柠檬酸盐稳定法制备直接甲醇燃料电池高活性Pt/C催化剂

采用不同还原剂和碳载体,通过柠檬酸盐稳定法制备直接甲醇燃料电池用担载量为60%的Pt/C催化剂,通过X射线衍射（XRD）,透射电子显微镜（TEM）和循环伏安（CV）等手段对催化剂进行表征。结果表明：柠檬酸盐加入和还原剂优化可以很好地控制铂纳米颗粒的粒径,而碳载体的选择对催化剂的电催化活性有很大影响。在采用柠檬酸钠做稳定剂、甲醛做还原剂、BP2000碳粉做载体的条件下,制备的60%Pt/BP2000催化剂性能最佳,平均粒径约2nm,电化学活性面积为66.46m2/g。使用该材料作为阴极催化剂的直接甲醇燃料电池单电池最大功率密度可达到78.8mW/cm2。     

碳载铂纳米微粒修饰的玻碳电极对甲醇的电催化氧化

利用X射线粉末衍射、透射电镜和扫描电镜对商用Pt/C催化剂反应前后的变化进行了物化表征，同时应用电化学方法研究了甲醇在碳载铂纳米微粒修饰的玻碳电极上的电催化氧化性能。结果表明，修饰电极对甲醇氧化呈现较高的电催化活性。铂氧化物的电化学还原在Pt/c催化剂中受到了抑制，该现象可能是由于Pt与载体碳间的强烈作用所引起的。通过扫描电镜和循环伏安研究表明，该催化剂对甲醇的氧化可能存在着表面结构敏感效应。     

喷雾干燥法制备碳载铂钴镍合金催化剂及其甲醇催化氧化性能研究

本文以氯铂酸、氯化镍和硝酸钴为原料,XC-72炭黑为载体,通过雾化干燥法结合煅烧还原制备碳载铂基（PtCo Ni）分散性好的多元合金纳米粒子催化剂。重点研究表面经过改性的炭黑对合金纳米粒子形成和分散的影响规律,研究碳载PtCoNi（原子比为1:1:1）合金纳米粒子的甲醇催化氧化活性、抗CO中毒能力和耐久性,以及不同原子比对催化氧化甲醇活性和抗CO中毒能力的影响规律。研究结果表明,采用表面改性后的炭黑作为载体,制备的碳载铂基（PtCoNi）催化剂为合金纳米粒子,且纳米粒子在炭黑表面分散均匀,粒径分布在1-4nm,平均粒径为2.3nm;与商用的Pt/C催化剂相比,PtCoNi/C（原子比为1:1:1）催化剂具有更高的甲醇催化氧化活性、耐久性和抗CO中毒性;不同原子比铂基多元催化剂在催化氧化甲醇活性上的顺序为：PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C,抗CO中毒性顺序为：PtCoNi/C>Pt3CoNi/C>Pt5CoNi/C。     

Preparation and electrocatalytic property of Au-Pt/SnO2/GC composite electrode

Au-Pt/SnO2/GC composite electrode was prepared by self-assembling Au-Pt nanoparticles on SnO2 film, which was deposited on actived glassy carbon (GC). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) images revealed that dense and uniform Au-Pt particles with 25-nm diameter were dispersed on SnO2 film. X-ray photoelectron spectroscopy (XPS) results proved that there was an interaction between Au-Pt nanoparticles and SnO2 support. Electrochemical experiments showed that Au-Pt/SnO2/GC composite electrode had a good electrocatalytic activity to the oxidation of methanol.     

Preparation and characterization of polyvinylchloride membrane embedded with Cu nanoparticles for electrochemical oxidation in direct methanol fuel cell

Copper nanoparticles were prepared by the chemical reduction method. These copper particles were embedded into the polyvinylchloride (PVC) matrix as support and used as an electrode (PVC/Cu) for the oxidation of methanol fuel for improving the current response. The PVC/Cu electrodes were characterized by thermal gravimetric analysis (TGA) for thermal stability of the electrode, X-ray diffraction (XRD) for identification of copper nanoparticles in the electrode, Fourier transform infrared spectroscopy (FTIR) to identify the interaction between PVC and Cu and scan electron microscopy (SEM) with EDAX for the morphology of the electrode. The electrocatalytic activity of the electrode was characterized by the cyclic voltammetry, linear sweep voltammetry, and chronoamperometry techniques. An increase in the electrode activity was observed with the increase of copper quantity from 0.18 g (PVC/Cu-0.18 g) to 0.24 g (PVC/Cu-0.24 g) and the maximum was found at 0.24 g of copper in the electrode. Also, it was observed that the electrode achieved the maximum catalytic current in 0.5 mol/L CH₃OH + 1 mol/L NaOH solution. FTIR identified that water molecules, C—H group, copper nanoparticle and its oxide were available in the electrode. SEM images with EDAX showed that copper particles were properly embedded in the polyvinylchloride matrix.     

纳米碳/碳包铁材料合成及气相爆轰数值分析

本文从理论上分析了气相爆轰反应中爆轰产物组分与形成稳定爆轰的条件。通过以氧气与苯、氧气与溶有二茂铁的苯为原料,用气相爆轰形式制备了碳纳米材料与碳包铁纳米颗粒。爆炸产物经XRD与TEM表征发现,碳纳米材料呈球或准球状,颗粒尺寸在10~30nm,分散性较差。团簇区主要以无定型碳为主,分散区有少量洋葱状富勒烯。游离态碳与铁物质的量比影响碳包铁的形貌结构,其比值在10~28时,碳包铁纳米颗粒呈球状,核壳结构明显,分散性较好;大于50时,其形貌结构发生变化,部分碳以片状结构存在。     

碳载金铂双金属催化剂催化活性研究

采用KBH4做还原剂、PVP做保护剂,化学法一步合成Au-Pt合金纳米粒子,应用UV-Vis、TEM、XRD等手段对其进行了表征.将所合成的合金纳米粒子负载在碳黑上,获得Au-Pt双金属碳载催化剂,应用循环伏安法(CV)检测了催化剂对甲醇的电催化氧化活性.研究表明,Au-Pt/C催化剂的催化活性明显高于Pt/C的,说明...     

Synthesis and protection effect of fullerenol-<Emphasis Type="Italic">d</Emphasis>

Methods for synthesizing and identifying water-soluble fullerenes (fullerenols) were developed. When used as additives to corrosive media, fullerenes exhibit weak catalytic activity towards electrochemical corrosion of aluminum and steel. On the contrary, after the treatment of aluminum and steel with aqueous solution of fullerenols, the rate of electrochemical corrosion (in 0.25 N solution of sulfuric acid) increases by a factor of almost ten. At the same time, the specific surface electric conductance of aluminum and steel decreases by ten orders of magnitude. Thus, the metallic surface acquires insulating properties.     

Studies on Preparation of Onion-like Fullerenes by Vacuum Heat-treatment

Onion-like Fullerenes were produced at high-temperature in vacuum. The morphology of the carbon nano onion-like fullerenes was examined and characterized by high-resolution transmission electron microscopy (HRTEM). It can be seen that the nano-sized, onion-like fullerenes possess high degree of graphization. The results suggested that the catalyst is the main factor affecting the size and yield of the fullerenes. The method is very promising for simple mass production.     

Preparation and electrocatalytic property of Au-Pt/SnO<Subscript>2</Subscript>/GC composite electrode

Au-Pt/SnO₂/GC composite electrode was prepared by self-assembling Au-Pt nanoparticles on SnO₂ film, which was deposited on actived glassy carbon (GC). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) images revealed that dense and uniform Au-Pt particles with 25-nm diameter were dispersed on SnO₂ film. X-ray photoelectron spectroscopy (XPS) results proved that there was an interaction between Au-Pt nanoparticles and SnO₂ support. Electrochemical experiments showed that Au-Pt/SnO₂/GC composite electrode had a good electrocatalytic activity to the oxidation of methanol.     

The growth of nanophases in the clean room inside single-wall carbon nanotubes

The interior of single-wall carbon nanotubes is studied by filling fullerenes into the one-dimensional nanospace inside the tubes using different filling methods. Filling from solution is demonstrated as efficient as filling from the vapor phase. Evidence for successful filling comes from a transformation of the encapsulated carbon atoms to a secondary tube centered inside the primary tube. Isotope-labeled fullerenes are used to disentangle the Raman response from the two shells in double-wall carbon nanotubes.     

Electrocatalytic oxidation of methanol on carbon-nanotubes/graphite electrode modified with platinum and molybdenum oxide nanoparticles

Electrochemical codeposition and electrocatalytic properties of platinum and molybdenum oxide nanoparticles(Pt-MoOx) on carbon-nanotubes/graphite electrode for methanol oxidation were investigated.The micrograph and elemental composition of the resulting Pt-MoOx/CNTs/graphite electrode were characterized by scanning electron microscopy(SEM)and energy dispersive X-ray spectroscopy(EDS).The results show that the Pt-MoOx particles with the average size of about 50 nm are highly dispersed on the CNTs surface.The Pt-MoOx/CNTs/graphite electrode delivers excellent electrocatalytic properties for methanol oxidation.The highest mass activity(Am)reaches 264.8 A/g at the loading mass of 159.3μg/cm2.This may be attributed to the small particle size and high dispersion of Pt-MoOx catalysts deposited on the CNTs surface.The kinetic analysis from electrochemical impedance spectroscopy(EIS)reveals that the existed MoOx phase can improve the chemisorptive and catalytic properties for methanol oxidation.     

Pt-WC/Mnt三元纳米复合材料的制备及其电催化性能

以剥离后的蒙脱石(Mnt)片层为载体、六氯化钨(WCl6)为钨源,通过浸渍负载及原位还原碳化获得了碳化钨(WC)与蒙脱石(Mnt)纳米复合材料,然后将氯铂酸(H2PtCl6)通过浸渍负载于复合材料上,并在氢气(H2)中还原得到Pt-WC/Mnt三元纳米复合催化材料。采用X射线粉末衍射和透射电子显微镜对三元纳米复合催化材料的物相、形貌和结构进行表征,采用三电极体系和循环伏安法测试了样品的电催化性能。结果表明:样品物相主要为WO3和WC,蒙脱石片层结构明显,铂(Pt)纳米粒子均匀分布于WC/Mnt复合材料的外表面。Pt-WC/Mnt三元纳米复合材料对甲醇电催化氧化具有较高的催化活性,并且在酸碱体系中均具有良好的稳定性。     

纳米金刚石及相关材料的真空镀覆及应用进展

综述了以钛或锰金属粉与纳米金刚石、纳米碳化硅、氮化硅晶须或碳纳米管为原料,通过真空镀法对上述纳米粉体进行表面改性处理后在新能源方面的应用。介绍了钛镀覆纳米金刚石、纳米碳化硅和氮化硅晶须作为铂催化剂载体材料在直接甲醇燃料电池方面的应用,以及锰镀覆碳纳米管在超级电容器方面的应用。      

BaO对单Pd催化剂净化甲醇燃料车尾气性能的影响

利用FIB/SEM切片、XRD、TEM和EDX、EELS等先进分析技术对微球模板法所制备的Au/Ag泡沫材料的微观结构、形貌、成分及成分分布等进行了细致的研究.结果表明:由微球状Au/Ag球壳堆积而成的泡沫材料中微球直径约8 μm,微球壁厚200～1200 nm; Au/Ag泡沫材料的球壳可细分为3层,内层和外层为Au/Ag合金的微粒,中间主要是非晶碳层,夹杂有少量的Au/Ag微粒;Au/Ag泡沫材料的骨架由单个空心球壳组成,球壳之间通过接触点的金属镀层连接在一起;球壳上有小孔状结构,是在热分解法去除聚苯乙烯微球模板对形成的;球壳壁厚分布不均匀,少数球壳有塌陷、变形、破裂等现象.这些详细的分析有助于改进工艺,提高Au/Ag泡沫材料的制备质量.     

Structure,surface topography and electrochemical properties of cast films formed by fullerenes and their compositions with salt matrices

Some properties of films based on fullerene and pyridyl substituted fullerenopyrrolidines were studied. Both direct casting and immobilizing electroactive substances in the tetraoctylammonium bromide (TOAB) or tetraphenylphosphonium bromide matrices were used for modification of the ITO electrode surface. In accordance with X-ray diffraction, pyridyl substituted fullerenopyrrolidines are amorphous, and the lamellar structure of TOAB is retained when fullerene is present in the film. The differences, which are observed in the absorption spectra of the cast coatings of the individual fullerenes or fullerenes in the TOAB matrix as compared with solution spectra testify to the electronic interaction between fullerene molecules in a solid phase. At that, the quaternary ammonium salt participates immediately in the coating self-organization. Atomic force microscopy showed that both the solution composition and addends in the C₆₀ molecules influence the film morphology. Disintegration of fullerenes in the TOAB matrix and their interaction with hydrocarbon chains of TOAB provide the hydrophobic surrounding required for reversible electrochemical reduction of fullerene on an electrode in an aqueous solution. The differences observed for C₆₀ embedded in the tetraphenylphosphonium bromide and TOAB films accentuate the role of a layered structure of the matrix for the reversible electrochemical behavior of fullerene in aqueous solution.     

Low temperature methane oxidation on differently supported 2 nm Au nanoparticles

Low temperature CH₄ oxidation was studied on 2 nm gold nanoparticles supported on various metaloxides. The differences in reaction rates for the different systems suggest that the support material has an effect on the activity. From TEM analysis, we found that the gold particles were stable in size during the reaction. In addition to full oxidation to CO₂, traces of C₂H₆ were detected when Au/TiO₂ was used, indicating limited partial CH4 oxidation. TiO₂ was found to be the best support for gold nanoparticles both in terms of activity and gold particle stability.     

Magnetite nanoparticles by organic-phase synthetic route for carbon nanotube growth

In the present study, monodisperse Fe₃O₄ nanoparticles with diameters ranging from 10 nm to 25 nm were synthesized using a simple organic-phase synthetic route and these monodispersed nanoparticles were then used as catalyst for seed growth of carbon nanotube. Fe₃O₄ nanoparticles were reduced to iron nanoparticles assembly by Argon mixed with 5% Hydrogen gas at 400 °C and then it was examined by atomic force microscopy (AFM), thermomechanical analysis (TMA) and powder diffraction X-ray spectroscopic techniques. XRD indicates that iron clusters are bcc in nature and AFM image shows that the iron nanoparticles assemblies are 50–65 nm in size. To control the agglomeration of iron nanoparticles, nanoporous hybrid support material of Al₂O₃ and SiO₂ was used. However, this matrix also fails to stop the agglomeration of iron nanoparticles mainly due to the inhomogeneous distribution of pore diameters. TMA analysis of iron clusters shows a temperature-dependent morphology, therefore, the CNTs growth temperature critically ascertain the nature and structure of CNTs.     

Large-area network of polyaniline nanowires supported platinum nanocatalysts for methanol oxidation

Nanocomposites comprised of Pt nanoparticles and electrically conducting polymers were prepared and tested for the electrocatalytic performance towards oxidation of methanol. Films of polyaniline (PANI) synthesized independently by potentiostatic and galvanostatic method, PANI(V) and PANI(I), respectively, were used as the supporting matrix for loading Pt nanoparticles. PANI(V), PANI(I), PANI(V)/Pt, and PANI(I)/Pt films were characterized for structure and morphology using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). SEM image of PANI(I) reveals that the particles are highly porous and interconnected nanowires, whilst PANI(V) particles are granular. The large surface area in the nanofibrillar PANI(I) makes the dispersion of Pt particle with a lesser time for the deposition of Pt particles. The porous network structure of PANI(I) helps in effective dispersion of Pt particles (about 10–20 nm) and facilitates easy access of methanol to the catalytic sites. The electrocatalytic activity of PANI(I)/Pt is much higher (current density (24.7 mA/cm² mg) at 0.68 V) in comparison to PANI(V)/Pt and bulk Pt electrodes (the current density values of 5.5 and 7.5 mA/cm² mg).