Preparation and characterization of a PtRu/C nanocatalyst for direct methanol fuel cells

PtRu/C nanocatalysts were prepared by changing the molar ratio of citric acid to platinum and ruthenium metal salts (CA:PtRu) from 1:1, 2:1, 3:1 to 4:1 using sodium borohydride as a reducing agent. Transmission electron microscopy analysis indicated that well-dispersed smaller PtRu particles (2.6 nm) were obtained when the molar ratio was maintained at 1:1. X-ray diffraction analysis confirmed the formation of PtRu alloy; the atomic percentage of the alloy analyzed by the energy dispersive X-ray spectrum indicated an enrichment of Pt in the nanocatalyst. X-ray photoelectron spectroscopy measurements revealed that 83.34% of Pt and 79.54% of Ru were present in their metallic states. Both the linear sweep voltammetry and chronoamperometric results demonstrated that the 1:1 molar ratio catalyst exhibited a higher methanol oxidation current and a lower poisoning rate among all the other molar ratios catalysts. The CO stripping voltammetry studies showed that the E-TEK catalyst had a relatively higher CO oxidation current than did the 1:1 molar ratio catalyst. Testing of the PtRu/C catalysts at the anode of a direct methanol fuel cell (DMFC) indicated that the in-house PtRu/C nanocatalyst gave a slightly higher performance than did the E-TEK catalyst.     

Surfactant stabilized Pt and Pt alloy electrocatalyst for polymer electrolyte fuel cells

A simple process for the synthesis of carbon supported Pt and Pt/Ru electrocatalysts was investigated. Borrowing from the homogeneous catalyst preparation, this process uses a surfactant as a stabilizer which prevents the metal colloids from aggregation during the reduction process without influencing the deposition of the colloids onto the carbon support. Chemical, morphological and crystallographic properties of the newly prepared electrocatalysts were characterized using various surface techniques including X-ray diffraction (XRD), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). These techniques show that mono-size, well-dispersed metal colloids can be formed and successfully supported on the carbon black. Moreover, the size of metallic colloids prepared by this method can be manipulated by controlling the synthesis temperature and is independent of the catalyst loading. Electrochemical characterizations show that in comparison with commercial E-TEK electrocatalysts, surfactant-based Pt/C electrocatalysts possess similar catalytic activity in terms of oxygen reduction and higher CO tolerance performance can be obtained by the surfactant stabilized Pt,Ru/C.     

Synthesis and characterization of PDDA-stabilized Pt nanoparticles for direct methanol fuel cells

Pt nanoparticles are synthesized by the alcoholic reduction of H₂PtCl₆ in the presence of a polycation, poly(diallyldimethylammonium chloride) (PDDA). The size of the PDDA-Pt nanoparticle colloids is in the range of 2-4 nm, depending on the PDDA to Pt ratio in the solution. The PDDA-Pt nonoparticles can be self-assembled to the sulfonic acid group, SO₃⁻, at the Nafion membrane surface by the electrostatic interaction, forming a self-assembled monolayer (SAM). The study shows that such SAM reduced the methanol crossover and enhanced the power output of direct methanol fuel cells (DMFC) by as much as 34% as compared to the cell based on an un-modified Nafion membrane. In addition, PDDA-Pt nanoparticles synthesized with low PDDA/Pt ratios show considerable catalytic activity for the methanol oxidation reaction (MOR) in comparison to a commercial Pt/C catalyst. However, the electrocatalytic activity of PDDA-Pt nanoparticles decreased significantly with the increase in the PDDA/Pt molar ratio, indicating that the excess PDDA inhibits the MOR.     

Preparation and characterization of successively deposited Pt/Ru bimetallic electrocatalysts for the methanol oxidation

Two types of Pt/Ru electrocatalysts, which have different structural characteristics, were prepared with different synthetic routes. That is, Pt/Ru electrocatalysts were synthesized by the coreduction and successive deposition methods, respectively. The structural and catalytic properties of Pt/Ru electrocatalysts were characterized by XRD, TEM, voltammetry and chronoamperometry. From the XRD analysis, coreduced and successively deposited Pt/Ru electrocatalysts had an alloyed structure. TEM analyses showed that all the electrocatalysts had a highly dispersed state on the Vulcan XC-72R substrate. From the voltammetry, the coreduced electrocatalysts displayed higher catalytic activity than the successively deposited electrocatalysts for the electrooxidation of methanol. These results explain why coreduced catalysts are better able to dehydrogenate methanol and have a greater CO tolerance than the successively deposited ones. But chronoamperometry showed that successively deposited Pt/Ru electrocatalysts had stability similar to that of the coreduced ones. Although the successively deposited electrocatalysts showed lower catalytic activity than the coreduced ones, their enhanced catalytic activity was obtained by the successive deposition method in the comparison of methanol oxidation current density with pure platinum electrocatalyst.     

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.     

Poly(vinyl alcohol)-based polymer electrolyte membranes for direct methanol fuel cells

We have prepared polymer electrolyte membranes (PEMs) from poly(vinyl alcohol) (PVA) and modified PVA polyanion containing 2 or 4 mol% of 2-methyl-1-propanesulfonic acid (AMPS) groups as a copolymer. The PEMs of various AMPS content and cross-linking conditions were prepared to determine the effect of AMPS content and cross-linking conditions on PEM properties. Proton conductivity and permeability of methanol through the PEMs increased with increasing AMPS content, C_AMPS, and with decreasing cross-linker concentration, C_GA, because of the increase in the water content. The permeability coefficient of methanol through the PEM prepared under the conditions of C_AMPS = 2.7 mol% and C_GA = 0.35 vol% was about 30 times lower than that of Nafion^®117 under the same measurement conditions. The proton permselectivity of the PEM, which is defined as the ratio of the proton conductivity to the permeability coefficient of methanol, gave a maximum value of 66 × 10³ S cm⁻³ s. The value is about three times higher than that of Nafion^®117.     

Three-dimensional two-phase mass transport model for direct methanol fuel cells

A three-dimensional (3D) steady-state model for liquid feed direct methanol fuel cells (DMFC) is presented in this paper. This 3D mass transport model is formed by integrating five sub-models, including a modified drift-flux model for the anode flow field, a two-phase mass transport model for the porous anode, a single-phase model for the polymer electrolyte membrane, a two-phase mass transport model for the porous cathode, and a homogeneous mist-flow model for the cathode flow field. The two-phase mass transport models take account the effect of non-equilibrium evaporation/ condensation at the gas-liquid interface. A 3D computer code is then developed based on the integrated model. After being validated against the experimental data reported in the literature, the code was used to investigate numerically transport behaviors at the DMFC anode and their effects on cell performance.     

Synthesis and characterization of methanol tolerant Pt/TiOx/C nanocomposites for oxygen reduction in direct methanol fuel Cells

Pt/TiO_x/C nanocomposites have been synthesized by depositing hydrated titanium oxide on carbon-supported Pt (Pt/C), reducing H₂PtCl₆ with sodium formate on carbon-supported hydrated titanium oxide (TiO₂/C), and simultaneously depositing hydrated titanium oxide and reducing H₂PtCl₆ with formate on carbon support, followed by heat treatment at 500 and 900 °C in 90% Ar-10% H₂ mixture. The catalytic activity for oxygen reduction was evaluated in half cells with sulfuric acid electrolyte and in single direct methanol fuel cells (DMFC). Tolerance to methanol was studied with half cells containing sulfuric acid mixed with methanol. Charge transfer resistance and electrochemical active surface area of the Pt/TiO_x/C catalysts were studied with impedance and cyclic voltammetry measurements. Both the synthesis methods and heat treatments influence the catalytic activity, and some of the Pt/TiO_x/C composites exhibit higher catalytic activity than Pt/C. The Pt/TiO_x/C catalysts also exhibit better methanol tolerance than Pt/C. The mechanism for the enhanced catalytic activity of Pt/TiO_x/C is discussed.     

Investigation of direct methanol fuel cell performance of sulfonated polyimide membrane

Sulfonated polyimide (SPI) membranes have been evaluated as electrolyte membranes in direct methanol fuel cells (DMFCs). The membrane-electrode assembly (MEA) was made by hot-pressing the membrane, an anode and a cathode, catalyzed with PtRu/CB (PtRu dispersed on carbon black) and Pt/CB bound with Nafion^® ionomer, respectively. The performance of the cell based on SPI was compared with that of Nafion^® 112 in various operation conditions such as cell temperature (T_cell), cathode relative humidity (RH), and methanol concentration (C_MeOH). The methanol crossover at the cell based on SPI was a half of Nafion^® 112, resulting in the improved cell efficiency. Advantage of the use of SPI became much distinctive from the conventional Nafion^® 112 when the DMFC was operated at a higher T_cell or a higher C_MeOH.     

Characterization and application of electrodeposited Pt, Pt/Pd, and Pd catalyst structures for direct formic acid micro fuel cells

In this work, we study the preparation, structural characterization, and electrocatalytic analysis of robust Pt and Pd-containing catalyst structures for silicon-based formic acid micro fuel cells. The catalyst structures studied were prepared and incorporated into the silicon fuel cells by a post CMOS-compatible process of electrodeposition, as opposed to the more common introduction of nanoparticle-based catalyst by ink painting. Robust, high surface area, catalyst structures consisting of pure Pt, pure Pd, and Pt/Pd = 1:1 were obtained. In addition, Pt/Pd catalyst structures were obtained via spontaneous deposition on the electrodeposited pure Pt structure. The catalyst structures were characterized electrochemically using cyclic voltammetry and chronoamperometry. All Pd-containing catalyst structures facilitate formic acid oxidation at the lower potentials and deliver higher oxidation currents compared to pure Pt catalyst structures. Fuel cells of these catalyst structures show that pure Pd catalyst structures on the anode exhibit the highest peak power density, i.e. as high as 28.0 mW/cm². The MEMS compatible way of catalyst electrodeposition and integration presented here has yielded catalyst structures that are highly active towards formic acid oxidation and are sufficiently robust to be compatible with post-CMOS processing.     

CoPdx oxygen reduction electrocatalysts for polymer electrolyte membrane and direct methanol fuel cells

The electrochemical activity of carbon-supported cobalt-palladium alloy electrocatalysts of various compositions have been investigated for the oxygen reduction reaction in a 5 cm² single cell polymer electrolyte membrane fuel cell. The polarization experiments have been conducted at various temperatures between 30 and 60 °C and the reduction performance compared with data from a commercial Pt catalyst under identical conditions. Investigation of the catalytic activity of the CoPd_x PEMFC system with varying composition reveals that a nominal cobalt-palladium atomic ratio of 1:3, CoPd₃, exhibits the best performance of all studied catalysts, exhibiting a catalytic activity comparable to the commercial Pt catalyst. The ORR on CoPd₃ has a low activation energy, 52 kJ/mol, and a Tafel slope of approximately 60 mV/decade, indicating that the rate-determining step is a chemical step following the first electron transfer step and may involve the breaking of the oxygen bond. The CoPd₃ catalyst also exhibits excellent chemical stability, with the open circuit cell voltage decreasing by only 3% and the observed current decreasing by only 10% at 0.8 V over 25 h. The CoPd₃ catalyst also exhibits superior tolerance to methanol crossover poisoning than Pt.     

Nafion-impregnated polyethylene-terephthalate film used as the electrolyte for direct methanol fuel cells

An electrolyte system for direct methanol fuel cells (DMFC) was prepared by basing its design on combination of the existing concepts such as a composite membrane and a barrier against methanol cross-over. A composite membrane was prepared by impregnating Nafion ionomer into 6 μm thick hydrophilic PETE (polyethylene-terephthalate) film whose average pore diameter was 0.3 μm. Owing to some features of the film such as high mechanical strength and less than 30% of its surface being occupied by the openings for proton passage, it was far more effective to block the passage with a very thin palladium film with the aim of preventing methanol cross-over. The DMFCs utilizing such a thin composite membrane as the electrolyte exhibited improved performances over those using conventional Nafion in the possibility of ambient temperature operation, higher current densities, and substantial reduction of methanol cross-over.     

Nano-composite of PtRu alloy electrocatalyst and electronically conducting polymer for use as the anode in a direct methanol fuel cell

Nano-composites comprised of PtRu alloy nanoparticles and an electronically conducting polymer for the anode electrode in direct methanol fuel cell (DMFC) were prepared. Two conducting polymers of poly(N-vinyl carbazole) and poly(9-(4-vinyl-phenyl)carbazole) were used for the nano-composite electrodes. Structural analyses were carried out using Fourier transform nuclear magnetic resonance spectroscopy, AC impedance spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Electrocatalytic activities were investigated by voltammetry and chronoamperometry in a 2 M CH₃OH/0.5 M H₂SO₄ solution and the data compared with a carbon-supported PtRu electrode. XRD patterns indicated good alloy formation and nano-composite formation was confirmed by TEM. Electrochemical measurements and DMFC unit-cell tests indicate that the nano-composites could be useful in a DMFC, but its performance would be slightly lower than that of a carbon-supported electrode. The interfacial property between the PtRu-polymer nano-composite anode and the polymer electrolyte was good, as evidenced by scanning electron microscopy. For better performance in a DMFC, a higher electric conductivity of the polymer and a lower catalyst loss are needed in nano-composite electrodes.     

Preparation of Pt/CeO2/HCSs anode electrocatalysts for direct methanol fuel cells

Hollow carbon spheres (HCSs) were prepared through a simple hydrothermal method using silica particles and glucose as the template and carbon precursor, respectively. HCSs used as supports for platinum catalysts deposited with cerium oxide (CeO₂) were prepared for application as anode catalysts in direct methanol fuel cells. The composition and structure of the samples were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The electrocatalytic properties of the as-prepared catalysts for methanol oxidation were investigated by cyclic voltammetry (CV). The Pt/CeO₂/HCSs catalyst heated at 550 °C for 1 h exhibited the best catalytic activity for methanol oxidation.     

Prediction of methanol and water fluxes through a direct methanol fuel cell polymer electrolyte membrane

Development of a direct methanol fuel cell (DMFC) mass flux model, using conventional transport theory, is presented and used to predict the fluid phase superficial velocity, methanol and water molar fluxes, and the chemical species (methanol and water) dimensionless concentration profiles in the polymer electrolyte membrane, Nafion^® 117, of a DMFC. Implementation of these equations is illustrated to generate the numerical data as functions of the variables such as the pressure difference across the membrane, methanol concentration at the cell anode, temperature, and position in the membrane.     

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.     

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

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

Preparation of supported PtRu/C electrocatalyst for direct methanol fuel cells

In this work, high-surface supported PtRu/C were prepared with Ru(NO)(NO₃)₃ and [Pt(H₂NCH₂CH₂NH₂)₂]Cl₂ as the precursors and hydrogen as a reducing agent. XRD and TEM analyses showed that the PtRu/C catalysts with different loadings possessed small and homogeneous metal particles. Even at high metal loading (40 wt.% Pt, 20 wt.% Ru) the mean metal particle size is less than 4 nm. Meanwhile, the calculated Pt crystalline lattice parameter and Pt (2 2 0) peak position indicated that the geometric structure of Pt was modified by Ru atoms. Among the prepared catalysts, the lattice parameter of 40-20 wt.% PtRu/C contract most. Cyclic voltammetry (CV), chronoamperometry (CA), CO stripping and single direct methanol fuel cell tests jointly suggested that the 40-20 wt.% PtRu/C catalyst has the highest electrochemical activity for methanol oxidation.     

Preparation and characterization of Pt nanowire by electrospinning method for methanol oxidation

Pt nanowires are prepared by treating electrospun polyvinyl pyrrolidone (PVP)-Pt composite fibers at high temperatures in an air atmosphere and their activities toward a methanol oxidation reaction (MOR) are investigated. Thermogravimetric analysis (TGA) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) results indicate that the electrospun PVP-Pt composite fibers thermally decompose at 250 °C, which leads to the removal of 98 wt% of the PVP polymer and the simultaneous reduction of the Pt precursor to a Pt nanowire. The physical and electrochemical properties of Pt nanowires are found to be affected by the heat treatment conditions such as heating rate, time, temperature, and atmosphere. Furthermore, polymer fibers subjected to a pyrolization process in nitrogen followed by exposure to an air atmosphere enhance the surface area of the Pt nanowires, leading to high electrochemical activity toward a MOR. The detailed physical and electrochemical properties of the Pt nanowires are characterized by various spectroscopic and electrochemical techniques, and the possibilities of using them as electrocatalysts in a fuel cell are explored.     

The influence of sodium ion as a potential fuel impurity on the direct methanol fuel cells

Na⁺ is a likely intrinsic impurity in water and is a sort of common cation impurity in the direct methanol fuel cells (DMFCs). In this paper, the effect of Na⁺ on the DMFC electrochemical response is studied by adding Na⁺ into the methanol water solution fed in the anode of DMFC. The dynamic variation of cell voltage results shows that the DMFC performance degraded by the presence of Na⁺ impurity, and the higher concentration of Na⁺ impurity, the higher poisoning rate is observed. In the meantime, an external reference electrode is used to measure the potential and impedance of the cathode and anode. It is found that the dramatic decrease of the cell voltage is mainly ascribed to the increase of the cathode overpotential which is caused by Na⁺ exchange with protons in the cathode catalyst layer. The electrochemical impedance measurements suggest that the lack of available protons and low oxygen concentration at the cathode catalytic sites contributed to this degradation. Furthermore, the recovery strategy is introduced and it is found that the poisoned MEA could be partly recovered by immersing in 0.5 M H₂SO₄ solution for 4 h.