Performance Comparison of Pt1–xPdx/Carbon Nanotubes Catalysts in Both Electrodes of Polymer Electrolyte Membrane Fuel Cells

The catalytic activity of Pt_1–xPd_x nanoparticles supported on carbon nanotubes (CNTs) was evaluated for both the hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR) of polymer electrolyte membrane fuel cells (PEMFCs). Using a colloidal method, Pt_1–xPd_x/CNTs catalysts (x = 0, 0.46, 0.76, and 0.9) were prepared, and their physical and electrochemical characteristics were analyzed using a variety of characterization techniques, including XRD, TEM, energy dispersive spectrometer, cyclic voltammetry, and electrochemical impedance spectroscopy. Both Pt and Pd atoms formed a continuous solid solution and thus were randomly mixed in Pt_1–xPd_x nanoparticles. Due to the high hydrogen absorption of Pd, the use of Pd in the catalyst provided an advantage for HOR but a disadvantage for ORR. The Pt_0.53Pd_0.47/CNTs catalyst in the anode and cathode showed the best cell performance of PEMFCs.     

The inclusion of Mo, Nb and Ta in Pt and PtRu carbon supported electrocatalysts in the quest for improved CO tolerant PEMFC anodes

The effect of the inclusion of Mo, Nb and Ta in Pt and PtRu carbon supported anode electrocatalysts on CO tolerance in proton exchange membrane fuel cells (PEMFC) has been investigated by cyclic voltammetry and fuel cell tests. CO stripping voltammetry on binary Pt_xM/C (M: Mo, Nb, Ta) reveals partial oxidation of the CO adlayer at low potential, with PtMo (4:1)/C exhibiting the lowest value. At 80 °C, the operating temperature of the fuel cell, CO oxidation was observed at potentials close to 0 V versus the reversible hydrogen electrode (RHE). No significant difference for CO electro-oxidation at the lower potential limit, compared to PtRu/C, was observed for PtRuM_y/C (M: Mo, Nb). Fuel cell tests demonstrated that while all the prepared catalysts exhibited enhanced performance compared to Pt/C, only the addition of a relatively small amount of Mo to PtRu results in an electrocatalyst with a higher activity, in the presence of carbon monoxide, to PtRu/C, the current catalyst of choice for PEM fuel cell applications.     

Rapid Microwave‐Assisted Solvothermal Synthesis of Methanol Tolerant Pt–Pd–Co Nanoalloy Electrocatalysts

We report here a microwave‐assisted solvothermal (MW‐ST) method to synthesise carbon‐supported multimetallic nanostructured alloys of Pt, Pd and Co with high crystallinity and homogeneity for electrocatalytic application in fuel cells. Multimetallic nanoalloy electrocatalysts have been synthesised by a one‐pot, rapid MW‐ST method within 15 min at <300 °C without any post‐annealing in reducing gas atmospheres. For a comparison, same multimetallic alloys were also synthesised by heat treatment of co‐precipitated metals. Significant differences were observed in the phase structure and surface composition of the alloys synthesised by the two methods, which were rationalised based on the synthesis procedures adopted. Further, the multimetallic alloys were also explored for their electrocatalytic applications as cathode catalysts for oxygen reduction reaction (ORR). The multimetallic alloys, synthesised by the MW‐ST method, show much higher ORR activity compared to their counterparts synthesised by the conventional borohydride reduction method. While the ORR activity of Pt₇₀Pd₂₀Co₁₀ is comparable to that of commercial Pt, the ORR activity of Pt₅₀Pd₃₀Co₂₀ in direct methanol fuel cells (DMFC) is superior to that of commercial Pt at high methanol concentrations due to its high tolerance to methanol that may crossover from the anode to the cathode.     

Electrooxidation of formic acid on carbon supported PtxPd1−x (x = 0-1) nanocatalysts

In this work, carbon supported Pt_xPd_1−x (x = 0-1) nanocatalysts were investigated for formic acid oxidation. These catalysts were synthesized by a surfactant-stabilized method with 3-(N,N-dimethyldodecylammonio) propanesulfonate (SB12) as the stabilizer. They show better Pt/Pd dispersion and higher catalytic performance than the corresponding commercial catalysts. Furthermore, the electrocatalytic properties of Pt_xPd_1−x/C were found to depend strongly on the Pt/Pd deposition sequence and on the Pt/Pd atomic ratio. At a lower potential, formic acid oxidation current on co-deposited Pt_xPd_1−x/C catalysts increase with increasing Pd surface concentration. Nanoscale Pd/C is a promising formic acid oxidation catalyst candidate for the direct formic acid fuel cell.     

A Study on Process Parameters of Direct Ethanol Fuel Cell

Ethanol is one of the promising future fuels of Direct Alcohol Fuel Cells (DAFC). The electro‐oxidation of ethanol fuel on anode made of carbon‐supported Pt‐Ru electrode catalysts was carried out in a lab scale direct ethanol fuel cell (DEFC). Cathode used was Pt‐black high surface area. The membrane electrode assembly (MEA) was prepared by sandwiching the solid polymer electrolyte membrane, prepared from Nafion^® (SE‐5112, DuPont USA) dispersion, between the anode and cathode. The DEFC was fabricated using the MEA and tested at different catalyst loadings at the electrodes, temperatures and ethanol concentrations. The maximum power density of DEFC for optimized value of ethanol concentration, catalyst loading and temperature were determined. The maximum open circuit voltage (OCV) of 0.815 V, short circuit current density (SCCD) of 27.90 mA/cm² and power density of 10.30 mW/cm² were obtained for anode (Pt‐Ru/C) and cathode (Pt‐black) loading of 1 mg/cm² at a temperature of 90°C anode and 60°C cathode for 2M ethanol.     

Stability characteristics of Pt1Ni1/C as cathode catalysts in membrane electrode assembly of polymer electrolyte membrane fuel cell

To understand the difference in degradation characteristics between carbon-supported platinum (Pt/C) and platinum–nickel alloy (Pt₁Ni₁/C) cathode catalysts in membrane electrode assemblies (MEAs) of a polymer electrolyte membrane fuel cell (PEMFC), constant current operation of MEA in a single cell was conducted for 1100 h. A significant change in cell potential for the Pt₁Ni₁/C MEA was observed throughout the test. High-resolution transmission electron microscopy showed that sintering and detachment of metal particles in the Pt₁Ni₁/C catalyst occurred more sparingly than in the Pt/C catalyst. Instead, X-ray photoelectron spectroscopy element mapping revealed dissolution of Ni atoms in the Pt₁Ni₁ catalysts even when the Pt₁Ni₁/C catalyst used in the MEA was well synthesized.     

High Electrochemical Performance and Stability of Co-Deposited Pd–Au on Phase-Pure Tungsten Carbide for Hydrogen Oxidation

Co-deposited Pd and Au nanoparticles were loaded on phase-pure tungsten mono-carbide (WC) prepared by a polymer-induced carburization method. Among the electrocatalysts, Pd₃Au/WC displayed an excellent electrochemical activity for the hydrogen oxidation reaction comparable to the state-of-the-art Pt/C catalyst both in half-cell tests and single cell tests under proton exchange membrane fuel cell (PEMFC) conditions. This unique and strong synergistic effect was not observed on the carbon support, and thus the crucial role of WC was demonstrated as a strongly interacting support as well as an active component of the electrocatalyst. Dissolution of Pd observed on the carbon support was suppressed in this Pd₃Au/WC electrocatalyst, which showed good stability in a continuous operation for 3,000?min. Thus the proposed electrocatalyst could be a potential alternative anode catalyst of lower cost for PEMFC replacing Pt/C.     

Mathematical model for a direct propane phosphoric acid fuel cell

A mathematical model was developed and used to predict the performance of direct propane phosphoric acid (PPAFC) fuel cells, utilizing both Pt/C state-of the-art electrodes and older Pt black electrodes. It was found that the overpotential caused by surface processes on the platinum catalyst in the anode is much greater than the potential losses caused by either ohmic resistance or propane diffusion in gas-filled and liquid-filled pores. In one comparison, the anode overpotential (0.5 V) was larger than the cathode overpotential (0.3 V) at a current density of 0.4 A cm⁻² for Pt loadings 4 mg Pt cm⁻². The need for sufficient water concentration at the anode, where water is a reactant, was indicated by the large effect of H₃PO₄ concentration. In another comparison, the model predicted that at 0.2 A cm⁻², modern carbon supported Pt catalysts would produce 0.35 V compared to 0.1 V for unsupported Pt black catalysts that were used several decades ago, when the majority of the research on direct hydrocarbon fuel cells was performed. The propane anode and oxygen cathode catalyst layers were modeled as agglomerates of spherical catalyst particles having their interior spaces filled with liquid electrolyte and being surrounded by gas-filled pores. The Tafel equation was used to describe the electrochemical reactions. The model incorporated gas and liquid-phase diffusion equations for the reactants in the anode and cathode and ionic transport in the electrolyte. Experimental data were used for propane and oxygen diffusivities, and for their solubilities in the electrolyte. The accuracy of the predicted electrical potentials and polarization curves were normally within ±0.02 V of values reported in experimental investigations of temperature and electrolyte concentration. Polarization curves were predicted as a function of temperature, pressure, electrolyte concentration, and Pt loading. A performance of 0.45 V at 0.5 A cm⁻² was predicted at some conditions.     

Recent progress in selective CO removal in a H2-rich stream

In this review, recent works related to the selective CO removal in a H₂-rich stream for the application of the low-temperature fuel cell are discussed. The membrane separation, the selective CO hydrogenation, and the preferential CO oxidation (PROX) have been generally studied to meet the requirement for the polymer electrolyte membrane fuel cell (PEMFC) where the CO concentration should be controlled to be less than 10 ppm not to degrade the electrochemical performance of Pt anode. For the membrane separation, the thin layer of Pd-based alloy metal on the porous ceramic material coupled with the catalytic purification is the most advanced method at present. For PROX catalysts, supported Ru catalysts and Pt-based alloy catalysts have been successfully developed so far. The combination of highly selective PROX catalysts and the CO methanation catalyst can provide the extended temperature range to achieve the acceptable CO removal. Because each method has presently its own weak points, the further advance is still in need. The non-noble metal-based membrane requiring smaller pressure differentials is highly plausible in the membrane separation. The highly selective catalyst for CO methanation in the presence of excess CO₂ and H₂O can simplify the CO removal step. The PROX catalyst should be operative over a wide reaction temperature as well as at low temperatures not to cause the reverse water–gas shift reaction. During the development of these catalysts, the progress on the high-temperature PEM fuel cell or the CO-tolerant anode should be carefully evaluated.     

Sonochemical synthesis of Pt-doped Pd nanoparticles with enhanced electrocatalytic activity for formic acid oxidation reaction

Pt-doped Pd nanoparticle catalysts (Pd _n Pt, n is 12, 15 and 19) supported on carbon were synthesized by an ultrasound assisted polyol method. The catalysts were characterized by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The electrochemical activity of the electrocatalysts was investigated in terms of formic acid oxidation reaction (FAOR) at low concentration of formic acid in 0.1 M perchloric acid at room temperature. Formic acid oxidation on the Pd _n Pt/C commences at lower potential than a commercial Pt/C. Pd₁₉Pt/C catalyst showed the highest catalytic activity in FAOR compared to that of other catalysts. The obtained electrochemical results from voltammograms indicate that Pt-doped Pd catalysts can be a promising candidate for the anode material in direct formic acid fuel cells. The synthesis procedure is not only a very facile route but also a mass producible method for preparing carbon supported alloy nanoparticles.     

High Performance by Applying IrCo/C Nanoparticles as an Anode Catalyst for PEMFC

IrCo bimetallic anode catalysts for polymer electrolyte membrane fuel cell (PEMFC) have been synthesized with a modified ethylene glycol method. X‐ray diffraction, TEM, CV, and linear sweep voltammetry results show that after the modification of Co, Ir nanoparticles supported on carbon exhibit high activity for hydrogen oxidation reaction (HOR). The maximum power density of 610.5 mW cm^–2 of a 50 cm² single cell is achieved using 20%Ir–30%Co/C catalyst as the anode, with a loading of 0.2 mg_Ir cm^–2. It is suggested that IrCo/C proposed in this work may be used as anode catalyst of PEMFC.     

Importance of catalyst stability vis-à-vis hydrogen peroxide formation rates in PEM fuel cell electrodes

The role of catalyst stability on the adverse effects of hydrogen peroxide (H₂O₂) formation rates in a proton exchange membrane fuel cell (PEMFC) is investigated for Pt, Pt binary (PtX, X = Co, Ru, Rh, V, Ni) and ternary (PtCoX, X = Ir, Rh) catalysts supported on ketjen black (KB) carbon. The selectivity of these catalysts towards H₂O₂ formation in the oxygen reduction reaction (ORR) was measured on a rotating ring disc electrode. These measured values were used in conjunction with local oxygen and proton concentrations to estimate local H₂O₂ formation rates in a PEMFC anode and cathode. The effect of H₂O₂ formation rates on the most active and durable of these catalysts (PtCo and PtIrCo) on Nafion membrane durability was studied using a single-sided membrane electrode assembly (MEA) with a built-in reference electrode. Fluoride ion concentration in the effluent water was used as an indicator of the membrane degradation rate. PtIrCo had the least fluorine emission rate (FER) followed by PtCo/KB and Pt/KB. Though PtCo and PtIrCo show higher selectivity for H₂O₂ formation than unalloyed Pt, they did not contribute to membrane degradation. This result is explained in terms of catalyst stability as measured in potential cycling tests in liquid electrolyte as well as in a functional PEM fuel cell.     

Membrane electrode assembly with Pt/SiO2/C anode catalyst for proton exchange membrane fuel cell operation under low humidity conditions

In this work, a novel self-humidifying membrane electrode assembly (MEA) with Pt/SiO₂/C as anode catalyst was developed to improve the performance of proton exchange membrane fuel cell (PEMFC) operating at low humidity conditions. The characteristics of the composite catalysts were investigated by XRD, TEM and water uptake measurement. The optimal performance of the MEA was obtained with the 10 wt.% of silica in the composite catalyst by single cell tests under both high and low humidity conditions. The low humidity performance of the novel self-humidifying MEA was evaluated in a H₂/air PEMFC at ambient pressure under different relative humidity (RH) and cell temperature conditions. The results show that the MEA performance was hardly changed even if the RHs of both the anode and cathode decreased from 100% to 28%. However, the low humidity performance of the MEA was quite susceptible to the cell temperature, which decreased steeply as the cell temperature increased. At a cell temperature of 50 °C, the MEA shows good stability for low humidity operating: the current density remained at 0.65 A cm⁻² at a usual work voltage of 0.6 V without any degradation after 120 h operation under 28% RH for both the anode and cathode.     

Porous Carbon as Anode Catalyst Support to Improve Borohydride Utilization in a Direct Borohydride Fuel Cell

Our study explores the use of porous carbon as anode catalyst support to improve borohydride utilization in a direct borohydride fuel cell. Pt catalysts supported by carbon aerogel (CA) and macroporous carbon (MPC) are synthesized by template method. The pores in porous carbon materials catch hydrogen bubbles to regulate the contact of anolyte with catalytic sites, and this leads to the depression of hydrogen evolution during BH₄⁻ electrooxidation. However, the hydrogen bubbles in the pores simultaneously deteriorate charge carrier transport and thus increase anode polarization. The CA‐supported Pt catalyst improves the coulombic efficiency of BH₄⁻ electrooxidation. However, the MPC‐supported Pt catalyst performed better than the CA‐supported Pt catalyst. MPC also has a good pore distribution, which improves the coulombic efficiency of BH₄⁻ electrooxidation without decreasing anode performance.     

Insights on the SO2 poisoning of Pt3Co/VC and Pt/VC fuel cell catalysts

SO₂ poisoning of carbon-supported Pt₃Co (Pt₃Co/VC) catalyst is performed at the cathode of proton exchange membrane fuel cells (PEMFCs) in order to link previously reported results at the electrode/solution interface to the FC environment.First, the surface area of Pt₃Co/VC catalyst is rigorously characterized by hydrogen adsorption, CO stripping voltammetry and underpotential deposition (upd) of copper adatoms. Then the performance of PEMFC cathodes employing 30 wt.% Pt₃Co/VC and 50 wt.% Pt/VC catalysts is compared after exposure to 1 ppm SO₂ in air for 3 h at constant cell voltage of 0.6 V. In agreement with results reported for the electrode/solution interface, the Pt₃Co/VC is more susceptive to SO₂ poisoning than Pt/VC at a given platinum loading.Both catalysts can be recovered from adsorbed sulfur species by running successive polarization curves in air or cyclic voltammetry (CV) in inert atmosphere. However, the activity of Pt₃Co/VC having ∼3 times higher sulfur coverage is recovered more easily than Pt/VC. To understand the difference between the two catalysts in terms of activity recovery, platinum-sulfur interaction is probed by thermal programmed desorption at the catalyst/inert gas interface and CV at the electrode/solution interface and in the FC environment.     

Preparation of cost-effective Pt–Co electrodes by pulse electrodeposition for PEMFC electrocatalysts

Low loading platinum–cobalt (Pt–Co) cathode catalyst on a Nafion(Na⁺)-bonded carbon layer is fabricated by using galvanostatic pulse technique to show the advantage of electrodeposition for high utilization of catalyst in proton exchange membrane fuel cell (PEMFC). We observed that Pt–Co catalysts evenly exist on the surface of carbon electrode and its thickness is about 5.8 μm, which is four times thinner than conventional Pt/C. Improved single cell power performance of Pt–Co cathode catalysts with a ratio of 3.2:1 compared with Pt/C is clearly presented.     

Carbon supported and unsupported Pt–Ru anodes for liquid feed direct methanol fuel cells

A comparative study of the use of supported and unsupported catalysts for direct methanol fuel cells has been performed. The effect of catalyst loading, fuel concentration and temperature dependence on the anode, cathode and full fuel cell performance was determined in a fuel cell equipped with a reversible hydrogen reference electrode. Although the measured specific activities of supported catalysts were as much as 3-fold greater than the unsupported catalysts, membrane electrode assemblies prepared with supported catalysts showed no improvement with loadings above 0.5 mg/cm². Fuel cells utilizing 0.46 mg/cm² supported catalyst electrodes performed as well as unsupported catalyst electrodes with 2 mg/cm². The temperature dependence and methanol concentration dependence studies both suggest increased methanol permeation through the thinner supported catalyst layers relative to the unsupported catalyst layers.     

A comparison of three carbon nanoforms as catalyst supports for the oxygen reduction reaction

Defective graphene nanosheets (GNSs), single-walled carbon nanotubes (SWCNTs), and herringbone graphite nanofibres (GNFs) were used as Pd₃Pt₁ catalyst supports for an oxygen reduction reaction (ORR). Raman spectroscopy and cyclic voltammetry analyses revealed oxygen-containing functional groups and physical defects on the surfaces of the SWCNTs, GNFs, and synthesised GNSs. Mass-transfer-corrected Tafel diagrams obtained in an O₂-saturated electrolyte showed that the SWCNTs with a high curvature allowed for more surface Pt atoms; thus, these Pd₃Pt₁ catalysts are the first SWCNT system to promote the ORR. These catalysts, however, were slower than the GNS-supported catalysts after 0.875 V (vs. SCE; saturated calomel electrode). In terms of the kinetic current density, the highest mass activity was found for the Pd₃Pt₁/GNS composites. Additionally, according to rotating-ring disk electrode (RRDE) measurements, the H₂O production efficiencies for the Pd₃Pt₁/GNS, Pd₃Pt₁/SWCNT, and Pd₃Pt₁/GNF systems were 70.35%, 66.7%, and 9.58%, respectively. Among these carbon supports, Pd₃Pt₁ on GNS showed the greatest efficiency and durability for producing H₂O via an approximate four-electron pathway; this efficiency was ascribed to metal-support interaction.     

Screening of PdM and PtM catalysts in a multi-anode direct formic acid fuel cell

Direct formic acid fuel cells (DFAFC) currently employ either Pt-based or Pd-based anode catalysts for oxidation of formic acid. However, improvements are needed in either the activity of Pt-based catalysts or the stability of Pd-based catalysts. In this study, a number of carbon-supported Pt-based and Pd-based catalysts, were prepared by co-depositing PdM (M = Bi, Mo, or V) on Vulcan^® XC-72 carbon black, or depositing another metal (Pb or Sn) on a Pt/C catalyst. These catalysts were systematically evaluated and compared with commercial Pd/C, PtRu/C, and Pt/C catalysts in a multi-anode DFAFC. The PtPb/C and PtSn/C catalysts were found to show significantly higher activities than the commercial Pt/C catalyst, while the PdBi/C provided higher stability than the commercial Pd/C catalyst.     

Investigation of carbon-supported Pt and PtCo catalysts for oxygen reduction in direct methanol fuel cells

Carbon-supported Pt and Pt₃Co catalysts with a mean crystallite size of 2.5 nm were prepared by a colloidal procedure followed by a carbothermal reduction. The catalysts with same particle size were investigated for the oxygen reduction in a direct methanol fuel cell (DMFC) to ascertain the effect of composition. The electrochemical investigations were carried out in a temperature range from 40 to 80 °C and the methanol concentration feed was varied in the range 1-10 mol dm⁻³ to evaluate the cathode performance in the presence of different conditions of methanol crossover. Despite the good performance of the Pt₃Co catalyst for the oxygen reduction, it appeared less performing than the Pt catalyst of the same particle size for the cathodic process in the presence of significant methanol crossover. Cyclic voltammetry analysis indicated that the Pt₃Co catalyst has a lower overpotential for methanol oxidation than the Pt catalyst, and thus a lower methanol tolerance. Electrochemical impedance spectroscopy (EIS) analysis showed that the charge transfer resistance for the oxygen reduction reaction dominated the overall DMFC response in the presence of high methanol concentrations fed to the anode. This effect was more significant for the Pt₃Co/KB catalyst, confirming the lower methanol tolerance of this catalyst compared to Pt/KB. Such properties were interpreted as the result of the enhanced metallic character of Pt in the Pt₃Co catalyst due to an intra-alloy electron transfer from Co to Pt, and to the adsorption of oxygen species on the more electropositive element (Co) that promotes methanol oxidation according to the bifunctional theory.