Comparative study of oxygen reduction reaction on RuxMySez (M = Cr, Mo, W) electrocatalysts for polymer exchange membrane fuel cell

Electrochemical evaluation of the Ru_xM_ySe_z (M = Cr, Mo, W) type electrocatalysts towards the oxygen reduction reaction (ORR) is presented. The electrocatalysts were synthesized by reacting the corresponding transition metal carbonyl compounds and elemental selenium in 1,6-hexanediol under refluxing conditions for 3 h. The powder electrocatalysts were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). Results indicate the formation of agglomerates of crystalline particles with nanometric size embedded in an amorphous phase. The particle size decreased according to the following trend: Ru_xCr_ySe_z > Ru_xW_ySe_z > Ru_xMo_ySe_z. Electrochemical studies were performed by rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. Kinetic parameters exhibited Tafel slopes of 120 mV dec⁻¹; exchange current density of around 1 × 10⁻⁵ mA cm⁻² and apparent activation energies between 40 and 55 kJ mol⁻¹. A four-electron reduction was found in all three cases. The catalytic activity towards the ORR decreases according to the following trend: Ru_xMo_ySe_z > Ru_xW_ySe_z > Ru_xCr_ySe_z. However this trend was not maintained when the materials were tested as cathode electrodes in a single polymer exchange membrane fuel cell, PEMFC. The Ru_xW_ySe_z electrocatalyst showed poor activity compared to Ru_xMo_ySe_z and Ru_xCr_ySe_z which were considered suitable candidates to be used as cathode in PEMFCs.     

Electrocatalytic activity and durability study of carbon supported Pt nanodendrites in polymer electrolyte membrane fuel cells

In this paper, Pt nanodendrites are synthesized, and their use as an oxygen reduction catalyst in polymer electrolyte membrane fuel cells is examined. When the Pt nanoparticles are shape-controlled in a dendritic form, the Pt nanoparticles exhibit a high mass activity that is nearly twice as high as the commercial Pt/C catalyst for the oxygen reduction reaction. This high activity is only achieved when the Pt nanodendrites are supported on carbon. The unsupported Pt nanodendrites exhibit very poor catalytic activity due to the limited accessibility of the active sites in the catalyst layer of the fuel cells. Based on the durability study of Pt nanodendrites, however, the dendritic structure is not stable during repeated potential cycling test and its structure collapse is the primary reason for the performance loss in the fuel cells.     

An electro-kinetic study of oxygen reduction in polymer electrolyte fuel cells at intermediate temperatures

The oxygen reduction process in polymer electrolyte fuel cells (PEMFCs) was in-situ investigated at intermediate temperatures (80°–130 °C) by using a carbon supported PtCo catalyst and Nafion membrane as electrolyte. To overcome the Nafion dehydration above 100 °C, the experiments were carried out under pressurized conditions. Electro-kinetic parameters such as reaction order and activation energy were determined from the steady-state galvanostatic polarization curves obtained for the PEM single cell. Negative activation energies of 40 kJ mol⁻¹ and 18 kJ mol⁻¹ were observed at 0.9 V and 0.65 V, respectively, in the temperature range 100°–130 °C. This was a consequence of ionomer and membrane dry-out. The ionomer dry-out effect appears to depress reaction kinetics as the temperature increases above 100 °C since the availability of protons at the catalyst–electrolyte interface is linked to the presence of proper water contents. An oxygen reduction reaction of the first order with respect to the oxygen partial pressure was determined at low current densities. Maximum power densities of 990 mW cm⁻² and 780 mW cm⁻² at 100 °C and 110 °C (H₂–O₂) with 100% R.H., were achieved at 3 bars abs.     

Nitrogen-modified carbon-based catalysts for oxygen reduction reaction in polymer electrolyte membrane fuel cells

Nitrogen-modified carbon-based catalysts for oxygen reduction were synthesized by modifying carbon black with nitrogen-containing organic precursors. The electrocatalytic properties of catalysts were studied as a function of surface pre-treatments, nitrogen and oxygen concentrations, and heat-treatment temperatures. On the optimum catalyst, the onset potential for oxygen reduction is approximately 0.76 V (NHE) and the amount of hydrogen peroxide produced at 0.5 V (NHE) is approximately 3% under our experimental conditions. The characterization studies indicated that pyridinic and graphitic (quaternary) nitrogens may act as active sites of catalysts for oxygen reduction reaction. In particular, pyridinic nitrogen, which possesses one lone pair of electrons in addition to the one electron donated to the conjugated π bond, facilitates the reductive oxygen adsorption.     

The catalytic properties of the sputtered iron on carbon nanotubes for polymer electrolyte membrane fuel cells

Pure iron metal target was sputtered onto carbon nanotube grown on carbon paper to fabricate iron-based catalysts for the oxygen reduction reaction (ORR). The carbon nanotube-supported Fe-based catalysts have active sites which are believed to include iron cations coordinated by pyridinic nitrogen functionalities between the graphitic sheets. A Fe-based electrocatalyst treated at 950 °C displayed the highest mass activity. The treated sample at lower temperature could not form the Fe/N/CNT sufficiently. On the other hand, the formed Fe/N/CNTs were degraded thermally at higher temperature. Cyclic voltammetry of the Fe-based electrocatalysts showed similar trends with mass activity which is the largest value at 950 °C. Even though the catalytic activity is not comparable with that of Pt/C catalysts yet, sputtered Fe-based electrocatalysts are promising to explore the non-precious metal electrocatalysts.     

Evaluation of Palladium-based electrocatalyst for oxygen reduction and hydrogen oxidation in intermediate temperature polymer electrolyte fuel cells

A carbon-supported Palladium electrocatalyst was investigated for oxygen reduction and hydrogen oxidation in a polymer electrolyte fuel cell operating at intermediate temperatures (80–110 °C) and with low relative humidity (33%). A 30% Pd/C was synthesized by a colloidal method and subsequent carbothermal reduction. A mean particle size of 4.0 nm and a homogeneous dispersion of Pd particles on the support were obtained. The performance of the Pd catalyst was compared to those obtained with a 50% Pt/C catalyst and a 50% Pt₃Co₁/C as anode and cathode, respectively. The Pd/C catalyst showed low overpotential for hydrogen oxidation whereas its performance as cathode was significantly lower than the benchmark Pt₃Co₁ catalyst. The main limiting effects for the Pd-based electrocatalyst appeared to be associated to a larger mean particle size compared to the benchmark Pt catalysts and to the modification of the carbon support during the synthesis procedure. These effects led to a stronger activation control, a slight increase of the series resistance and some diffusion constraints.     

Electrocatalytic activity of iridium oxide nanoparticles coated on carbon for oxygen reduction as cathode catalyst in polymer electrolyte fuel cell

The iridium oxide nanoparticles supported on Vulcan XC-72 porous carbon were prepared for cathode catalyst in polymer electrolyte fuel cell (PEFC). The catalyst has been characterized by transmission electron microscopy (TEM) and in PEFC tests. The iridium oxide nanoparticles, which were uniformly dispersed on carbon surface, were 2-3 nm in diameter. With respect to the oxygen reduction reaction (ORR) activity was also studied by cyclic voltammetry (CV), revealing an onset potential of about 0.6 V vs. an Ag/AgCl electrode. The ORR catalytic activity of this catalyst was also tested in a hydrogen-oxygen single PEFC and a power density of 20 mW cm⁻² has been achieved at the current density of 68.5 mA cm⁻². This study concludes that carbon-supported iridium oxide nanoparticles have potential to be used as cathode catalyst in PEFC.     

Electrocatalytic stability of Ti based-supported Pt3Ir nanoparticles for unitized regenerative fuel cells

PtIr (3:1) nanoparticles supported on TiC, TiCN and TiN were investigated as bifunctional electrocatalysts for the oxygen electrode of unitized regenerative fuel cells. The electrocatalysts were prepared by the ethylene glycol method. Physicochemical characterization was carried out by X-ray Diffraction, Transmission Electronic Microscope and X-ray Photoelectron Spectroscopy, meanwhile rotating ring-disk electrode and in situ Fourier transform infrared spectroscopy were employed to determine the electrochemical activity and stability. Results reveal the highest activity toward oxygen reduction and evolution reactions on TiCN-based materials, in addition to the best compromise between catalytic activity and stability. In this context, nitrogen loading appears to be an important factor for the catalyst performance and noble metal anchoring. It is observed an increment of particle agglomeration with nitrogen content in the catalyst support. Also, TiN-based catalyst presents the lowest noble metal inclusion and high passivation degree by dissolved oxygen; whereas TiC and TiCN based catalysts develop an anodic peak at ca. 1.1 V, which is associated to TiO₂ and CO₂ formation.     

Freestanding palladium nanonetworks electrocatalyst for oxygen reduction reaction in fuel cells

Still it's a main challenge to design of highly efficient electrocatalysts to reduce the high overpotential of the oxygen reduction reaction (ORR). The 1 dimensional (1D) palladium nanonetworks (Pd-Net) can be a promising alternative to platinum (Pt)-based electrocatalyst for ORR. In this study, the Pd-Net electrocatalysts have been synthesized via a simple wet-chemical method with the assistance of cetyltrimethylammonium bromide (CTAB) and zinc precursor. Further investigation indicates that the thickness of Pd-Net can be regulated by simply changing the molar ratio of CTAB and the 5 ± 0.1 nm is proven as an efficient ORR electrocatalyst without any support material. The freestanding 1D Pd-Net has shown 2.2 and 3.6-fold higher electrochemical surface area than that of commercially available Pt/C and homemade Pd nanoparticles (PdNPs) catalysts, respectively. As a result, it provides a higher density of ORR active sites and facilitated the electron transport. The Pd-Net catalyst shows 2.1 and 4.1 times higher mass activity and 1.3 and 3.1 higher specific activity at 0.85 V (vs. RHE) with better ORR kinetics than that of Pt/C and PdNPs, respectively. Additionally, the Pd-Net catalyst has been demonstrated a significant tolerance to the anodic fuels (i.e. methanol) and enhanced durability than the Pt/C and PdNPs catalysts for ORR.     

Enhanced diffusion in polymer electrolyte membrane fuel cells using oscillating flow

This study investigates the enhancement of the oxygen diffusion rate at the cathode of a proton exchange membrane fuel cell (PEMFC) due to pure oscillating flow. A unit cell of PEMFC using hydrogen fuel and oscillating air was tested. The experimental results show that the non-dimensional effective diffusivity varies linearly with the square of the Womersley number, when the Womersley number is close to unity. The non-dimensional effective diffusivity varies linearly with the Womersley number itself when the Womersley number is much larger than unity. Similar trend has been confirmed from the theoretical approach. Under the experimental conditions in this study, the reaction rate of oxygen increased linearly with respect to the sweep distance. The experimental results showed that a power density of 115.4 mW/cm² was obtained from the unit cell with oscillating flow, which is comparable to that obtained with forced flow. Therefore, an oscillating flow is found to be able to increase the concentration of the oxygen in the channel of PEMFCs, and consequently enhances mass-transfer, similarly to the use of forced flow using blowers or compressors.     

Water transport in polymer electrolyte membrane fuel cells

Polymer electrolyte membrane fuel cell (PEMFC) has been recognized as a promising zero-emission power source for portable, mobile and stationary applications. To simultaneously ensure high membrane proton conductivity and sufficient reactant delivery to reaction sites, water management has become one of the most important issues for PEMFC commercialization, and proper water management requires good understanding of water transport in different components of PEMFC. In this paper, previous researches related to water transport in PEMFC are comprehensively reviewed. The state and transport mechanism of water in different components are elaborated in detail. Based on the literature review, it is found that experimental techniques have been developed to predict distributions of water, gas species, temperature and other parameters in PEMFC. However, difficulties still remain for simultaneous measurements of multiple parameters, and the cell and system design modifications required by measurements need to be minimized. Previous modeling work on water transport in PEMFC involves developing rule-based and first-principle-based models, and first-principle-based models involve multi-scale methods from atomistic to full cell levels. Different models have been adopted for different purposes and they all together can provide a comprehensive view of water transport in PEMFC. With the development of computational power, application of lower length scale methods to higher length scales for more accurate and comprehensive results is feasible in the future. Researches related to cold start (startup from subzero temperatures) and high temperature PEMFC (HT-PEMFC) (operating at the temperatures higher than 100 °C) are also reviewed. Ice formation that hinders reactant delivery and damages cell materials is the major issue for PEMFC cold start, and enhancing water absorption by membrane electrolyte and external heating have been identified as the most effective ways to reduce ice formation and accelerate temperature increment. HT-PEMFC that can operate without liquid water formation and membrane hydration greatly simplifies water management strategy, and promising performance of HT-PEMFC has been demonstrated.     

Preparation of carbon alloy catalysts for polymer electrolyte fuel cells from nitrogen-containing rigid-rod polymers

‘Carbon Alloy Catalysts’ (CAC), non-precious metal catalysts for the oxygen reduction reaction (ORR), were prepared from various kinds of nitrogen-containing rigid-rod aromatic polymers, polyimides, polyamides and azoles, by carbonization at 900 °C under nitrogen flow. The catalytic activity for ORR was evaluated by the onset potential, which was taken at a current density of −2 μA cm⁻². Carbonized polymers having high nitrogen content showed higher onset potential. In particular, CACs derived from azole (Az5) had an onset potential of 0.8 V, despite being was prepared without any metals.     

Nitrogen-doped carbon supported platinum catalyst via direct soft nitriding for high-performance polymer electrolyte membrane fuel cell

Control of doping levels of nitrogen to carbon support plays a key role to enhance the catalytic activity of the Pt/C catalyst toward oxygen reduction reaction. Mass-production of such materials is still challenging issue for the practical use. Here, we demonstrate a facile approach for fabrication of the nitrogen-doped Pt/C catalysts via direct soft nitriding of the Pt/C catalyst. The commercial 40 wt% Pt/C is first physically mixed with urea and then heat-treated at 300 °C, which allowed a massive production of the 6.6 atom% nitrogen-doped Pt/C catalysts without sacrificing the Pt catalysts. The specific activity increases by 46.9% after the thermal treatment, while the particle size and crystallinity of Pt remain similar to those before the thermal treatment. As a result, the fuel cell test showed a notable increase in the current density by 100% and 18.5% at 0.8 V and 0.5 V, respectively, for the membrane electrode assembly employing urea treated Pt/C catalyst. Hence, the soft nitriding by urea offers great promise as a simple, energy-efficient and eco-friendly way in manufacturing the nitrogen-doped Pt/C catalyst for the polymer electrolyte membrane fuel cell applications.     

Carbon-supported Pd-Pt cathode electrocatalysts for proton exchange membrane fuel cells

A series of carbon-supported Pd-Pt alloy (Pd-Pt/C) catalysts for oxygen reduction reaction (ORR) with low-platinum content are synthesized via a modified sodium borohydride reduction method. The structure of as-prepared catalysts is characterized by powder X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The prepared Pd-Pt/C catalysts with alloy form show face-centered-cubic (FCC) structure. The metal particles of Pd-Pt/C catalysts with mean size of around 4-5 nm are uniformly dispersed on the carbon support. The electrocatalytic activities for ORR of these catalysts are investigated by rotating disk electrode (RDE), cyclic voltammetry (CV), single cell measurements and electrochemical impedance spectra (EIS) measurements. The results suggest that the electrocatalytic activities of Pd-Pt/C catalysts with low platinum are comparable to that of the commercial Pt/C with the same metal loading. The maximum power density of MEA with a Pd-Pt/C catalyst, the Pd/Pt mass ratio of which is 7:3, is about 1040 mW cm⁻².     

Tantalum carbide as a novel support material for anode electrocatalysts in polymer electrolyte membrane water electrolysers

Iridium oxide (IrO₂) currently represents a state of the art electrocatalyst for anodic oxygen evolution. Since iridium is both expensive and scarce, the future practical application of this process makes it essential to reduce IrO₂ loading on the anodes of PEM water electrolysers. In the present study an approach to utilising a suitable electrocatalyst support was followed. Of the materials selected from a literature review, TaC has proved to be stable under the conditions of the accelerated stability test proposed in this study. The test involved dispersing each potential support material in a mixture of trifluoromethanesulfonic acid (TFMSA) and hydrogen peroxide at 130 °C. The liquid phase was subsequently analysed using ICP-MS with respect to the occurrence of ions potentially originating from the support material tested. The TaC support selected was additionally characterised by thermogravimmetric and differential thermal analysis to prove its thermal stability. A modified version of the Adams fusion method was used to deposit IrO₂ on the support surface. A series of electrocatalysts was prepared with a composition of (IrO₂)_x(TaC)_1−x, where x represents the mass fraction of IrO₂ and was equal to 0.1, 0.3, 0.5, 0.7, 0.9 and 1. The thin-film method was used for electrochemical characterisation of the electrocatalysts prepared. SEM–EDX analysis, X-ray diffraction, N₂ adsorption (BET) and powder conductivity measurements were used as complementary techniques to complete characterisation of the electrocatalysts prepared. The electrocatalysts with x ≥ 0.5 showed stable specific activity. This result is consistent with the conductivity measurements.     

Cobalt oxyphosphide as oxygen reduction electrocatalyst in proton exchange membrane fuel cell

The cobalt oxyphosphides supported on carbon black were prepared using incipient wetness method and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The possibility of their application as the electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC) was investigated and the electrocatalytic activities were evaluated by the electrochemical measurements and single cell test, respectively. The electrocatalyst presents attractive catalytic activity towards ORR and good stability in acid media and exhibits an onset potential for oxygen reduction as high as 0.69 V (RHE) in H₂SO₄ solution. The maximum power density obtained in a H₂/O₂ PEMFC is 57 mW cm⁻² with Co₄P₂O₉/C loading of 1.13 mg cm⁻². No significant performance degradation is observed over 50 h of continuous fuel cell operation. The combination of heteroatom P with nanostructured oxides with high stability, excellent functionality and low cost which are prerequisites for large-scale applications, probably provide a new solution for the critical challenge of finding effective cathode materials for PEMFC.     

Highly efficient supported PtFe cathode electrocatalysts prepared by homogeneous deposition for proton exchange membrane fuel cell

A simple and efficient approach has been developed for the synthesis of carbon-supported binary PtFe (50:50) electrocatalyst with high metal loading that combines homogeneous deposition (HD) of PtFe hydroxide complex species through generation of OH⁻ ions realized by in situ hydrolysis of urea and subsequent uniform reduction of the complex by ethylene glycol (EG) in a polyol process, providing control over the size and dispersion of PtFe nanoparticles (NPs). Compared to PtFe catalysts prepared with other common synthesis methods using NaBH₄ and EG and commercial PtFe catalyst, the supported PtFe catalyst prepared by the HD-EG method reveals more uniform homogenous dispersion of PtFe NPs with much smaller particle size, thus demonstrating excellent electrocatalytic ability and fuel cell performance. The structural properties and catalytic activities of Pt–Fe catalysts prepared in various synthesis methods were evaluated on the basis of the analysis of HR-TEM, HR-SEM, XRD, electrochemical surface area and fuel cell polarization performance.     

Advanced Pd-based nanomaterials for electro-catalytic oxygen reduction in fuel cells: A review

Devising cost-effective and high-performance nanocatalysts for the inherently slow oxygen reduction reaction (ORR) represents a critical hurdle in the commercial improvement of fuel cells for energy conversion. Recently, considerable attempts have concentrated on exploring Pd-based nanocatalysts with advanced stability to utilize as substitutes for Pt. In this review, we first describe ORR mechanisms and summarize research conducted with Pd electro-catalysts, including single and alloyed Pd nanostructures on different substrates. The application of Pd catalysts as cathode nanomaterials in proton exchange membrane fuel cells (PEMFCs), direct methanol fuel cells (DMFCs), and anion exchange membrane fuel cells (AEMFCs) is also reviewed. The insights into the connections between catalytic performance, structure, and preparation process are addressed. In particular, approaches for fabricating efficient Pd electro-catalysts, such as increasing the number of reactive centers and modifying nanoparticle-support interactions, are discussed. Challenges and prospects for upcoming investigations in developing desirable ORR nanocatalysts are highlighted.     

Pd5Cu4Pt oxygen reduction nanocatalyst for PEM fuel cells

Carbon dispersed Pd₅Cu₄Pt nanocatalyst synthesized by chemical reduction with NaBH₄ for the oxygen reduction reaction (ORR) in acid media is investigated. Nanocatalyst is physically characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (DRX). Results demonstrate the formation of conglomerate nanometric particles ranging from 2 to 10 nm in size. Electrochemical activity is demonstrated by cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results show that the onset potential for the ORR on Pd₅Cu₄Pt is shifted by ca. 50 mV to more positive values and enhanced catalytic current densities are observed in comparison to carbon dispersed PdCu and Pd catalysts. The Pd₅Cu₄Pt tested as cathode electrode in a membrane-electrode assembly (MEA) shows a power density of 330 mW cm⁻² at 0.5 V and 80 °C, resulting an attractive low Pt content cathode nanocatalyst for PEM fuel cells.     

A new Pt-Rh carbon nitride electrocatalyst for the oxygen reduction reaction in polymer electrolyte membrane fuel cells: Synthesis, characterization and single-cell performance

In this paper the preparation of a new bimetal electrocatalyst for the oxygen reduction reaction (ORR), which is one of the most important bottlenecks in the operation of polymer electrolyte membrane fuel cells (PEMFCs), is described. This material was synthesized through a pyrolysis process of a zeolitic inorganic-organic polymer electrolyte (Z-IOPE-like) precursor, followed by suitable washing and activation procedures of the product. The electrocatalyst, whose active sites consist of platinum and rhodium, was: (a) extensively characterized from the chemical, structural, morphological and electrochemical points of view and (b) used to prepare a membrane-electrode assembly (MEA) which was tested under operative conditions in a single-cell configuration. It was observed that, with respect to a reference material based on supported platinum, rhodium did not compromise the performance of the electrocatalyst in the ORR. This behaviour was interpreted in the framework of a general model concerning the enhancement of ORR performance in bimetal systems supported on carbon nitrides. Finally, the material shows a slightly better tolerance toward a few common contaminants for the ORR such as methanol and chloride anions, typical of direct methanol fuel cells (DMFCs) and vehicular applications, respectively.