钴/碳纳米管催化剂CVD法制备碳纳米管

以乙烯为碳源、多壁碳纳米管为载体负载钴作为催化剂,利用CVD法制备出了高质量的多壁碳纳米管.利用扫描电子显微镜(SEM)对催化剂的形貌进行了表征,利用透射电子显微镜(TEM)、X射线衍射仪(XRD)以及差热-热重(TG-DTA)方法对产物进行了表征.发现在最佳裂解温度770℃下制备的多壁碳纳米管直径分布均匀、曲率小、纯净、产率高,更重要的是不具有难处理的氧化物(如Al2O3)载体,充分体现了碳纳米管作为载体的优越性.     

催化剂在碳纳米管制备中的影响

催化裂解法操作简单,便于控制参数,有望成为碳纳米管连续生产的最佳方法.在催化裂解法中最重要的是催化剂,主要从催化剂的选取、制备、颗粒大小、失活等方面对碳纳米管生长速度、管径、密度、产物含量的影响进行浅析.     

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。     

催化剂加载对连续碳纤维表面生长碳纳米管的影响

通过化学气相沉积(CVD)在碳纤维表面还原得到均匀细小的催化剂颗粒并在碳纤维表面催化生长了均匀、规整的碳纳米管(CNTs)。系统研究了催化剂种类以及浓度对碳纳米管产量和微观组织结构的影响,探究了碳纤维的浸润性能和单丝强度的变化。结果表明,Ni的催化活性最高,Co的催化活性适中,产生的CNTs较为均匀、规整,当催化剂浓度为0.02mol/L时,碳纤维表面生长CNTs多尺度增强体的拉伸强度最大。碳纤维表面生长CNTs,促使碳纤维的表面粗糙度增加,与树脂之间的结合变强,从而提高了碳纤维与环氧树脂之间的浸润性。     

催化剂晶体结构对碳纳米管生长影响的微观解释

通过对催化剂晶体结构的分析，讨论了温度对催化剂金属晶格结构的影响，温度对催化剂中碳的溶解度与扩散速度的影响；催化剂金属中其他元素的加入对碳活度的影响，以及析出能量、晶体界面等对碳纳米管生长的影响。温度在1000℃左右时，催化剂金属铁具有面心立方结构，碳管产量比在其它温度下高；催化剂金属中加入其他可提高碳原子活度的元素，可促使碳从催化剂金属中析出，有助于提高碳管的产量。     

催化剂前驱体对碳纳米管生长影响的研究

采用柠檬酸络合法, 通过改变La和Ni的摩尔比例获得了一系列的La-Ni-O催化剂前驱体, 以H₂作为还原气体, N₂为保护气体, C₂H₂为碳源, 采用化学气相沉积法制备碳纳米管(CNT). 用XRD研究所得催化剂前驱体还原前后的结构, TEM观察所得CNT的形貌. 结果发现: 在所制备的一系列La-Ni-O催化剂前驱体中, 具有催化活性的物质只有: LaNiO₃和La₂NiO₄. 但由LaNiO₃所制备的CNT的产率却大大高于由La₂NiO₄所制备的CNT的产率. 经分析认为, 这主要是与两者被还原后的产物中的纳米级金属Ni的(111)晶面含量有关, 纳米级金属Ni的(111)晶面含量和晶粒度越大, 其CNT的产率和内径也就越大.     

裂解温度对碳纳米管制备的影响

以纳米级复合物NiO/SiO2为催化剂，甲烷为碳源，采用催化分解法制备了碳纳米管，并运用TEM对不同实验条件下得到的纳米碳管进行了形貌分析，结果表明：反应温度对碳纳米管的产率和形貌有着很重要的影响。反应温度过高或过低，碳纳米管的产率都很低。适合碳纳米管生长的温度范围是620℃-720℃，在660℃-680℃之间反应可得到稳定的产率。在640℃-680℃之间可以得到高纯度的产物，温度过高或过低时得到的碳纳米管形貌不均一而且含有很多杂质。     

碳纳米管--新型的催化剂载体

从催化剂负载于碳纳米管的方法，碳纳米管的电学性能、储氢性能及独特的管腔结构对催化反应的影响几方面对碳纳米管作为催化剂载体的研究进展进行了论述，指出由于碳纳米管的疏水性，使得制备催化剂时，溶剂的选择十分重要；碳纳米管独特的电学性能使之成为催化剂载体的同时亦充当了助剂；碳纳米管的储氢性能使之在催化加氢反应中得到了最为广泛的应用；其独特的管腔结构则成为择形催化的好场所。而制约碳纳米管应用的因素在于其制备的规模和工艺。     

Cu-Cr-O催化剂的合成及其用于碳纳米管的制备

采用醇-水共沉淀法制备Cu-Cr-O纳米复合粉体催化剂,并将其用于碳纳米管的制备。利用TG-DSC、XRD、TEM和SEM手段分别对其热分解过程、晶相、微观结构形态进行表征。结果表明,不同煅烧温度下所得催化剂存在差异,其中600℃煅烧条件下可制备出结晶良好的Cu-Cr-O纳米复合催化剂。不同煅烧温度下所得复合粉体催化合成的碳纳米管品质形貌不一,其中600℃条件下可得到纯度高、表面光滑的碳纳米管。     

以NiZnAl催化剂制备碳纳米管及其反应活性的研究

采用FC化合物作为一种新型催化剂--NiZnAl催化剂的前驱物,以催化热解法合成出了碳纳米管.管状、竹节状、鱼骨状和分叉状等多种形态的碳纳米管均被观测到.在碳纳米管生长过程中位于其顶端的准液态金属颗粒是其形成多种形态碳纳米管的关键.Zn的添加可能使得经煅烧和还原后的Ni催化剂的活性产生了微妙的变化.     

碳纳米管/羟基磷灰石生物复合涂层的制备与微观结构研究

采用电泳沉积的方法在钛板表面制备了碳纳米管/羟基磷灰石复合涂层。XRD研究发现,复合涂层的成分主要是羟基磷灰石和碳纳米管;IR研究发现,复合涂层中含有羟基、磷酸根等官能团;SEM研究发现,复合涂层均匀致密,碳纳米管与羟基磷灰石颗粒混合均匀,且碳纳米管的表面已被1层羟基磷灰石薄膜均匀包覆。随着碳纳米管含量从20%增加到40%,复合涂层的致密度逐渐提高,其表面质量逐渐改善。     

CNTs含量对CNTs/Al微观组织及力学性能的影响

为增加碳纳米管(CNTs)在铝基体中的分散性,利用机械球磨-真空热压烧结工艺制备碳纳米管/铝(CNTs/Al)复合材料,采用扫描电子显微镜(SEM)、电子万能试验机和万能摩擦磨损实验机,研究了CNTs质量分数对CNTs/Al复合材料微观组织、力学性能及摩擦磨损性能的影响.结果表明:CNTs经超声波预先分散后分散性增加;当CNTs质量分数为2.0%时,复合材料中CNTs与Al粉之间表现出较好的相容性;随着CNTs含量进一步增加,CNTs团聚现象严重;热压烧结温度600℃时,随着CNTs添加量的增加,铝基复合材料的屈服强度和抗拉强度呈现出明显的先增大后降低的趋势,同时,CNTs/Al复合材料的摩擦因数和磨损率随CNTs含量的增大先减小后增加;CNTs质量分数为2.0%时,复合材料的屈服强度最大值为116 MPa,抗拉强度最大值为245 MPa,与纯Al基体相比,分别提高了78%和1.9倍.2.0%CNTs/Al复合材料可获得较好的摩擦磨损性能,其摩擦系数和磨损率呈现平缓趋势,复合材料的磨痕最浅.     

Influence of cation-adsorption and sonochemical approaches on the preparation of gold catalyst

Nanosize mesoporous ZrO2 support was synthesized via a solid-state reaction route. A new preparation method involving cation-adsorption and sono-chemical procedure was developed for mesoporous ZrO2 supported nano-gold catalyst.     

浮动催化CVD法CNTs膜及CNTs膜/环氧复合材料拉伸特性

针对浮动催化化学气相沉积(CVD)法制备的碳纳米管(CNTs)膜,首先采用红外光谱表征分析了包覆在CNTs表面的无定形物质的组成,然后分别采用热处理和酸洗处理方法,考察了CNTs膜中无定形物和残留Fe催化剂对CNTs膜拉伸取向行为的影响。结果表明:采用CVD法制备的CNTs膜中CNTs表面无定形物为含氧或烷烃、烯烃类低聚物,可通过350℃有氧热处理基本去除。该CNTs膜的牵伸取向重排行为受组成影响显著,CNTs表面的低聚物可增强CNTs的管间黏结作用,Fe催化剂颗粒成为CNTs网络结构的交联结点,两者均有利于提高CNTs的取向程度和聚并成束的尺寸,进而提高CNTs膜的拉伸稳定性和断裂韧性。牵伸取向后CNTs膜与环氧树脂溶液的浸润性提高,其CNTs膜/环氧复合材料的拉伸强度和模量达到1228MPa和94.5GPa,相比初始无规CNTs膜/环氧复合材料的分别提高了337%和729%。      

Influence of a fiber-network microstructure of paper-structured catalyst on methanol reforming behavior

A novel microstructured catalyst that consists of Cu/ZnO catalyst powders and ceramic fibers was successfully prepared using pulp fibers as a tentative matrix by a papermaking technique. As-prepared material, called a paper-structured catalyst, possessed porous microstructure with layered ceramic fiber networks (average pore size ca. 20 μm, porosity ca. 50%). In the process of methanol autothermal reforming (ATR) to produce hydrogen, paper-structured catalysts demonstrated both high methanol conversion and low concentration of undesirable carbon monoxide as compared with catalyst powders and pellets. The catalytic performance of paper-structured catalysts depended on the use of pulp fibers, which were added in the paper-forming process and finally removed by thermal treatment before ATR performance tests. Confocal laser scanning microscopy and mercury intrusion analysis suggested that the tentative pulp fiber matrix played a significant role in regulating the fiber-network microstructure inside paper composites. Various metallic filters with different average pore sizes, used as supports for Cu/ZnO catalysts, were subjected to ATR performance tests for elucidating the pore effects. The tests indicated that the pore sizes of catalyst support had critical effects on the catalytic efficiency: the maximum hydrogen production was achieved by metallic filters with an average pore size of 20 μm. These results suggested that the paper-specific microstructures contributed to form a suitable catalytic reaction environment, possibly by promoting efficient diffusion of heat and reactants. The paper-structured catalyst with a regular pore microstructure is expected to be a promising catalytic material to provide both practical utility and high efficiency in the catalytic gas-reforming process.     

Influence of acetic acid and ammonia catalyst on microstructure and properties of fluorinated polyimide-organosilicate hybrids

This work investigates the preparation, microstructure and thermal/electrical properties of fluorinated polyimide-organosilicate hybrids utilizing acetic acid and ammonia as the catalysts for sol-gel process to grow organosilicate filler particles. Nano-scale organosilicate was observed in the base-catalyzed hybrids, which was ascribed to the relative inertness of base catalysts in promoting the hydrolysis reaction. This postponed the formation of particles and hence smaller particle size. Electrical measurements found that the base-catalyzed hybrids possess lower dielectric constants (κ = 2.40 at nominal Si content = 0.4 mol) due to the absence of polar groups and formation of silica xerogels with high porosity in the samples. In both hybrids, leakage current densities increase with the increase of Si content. However, leakage current density of base-catalyzed hybrid was higher than that of acid-catalyzed hybrid at the same Si content due to the smaller particle size and highly porous feature of organosilicate embedded in the base-catalyzed hybrids.     

Influence of preparation method on hydroxyapatite porous scaffolds

Hydroxyapatite (HA) is extensively used in medical applications as an artificial bone because of its similarity to the natural components of human bones and for its excellent biocompatibility. The porous structure of HA ceramics is more generally used as a scaffold. Many techniques, which are performed under fluid system, have been applied to fabricate HA porous scaffolds. In this work, polymeric sponge technique was employed in the preparation of HA slurry appropriated for porous ceramic fabrication. Effort for strength improvement was made on porous HA ceramic in several aspects. The effect of HA/water, binder/plasticizer ratios and dispersant content on the rheological properties of HA suspension in combination with the addition of SiC and SiO₂ on the compressive strength of porous bodies were investigated and discussed.     

镁-镍合金催化剂制备及纳米碳管生长模式研究

采用多元醇法制备镁-镍合金纳米粉末,并以此为催化剂制备纳米碳管,利用比表面和孔径分布测定仪、X射线衍射仪和透射电镜,研究镁-镍合金催化剂的性能和纳米碳管的生长模式。结果表明:Mg∶Ni值对镁-镍合金催化剂特性影响较大,其中Mg∶Ni为1的催化剂颗粒比表面积较大且平均粒径较小;聚乙烯吡咯烷酮(PVP)用量增大,有利于提高催化剂颗粒的比表面积、减小平均粒径,但用量过大不利于Mg2Ni合成。在以镁-镍合金为催化剂制备碳纳米管的过程中,首先在催化剂表面形成碳膜,随后形成的碳膜将前期形成的碳膜及催化剂颗粒向外推挤,催化剂颗粒移动后遗留下中空隧道,最终形成碳管,由于纳米碳管尖端的催化剂颗粒反应后失去催化活性,碳管的生长动力主要来自碳管根部。