溶剂热合成碳纳米管

自1991年Iijima发现碳纳米管以来,碳纳米管因其独特的结构和物理化学性质而成为人们的研究热点。     

溶剂热还原法制备蛋壳状碳材料

Eggshell-like carbon materials with high yields have been synthesized by a solvothermal route in a stainless steel autoclave using metallic zinc and absolute ethanol as starting materials. The products were characterized by X-ray powder diffractometry (XRD)， energy-dispersive X-ray spectroscopy (EDX)， Raman spectroscopy and scanning electron microscopy (SEM). The eggshell-like carbon spheres had diameters ranging from 500 nm to 1 μm. The optimal reaction conditions to obtain eggshell-like carbon materials were 600 ℃ and 12 h.     

溶剂热法制备MWNTs/CdS复合材料

分别以醋酸镉和硫脲为原料,二乙三胺和去离子水为混合溶剂,采用溶剂热技术制备了MwNTs/CdS复合材料,并用TEM、XRD、FT-IR及UV-vis等技术对材料的结构、形貌和性质进行表征.研究结果表明:硫化镉纳米粒子附着在多壁碳纳米管表面,且无团聚现象.     

溶剂热法制备磷掺杂碳纳米管作为氧气还原和氧气析出反应双功能电催化剂的研究

对氧气还原(ORR)和氧气析出(OER)反应都具有催化活性的双功能催化剂在金属-空气电池中起着关键作用.本文通过溶剂热反应,一步原位合成了磷掺杂碳纳米管(P-CNT).旋转环盘电极测试表明磷掺杂能够明显提高碳纳米管的催化活性,P-CNT在碱性电解质中对ORR和OER都具有优异的催化活性.P-CNT对ORR的催化还原为近4电子反应,可与商业催化剂Pt/C(20 wt%)相比;而其对OER的催化活性则高于Pt/C(20 wt%).此外,P-CNT的长期稳定性优于Pt/C(20 wt%).P-CNT对ORR和OER的高催化活性和稳定性主要归因于磷对碳的掺杂以及磷与碳间强的化学键合.     

溶剂热助乙二醇还原法制备Pt/C催化剂过程中酸碱配位机制及工艺参数优化

质子交换膜燃料电池(PEMFCs)能量转换率高,反应产物仅为H2O、不造成污染,是一种极具发展前景的能源转换装置.然而, PEMFCs的阴极氧还原反应(ORR)动力学缓慢、过电位高.由于Pt对ORR中间产物脱吸附能适中,因此, Pt/C成为电催化ORR的商业化催化剂,对其制备技术的研究成为该领域的研究热点.乙二醇(EG)还原法制备碳载Pt基催化剂是一种常见方法, EG作为还原剂的同时,还起到保护剂和分散剂的作用,使制备的催化剂具有均一性.EG在外界能量的活化下,分解生成H2O和CH3CHO, CH3CHO作为还原剂将H2Pt Cl6还原生成Pt单质颗粒,同时生成的CH3COO-由于静电排斥可以防止Pt粒子团聚.常见的外界能量的活化方法有脉冲微波法、回流法、溶剂热法等,其中溶剂热法采用高压釜作为反应容器,抗干扰能力强,工艺操作简单、反应快速、耗能较少、成本低廉,极易于实现工业化生产;值得注意的是,无论使用何种方法对Pt前驱体混合液给予活化能使其发生还原,其碱的含量都会对最终所得催化剂的电催化ORR活性有着显著的影响,因此,通过跟踪前驱体混合液中含Pt物种的变化路径,揭示催化剂制备过程中的碱调控机理,实现加入碱的定量化,对于大规模制备高效Pt/C催化剂具有重要的意义.因此,本文采用溶剂热助EG还原法合成Pt/C催化剂的技术,创新联用UV-vis和H+浓度探针技术,揭示了前驱体混合液中含Pt物种的配位过程,实现了加入碱的定量化.发现当m(Na OH):m(Pt)达到2:1时, Pt配位完成;进而通过优化反应温度、反应时间等参数,成功制备了高效Pt/C催化剂:当反应温度为140 oC,反应时间为2 h时,所得催化剂在酸性条件下,相对于商业化Pt/C具有更高的电催化ORR活性,其起始ORR还原电位达到0.95 V(商业化Pt/C为0.90 V),半波电位为0.82 V(商业化Pt/C为0.75 V),该工作对于工业化大批量生产高效Pt/C催化剂具有重要的意义.     

溶剂热法制备纳米MnOOH

MnOOH在常温常压下为黑色固体粉末,经氧化或还原可制成电子工业中生产锰锌铁氧体软磁材料的重要原料.以KMnO4与MnSO4为原料,在水与正丙醇混合溶剂中反应制备了MnOOH纳米棒;采用X射线粉末衍射仪(XRD)、差热-热重(DTA-TG)分析系统、红外光谱仪(IR),以及扫描电镜(SEM)、透射电镜(TEM)、X射线...     

溶剂热法合成碳纳米材料

本文综述了溶剂热法合成多种碳纳米管、纳米电缆、纳米棒、纳米球和纳米空心锥的研究现状。350 ℃下用金属钾还原六氯代苯,在用不同催化剂时,可分别得到碳纳米管和碳球,碳球的形成可以解释为石墨层的微条卷曲而成。600 ℃下金属镁还原乙醇得到了竹节状和Y-型碳纳米管。500 ℃下还原四氯化碳和碳酸钠可得到平均直径为100 nm的碳纳米管。700 ℃下金属锌还原乙醚制成了左右螺旋型交织的碳纳米管。在硫的存在下,200 ℃以下二茂铁热解成非晶碳纳米管和Fe/非晶碳纳米同轴电缆。     

乙二胺接枝改性碳纳米管负载的乙醇氧化电催化剂Pt及Pt-Ru的制备及电催化性质

采用化学法制备了乙二胺接枝改性碳纳米管（ED/MWNTs）负载的Pt及Pt-Ru催化剂,并用红外光谱法、透射电镜分析（TEM）及X射线能谱技术对催化剂进行了表征。结果表明：乙二胺对碳纳米管的改性使Pt及Pt-Ru在碳管上的分布更均匀,粒径更小。同时,催化剂对乙醇电催化氧化活性的电化学研究结果表明：乙二胺改性可明显提高Pt-Ru/MWNTs/C 和Pt/MWNTs/C的电催化活性,而且Pt/ED/MWNTs/C的活性甚至比Pt-Ru/MWNTs/C的活性还高。由此,ED/MWNTs作为乙醇电氧化催化剂的载体有着很好的应用前景。     

溶剂热制备氧化锌纳米线

ZnO nanowires were synthesized mildly through an absolute alcohol solvothermal process at 120 ℃ for 12 h using ZnAc₂·2H₂O and NaOH as raw materials and PEG400 as a soft template. The cyrstal structure and morphology of the nanowires were characterized by XRD, SEM, TEM and HRTEM. The results indicate that the diameter of ZnO nanowires is 40 nm, the length can reach 2 μm and the nanowires are of high purity, homogeneity and well crystallinty. The influence of the various factors on the formation of ZnO nanowires and formation mechanism were also discussed.     

氢氧化镍/多壁碳纳米管复合材料的溶剂热法制备及电容性能

采用溶剂热法制备了氢氧化镍/多壁碳纳米管[Ni(OH)2/MWCNTs]复合纳米材料;借助X射线衍射仪和透射电镜分析了产物的结构和形貌,利用循环伏安测试测定了复合材料的电容特性.结果表明:片状β-Ni(OH)2较好地附着在MWCNTs上;复合样品的循环伏安行为明显有别于空白样品Ni(OH)2,峰电流较高.这表明引入MWCNTs可改善Ni(OH)2的电化学性能.与此同时,当MWCNTs的质量分数为10%时,相应的Ni(OH)2/MWCNTs复合物的氧化还原峰电位差最小,循环可逆性最佳.     

Synthesis of carbon nanotubes using scrap tyre rubber as carbon source

Carbon nanotubes(CNTs) were successfully synthesized through chemical vapor deposition(CVD) method over cobalt catalysts using scrap tyre rubber as carbon source.The CNTs as produced were investigated by means of X-ray diffraction, thermogravimetric analysis,scanning electron microscope,transmission electron microscopy and Raman spectrum techniques.It was found that the obtained carbon material mainly existed in the form of CNTs.     

Effects of carbon nanotubes on polymer physics

A single carbon nanotube has many similarities with an individual polymer chain including the fact that the end‐to‐end length of both are often about the same and the diameter of the chain is about the same (for single‐walled nanotubes) or only ～10 to 20 times larger (for multiwalled nanotubes). The combination of the solid surface and the similarity of the two materials means that polymer physics are altered in manners not seen with any other type of commonly used filler. The purpose of this review is to update a chapter that appears in a recent tome by Grady (2011) and describe how polymer physics is altered in composites that contain carbon nanotubes. Subjects that will be discussed include chain configuration, glass transition, polymer diffusion, unit cells and crystalline superstructure (lamellae, spherulites and shish‐kebabs), and crystallization kinetics. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Cytotoxicity of carbon nanotubes

With large-scale production and application at large scale, carbon nanotubes (CNTs) may cause ad-verse response to the environment and human health. Thus, study on bio-effects and safety of CNTs has attracted great attention from scientists and governments worldwide. This report briefly summa-rizes the main results from the in vitro toxicity study of CNTs. The emphasis is placed on the descrip-tion of a variety of factors affecting CNTs cytotoxicity, including species of CNTs, impurities contained, lengths of CNTs, aspect ratios, chemical modification, and assaying methods of cytotoxicity. However, experimental information obtained thus far on CNTs' cytotoxicity is lacking in comparability, and some-times there is controversy about it. In order to assess more accurately the potential risks of CNTs to human health, we suggest that care should be taken for issues such as chemical modification and quantitative characterization of CNTs in cytotoxicity assessment. More importantly, studies on physical and chemical mechanisms of CNTs' cytotoxicity should be strengthened; assaying methods and evaluating criteria characterized by nanotoxicology should be gradually established.     

Synthesis and characterization of polyethylene chains grafted onto the sidewalls of single‐walled carbon nanotubes via copolymerization

Polyethylene (PE) chains grafted onto the sidewalls of SWCNTs (SWCNT‐g‐PE) were successfully synthesized via ethylene copolymerization with functionalized single‐walled carbon nanotubes (f‐SWCNTs) catalyzed by rac‐(en)(THInd)₂ZrCl₂/MAO. Here f‐SWCNTs, in which α‐alkene groups were chemically linked on the sidewalls of SWCNTs, were synthesized by Prato reaction. The composition and microstructure of SWCNT‐g‐PE were characterized by means of ¹H NMR, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, thermogravimetric analyses (TGA), field‐emission scanning electron microscope (FESEM), and transmission electron microscope (TEM). Nanosized cable‐like structure was formed in the SWCNT‐g‐PE, in which the PE formed a tubular shell and several SWCNTs bundles existed as core. The formation of the above morphology in the SWCNT‐g‐PE resulted from successfully grafting of PE chains onto the surface of SWCNTs via copolymerization. The grown PE chains grafted onto the sidewall of the f‐SWCNTs promoted the exfoliation of the mass nanotubes. Comparing with pure PE, the physical mixture of PE/f‐SWCNTs and in situ PE/SWCNTs mixture, thermal stability, and mechanical properties of SWCNT‐g‐PE were higher because of the chemical bonding between the f‐SWCNTs and PE chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5459–5469, 2007     

Preparation of stimulus-responsive,polyfluorene-wrapped carbon nanotubes via palladium cross coupling

Decoration of carbon nanotube surfaces without damaging nanotube optoelectronic properties is an ongoing challenge. Here, we utilize Sonogashira coupling chemistry to decorate the nanotube surface without perturbing optoelectronic properties. Reactive, noncovalently functionalized polymer–nanotube complexes were prepared using a polyfluorene with aryl iodide groups in its side chains. The aryl iodides enable Pd cross coupling between polymer–nanotube complexes and small molecules or polymers derivatized with an alkyne. Modestly efficient coupling was found to occur under dilute conditions at elevated temperatures. Successful coupling between aryl iodide and alkyne partners was observed using infrared spectroscopy via the appearance of carbonyl stretches that originate from covalently linked, carbonyl-containing alkynes, and thermogravimetric analysis was used to measure reaction conversion under various conditions. Grafting of the hydrophobic polymer–nanotube complex with poly(ethylene glycol) enabled the dispersion to be transferred from organic to aqueous solution. This chemistry resulted in no damage to the nanotube sidewall, as evidenced by Raman spectroscopy. The aryl iodide-containing polyfluorene–nanotube complex was also coupled to a photoswitchable alkyne-containing spiropyran moiety and it was found that the photoswitch retained its functionality after coupling to the polymer–nanotube complex. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2723–2729     

Stability of narrow zigzag carbon nanotubes

First principles calculations of the electronic structure and total energy of narrow zigzag carbon nanotubes and their corresponding flat graphene strips have been carried out to assess the relative stability of the tube form. The results indicate that the smallest energetically stable carbon nanotube has a radius of about 0.2 nm. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2003