预还原催化剂LaNiO3, La4Ni3O10, La3Ni2O7和La2NiO4 催化分解CH4制碳纳米管 的研究

通过预还原的LaNiO3,La4Ni3O10,La3Ni2O7和La2NiO4催化分解CH4可以制备大量高度石墨化的碳纳米管。还原前后的催化剂的结构和组分通过X射线衍射(XRD)测定。所制得的碳纳米管由扫描电镜(TEM)、X射线光电子能谱(XPS)表征。碳纳米管在空气在的热氧化性由热重实验(TG)测定。实验结果表明不同催化剂前驱中的La/Ni比会影响碳纳米管的管径分布和石墨化程度。La/Ni比越小,碳纳米管的管径越大,石墨化程度越高。     

气凝胶催化剂上甲烷裂解制备的碳纳米管结构特征

采用XRD、TGA、SEM、TEM、 Raman光谱等多种表征手段,考察了Al2O3气凝胶催化剂上甲烷裂解生长的碳纳米管的结构特征.制得的碳纳米管形态单一,为管径均匀、管壁光滑的中空纳米管,平均直径在10～20 nm.碳纳米管的比表面积较大,具有较强的抗氧化能力,其结构的长程有序度较石墨低.由碳纳米管的Raman光谱分析可知,碳纳米管存在碳层缺陷和无定形碳.当反应温度升高或甲烷浓度下降时,碳纳米管石墨化程度逐渐提高.     

金属氢氧化物直接制备对苯二甲酸插层水滑石及其应用

以新制备的Mg(OH)_2和Al(OH)_3滤饼与对苯二甲酸通过水热反应制备了对苯二甲酸插层水滑石(TALDHs).使用X射线衍射(XRD)、热重-差热分析、扫描电镜(SEM)等技术对TA-LDHs与碳酸根型水滑石(CO3-LDHs)进行对比研究,结果显示,对苯二甲酸离子成功插入到LDHs层间,产物结构完整、晶相单一,所制得的TA-LDHs为片状.CO3-LDHs和TA-LDHs分别作为纳米填料,以两种不同的添加方式制备聚对苯二甲酸乙二醇酯(PET)/LDHs纳米复合材料.对复合材料进行XRD和SEM研究,结果表明在酯交换反应前添加2%TA-LDHs所制备的PET/LDHs纳米复合材料的层板被部分剥离,分散性最好.     

Utilizing Non-ferrous Metal Tailings to Propare Ni/SiO2 -CaO-Fe2O3 Catalyst for CO2 Reforming of CH4 to Syngas

以尾矿为载体原料,经不同温度焙烧预处理、等体积浸渍制备了一系列负载型Ni/SiO2-CaO-Fe2O3催化剂并用于CO2重整CH4制合成气,重点考察了载体原料的焙烧温度对催化剂性能的影响.用ICP-AES,XRD测定了有色金属尾矿的成分,用H2-TPR,CO2-TPD,TPO等对催化剂的还原性能、吸附性能、抗积炭性能进行了表征.结果表明,载体原料经850℃焙烧后所负载的镍催化剂在800℃条件下CO2转化率为78.5%,CH4转化率为71.2%,CO和H2选择性分别达到92.2%,89.5%.     

焙烧温度对有色金属尾矿载体及Ni基催化剂的性能影响

以尾矿为载体原料,经不同温度焙烧预处理、等体积浸渍制备了一系列负载型Ni/SiO2-CaO-Fe2O3催化剂并用于CO2重整CH4制合成气,重点考察了载体原料的焙烧温度对催化剂性能的影响.用ICP-AES,XRD测定了有色金属尾矿的成分,用H2-TPR,CO2-TPD,TPO等对催化剂的还原性能、吸附性能、抗积炭性能进行了表征.结果表明,载体原料经850℃焙烧后所负载的镍催化剂在800℃条件下CO2转化率为78.5%,CH4转化率为71.2%,CO和H2选择性分别达到92.2%,89.5%.     

氧化程度对微细鳞片可膨胀石墨结构及膨胀性的影响

以平均粒径为19.71μm的天然微细鳞片石墨为原料,通过化学氧化法制备了具有不同氧化程度的可膨胀石墨,采用XRD、FTIR、Raman、SEM等对可膨胀石墨的结构与膨胀性进行了表征。结果表明:当氧化程度较低时制得的微细鳞片可膨胀石墨由石墨、石墨层间化合物和氧化石墨三相组成;随着氧化程度的增加,氧化石墨相含量与可膨胀石墨结构无序程度逐渐增高,石墨层间化合物相含量先增加后减少,石墨相含量则逐渐降低;氧化促使HSO4-或SO42-插入石墨层间,插入层间的HSO4-或SO42-量是决定可膨胀石墨膨胀容积的关键因素,制备的微细鳞片膨胀石墨的膨胀容积可达65.9mL·g-1。     

稀土烧绿石型催化剂上CO2重整CH4制合成气反应研究

通过溶胶-凝胶法合成了La-Zr-O和Ni-La-Zr-O体系催化剂,采用XRD,BET和TPR技术对其物理化学性质进行了表征,以CO2重整CH4制合成气反应为探针反应对其重整活性进行了研究.结果表明,在空气中1100 ℃焙烧后,La-Zr-O体系催化剂形成了单相烧绿石结构复合氧化物,对CO2重整CH4制合成气反应表现出了优良的抗积炭能力,而以镍修饰后XRD方法只测量到了单相烧绿石结构La2Zr2O7衍射峰,说明NiO很有可能以无定形的细小晶粒均匀分散在La2Zr2O7表面.值得指出的是镍修饰后的烧绿石型催化剂对CO2重整CH4制合成气反应表现出了更加优良的催化活性,同时具有一定的抗积炭能力,优于相同方法制备的Ni-ZrO2和Ni-La2O3催化剂.     

La2NiO4／Al2O3催化剂上CH4／CO2的重整

 通过溶胶－凝胶方法制备了尖晶石结构的La2NiO4／Al2O3催化剂，采用BET，XRD和TG表征了催化剂的孔分布、比表面积、体相组成以及凝胶样品的热失重和热分解过程．将催化剂应用于CH4／CO2重整反应制合成气，考察了惰性气体和反应温度对转化率、选择性以及积碳的影响．结果表明，在高空速（GHSV＝4．8×104ml／（g·h））下，CH4和CO2转化率分别为51％和60％，CO和H2的选择性约为98％和92％，惰性气体He的引入明显地提高了CH4和CO2的转化率．     

焙烧法纯化多壁碳纳米管

自碳纳米管[1 ] 发现以来 ,已在世界范围内掀起了碳纳米管研究和应用的热潮 .其中一些文献报道了纯化单壁碳纳米管的方法 ,如超声波助滤法 [2 ] ,酸洗法 [3,4] ,微孔膜过滤法 [5,6] ,离心法[5] ,氧化法[5,7] ;另有少量文献报道了纯化多壁碳纳米管的方法 ,如氧化法 [5,8] ,石墨插层化合物纯化法 [9] 等 .本文使用焙烧法纯化实验室自制的多壁碳纳米管 .通过 TEM、XRD和比表面积等的测定 ,考察了不同焙烧时间的纯化效果 .采用催化甲烷裂解方法 ,在 6 0 0℃反应 4h制得多壁碳纳米管 ,粗产物收率接近 2 0 % .于干燥、洁净的坩埚中 ,分别称取 6…     

不同载体负载Pd催化剂对甲酸的电催化氧化活性比较

应用Hummers法氧化合成氧化石墨(GO).然后用化学一步还原法制得石墨烯(graphene)负载Pd催化剂.同法以多壁碳纳米管(MWCNTs)、单壁碳纳米管(SWCNTs)和Vulcan XC-72为载体制备了不同负载型的Pd催化剂.X射线衍射(XRD)、透射电镜(TEM)表征表明,在石墨烯载体上Pd纳米粒子粒径较...     

Effect of surface structure on the charge storage capacity of carbon black electrodes

In this work we study the effect of surface structure on the charge storage capacity of carbon black electrodes with various changes in surface chemistry, morphology, and doping species. Cyclic voltammetry and chronopotentiometry studies, performed under alkaline conditions with carbon paste electrodes, indicate the importance of surface structure and grain size on the faradic and capacitive charge contributions of these materials. Among the various carbon blacks studied, the lithiated material shows superior charge storage capacity, suggesting the importance of alkaline metals and oxygenated groups on the carbon surface. For the graphitic carbon, the appearance of a reversible redox process with cycling resembles the electrochemical behavior reported for hydrogen storage in carbon nanotubes. Electronic Publication     

碳纳米管的激光溅射产生

碳纳米管的激光溅射产生程大典，余荣清，刘朝阳，张强，王育煌，黄荣彬，詹梦熊，郑兰荪（固体表面物理化学国家重点实验室，厦门大学化学系，厦门，３６１００５）关键词碳纳米管，激光溅射，碳球Ｓｍａｌｌｅｙ等［１］曾以脉冲激光束在超声分子束喷口的喉道处蒸发石墨...     

交流放电法合成多种形态的碳纳米管

碳纳米管的发现［１］引起了科学界的广泛重视，人们对于这种新型材料在纳米导线、高强纤维、超导等方面的应用寄予厚望．目前，合成碳纳米管的方法主要是采用不等径石墨棒直流放电，在阴极上得到含有碳纳米管的沉积物［２］．对于碳纳米管的应用，有关的理论研究［３］及...     

非晶碳纳米球的低温石墨化(英文)

The investigation by SEM/TEM, porosity, and X-ray diffraction measurements of the graphitization process starting from amorphous carbon nanospheres, prepared by glucose carbonization, is reported. Aspects studied are the annealing temperature in the 750–1000 °C range, the type of inert carrier gas, and time of treatment in the 2–6 h range. It is investigated how these parameters influence the structural and morphological characteristics of the carbon materials obtained as well as their nanostructure. It is shown that it is possible to maintain after graphitization the round-shaped macro morphology, a high surface area and porosity, and especially a large structural disorder in the graphitic layers stacking, with the presence of rather small ordered domains. These are characteristics interesting for various catalytic applications. The key in obtaining these characteristics is the thermal treatment in a flow of N2. It was demonstrated that the use of He rather than N2 does not allow obtaining the same results. The effect is attributed to the presence of traces of oxygen, enough to create the presence of oxygen functional groups on the surface temperatures higher than 750 °C, when graphitization occurs. These oxygen functional groups favor the graphitization process.     

Electrochemical storage of hydrogen in nanocarbon materials: electrochemical characterization of carbon black matrices

In this work, various types of carbon black are electrochemically characterized to study their possible use in the electrochemical evaluation of fullerene materials as hydrogen storage candidates. The cyclic voltammetry and chronopotentiometry studies were performed in alkaline media, 6 M KOH, with carbon paste electrodes. Differences in the electrodes' electrochemical response and their correlation with the various surface chemistries, morphology and doping species of carbon blacks suggest a stronger dependency on the presence of doping agents (foreign metals) and on the surface structure than on the carbon black surface area. The study allows the selection of appropriate carbon black materials to be used as matrixes in future fullerene composite studies. Electronic Publication     

Pt-CNTs 修饰玻碳电极(Pt-CNTs/GC)电氧化活性的研究

采用透射电镜(TEM)和选区电子衍射(SAED)技术, 分别表征了Pt-CNTs/GC电极的表面形貌和所负载铂纳米原子簇的结构. 以CO和CH3OH为探针分子, 用循环伏安和计时电流等常规电化学方法检测了CO和CH3OH在Pt-CNTs/GC电极上的氧化行为. 研究结果表明, CO在Pt-CNTs/GC电极上有3个氧化电流峰(Ⅰ, Ⅱ, Ⅲ), 其中峰Ⅰ为CO桥式吸附的氧化峰, 而峰Ⅱ和Ⅲ则分别为CO线形吸附在碳纳米管负载的不同粒径的Pt纳米原子簇以及Pt原子薄膜上所分裂的氧化峰; CH3OH在Pt-CNTs/GC电极上也能自发解离吸附强吸附中间体CO; Pt-CNTs/GC电极对CH3OH的氧化峰电流不总是随CNTs上载铂量的增加而增大, 表明在制备直接甲醇燃料电池阳极时, 应选择合适的载铂量.     

First-principles study of a new type nanojunction: Finite length carbon chain inserted into half of a carbon nanotube

Based on first-principles calculations, we investigate the structure and electronic properties of a carbon atomic chain in finite length inserted into half of a single walled carbon nanotube (SWCNT), which we called half chain@SWCNT or more generally HCS. Comparing the optimized structure of HCS with that of the same chiral indices SWCNT and all carbon chain inserted SWCNT, we find that the geometry of the tube in HCS is slightly altered due to the weakly interacting between the inserted chain and the outer tube wall of HCS. Our calculation of band structure indicates that the armchair (5, 5) HCS exhibits metallic character, which is as that of (5, 5) SWCNT and all carbon chain inserted (5, 5) SWCNT. The zigzag (8, 0) and (9, 0) HCSs have small change in the energy gap compared to the corresponding pristine ones. Due to the downshift of conduction bands originating from the carbon chain, the calculation of band structure shows that chiral (6, 4) HCS is a semiconductor system with a small band gap of 0.94 eV, less than 1.125 eV in pristine SWCNT. The studied HCSs with unique structure and electronic property may construct a new generation nanoscale junctions without the usual heptagon–pentagon defect pair considerations.     

The preparation, properties and application of carbon fibers for SPME

The conditions of preparation of new types of carbon fibers for solid phase micro extraction (SPME) prepared by methylene chloride pyrolysis (at 600 °C) on the quartz fiber (100 μm) as well as by supporting synthetic active carbon (prepared especially for this purposes) supported in a special epoxide-acrylic polymer is described. The properties of such carbon fibers for SPME were defined by determination of the partition coefficient of the tested substances (i.e., benzene, toluene, xylenes, trichloromethane and tetrachloromethane) and by the microscopic investigations with the application of the optical and scanning electron microscope.

The obtained carbon SPME fibers were applied to the analysis of some volatile organic compounds from its aqueous matrix. During chromatographic GC test, at the investigated SPME carbon fibers, we obtained different but mostly high partition coefficients for the determined compounds (Kfs from 120 for trichloromethane up to 11,500 for tetrachloromethane).

Owing to the high partition coefficients of the studied substances obtained on carbon fibers, it was possible to do the analysis of organic substances occurring in trace amounts in different matrices. In this paper, we present the analysis of BTX contents in the petrol analyzed with the application carbonized with CH₂Cl₂ SPME fiber (C1NM) and a headspace over the petrol sample (concentration of each BTX g/dm³).     

析因设计结合响应面法分析甲烷干重整过程中通过形成碳纳米管进行二氧化碳减排(英文)

A factorial experimental design was combined with response surface methodology(RSM) to opti-mize the catalyzed CO2 consumption by coke deposition and syngas production during the dry re-forming of CH4. The CH4 /CO2 feed ratio and the reaction temperature were chosen as the variables, and the selected responses were CH4 and CO2 conversion, the H2 /CO ratio, and coke deposition. The optimal reaction conditions were found to be a CH4 /CO2 feed ratio of approximately 3 at 700 °C, producing a large quantity of coke and realizing high CO2 conversion. Furthermore, Raman results showed that the CH4 /CO2 ratio and reaction temperature affect the system's response, particularly the characteristics of the coke produced, which indicates the formation of carbon nanotubes and amorphous carbon.     

碳微线圈的气-液-固-固生长机理

碳微线圈具有类似DNA的双螺旋结构, 通常以镍为催化剂, 噻吩为助剂采用CVD法制备, 但是对于它的生长机理人们仍不十分清楚. 本文发现构成碳微线圈的碳纤维由三条亚纤维组成, 提出了碳微线圈的气-液-固-固生长机理, 并以此对实验事实做出合理解释.