甲烷在Ni/Al2O3催化剂上积碳与失活行为研究

采用浸渍法制备Ni/Al2O3催化剂,研究反应条件对甲烷裂解生成碳产物形貌的影响和催化剂的失活机制.结果表明:在40Ni/Al2O3催化剂上碳生成物的沉积形式均呈纤维状结构,反应温度越高、空速越大,碳纤维的直径越小;碳在金属颗粒体相中的扩散是碳纳米纤维生长过程的速率控制步骤,当碳的生成速率低于碳在Ni中的体相扩散和迁移速率,生成的炭以纤维状结构生长.     

碳纳米管负载Fe2O3催化剂的制备及其乙苯脱氢催化活性

采用FeSO4-H2O2体系对碳纳米管氧化修饰的同时,氢氧化铁被吸附在碳纳米管管壁上,然后分别通过氢气、氮气、空气在723K下处理2h,制备了碳纳米管负载的γ-Fe2O3催化剂、γ-Fe2O3和α-Fe2O3复合催化剂和非晶态Fe2O3催化剂。采用XRD、TEM和TG-DSC表征了催化剂结构,采用连续流动乙苯气相脱氢生成苯乙烯反应对催化剂性能进行评价,结果表明：热处理条件对催化剂乙苯脱氢的催化性能影响明显,碳纳米管负载的晶态Fe2O3纳米催化剂对乙苯脱氢具有高的活性与选择性。     

乙酰丙酮铁为催化剂源在碳纤维表面生长碳纳米管的工艺研究

以乙酰丙酮铁为催化剂源,三甘醇为溶剂,通过溶剂热法在碳纤维表面负载催化剂前驱体,在H2与N2中一定温度下进行还原,采用化学气相沉积法在碳纤维表面生长碳纳米管。研究了催化剂的负载条件和碳纳米管的生长条件,采用XRD、FTIR、RAMAN对乙酰丙酮铁在三甘醇中反应在碳纤维表面负载催化剂前驱体产物进行分析,用SEM、TEM对催化剂前驱体粒子及碳纳米管的形貌进行表征。结果表明:催化剂前驱体为粒径30nm左右的Fe3O4颗粒,当催化剂的还原温度为415℃、还原时间为60min时,Fe3O4颗粒还原成纳米Fe颗粒;当碳纳米管的生长温度为750℃、生长时间为30min、气流体积比为V(N2)∶V(H2)∶V(C2H2)=50∶10∶10时能在碳纤维表面生长出形貌均一、管径为30~60nm的碳纳米管。     

洁净单壁碳纳米管在Fe2O3／Al2O3二元气凝胶催化剂上的水辅助合成

分别以甲烷-氧气和甲烷-氢气-水的混合气作为反应气源,利用Fe2O3/Al2O3二元气凝胶作为催化剂于900℃反应30min合成了单壁碳纳米管.并采用SEM、XRD、TEM,高分辨透射电子显微镜(HRTEM)以及Raman光谱等分析技术对所制得的碳产物的结构和形貌进行了表征,以研究反应气氛中水蒸气的引入对单壁碳纳米管生长的影响.结果表明:反应气氛的组成对最终所形成的碳产物的产率和结构有着密切的关联.通过控制氢气载入甲烷-氢气-水的混合气氛中水蒸气的量可以合成低无定形碳的沽净单壁碳纳米管.     

不同催化剂作用下生长的碳纳米管和碳纳米纤维复合膜的电吸附性能(英文)

采用低压低温气相沉淀法在不同催化剂(Fe和Ni)作用下制备碳纳米管-碳纤维复合薄膜,并研究其电容去离子行为,结果表明:在Ni催化作用下石墨上生长的碳纳米复合薄膜电极的去离子能力比Fe催化作用下生长的碳纳米复合薄膜电极的强;并且碳纳米复合薄膜的电吸附遵循langmuir单层等温吸附.     

煅烧温度对气凝胶催化剂合成 SWNTs催化活性的影响

研究了不同煅烧温度对Fe／Mo／A12O3气凝胶催化剂合成单壁碳纳米管（SWNTs）催化活性的影响．考察了不同煅烧温度下该催化剂自身的物理化学变化以及催化生长的无定型碳含量，SWNTs的含量、直径及石墨化程度．研究结果表明：不同温度的煅烧处理会影响催化剂的表面形态以及A12O3载体的晶化程度，进而影响了SWNTs的生长．600℃煅烧时，气凝胶催化剂具有最高的活性，此时催化生长的无定型碳含量仅占粗产品的1．7％，SWNTs的含量高达54．6％，且合成的SWNTs质量高、管径分布非常均一，为0．86nm左右．     

氨气等离子体下游区合成碳纳米管的研究

利用介质阻挡放电等离子体化学气相沉积技术，在蒸镀有13nm Ni催化剂层的Si基材上，以CH4为碳源，H2与NH3的混和物为刻蚀和稀释气体，在630和750℃的不同温度条件下合成碳纳米管。实验研究了不同氨气比例条件下碳纳米管的生长情况，并给出了合成碳纳米管的最佳氨气含量区间,SEM和TEM测试发现，所合成的碳纳米管具有竹节型结构，Ni催化剂形貌表明碳纳米管生长符合顶端机制,实验还发现氨气含量对碳纳米管的生长影响很大，并对其原因进行了初步的分析．     

Fe-Ni双活性金属催化剂制备碳纳米管的研究

利用催化化学气相沉积法,以Fe-Ni双活性金属为催化剂来制备碳纳米管.其中,Fe-Ni双活性金属催化剂由柠檬酸络合法制得.催化剂的组成和碳纳米管的形貌分别用XRD和TEM来进行了表征.实验结果表明,由于催化剂中的活性成分Fe-Ni形成了固溶体,相互之间产生了协同作用,使得其催化性能大大提高,因而由其制备的碳纳米管的产率明显高于由单一活性金属Fe或Ni催化剂所制备碳纳米管的产率.特别当双活性金属催化剂中的Fe的摩尔百分含量为75%时,产率为最高,达到2000%(gCNTs/gcatalyst precursor·h),这约是相同制备条件下,由单一活性金属Fe或Ni所得到碳纳米管产率的6或4倍.     

用于制备优质单壁碳纳米管管束的MgO负载Fe3O4纳米粒子的合成

采用沉淀方法制备了直径分布狭窄的均匀Fe3O4纳米颗粒.Fe3O4纳粒形体几近一致,平均粒径为10.33 nm±2.99 nm(平均粒径±标准偏差).在超声作用下将MgO纳米颗粒分散在一定量Fe3O4纳米颗粒的水溶液中获得MgO负载Fe3O4的纳米颗粒.以甲烷为碳源,Fe3O4/MgO为催化剂,经化学气相沉积,在Fe3O4纳粒上制得了大量直径近乎均匀的单壁碳纳米管(SWCNTs)束.TEM显示:SWCNTs的平均直径1.22rm.热重分析显示:样品在400℃～600℃温度区间失重量约19％.拉曼光谱显示:SWCNTs的ID/IG的强度比为0.03,表明采用Fe3O4/MgO催化剂可制得高石墨化程度的单壁碳纳米管.     

Ni催化剂在N2O／N2／NH3中退火对碳纳米管表面结构及场发射特性的影响

研究在N2O/N2/NH3氛围中对Ni催化剂进行退火处理,旨在探讨退火处理对所生成碳纳米管的表面结构及其发射特性的影响.从表面结构及表面元素分析结果发现:Ni催化剂在N2O/N2/NH3氛围中退火处理之后,Ni催化剂的颗粒大小及催化剂的化学成分发生改变,进而影响所合成的碳纳米管的表面结构及场发射特性.扫描电镜显示:经过N2O退火前处理后,催化金属薄膜在成核时较易形成均匀性的金属颗粒,且金属颗粒较小.比较经N2O/N2/NH3氛围退火处理之后所合成的碳纳米管结果,经过N2O前处理可以有效抑制非品质碳的成长,使所成长出的碳纳米管数量最多、场发射电流最大.原因主要是因为N2O对催化剂镍膜金属前处理过程中分解出的氮原子及氧原子会活化及氧化催化剂Ni金属,并使所形成的Ni金属颗粒较小且更为均匀,造成表面型态上的显著改变,有助于使合成的碳纳米管场发射电流变大.     

Low temperature synthesis of multiwalled carbon nanotubes and incorporation into an organic solar cell

ABSTRACT

Metal nanoparticle (MNP) catalysts used for the synthesis of multiwalled carbon nanotubes (MWCNTs) consisted of single metals (Fe, Ni or Co) and bimetallic mixture (CoFe, NiFe or NiCo). MWCNTs were successfully synthesised at 200 °C in 10 min using liquefied petroleum gas as carbon source with non-equilibrium plasma enhanced chemical vapour deposition (PECVD) method. The nanostructures and the morphology of the MNPs and the MWCNTs film were characterised using relevant microscopic and spectroscopic methods. The synthesised MWCNTs were used as part of the electrode material in organic solar cell (OSC) set-up. Poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) was used as an electron transporter and poly-3-hexyl thiophene (P3HT) as an electron donor. The performance of OSC devices was tested using standard electrical measurements and solar simulator operating at 100 mW/cm². The measured power conversion efficiencies was found to be dependent on the metal catalyst used during synthesis. Among all the catalysts employed in this investigation, the best device performance was found from the synthesis of MWCNTs using Fe as a catalyst followed by Co and then Ni, respectively.     

Comparison of Fe/Al/sub 2/O/sub 3/ and Fe, Co/Al/sub 2/O/sub 3/ catalysts used for production of carbon nanotubes from acetylene by CCVD

Characterization of iron containing alumina supported catalysts was performed by transmission electron microcopy (TEM), Mo/spl uml/ssbauer, and XPS spectroscopy during formation of multiwall carbon nanotubes from acetylene at 1000 K. TEM images showed that carbon fibers (outer diameter is around 20-40 nm) were generated on Fe/Al/sub 2/O/sub 3/ samples while on the bimetallic Fe,Co/Al/sub 2/O/sub 3/ carbon nanotubes with an average diameter of 8-12 nm were formed. XPS spectra revealed that Fe-Co alloy formed during the interaction of Fe,Co/Al/sub 2/O/sub 3/ and acetylene at 1000 K. The formation of the bimetallic alloy was proven by Mo/spl uml/ssbauer spectroscopy as well.     

Synthesis and field electron emission properties of hybrid carbon nanotubes and nanoparticles

Hybrid ZnO-carbon nanotubes as well as nanodiamond-carbon nanotubes were synthesized via a straightforward process of plasma enhanced chemical vapor deposition. For the former, ZnO nanoparticles were instantly coated on the tube surface in the final growing process of carbon nanotubes, while for the latter diamond nanoparticles were grown using pretreatment of a silicon substrate with Ni(NO(3))(2)·6H(2)O/Mg(NO(3))(2)·6H(2)O alcohol solution prior to deposition and a high H(2)/CH(4) gas flow ratio in the deposition process. The morphology and microstructure of the obtained hybrid materials were characterized by transmission electron microscopy. Both hybrid ZnO-carbon nanotubes and nanodiamond-carbon nanotubes exhibited excellent field emission properties.     

Ni／CNTs及钙改性Ni／CNTs催化剂在二氧化碳甲烷化反应中性能

分别以碳纳米管（CNTs）和活性氧化铝（Al2O3）为载体,通过浸渍法制备了负载型镍基催化剂和钙改性的镍基催化剂,用二氧化碳甲炕化反应评价其催化性能,通过X射线衍射（XRD）、程序升温还原（H2-TPR）、程序升温脱附（H2-TPD）和氮气等温吸附脱附等手段对催化剂进行表征,结果表明,Ni／CNTs催化剂中的镍物种比Ni／Al2O3中的镍物种容易还原,同时钙改性Ni／CNTs催化剂更能促进镍物种的还原,添加钙可以促进CNTs载体催化剂的分散度,这些特性能提高钙改性Ni／CNTs催化剂的催化活性和稳定性。     

Effect of Ni+2-substituted Fe2TiO5 on the H2-reduction and CO2 Catalytic Decomposition Reactions at 500℃

CO2 is a major component of the greenhouse gases, which causes the global warming. To reduce CO2 gas, high activity nanosized Ni＋2 substituted Fe2TiO5 samples were synthesized by conventional ceramic method. The effect of the composition of the synthesized ferrite on the H2-reduction and CO2-catalytic decomposition was investigated. Fe2TiO5 （iron titanate） phase that has a nanocrystallite size of -80 nm is formed as a result of heating Fe2O3 and TiO2 while the addition of NiO leads to the formation of new phases （-80 nm） NiTiO3 and NiFe2O4, but the mixed solid of NiO and Fe2O3 results in the formation of NiFe2O4 only. Samples with Ni^＋2=0 shows the lowest reduction extent （20%）; as the extent of Ni＋2 increases, the extent of reduction increases. The increase in the reduction percent is attributed to the presence of NiTiO3 and NiFe2O4 phases, which are more reducible phases than Fe2TiO5. The CO2 decomposition reactions were monitored by thermogravimetric analysis （TGA） experiments. The oxidation of the H2-reduced Ni＋2 substituted Fe2TiO5 at 500℃ was investigated. As Ni^＋2 increases, the rate of reoxidation increases. Samples with the highest reduction extents gave the highest reoxidation extent, which is attributed to the highly porous nature and deficiency in oxygen due to the presence of metallic Fe, Ni and/or FeNi alloy. X-ray diffraction （XRD） and transmission electron microscopy （TEM） of oxidized samples show also the presence of carbon in the sample containing Ni＋2〉0, which appears in the form of nanotubes （25 nm）.     

Effect of Ni+2-substituted Fe2TiO5 on the H2-reduction and CO2 Catalytic Decomposition Reactions at 500℃

CO2 is a major component of the greenhouse gases, which causes the global warming. To reduce CO2 gas,high activity nanosized Ni 2 substituted Fe2TiO5 samples were synthesized by conventional ceramic method.The effect of the composition of the synthesized ferrite on the H2-reduction and CO2-catalytic decomposition was investigated. Fe2TiO5 (iron titanate) phase that has a nanocrystallite size of ～80 nm is formed as a result of heating Fe2O3 and TiO2 while the addition of NiO leads to the formation of new phases (～80 nm)NiTiO3 and NiFe2O4, but the mixed solid of NiO and Fe2O3 results in the formation of NiFe2O4 only.Samples with Ni 2=0 shows the lowest reduction extent (20%); as the extent of Ni 2 increases, the extent of reduction increases. The increase in the reduction percent is attributed to the presence of NiTiO3 and NiFe2O4 phases, which are more reducible phases than Fe2TiO5. The CO2 decomposition reactions were monitored by thermogravimetric analysis (TGA) experiments. The oxidation of the H2-reduced Ni 2 substituted Fe2TiO5 at 500℃ was investigated. As Ni 2 increases, the rate of reoxidation increases. Samples with the highest reduction extents gave the highest reoxidation extent, which is attributed to the highly porous nature and deficiency in oxygen due to the presence of metallic Fe, Ni and/or FeNi alloy. X-ray diffraction (XRD) and transmission electron microscopy (TEM) of oxidized samples show also the presence of carbon in the sample containing Ni 2＞0, which appears in the form of nanotubes (25 nm).     

Synthesis of multi-walled carbon nanotubes by microwave plasma-enhanced chemical vapor deposition

Microwave plasma-enhanced chemical vapor deposition (MW-PECVD) has been employed to synthesize carbon nanostructures by using Fe (or Co, Ni)/γ-Al₂O₃ as catalysts and a mixture of benzene, hydrogen, and argon as precursors. By regulating the types of catalyst, the microwave incident power, the ratio and flux of the precursors, many morphologies such as ordinary geometric, helix-shaped, and planar spiral carbon nanotubes with aspect ratios of 100–1000 have been observed. Furthermore, two novel nanostructures, which are probably the missing link between onion-like carbon particles and nanotubes, have also been obtained. The striking feature of this new approach is the low synthesis temperature (<520°C) due to the non-equilibrium characteristic of microwave plasma operated at low pressure, which is crucial for some fascinating applications.     

Synthesis of carbon nanotubes using mesoporous Fe-MCM-41 catalysts

MWNTs (multi-walled carbon nanotubes) were made by catalytic CVD process using iron-containing mesoporous silica, Fe-MCM-41, with 4 mol% Fe loading prepared by direct synthesis route. Uniform 5 nm size Fe2O3 nano-particles impregnated onto a mesoporous silica support, SBA-15 were also prepared for CNTs synthesis. The catalysts were characterized using XRD, SEM/TEM, N2 physisorption, UV-vis diffuse reflectance and FT-IR spectroscopies. Acetylene gas was introduced as a carbon source, and the gas mixture of Ar:H2:C2H2 = 14:5:1 pyrolyzed at 750 degrees C for 60 min was found to be the optimum synthesis condition. Fe-MCM-41 due to higher dispersion of nano-sized Fe-species was efficient as catalyst for MWNTs with more uniform size distribution. Cobalt-impregnated Fe-MCM-41 (Co/Fe = 1) produced a small fraction of SWNTs of ca. 2 nm diameter mixed with MWNTs.     

Influence of the nanoscale support on carbon deposition and carbon elimination over Ni/gamma-Al2O3 catalyst for CH4 conversion

Characteristics of carbon deposition by CH4 and carbon elimination by CO2 over conventional and nanoscale Ni/gamma-Al2O3 catalysts were investigated by using a pulse reaction, as well as by TGA, TEM, TPO-MS, H2-TPR and H2-chemisorption techniques. It was found that the behaviors of carbon deposition by CH4 decomposition and carbon elimination by CO2 depend on the active metal dispersion and the metal-support interaction. The filamentous carbon was formed on the conventional Ni/gamma-Al2O3 catalyst with low metal dispersion and relatively large particles, this type of filamentous carbon was far from the active centers and difficult to eliminate by CO2. On the other hand, the carbon deposition originated from CH4 decomposition on the nanoscale Ni/gamma-Al2O3 catalyst would mainly cover the surface of active centers, this type of highly active carbon was easily eliminated by CO2 because it is close to the active center Ni atoms. As a result, the improvement of coking-resistance was ascribed to the high metal dispersion and strong metal-support interaction, a model of CH4 decomposition carbon deposition on Ni/gamma-Al2O3 catalyst was proposed.