Preparation of PtSn/C and PtSnNi/C electrocatalysts using the alcohol-reduction process

PtSn/C electrocatalyst with Pt:Sn molar ratio of 50:50 and PtSnNi/C electrocatalyst with a Pt:Sn:Ni molar ratio of 50:40:10 were prepared by the alcohol-reduction process using ethylene glycol as solvent and reducing agent. The electrocatalysts were characterized by EDX, XRD, TEM and cyclic voltammetry. The electro-oxidation of ethylene glycol was studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. PtSnNi/C electrocatalyst showed a superior performance compared to PtSn/C electrocatalysts in the potential range of interest for direct ethylene glycol fuel cell.     

薄壳层核壳型Ni/Pt纳米粒子的制备及电催化性能

通过胶体-化学镀法制备不同厚度薄壳层核壳型Ni/Pt纳米粒子, 采用HRTEM、EDS、XPS和XRD手段对粒子的形貌、晶型和组成进行物理表征. 采用动电位、循环伏安法对其氧电还原和甲醇电氧化活性进行测试. 实验结果表明, 核壳结构Ni/Pt纳米颗粒基本为球形, 其中Ni₁-Pt_0.067平均直径为7 nm左右, 壳层厚度约1 nm. 与Pt/C相比, 核壳型Ni/Pt纳米粒子对氧电还原和甲醇电氧化的催化活性显著提高. 在所制备的不同壳层厚度催化剂中, Ni₁-Pt_0.067/C在0.5 mol/L H₂SO₄中氧电还原的最大峰电流密度可达到143.06 mA/mg, 是相同反应条件Pt/C峰电流密度的1.4倍; 而Ni₁-Pt_0.067/C在0.5 mol/L H₂SO₄+1.0 mol/L CH₃OH溶液中甲醇电氧化峰电流密度可达538.3 mA/mg, 是Pt/C峰电流密度的5.2倍. 若以1 mg贵金属Pt为基准, Ni₁-Pt_0.067/C的比质量活性相对Pt/C的提高了30倍.     

A comprehensive study on the effect of Ru addition to Pt electrodes for direct ethanol fuel cell

The electro-oxidation of ethanol was studied over nanosized Pt and different compositions of PtRu catalysts synthesized by the borohydride reduction method. Physicochemical characterizations of the catalyst material were made by X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with EDX analysis and transmission electron microscopy (TEM). XRD patterns showed that Ru induces a contraction of the Pt lattice. EDX provided the composition of binary catalysts while TEM images indicated uniform distribution of discrete nanoparticle of the catalysts with narrow range. The electro-catalytic activities of the materials towards ethanol oxidation were investigated through electrochemical techniques, viz. cyclic voltammetry (CV), potentiodynamic polarization, chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) at room temperature. The onset potential of ethanol electro-oxidation is lowered on bimetallic PtRu catalysts compared to that on Pt alone. Of the investigated catalyst compositions the one with the highest electrocatalytic activity was found to be Pt₈₂Ru₁₈. This enhancement towards ethanol oxidation is explained on the basis of a structural effect and modified bi-functional mechanism.     

Performance of ethanol electro-oxidation on Ni-Cu alloy nanowires through composition modulation

To reduce the cost of the catalyst for direct ethanol fuel cells and improve its catalytic activity, highly ordered Ni-Cu alloy nanowire arrays have been fabricated successfully by differential pulse current electro-deposition into the pores of a porous anodic alumina membrane (AAMs). The energy dispersion spectrum, scanning and transmission electron microscopy were utilized to characterize the composition and morphology of the Ni-Cu alloy nanowire arrays. The results reveal that the nanowires in the array are uniform, well isolated and parallel to each other. The catalytic activity of the nanowire electrode arrays for ethanol oxidation was tested and the binary alloy nanowire array possesses good catalytic activity for the electro-oxidation of ethanol. The performance of ethanol electro-oxidation was controlled by varying the Cu content in the Ni-Cu alloy and the Ni-Cu alloy nanowire electrode shows much better stability than the pure Ni one.     

羟基锡酸盐载铂复合催化剂Pt/(Co,Zn)Sn(OH)6的合成及其甲醇电催化氧化性能

以羟基锡酸盐CoSn（OH）₆和ZnSn（OH）₆纳米空心立方体为前体,采用抗坏血酸作为弱还原剂,经过超声过程分别合成了羟基锡酸钴载Pt/CoSn（OH）₆和羟基锡酸锌载Pt/ZnSn（OH）₆复合催化剂,并在甲醇氧化反应（MOR）中表现出良好的性能。Pt/CoSn（OH）₆和Pt/ZnSn（OH）₆催化剂的单位质量活性分别为1 095.6 mA/mg和699.5 mA/mg,高于C载Pt（Pt/C）的594.6 mA/mg。利用XRD、SEM、TEM、XPS和电化学测试对催化剂晶体结构和性能间的关系进行了探索。CO溶出实验结果表明,羟基锡酸盐载体有利于Pt表面CO的去除,载体与Pt间的强相互作用和载体表面的大量羟基基团增强了催化剂的催化活性和CO抗毒性。此外,Pt/（Co,Zn）Sn（OH）₆催化剂中单质Pt高的相对含量也有利于提高MOR活性。通过研究载铂羟基锡酸盐电催化氧化甲醇性能,能够揭示载体结构对催化性能的影响,有助于羟基锡酸盐载铂复合催化剂在直接甲醇燃料电池（DMFCs）领域的应用。     

Pt/C催化剂制备及CO催化氧化性能研究

采用大气压介质阻挡放电辅助氢气热还原方法和氢气热还原方法制备Pt/C催化剂,考察了制备方法及Pt负载量对Pt/C催化性能的影响。采用X-射线衍射(XRD)、循环伏安法、CO催化氧化反应研究Pt/C催化剂的晶相结构、电催化性能和CO催化氧化活性。结果表明:大气压介质阻挡放电辅助氢气热还原所制备的样品具有更高的电化学活性和CO催化氧化活性。当Pt负载量在2%到10%之间变化时,Pt/C-PC催化活性随负载量增加而增加。XRD测试结果显示当Pt负载量为2%,5%和10%时,Pt粒径分别为:10.6 nm,9.1 nm和6.4 nm,说明采用等离子体辅助氢气热还原方法制备的Pt/C-PC催化剂,Pt负载量越大,Pt粒径越小,CO催化氧化活性更高。     

A facile route to prepare PdPt alloys for ethanol electro-oxidation in alkaline electrolyte

We adopted a displacement reaction in acidic solution that enabled the spontaneous reduction of Pd and Pt cations in conjunction with corrosive dissolution of Ni. The composition for the PdPt was adjusted by varying the concentration of Pd and Pt cations. From SEM images and XRD patterns, the PdPt formed an fcc alloy uniformly deposited on the Ni substrate. Electro-oxidation of ethanol was conducted in alkaline electrolyte for samples of Pd, Pt, and PdPt alloys. In cyclic voltammetric profiles, the Pd₇₇Pt₂₃ revealed the highest electrocatalytic ability in both apparent current and mass activity, followed by Pd₈₇Pt₁₃, Pd, and Pt. Similar behaviors were observed in life time measurements in which stable performances for ethanol electro-oxidation were obtained.     

Facile syntheses and enhanced electrocatalytic activities of Pt nanocrystals with {<Emphasis Type="Italic">hkk</Emphasis>} high-index surfaces

Platinum (Pt) is an outstanding catalyst for many important industrial products. Because of its high cost and scarce reserves, it is very important to improve the performance of Pt catalysts. As the metal nanocrystals (NCs) with high-index surfaces usually show very good catalytic activity because of their high density of atomic steps and kinks, the preparation of Pt NCs with high-index facets has become a very important and hot research topic recently. In this article, we report a facile synthesis of high-yield Pt NCs with a series of {hkk} high-index facets including {211} and {411} via a solvothermal method using Pt(II) acetylacetonate as the Pt source, 1-octylamine as the solvent and capping agent, and formaldehyde as an additional surface structure regulator. Multipod Pt NCs with dominant {211} side surfaces were produced without formaldehyde, while concave Pt NCs with dominant {411} surfaces formed under the influence of formaldehyde. By analyzing the products by IR spectroscopy, we found the presence of CO on the surface of concave Pt NCs with {411} surfaces prepared from the solution containing formaldehyde. It was concluded that amine mainly stabilized the monoatomic step edges, resulting in the {211} exposed surface; with addition of formaldehyde, it decomposed into CO, leading to the formation of {411} surfaces by the additional adsorption of the CO on the {100} terraces. In addition, it was found that the as-prepared Pt NCs with high-index {211} and {411} surfaces exhibited much better catalytic activity in the electro-oxidation of ethanol than a commercial Pt/C catalyst or Pt nanocubes with low-index {100} surfaces, and the catalytic activities of Pt crystal facets decreased in the sequence {411}>{211}>{100}.      

Preparation of highly crystalline graphitic nanocarbon for the electro-oxidation of methanol

Highly crystalline graphitic nanocarbons (GNC) have been prepared by the wet-air treatment of hydrothermallyderived graphitic porous carbon. The materials were characterized by scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and electrochemical methods. The experimental results revealed that the treatment temperature has a significant effect on the morphology and degree of graphitic crystallinity. When GNC was treated at 450 °C under a wet-air atmosphere, the product (GNC-450) consisted of aggregates of silkworm-shaped carbon nanoparticles with enhanced graphitic characteristics. GNC-450 was evaluated as a catalyst support in the electro-oxidation of methanol. The Pt/GNC-450 catalyst contained smaller Pt particles and had a higher electrochemically active surface area than a commercial carbon black-supported Pt catalyst. In the electro-oxidation of methanol, the Pt/GNC-450 catalyst showed the highest performance among the Pt catalysts examined in this study. The superior catalytic performance appears to be closely related to the enhanced graphitic characteristics with highly dispersed Pt nanoparticles on the graphitic layers, which have a positive effect on the electrochemical performance.     

Pt/AlPO4 nanocomposite thin-film electrodes for ethanol electrooxidation

The enhanced catalytic properties toward ethanol electrooxidation on Pt/AlPO₄ nanocomposite thin-film electrodes were investigated. The Pt/AlPO₄ nanocomposites with various Al/Pt ratios (0.27, 0.57, and 0.96) were fabricated by a co-sputtering method. All of the Pt/AlPO₄ nanocomposites showed a negative shift in the onset potential and a higher current density than those of pure Pt electrode for the electrooxidation of ethanol. Among the various Pt/AlPO₄ nanocomposite thin-film electrodes, the electrode with an atomic ratio of Al to Pt of 0.57 showed the highest electrocatalytic activity for ethanol electrooxidation. The activation enthalpy for the optimum Pt/AlPO₄ nanocomposite was approximately 0.05 eV lower than that of pure Pt. It is believed that the enhancement in catalytic activity is due to the electron-rich Pt resulting from the Fermi-energy difference between Pt and AlPO₄.     

Ethylene glycol oxidation on Pt and Pt-Ru nanoparticle decorated polythiophene/multiwalled carbon nanotube composites for fuel cell applications

A novel supporting material containing polythiophene (PTh) and multiwalled carbon nanotubes (MWCNTs) (PTh-CNTs) is prepared by in?situ polymerization of thiophene on carbon nanotubes using FeCl(3) as oxidizing agent under sonication. The prepared polythiophene/CNT composites are further decorated with Pt and Pt-Ru nanoparticles by chemical reduction of the corresponding metal salts using HCHO as reducing agent at pH = 11 (Pt/PTh-CNT and Pt-Ru/PTh-CNT). The fabricated composite films decorated with nanoparticles were investigated towards the electrochemical oxidation of ethylene glycol (EG). The presence of carbon nanotubes in conjugation with a conducting polymer produces a good catalytic effect, which might be due to the higher electrochemically accessible surface areas, electronic conductivity and easier charge-transfer at polymer/electrolyte interfaces, which allows higher dispersion of Pt and Pt-Ru nanoparticles. Such nanoparticle modified PTh-CNT electrodes exhibit better catalytic behavior towards ethylene glycol oxidation. Results show that Pt/PTh-CNT and Pt-Ru/PTh-CNT modified electrodes show enhanced electrocatalytic activity and stability towards the electro-oxidation of ethylene glycol than the Pt/PTh electrodes, which shows that the composite film is more promising for applications in fuel cells.     

Methanol and ethanol electro-oxidation on Pt–SnO2 and Pt–Ta2O5 sol–gel-modified boron-doped diamond surfaces

The search for more efficient anode catalyst than platinum to be used in direct alcohol fuel cell systems is an important challenge. In this study, boron-doped diamond film surfaces were modified with Pt, Pt–SnO₂ and Pt–Ta₂O₅ nano-crystalline deposits by the sol–gel method to study the methanol and ethanol electro-oxidation reactions in acidic medium. Electrochemical experiments carried out in steady-state conditions demonstrate that the addition of SnO₂ to Pt produces a very reactive electrocatalyst that possibly adsorbs and/or dissociate ethanol more efficiently than pure Pt changing the onset potential of the reaction by 190 mV toward less positive potentials. Furthermore, the addition of Ta₂O₅ to Pt enhances the catalytic activity toward the methanol oxidation resulting in a negative shift of the onset potential of 170 mV. These synergic effects indicate that the addition of these co-catalysts inhibits the poisoning effect caused by strongly adsorbed intermediary species. Since the SnO₂ catalyst was more efficient for ethanol oxidation, it could probably facilitate the cleavage of the C–C bond of the adsorbed intermediate fragments of the reaction.     

Facile Synthesis of Bimetallic Au@Pd Nanoparticles with Core-shell Structures on Graphene Nanosheets

In this paper, we report a simple one-step thermal reducing method for synthesis of bimetallic Au@Pd nanoparticles with core-shell structures on the graphene surface. This new type of Au@Pd-G composites is characterized by transmission electron microscopy, high resolution transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. It is found that Au@Pd nanoparticles with an average diameter of 11 nm are well dispersed on the graphene surface, and the Au core quantity as well as the Pd shell thickness can be quantitatively controlled by loading different amounts of metallic precursors, and the involved core-shell structure formation mechanism is also discussed. The ternary Pt/Au@Pd-G composites can also be synthetized by the subsequent Pt doping. The catalytic performance of Au@Pd-G composites toward methanol electro-oxidation in acidic media is investigated. The results show that Au@Pd-G composites exhibit higher catalytic activity, better stability and stronger tolerance to CO poisoning than Pd-G and Au-G counterparts.     

炭化温度对中间相炭微球结构的影响

以煤沥青为原料,采用热聚合的方法,在不同的温度下制备出中间相炭微球(MCMB).通过SEM、激光粒径分析和XRD等分析手段对MCMB的表面形貌、粒径分布和微晶结构进行了分析.结果表明,随着温度的升高,MCMB的粒径变大,不同温度下制备的MCMB是由具有类似石墨结构的微晶组成的.420与450℃形成的MCMB微晶层间距d002较小,430与440℃形成的MCMB微晶层间距d002较大,随着温度的升高微晶宽度La变大.     

Fabrication of nanoporous Cu-Pt(Pd) core/shell structure by galvanic replacement and its application in electrocatalysis

We describe a general strategy to fabricate a new type of nanoporous core/shell structured bimetallic nanocomposites with controllable metal components. Nanoporous copper (NPC) obtained by dealloying Cu/Al alloy is used as both reducing agent and three-dimensional substrate. Electron microscope and X-ray diffraction characterizations demonstrated that a simply galvanic-replacement reaction with H(2)PtCl(6) aqueous solution can easily generate nanoporous core/shell structure with a thin Pt/Cu alloy shell and Cu (or Pt/Cu alloy) core. The morphology and crystal structure evolution of the nanocomposites are studied and discussed in detail. The as-prepared bimetallic PtCu nanocomposites show greatly enhanced catalytic activity and stability toward methanol electro-oxidation as compared with commercial Pt/C catalyst. This facile in situ preparation strategy is also suitable for large-scale production of this novel and inexpensive catalyst.     

不同碱辅助的沉积沉淀法对三效催化剂稳定性的影响

老化处理会导致三效催化剂(TWCs)严重失活,因此提高催化剂的耐久性能是TWCs设计的目标.本工作采用不同碱辅助的沉积沉淀法,即尿素辅助沉积沉淀法和氨水辅助沉积沉淀法制备了Pt/Ce0.4Zr0.5La0.05Pr0.05O2(Pt/CZ)三效催化剂,分析了不同碱对催化剂物理化学性质、催化活性和耐久性的影响.结果表明,...     

氧还原电催化剂Pt/WO3-C的制备及稳定性研究

采用化学沉淀法由HCl-Na₂WO₄制备WO₃-C复合载体, 通过微波辅助乙二醇还原法制备Pt/WO₃-C复合载体催化剂。研究了WO₃含量以及热处理温度对Pt/WO₃-C催化剂性能的影响, 采用X射线衍射、透射电子显微镜和能量散射光谱对Pt/WO₃-C的物化结构和组成进行了表征。结果表明, WO₃的最佳含量为10wt%, N₂气氛中热处理适宜温度为250℃。所制备的Pt/WO₃-C催化剂中WO₃以单斜晶型存在, Pt颗粒的平均粒径为2.77 nm。通过循环伏安法和单体质子交换膜燃料电池极化曲线测试了Pt/WO₃-C催化剂的电化学性能, 证实了Pt与WO₃之间存在协同催化作用, 与Pt/C催化剂相比, Pt/WO₃-C的催化活性和稳定性都有明显改善。     

Simple preparation of tungsten carbide supported on carbon for use as a catalyst support in a methanol electro-oxidation

Two types of supported tungsten carbides were prepared via the impregnation of tungsten precursors on carbon support followed by heat treatment. Depending on whether ammonium metatungstate (AMT) or tungsten chloride (WCl₆) was used as the precursor, this process resulted in samples that are referred to as either WC-A or WC-W, respectively. Both WC-A and WC-W showed tungsten subcarbide (W₂C) as the major crystalline phase, with tungsten monocarbide (WC) as a minor phase. More amount of tungsten carbide being formed when WCl₆ was used as the precursor. This increased formation has occurred because the thermodynamically favorable properties of WCl₆ caused the contact area between the tungsten precursor and the carbon support to promote formation of tungsten carbide. The prepared tungsten carbides were used as a catalyst support of the Pt catalyst in a methanol electro-oxidation. The metal dispersion and the catalytic performance were increased as follows: Pt/C<Pt/WC-A<Pt/WC-W. It is believed that the tungsten carbides supported on the carbon support improved the dispersion of Pt and the activation of water for removal of intermediate CO, which enhanced the catalytic performance during the methanol electro-oxidation.     

Leveraging Ligand and Composition Effects: Morphology-Tailorable Pt–Bi Bimetallic Aerogels for Enhanced (Photo-)Electrocatalysis

Metal aerogels (MAs) are emerging porous materials displaying unprecedented potential in catalysis, sensing, plasmonic technologies, etc. However, the lack of efficient regulation of their nano-building blocks (NBBs) remains a big hurdle that hampers the in-depth investigation and performance enhancement. Here, by harmonizing composition and ligand effects, Pt- and Bi-based single- and bimetallic aerogels bearing NBBs of controlled dimensions and shapes are obtained by facilely tuning the metal precursors and the applied ligands. Particularly, by further modulating the electronic and optic properties of the aerogels via adjusting the content of the catalytically active Pt component and the semiconducting Bi component, both the electrocatalytic and photoelectrocatalytic performance of the Pt–Bi aerogels can be manipulated. In this light, an impressive catalytic performance for electro-oxidation of methanol is acquired, marking a mass activity of 6.4-fold higher under UV irradiation than that for commercial Pt/C. This study not only sheds light on in situ manipulating NBBs of MAs, but also puts forward guidelines for crafting high-performance MAs-based electrocatalysts and photoelectrocatalysts toward energy-related electrochemical processes.     

A novel multi-walled carbon nanotube (MWNT)-based nanocomposite for PEFC electrodes

A novel nanocomposite comprising MWNTs and mixed-conducting polymeric components (electronic and ionic) is prepared, characterized and investigated as a support for platinum (Pt). Nanocomposite of MWNTs and poly (3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT?CPSS) is prepared by in situ polymerization and characterized using Fourier?CTransform infrared spectroscopy (FT?CIR), thermogravimetric analysis (TGA) in conjunction with scanning electron microscopy (SEM). Atomic force microscopy (AFM) studies are also carried out to characterize the surface topography of MWNTs/PEDOT?CPSS nanocomposite. X-ray diffraction (XRD) studies reveal that MWNTs/PEDOT?CPSS nanocomposite provides better backbone for the improved dispersion of Pt as evidenced by the reduced Pt crystallite size over MWNTs/PEDOT?CPSS nanocomposite compared to MWNTs. Electrochemical characterization studies performed with Pt/nanocomposite and Pt/MWNTs demonstrate the superior catalytic activity of Pt/nanocomposite under reduced Nafion loadings in relation to Pt/MWNTs. It is observed that mixed conducting nanoporous network of MWNTs/PEDOT?CPSS composite structure promotes the catalytic activity of Pt by enhancing catalyst utilization.