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.     

High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN_x NTs) directly grown on the carbon cloth have been investigated. The CN_x NTs directly grown on the carbon cloth (CN_x NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN_x NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN_x NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN_x NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications.     

Preparation of Pt-Co nanocatalysts on carbon nanotube electrodes for direct methanol fuel cells

The electrochemical activities of three types of Pt-Co/CNT catalysts, prepared from different Co depositions, in methanol oxidation have been investigated. X-ray diffraction reveals that these Pt-Co/CNT catalysts possess not only different crystalline sizes but also different levels of atomic distribution. The use of strong reducing agent (NaBH₄) enables the formation of a cobalt layer over the Pt surface, inducing bimetallic Pt-Co particles, whereas direct thermal reduction enables the formation of Pt-Co nanoalloy with a high degree of alloying. It has been shown that the normalized active surface coverage increases the alloying degree of Pt-Co catalysts, indicating the importance of atomic distribution. Cyclic voltammetric measurement also reveals that the Pt-Co/CNT catalyst with a good alloying degree exhibits a better electrochemical activity, high CO tolerance, and long-term durability (> 100 cycles).     

Synthesis and electro-catalytic activity of methanol oxidation on nitrogen containing carbon nanotubes supported Pt electrodes

Template synthesis of various nitrogen containing carbon nanotubes using different nitrogen containing polymers and the variation of nitrogen content in carbon nanotube (CNT) on the behaviour of supported Pt electrodes in the anodic oxidation of methanol in direct methanol fuel cells was investigated. Characterizations of the as-prepared catalysts are investigated by electron microscopy and electrochemical analysis. The catalyst with N-containing CNT as a support exhibits a higher catalytic activity than that carbon supported platinum electrode and CNT supported electrodes. The N-containing CNT supported electrodes with 10.5% nitrogen content show a higher catalytic activity compared to other N-CNT supported electrodes. This could be due to the existence of additional active sites on the surface of the N-containing CNT supported electrodes, which favours better dispersion of Pt particles. Also, the strong metal-support interaction plays a major role in enhancing the catalytic activity for methanol oxidation.     

Synthesis of Pt and Pd nanosheaths on multi-walled carbon nanotubes as potential electrocatalysts of low temperature fuel cells

Pt and Pd nanosheaths are successfully synthesized on multi-walled carbon nanotubes (MWCNTs) using the non-covalent poly(diallyldimethylammonium chloride) (PDDA) functionalization and seed-mediated growth methods. In this method, negatively charged Pt or Pd metal precursors are self-assembled with positively charged PDDA-functionalized MWCNTs, forming uniformly distributed Pt or Pd nanoseeds on MWCNTs supports. The contiguous and highly porous Pt and Pd nanosheath structured catalysts are then formed by the seed-mediated growth in corresponding metal precursors using ascorbic acid as the reducing agent. The essential role of uniformly dispersed Pt and Pd nanoseeds on PDDA-MWCNTs is demonstrated. The results indicate that both Pt and Pd nanosheaths show an enhanced catalytic activity for the methanol and formic acid oxidation reaction in acid solution, respectively, as compared with conventional Pt/C and Pd/C catalysts. The enhanced activities are most likely due to the reduced oxophilicity, which results in a weakened chemisorption energy with oxygen-containing species such as CO_ad, and the increased reactive sites due to the large number of grain boundaries of the Pt and Pd nanosheath structured electrocatalysts.     

Hollow graphitic carbon spheres for Pt electrocatalyst support in direct methanol fuel cell

Hollow graphitic carbon spheres (HGCSs) with a high surface area are produced by the carbonization of hollow polymer spheres obtained by the polymerization of core/shell-structured pyrrole micelles. HGCSs are employed as a carbon support material in a direct methanol fuel cell catalyst, and their effect on the electrocatalytic activity toward methanol oxidation is investigated. Pt catalyst supported on HGCSs shows a better electrocatalytic activity compared to that on Vulcan XC-72, which has been commonly used in fuel cell catalysts. The observed enhancement in the electrocatalytic activity is attributed to the improved electronic conductivity and high surface area of HGCSs.     

Pt-CeO2/C anode catalyst for direct methanol fuel cells

In order to develop a cheaper and durable catalyst for methanol electrooxidation reaction, ceria (CeO₂) as a co-catalytic material with Pt on carbon was investigated with an aim of replacing Ru in PtRu/C which is considered as prominent anode catalyst till date. A series of Pt-CeO₂/C catalysts with various compositions of ceria, viz. 40 wt% Pt-3–12 wt% CeO₂/C and PtRu/C were synthesized by wet impregnation method. Electrocatalytic activities of these catalysts for methanol oxidation were examined by cyclic voltammetry and chronoamperometry techniques and it is found that 40 wt% Pt-9 wt% CeO₂/C catalyst exhibited a better activity and stability than did the unmodified Pt/C catalyst. Hence, we explore the possibility of employing Pt-CeO₂ as an electrocatalyst for methanol oxidation. The physicochemical characterizations of the catalysts were carried out by using Brunauer Emmett Teller (BET) surface area and pore size distribution (PSD) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) techniques. A tentative mechanism is proposed for a possible role of ceria as a co-catalyst in Pt/C system for methanol electrooxidation.     

Pyrene functionalized single-walled carbon nanotubes as precursors for high performance biosensors

The attachment of biotin to nanotube modified electrodes by formation of π-stacking interactions using a biotinylated pyrene derivative is reported. The specific anchoring of biological macromolecules via avidin bridges was investigated using biotinylated glucose oxidase (GOX-B) as model enzyme. Further studies focus the possibility of the electropolymerization of pyrene derivatives. Four types of biotin-SWCNT modified electrodes were investigated: (1) deposits of biotin-pyrene functionalized nanotubes (B-SWCNTs); (2) deposits of regular nanotubes, functionalized by incubation in a biotin-pyrene solution; (3) the latter configuration and subsequent electropolymerization of the adsorbed biotin-pyrene; and (4) deposits of regular nanotubes subsequently modified by electropolymerization of a pyrene-biotin monomer (2 mM). The nanotubes deposits were characterized by SEM imaging and the electropolymerization of the pyrene derivatives were investigated using cyclic voltammetry. These types of biotin-SWCNT modified electrodes were tested due to their capacity to immobilize biotinylated biomolecules (GOX-B) via avidin bridges and their performances in glucose detection were examined using amperometry. The best configuration (3) was obtained with SWCNT coatings modified by specific adsorption and electropolymerization of biotin-pyrene. A maximum current density of 584 μA cm⁻² could be realized with a sensitivity of 37 mA M⁻¹ cm⁻² for a linear range between 5 μM and 13 mM.     

Polyoxometallate-stabilized platinum catalysts on multi-walled carbon nanotubes for fuel cell applications

A novel catalyst, Pt-PMo₁₂-CNT, with well-dispersed Pt nanoparticles and monolayer PMo₁₂ on multi-walled carbon nanotubes (CNTs) is reported. A polyoxometallate (PMo₁₂) was chemically adsorbed on the surface of Pt nanoparticles and on outer walls of CNTs. These effectively prevented the agglomeration of Pt nanoparticles and CNTs due to the electrostatic repulsive interactions between negatively charged PMo₁₂ monolayers. The as-prepared Pt-PMo₁₂-CNT materials show higher electrocatalytic activity, higher cycle stability, and better tolerance to poisoning species in methanol oxidation than do Pt-CNT catalysts prepared by the same method. The reasons for the improved catalytic performance of the Pt-PMo₁₂-CNT catalysts are discussed.     

A nonelectrochemical reductive deposition of ruthenium adatoms onto nanoparticle platinum: anode catalysts for a series of direct methanol fuel cells

The surface of Pt nanoparticles was cleaned and saturated with hydrogen by treatment first with a 3% aqueous solution of H₂O₂ and then with hydrogen gas under water at room temperature. Reaction between the surface hydrogen and aqueous RuCl₃ deposited 0.18 surface equivalents of Ru_ad onto the Pt nanoparticles. The deposition was repeated several times, with each reaction depositing ∼0.18 surface equivalents more Ru_ad onto the Pt-Ru_ad nanoparticles. The resulting Pt-Ru_ad nanoparticles were analysed using cyclic voltammetry, CO stripping voltammetry, and as catalysts for electrooxidation of MeOH in three-electrode experiments and in prototype direct methanol fuel cells. The optimum surface coverage (θ_Ru) for electrooxidation of MeOH was ∼0.33 under these conditions.     

Hierarchical morphology of carbon single-walled nanotubes during sonication in an aliphatic diamine

Dispersion of single-walled carbon nanotubes (SWNTs) by sonication into diamine curing agents is studied as a means to improve the dispersion of SWNTs in cured epoxy. Cured and uncured specimens are analyzed by light microscopy, electron microscopy, light scattering (LS), ultra small-angle X-ray scattering (USAXS), electrical conductivity and Raman spectroscopy. A flexible diamine (D2000) forms a stable SWNT suspension leading to good homogeneity in both the diamine and the cured epoxy. High resolution transmission electron microscopy (TEM) shows that small ropes of SWNTs (mostly under 15 nm) are present despite the sample's visual homogeneity. Further morphological investigation of cured and uncured D2000 resins using light and small-angle X-ray scattering indicates that the SWNTs are networked into fractal clusters that electrically percolate at low SWNTs loadings (0.05 wt%).     

Electrocatalytic reduction of dioxygen by cobalt porphyrin-modified glassy carbon electrode with single-walled carbon nanotubes and nafion in aqueous solutions

Cobalt porphyrin (CoP)-modified glassy carbon electrode (GCE) with single-walled carbon nanotubes (SWNTs) and Nafion demonstrated a higher electrocatalytic activity for the reduction of dioxygen in 0.1 M H₂SO₄ solution. Cyclic and hydrodynamic voltammetry at the CoP-SWNTs/GCE-modified electrodes in O₂-saturated aqueous solutions was used to study the electrocatalytic pathway. Compared with the CoP/GCE-modified electrodes, the reduction potential of dioxygen at the CoP-SWNTs/GCE-modified electrodes was shifted to the positive direction and the limiting current was greatly increased. Especially, the Co(TMPP)-SWNTs/GCE-modified electrode was catalyzed effectively by the 4e⁻ reduction of dioxygen to water, because hydrodynamic voltammetry revealed the transference of approximately four electrons for dioxygen reduction and the minimal generation of hydrogen peroxide in the process of dioxygen reduction.     

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.     

Effect of heat treatment on stability of gold particle modified carbon supported Pt-Ru anode catalysts for a direct methanol fuel cell

Carbon supported Au-PtRu (Au-PtRu/C) catalysts were prepared as the anodic catalysts for the direct methanol fuel cell (DMFC). The procedure involved simple deposition of Au particles on a commercial Pt-Ru/C catalyst, followed by heat treatment of the resultant composite catalyst at 125, 175 and 200 °C in a N₂ atmosphere. High-resolution transmission electron microscopy (HR-TEM) measurements indicated that the Au nanoparticles were attached to the surface of the Pt-Ru nanoparticles. We found that the electrocatalytic activity and stability of the Au-PtRu/C catalysts for methanol oxidation is better than that of the PtRu/C catalyst. An enhanced stability of the electrocatalyst is observed and attributable to the promotion of CO oxidation by the Au nanoparticles adsorbed onto the Pt-Ru particles, by weakening the adsorption of CO, which can strongly adsorb to and poison Pt catalyst. XPS results show that Au-PtRu/C catalysts with heat treatment lead to surface segregation of Pt metal and an increase in the oxidation state of Ru, which militates against the dissolution of Ru. We additionally find that Au-PtRu/C catalysts heat-treated at 175 °C exhibit the highest electrocatalytic stability among the catalysts prepared by heat treatment: this observation is explained as due to the attainment of the highest relative concentration of gold and the highest oxidation state of Ru oxides for the catalyst pretreated at this temperature.     

PtRu nanoparticles supported on nitrogen-doped multiwalled carbon nanotubes as catalyst for methanol electrooxidation

Nitrogen-doped carbon nanotubes (N-CNT) obtained by plasma treatment were compared to the conventional acid-treated carbon nanotubes (O-CNT) as catalyst support for platinum-ruthenium (PtRu) nanoparticles in the anodic oxidation of methanol in direct methanol fuel cells. PtRu catalysts were prepared by an impregnation-reduction method from chloride precursors with metal loadings of 20 wt.%, and were characterised by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical methods. Voltammetry and chronoamperometry studies showed that the performance of PtRu/N-CNT was significantly higher compared to PtRu/O-CNT and also to the commercial E-TEK PtRu/C catalyst, indicating that N-CNT are an interesting support material for fuel cell electrocatalyst. Nitrogen plasma treatment produced pyridinic and pyrrollic species on the CNT surface, which acts as the anchoring sites for the deposition of PtRu particles. A mechanism for the deposition of PtRu on N-CNT is tentatively proposed and discussed.     

Preparation of hollow platinum nanospheres/carbon nanotubes nanohybrids and their improved stability for electro-oxidation of methanol

We report a facile method for the synthesis of hollow platinum nanospheres/carbon nanotubes nanohybrids (CNTs-G-PtHNs). Silver nanoparticles were used as sacrificial templates and uniformly deposited on the functionalized carbon nanotubes (CNTs). By galvanic replacement reaction between CNTs-supported silver and PtCl₆²⁻, well-dispersed hollow platinum nanospheres (PtHNs) were “grown” on CNTs. The morphology and electrochemical properties of the CNTs-G-PtHNs nanohybrids have been investigated by transmission electron microscopy and cyclic voltammetry, respectively. PtHNs in the CNTs-G-PtHNs nanohybrids have an average diameter of about 8 nm and the CNTs-G-PtHNs nanohybrids have higher electrochemical surface area and better electrocatalytic performance towards methanol oxidation than CNTs-A-PtHNs nanohybrids which were obtained by adsorbing the pre-synthesized PtHNs onto CNTs. Most importantly, the long-term stability of CNTs-G-PtHNs nanohybrids for methanol electro-oxidation has obviously improved compared with that of the CNTs-A-PtHNs nanohybrids.     

Effect of pH on PtRu electrocatalysts prepared via a polyol process on carbon nanotubes

This paper reports a study on the pH effects on the PtRu nanoparticles synthesized in a polyol process that were deposited on carbon nanotubes (CNTs) by reducing metal salts using ethylene glycol at various pHs. It was found that the nanoparticle size, composition, and catalytic activity all were sensitive to pH. The nanoparticles decreased in size as the preparation pH increased from 1.6 to 10.0, with the largest size at 2.47 nm and the smallest at 1.13 nm. An exception was found for pH at 0.7, which resulted in an average size of only 1.01 nm. Preparation pH was found to affect polyol reaction mechanisms, which are believed to be dominated by direct metal reduction at low pH and by both direct metal reduction and hydroxide reduction at high pH. However, at high pH the reactions were limited by hydroxide reductions, and longer reaction durations were needed to fully deposit the metals. To study the pH effect on the electrochemical activity of the catalysts, CO stripping techniques were used to determine peak potentials and active surface areas. Together with cyclic voltammetry in the electro-oxidation of methanol, it was found that the catalyst prepared at pH 8.4 has the best performance.