Pt-WO3 supported on carbon nanotubes as possible anodes for direct methanol fuel cells

The carbon nanotube (CNT) synthesised by the template carbonisation of polypyrrole on alumina membrane has been used as the support for Pt-WO₃, Pt-Ru, and Pt. These materials have been used as the electrodes for methanol oxidation in acid medium in comparison with E-TEK 20 wt% Pt and Pt-Ru on Vulcan XC72R carbon. The higher electrochemical surface of the carbon nanotube (as evaluated by cyclic voltammetry) has been effectively used to disperse the catalytic particles. The morphology of the supported and unsupported CNT has been characterised by scanning electron micrograph and high-resolution transmission electron micrograph. The particle size of Pt, Pt-Ru, and Pt-WO₃ loaded CNT was found to be 1.2, 2, and 5 nm, respectively. The X-ray photoelectron spectra indicated that Pt and Ru are in the metallic state and W is in the +VI oxidation state. The electrochemical activity of the methanol oxidation electrode has been evaluated using cyclic voltammetry. The activity and stability (evaluated from chronoamperometric response) of the electrodes for methanol oxidation follows the order: GC/CNT-Pt-WO₃-Nafion>GC/E-TEK 20% Pt-Ru/Vulcan Carbon-Nafion>GC/CNT-Pt-Nafion>GC/E-TEK 20% Pt/Vulcan carbon-Nafion>Bulk Pt. The amount of nitrogen in the CNT plays an important role as observed by the increase in activity and stability of methanol oxidation with N₂ content, probably due to the hydrophilic nature of the CNT.     

碳纳米管表面Pd纳米颗粒对甲醇的电催化氧化研究

采用电化学循环伏安法分别在碳纳米管(CNT)和玻碳(GC)电极表面沉积Pd纳米颗粒。扫描电镜(SEM)和XRD分析显示了Pd纳米颗粒均匀分散于碳纳米管表面,而在GC表面则趋向于堆积形成Pd金属薄膜。比较研究了Pd/CNT和Pd/GC电极在碱液中对甲醇的电催化氧化性能,循环伏安结果发现,Pd/CNT对甲醇的催化活性要高于Pd/GC电极;而交流阻抗谱研究发现,Pd/CNT电极对甲醇具有更快的催化氧化速率。另外,不同Pd载量,不同环境温度以及不同甲醇浓度的研究表明,相对于Pd/GC电极,Pd/CNT电极对甲醇的催化氧化具有更高的灵敏度和电化学稳定性。     

碳纳米管上电沉积钯对乙醇的电催化氧化研究

采用电化学循环伏安法沉积Pd纳米颗粒,在碳纳米管(CNT)电极表面获得了粒径约为20 nm而且分散性良好的Pd纳米颗粒,而玻碳(GC)电极表面上Pd纳米颗粒趋向于堆积形成紧密的Pd金属薄膜。研究发现,在碱液中Pd/CNT电极对乙醇的催化活性要高于Pd/GC电极,而交流阻抗实验发现,Pd/GC电极的阻抗半圆明显大于碳纳米管,表明了Pd/CNT电极对乙醇的催化速率明显优于Pd/GC电极。不同Pd载量以及环境温度影响实验发现,Pd/CNT电极上峰电流的增长速率要明显大于Pd/GC电极,而不同乙醇浓度实验进一步表明,Pd/CNT电极对于乙醇浓度的响应要比Pd/GC的灵敏。     

Graphite Electrodes Modified with Platinum‐Nickel Nano‐Particles for Methanol Oxidation

Methanol electro‐oxidation is investigated at graphite electrodes modified with various platinum and nickel nano‐particle deposits using cyclic voltammetry. The modified electrodes are prepared by the simultaneous electrodeposition of metals from their salt solutions using potentiostatic and galvanostatic techniques. They show enhanced catalytic activity towards methanol oxidation in KOH solution. The catalytic activity of platinum nano‐particles is found to be significantly affected by the presence of relatively small amounts of nickel deposits. A comparison is made between the electrocatalytic activity of Pt/C and (Pt‐Ni)/C electrodes. The results show that the methanol electro‐oxidation current increases with an increase in the nickel content. In particular, the highest catalytic activity is achieved for platinum to nickel deposits of 95%:5% (wt.‐%), in other cases the catalytic activity decreases. It is found that Ni enhances the catalytic activity of Pt by increasing the number of active sites, as well as through an electron donation process from Ni to Pt. This process takes place once the nickel hydroxide (Ni(OH)₂)/nickel oxy‐hydroxide (NiOOH) transformation begins. The effect of the methanol concentration on the methanol oxidation reaction is investigated. The order of reaction, with respect to methanol, at the modified (Pt‐Ni)/C electrode is found to be 0.5.     

Enhanced methanol electro-oxidation activity of PtRu catalysts supported on heteroatom-doped carbon

A typical heteroatom (nitrogen)-doped carbon materials were successfully synthesized through the carbonization of a hybrid containing traditional carbon black covered by in situ polymerized polyaniline. The nitrogen content onto carbon can be adjusted up to 5.1 at.% by changing the coverage of polyaniline. The effects of nitrogen doping on the surface physical and electrochemical properties of carbon were studied using XPS, XRD and HRTEM, as well as CV and EIS techniques. With increasing nitrogen doping, the carbon structure became more compact, showing curvatures and dislocations in the graphene stacking. The nitrogen-doped carbon also exhibited a higher accessible surface area in electrochemical reactions, and a lower charge transfer resistance at the carbon/electrolyte interface. Moreover, to investigate the influence of nitrogen doping on the electrocatalytic activity of the PtRu/C catalyst, comparisons in CO stripping and methanol oxidation were carried out on PtRu catalysts supported by non-doped and nitrogen-doped carbon. Since the promotional roles of nitrogen doping, including the high electrochemically accessible surface area, the richness of the disordered nanostructures and defects, and the high electron density on N-doped carbon supports, contribute to the synthesis of well-dispersed PtRu particles with high Pt utilization and stronger metal-support interactions, an enhanced catalytic activity for methanol oxidation was obtained in the case of the PtRu/N-C catalyst in comparison with the traditional PtRu/C catalyst.     

The role of nitrogen in a carbon support on the increased activity and stability of a Pt catalyst in electrochemical hydrogen oxidation

Nitrogen-containing carbon materials were prepared by acetonitrile pyrolysis on carbon black and used as a support for a Pt catalyst. The Pt particles on N-containing carbon exhibited increased activity and stability in electrochemical hydrogen oxidation relative to Pt on pristine carbon black. The N-doped carbon had a graphitic structure and contained pyridinic and quaternary nitrogen species. The Pt nanoparticles were better-dispersed because of increased hydrophilicity induced by the nitrogen species. The Pt/N-containing carbon showed higher stability in a potential cycling test than Pt/C, because of an increased metal-support interaction. Using XPS and EELS mapping, we demonstrated that the metal-support interaction became stronger and more specific by adding nitrogen into carbon.     

Pt based nanocomposites (mono/bi/tri-metallic) decorated using different carbon supports for methanol electro-oxidation in acidic and basic media

Pt based mono/bi/tri-metallic nanocomposites on different carbon based supports (activated carbon (AC), carbon nanotubes (CNTs) and carbon nanofibers (CNFs)) were synthesised and Pt surface enrichment achieved. The overall theoretical metallic content (Pt + Au + Sn) was 20% (w/w) in all mono/bi/tri-metallic nanocomposites and was found to be uniformly distributed in the supporting matrix (80%). The surface morphology and composition of the synthesised materials was characterised using scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDX), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermo-gravimetric analysis (TGA), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), while cyclic voltammetry was employed in order to confirm their typical metallic electrochemical characteristics. Electrochemical measurements indicated that Pt(2)Au(1)Sn(1) trimetallic catalysts demonstrated a significantly higher electrochemically active surface area relative to activated carbon supported PtAu based bimetallic counterparts. The results show that the CNT based trimetallic catalyst (Pt(2)Au(1)Sn(1)/CNT) showed greatest electroactive surface area (49.3 m(2)/g) and current density for methanol oxidation in acidic (490 mA mg(-1) Pt) as well as basic (1700 mA mg(-1) Pt) conditions. Results demonstrated that in comparison to Au/C and Sn/C (no/negligible response), the presence of a small amount of Pt in the Au and Sn based nanocomposites, significantly modified the catalytic properties. The activated carbon supported bimetallic (Pt(1)Au(3)/C) catalyst showed reasonably good response (260 mA mg(-1) Pt) among all bimetallic nanomaterials examined. The current response achieved for Pt(2)Au(1)Sn(1)/CNT was 1.9 times (in acidic media) and 2.1 times (in basic media) that for synthesised Pt/C in terms of per mg Pt activity. Overall the methanol oxidation studies demonstrated that the presence of Au and Sn in Pt based catalysts strongly indicated their capacity to reduce the precious Pt content required for this application, demonstrating the role of Au in improving current/potential response and signifying the importance of supporting matrices.     

Improved kinetics of methanol oxidation on Pt/hollow carbon sphere catalysts

Hollow carbon spheres (HCSs) have been prepared by combining the hydrothermal method and intermittent microwave heating (IMH) technique. The preparation factors affecting the performance of the HCSs are studied. The results show that Pt nanoparticles supported on HCSs (Pt/HCS), which were heated for 3 min in a microwave oven, give the best performance for methanol oxidation. The higher electrochemical active surface area of the Pt/HCS catalysts results in higher catalytic activity for methanol oxidation compared to that of the commercial Pt/C catalyst at the same Pt loadings. Higher exchange current density and lower reaction activation free energy are observed on Pt/HCS catalysts, indicating improved kinetics. It is recognized that the hollow structure of the Pt/HCS with open microspores and nanochannels is responsible for this higher catalytic activity for methanol oxidation.     

Carbon paste electrodes modified by Pt and Pt-Ni microparticles dispersed in polyindole film for electrocatalytic oxidation of methanol

Electrocatalytic activity of the Pt microparticles dispersed into polyindole (PIn) films obtained by electropolymerization on carbon paste electrodes (CPE) towards methanol oxidation in perchloric acid medium has been demonstrated and investigated using cyclic voltammetry, potentiodynamic polarization, chronoamperometry and impedance spectroscopic techniques. The results show that PIn films obtained on these electrodes serve as good host matrices for the dispersion of Pt microparticles and exhibit good catalytic activity towards the electrooxidation of methanol compared to bulk Pt and CPE modified with Pt. The morphology and composition of the modified and unmodified films were obtained using SEM and EDX techniques. The effect of scan rate, amount of Pt and concentration of methanol, on the activity of the electrode has been tested. The effect of alloying Pt with different amounts of Ni was studied and it was found that when the metals are deposited from a solution containing the metal salts in 1:1 ratio the activity towards methanol oxidation was significantly enhanced.     

Electrocatalytic oxidation of methanol on platinum nanoparticles electrodeposited onto porous carbon substrates

To achieve methanol fuel cell electrodes allowing a high catalyst use, thin layers of various carbon powders and recast Nafion® were electrochemically plated with platinum. The resulting Pt deposits were characterized by hydrogen and carbon monoxide electrosorption, as well as by transmission electron microscopy. Methanol oxidation was then carried out using cyclic voltammetry. The influence of the amount of carbon surface oxides and the effect of Pt specific surface area on the Pt catalytic activity were thus investigated.     

Highly dispersed Pt nanoparticles by pentagon defects introduced in bamboo-shaped carbon nanotube support and their enhanced catalytic activity on methanol oxidation

Bamboo-shaped carbon nanotubes (BCNTs), which were synthesized through chemical vapor deposition by using cresol as the carbon source, were explored as Pt catalyst support in comparison with conventional carbon nanotubes (CNTs) and Vulcan XC carbon blacks. The pyrolysis of cresol produced a large amount of pentagon defects introduced in the walls of BCNTs, which could possess higher chemical activity and stronger interaction with metal particles. After a mild purification, the BCNTs exhibited more oxygen-containing functional groups than CNTs, as shown by Fourier transform infrared spectra and cyclic voltammetry. The formed oxygen-containing functional groups as well as the pentagon defects could act as uniform active sites for metal particle loading. By ethylene glycol reduction, highly dispersed Pt nanoparticles with a narrow size distribution of 2-3 nm were easily supported on BCNTs, as shown by transmission electron microscope. The Pt/BCNT catalyst showed higher electro-catalytic activity on the methanol oxidation than the Pt/CNT and Pt/Vulcan XC catalyst, which could be largely ascribed to the highly dispersed Pt nanoparticles due to the introduced pentagon defects in the tube-walls (comparing with Pt/CNT) and the graphitic nanotube network that could provide good electron conduction (comparing with Pt/Vulcan XC).     

Using formic acid vapor as reducer to prepare Pt nanoparticles supported on carbon nanofiber mats for methanol electrooxidation

A novel process has been developed to prepare well-dispersed Pt nanoparticles on electrospinning-derived carbon fibrous mats (CFMs), which involved the physical adsorption of H₂PtCl₆ on CFMs and the reduction of H₂PtCl₆ with formic acid vapor. The most important advantage of this method is its simplicity, solvent-saving and benign to the environment. The performance of the prepared Pt-CFMs electrodes for methanol oxidation has been investigated and the results demonstrate that Pt-CFMs exhibit higher electrocatalytic activity and stability towards methanol oxidation and better tolerance towards reaction intermediates than commercial Pt/C supported on CFMs.     

Catalysts for Direct Methanol Fuel Cells

The activity of in house prepared carbon-supported Pt-Ru catalysts for methanol oxidation and carbon-supported RuSe for the oxygen reduction reaction in direct methanol fuel cells (DMFCs) was investigated. The composition of Pt-Ru/C was varied both in terms of weight loading (ratio of total metal content to carbon) as well as the ratio of Pt to Ru. The measurements were carried out in a half cell arrangement in sulphuric acid at various temperatures. The weight loading and ratio of Pt to Ru were varied in order to find out the optimum weight loading of precious metal and the temperature dependence of Pt to Ru ratio on methanol oxidation reaction. It has been found that there exists an optimum in the weight loading at 60 wt.% for carbon-supported Pt-Ru catalyst towards its maximum mass activity. While 1:1 Pt to Ru ratio exhibits a higher activity than 3:2 Pt:Ru above 60 °C, 3:2 ratio exhibits a higher activity at lower temperature. It has been observed that RuSe is inactive towards methanol and it is realised that RuSe is a potential candidate as methanol tolerant oxygen reduction catalyst. The activity of carbon supported RuSe for oxygen reduction reaction (ORR) was tested in sulphuric acid in the presence of methanol. Even though the mass specific activity of the RuSe catalyst is somewhat lower than that of Pt/C, the surface activity of carbon-supported RuSe is superior than that of carbon supported Pt which indicate the unfavourable size distribution of RuSe/C catalyst.     

Investigation of electrochemical oxidation of methanol in a cyclone flow cell

Electrochemical oxidation of methanol on carbon supported Pt/Ru gas diffusion electrodes was investigated in a cyclone flow cell at room temperature using chronoamperometry, cyclic voltammetry and electrochemical impedance spectroscopy. The influence of the flow rate was checked. It was proved that the cyclone cell is suitable for the investigation of methanol electrooxidation and provides additional information on the mass transfer limitations in the electrode assembly. Chronoamperometric measurements showed slow, but constant current decay at all investigated potentials. Impedance measurements in water and methanol containing solutions were performed and the experimental data were fitted to an appropriate equivalent circuit.     

碳化钨/碳气凝胶纳米复合材料增强Pt电催化甲醇性能的研究

以间苯二酚和甲醛为原料,采用溶胶-凝胶法原位合成WC纳米颗粒制备了碳化钨/碳气凝胶(WC/CAs);以WC/CAs为载体,利用微波加热乙二醇还原法制备了Pt/WC/CAs催化剂。运用循环伏安法(CV)、线性扫描(LSV)、计时电流法(CA)、能谱(EDS)、透射电子显微镜(TEM)和X射线衍射(XRD)等技术分析Pt/WC/CAs催化剂的组成、结构及其对甲醇的电催化氧化活性的影响。实验结果表明,载体中WC纳米颗粒的加入促进Pt贵金属颗粒对甲醇的电催化氧化活性,正扫电流峰ip与扫描速率的平方根v1/2线性相关,Pt/WC/C催化氧化甲醇的过程受扩散控制;且电催化活性比Pt/C要好。     

High utilization platinum deposition on single-walled carbon nanotubes as catalysts for direct methanol fuel cell

This research aims to enhance the activity of Pt catalysts, thus to lower the loading of Pt metal in fuel cell. Highly dispersed platinum supported on single-walled carbon nanotubes (SWNTs) as catalyst was prepared by ion exchange method. The homemade Pt/SWNTs underwent a repetition of ion exchange and reduction process in order to achieve an increase of the metal loading. For comparison, the similar loading of Pt catalyst supported on carbon nanotubes was prepared by borohydride reduction method. The catalysts were characterized by using energy dispersive analysis of X-ray (EDAX), transmission electron micrograph (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrum (XPS). Compared with the Pt/SWNTs catalyst prepared by borohydride method, higher Pt utilization was achieved on the SWNTs by ion exchange method. Furthermore, in comparison to the E-TEK 20 wt.% Pt/C catalyst with the support of carbon black, the results from electrochemical measurement indicated that the Pt/SWNTs prepared by ion exchange method displayed a higher catalytic activity for methanol oxidation and higher Pt utilization, while no significant increasing in the catalytic activity of the Pt/SWNTs catalyst obtained by borohydride method.     

Carbon nanotube counter electrode for high-efficient fibrous dye-sensitized solar cells

ABSTRACT: High-efficient fibrous dye-sensitized solar cell with carbon nanotube (CNT) thin films as counter electrodes has been reported. The CNT films were fabricated by coating CNT paste or spraying CNT suspension solution on Ti wires. A fluorine tin oxide-coated CNT underlayer was used to improve the adherence of the CNT layer on Ti substrate for sprayed samples. The charge transfer catalytic behavior of fibrous CNT/Ti counter electrodes to the iodide/triiodide redox pair was carefully studied by electrochemical impedance and current-voltage measurement. The catalytic activity can be enhanced by increasing the amount of CNT loading on substrate. Both the efficiencies of fibrous dye-sensitized solar cells using paste coated and sprayed CNT films as counter electrodes are comparative to that using Pt wires, indicating the feasibility of CNT/Ti wires as fibrous counter electrode for superseding Pt wires.     

Preparation of High Performance Pt/CNT Catalysts Stabilized by Ethylenediaminetetraacetic Acid Disodium Salt

A novel method with ethylenediaminetetraacetic acid disodium salt (EDTA‐2Na) as a stabilizing agent was developed to prepare highly dispersed Pt nanoparticles on carbon nanotubes (CNTs) to use as proton exchange membrane (PEM) fuel cell catalysts. These nanocatalysts were obtained by altering the molar ratio of ethylenediaminetetraacetic acid disodium salt to chloroplatinic acid (EDTA‐2Na/Pt) from 1:2, 1:1, 2:1 to 3:1. The well‐dispersed Pt nanoparticles of around 1.5 nm in size on CNTs were obtained when the EDTA‐2Na/Pt ratio was maintained at 1:1. And the Pt/CNT catalyst exhibited large electrochemical active surface areas, very high electrocatalytic activity and excellent stability in the oxidation of methanol at room temperature. The Pt/XC‐72R catalyst with narrow size distribution was also prepared by this method for comparison purposes. Comparison of the catalytic properties of these catalysts revealed that the activity of the Pt/CNT catalyst was a factor of ∼3 times higher than that of the Johnson Matthey catalyst and ∼2 times higher than that of our Pt/XC‐72R catalyst, which can be assigned to the high level of dispersion of Pt nanoparticles and the particular properties of the CNT supports.     

Carbon supported Pt–Co alloys as methanol-resistant oxygen-reduction electrocatalysts for direct methanol fuel cells

The electrocatalysis of the oxygen reduction reaction on carbon supported Pt and Pt–Co (Pt/C and Pt–Co/C) alloy electrocatalysts was investigated in sulphuric acid (both in the absence and in the presence of methanol) and in direct methanol fuel cells (DMFCs). In pure sulphuric acid Pt–Co/C alloys showed improved specific activity towards the oxygen reduction compared to pure platinum. In the methanol containing electrolyte a higher methanol tolerance of the binary electrocatalysts than Pt/C was observed. The onset potential for methanol oxidation at Pt–Co/C was shifted to more positive potentials. Accordingly, Pt–Co/C electrocatalyts showed an improved performance as cathode materials in DMFCs.     

Template synthesis of microporous carbon for direct methanol fuel cell application

Ordered microporous carbon with a structure of amorphous carbon core and graphitic carbon shell was prepared using hydrogen-form zeolite Y as the template. Impregnation and chemical vapor deposition methods were employed to infiltrate carbon in the pores of the template. Physical adsorption of nitrogen, X-ray diffraction, thermogravimetric analysis, field-emission scanning electron microscope, and field-emission transmission electron microscope techniques were employed to study the structural and morphological properties of the samples. The electrochemical properties of Pt supported on the carbon samples were examined and compared with a commercial catalyst. It was observed that Pt catalyst supported on a carbon with a core/shell structure has a higher specific activity for room-temperature methanol oxidation than the commercial catalyst.