金属铂-稀土合金电催化剂的制备研究

基于贵金属铂在甲醇燃料电池上的广泛应用,采用不同稀土金属(如钪、钇、镧系等)与铂形成合金在酸性条件下研究其对甲醇的电催化性能,并利用多壁碳纳米管增强对甲醇小分子的吸附性,提高酸性环境下甲醇的电催化氧化效率。多壁碳纳米管(MWNTs)具备纳米级别的管状结构,比表面积大,是一种优良载体,将铂-稀土合金和多壁碳纳米管充分混杂,并修饰在玻碳电极(GC)表面,具有良好的化学和物理稳定性。通过上述分析和实验制备了铂-稀土(M-Pt)合金催化剂、铂-稀土/多壁碳纳米管(M-Pt/MWNTs)催化剂。实验证明铂与稀土金属钪、钇、镧系等形成的合金的电催化性能最佳,且加入多壁碳纳米管,形成的铂-稀土/多壁碳纳米管(M-Pt/MWNTs)催化剂电化学催化效率得到明显地提升,所制备的铂-稀土合金电催化剂实用价值高。     

聚甲基丙烯酸甲脂/多壁碳纳米管复合材料的制备与电性能

对碳纳米管进行表面改性,改变纳米碳管表面性质。采用溶液共混法制备了多壁碳纳米管/聚甲基丙烯酸甲酯复合材料,采用扫描电镜(SEM)、透射电镜(TEM)观察了复合材料的微观结构,测试了复合材料的物理机械性能及导电性能。结果表明:采用溶液共混并用超声波分散的方法使多壁碳纳米管(MWNTs)分散在PMMA基体中,随着MWNTs含量的增加,复合材料的电导率呈先上升后持平的趋势。并发现MWNTs质量分数为3%时,其拉伸强度为84 MPa;MWNTs质量分数为4%时,其冲击强度为24.19 kJ/m2。     

碳纳米管/四氧化三钴复合材料制备及电化学性能

以Co(NO3)2·6H2O为原料、尿素为沉淀剂,并与多壁碳纳米管(multiwalled carbon nanotubes,MWNTs)复合,采用微波溶剂热法制备Co3O4粉体及Co3O4/MWNTs复合材料.对样品的物相结构、微观形貌和电化学性能进行表征及测试.结果表明:制备的Co3O4纳米线是由尺寸为10~20 ...     

顺序化学沉积法制备PB/MWNTs复合修饰电极及电化学性能研究

利用Fe3+和[Fe(CN)6]4-溶液,采用顺序化学沉积法制得普鲁士蓝/多壁碳纳米管(PB/MWNTs)修饰电极.FTIR、SEM等结构表征表明普鲁士蓝(PB)直接沉积在多壁碳纳米管(MWNTs)的表面.电化学研究表明PB/MWNTs修饰电极上的电子传递过程受支持电解液中K+、H+浓度影响.在pH=5.6、K+浓度为0.2 mol/L的KOH-KH2PO4-KCl支持电解液中,电极表现出优异的电化学稳定性,且可用于定量测定H2O2浓度.     

磺胺的电化学检测研究

以多壁碳纳米管和亚甲基蓝为修饰材料,制备了聚亚甲基蓝和多壁碳纳米管修饰电极(PMB/MWNTs/GCE),探讨确定了磺胺电化学检测的最优条件,获得了较好的研究结果,研究了所制备电极检测磺胺的电化学性能。结果表明,PMB/MWNTs/GCE在磺胺检测中有较好的线性范围,且在实际废水中检测低浓度磺胺有较好的可行性。     

PAN/MWNTs纳米纤维薄膜的制备和性能(英文)

采用浓硝酸和浓硫酸混合溶液将多壁碳纳米管(MWNTs)进行功能化处理,与聚丙烯腈(PAN)共混,通过静电纺丝制备了PAN/MWNTs纳米纤维薄膜。分析了MWNTs的结构和分散性及PAN/MWNTs纳米纤维的性能。结果表明,经过混酸处理后,MWNTs表面产生了羧基官能团,可以长时间稳定均匀分散在N,N′-二甲基乙酰胺(DMF)溶液中。混酸处理后的MWNTs在PAN基体中均匀分散,减少了静电纺丝过程中珠滴地形成。添加MWNTs后,PAN纳米纤维的强度提高,含MWNTs质量分数5%的PAN纳米纤维的拉伸强度提高了35.48%。     

纳米碳管改性聚哌嗪酰胺复合纳滤膜的制备

采用混酸(H2SO4/HNO3=3/1(V/V))处理多壁碳纳米管(MWNTs)制备了羧基化碳管(Carboxylated MWNTs),并与哌嗪(PIP)反应,制备了胺化的多壁纳米碳管(Amine functionalized MWNTs)。以聚砜(PSf)超滤膜为基膜,以均苯三甲酰氯(TMC)为油相单体和胺化的多壁纳米碳管与哌嗪(PIP)为水相单体,采用界面聚合法制得多壁碳纳米管改性聚哌嗪酰胺复合纳滤膜。采用傅里叶红外光谱(FT-IR)、拉曼光谱(RAM)、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)和静态接触角表征了改性前后碳纳米管和复合膜的结构,结果表明哌嗪成功氨化改性了碳纳米管,基膜表面复合了一层聚哌嗪酰胺膜。重点考察了碳管在水相中添加量、TMC浓度、聚合时间对复合膜性能的影响,结果显示,在有机相单体浓度为1 g?L?1,水相单体浓度为2 g?L?1,水相中多壁碳纳米管的浓度为0.1 g?L?1,反应时间为45 s,复合膜的纯水通量为85.6 L?m?2?h?1,Na2SO4的截留率达到98%,对不同盐溶液的截留效果分别为:Na2SO4MgSO4MgCl2NaCl。水相中碳纳米管的加入,能有效改善膜的分离性能。     

机械球磨对碳纳米管电化学性能的影响

通过改变机械球磨时间制备了不同长度的多壁碳纳米管(MWNTs).透射电子显微镜(TEM)显示随着球磨时间的增加,碳纳米管的长度变短,管壁缺陷增多.利用循环伏安(CV)和交流阻抗(EIS)考察了球磨0、0.5、2、5 h MWNTs修饰电极在K3[Fe(CN)6]溶液中的电化学行为.CV显示球磨5 h碳纳米管修饰电极的氧化峰电流Ipa为18.53 μA,比没有球磨的碳纳米管修饰电极的氧化峰电流Ipa(12.50 μA)增大约50%.EIS谱图显示球磨后的MWNTs更能有效地促进Fe(CN)63-的扩散和电子转移,具有更高的电化学活性.     

聚(3,4-乙撑二氧噻吩)/多壁碳纳米管导电复合材料制备与性能

通过3,4-乙撑二氧噻吩(EDOT)在多壁碳纳米管(MWNTs)表面的原位氧化聚合,得到聚苯乙烯磺酸钠(PSSNa)掺杂聚(3,4-乙撑二氧噻吩)(PEDOT)/多壁碳纳米管导电复合材料。复合材料中PEDOT-PSSNa包覆在MWNTs表面,形成MWNTs为核、PEDOT-PSSNa为壳的纳米复合结构,PEDOT与MWNTs间存在较强的π-π*共轭效应。复合材料的热失重受PEDOT分子骨架热降解和MWNTs热分解的双重控制,在300~500℃的热稳定性较PEDOT-PSSNa明显提高。聚合得到的核(MWNTs)-壳(PEDOT-PSSNa)结构能均匀分散在水中,形成具有良好透光性的水溶性复合分散体系。将水溶性复合材料涂覆于PET薄膜表面,室温电导率比PEDOT-PSSNa提高2个数量级。     

基于碳纳米管分子印迹聚合膜的西玛津电极研究

以除草剂西玛津(SMZ)为模板,在修饰有多壁碳纳米管(MWNTs)的玻碳电极表面通过电化学聚合邻氨基苯酚(oAP),制备了一种可对SMZ进行选择性测定的分子印迹聚合物膜电极。该印迹膜电极能在1.5~160μmol/L浓度范围内间接对SMZ进行检测,检出限为0.5μmol/L。并可在与SMZ结构相似的除草剂存在下选择性识别SMZ。     

Effect of support type and synthesis conditions on the oxygen reduction activity of RuxSey catalyst prepared by the microwave polyol method

Ru_xSe_y nanoparticles supported on different carbon substrates were synthesized by microwave heating of ethylene glycol solutions of Ru(III) chloride and sodium selenite at different pH and Ru/Se mole ratios. The resulting catalysts were used for the electrochemical oxygen reduction reaction (ORR) in acidic solution. The electrochemical activity was highest for the supported catalyst synthesized at pH 8. Increasing the Se concentration of the catalyst up to 15 mol% increased the catalytic activity for the ORR; at this Se concentration, the activity of the catalyst was considerably higher than that observed for pure Ru catalyst synthesized at exactly the same conditions. The influence of the type of carbon support on the activity of the electrocatalyst was also investigated. Among the different supports, including carbon black (Vulcan XC-72R) (C1), and nanoporous carbons synthesized from resorcinol- (C2) and phloroglucinol-formaldehyde (C3) resins, the Ru_xSe_y catalyst supported on C3 exhibited highest activity for ORR.     

络合还原法制备的Pd/C催化剂对甲酸氧化的电催化性能

分别以硼氢化钠和乙二醇为还原剂,经络合还原法制备了炭载钯（Pd/C）催化剂。透射电镜（TEM）和X射线粉末衍射谱（XRD）结果表明,以乙二醇为还原剂制备的Pd/C催化剂中Pd粒子具有较小的粒径、均匀的粒径分布和较大的相对结晶度,Pd粒子的平均粒径和相对结晶度分别为4.2±2 nm和1.88。电化学测试结果显示,以乙二醇为还原剂制备的Pd/C催化剂具有较大的电化学活性面积,对甲酸氧化表现出较高的电催化活性和稳定性。     

Synthesis of an improved hierarchical carbon-fiber composite as a catalyst support for platinum and its application in electrocatalysis

A hierarchical carbon-fiber composite was synthesized based on carbon cloth (CC) modified with primary carbon microfibers (CMF) and subsequently secondary carbon nanotubes (CNT), thus forming a three-dimensional hierarchical structure with high BET surface area. The primary CMFs and the secondary CNTs are grown with electrodeposited iron nanoparticles as catalysts from methane and ethylene, respectively. After deposition of Pt nanoparticles by chemical vapor deposition from (trimethyl)cyclopentadienylplatinum, the resulting hierarchical composite was used as catalyst in the electrocatalytic oxygen reduction (oxygen reduction reaction, ORR) as specific test reaction. The modification of the CC with CMFs and CNTs improved the electrochemical properties of the carbon composite as revealed by electrochemical impedance measurements evidencing a low charge transfer resistance for redox mediators at the modified CC. X-ray photoelectron spectroscopy measurements were carried out to identify the chemical state and the surface atomic concentration of the Pt catalysts deposited on the hierarchical carbon composites. The ORR activity of Pt supported on different composites was investigated using rotating disk electrode measurements and scanning electrochemical microscopy. These electrochemical studies revealed that the obtained structured catalyst support is very promising for electrochemical applications, e.g. fuel cells.     

Highly efficient supporting material derived from used cigarette filter for oxygen reduction reaction

Bimodal porous nitrogen (N) doped carbon supported Pt composite was prepared as a catalyst for oxygen reduction reaction (ORR). The N-doped carbon (NCF) support was obtained via one-pot pyrolysis of the used cigarette filters. Physical characterizations and electrochemical tests proved that the presence of N dopant on the surface of the NCF not only provided highly dispersive active sites for the growth of the Pt nanoparticles but also the active centers for ORR itself. It was demonstrated that these combinative effects contributed on higher ORR activity and durability than those for the commercial carbon (Vulcan XC) supported Pt composites.     

络合还原法制备Pd/C催化剂及甲酸电催化氧化性能

分别以硼氢化钠和乙二醇为还原剂,经络合还原法制备了炭载钯(Pd/C)催化剂。透射电镜(TEM)和X射线粉末衍射谱(XRD)结果表明,以乙二醇为还原剂制备的Pd/C催化剂中Pd粒子具有较小的粒径、均匀的粒径分布和较大的相对结晶度,Pd粒子的平均粒径和相对结晶度分别为(4.2±2)nm和1.88。电化学测试结果显示,Pd/C催化剂具有较大的电化学活性面积,对甲酸氧化表现出较高的电催化活性和稳定性。     

Electrocatalytic enhancement of methanol oxidation by graphite nanofibers with a high loading of PtRu alloy nanoparticles

The geometric effect of graphite nanofibers (GNFs) as a support for PtRu electrocatalysts on the oxidation of methanol for direct methanol fuel cells (DMFCs) was studied using X-ray diffraction, field emission transmission electron microscopy (FETEM) and electrochemical measurements. A high loading of 60 wt% PtRu catalyst, which is readily applicable to DMFCs, was well dispersed on GNFs. Further, the shape of the supported metal particles was affected by interactions with the GNFs. Electrochemical analysis indicated that GNF-supported PtRu catalysts resulted in an increased catalytic activity of about 100% over that of Vulcan XC-72 supported catalysts. FETEM data indicate that the enhanced activities result from a geometric modification of the catalyst particles by specific interactions between the GNFs and the supported PtRu nanoparticles.     

Electrochemical characterization and reactivity of Pt nanoparticles supported on single-walled carbon nanotubes

Carbon nanotubes have been proposed as advanced metal catalyst support for electrocatalysis. In this paper, Pt nanoparticles supported on single-walled carbon nanotubes (SWCNTs)-Pt, were prepared using a solid-state reaction between the SWCNTs and two different Pt precursors, bis(dibenzylideneacetone)platinum [Pt(DBA)₂] or tri(dibenzylideneacetone)platinum [Pt(DBA)₃]. TEM images of the samples show Pt nanoparticles with a particle size around 2.5 nm with a high degree of dispersion on the SWCNTs. A detailed electrochemical characterization of the surface of the samples including irreversibly adsorbed adatoms of Bi and Ge as probe reactions has been carried out. It has been stated that SWCNTs-Pt samples subjected to the classical electrochemical activation induce a serious sintering of the Pt nanoparticles.     

Microwave heated polyol synthesis of Pt3Te/C catalysts

Pt₃Te/C nanoparticles supported on Vulcan XC-72 carbon were prepared within a few minutes under different reaction conditions by using a microwave-polyol method. Their physical and electrochemical characterization were carried out by X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectrometer (XPS), selected-area electron diffraction (SAED), H₂ adsorption-desorption, ethanol oxidation and CO stripping. TEM shows that the Pt₃Te/C (pH 3) catalyst has uniform nanoparticles and is well dispersed with average particle size of about 2.8 nm. Electrochemical results show that the electrochemical activity of Pt₃Te/C catalysts synthesized at different pH values are in the order of pH 3 > pH 7 > pH 9 > pH 13. The Pt₃Te/C catalyst (pH 3) is also better than the Pt₃Te/C catalyst synthesized by formic acid as reductant. From a practical point of view, the microwave-polyol method at the pH value of 3 could be an appropriate method for synthesizing nanocatalysts.     

Nanoporous PdNi/C Electrocatalyst Prepared by Dealloying High‐Ni‐content PdNi Alloy for Formic Acid Oxidation

To improve the electrochemical performance of Pd‐based catalysts for formic acid oxidation, a carbon supported nanoporous PdNi catalyst is prepared by dealloying high‐Ni‐content PdNi alloy nanoparticles in acid solution. The structure of nanoporous PdNi/C catalyst is characterized by X‐ray diffraction, transmission electron microscopy and X‐ray photoelectron spectroscopy. The electrocatalytic results show that the activity of the nanoporous PdNi/C catalyst is higher than that of nonporous Pd/C catalyst. The results demonstrate that the carbon‐supported nanoporous PdNi catalyst has a potential for application in direct formic acid fuel cells.     

Nanoscale graphite-supported Pt catalysts for oxygen reduction reactions in fuel cells

The nanoscale graphite particles were prepared and the Pt catalysts supported on such graphites were developed for oxygen reduction in the polymer electrolyte membrane fuel cells. Catalytic activity and carbon corrosion of the developed catalysts were evaluated using rotating disc electrode techniques and results were compared with those of a state-of-the-art commercial E-TEK Pt catalyst supported on carbon black Vulcan XC72. The results showed that the particle distribution and the structure of the developed Pt nanoparticles supported on the nanoscale graphite were similar to those of the commercial catalyst. The accelerated degradation testing results showed that the electrochemical active surface area losses after 1500 cycles were 46.92% and 62.2% for the developed catalyst and the commercial catalyst, respectively, while mass activity losses were 45.3% and 84.2%, respectively. The temperature-programmed oxidation results suggest that the developed catalysts had better corrosion resistance than the commercial catalyst. The developed Pt catalysts had similar catalytic performance to the commercial catalyst; however, the developed catalysts had much better corrosion resistance than the commercial catalyst. Overall, nanoscale graphite can be a promising electrocatalyst support to replace the currently used Vulcan XC72 carbon black.