铜/碳纳米管复合粒子的制备及其对高氯酸铵热分解性能研究

以碳纳米管为载体, 用化学沉积法制备了Cu/CNTs复合粒子, 并用TEM、SEM、FT-IR、XRD、XPS和DTA对其表观形貌、结构及催化性能进行了表征. 结果表明, CNTs和Cu之间无论是简单混合还是复合, 对高氯酸铵(AP)的热分解均有催化作用. 与纯AP相比, Cu/CNTs复合粒子中的AP高温分解峰温降低126.3℃, 低温分解峰几乎消失, 表观分解热由309.92J/g提高到711.13J/g; 与简单混合物相比, 复合粒子中的AP高温分解峰温降低11.4℃, 表观分解热由494.06J/g提高到711.13J/g. 表明CNTs与Cu的复合处理可显著提高其对AP热分解反应的催化作用.     

Preparation and characterization of rice-shaped MnO2/CNTs composite and superior catalytic activity on thermal decomposition of ammonium perchlorate

Manganese dioxides (MnO₂) were successfully deposited on carbon nanotubes (CNTs) surface by redox reaction between potassium permanganate and CNTs. The characterization results showed that the MnO₂ exhibited the rice-shaped nanostructure with about 5～10 nm in width and 10～30 nm in the length on CNTs. The solvothermal temperature of composite can greatly affected its morphology and structure to improve the thermal catalytic on ammonium perchlorate (AP) decomposition. Compared with other samples, the prepared composite at 120°C exhibited superior catalytic performance, as 3wt% of composite added in AP, the second exothermic peak temperature decreased by 160.2°C and the apparent release heat of the thermal decomposition of AP which is four times of that of pure AP. A possible mechanism for formation the rice shaped MnO₂/CNTs composite is also presented.     

纳米金刚石负载Fe2O3的制备及其对高氯酸氨的热分解催化作用

对纳米金刚石（ND）进行羧基化处理以提高其分散性,然后采用沉淀法制备了羧基化ND负载Fe₂O₃的催化剂。利用XRD、TG、BET和TEM对该负载型催化剂进行表征,通过DSC研究其对高氯酸铵(AP)热分解的催化作用。结果表明:ND经过羧基化处理后,在水中的分散性大幅度提高。沉淀法制备了直径5 nm、长50 nm的Fe₂O₃包裹或附着于ND的负载型复合催化剂,该催化剂对AP高温热分解的催化效果优于单一的Fe₂O₃或ND。当Fe₂O₃和ND的质量比为5∶1、在AP中添加质量分数2%的复合催化剂时,AP的高温分解峰温降低约30 ℃,ND负载Fe₂O₃催化剂具有一定的协同催化作用。     

Simple method for synthesis of carbon nanotubes over Ni-Mo/Al2O3 catalyst via pyrolysis of polyethylene waste using a two-stage process

Synthesis of valuable multi-walled carbon nanotubes (MWCNTs) by thermal pyrolysis of low-density polyethylene (LDPE) waste was investigated via a two-stage process. The first stage was the thermal pyrolysis of LDPE to gaseous hydrocarbons, and the second stage was the catalytic decomposition of the pyrolysis gases over Ni-Mo/Al₂O₃ catalysts. Two catalysts with the compositions of 5.2%Ni-10.96%Mo/Al₂O₃ and 10%Ni-9.5%Mo/Al₂O₃ were tested for carbon nanotubes (CNTs) formation. The catalyst containing 10%Ni showed better activity in terms of CNTs production. Accordingly, the impact of either pyrolysis or decomposition temperatures was investigated using the 10%Ni-9.5%Mo/Al₂O₃ catalyst. TEM, XRD, Raman spectroscopy, TGA, TPR, and BET analysis tools were used to characterize the fresh catalysts as well as the obtained carbon nanomaterials. TEM images proved that MWCNTs with various morphological structures were obtained at all pyrolysis and decomposition temperatures. Moreover, cup-stacked carbon nanotubes (CS-CNTs) were observed at the decomposition temperature of 600°C. MWCNTs with the best quality were produced at decomposition temperature of 750°C. The optimum pyrolysis and decomposition temperatures in terms of CNTs production were at 700 and 650°C, respectively.     

碳纳米管负载金属氮化物催化剂的制备及其性能研究

采用等体积浸渍法结合程序升温还原技术制备出一系列负载型过渡金属氮化物催化剂。利用XRD、BET、TPR等表征手段,结合氨分解制氢反应,研究了它们的表面性质和反应性能。发现改性碳纳米管负载的氮化钴催化剂具有较大的比表面积,对氨分解制氢反应的催化活性最高。新鲜态CoNx/CNTs催化剂的比表面积可达151.85m2/g,在650℃时氨转化率为80.3%,850℃达到完全转化。     

Fe2O3纳米粒子的醋酸改性对其催化高氯酸铵热分解的影响

利用表面改性法对Fe2O3纳米粒子进行醋酸改性,用TEM和纳米粒度测试仪对Fe2O3纳米粒子进行了形貌和粒度表征,用FTIR和XPS对改性后的Fe2O3纳米粒子进行了结构表征,用DTA研究了醋酸改性处理对Fe2O3纳米粒子的高氯酸铵(AP)热分解催化性能的影响.结果表明,用凝胶-溶胶法制备了平均粒径为40nm,窄粒度分布的Fe2O3纳米粒子,醋酸改性处理改善了Fe2O3纳米粒子的分散性.FTIR和XPS结果表明,Fe2O3纳米粒子与醋酸分子发生了化学键合.DTA结果表明,Fe2O3纳米粒子的醋酸改性能提高Fe2O3纳米粒子的AP热分解催化性能;随着Fe2O3纳米粒子含量的增加,醋酸改性的效果越明显.     

Patterning of catalysts for the selective growth of carbon nanotubes using laser irradiation of nickel nitrate

We developed a simple method to produce patterned catalysts for the growth of carbon nanotubes (CNTs) on Si substrate using laser irradiation of Ni nitrate. We found that Ni nitrate can easily be decomposed into Ni oxide by KrF laser irradiation and that unexposed Ni nitrate can be removed using deionized (DI) water. Once we obtained patterned Ni oxide, we were able to synthesize multi-walled CNTs using a conventional thermal CVD. This new method does not require any photoresist or vacuum processes. Not only is the method compatible with low-temperature and large-area fabrication, it also significantly reduces the total processing steps required for conventional lithographic patterning technology. A detailed investigation of the decomposition process of this patterned catalyst and the microstructure of the patterned multi-walled CNTs was carried out using IR, SEM and TEM.     

Solution-processed Ni–CNTs filled ferroelectric P(VDF–TrFE) composites with improved dielectric properties and thermal conductivity

Dielectric composites made using two kinds of poly(vinylidene fluoride–trifluoroethylene) [P(VDF–TrFE)] (70/30 and 80/20 mol%) as polymer matrices and nickel particles coated carbon nanotubes (Ni–CNTs) as filler were developed via solution-processed method. The scanning electron microscopy (SEM) indicated good compatibility and dispersion of Ni–CNTs in the P(VDF–TrFE) matrix. Ni–CNTs/P(VDF–TrFE) composites exhibited high dielectric constants with low dielectric losses. The maximum dielectric constants of Ni–CNTs/P(VDF–TrFE) composites of 198 and 185 at 100 Hz were obtained at 18.0 wt% Ni–CNTs loading, respectively. The incorporation of Ni–CNTs in the P(VDF–TrFE) matrix resulted in enhanced thermal conductivity. The highest values, obtained at 18.0 wt% Ni–CNTs loading, were 1.05 and 1.03 W/m K, respectively. Although there were no very obvious difference, the dielectric properties and thermal conductivity of Ni–CNTs/P(VDF–TrFE) 70/30 mol% composites were slightly better to those of Ni–CNTs/P(VDF–TrFE) 80/20 mol% composites in many cases. The aforementioned results suggest that these high-performance composites hold great promise for application in electrical and electronic field.     

Cu/Fe hydrotalcite derived mixed oxides as new catalyst for thermal decomposition of ammonium perchlorate

Cu/Fe mixed oxides (Cu/Fe-MOs) were prepared by calcination of Cu/Fe hydrotalcite (Cu/Fe-HT) precursors. They were used as new catalyst for thermal decomposition of ammonium perchlorate (AP) and their catalytic activity was studied by thermal gravimetric and differential thermal analysis. With the addition of 4 wt.% Cu/Fe-MOs, thermal decomposition of AP was accelerated by 104 °C. Higher catalyst addition favors further decomposition of AP. The catalytic activity order is: Cu/Fe-MOs-500 > Cu/Fe-MOs-800 > CuO·Fe₂O₃. The proposed catalytic mechanism is the presence of O₂⁻ on the surface of Cu/Fe-MOs which can simplify thermal decomposition of AP.     

Influence of co-catalyst on growth of carbon nanotubes using alcohol catalytic CVD method

This paper describes the influence of a co-catalyst on growth of carbon nanotubes (CNTs) by alcohol catalytic chemical vapour deposition (ACCVD) method. Silicon wafers covered with thermal oxide or polycrystalline diamond thin film were used as substrates. Ni thin film supported with Al, Cu or Ti was used as a catalyst. The films were deposited by pulsed laser deposition technique. Comparison of the various types of the co-catalyst (Al, Cu, Ti) leads to the conclusion that Cu co-catalyst is suitable for producing very thin single wall carbon nanotubes (SWCNTs) and combination of Al and Ni provide a good condition to the catalytic growth of CNTs. In addition, we observed also the influence of the various diffusion barriers (thermal oxide and polycrystalline diamond) on growth of CNTs. Prepared samples were analysed by Raman spectroscopy (RS) and scanning electron microscopy (SEM).     

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。     

Synthesis of binary and triple carbon nanotubes over Ni/Cu/Al2O3 catalyst by chemical vapor deposition

Novel binary and triple carbon nanotubes (CNTs) with one common catalytic particle encapsulated have been synthesized using Ni/Cu/Al₂O₃ catalyst, which was produced by a sol-gel method. But when using Ni/Al₂O₃ as catalyst, a mass of common CNTs, that is, one CNT with one catalytic particle encapsulated, was obtained. The results showed that copper-element doping to the Ni/Al₂O₃ catalyst played a key role in the synthesis of CNTs, signifying a novel approach to modify the Ni/Al₂O₃ catalyst. Based on the transmission electron microscopy observations, a simple growth mechanism was developed to describe the growth of the binary or triple CNTs, which could be well explained by a diffusion segregation process.     

负载型纳米NiO催化高氯酸铵热分解的DSC/TG-MS研究

采用浸渍法制备出纳米NiO/MgO,运用X射线衍射(XRD)、透射电子显微镜(TEM),X射线能谱仪(EDS)等对产物的物相和组成进行了表征,利用DSC/TGMS研究了纳米NiO/MgO对高氯酸按(AP)热分解的催化作用.结果表明,在纳米NiO/Mgo的催化作用下,AP的热分解高温分解峰温度降低92.2℃,表观分解热增...     

Hydrocarbon and Fluorocarbon Monitoring by MIS Sensors Using an Ni Catalytic Thermodestructor

An increase in the number of gases detectable by sensors based on Pd-SiO₂-Si (MIS) and Pt-LaF₃-Si₃N₄ -SiO₂-Si (MEIS) structures was achieved by the application of an external catalyst element (CE). It was shown that as a result of the decomposition of hydrocarbon and fluorocarbon molecules on a Ni coil (CE), the products detectable by metal-insulator-semiconductor (MIS) and metal-electrolyte-insulator-semiconductor (MEIS) sensors are formed. The simultaneous catalytic oxidation of hydrocarbons and their thermal decomposition result in an optimum CE temperature of about 1050 K for propane. The kinetics of the thermal decomposition of gases on Ni were investigated. The activation energy of the reaction for C₃ H₈ and the enthalpy in the case of CF₃-CCl were estimated     

Synthesis and characterization of KNd2Ti3O9.5 nanocrystal and its catalytic effect on decomposition of ammonium perchlorate

A novel kind of perovskite type oxide KNd₂Ti₃O_9.5 nanocrystals with an average size of 12 nm were successfully fabricated by a stearic acid sol–gel method (SAM) using Ti(OBu)₄, KOH, Nd₂O₃ and stearic acid as the raw materials. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the products. The catalytic effect of the KNd₂Ti₃O_9.5 nanoparticles on thermal decomposition of ammonium perchlorate (AP) was investigated by differential thermal analysis (DTA) and thermal gravimetry (TG) experiments. Results indicated that the obtained KNd₂Ti₃O_9.5 nanocrystals took on cubic structure and presented both good dispersibility and uniform crystallite size. Also, they have an intense catalytic effect on the thermal decomposition of AP. Adding 2% of KNd₂Ti₃O_9.5 nanoparticles to AP can obviously decrease the thermal decomposition temperature of AP by 50 °C, increase the heat of decomposition from 590 J g⁻¹ to 1659 J g⁻¹ and obviously quicken the decomposition reaction rate.     

Preparation,characterization and catalytic behavior of copper oxide nanoparticles on thermal decomposition of ammonium perchlorate particles

In this study, copper oxide nanoparticles (CuO NPs) with mean particle size of 43–32?nm were prepared by wet grinding of commercial micronized CuO powders in a high-energy wet ball-milling apparatus during 20 and 30?h, respectively. X-ray diffraction (XRD) and field emission scanning electron microscope (FE-SEM) analyses were used to characterize the structure, mean particle size and morphology of the resulting CuO NPs. The results confirmed that the CuO NPs obtained at different milling times consist of nanostructures with nearly spherical morphology and by increasing the milling time, smaller particle size was obtained. The catalytic activities of the synthesized CuO NPs on the thermal decomposition of ammonium perchlorate (AP) particles were examined through differential scanning calorimetry and thermogravimetry (DSC/TG) analyses. Evaluation of the experimental results illustrated that the surfaces of CuO NPs were effectively coated with AP particles and by adding 5%CuO NPs with 32?nm, the thermal decomposition temperature of the treated particles reduced by 83.0°C and the heat of decomposition reached 1553.7?Jg^?1. Moreover, the kinetic and thermodynamic parameters of the thermal decomposition of pure and AP?+?5%CW30 nanocomposites have been investigated by using the Kissinger, Boswell and Ozawa methods.     

Growth of carbon nanotubes on glass substrate by MPECVD

We have grown carbon nanotubes (CNTs) with a microwave plasma-enhanced chemical vapor deposition (MPECVD) method, which has been regarded as one of the most promising candidates for the synthesis of CNTs due to the vertical alignment, the low temperature and the large area growth. We had used methane (CH₄) and hydrogen (H₂) gas for the growth of CNTs. 10-nm-thick Ni catalytic layer were deposited on the Ti-coated glass substrate by RF magnetron sputtering method. In this work, we report the low-temperature growing properties of the CNTs on glass substrate with a MPECVD. We have pretreated the Ni/Ti/glass catalytic layer in different microwave power (600, 700, 800, and 900 W) and grown the CNTs in the same microwave power (800 W). SEM (Scanning electron microscopy) images of the Ni catalytic layer shows the diameter and density variation to be dependent with the pretreatment conditions. Raman spectroscopy of CNTs shows that the synthesized CNTs were multi-wall CNTs.     

Growth of carbon nanotubes over Fe-Co and Ni-Co catalysts supported on different phases of TiO2 substrate by thermal CVD

The aim of this work is to examine the properties of CNTs formed on Fe-Co and Ni-Co bimetallic catalysts supported on different phases of TiO₂ (anatase and rutile) by wet impregnation method. The CNTs are grown from decomposition of acetylene via Thermal CVD at 700°C using the prepared catalysts. The nanomaterials were characterized by XRD, Xmap, BET, FESEM, TEM, and Raman spectroscopy. It was found that the catalyst samples supported on rutile TiO₂ have higher specific surface area, smaller catalytic nanoparticles with denser distribution and very more activity compared to anatase ones. Consequently, the CNTs nucleated from nanoparticles supported on rutile TiO₂ possess higher density, smaller average diameters and narrower diameter distribution compared to grown CNTs on anatase samples. Moreover, it was observed that the Fe-Co bimetallic catalysts regardless of TiO₂ support phase, possesses more catalytic activity and higher average growth rate of CNTs in compare with Ni-Co catalysts.     

Preparation of nanometer CuFe2O4 by auto-combustion and its catalytic activity on the thermal decomposition of ammonium perchlorate

Nanometer copper ferrite was synthesized by auto-combustion method using cupric nitrate, ferric nitrate and malic acid as raw materials. The precursor and as-burnt sample were characterized by X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) . Average particle size of sample is 26nm. The catalytic performance of nanometer CuFe₂O₄ on the thermal decomposition of ammonium perchlorate (AP) was investigated by DTA. The results show that the nanometer CuFe₂O₄ has high a catalytic activity, and the thermal decomposition temperature of AP shift 105 °C downward with the effect of nanometer copper ferrite. When the content of CuFe₂O₄ comes to 5%, the catalytic performance is the best.     

水热法合成氧化镍-二氧化硅催化剂及其用于碳纳米管的制备

以硝酸镍和正硅酸乙酯为原料，制得Ni(OH)2／SiO2二元胶体，经水热晶化法和常压干燥法分别合成了纳米级氧化镍-二氧化硅复合粉体催化剂}用这两种催化剂在相同催化裂解条件下分别制得了多壁碳纳米管；采用XRD和TEM等测试手段对两种催化剂物相、形貌及由两种催化剂制得的碳纳米管形态、收率及纯度作了比较，结果表明：水热晶化法比常压干燥法合成的催化剂粉体颗粒粒径小(为10～20nm），分散性好，催化活性高，使得所制得的碳纳米管管径小(为10～16nm)、分布窄、纯度和收率都相对较高；同时对用不同水热反应温度合成的催化剂(物相不同)制备碳纳米管进行了研究。