Transition metal carbides and nitrides as oxygen reduction reaction catalyst or catalyst support in proton exchange membrane fuel cells (PEMFCs)

Fuel cells are potentially efficient, silent, and environmentally friendly tools for electrical power generation. One of the obstacles facing the development and the commercialization of fuel cells is the dependence on the precious metal catalyst, i.e., Platinum (Pt) and Pt - alloy, especially at the cathode where high catalyst loading used to compensate the sluggish oxygen reduction reaction (ORR). Pt is not only an expensive and rare element but also has insufficient durability. The development of an efficient non-precious catalyst, i.e., electrochemically active, chemically and mechanically stable, and electrically conductive, is one of the basic requirements for the commercialization of fuel cells. The bonding to carbon and nitrogen to form metal carbides and nitrides modify the nature of the d-band of the parent metal, thus improve its catalytic properties relative to the parent metals to be similar to those of group VIII noble metals. In this article, we summarize the progress in the development of the transition metal carbides (TMCs) and transition metals nitrides (TMNs) relative to their application as catalysts for the ORR in fuel cells. The preparation of TMCs and TMNs via different routes which significantly affects its activity is discussed. The ORR catalytic activity of the TMCs and TMNs as a non-precious catalyst or catalyst support in fuel cells is discussed and compared to that of the Pt-based catalyst in this review article. Moreover, the recent progress in the preparation of the nano-sized (which is a critical factor for increasing the activity at low temperature) TMCs and TMNs are discussed.     

A study on novel pulse preparation and electrocatalytic activities of Pt/C-Nafion electrodes for proton exchange membrane fuel cell

To aim at reducing the platinum loading and increasing the utilization of platinum in PEMFC electrode, a new pulse electrodeposition technique for preparing proton exchange membrane fuel cell (PEMFC) electrodes has been developed in this paper. This method combines coating Pt seeds on the C-Nafion substrate and introducing polyethylene glycol (PEG) into the deposition solution. SEM images of the samples show that Pt seeds and PEG take an important role in the morphology of the Pt deposit. The surface area and average particle size of Pt were determined by charge integration under the hydrogen desorption peaks of cyclic voltammetry. The electrocatalytic activities of these electrodes towards oxygen reduction reaction (ORR) were investigated by using rotating disc electrode (RDE). The Pt catalyst which was prepared by Pt seeds and PEG, its active surface area and electrocatalytic activity towards ORR were improved remarkably. And the optimized electrode displayed higher catalytic activity than a conventional electrode made from commercial Pt/C catalyst. The possible reasons for the effects of Pt seeds and PEG on the higher catalytic activity of prepared Pt catalysts have been preliminarily discussed.     

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.     

Highly efficient,cell reversal resistant PEMFC based on PtNi/C octahedral and OER composite catalyst

In order to obtain a fuel cell with both enhanced power generation performance and cell reversal resistance, the composite catalyst consisting of the self-made PtNi/C octahedral and the oxygen evolution reaction (OER) catalyst IrO₂ and RuO₂ is mixed and applied in the anode, and the only octahedral catalyst is employed as the cathode to prepare the membrane electrode assembly (MEA). The electrochemical activity of the composite catalyst decreases slightly, but its performance retention after the accelerated durability test (ADT) is higher. In the single cell test, the MEA fabricated using the composite catalyst maintains good single cell power generation performance. Compared with the control fabricated with Pt/C (JM), the cell voltage at 1 A cm⁻² and the maximum power density are increased by 23 mV and 119 mW cm⁻², respectively. Especially, its durability under continuous cell reversal condition is also improved significantly, and the holding time is prolonged by 1 h. This work realizes the transformation of the octahedral catalyst from the laboratory research to the actual application, and solves the difficulties in fuel cell application, and promotes its commercialization.     

Effect of mesoporous carbon on oxygen reduction reaction activity as cathode catalyst support for proton exchange membrane fuel cell

In this paper, a new carbon support with a large number of mesoporous-structures is selected to prepare Pt/C catalysts. Transmission electron microscope (TEM) results show that the Pt/3# catalyst presents a sponge-like morphology, Pt particles are not only evenly distributed on the surface of carbon support, but also the smaller Pt particles are deposited in the mesoporous inside the support. The average diameter of Pt particles is only 2.8 nm. The membrane electrode assembly (MEA) based on Pt/3# catalyst also shows excellent performance. In conclusion, the 3# support is an idea carbon support for PEMFC, which helps to improve the oxygen reduction reaction (ORR) activity of the catalyst. Based on the “internal-Pt” structure of the support mesoporous, the efficient three-phase boundaries (TPBs) are construct to avoid the poisoning effect of ionomer on the nano-metal particles, reduce the activation impedance and oxygen mass transfer impedance, and improve the reaction efficiency.     

Ag nanoparticles on mesoporous carbon support as cathode catalyst for anion exchange membrane fuel cell

Silver nanocatalyst (40 wt%) is deposited on commercial mesoporous carbon support material (Ag/C) using two different wet chemical methods, to obtain high electrochemically active surface area. The catalyst materials are characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis and are evaluated toward the oxygen reduction reaction (ORR) in alkaline media employing the rotating disk electrode method. It is worth noting that the Ag/C leads to oxygen reduction through a direct four-electron pathway in alkaline medium. The silver catalyst on mesoporous carbon exhibits relatively higher mass activity for ORR (38 A g⁻¹) compared to that with Vulcan carbon (32 A g⁻¹) at −0.2 V vs SCE at room temperature. Anion exchange membrane fuel cell shows maximum power density of 310 mW cm⁻² with Ag/C cathode catalyst using H₂ and O₂ gases at 65% RH conditions at 65 °C.     

An innovative membrane-electrode assembly for efficient and durable polymer electrolyte membrane fuel cell operations

An innovative membrane-electrode assembly, based on a polyoxometalate (POM)-modified low-Pt loading cathode and a sulphated titania (S-TiO₂)-doped Nafion membrane, is evaluated in a polymer electrolyte membrane fuel cell. The modification of fuel cell cathode with Cs₃HPMo₁₁VO₄₀ polyoxometalate is performed to enhance particles dispersion and increase active area, allowing low Pt loading while maintaining performance. The POM's high surface acidity favors kinetics of oxygen reduction reaction. The mesoporous features of POM allow the embedding of Pt inside the micro-mesopores, avoiding the Pt aggregation during fuel cell operation and delaying the aging process, with consequent increase of lifetime. On the other hands, commercial Nafion is modified with superacidic sulphated titanium oxide nanoparticles, allowing operation at low relative humidity and controlled polarization of the MEA. Further MEAs, formed by unmodified Nafion membrane and the POM-based cathode, as well as sulphated titanium-added Nafion and commercial Pt-based electrodes, are used as terms of comparison. The cell performances are studied by polarization curves, electrochemical impedance spectroscopy, Tafel plot analysis and high frequency resistance measurements. The dependence of cell performances on relative humidity is also studied. The catalytic and transport properties are improved using the coupled system, despite the reduced Pt loading, thanks to rich proton environment provided by cathode and membrane.     

Highly active robust oxide solid solution electro-catalysts for oxygen reduction reaction for proton exchange membrane fuel cell and direct methanol fuel cell cathodes

The identification and development of novel non-noble metals based electro-catalyst exhibiting excellent electrochemical activity and stability than noble metal electro-catalyst is important for commercial development of proton exchange membrane fuel cells (PEMFCs). Such non-noble electro-catalyst with unique electronic structure and superior electrochemical performance will immensely contribute to lowering the capital cost of PEMFCs. Herein, we have identified solid solution electro-catalysts of WO₃ and IrO₂ for oxygen reduction reaction (ORR) in PEMFCs exploiting theoretical first principles approaches. The theoretical results were experimentally validated by generation of nanostructured (W_1-xIr_x)O_y (x = 0.2, 0.3; y = 2.7–2.8) electro-catalysts for ORR. (W_0.7Ir_0.3)O_y demonstrated ～43% improved electrochemical activity than Pt/C with similar loading at 0.9 V (vs RHE), respectively. Moreover, single full cell PEMFC study revealed an acceptable ～81% improved maximum power density for (W_0.7Ir_0.3)O_y than Pt/C combined with excellent long term stability. These results thus, show the potential of (W_0.7Ir_0.3)O_y as ORR electro-catalyst for replacing of Pt/C in PEMFCs and direct methanol fuel cells on the additional grounds of superior methanol tolerance.     

Microwave assisted,facile synthesis of Pt/CNT catalyst for proton exchange membrane fuel cell application

The present study aims at developing a high performing Pt/CNT catalyst for ORR in PEM fuel cell adopting modified chemical reduction route using a mixture of NaBH₄ and ethylene glycol (EG) as reducing agent. In order to select the most suitable reduction conditions to realize high performing catalyst, heating of the reaction mixture is done following two methods, conventional heating (CH) or microwave (MW) irradiation. The synthesized Pt/CNT catalysts were extensively characterized and evaluated in-situ as ORR catalyst in PEM fuel cell. A comparison of their performance with the standard, commercial Pt/C catalyst was also made. The results showed deposition of smaller Pt nanoparticles with uniform distribution and higher SSA for Pt/CNT-MWH compared to Pt/CNT-CH. In-situ electrochemical characterization studies revealed higher ESA, lower charge transfer resistance, lower activation over-potential loss and higher peak power density compared to the cathode with Pt/CNT-CH and Pt/C. This study suggests the viability of MW assisted, metal particle deposition as a simple, yet effective method to prepare high performing Pt/CNT catalyst for ORR in PEM fuel cell.     

Highly durable and active non-precious air cathode catalyst for zinc air battery

The electrochemical stability of non-precious FeCo-EDA and commercial Pt/C cathode catalysts for zinc air battery have been compared using accelerated degradation test (ADT) in alkaline condition. Outstanding oxygen reduction reaction (ORR) stability of the FeCo-EDA catalyst was observed compared with the commercial Pt/C catalyst. The FeCo-EDA catalyst retained 80% of the initial mass activity for ORR whereas the commercial Pt/C catalyst retained only 32% of the initial mass activity after ADT. Additionally, the FeCo-EDA catalyst exhibited a nearly three times higher mass activity compared to that of the commercial Pt/C catalyst after ADT. Furthermore, single cell test of the FeCo-EDA and Pt/C catalysts was performed where both catalysts exhibited pseudolinear behaviour in the 12-500 mA cm⁻² range. In addition, 67% higher peak power density was observed from the FeCo-EDA catalyst compared with commercial Pt/C. Based on the half cell and single cell tests the non-precious FeCo-EDA catalyst is a very promising ORR electrocatalyst for zinc air battery.     

Tungsten carbide modified high surface area carbon as fuel cell catalyst support

Phase pure WC nanoparticles were synthesized on high surface area carbon black (800 m² g⁻¹) by a temperature programmed reaction (TPR) method. The particle size of WC can be controlled under 30 nm with a relatively high coverage on the carbon surface. The electrochemical testing results demonstrated that the corrosion resistance of carbon black was improved by 2-fold with a surface modification by phase pure WC particles. However, the WC itself showed some dissolution under potential cycling. Based on the X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis, most of the WC on the surface was lost or transformed to oxides after 5000 potential cycles in the potential range of 0.65-1.2 V. The Pt catalyst supported on WC/C showed a slightly better ORR activity than that of Pt/C, with the Pt activity loss rate for Pt/WC/C being slightly slower compared to that of Pt/C. The performance and decay rate of Pt/WC/C were also evaluated in a fuel cell.     

Optimization of the amount of Nafion in multi-walled carbon nanotube/Nafion composites as Pt supports in gas diffusion electrodes for proton exchange membrane fuel cells

The Nafion loading in multi-walled carbon nanotube (MWCNT) composites with Nafion used as Pt support in the oxygen reduction reaction (ORR) has been studied. We varied the amount of Nafion in these composites and added a Pt loading of 0.3 mg cm⁻² to the catalyst layer. The performance of these electrodes in the ORR was measured with linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), chronoamperometry, inductive coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). In addition, we compared the performance of the MWCNTs as Pt supports with those of the composites. Our results indicate that the composites are better Pt supports in comparison with MWCNT.     

Graphitic mesoporous carbon as a durable fuel cell catalyst support

Highly stable graphitic mesoporous carbons (GMPCs) are synthesized by heat-treating polymer-templated mesoporous carbon (MPC) at 2600 °C. The electrochemical durability of GMPC as Pt catalyst support (Pt/GMPC) is compared with that of carbon black (Pt/XC-72). Comparisons are made using potentiostatic and cyclic voltammetric techniques on the respective specimens under conditions simulating the cathode environment of PEMFC (proton exchange membrane fuel cell). The results indicate that the Pt/GMPC is much more stable than Pt/XC-72, with 96% lower corrosion current. The Pt/GMPC also exhibits a greatly reduced loss of catalytic surface area: 14% for Pt/GMPC vs. 39% for Pt/XC-72.     

Highly microporous nitrogen doped graphene-like carbon material as an efficient fuel cell catalyst

Nitrogen-doped carbon materials are known to be promising candidates as oxygen reduction reaction electrocatalysts used in fuel cells. However, developing metal-free catalysts with high performance and stability still remains a big challenge. Herein we report a new route by using the Maillard reaction, to caramelize ribose in a dispersing salt matrix, followed by carbonization of this caramel to synthesize metal-free catalysts. This catalytic material has the morphology of microporous nitrogen doped graphene-like carbon, and a highest surface area of 1261 m² g^?1 with a large amount of micropores. Such microporous structure offers numerous defects that generate a large number of reactive sites. As a result, when used as the cathode materials in fuel cells, the fuel cell shows a high power density of 547 mW cm^?2 under 1.0 atm back pressure with good stability with only 12.5% loss after 250 h. Such catalyst has good performance in the class of metal-free oxygen reduction reaction catalysts, and is possible for commercial use.     

Effect of Nafion gradient in dual catalyst layer on proton exchange membrane fuel cell performance

The role of Nafion^® binder in the electrodes was evaluated by changing its content for the membrane electrode assembly (MEA) fabrication. In the study, we prepared MEAs that have two different compositions of catalyst layers in electrodes. One layer which is close to the electrolyte membrane has the higher Nafion^® content. The other which is near the gas diffusion media (GDM) has the lower one. Also, we changed the thickness of two layers to find the ideal composition of the binder and Pt/C in the electrode. The dual catalyst layer coated MEA showed higher cell performance at high current density region than the pristine MEA.     

Development of shut-down process for a proton exchange membrane fuel cell

Several different shut-down procedures were carried out to reduce the degradation of membrane electrode assembly (MEA) in a proton exchange membrane fuel cell (PEMFC). The effects of close/open state of outlets of a single cell and application of a dummy load during the shut-down on the degradation of the MEA were investigated. Also, we elucidated the relationship between the thickness of the electrolyte membrane and the degradation of the MEA for different shut-down procedures. When a thin electrolyte membrane was used, the closer of outlets mitigated the degradation during on/off operation. For the thicker electrolyte membrane, the dummy load which eliminates residual hydrogen and oxygen in the electrodes should be applied to lower the degradation.     

A solution-phase synthesis method to highly active Pt-Co/C electrocatalysts for proton exchange membrane fuel cell

A solution-phase synthesis method was studied to prepare carbon supported Pt-Co alloy catalysts. The organic precursors of Pt acetylacetonate and Co acetylacetonate were reduced in a high boiling point solvent of octyl ether in the presence of oleic acid (OAc) and oleylamine (OAm) to produce fine Pt-Co nanoparticles, which were subsequently deposited on carbon support to obtain Pt-Co/C catalysts. Thermogravimetric analysis suggests that the stabilizers (OAc and OAm) can be removed by copious ethanol washing and subsequent moderate temperature heat-treatment (250 °C, under Argon atmosphere). X-ray diffraction patterns indicate that the average particle size is around 2.3 nm, and the lattice parameter is 3.868 Å for the heat-treated Pt-Co/C (40 wt%). Transmission electron microscopy images show very small Pt-Co alloy nanoparticles homogeneously dispersed on the carbon support with a particle size distribution of 2-4 nm for all Pt-Co/C samples. The elements composition of Pt and Co in the final Pt-Co/C catalyst can be well controlled, as evidenced by inductively coupled plasma atomic emission spectroscopy and energy dispersive spectroscopy analyses. Proton exchange membrane fuel cell tests show the heat-treated Pt-Co/C cathode catalyst has higher mass activity of oxygen reduction reaction than Pt/C at an operation voltage of 0.9 V, this can be attributed to its smaller particle size and reduced lattice parameter.     

Durable ultra-low-platinum ionomer-free anode catalyst for hydrogen proton exchange membrane fuel cell

An ultra-low-platinum catalyst based on finely dispersed platinum (Pt) deposited on a highly porous complex microporous layer was investigated as a candidate of durable anode catalyst for hydrogen oxidation reaction (HOR) in proton exchange membrane fuel cells. Etching of teflonated and nitridized base carbon substrate in oxygen plasma and simultaneous deposition of cerium oxide were applied to increase active surface area and electrochemical activity of the platinum nanocatalyst. Ultra-low loadings of Pt (between 0.85 and 8.5 μg cm⁻²) deposited by magnetron sputtering on this substrate were assembled with Nafion 212 membrane and commercially available Pt/C cathodes (300-400 μg cm⁻² Pt). Such membrane electrode assembly (MEA) with extremely low Pt content at anode can deliver high output power densities, reaching 0.95 W cm⁻² or 0.65 W cm⁻² with only 1.7 μg cm⁻² of Pt, using H₂ as fuel and pure O₂ or air as an oxidant, respectively. Although electrocatalysts with highly dispersed active metals are known to often suffer from irreversible degradation, the above MEAs proved to be very stable when the cell was subjected to a durability test under heavy duty conditions of on/off cycling. The system with lower Pt content is more prone to water flooding which can, however, be eliminated by maintaining better control over the fuel humidity. Average decay of the cell voltage less than 50 μV h⁻¹ was obtained in the cycling regime, while excellent stability <10 μV h⁻¹ is achievable under the static load of 0.4 A cm⁻².     

Tuning lattice strain in biphenylene for enhanced electrocatalytic oxygen reduction reaction in proton exchange membrane fuel cells

As proton-exchange membrane fuel cell technology has grown and developed, there has been increasing demand for the design of novel catalyst architectures to achieve high power density and realize wide commercialization. Herein, based on the two-dimensional biphenylene, we compare the oxygen reduction reaction (ORR) activity on the active sites with different biaxial lattice strains using first-principles calculations. The ORR free energy diagrams of biphenylene monolayers with varying lattice strains suggest that the biaxial tensile strains are unfavorable for catalytic activity. In contrast, the biaxial compressive strains could improve the catalytic performance. The biphenylene systems with the strain of ?2% ～ ?6% (S_{-0.02～-0.06}) display overpotentials of 0.37–0.49 V. This performance is comparable to or better than the Pt (111) surface. The Bader charge transfer of adsorbed O species on various biaxial strain biphenylene catalysts could be a describer to examine the catalytic activity. The catalysts possessed the moderate transferred charge of O adsorbed species often promotes catalytic process and give the high catalysis efficiency. Overall, this work suggests that the lattice strain strategy can significantly enhance the catalytic activity of biphenylene materials and further provide guidance to design biphenylene-based catalysts in various chemical reactions.     

Durability investigation of carbon nanotube as catalyst support for proton exchange membrane fuel cell

Electrochemical surface oxidation of carbon black Vulcan XC-72 and multiwalled carbon nanotube (MWNT) has been compared following potentiostatic treatments up to 168 h under condition simulating PEMFC cathode environment (60 °C, N₂ purged 0.5 M H₂SO₄, and a constant potential of 0.9 V). The subsequent electrochemical characterization at different treatment time intervals suggests that MWNT is electrochemically more stable than Vulcan XC-72 with less surface oxide formation and 30% lower corrosion current under the investigated condition. As a result of high corrosion resistance, MWNT shows lower loss of Pt surface area and oxygen reduction reaction activity when used as fuel cell catalyst support.