Plasma Syntheses of Carbon Nanotube-Supported Pt-Pd Nanoparticles

It is reported that the highly dispersed Pt nanoparticles on carbon nanotubes can be synthesized under mild conditions by in situ plasma treatment.The carbon nanotube was pretreated by O₂ plasma to transform into oxide carbon nanotubes（O-CNTs）,and then it was mixed with the precursors（the mixture of H₂ PtCl₆and PdCl₆）.After that,the O-CNTs and the precursors were simultaneously treated by H₂ plasma.The precursors were transformed into Pt-Pd nanoparticles（NPs）and the O-CNTs transformed into CNT.The synthesized CNT-based Pt-Pd nanoparticles were characterized by scanning electron microscopy,transmission electron microscopy,X-ray diffraction and X-ray photoelectron spectroscopy.All the analysis showed that the Pt-Pd nanoparticles were deposited on CNT as a form of face-centered cubical structure.     

Preparation and characterization of graphene nanoribbons

Graphene nanoribbons(GNRs) have been synthesized by unzipping oxidized multiwalled carbon nanotubes.The thickness of the GNRs synthesized is ranged from mono-layer to four layers.The morphology of prepared GNRs is strongly dependent on structure and defects of the MWCNTs.The synchrotron radiation X-ray diffractions show the d(002) spacing of the GNRs decreases with the increase of the annealing temperature.This may be caused by the removing of water molecules and oxygen-containing functional groups in the GNRs.     

Study on deposition of Al2O3 films by plasma-assisted atomic layer with different plasma sources

In this paper,A12O3 thin films are deposited on a hydrogen-terminated Si substrate by using two home-built electron cyclotron resonance (ECR) and magnetic field enhanced radio frequency plasma-assisted atomic layer deposition (PA-ALD) devices with Al(CH3)3 (trimethylaluminum,TMA) and oxygen plasma used as precursor and oxidant,respectively.The thickness,chemical composition,surface morphology and group reactions are characterized by in situ spectroscopic ellipsometer,x-ray photoelectric spectroscopy,atomic force microscopy,scanning electron microscopy,a high-resolution transmission electron microscope and in situ mass spectrometry (MS),respectively.We obtain that both ECR PA-ALD and the magnetic field enhanced PA-ALD can deposit thin films with high density,high purity,and uniformity at a high deposition rate.MS analysis reveals that the A12O3 deposition reactions are not simple reactions between TMA and oxygen plasma to produce alumina,water and carbon dioxide.In fact,acetylene,carbon monoxide and some other by-products also appear in the exhaustion gas.In addition,the presence of bias voltage has a certain effect on the deposition rate and surface morphology of films,which may be attributed to the presence of bias voltage controlling the plasma energy and density.We conclude that both plasma sources have a different deposition mechanism,which is much more complicated than expected.     

利用粒子辐照技术实现碳纳米管向金刚石的转变

采用低能氢等离子体和中能C^ 离子束辐照技术相结合的方法,实现了碳纳米管向金刚石纳米晶粒的转变,完成了一个从有序(碳纳米管)到无序(无定形碳纳米线)再到有序(金刚石纳米晶)的转变过程。利用透射电子显微镜(TEM)、选区电子衍射(SAD)和拉曼光谱(Raman)等研究了晶粒的微观结构,并对纳米金刚石晶粒的生成机理进行了初步探讨。     

EACVD沉积金刚石过程中气相化学研究

利用热阴极直流等离子体化学气相沉积技术分别在ＣＨ４－Ｈ２和Ｃ２Ｈ５ＯＨ－Ｈ２两种不同的工作环境中沉积金刚石膜,同时利用发射光谱对等离子体气相环境进行了原位诊断。在ＣＨ４－Ｈ２和Ｃ２Ｈ５ＯＨ－Ｈ２两种体系中,探测到Ｈ原子和ＣＨ、ＣＨ＾＋、Ｃ２等多种碳氢粒子,发现ＣＨ和ＣＨ＾＋有益于金刚石生长,而Ｃ２是非金刚石相的生长基团。与ＣＨ４－Ｈ２体系所不同的是,在Ｃ２Ｈ５ＯＨ－Ｈ２体系中,还产生了ＣＨＯ、ＣＨ     

Plasma Activation of Integrated Carbon Nanotube Electrodes for Electrochemical Detection of Catechol

In this study, integrated multi-wall carbon nanotube （MWCNT） electrodes were prepared in the holes of glass directly by microwave plasma chemical vapour deposition （MWPCVD）. The electrochemical behaviour of catechol at the integrated MWCNT electrodes was investigated. The oxygen plasma treated CNT electrodes had better electrochemical performance for the analysis of catechol than that of as-synthesized CNT electrodes. Both the as-synthesized CNTs and plasma treated CNTs were characterized by TEM（transmission electron microscopy, XPS（X-ray photoelectron spectroscopy） and Raman spectroscopy. The results revealed that the oxygen plasma activation is an effective method to enhance the electrochemical properties of CNT electrodes.     

N_2O Decomposed by Discharge Plasma with Catalysts

A great deal of attention has been focused on discharge plasma as it can rapidly decompose N_2O without additives,which is not only a kind of greenhouse gas but also a kind of damages to the ozone layer.The thermal equilibrium plasma is chosen to combine with catalysts to decompose N_2O,and its characteristics are analyzed in the present paper.The results indicate that NO and NO_2 were formed besides N_2 and O_2 during N_2O decomposition when N_2O was treated merely by discharge plasma.Concentration of NO declined greatly when the discharge plasma was combined with catalysts.Results of Raman spectra analysis on CeO_2,Ce_(0.75)Zr_(0.25)O_2and Ce_(0.5)Zr_(0.5)O_2 imply that the products selectivity has been obviously improved in discharge plasma decomposing N_2O because of the existence of massive oxygen vacancies over the composite oxide catalysts.     

CO2 Reforming of CH4 by Atmospheric Pressure Abnormal Glow Plasma

A novel plasma atmospheric pressure abnormal glow discharge was used to investigate synthesis gas production from reforming methane and carbon dioxide. Special attentions were paid to the discharge characteristics and CH4, CO2 conversion, H2, CO selectivity, and ratio of H2/CO varied with the changing of discharging power, the total flux, and the ratio of CH4/CO2. Experiments were performed in wider operation variables, the discharging power of 240 to 600 W, the CH4/CO2 of 0.2 to 1.0 and the total flux of 140 to 500mL/min. The experiments showed that the conversion of CH4 and CO2 was up to 91.9% and 83.2%, the selectivity of CO and H2 was also up to 80% and 90% and H2/CO mole ratio was 0.2 to 1.2, respectively. A brief analysis for discharge characteristics and the experimental results were given.     

Effect of Gas Sources on the Deposition of Nano-Crystalline Diamond Films Prepared by Microwave Plasma Enhanced Chemical Vapor Deposition

Nano-crystalline diamond (NCD) films were deposited on silicon substrates by a microwave plasma enhanced chemical vapor deposition (MPCVD) reactor in C2H5OH/H2 and CH4/H2/O2 systems, respectively, with a constant ratio of carbon/hydrogen/oxygen. By means of atomic force microscopy (AFM) and X-ray diffraction (XRD), it was shown that the NCD films deposited in the C2H5OH/H2 system possesses more uniform surface than that deposited in the CH4/H2/O2 system. Results from micro-Raman spectroscopy revealed that the quality of the NCD films was different even though the plasmas in the two systems contain exactly the same proportion of elements. In order to explain this phenomenon, the bond energy of forming OH groups, energy distraction in plasma and the deposition process of NCD films were studied. The experimental results and discussion indicate that for a same ratio of carbon/hydrogen/oxygen, the C2H5OH/H2 plasma was beneficial to deposit high quality NCD films with smaller average grain size and lower surface roughness.     

CxH1-x薄膜制备

以反式－２－丁烯为主工作气体,采用低压等离子体化学气相沉积法制备ＣｘＨ１－ｘ薄膜,研究了在不同的Ｈ２与反式２－丁烯流量比下制备的ＣｘＨ１－ｘ薄膜的傅里叶变换红外光谱（ＦＴ－ＩＲ）及ＸＰＳ谱的特性,初步探讨了ＣｘＨ１－ｘ的生长机理,膜中ｓｐ＾３杂化碳原子和ｓｐ＾２杂化碳原子的数量以及两者的比例与沉积条件有关。     

Synthesis of Carbon Nanotubes by MWPCVD at Low Temperature

Growth of carbon nanotubes(CNTs) at low temperature is very important to the applications of nanotubes.In this paper,under the catalytic effect of cobalt nanoparticles supported by SiO2,CNTs were synthesized by microwave plasma chemical vapor deposition(MWPCVD) below 500℃.It demonstrates that MWPCVD can be a very efficient process for the synthesis of CNTs at low temperature.     

Conversion of coalbed methane surrogate into hydrogen and graphene sheets using rotating gliding arc plasma

The use of atmospheric rotating gliding arc(RGA) plasma is proposed as a facile, scalable and catalyst-free approach to synthesizing hydrogen(H_2) and graphene sheets from coalbed methane(CBM). CH_4 is used as a CBM surrogate. Based on a previous investigation of discharge properties, product distribution and energy efficiency, the operating parameters such as CH_4 concentration, applied voltage and gas flow rate can effectively affect the CH_4 conversion rate,the selectivity of H_2 and the properties of solid generated carbon. Nevertheless, the basic properties of RGA plasma and its role in CH_4 conversion are scarcely mentioned. In the present work, a 3D RGA model, with a detailed nonequilibrium CH_4/Ar plasma chemistry, is developed to validate the previous experiments on CBM conversion, aiming in particular at the distribution of H_2 and other gas products. Our results demonstrate that the dynamics of RGA is derived from the joint effects of electron convection, electron migration and electron diffusion, and is prominently determined by the variation of the gas flow rate and applied voltage. Subsequently,a combined experimental and chemical kinetical simulation is performed to analyze the selectivity of gas products in an RGA reaction, taking into consideration the formation and loss pathways of crucial targeted substances(such as CH_4, C_2H_2, H_2 and H radicals) and corresponding contribution rates. Additionally, the effects of operating conditions on the properties of solid products are investigated by scanning electron microscopy(SEM) and Raman spectroscopy. The results show that increasing the applied voltage and decreasing CH_4 concentration will change the solid carbon from its initial spherical structure into folded multilayer graphene sheets, while the size of the graphene sheets is slightly affected by the change in gas flow rate.     

Radionuclides in primary coolant of a fluoride salt-cooled high-temperature reactor during normal operation

The release of fission products from coated particle fuel to primary coolant,as well as the activation of coolant and impurities,were analysed for a fluoride salt-cooled high-temperature reactor (FHR) system,and the activity of radionuclides accumulated in the coolant during normal operation was calculated.The release rate (release fraction per unit time) of fission products was calculated with STACY code,which is modelled mainly based on the Fick's law,while the activation of coolant and impurities was calculated with SCALE code.The accumulation of radionuclides in the coolant has been calculated with a simplified model,which is generally a time integration considering the generation and decay of radionuclides.The results show that activation products are the dominant gamma source in the primary coolant system during normal operation of the FHR while fission products become the dominant source after shutdown.In operation condition,health-impacts related nuclides such as 3H,and 14C originate from the activation of lithium and coolant impurities including carbon,nitrogen,and oxygen.According to the calculated effective cross sections of neutron activation,6Li and 14N are the dominant 3H production source and 14C production source,respectively.Considering the high production rate,3H and 14C should be treated before being released to the environment.     

Colorimetric quantification of aqueous hydrogen peroxide in the DC plasma-liquid system

The quantification of hydrogen peroxide(H_2O_2) generated in the plasma-liquid interactions is of great importance, since the H_2O_2 species is vital for the applications of the plasma-liquid system.Herein, we report on in situ quantification of the aqueous H_2O_2(H_2O_2 aq) using a colorimetric method for the DC plasma-liquid systems with liquid as either a cathode or an anode. The results show that the H_2O_2 aqyield is 8–12 times larger when the liquid acts as a cathode than when the liquid acts as an anode. The conversion rate of the gaseous OH radicals to H_2O_2 aqis 4–6 times greater in the former case. However, the concentrations of dissolved OH radicals for both liquid as cathode and anode are of the same order of tens of n M.     

Radionuclides in primary coolant of a fluoride salt-cooled high-temperature reactor during normal operation

The release of fission products from coated particle fuel to primary coolant,as well as the activation of coolant and impurities,were analysed for a fluoride saltcooled high-temperature reactor (FHR) system,and the activity of radionuclides accumulated in the coolant during normal operation was calculated.The release rate (release fraction per unit time) of fission products was calculated with STACY code,which is modelled mainly based on the Fick's law,while the activation of coolant and impurities was calculated with SCALE code.The accumulation of radionuclides in the coolant has been calculated with a simplified model,which is generally a time integration considering the generation and decay of radionuclides.The results show that activation products are the dominant gamma source in the primary coolant system during normal operation of the FHR while fission products become the dominant source after shutdown.In operation condition,health-impacts related nuclides such as 3H,and 14C originate from the activation of lithium and coolant impurities including carbon,nitrogen,and oxygen.According to the calculated effective cross sections of neutron activation,6Li and 14N are the dominant 3H production source and 14C production source,respectively.Considering the high production rate,3H and 14C should be treated before being released to the environment.     

Synthesis of (B-C-N) Nanomaterials by Arc Discharge Using Heterogeneous Anodes

In spite of the current prevalence of the CVD-based processes,the electric arc remains an interesting process for the synthesis of carbon nanoforms,thanks to its versatility,robustness and easiness.It also allows performing in-situ substitution of carbon atoms by hetero-elements in the graphene lattice.Our work aims to establish a correlation between the plasma properties,type and chemical composition (and the substitution rate) of the obtained single-wall carbon nanotubes.The plasma was characterized by optical emission spectroscopy and the products were analyzed by high resolution transmission electron microscopy and core level Electron Energy-Loss Spectroscopy (EELS).Results show that a high boron content leads to a plasma temperature decrease and hinders the formation of nanotubes.This effect can be compensated by increasing the arc current and/or yttrium content.The optimal conditions for the synthesis of boron-and/or nitrogen-substituted nanotubes correspond to a high axial plasma temperature associated to a strong radial gradient.EELS analysis confirmed that the boron incorporates into the graphenic lattice.     

Plasma-assisted Ru/Zr-MOF catalyst for hydrogenation of CO2 to methane

As an important type of metal–organic framework (MOF), Zr-MOF shows excellent CO₂ adsorption performance. In this work, a Zr-MOF was synthesized by a solvothermal method and adopted to support Ru through simple incipient-wetness impregnation. Then the Ru/Zr-MOF was applied for CO₂ hydrogenation (V_H2 : V_CO2= 4:1) with the assistance of dielectric barrier discharge (DBD) plasma. The hydrogenation of CO₂ results showed that methane was produced selectively under the synergistic effect between plasma and the Ru/Zr-MOF catalyst, and the selectivity and yield of methane reached 94.6% and 39.1%, respectively. The XRD and SEM analyses indicate that the basic crystalline phase structure and morphology of the Zr-MOF and Ru/Zr-MOF remained the same after DBD plasma treatment, suggesting that the catalysts are stable in plasma. The guest molecules in the pores of the Zr-MOF are removed and the Ru³⁺ ions are reduced to metallic Ru⁰ in the reduction atmosphere according to the BET and XPS results, which are responsible for the high performance of plasma with the Ru/Zr-MOF catalyst. In situ optical emission spectra of pure plasma, plasma with Zr-MOF, and plasma with Ru/Zr-MOF were measured, and the active species of C, H and CH for CO₂ hydrogenation were detected. The plasma-assisted Ru/Zr-MOF exhibited high catalytic activity and stability in CO₂ hydrogenation to methane, and it has great guiding significance for CO₂ hydrogenation by using plasma and MOF materials.     

碳掺杂氮化硼纳米管吸附气体小分子的DFT计算

采用密度泛函理论研究了氮化硼纳米管(Boron nitride nanotubes,BNNTs)及碳掺杂氮化硼纳米管对O2、NO2、F2气体小分子的气敏特性。计算了三种气体小分子吸附在氮化硼纳米管及碳掺杂氮化硼纳米管表面不同位置时的吸附能、相互作用距离,同时还计算得到了气体分子分别吸附在碳掺杂BNNTs不同位置时的电子态密度。研究结果表明,氮化硼纳米管对O2、NO2、F2气体分子比较敏感,碳掺杂氮化硼纳米管可以明显地改变其表面的化学反应活性,增强气体分子与氮化硼纳米管之间的相互作用。     

OH and O radicals production in atmospheric pressure air/Ar/H2O gliding arc discharge plasma jet

Atmospheric pressure air/Ar/H_2O gliding arc discharge plasma is produced by a pulsed dc power supply. An optical emission spectroscopic(OES) diagnostic technique is used for the characterization of plasmas and for identifications of OH and O radicals along with other species in the plasmas. The OES diagnostic technique reveals the excitation Tx?≈?5550–9000 K, rotational Tr?≈?1350–2700 K and gas Tg?≈?850–1600 K temperatures, and electron density n?(1.1-1.9) ′101 4 cm~(-3) e under different experimental conditions. The production and destruction of OH and O radicals are investigated as functions of applied voltage and air flow rate. Relative intensities of OH and O radicals indicate that their production rates are increased with increasing Ar content in the gas mixture and applied voltage. nereveals that the higher densities of OH and O radicals are produced in the discharge due to more effective electron impact dissociation of H_2O and O_2 molecules caused by higher kinetic energies as gained by electrons from the enhanced electric field as well as by enhanced n e.The productions of OH and O are decreasing with increasing air flow rate due to removal of Joule heat from the discharge region but enhanced air flow rate significantly modifies discharge maintenance properties. Besides, Tgsignificantly reduces with the enhanced air flow rate. This investigation reveals that Ar plays a significant role in the production of OH and O radicals.     

内嵌金属的多壁碳纳米管辐射损伤研究

辐射损伤性能是制约核电池效能和使用寿命的重要因素。美国研究者Popa-Simil提出基于碳纳米管、金属复合结构材料的概念核电池,可实现核能到电能的高效转换,其设计中利用了碳纳米管的抗辐射损伤特性。本文通过建立包覆金属铜的多壁碳纳米管模型,采用分子动力学方法,对内嵌金属的多壁碳纳米管体系进行了辐射损伤的模拟研究。从配位缺陷数、溅射原子数、完美结构缺陷(Perfect structure defect,PST)原子数以及总的辐射损伤量等方面,与无内嵌金属的碳纳米管体系进行了分析对比。发现在有金属铜内嵌的情况下,溅射原子产额与无金属内嵌情况差别不大,但配位数缺陷和PST缺陷减小。表明内嵌金属起到支撑的效果,降低多壁碳纳米管在辐照下的形变,增强了其自修复能力,从而使得辐照耐受性能有所增强。