Pt–NiO/C anode electrocatalysts for direct methanol fuel cells

Pt catalyst was supported on Vulcan XC-72R containing 5 wt.% NiO using NaBH₄ as a reducing agent. The prepared catalyst was heat-treated at 400 °C. XRD, TEM and EDX analyses were applied to characterize Pt–NiO/C electrocatalyst. The introduction of NiO reduces the particle size of Pt crystallites. The electrocatalytic activity of Pt–NiO/C electrocatalysts was examined towards methanol oxidation reaction in 0.5 M H₂SO₄ solution using cyclic voltammetry and chronoamperometry techniques. A three fold increment in the oxidation current density was gained at Pt–NiO/C electrocatalyst compared to Pt/C one. The corresponding chronoamperograms showed high steady state current density values suggesting better stability of Pt–NiO/C electrocatalyst towards the carbonaceous poisoning species. The enhanced electrocatalytic performance and the long-term cycle durability of Pt–NiO/C electrocatalyst are attributed to the strong interaction between Pt and NiO and the formation of small Pt crystals.     

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.     

Low-Pt Content Carbon-Supported Pt–Ni–TiO2 Nanotube Electrocatalyst for Direct Methanol Fuel Cells

Low-Pt content (5%) carbon-supported Pt–Ni–TiO₂ nanotube electrocatalysts were prepared via a microwave-assisted polyol strategy. Physical and morphological properties of these electrocatalysts were characterized by X-ray diffraction (XRD), high resolution transmission electron microscope (HRTEM), and energy dispersive X-ray spectroscopy (EDX). Cyclic voltammetry and chronoamperometry studies clearly suggested that the Pt(5%)–Ni(10%)–TiO₂ nanotube (10%) supported by Vulcan XC-72 is better than the commercial 20% Pt/C electrocatalyst for methanol electro-oxidation in direct methanol fuel cells (DMFCs).     

Functionalized-carbon nanotube supported electrocatalysts and buckypaper-based biocathodes for glucose fuel cell applications

The preparation and testing for electrocatalytic activity of functionalized carbon nanotube (f-CNT) supported Pt and Au–Pt nanoparticles (NPs), and bilirubin oxidase (BOD), are reported. These materials were utilized as oxygen reduction reaction (ORR) cathode electrocatalysts in a phosphate buffer solution (0.2 M, pH 7.4) at 25 °C, in the absence and presence of glucose. Carbon monoxide (CO) stripping voltammetry was applied to determine the electrochemically active surface area (ESA). The ORR performance of the Pt/f-CNTs catalyst was high (specific activity of 80.9 μA cm_Pt⁻² at 0.8 V vs. RHE) with an open circuit potential within ca. 10 mV of that delivered by state-of-the-art carbon supported platinum catalyst and exhibited better glucose tolerance. The f-CNT support favors a higher electrocatalytic activity of BOD for the ORR than a commercially available carbon black (Vulcan XC-72R). These results demonstrate that f-CNTs are a promising electrocatalyst supporting substrate for biofuel cell applications.     

Carbon-supported ternary PtSnIr catalysts for direct ethanol fuel cell

Binary PtIr, PtSn and ternary PtSnIr electrocatalysts were prepared by the Pechini-Adams modified method on carbon Vulcan XC-72, and these materials were characterized by TEM and XRD. The XRD results showed that the electrocatalysts consisted of the Pt displaced phase, suggesting the formation of solid solutions between the metals Pt/Ir and Pt/Sn. However, the increase in Sn loading promoted phase separation, with the formation of peaks typical of cubic Pt₃Sn. The electrochemical investigation of these different electrode materials was carried out as a function of the electrocatalyst composition, in a 0.5 mol dm⁻³ H₂SO₄ solution, with either the presence or the absence of ethanol. Cyclic voltammetric measurements and chronoamperometric results obtained at room temperature showed that PtSn/C and PtSnIr/C displayed better electrocatalytic activity for ethanol electrooxidation compared to PtIr/C and Pt/C, mainly at low potentials. The oxidation process was also investigated by in situ infrared reflectance spectroscopy, to identify the adsorbed species. Linearly adsorbed CO and CO₂ were found, indicating that the cleavage of the CC bond in the ethanol substrate occurred during the oxidation process. At 90 °C, the Pt₈₉Sn₁₁/C and Pt₆₈Sn₉Ir₂₃/C electrocatalysts displayed higher current and power performances as anode materials in a direct ethanol fuel cell (DEFC).     

Effect of W on PtSn/C catalysts for ethanol electrooxidation

Binary and ternary Pt-based catalysts were prepared by the Pechini–Adams modified method on carbon Vulcan XC-72, and different nominal compositions were characterized by TEM and XRD. XRD showed that the electrocatalysts consisted of the Pt displaced phase, suggesting the formation of a solid solution between the metals Pt/W and Pt/Sn. Electrochemical investigations on these different electrode materials were carried out as a function of the electrocatalyst composition, in acid medium (0.5 mol dm⁻³ H₂SO₄) and in the presence of ethanol. The results obtained at room temperature showed that the PtSnW/C catalyst display better catalytic activity for ethanol oxidation compared to PtW/C catalyst. The reaction products (acetaldehyde, acetic acid and carbon dioxide) were analyzed by HPLC and identified by in situ infrared reflectance spectroscopy. The latter technique also allowed identification of the intermediate and adsorbed species. The presence of linearly adsorbed CO and CO₂ indicated that the cleavage of the C–C bond in the ethanol substrate occurred during the oxidation process. At 90 °C, the Pt₈₅Sn₈W₇/C catalyst gave higher current and power performances as anode material in a direct ethanol fuel cell (DEFC).     

Synthesis of Pt3Co Alloy Nanocatalyst via Reverse Micelle for Oxygen Reduction Reaction in PEMFCs

Monodispersed, uniformly alloyed Pt₃Co alloy nanoparticle electrocatalysts were synthesized via reduction of metallic precursors by sodium borohydride in heptane/polyethylene glycol dodecylether (Brij)/water reverse micelles. These particles were further adsorbed on XC-72R carbon powder, separated from micelles, and characterized using X-ray diffraction (XRD), transmission electronic microscopy (TEM). The electrochemical activity for the oxygen reduction reaction (ORR) was characterized using a Rotating Disk Electrode (RDE) technique. Even though residual surfactants on the metallic nanoparticle reduced the active surface area of the electrocatalytic particles, the catalytic activity of the prepared Pt₃Co nanoparticles exhibited higher Pt mass and Pt surface area specific activities compared to pure Pt. The impact of heat treatment on the mean particle size, the electrochemical surface area (ESA), and on the activity was investigated and correlated to the residual surfactant coverage. Intermediate annealing temperatures resulted in larger ESA, despite particle growth pointing to lower surfactant coverage. Higher annealing temperatures caused large particle growth and reduced ESA, yet significant activity gains. A surface segregation mechanism resulting in a catalytically active Pt skin structure is hypothesized.     

The effect of plasma pre-treatment of carbon used as a Pt catalyst support for methanol electrooxidation

Vulcan XC-72 carbon black for use as a catalyst support was treated in three different plasma atmospheres, H₂, Ar and O₂. The results showed that the microstructure and surface functional groups were significantly changed after plasma treatment. Pt/C catalysts were prepared by chemical reduction of H₂PtCl₆ with HCHO and those with untreated and plasma treated carbon black supports were characterized and tested for methanol electrooxidation. TEM showed that the platinum nanoparticles on H₂ and Ar plasma treated carbon were uniform and well distributed. Those on untreated carbon were uniform in most regions but coalesced in others. On O₂ plasma treated carbon agglomeration of the platinum nanoparticles was significant. XRD showed that the catalysts were composed of face-centered cubic Pt nanoparticles and XPS showed that they were metallic with no oxides present. Cyclic voltammetry and chronoamperometry were used to study methanol electrooxidation on the Pt/C catalysts in a solution of 0.5 M H₂SO₄ + 0.5 M CH₃OH, and showed that the catalytic activity those using H₂ and Ar plasma treated carbon was higher than for the untreated one. Catalysts supported by O₂ plasma treated carbon showed no catalytic activity. The treatment atmosphere of carbon therefore had a large effect on the catalyst performance, with the H₂ plasma being the best.     

Synthesis and characterization of Nafion-stabilized Pt nanoparticles for polymer electrolyte fuel cells

Platinum nanoparticles are synthesized by alcohol reduction method using Nafion as a stabilizer under various conditions such as the Nafion/Pt molar ratio and reflux temperature. Nafion-Pt nanoparticles are characterized by agglomeration and the particle size is typically in the range of 2-4 nm. The electrocatalytic activity of Nafion-Pt nanoparticles for polymer electrolyte and direct methanol fuel cells (PEFCs and DMFCs) is investigated in comparison to that of unsupported Pt black and carbon-supported Pt/C electrocatalysts. Nafion-Pt nanoparticles prepared with low Nafion/Pt ratios show higher and/or comparable activities towards O₂ reduction reaction in the absence and presence of methanol in comparison to that of Pt black and Pt/C electrocatalysts. In contrast, the electrocatalytic activity of the Nafion-Pt nanoparticles for the methanol oxidation reaction is very low. The results indicate that Pt nanoparticles embedded in Nafion polyelectrolyte are potential methanol tolerant electrocatalysts for the O₂ reduction reaction in DMFCs.     

Controlled Synthesis of Pt3Sn/C Electrocatalysts with Exclusive Sn–Pt Interaction Designed for Use in Direct Methanol Fuel Cells

Alloy-type Sn–Pt/C electrocatalysts with Pt/Sn = 1.8–3.0 ratios and exclusive Sn–Pt interaction have been prepared by means of controlled surface reactions (CSRs). As demonstrated by XRD, the incorporation of Sn onto Pt/C was achieved satisfactorily yielding a near-stoichiometric fcc Pt₃Sn alloy phase along with a certain amount of the Pt_(1 ? x)Sn_x solid solution. The content and dispersion of the fcc Pt₃Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. No evidence of the presence of SnO₂ phases in the Sn-modified Pt/C samples was found by means of the XRD and EDS analysis. According to in situ XPS studies, the pre-treatment in hydrogen at 350 °C resulted in complete reduction of tin to Sn⁰. These results demonstrate that the method of CSRs is a powerful tool to create of Pt–Sn bimetallic nanoparticles exclusively, without tin introduction onto the carbon support. The performance of the intermetallic SnPt/C catalysts in the CO and methanol electrooxidation reactions depends on the actual composition of the exposed surface and the size of bimetallic particles. In the consecutive tin introduction the decrease of the amount of SnEt₄ precursor added per period, accompanied with an increase of the number of anchoring periods, resulted in an increase of the activity in both electrooxidation reactions as a consequence of an optimal balance of Pt/C ratio, the content of fcc Pt₃Sn phase and metal particle size. It was demonstrated that the increasing tin content above a certain (optimal) amount gives rise to a negative effect on the catalyst performance in the CO and methanol electrooxidation.     

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.     

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.     

The efficiency of methanol conversion to CO2 on thin films of Pt and PtRu fuel cell catalysts

Yields were determined for the CO₂ produced upon the electrochemical oxidation of 1.0 M methanol in 0.1 M HClO₄ at the following four fuel cell catalyst systems: Pt black, Pt at 10 wt.% metal loading on Vulcan XC-72R carbon (C/Pt, 10%), PtRu black at 50 at.% Pt, 50 at.% Ru (PtRu (50:50) black), and PtRu at 30 wt.% Pt, 15 wt.% Ru loading on Vulcan XC-72R carbon (C/PtRu, 30 wt.% Pt, 15 wt.% Ru). Samples were electrolyzed in a small volume (50 μl) arrangement for a period of 180 s keeping the reactant depletion in the cell below 1%. The dissolved CO₂ produced was determined ex situ by infrared spectroscopy in a micro-volume transmission flow cell. For the PtRu materials, the efficiencies for CO₂ formation were near 100% at reaction potentials in the range between 0.4 V (versus the reversible hydrogen electrode (RHE), V_RHE ) and 0.9 V_RHE. At the Pt catalysts, the yields of CO₂ approached 80% between 0.8 and 1.1 V_RHE and declined rapidly below 0.8 V_RHE.     

Pt0．55Co0．45合金应用不同的碳基体作为质子交换膜燃料电池阴极催化剂的研究

分别选用VulcanXC-72和双壁碳纳米管（DWCNTs）作为碳基体,采用化学还原法制备了20％的Pt0.5Co0．45／C催化剂。合成的材料Pt055co0.45／C采用XRD和TEM手段进行表征,电化学性能通过循环伏安（CV）和稳态技术进行了检测。电化学测试结果表明,Pr0.55Co0.45／DWCNTs对氧还砸催化性能优于Pt055C0045／VulcanXC-72,并HDWCNTs具有比VulcanXC．72更好的稳定性。这说明DWCNTs是比VulcanXC－72更有效地催化剂载体。     

Colloid-imprinted carbon with tailored nanostructure as an unique anode electrocatalyst support for formic acid oxidation

Colloid-imprinted carbon (CIC) with tailored mesopore size of ca. 22 nm and highly developed interconnected nanoporous structure was synthesized and explored for the first time as an anode catalyst support in direct formic acid fuel cell. The CIC-22 possesses superb structural characteristics such as uniform morphology, well-developed porosity, large specific surface area and pore volume, and high electrical conductivity. The unique characteristics make the CIC-22 a potentially effective support for Pt–Ru anode electrocatalysts toward oxidation of formic acid. Enhancement by 78% in electrocatalytic activity toward the formic acid oxidation has been demonstrated by the CIC-22-supported Pt₅₀Ru₅₀ (60 wt%) catalyst compared with the commercial carbon black Vulcan XC-72-supported one.     

Nitrogen-containing graphitized carbon support for methanol oxidation Pt catalyst

Graphitized carbon (GrC) with a relatively uniform pore size was synthesized using polyvinylpyrrolidone as a nitrogen-containing carbon source. Ni was employed as both a graphitization catalyst and a pore structure template. The polyol method was applied to load Pt nanoparticles with a narrow distribution of sizes on the synthesized GrC. The Pt catalyst supported on GrC showed higher electrocatalytic activity than that supported on heat-treated Vulcan XC-72R carbon despite the small specific surface area of GrC. Mass- and area-normalized current densities of Pt/GrC were 2.2 and 3.0 times greater than those for Pt catalyst supported on the commercial carbon, respectively. The better performance of the Pt/GrC could be due to high electric conductivity and interaction between GrC and Pt nanoparticles resulting from the presence of nitrogen in the prepared GrC.     

On the influence of Pt particle size on the PEMFC cathode performance

Colloidal suspensions of almost spherical and crystalline Pt nanoparticles between 1.6 and 2.6 nm in diameter and with narrow size distribution were synthesized using the phase transfer method (PTM) with alkylamines, C_nNH₂, as stabilizing agents. Batches of such homogenous Pt-C_nNH₂ (n = 8, 12) nanocrystals were deposited onto Vulcan XC-72 carbon powder, and the activity for the oxygen reduction reaction (ORR) of this series of Pt/C materials was evaluated under PEMFC conditions. The aim was to elucidate whether this type of stabilized Pt nanoparticles were as active for the ORR as a corresponding commercial Pt/C material, and if any difference in mass activity could be observed between catalysts with different Pt particle size. In the PEMFC experiments, i.e. voltammetry in oxygen and nitrogen, it was found that, after an initial electrode activation, the ORR activity of the catalysts prepared from the alkylamine-stabilized Pt nanoparticles deposited on carbon was as high as that of the employed commercial reference catalyst. In fact, all samples in the Pt/C series showed high and very similar ORR activity normalized to Pt-loading, without significant dependence on the initial Pt particle size. However, pre- and post-electrochemical characterization of the Pt/C material series with TEM showed that structural changes of the Pt nanoparticles occurred during electrochemical evaluation. In all samples studied the mean Pt particle size increased during the electrochemical evaluation resulting in decreased differences between the samples explaining the observed similar ORR performance of the different materials. These results emphasize the necessity of post-operation characterization of fuel cell catalysts when discussing electrocatalytic activity. In addition, employing complex preparation efforts for lowering the Pt particle size below 3 nm may have limited practical value unless the particles are stabilized from electrochemical sintering.     

Enhancement of oxygen reduction by incorporation of heteropolytungstate into the electrocatalytic ink of carbon supported platinum nanoparticles

Nafion stabilized inks of Vulcan XC-72 supported platinum (20 wt.%) nanoparticles (Pt/XC-72) were utilized to produce electrocatalytic films on glassy carbon. The catalysts were modified (activated) with phosphododecatungstic acid H₃PW₁₂O₄₀ (PW₁₂). Comparison was made to bare (PW₁₂-free) electrocatalytic films. Electroreduction of dioxygen was studied at 25 °C in 0.5 mol dm⁻³ H₂SO₄ electrolyte using rotating disk voltammetry. For the same loading of platinum (≈95 μg cm⁻²) and for the approximately identical distribution of the catalyst, the reduction of oxygen at a glassy carbon electrode modified with the ink containing PW₁₂ proceeded at ca. 30-60 mV more positive potential (depending on the PW₁₂ content), and the system was characterized by a higher kinetic parameter (rate of heterogeneous electron transfer), when compared to the PW₁₂-free electrocatalyst. Gas diffusion electrodes with Pt/XC-72 supported on carbon paper (Pt loading 1 mg cm⁻²) were also tested. Under the same experimental conditions, while the exchange current density and the total resistance contribution to polarization components, computed from the galvanostatic polarization curves were found to be clearly higher and lower, respectively, for the ink modified with PW₁₂ relative to the unmodified system. The results demonstrate that addition of heteropolytungstatic acid (together with Nafion) enhances the electrocatalytic activity of platinum towards reduction of oxygen.     

TiO2@carbon core-shell nanostructure supports for platinum and their use for methanol electrooxidation

Nanostructures consisting of TiO₂ particles as a core and carbon as a shell (TiO₂@C) were prepared by heat treatment of TiO₂ nanoparticles at 700 or 900 °C in a methane atmosphere. X-ray diffraction and transmission electron microscopy showed that a carbon shell layer was formed whose thickness increased with increasing reaction temperature. These structures were used as supports for platinum nanoparticles and the hybrid particles exhibit improved catalytic activity and stability toward methanol electrooxidation compared to Pt on a carbon black (Vulcan XC-72R). It is likely that enhanced catalytic properties of the Pt on TiO₂@C could be due to the stability of the core-shell support in comparison with carbon black support.     

Polyaniline-carbon composite films as supports of Pt and PtRu particles for methanol electrooxidation

Vulcan XC-72 carbon black particles (average size: ca. 50 nm) was incorporated into polyaniline (PANI) matrix by an electrochemical codeposition technique during the electropolymerization process. The doping by carbon particles leads to a higher polymeric degree and a lower defect density in the PANI structure. Furthermore, the incorporation of carbon particles not only increases the electrochemical accessible surface areas (S_a) and electron conductivity of the PANI film, but also decreases charge transfer resistance at PANI/electrolyte interfaces. Therefore, as expected, a fabricated PANI + C composite film with dispersed Pt and PtRu particles exhibited excellent electrocatalytic activity for methanol oxidation due to better Pt dispersion and utilization. The PANI + C composite film is more promising as a support material in electrocatalysis than a PANI film. Meanwhile, a new application for regular carbon black as a doping material into conducting polymer for electrocatalysis was thus demonstrated.