Electrochemical deposition of Pt nanoparticles on CNTs for fuel cell electrode

In order to increase the performance of fuel cell electrode, carbon nanotubes (CNTs) were used as support instead of conventional carbon black, and the Pt catalyst was synthesized by using electrochemical deposition (ECD) method which has recently been adopted as a synthetic tool of metal nanoparticles. CNTs used in this paper were grown directly on carbon paper by chemical vapor deposition (CVD) of acetylene. Highly dispersed and nano-sized Pt particles were electrochemically deposited on CNTs surface, which would simplify the manufacturing process of membrane-electrode-assembly (MEA). Pt particles on CNTs were investigated by SEM and TEM. The particle size of Pt is less than 2 nm, which is relatively small compared to that of conventional wet impregnated catalyst (2–8 nm). CO chemisorption results show that the amounts of catalytic sites are about three times larger in Pt/CNT prepared by ECD than those in conventional wet-impregnated one. The mass activity of the former catalyst for oxygen reduction is more than three times higher compared to that of the latter one. This paper was presented at the 11th Korea-Japan Symposium on Catatysis held at Seoul, Korea, May 21–24, 2007.     

Synthesis and activity of the Pt catalyst supported on CNT

Carbon nanotubes (CNT) were obtained by the decomposition of methane on a Ni catalyst supported on Al₂O₃. After the removal of the catalyst materials from CNT, a CNT-supported Pt catalyst was prepared, and this catalyst was characterized by XRD, XPS, and TEM. Activity of the CNT-supported Pt catalyst for hydrogenation of carbon–carbon double bonds at room temperature under the atmospheric pressure of hydrogen was examined. The CNT-supported Pt catalyst showed higher activity than the commercial Pt catalysts supported on activated carbon.     

Fabrication of CNTs with controlled diameters and their applications as electrocatalyst supports for DMFC

A facile synthesis procedure based on chemical vapor deposition (CVD) process has been developed to fabricate carbon nanotubes (CNTs) with controlled diameters and high yields utilizing Fe-containing ordered hexagonal mesoporous silicas (HMSs) such as MCM-41 and SBA-15 having varied pore sizes as the catalysts as well as the templates. It is found that unlike Fe/HMS catalysts prepared by co-precipitation method, samples prepared by the impregnation method gave rise to multi-wall CNTs with uniform diameters, which were largely dictated by the pore size of the Fe/HMS catalysts. Among these uniform MWCNTs, sample with a larger diameter (≥ 8 nm) was found to be more favorable as support for Pt catalyst, leading to a homogeneous dispersion of metal nanoparticles. Consequently, the Pt/CNT electrocatalysts so prepared gave rise to superior methanol oxidation activities as well as tolerances for CO poisoning compared to Pt supported on commercial single-wall CNT (Pt/SWCNT) and XC-72 activated carbon (Pt/XC-72) having a similar metal loading.     

Controllable‐Nitrogen Doped Carbon Layer Surrounding Carbon Nanotubes as Novel Carbon Support for Oxygen Reduction Reaction

Novel nitrogen‐doped carbon layer surrounding carbon nanotubes composite (NC‐CNT) (N/C ratio 3.3–14.3 wt.%) as catalyst support has been prepared using aniline as a dispersant to carbon nanotubes (CNTs) and as a source for both carbon and nitrogen coated on the surface of the CNTs, where the amount of doped nitrogen is controllable. The NC‐CNT so obtained were characterized with scanning electron microscopy (SEM), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and nitrogen adsorption and desorption isotherms. A uniform dispersion of Pt nanoparticles (ca. 1.5–2.0 nm) was then anchored on the surface of NC‐CNT by using aromatic amine as a stabilizer. For these Pt/NC‐CNTs, cyclic voltammogram measurements show a high electrochemical activity surface area (up to 103.7 m² g^–1) compared to the commercial E‐TEK catalyst (55.3 m² g^–1). In single cell test, Pt/NC‐CNT catalyst has greatly enhanced catalytic activity toward the oxygen reduction reaction, resulting in an enhancement of ca. 37% in mass activity compared with that of E‐TEK.     

Monodispersed hard carbon spherules as a catalyst support for the electrooxidation of methanol

Hard carbon spherules (HCS) were used as support of Pt nanoparticles as electrocatalyst for direct methanol fuel cells (DMFCs). Scanning electron microscopy (SEM) images show that the size of the Pt particles on HCS by reduction of K₂PtCl₆ with ethylene glycol is 4-5 nm. High-resolution transmission electron microscopy (HRTEM) study reveals that the Pt particles on the HCS surface have faceted crystalline structures. The size and aggregation of the Pt particles depend on the surface properties of the carbon support and the medium of the reduction reaction. Cyclic voltammetry and galvanostatic polarization experiments show that the Pt/HCS catalyst exhibits a higher catalytic activity in the electrooxidation of methanol than either the Pt/MCMB or the commercial Pt/Vulcan XC-72 catalyst does.     

Silica-sol-templated mesoporous carbon as catalyst support for polymer electrolyte membrane fuel cell applications

Mesoporous carbon (MC) samples having especially high specific surface area, pore size, and pore volume (e.g. pore volume in excess of 4 cm³ g⁻¹) were prepared and their suitability as Pt catalyst supports in polymer electrolyte membrane fuel cells was examined. Pt particles on the MC support were slightly larger than those on commercial samples of Pt on carbon black, and they showed a greater tendency to agglomerate on the MC support than on carbon black. Ex situ cyclic voltammetry gave values for electrochemically active surface area that were about half that for a commercial Pt-on-carbon black sample. Preliminary attempts to prepare thin-film electrodes from Pt/MC samples with a Nafion binder using conventional ink formulations failed, probably because much of the Nafion electrolyte was taken up inside support pores and was not available to bind the support particles together. An alternate approach involving painting of catalyst inks directly onto gas diffusion layers was used to prepare membrane electrode assemblies (MEAs) from Pt/MC samples, which were tested using single-cell test hardware. Performance of these Pt/MC sample MEAs was compared with that prepared by decal transfer method with commercially obtained Vulcan XC-72R supported Pt catalyst. The reasons for the lower performance of Pt/MC were discussed.     

Synthesis and characterisation of silica–carbon nanotube hybrid microparticles and their effect on the electrical properties of poly(vinyl alcohol) composites

Hybrid silica–carbon nanotube (CNT) particles with a radial symmetry were produced by the growth of nanotubes onto spherical, mesoporous silica gel particles using the floating catalyst chemical vapour deposition (FC-CVD) method. Characterisation of the hybrid particles, using electron microscopy, Raman spectroscopy and thermogravimetry showed the geometry and porosity of the silica particles to influence the alignment and density of the CNTs produced. CNT growth initiated in the pores of the gel particles and three hours of CVD growth were required to get extensive surface coverage. In the early stages of growth, the reactants diffused inside the mesoporous silica and consequently the CNTs grew mainly within the silica gel rather than on the surface. Some indication of catalyst templating was observed within the smaller (<10 nm) pores, but this templating did not result in aligned CNTs. Composite films of hybrid silica–CNT particles in poly(vinyl alcohol) were cast and their impedance measured. An electrical percolation threshold of 0.62 wt.% was found for the hybrid particles, of which 0.20 wt.% were CNTs.     

Perfluorosulfonic acid-functionalized Pt/carbon nanotube catalysts with enhanced stability and performance for use in proton exchange membrane fuel cells

To further improve lifetime and performance of carbon nanotube (CNT) supported Pt catalysts for proton exchange membrane fuel cells, perfluorosulfonic acid (PFSA) was introduced by a simple colloid route to functionalize Pt (PFSA-Pt/CNT) catalysts. Here the PFSA is available as a binder to tightly anchor Pt nano-particles onto the CNT surfaces, and as a proton conductor to increase the triple phase boundary zone of the catalysts. The prepared Pt nano-particles ranging from 2 to 5 nm in diameter are uniformly deposited on CNTs. A high catalytic activity of this novel composite catalyst was observed by both cyclic voltammetry and oxygen reduction reaction (ORR) measurements. The loss rate of the electrochemically active area of the PFSA-Pt/CNT catalyst decreases by a factor of two in comparison with that of the plain Pt/CNT catalyst. Meanwhile, a lower loss rate for the new catalyst was also observed by electrochemically-accelerated durability testing for the ORR activity. These results indicate that the stability of the new catalyst is significantly improved over that of the plain Pt/CNT catalyst by introduction of PFSA.     

Carbon cryogel as support of platinum nano-sized electrocatalyst for the hydrogen oxidation reaction

The kinetics of hydrogen oxidation reaction was studied in perchloric acid solution on carbon-supported Pt nanoparticles using the rotating disk electrode technique. Carbon cryogel and commercial carbon black. Vulcan XC-72 were used as catalyst supports. Pt/C catalysts were prepared by a modified polyol synthesis method in an ethylene glycol (EG) solution. Considerable effect has been observed for the specific surface area of carbon support on the fundamental properties of Pt/C catalyst, such as catalyst particle size distribution and dispersion as well as catalytic activity for the oxidation of hydrogen. X-ray diffraction (XRD) and transmission electron microscopy (TEM) images show that the particle size of the catalyst decreases with the increase of specific surface area of carbon support. Cyclic voltammetry (CV) was used for determination of the actual exposed surface area of catalyst particles. It was found that Pt catalyst prepared by using the novel carbon material displayed better hydrogen electrochemical oxidation activity than the catalyst prepared by using Vulcan XC-72.     

Morphology controllable growth of Pt nanoparticles/nanowires on carbon powders and its application as novel electro-catalyst for methanol oxidation

Pt nanowires (PtNWs) have been controllably synthesized on carbon powders by the reduction of H(2)PtCl(6) with HCOOH. By adjusting the pH value of the solution, PtCl(6)(2-) can be controllable reduced into particles or nanowires. The Pt nanowires are single crystals growing along the <111> direction with a diameter of 3 nm and a length of 10 nm. The dispersion of Pt nanowires on the surface of carbon powders can be controlled by changing the loading of Pt. The PtNWs/C is evaluated as the catalyst for methanol oxidation. The PtNWs/C with 20 wt% Pt has a larger electrochemical active surface area and much higher mass activity for methanol oxidation than that of commercial Pt/C catalyst. The PtNWs/C catalyst shows significant improvement in the kinetics for methanol oxidation and mass transfer property due to the single crystal structure of the Pt nanowires. The PtNWs/C catalyst holds promising potential applications in energy converting devices and environmental protection.     

Properties of Pt/C catalyst modified by chemical vapor deposition of Cr as a cathode of phosphoric acid fuel cell

Cr-modified Pt/C catalysts were prepared by the chemical vapour deposition (CVD) of Cr on Pt/C, and their performance as a cathode of phosphoric acid fuel cell (PAFC) was compared with the case of catalysts containing Cr added by impregnation (IMP).The catalyst prepared by CVD showed a higher activity for oxygen reduction reaction (ORR) than one prepared by IMP. There was an optimum amount of Cr that yielded the maximum mass activity of the catalyst because the gain in the intrinsic activity due to the promotional effect of Cr was counterbalanced by the loss of exposed Pt surface area as a result of the Cr introduction. Nevertheless, the activity increase at the optimum amount of Cr was greater for the CVD catalyst than for the IMP catalyst. Also, the optimum amount of Cr to yield the maximum activity was smaller for the former catalyst [Cr/Pt]_CVD = 0.6, than for the latter, [Cr/Pt]_IMP = 1.0.The enhancement of the Pt catalyst activity by Cr addition is attributed to two factors: changes in the surface Pt-Pt spacing and the electronic modification of the Pt surface. The formation of a Pt-Cr alloy, as confirmed by X-ray diffraction, decreased the lattice parameter of Pt, which was beneficial to the catalyst activity for ORR. X-ray photoelectron spectroscopy results showed that the binding energies of Pt electrons were shifted to higher energies due to Cr modification. Accordingly, the electron density of Pt was lowered and the Pt-O bond became weak on the Cr-modified catalysts, which was also beneficial to the catalyst activity for ORR.The promotion of oxygen reduction on Cr-modified catalysts was confirmed by measuring the cyclic voltammograms of the catalysts. All the above changes were made more effectively for catalysts prepared by CVD than for those prepared by IMP because the former method allowed Cr to interact more closely with the Pt surface than the latter, which was demonstrated by the characterization of catalysts in this study.     

Influence of Pyridine‐Polybenzimidazole Film Thickness of Carbon Nanotube Supported Platinum on Fuel Cell Applications

Pyridine‐polybenzimidazole (PyPBI) films of different thickness (∼1.0–2.4 nm) are wrapped on the surfaces of multi‐walled carbon nanotubes (CNTs). To prepare Pt on PyPBI/CNT (Pt‐PyPBI/CNT) catalysts, Pt⁴⁺ ions are immobilized on these PyPBI wrapped CNTs (PyPBI/CNTs) via Lewis acid‐base coordination between Pt⁴⁺ and :N‐ of imidazole groups, followed by reducing Pt⁴⁺ to Pt nanoparticles. The influence of PyPBI film thickness on the Pt particle size, loading and electrochemical surface area, respectively, of Pt‐PyPBI/CNTs is investigated. Fuel cell performances of the PBI/H₃PO₄ based membrane electrode assemblies (MEAs) prepared from these Pt‐PyPBI/CNT catalysts are also evaluated at 160 °C with unhumidified H₂/O₂ gases. Among the catalysts, the Pt‐PyPBI/CNT catalyst with a PyPBI film thickness of ∼1.6 nm (which is around half of the Pt particle size), a Pt loading of ∼44 wt.%, and a Pt particle size of ∼3.3 nm exhibits the best fuel cell performance.     

An Extremely Active Pt/Carbon Nano-Tube Catalyst for Selective Oxidation of CO in H2 at Room Temperature

Pt catalyst supported on carbon nano-tube (CNT) was extremely active for the selective oxidation of CO in H₂ at room temperature, which was remarked contrast to the Pt supported on an active carbon (Vulcan carbon) and a graphite powder. Complete oxidation of CO was attained on a 5 wt.% Pt/CNT catalyst (0.8 g) at ca. 40 °C when the O₂/CO ratio in a flow of H₂ (20 mL/min) + CO (3.0 mL/min) + O₂ + N₂ was adjusted to be larger than 0.75 at the total flow rate of 100 mL/min. Specific activity of the Pt/CNT catalyst was explained by efficient provision of reactant molecules diffusing on CNT surface to Pt particles.     

Carbon nanotube growth from alkali metal salt nanoparticles

We demonstrate that alkali metal salts, including KCl, NaCl, K₂SO₄, Na₂SO₄, K₂CO₃, and Na₂CO₃, can act as catalysts for carbon nanotube (CNT) growth in chemical vapor deposition (CVD). The solution of alkali metal salt, water and ethanol was nebulized and was introduced into the CVD reactor, producing CNT with a multi-walled structure. Individual CNT are terminated with an onion-shaped carbon tip even when different alkali metal salt catalysts are used. Through observation and analysis of the catalyst particles and the resulting product, we elucidate the mechanism by which the alkali metal salt nanoparticles are served as “seeds” and provide nucleation sites for CNT growth. The ethanol decomposes to release carbon atoms into the catalyst particles, and the carbon nucleates and then begins to assemble on the surface of the catalyst particles, resulting in the CNT growth. By altering growth conditions, branched CNT and single-walled CNT also can be grown on alkali metal salt nanoparticles.     

Preparation and application of mesocellular carbon foams to catalyst support in methanol electro-oxidation

A novel and simple preparation method for preparing a mesocellular carbon foam (MCF-C) is described. A silica–polymer composite as an amphi-templating material was synthesized by a sol–gel method using tetraethyoxy-orthosilicate (TEOS), P123 and divinylbezene (DVB) as a silica precursor, a template and a polymer precursor, respectively. The silica–polymer composite was subsequently transformed to either mesocellular carbon foam (MCF-C) or mesocellular silica foam (MCF-S). The prepared MCF-C exhibited well-developed mesocell pore structures with uniform windows. Compared to conventional methods, the method used for preparing MCF-C was economical and simple. MCF-C was used as a catalyst support in methanol electro-oxidation. The Pt/MCF-C-ETX (MCF-C-supported Pt catalyst which was prepared using sodium ethoxide) catalyst has smaller Pt nanoparticles and a larger electrochemically active surface area (EAS) value than the commercial Pt/C catalyst. In methanol electro-oxidation, the prepared Pt/MCF-C-ETX catalyst showed a higher catalytic performance than the commercial Pt/C catalyst.     

Preparation of platinum-based electrode catalysts for low temperature fuel cell

We have studied systematically the effects of synthesis parameters in both precipitation and colloidal methods to obtain highly dispersed Pt/carbon catalyst and compared the characteristics of prepared catalysts with commercial ones. The average Pt particle size at optimum condition for 10–60 wt.% Pt/carbon was in the range 1.7–3.8 nm which was about 70–80% of the commercial catalysts at the same Pt loading. The Pt surface area was also 20–40% higher than those of the commercial catalysts. The activities of prepared catalysts, measured by a single cell unit, were comparable with those of commercial ones.     

The role of mechanically induced defects in carbon nanotubes to modify the properties of electrodes for PEM fuel cell

The characteristics and reactivity of two anodes based on Pt supported on carbon nanotubes (CNTs) without or with defects induced by ball-milling are studied by SEM, TEM, cyclic voltammetry (CV) and single-cell measurements using a flow of pure H₂ or containing 50 ppm CO. It is evidenced that the presence of defects influences several properties and not only the dispersion of Pt particles. Therefore, the performances cannot be correlated neither with the geometrical surface area of Pt particles, neither with the electrochemical active surface area determined from CV tests. The presence of defects, enhancing the amount of surface functional groups on CNT, influences various aspects: (i) the efficiency of three-phase boundary and thus the transport of protons to or from the active metal particles, (ii) the resistance of electron transfer and (iii) the tolerance of the catalyst to CO poisoning. The latter is attributed to carbon functional groups in close contact with very small Pt particles favoring the reactivation of Pt sites poisoned by CO.     

Relationship among the physicochemical properties, electrocatalytic performance and kinetics of carbon supported Pt catalyst for ethanol oxidation

A new carbon supported Pt (Pt/C(b)) catalyst was prepared by reducing H₂PtCl₆ in glycol solution using formic acid as a reducing agent, and has been found in this work to be highly active and stable for the electrochemical oxidation of ethanol. The preparation produces highly dispersed Pt particles, of 2.6 nm average size, and with high electrochemical surface area, 98 m²/g. The apparent activation energy of ethanol oxidation over the Pt/C(b) catalyst electrode is low, 10–14 kJ/mol, over the range of potentials from 0.3 to 0.6 V.     

Efficient usage of highly dispersed Pt on carbon nanotubes for electrode catalysts of polymer electrolyte fuel cells

A Pt-deposited carbon nanotube (CNT) shows higher performance than a commercial Pt-deposited carbon black (CB) with reducing 60% Pt load per electrode area in polymer electrolyte fuel cells (PEFCs) below 500 mA/cm². K₂PtCl₄ and H₂PtCl₆·6(H₂O) are used for the Pt deposition onto multi-walled CNTs (MWCNTs), which are produced by the catalytic decomposition of hydrocarbons. The electric power densities produced using the Pt/CNT electrodes are greater than that of the Pt/CB by a factor of two to four on the basis of the Pt load per power. CNTs are thus found to be a good support of Pt particles for PEFC electrodes. TEM images show 2–4-nm Pt nanoparticles dispersed on the CNT surfaces. These high performances are considered to be due to the efficient formation of the triple-phase boundaries of gas–electrode–electrolyte. The mechanisms of Pt deposition are discussed for these Pt-deposited CNTs.     

Electro-catalytic oxidation of CO on Pt catalyst supported on carbon nanotubes pretreated with oxidative acids

Characteristics of nanosized Pt electro-catalyst deposited on carbon nanotubes (CNTs) were studied with CO-stripping voltammogram and chronoamperometry measurements. The CNTs were pretreated by oxidation in HNO₃, mixed HNO₃ + H₂SO₄ and H₂SO₄ + K₂Cr₂O₇ solution, respectively, to enable surface modification. Well-homogenized Pt particles (average size: ≈3 nm) were loaded onto the pretreated CNT samples by a modified colloidal method. TEM, BET, FTIR and XRD techniques were used to characterize the physicochemical properties of the pretreated CNT samples. In the electro-oxidation of CO, all the Pt/CNT samples showed lower on-set as well as peak potentials than the conventional Pt/XC-72 electro-catalyst, indicating that the Pt/CNT samples were more resistant to CO poisoning and could be superior anode electro-catalyst for the proton exchange membrane fuel cells (PEMFCs). Moreover, we found that the pretreatment of CNTs in mixed HNO₃ + H₂SO₄ solution was very beneficial for the performance enhancement of Pt/CNT electro-catalyst; the catalyst obtained as such gave the lowest peak potential and the highest catalytic activity for the electro-oxidation of CO. Larger amount of oxygen-containing functional groups, higher percentage of mesopores, and higher graphitic crystallinity of the pretreated CNTs were considered crucial for the performance enhancement, e.g., by strengthening the interaction between Pt nanoparticles and the CNT support and enhancing the mass diffusion in the electro-chemical reaction.