反应的发生.通过溶液法制备了聚乳酸/改性多壁碳纳米管复合物.考察了聚乳酸和改性多壁碳纳米管复合体系的相容性.扫描电镜分析结果说明了聚乳酸和改性多壁碳纳米管复合物相容性的变化.随着改性多壁碳纳米管在复合物中含量的增加,体系的分散效果也越好,相容性也有提高.实验结果表明,在聚乳酸材料中添加改性碳纳米管材料到一定值对,可以提高材料的力学性能,且当改性碳纳米管添加量达到1.5％的时候材料力学性能达到了一个最大值,拉伸强度可达120.4MPa.     

CVD法制备碳纳米管的TG-DTA研究--温度对CVD法制备碳纳米管的影响

基于碳纳米管粗产品中无定形碳和不同直径碳纳米管对氧的反应活性的差异,通过差热-热重(TG-DTA)方法,结合透射电镜(TEM)和X射线衍射(XRD)的测试结果,研究了合成温度对以乙炔气体为碳源,用CVD法制备碳纳米管的石墨化程度、碳纳米管直径以及直径分布的影响.结果表明:反应中,由于催化剂Co/SiO2中活性组分(Co)微晶随合成温度的升高而增大,导致所制备的碳纳米管的直径增大,从20～30 nm(650℃)增加到30～50nm(750℃).碳纳米管的石墨化程度随着反应温度的升高而增加.XRD实验结果还表明,当合成温度从650℃增加到850℃时,2θ值从25.8°增加到26.8°,(002)晶面的层间距从3.45 A减小到3.32 A,即随着合成温度的升高,碳纳米管(002)晶面的层间距减小.通过DTA放热峰的峰温和半峰宽的分析得出,无定形碳的放热峰峰温Tp＜380℃,其含量随着温度的升高而减小.碳纳米管的DTA放热峰的峰温Tp随着碳纳米管的直径和石墨化的程度的增加而升高,半峰宽随着碳纳米管的直径的分布范围增大而增宽.低温(650℃)有利于生成直径小且均匀的多层碳纳米管(20～30nm),而高温(大于750℃)则有利于生成直径大的多层碳纳米管(大于30～50 nm).     

BaCO3单晶纳米线的制备和表征

本文以有机钛偶合体胶束作模板剂，采用溶剂热技术，成功制备了单晶碳酸钡纳米线，并通过X-射线衍射(XRD)、能量损失谱(EDX)、透射电子显微镜(TEM)、高分辨电子显微镜(HRTEM)、选区电子衍射(SAED)对纳米线进行了表征。碳酸钡纳米线呈均匀的直线形，直径为25～60nm，长度达到十几微米。并对BaCO₃纳米线的形成机理进行了浅析。     

纳米CaCO3负载过渡金属CVD法制备多壁碳纳米管的研究

以纳米碳酸钙粉体为载体,用浸渍法制备了可用于化学气相沉积(CVD)法制备碳纳米管的高产率催化剂.应用FESEM,HRTEM,TEM,XRD和激光拉曼谱对产物进行了表征.结果表明,由于纳米碳酸钙具有较大的比表面积,可高密度地承载催化剂活性组分.在碳纳米管生长初期,处于缓慢分解状态的纳米碳酸钙才能有效地起到载体作用,且反应温度为700～750℃时,碳纳米管的产率较高.Fe-Co双金属催化剂在700℃,催化生长60min后,可增重10倍,而且产物中无定形碳含量极少.纳米碳酸钙载体易于提纯,用质量分数为30%的硝酸超声提纯粗产品1h,可使纯度提高到97%,且不破坏碳纳米管结构.     

碳纳米管负载的Fe2O3催化剂制备

Carbon nanotubes were modified by FeSO₄-H₂O₂ system, iron hydroxides were adsorbed on the wall of carbon nanotubes simultaneously. These precursors were treated at 723K for 2 h under hydrogen, nitrogen and air atmosphere to prepare carbon nanotubes supported γ-Fe₂O₃catalyst, γ-Fe₂O₃and α-Fe₂O₃compound catalyst and amorphous Fe₂O₃catalyst, respectively. This is green method to prepare high Fe₂O₃loading (≥50 %) catalyst without adding other cation. The different structures Fe₂O₃catalysts can be synthesized by controlling the condition of thermal treatment to content active phase requirements for different catalytic reactions. The paper presents a new method to prepare carbon nanotubes supported catalysts.     

多壁碳纳米管的纯化研究

采用正交实验法考察了硝酸浓度、加热温度和加热时间对多壁碳纳米管（MWCNs)粗产物纯化效果的影响;利用透射电镜（TEM）、X-射线粉末衍射（XRD）和磁化率测量对纯化产物进行表征;得到纯化实验的优化条件为：加热温度60℃,加热时间4h,硝酸浓度2mol/L。在优化条件下,纯化收率可以达到90%以上,绝大部分过渡金属可被除去。     

多壁碳纳米管/聚丙烯酸/MOF-5的制备及其N2吸附性能

用化学修饰法制备出复合物多壁碳纳米管/聚丙烯酸(MWCNTs/PAA),用溶剂热法合成Zn₄O(1,4-benzenedicarboxylate)₃(MOF-5)和MWCNTs/PAA/MOF-5。通过XRD、FTIR、TG、HRTEM和比表面积和孔隙度分析仪对MWCNTs,MOF-5,MWCNTs/PAA和MWCNTs/PAA/MOF-5的结构和性质进行表征。结果表明:复合材料MWCNTs/PAA中PAA包覆在碳纳米管外壁上,含量为4.3%,在FTIR中有PAA特征官能团的吸收峰;MWCNTs/PAA/MOF-5和MOF-5的形貌一样,MWCNTs/PAA/MOF-5的热分解温度比MOF-5的提高了49℃;MOF-5和MWCNTs/PAA/MOF-5的N₂吸附曲线为Ⅰ型,77K和100kPa条件下,N₂的吸附量达到最大值,分别为265、299.03 cm³·g^-1。     

C纳米管包裹的金属钴纳米线(管)同心电缆的制备与表征

The concentric cable of cobalt nanowires(nanotubes) encapsulated in carbon nanotubes has been prepared by using “second-order template” method, combined with electrodeposition. The products were characterized by SEM, TEM, XRD and Raman, respectively. The C/Co composite nanowires(nanotubes) were about 60μm in length, and the thickness can be adjusted by changing the reaction conditions. This method could be extended to construct an array of multi-layer nanotubes, composed of various metals, encapsulated in carbon nanotubes.     

Electrochemical Characterization of the Interaction of Multiwalled Carbon Nanotubes with Doxorubicin

It has been suggested that multiwalled carbon nanotubes (MWCNTs) interacting with pharmaceutics may be introduced into the body as nanocarriers. To deliver the anticancer drugs, covalent or noncovalent functionalization of MWCNTs is required. In this study, the influence of oxidation on MWCNTs in the interaction with chemotherapeutic drug, doxorubicin, was characterized. The binding of doxorubicin with MWCNTs decreased rapidly with the increasing oxidation period with sulfuric acid. However, with nitric acid, the interaction increased initially and slowly decreased with time. The best results were obtained for sulfuric and nitric acid following 1 and 3?h of oxidation, respectively. The results show that sulfuric acid provided more favorable interaction for MWCNTs with doxorubicin than nitric acid.     

化学气相沉积合成碳包裹镍纳米晶的初步研究

Nickel nanocrystals encapsulated in carbon shells were prepared by the large body knowledge developed for the growth of carbon nanotubes (CNTs), i.e. chemical vapor deposition. The products were characterized by transmission electron microscopy, XRD and FTIR. The results showed that the oxidization of CNT surface made it possible to interreact with nickel ions in solution. Ni-impregnated CNTs transformed into monocrystalline nickel nanoparticles supported on CNTs at 600 ℃ in nitrogen atmosphere. Subsequently, they would be covered with graphene layers during reaction with acetylene at 600 ℃. The formation mechanism has been preliminarily discussed on experimental results.     

催化辅助爆炸法合成碳纳米管

报道了以三硝基苯酚(苦味酸,C₆H₃N₃O₇)、乙酸钴[Co(Ac)₂]和菲(C₁₄H₁₀)作为爆炸物,通过热引发方式使其在不锈钢耐高压容器中发生爆炸反应来制备多壁碳纳米管.利用TEM,HRTEM和XRD等手段对碳纳米管和催化剂的形貌和结构进行表征,综合TEM和TG测试结果确定产物中碳纳米管的含量.结果表明,随着反应条件的变化,可获得外径分布在20～40nm范围内,管长为数十微米的多壁碳纳米管.金属钴催化剂在爆炸过程中原位生成.苦味酸装填密度的增大有利于碳纳米管含量的提高,优化条件(苦味酸的装填密度为0.2g/cm³)后碳纳米管的含量可达70%左右.     

Polypeptide Modification of Multiwalled Carbon Nanotubes by a Graft‐From Approach

Summary: Covalent surface functionalization of carbon nanotubes with polypeptides is promising for possible medical applications. This work presents a graft‐from approach to perform the polypeptide modification of multiwalled carbon nanotubes (MWNTs). The raw MWNTs are first amine‐functionalized. The amine‐functionalized MWNTs are then used as the initiator to initiate the ring‐opening polymerization of γ‐benzyl‐L ‐glutamate N‐carboxyanhydride (BLG‐NCA), to result in the polypeptide‐grafted MWNTs. FT‐IR, XPS, and TGA data demonstrate that the functionalization is successful. The TEM images of the products show that the thickness of the polypeptide shell of the PBLG‐MWNT is about 4.5–22 nm. Using the facile route developed here, carbon nanotubes functionalized with other types of polypeptides can be easily fabricated using the corresponding NCAs.

Strategy for the polypeptide modification of multiwalled carbon nanotubes by a graft‐from approach.     

Insight into the Structural Variation and Sodium Storage Behavior of Polyoxometalates Encapsulated within Single-Walled Carbon Nanotubes

The host–guest interaction can remarkably alter the physiochemical properties of composite materials. It is crucial to clarify the mechanism by revealing the influence of the host on the electronic structure of the guest molecules. Herein, we study the structural variation of polyoxometalates (POMs) after being confined in single-walled carbon nanotubes (SWNT). What we found is that in addition to the reported charge transfer from SWNT to POM, an intramolecular electron transfer within a single POM cluster can be observed in the POM@SWNT composites. Moreover, the charge density on the bridged oxygen of POMs is prominently enhanced. The structural change and electron reconfiguration of POMs upon encapsulation in SWNT significantly speed up electron and ion transport, leading to the improved electrochemical performance for sodium ions storage.     

The Heterogeneity of Multiwalled and Single‐Walled Carbon Nanotubes: Iron Oxide Impurities Can Catalyze the Electrochemical Oxidation of Glucose

It is well established that the heterogeneity of carbon nanotubes must be determined before the origin of the electrochemical performance can be attributed. Recently it has been diligently reported that for the case of multiwalled carbon nanotube modified electrodes, copper oxide impurities are responsible for the electrochemical activity facilitating a nonenzymatic sensing strategy towards glucose. We have explored both commercially available multiwalled and single‐walled carbon nanotubes for the sensing of glucose and find that iron oxide impurities remaining from the fabrication process are the electroactive sites facilitating the nonenzymatic detection of glucose. Given that the multiwalled carbon nanotubes in this work are purchased from the same leading supplier as that used recently, discrepancies in the fabrication process exist which clearly has implications in the commercialization of electrochemical sensors based on multiwalled carbon nanotubes.