A comparative study of electrochemical methods on Pt–Ru DMFC anode catalysts: The effect of Ru addition

In the present study comparative electrochemical study of methanol electro-oxidation reaction, the effect of ruthenium addition and experimental parameters on methanol electro-oxidation reaction at high performance carbon supported Pt and Pt–Ru catalysts have been studied by cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) in H₂SO₄ (0.05–2.00 M) + CH₃OH (0.01–4.00 M) at 20–70 °C. Tafel plots for the methanol oxidation reaction on Pt and Pt–Ru catalysts show reasonably well-defined linear region with the slopes of 128–174 mV dec⁻¹(α = 0.34–0.46). The activation energies from Arrhenius plots have been found as 39.06–50.65 kJ mol⁻¹. As a result, methanol oxidation is enhanced by the addition of ruthenium. Furthermore, Pt–Ru (25:1) catalyst shows best electro–catalytic activity, higher resistance to CO, and better long term stability compared to Pt–Ru (3:1), Pt–Ru (1:1), and Pt. Finally, the EIS measurements on Pt–Ru (25:1) catalyst reveals that methanol electro-oxidation reaction consists of two process: methanol dehydrogenation step at low potentials (<700 mV) and the oxidation removal of CO_ads by OH_ads at higher potentials (>700 mV).     

Electrochemical impedance studies of electrooxidation of methanol and formic acid on Pt/C catalyst in acid medium

Cyclic voltammetry (CV), amperometric i − t experiments, and electrochemical impedance spectroscopy (EIS) measurements were carried out by using glassy carbon disk electrode covered with the Pt/C catalyst powder in solutions of 0.5 mol L⁻¹ H₂SO₄ containing 0.5 mol L⁻¹ CH₃OH and 0.5 mol L⁻¹ H₂SO₄ containing 0.5 mol L⁻¹ HCOOH at 25 °C, respectively. Electrochemical measurements show that the activity of Pt/C for formic acid electrooxidation is prominently higher than for methanol electrooxidation. EIS information also discloses that the electrooxidation of methanol and formic acid on the Pt/C catalyst at various polarization potentials show different impedance behaviors. The mechanisms and the rate-determining steps of formic acid electrooxidation are also changed with the increase of the potential. Simultaneously, the effects of the electrode potentials on the impedance patterns were revealed.     

Methanol oxidation on carbon-supported Pt–Ru–Ni ternary nanoparticle electrocatalysts

Methanol oxidation on carbon-supported Pt–Ru–Ni ternary alloy nanoparticles was investigated based on the porous thin-film electrode technique and compared with that on Johnson–Matthey Pt–Ru alloy catalyst. Emphasis is placed on the effect of alloying degree on the electrocatalytic activity and stability of the ternary catalysts. The as-prepared Pt–Ru–Ni nanoparticles exhibited a single phase fcc disordered structure, and a typical TEM image indicates that the mean diameter is ca. 2.2 nm, with a narrow particle size distribution. Also, the as prepared Pt–Ru–Ni catalysts exhibited significantly enhanced electrocatalytic activity and good stability for methanol oxidation in comparison to commercial Pt–Ru catalyst available from Johnson–Matthey. The highest activity of methanol oxidation on Pt–Ru–Ni catalysts was found with a Pt–Ru–Ni atomic ratio of 60:30:10 and at a heat-treatment temperature of ca. 175 °C. The significantly enhanced catalytic activity for methanol oxidation is attributed to the high dispersion of the ternary catalyst, to the role of Ni as a promotion agent, and especially to the presence of hydroxyl Ru oxide. Moreover, the stability of the ternary nanocatalytic system was found to be greatly improved at heat-treatment temperatures higher than ca. 250 °C, likely due to a higher alloying degree at such temperatures for the ternary catalysts.     

Electroactivity of high performance unsupported Pt–Ru nanoparticles in the presence of hydrogen and carbon monoxide

The electrochemical activity of high performance unsupported (1:1) Pt–Ru electrocatalyst in the presence of hydrogen and carbon monoxide has been studied using the thin-film rotating disk electrode (RDE) technique. The kinetic parameters of these reactions were determined in H₂- and CO-saturated 0.5 M H₂SO₄ solutions by means of cyclic voltammetry, including CO stripping, and RDE voltammetry. Pt–Ru/Nafion inks were prepared in one step with different Nafion mass fractions, allowing determining the ionomer influence in electrocatalytic response and obtaining the kinetic current density in absence of mass-transfer effects, being 41 and 12 mA cm² (geometrical area), for H₂ and CO oxidation, respectively. These values correspond to mass activities of 1.37 and 0.40 A mg_Pt¹ and to specific activities of 1.52 and 0.44 mA cm_Pt². The Tafel analysis confirmed that hydrogen oxidation was a two-electron reversible reaction, while CO oxidation exhibited an irreversible behavior with a charge-transfer coefficient of 0.42. The kinetic results for CO oxidation are in agreement with the bifunctional theory, in which the reaction between Pt–CO and Ru–OH is the rate-determining step. The exchange current density for hydrogen reaction was 0.28 mA cm² (active surface area), thus showing similar kinetics to those found for carbon-supported Pt and Pt–Ru electrocatalyst nanoparticles.     

Evaluation of Pt–Ru–Ni and Pt–Sn–Ni catalysts as anodes in direct ethanol fuel cells

In this study, the electrooxidation of ethanol on carbon supported Pt–Ru–Ni and Pt–Sn–Ni catalysts is electrochemically studied through cyclic voltammetry at 50 °C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt₇₅Ru₁₅Ni₁₀/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials.     

Impacts of air bleeding on membrane degradation in polymer electrolyte fuel cells

A long-term accelerated test (4600 h) of a 25 cm² single cell with excess air bleeding (5%) was carried out to investigate the effects of air bleeding on membrane degradation in polymer electrolyte fuel cells. The rate of membrane degradation was negligibly low (fluoride-ion release rate = 1.3 × 10⁻¹⁰ mol cm⁻² h⁻¹ in average) up to 2000 h. However, membrane degradation rate was gradually increased after 2000 h. The CO tolerance of the anode gradually dropped, which indicated that the anode catalyst was deteriorated during the test. The results of the rotating ring–disk electrode measurements revealed that deterioration of Pt–Ru/C catalyst by potential cycling greatly enhances H₂O₂ formation in oxygen reduction reaction in the anode potential range (∼0 V). Furthermore, membrane degradation rate of the MEA increased after the anode catalyst was forced to be deteriorated by potential cycling. It was concluded that excess air bleeding deteriorated the anode catalyst, which greatly enhanced H₂O₂ formation upon air bleeding and resulted in the increased membrane degradation rate after 2000 h.     

Methanol electrooxidation on synthesized PtRu nanocatalyst supported on acetylene black in half cell and in direct methanol fuel cell

We reported the direct reduction of H₂PtCl₆ and RuCl₃ solution containing acetylene black powder by Na₂S₂O₄ to make Pt–Ru (20–10 wt%) supported on acetylene black (Pt–Ru/AB) as a nanocatalyst for methanol electrooxidation in acidic media. The electrochemical activity of catalyst was studied by electrochemical impedance spectroscopy, linear sweep voltammetry, cyclic voltammetry and chronoamperometry. Structural aspects of the Pt–Ru (20–10 wt%)/AB were studied by transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques. The analysis of electrochemical results indicated lower charge transfer resistance, higher peak current for Pt–Ru (20–10 wt%)/AB compared to the commercial catalyst, Pt–Ru (20–10 wt%)/carbon Vulcan. XRD spectra verified a face centered cubic structure for the synthesized Pt–Ru/AB and its particle size was mostly 10 nm according to TEM and XRD images. In DMFC, Pt–Ru/AB had superior performance compared to the commercial catalyst in all current densities, which could be attributed to enhancement of the methanol oxidation kinetics, higher conductivity, and more uniform distribution of the ionomer in anode catalyst layer.     

Carbon supported nano-sized Pt–Pd and Pt–Co electrocatalysts for proton exchange membrane fuel cells

Nano-sized Pt–Pd/C and Pt–Co/C electrocatalysts have been synthesized and characterized by an alcohol-reduction process using ethylene glycol as the solvent and Vulcan XC-72R as the supporting material. While the Pt–Pd/C electrodes were compared with Pt/C (20 wt.% E-TEK) in terms of electrocatalytic activity towards oxidation of H₂, CO and H₂–CO mixtures, the Pt–Co/C electrodes were evaluated towards oxygen reduction reaction (ORR) and compared with Pt/C (20 wt.% E-TEK) and Pt–Co/C (20 wt.% E-TEK) and Pt/C (46 wt.% TKK) in a single cell. In addition, the Pt–Pd/C and Pt–Co/C electrocatalyst samples were characterized by XRD, XPS, TEM and electroanalytical methods. The TEM images of the carbon supported platinum alloy electrocatalysts show homogenous catalyst distribution with a particle size of about 3–4 nm. It was found that while the Pt–Pd/C electrocatalyst has superior CO tolerance compared to commercial catalyst, Pt–Co/C synthesized by polyol method has shown better activity and stability up to 60 °C compared to commercial catalysts. Single cell tests using the alloy catalysts coated on Nafion-212 membranes with H₂ and O₂ gases showed that the fuel cell performance in the activation and the ohmic regions are almost similar comparing conventional electrodes to Pt–Pd anode electrodes. However, conventional electrodes give a better performance in the ohmic region comparing to Pt–Co cathode. It is worth mentioning that these catalysts are less expensive compared to the commercial catalysts if only the platinum contents were considered.     

Alcohol electrooxidation at Pt and Pt–Ru sputtered electrodes under elevated temperature and pressurized conditions

The electrooxidation properties of methanol and 2-propanol, which are both promising candidates for direct alcohol fuel cells (DAFCs), have been studied under elevated temperature and pressurized conditions. Sputter-deposited Pt and Pt–Ru electrodes were well-characterized and utilized for the electrochemical measurement of the alcohol oxidation at 25–100 °C. The Pt electrode prepared at 600 °C had a flat surface, and the Pt–Ru formed an alloy. The electrochemical measurements were carried out in a gas-tight cell under elevated temperature, which accompanies the pressurized condition. This is a representative example of the DAFC rising temperature operation. As a result, at 25 °C, the onset potential of the 2-propanol oxidation is about 400 mV more negative than that of the methanol oxidation, and current density of the 2-propanol oxidation exceeds that of the methanol oxidation. Conversely, at 100 °C, the methanol oxidation current density overcomes that of 2-propanol, and the onset potentials of the two are almost the same. The highest current density for the methanol oxidation is obtained at the Pt:Ru = 50:50 electrode, whereas at the Pt:Ru = 35:65 for the 2-propanol oxidation. A Tafel plot analysis was employed to investigate the reaction mechanism. For the methanol oxidation, the number of electrons transferred during the rate-determining process is estimated to be 1 at 25 °C and 2 at 100 °C. This suggests that the methanol reaction mechanism differs at 25 and 100 °C. In contrast, the rate-determining process of the 2-propanol oxidation at 25 and 100 °C was expected to be 1-electron transfer which accompanies the proton-elimination reaction to produce acetone. Consequently, it is deduced that methanol and 2-propanol have an advantage under the rising temperature and room temperature operation, respectively.     

Operating characteristics of direct methanol fuel cell using a platinum–ruthenium catalyst supported on porous carbon prepared from mesophase pitch

The characteristics of a platinum–ruthenium catalyst supported on porous carbon (PC) are analysed by X-ray diffraction, scanning electron microscopy, cyclic voltammetry and chemisorption techniques. Single-cell tests are carried out in order to compare the performance of these catalysts as an anode in a direct methanol fuel cell with respect to that of a commercial-grade catalyst. The methanol oxidation rate on a Pt–Ru catalyst supported on PC with a pore size of 20 nm is about 35% higher than that on a commercial E-TEK catalyst. The catalyst (Pt–Ru/K20) in the single-cell test gives a power density of 90 and 126 mW cm⁻² under air and oxygen at 60 °C, respectively. These values are 15–16% higher than those obtained with a commercial E-TEK catalyst.     

Co-electrodeposition of Pt–Ru electrocatalysts in electrolytes with varying compositions by a double-potential pulse method for the oxidation of MeOH and CO

The co-eletrodeposition of Pt–Ru on carbon electrodes was carried out using a double-potential pulse method in electrolytes containing varying concentrations of RuCl₃ + H₂PtCl₆ in an attempt to deposit highly dispersed Pt–Ru electrocatalyst with a controlled composition. The amounts of the Pt and Ru deposited on the electrodes were analyzed using an inductively coupled plasma atomic emission spectrometer (ICP-AES). The results revealed that the Pt loading on the substrates increases linearly with H₂PtCl₆ concentrations in the bath while the Ru loading is not related to the concentration of RuCl₃, indicating that the reduction of Pt ions is the dominant reaction in the cathodic deposition of Pt–Ru clusters on the substrate. The Pt–Ru/C electrodes were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The optimum Ru content in the deposited Pt–Ru electrode for promoting the electro-oxidation of MeOH and adsorbed CO was found to be 25 atm%, by CO-stripping measurements in 0.5 M H₂SO₄ and by cyclic voltammography in a solution comprising CH₃OH (2.0 M) +0.5 M H₂SO₄ (0.5 M). SEM results showed that the generation of nucleation sites and growth of the deposits progresses continuously on carbon substrate and already deposited Pt–Ru particles. The particle size and loading amount of the deposits was found to increase with an increase in the number of cycles of the repeating double-potential pulse.     

Evaluation of the stability and durability of Pt and Pt–Co/C catalysts for polymer electrolyte membrane fuel cells

Carbon supported Pt and Pt–Co nanoparticles were prepared by reduction of the metal precursors with NaBH₄. The activity for the oxygen reduction reaction (ORR) of the as-prepared Co-containing catalyst was higher than that of pure Pt. 30 h of constant potential operation at 0.8 V, repetitive potential cycling in the range 0.5–1.0 V and thermal treatments were carried out to evaluate their electrochemical stability. Loss of non-alloyed and, to a less extent, alloyed cobalt was observed after the durability tests with the Pt–Co/C catalyst. The loss in ORR activity following durability tests was higher in Pt–Co/C than in Pt/C, i.e. pure Pt showed higher electrochemical stability than the binary catalyst. The lower stability of the Pt–Co catalyst during repetitive potential cycling was not ascribed to Co loss, but to the dissolution–re-deposition of Pt, forming a surface layer of non-alloyed pure Pt. The lower activity of the Pt–Co catalyst than Pt following the thermal treatment, instead, was due to the presence of non-alloyed Co and its oxides on the catalyst surface, hindering the molecular oxygen to reach the Pt sites.     

Carbon-ceramic supported bimetallic Pt–Ni nanoparticles as an electrocatalyst for electrooxidation of methanol and ethanol in acidic media

The electrooxidation of methanol and ethanol was investigated in acidic media on the platinum–nickel nanoparticles carbon-ceramic modified electrode (Pt–Ni/CCE) via cyclic voltammetric analysis in the mixed 0.5 M methanol (or 0.15 M ethanol) and 0.1 M H₂SO₄ solutions. The Pt–Ni/CCE catalyst, which has excellent electrocatalytic activity for methanol and ethanol oxidation than the Pt–Ni particles glassy carbon modified electrode (Pt–Ni/GCE), Pt nanoparticles carbon-ceramic modified electrode (Pt/CCE) and smooth Pt electrode, shows great potential as less expensive electrocatalyst for these fuels oxidation. These results showed that the presence of Ni in the structure of catalyst and application of CCE as a substrate greatly enhance the electrocatalytic activity of Pt towards the oxidation of methanol and ethanol. Moreover, the presence of Ni contributes to reduce the amount of Pt in the anodic material of direct methanol or ethanol fuel cells, which remains one of the challenges to make the technology of direct alcohol fuel cells possible. On the other hand, the Pt–Ni/CCE catalyst has satisfactory stability and reproducibility for electrooxidation of methanol and ethanol when stored in ambient conditions or continues cycling making it more attractive for fuel cell applications.     

Polyoxometallate-stabilized Pt–Ru catalysts on multiwalled carbon nanotubes: Influence of preparation conditions on the performance of direct methanol fuel cells

A novel catalyst, polyoxometallate-stabilized platinum–ruthenium alloy nanoparticles supported on multiwalled carbon nanotubes (Pt–Ru–PMo₁₂-MWNTs), was synthesized by a microwave-assisted polyol process. The effects of microwave reaction time, microwave reaction power, and pH value of the reaction solution on the electrocatalytic properties of Pt–Ru–PMo₁₂-MWNTs catalysts were also investigated. The polyoxometallate (PMo₁₂) formed a self-assembled monolayer on the surface of the Pt/Ru nanoparticles and MWNTs, which effectively prevented the agglomeration of Pt, Ru nanoparticles and MWNTs, due to the electrostatic repulsive interactions between the negatively charged PMo₁₂ monolayers. Energy dispersive spectroscopy examination and electrochemical measurements showed that the loading content of Pt/Ru and their electrochemical activity vary with the synthesis conditions, such as pH, reaction time, and microwave power. It was found that the a Pt–Ru–PMo₁₂-MWNTs electrocatalyst with high Pt loading content, small crystallite size, and good electrocatalytic activity could be synthesized using a long reaction time, intermediate microwave power, and a pH value of 7. The electrocatalysts obtained were characterized using X-ray diffraction, and scanning and transmission electron microscopy. Their electrocatalytic properties were also investigated by using the cyclic voltammetry technique.     

Ni–Pt/C as anode electrocatalyst for a direct borohydride fuel cell

In this study, a series of Ni–Pt/C and Ni/C catalysts, which were employed as anode catalysts for a direct borohydride fuel cell (DBFC), were prepared and investigated by XRD, TEM, cyclic voltammetry, chronopotentiometry and fuel cell test. The particle size of Ni₃₇–Pt₃/C (mass ratio, Ni:Pt = 37:3) catalyst was sharply reduced by the addition of ultra low amount of Pt. And the electrochemical measurements showed that the electro-catalytic activity and stability of the Ni₃₇–Pt₃/C catalysts were improved compared with Ni/C catalyst. The DBFC employing Ni₃₇–Pt₃/C catalyst on the anode (metal loading, 1 mg cm⁻²) showed a maximum power density of 221.0 mW cm⁻² at 60 °C, while under identical condition the maximum power density was 150.6 mW cm⁻² for Ni/C. Furthermore, the polarization curves and hydrogen evolution behaviors on all the catalysts were investigated on the working conditions of the DBFC.     

Preparation of a high performance Pt–Co/C electrocatalyst for oxygen reduction in PEM fuel cell via a combined process of impregnation and seeding

The preparation of a Pt–Co/C electrocatalyst for the oxygen reduction reaction in PEM fuel cells was achieved via a combined process of impregnation and seeding. The effects of initial pH of the precursor solution and Pt loading were all found to have a significant effect on both the electrocatalyst morphology and the cell performance when tested in a single PEM fuel cell. The optimum condition found for preparing the Pt–Co/C electrocatalyst was from an initial precursor solution pH of 2 at the metal loading of 23.6–30.3% (w/w). The Pt–Co/C electrocatalysts, formed under these optimal conditions, tested in a single PEM fuel cell with the carbon sub-layer, gave a cell performance of 772 mA/cm² or 460 mW/cm² at 0.6 V in a H₂/O₂ system. An electron pathway of oxygen reduction on the prepared Pt–Co/C electrocatalyst was also determined using a rotating disk electrode.     

Carbon supported Pt–Co (3:1) alloy as improved cathode electrocatalyst for direct ethanol fuel cells

In direct alcohol fuel cells, ethanol crossover causes a less serious effect compared to that of methanol because of both its smaller permeability through the Nafion^® membrane and its slower electrochemical oxidation kinetics on a Pt/C cathode. The main interest in direct ethanol fuel cells (DEFCs) is to find an anode catalyst with high activity for the oxidation of ethanol. However, due to the low activity of pure platinum for the oxygen reduction reaction (ORR), research on cathode electrocatalysts with improved ORR and the same or improved ethanol tolerance than that of Pt are also in progress. In this work, a commercial carbon supported Pt–Co (3:1) electrocatalyst (E-TEK) was investigated as cathode material in DEFCs and the activity compared to that of Pt. In the cathodic potential region (0.7–0.9 V versus RHE) Pt/C and Pt–Co/C showed the same activity for the oxidation of crossover ethanol. But the performance of Pt–Co/C as cathode material in DEFCs in the temperature range 60–100 °C is better than that of Pt/C both in terms of mass activity and specific activity, due to an improved activity of the alloy for oxygen reduction.     

Synthesis and characterization of Pt–Se/C electrocatalyst for oxygen reduction and its tolerance to methanol

Pt–Se/C catalyst for oxygen reduction reaction (ORR) was prepared by a modified organic colloid method with sodium citrate and triphenyl phosphine as complexing agents. The active components were highly dispersed on the carbon black support. The addition of Se improved the dispersion of platinum significantly and reduced the particle size to be less than 1.8 nm. The catalyst showed similar activity compared to Pt/C catalyst, and had a higher tolerance to methanol than Pt/C catalyst. The catalyst was characterized with X-ray diffraction (XRD) and transmission electron microscope (TEM). Electrochemical measurements showed that the synthesized Pt–Se/C catalyst had a four-electron transfer mechanism for oxygen reduction.     

Influence of different buffer solutions on the performance of anodic Pt-Ru/C nanoparticle electrocatalysts for a direct methanol fuel cell

This research aims to improve the activity of Pt-Ru nanoparticle electrocatalysts and thus, to lower the catalyst loading in anodes for methanol electrooxidation. The direct methanol fuel cell (DMFC) anodic Pt-Ru/C nanoparticle electrocatalysts were prepared using a chemical reduction method. The pH values of the reductive solutions were adjusted by different buffer solutions of CH₃COONa–NaOH, C₆H₅Na₃O₇–NaOH, and Na₂CO₃–NaHCO₃, respectively. The performance of the nanoparticle electrocatalysts were examined by cyclic voltammetry, chronoamperometry, and amperometric i–t curves using a glassy carbon working electrode in a solution of 0.5 mol L⁻¹ CH₃OH and 0.5 mol L⁻¹ H₂SO₄. The structures and micro-morphology of the Pt-Ru/C nanoparticles were determined and observed by X-ray diffraction (XRD) and transmission electron microscopy. XRD analysis showed that all of catalysts exhibited face-centered cubic (fcc) structures. No diffraction peaks indicated the presence of either pure Ru or Ru-rich hexagonal close packed (hcp) phase. The size of the Pt-Ru/C nanoparticles prepared with a C₆H₅Na₃O₇–NaOH solution was relatively small ∼4.3 nm. Its size distribution in carbon was more homogeneous. The electrochemical active measurements results showed that the catalytic activity and the stability of Pt-Ru/C nanoparticle electrocatalyst prepared with a C₆H₅Na₃O₇–NaOH solution for methanol electrooxidation was higher than that from the other solutions due to the citrate complexation stabilizing effect and a competing adsorption effect.     

The roles of metals and their oxide species in hydrophobic Pt–Ru catalysts for the interphase H/D isotope separation

Liquid phase catalytic exchange is mainly used for separation of hydrogen isotopes from liquid water. Based on the carbon-supported Pt and Pt–Ru catalysts with different metal and oxide species distributions, several hydrophobic catalysts, used in the reaction, were fabricated. The characterization results indicated that alloy and amorphous nanoparticles were formed in the Pt_0.5Ru_0.5/C catalyst using the microwave-irradiated polyol method. After reduction, the content of metallic species increased and that of hydrous Ru oxide species significantly decreased. A Pt_0.5Ru_0.5O₂/C catalyst containing more oxide species was also synthesized by the microwave-irradiated oxidation precipitation method. Performance tests demonstrated that the presence of more metallic Pt species in both the hydrophobic Pt and Pt–Ru catalysts resulted in higher catalytic activity. The addition of Ru, as an alloy or as a hydrous oxide, can improve the catalytic activity of pure Pt. These experimental results were explained by the reaction mechanisms.