Preparation,characterization of ZrOxNy/C and its application in PEMFC as an electrocatalyst for oxygen reduction

In this paper, a noble-metal-free electrocatalyst based on carbon-supported zirconium oxynitride (ZrO_xN_y/C) was prepared by ammonolysis of carbon-supported zirconia (ZrO₂/C) at 950 °C and investigated as cathode electrocatalyst towards oxygen reduction reaction (ORR) in PEMFCs. The electrocatalyst was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. The catalytic activity of the catalyst towards ORR was investigated by using the rotating disk electrode (RDE) technique in an O₂-saturated 0.5 M H₂SO₄ solution. The ZrO_xN_y/C electrocatalyst presented attractive catalytic activity for ORR. The onset potential of ZrO_xN_y/C electrocatalyst for oxygen reduction was 0.7 V versus RHE and the four-electron pathway for the ORR was achieved on the surface of ZrO_xN_y/C electrocatalyst. The ZrO_xN_y/C electrocatalyst showed a comparatively good cell performance to ORR in PEMFCs, especially when operated at a comparatively high temperature.     

Iron-based sulfur and nitrogen dual doped porous carbon as durable electrocatalysts for oxygen reduction reaction

The widespread use of fuel cell technology is hampered by the use of expensive and scarce platinum metal in electrodes which is required to facilitate the sluggish oxygen reduction reaction (ORR). In this work, a viable synthetic approach was developed to prepare iron-based sulfur and nitrogen dual doped porous carbon (Fe@SNDC) for use in ORR. Benzimidazole, a commercially available monomer, was used as a precursor for N doped carbon and calcined with potassium thiocyanate at different temperatures to tune the pore size, nitrogen content and different types of nitrogen functionality such as pyridinic, pyrrolic and graphitic. The Fe@SNDC–950 with high surface area, optimum N content of about 5 at% and high amount of pyridinic and graphitic N displayed an onset potential and half-wave potential of 0.98 and 0.83 V vs RHE, respectively, in 0.1 M KOH solution. The catalyst also exhibits similar oxygen reduction reaction performance compared to Pt/C (20 wt%) in acidic media. Furthermore, when compared to commercially available Pt/C (20 wt%), Fe@SNDC–950 showed enhanced durability over 6 h and poison tolerance in case of methanol crossover with the concentration up to 3.0 M in oxygen saturated alkaline electrolyte. Our study demonstrates that the presence of N and S along with Fe-N moieties synergistically served as ORR active sites while the high surface area with accessible pores allowed for efficient mass transfer and interaction of oxygen molecules to the active sites contributing to the ORR activity of the catalyst.     

Metallic iron doped vitamin B12/C as efficient nonprecious metal catalysts for oxygen reduction reaction

The development of efficient nonprecious metal catalysts for oxygen reduction reaction (ORR) is crucial but challenging. Herein, one simple and effective strategy is developed to synthesize bimetallic nitrogen-doped carbon catalysts by pyrolyzing Fe-doped Vitamin B12 (VB12) supported carbon black (Fe-VB12/C). A typical Fe₂₀-VB12/C catalyst with a nominal iron content of 20 wt% pyrolyzed at 700 °C exhibits remarkably ORR activity in alkaline medium (half-wave potential of 0.88 V, 10 mV positive than that of commercial Pt/C), high selectivity (electron transfer number > 3.93), excellent stability (only 6 mV negative shift of half-wave potential after 5000 potential cycles) and good methanol-tolerance. The superior ORR activity of the composite is mainly attributed to the improved mesoporous structure and co-existence of abundant Fe-N_x and Co-N_x active sites. Meanwhile, the metallic Fe are necessary for the improved ORR activity by means of the interaction of metallic Fe with neighboring active sites.     

FeCo alloys in-situ formed in Co/Co2P/N-doped carbon as a durable catalyst for boosting bio-electrons-driven oxygen reduction in microbial fuel cells

Non-noble metal catalyst with high catalytic activity and stability towards oxygen reduction reaction (ORR) is critical for durable bioelectricity generation in air-cathode microbial fuel cells (MFCs). Herein, nitrogen-doped (iron-cobalt alloy)/cobalt/cobalt phosphide/partly-graphitized carbon ((FeCo)/Co/Co₂P/NPGC) catalysts are prepared by using cornstalks via a facile method. Carbonization temperature exerts a great effect on catalyst structure and ORR activity. FeCo alloys are in-situ formed in the catalysts above 900 °C, which are considered as the highly-active component in catalyzing ORR. AC-MFC with FeCo/Co/Co₂P/NPGC (950 °C) cathode shows the highest power density of 997.74 ± 5 mW m^?2, which only declines 8.65% after 90 d operation. The highest Coulombic efficiency (23.3%) and the lowest charge transfer resistance (22.89 Ω) are obtained by FeCo/Co/Co₂P/NPGC (950 °C) cathode, indicating that it has a high bio-electrons recycling rate. Highly porous structure (539.50 m² g^?1) can provide the interconnected channels to facilitate the transport of O₂. FeCo alloys promote charge transfer and catalytic decomposition of H₂O₂ to ?OH and ?O₂^?, which inhibits cathodic biofilm growth to improve ORR durability. Synergies between metallic components (FeCo/Co/Co₂P) and N-doped carbon energetically improve the ORR catalytic activity of (FeCo)/Co/Co₂P/NPGC catalysts, which have the potential to be widely used as catalysts in MFCs.     

Facile synthesis of efficient core-shell structured iron-based carbon catalyst for oxygen reduction reaction

Controlled synthesis of efficient core-shell non-precious metal catalysts for oxygen reduction reaction (ORR) is undoubtedly crucial but challenging for the extensive application of fuel cells and metal-air batteries. Herein, we prepared a core-shell structured Fe/FeC_x nanoparticles and porous carbon composited catalyst (Fe/FeC_x@NC) via a facile two-step heat treatment strategy. The Fe/FeC_x@NC-800_?0.5 prepared with secondary anneal at 800 °C for 0.5 h exhibits superior ORR performance to the commercial Pt/C in terms of comparable onset potential, higher half-wave potential, and outstanding long-term durability in alkaline media. Through combining the physical and electrochemical characterizations of Fe/FeC_x@NC-T_?t with different anneal temperature and precursors, the outstanding ORR performance of Fe/FeC_x@NC-800_?0.5 is caused by the synergistic effect between Fe/FeC_x core and enriched pyridinic N- and graphitic N-doped carbon shell as well as porous carbon with large specific surface area. The structure-activity relationship of core-shell structured Fe–N–C catalysts for ORR provides directions for the development of advanced nonprecious metals catalysts.     

Pyrolyzed CoN4-chelate as an electrocatalyst for oxygen reduction reaction in acid media

A novel platinum-free electrocatalyst CoTETA/C for oxygen reduction reaction (ORR) was prepared from pyrolysis of carbon-supported cobalt triethylenetetramine chelate under an inert atmosphere. X-ray diffraction (XRD) measurement showed that nanometallic face-centered cubic (fcc) crystalline α-Co phase embedded in graphitic carbon was present on the pore surface of this catalyst. Cyclic voltammogram experiment showed that the ORR peak potential appears at 710 mV (vs. NHE) in oxygen-saturated acidic media (0.5 M H₂SO₄). The Koutecky–Levich analysis indicated that the ORR follows the first-order kinetic reaction and the ORR proceeds via both the two-electron reduction and the four-electron reduction, while the latter is the main process. The actual performance of a single cell with the obtained CoTETA/C electrocatalyst was examined under a hydrogen-oxygen fuel cell system, and the maximal output power density reached 135 mW cm⁻² at 25 °C.     

Highly active electrocatalysts for oxygen reduction from carbon-supported copper-phthalocyanine synthesized by high temperature treatment

The active, carbon-supported copper phthalocyanine (CuPc/C) nano-catalyst, as a novel cathode catalyst for oxygen reduction reaction, is synthesized via a combined solvent-impregnation along with the high temperature treatment. The catalytic activities of both pyrolyzed and unpyrolyzed catalysts are screened by linear sweep voltammetry (LSV) employing a rotating disk electrode (RDE) technique to quantitatively obtain the oxygen reduction reaction (ORR) kinetic constants and the reaction mechanisms. The results show that heat-treatment can significantly improve the ORR activity of the catalyst, and the optimal heat-treated temperature is around 800 °C, under which, an onset potential of 0.10 V and a half-wave potential of −0.05 V are achieved in alkaline electrolyte. Besides the ORR kinetic rate is increased, the ORR electron transfer number is also increased from 2.5 to 3.6 with increasing heat-treatment temperature from 600 to 800 °C. Also, the effect of catalyst loading in the catalyst layer on the corresponding ORR activity is also studied, and finds that increasing the catalyst loading, the catalyzed ORR kinetic current density can be significantly increased. For a fully understanding of this heat-treatment temperature effect, XRD, TEM, SEM–EDX, TG and XPS are used to identify the catalyst structure and composition. TG results demonstrated that the presence of Cu prevents phthalocyanine from thermal decomposition, thus contribute to higher nitrogen content which can form more Cu–N_x activity sites for the ORR. XPS analysis indicates that both pyridinic-N and graphitic-N may be responsible for the enhanced ORR activity.     

Iron (II) phthalocyanine/N-doped graphene: A highly efficient non-precious metal catalyst for oxygen reduction

Non-precious metal electrocatalysts (NPMCs) are a promising alternative to platinum-based catalysts towards the large-scale commercial application of hydrogen fuel cells and metal-air batteries. However, hazardous chemicals or high-temperature pyrolysis are generally involved in the synthesis of these highly-active NPMCs, leading to environmental and safety issues, particularly in scaling up. Exploration of low-cost and straightforward strategies to fabricate high-performance catalysts for ORR are urgently needed. Herein, we report a simple approach to fabricate a new class of the NPMCs by immobilizing iron phthalocyanine (FePc) into a surface of nitrogen-doped electrochemical exfoliated graphene (N-GP950). We highlight that at optimum content of 33 wt% FePc in the composite (FePc-33/N-GP950), the ORR performance significantly improves, exhibiting high current density at 0.8 V (5.0 mA cm⁻²), which is comparable to 4.0 mA cm⁻² of commercial Pt/C in an alkaline media. The optimized sample also displays excellent long-term durability. The present study offers a low cost and straightforward strategy to fabricate inexpensive and durable ORR catalysts for practical hydrogen fuel cells applications and metal-air batteries.     

Soybean powder enables the synthesis of Fe–N–C catalysts with high ORR activities in microbial fuel cell applications

The development of microbial fuel cells (MFCs) into a new type of carbon-neutral wastewater treatment technology requires efficient and low-cost oxygen reduction reaction catalysts in air cathodes. The use of raw soybean powder was investigated for synthesizing Fe–N–C ORR catalysts in a sacrificial SiO₂ support method. ZnCl₂ etching in the synthesis was found to facilitate the formation of hierarchical porous structures of Fe–N–C catalysts. Fe–N–C(1-1) catalyst synthesized with an optimal soybean/ZnCl₂ mass ratio of 1:1 exhibited the highest ORR activity in air cathodes. The use of the obtained Fe–N–C(1-1) catalyst enables a maximum power production of ~0.480 mW cm⁻² in MFCs, higher than commercial Pt/C (0.438 mW cm⁻²) with the same catalyst loading of 2 mg cm⁻². Long-term MFC operations demonstrated that the Fe–N–C synthesized from raw soybean have high stability and toxic tolerance, indicating that abundant low cost soybean biomass is a potential material for ORR catalyst development in MFC applications.     

Conversion of peanut biomass into electrocatalysts with vitamin B12 for oxygen reduction reaction in Zn-air battery

The conversion of biomass into functional carbon materials as electrocatalysts for oxygen reduction reaction (ORR) is a new bridge to use agricultural residues for renewable energy industries. Herein, hierarchical porous carbon material doped with nitrogen and cobalt (Co)-based nanoparticles (N/CoPSAC) has been prepared from biomass (i.e. peanut shells and vitamin B12). The resulting catalyst of N/CoPSAC demonstrates excellent electrocatalytic activities in alkaline media, such as more positive on-set potential and half-wave potential, 4-electron oxygen reduction (n = 3.81) and outstanding stability. The observed ORR activities of N/CoPSAC can be attributed to the synergistic effect of interconnected 3D porous structure and heteroatom doping. Furthermore, the performance evaluation of N/CoPSAC in a more practical setup of Zn-air batteries shows superior durability to that of the benchmark Pt-based electrocatalysts. Hence, the N/CoPSAC electrocatalyst derived from peanut biomass holds a good potential to be used as an alternative for commercial Pt/C in Zn-air batteries.     

Boron doping induced electronic reconfiguration of Fe-Nx sites in N-doped carbon matrix for efficient oxygen reduction reaction in both alkaline and acidic media

Developing non-precious metal-based catalysts as the substitution of precious catalysts (Pt/C) in oxygen reduction reaction (ORR) is crucial for energy devices. Herein, a template and organic solvent-free method was adopted to synthesize Fe, B, and N doped nanoflake-like carbon materials (Fe/B/N–C) by pyrolysis of monoclinic ZIF-8 coated with iron precursors and boric acid. Benefiting from introducing B into Fe–N–C, the regulated electron cloud density of Fe-N_x sites enhance the charge transfer and promotes the ORR process. The as-synthesized Fe/B/N–C electrocatalyst shows excellent ORR activity of a half-wave potential (0.90 V vs 0.87 V of Pt/C), together with superior long-term stability (95.5% current density retention after 27 h) in alkaline media and is even comparable to the commercial Pt/C catalyst (with a half-wave potential of 0.74 V vs 0.82 V of Pt/C) in an acidic electrolyte. A Zn-air battery assembled with Fe/B/N–C as ORR catalyst delivers a higher open-circuit potential (1.47 V), specific capacity (759.9 mA h g^?1_Zn at 10 mA cm^?2), peak power density (62 mW cm^?2), as well as excellent durability (5 mA cm^?2 for more than 160 h) compared to those with commercial Pt/C. This work provides an effective strategy to construct B doped Fe–N–C materials as nonprecious ORR catalyst. Theoretical calculations indicate that introduction of B could induce Fe-N_x species electronic configuration and is favorable for activation of OH1 intermediates to promote ORR process.     

Electrocatalytic activity of platinum nanoparticles supported on different phases of tungsten carbides for the oxygen reduction reaction

Carbon-supported tungsten carbides with cubic (β-WC_1-x/C) and hexagonal (α-WC/C) are evaluated as support materials of Pt-nanoparticles, to be used as electrocatalysts for the oxygen reduction reaction (ORR) in acid media. The produced materials are characterized by X-Ray diffraction (XRD), energy dispersive X-ray spectroscopy, (EDS), X-ray photoelectron spectroscopy (XPS), in situ X-ray absorption near edge structure (XANES), and transmission electron microscopy (TEM). Cyclic voltammetry and polarization measurements on stationary and rotation disk electrodes are employed for the electrochemical investigations. It is seen that all Pt-α-WC/C catalysts present specific activity for the ORR similar to that of a standard carbon supported Pt catalyst (Pt/C), while for the Pt-β-WC_1-x/C composites the specific activitiy is 3.6 times higher than that of Pt/C, when a carbide-to-carbon load of 40 wt% is used. These differences in reactivity for the ORR may be associated to differences in the binding energy of adsorbed oxygen on Pt, introduced by the tungsten carbide substrates. Pt XANES results for the β-WC/C_1-x materials evidence a small increase in the Pt 5d band occupancy, which may lead to a weaker Pt-OH_x interaction, increasing the ORR kinetics.     

H2-induced thermal treatment significantly influences the development of a high performance low-platinum core-shell PtNi/C alloyed oxygen reduction catalyst

In the purpose of maximizing the utilization of noble metal Pt in oxygen reduction catalysts, we illustrate a synthesis method of preparing the low-platinum PtNi/C alloyed oxygen reduction reaction (ORR) catalyst, which is developed through the H₂-induced treatment to a glucose reduced PtNi/C alloy. After post-treatment with H₂/N₂ mixture gases, this catalyst displays excellent ORR catalytic activity and durability for the synergetic influences of electronic and geometry effects on catalysts during the alloying. Specifically, the as-prepared PtNi/C (350°C-6 h) sample delivers preponderant ORR activity with only 53.5% Pt usage than the commercial Pt/C. The specific activity and mass activity are corresponding 7.49 times and 3.5 times to the commercial Pt/C. This catalyst exhibits excellent ORR catalytic activity after 10 000 potential cycles in acid, which benefits from the well alloyed core-shell structure of PtNi/C. H₂-induced thermal treatment has significant effects on the development of high performance low-platinum PtNi/C alloy catalyst, and plays the significant role in the formation of well-alloyed core-shell structures. The lowered d-band center is believed to facilitate ORR catalysis through weakening the adsorption of intermediate oxygen species on the alloyed Pt surface. Therefore, PtNi/C(350°C-6 h) alloyed catalyst possesses outstanding ORR catalytic activity with much lower Pt loading.     

Natural aloe vera derived Pt supported N-doped porous carbon: A highly durable cathode catalyst of PEM fuel cell

Evolution of highly durable electrocatalyst for oxygen reduction reaction (ORR) is the most critical barrier in commercializing polymer electrolyte membrane fuel cell (PEMFC). In this work, Pt deposited N-doped mesoporous carbon derived from Aloe Vera is developed as an efficient and robust electro catalyst for ORR. Due to its high mesoporous nature, the aloe vera derived carbon (AVC) play a very vital role in supporting Pt nanoparticles (NPs) with N-doping. After doping N into AVC, more defects are created which facilitates uniform distribution of Pt NPs leading to more active sites towards ORR. Pt/N-AVC shows excellent ORR activity when compared with commercial Pt/C and showing a half wave potential (E_1/2–0.87 V Vs. RHE) and reduction potential (E_red ~ 0.72 V Vs. RHE) towards ORR. Even after 30,000 potential cycles, Pt/N-AVC shows in its E_1/2 only ~5 mV negative shift and lesser agglomeration of Pt NPs is seen in the catalyst. In membrane electrode assembly (MEA) fabrication, Pt/N-AVC as a cathode catalyst in a PEMFC fixture and performance were studied. The Pt/N-AVC shows good performance, which proves the potential application of this naturally available bio derived carbon, which serves as an excellent high durable support material in PEMFC. All these features show that the Pt/N-AVC is the most stable, efficient and suitable candidate for ORR catalyst.     

Carbon paper supported Pt/Au catalysts prepared via Cu underpotential deposition-redox replacement and investigation of their electrocatalytic activity for methanol oxidation and oxygen reduction reactions

Through a simple and rapid method, carbon papers (CPs) were coated with Au and the resulting Au/CP substrates were used for the preparation of Pt/Au/CP by Cu underpotential deposition (Cu UPD) and redox replacement technique. A series of Pt_n/Au/CP catalysts (where n = number of UPD-redox replacement cycles) were synthesized and their electrochemical properties for methanol oxidation reaction (MOR), and oxygen reduction reaction (ORR) were investigated by electrochemical measurements. The Pt_n/Au/CP electrodes show higher electrocatalytic activity and enhanced poison tolerance for the MOR as compared to a commercial Pt/C on CP (Pt/C/CP). The highest mass specific activity and Pt utilization efficiency for MOR was observed on Pt₁/Au/CP with a thickness close to a monatomic Pt layer. Chronoamperometric tests in methanol solution revealed that Pt_n/Au/CPs have much higher CO tolerance compared to Pt/C/CP. Among the Pt_n/Au/CPs, CO tolerance decreases with increasing the amount of deposited Pt, indicating that the exposed Au atoms in close proximity to Pt plays a positive role against CO poisoning. Compared with the Pt/C/CP, all the Pt_n/Au/CP electrodes show more positive onset potentials and lower overpotentials for ORR. For instance, the onset potential of ORR is 150 mV more positive and the overpotential is ∼140 mV lower on Pt₄/Au/CP with respect to Pt/C/CP.     

Template-assisted polymerization-pyrolysis derived mesoporous carbon anchored with Fe/Fe3C and Fe−NX species as efficient oxygen reduction catalysts for Zn-air battery

Constructing highly efficient and durable non-noble metal modified carbon catalysts for oxygen reduction reaction (ORR) in the whole pH range is essential for energy conversion devices but still remains a challenge. Herein, the Fe/Fe₃C nanoparticles and Fe-N_X species anchored on the interconnected mesoporous carbon materials are fabricated through an economical and facile template-assisted polymerization-pyrolysis strategy. The catalyst exhibits unique features with the electronic interaction between Fe/Fe₃C and Fe−N_X, large specific surface area and high mesoporous structure as well as nitrogen doping in porous carbon skeletons, which can effectively catalyze ORR over the full pH range. In an alkaline electrolyte, the optimized catalyst displays favorable ORR performance with positive onset potential (E_onset = 0.91 V), half-wave potential (E_1/2 = 0.83 V), long-term cycles stability and methanol tolerance, exceeding those for the commercial Pt/C. Furthermore, the prepared catalyst could be directly assembled into the alkaline Zn−air battery that exhibits the open-circuit voltage of 1.44 V, high power density of 96.0 mW cm⁻² and long-term durability. Therefore, the template-assisted polymerization-pyrolysis strategy provides a promising route for designing high-performance non-noble metal decorated ORR electrocatalysts.     

Facile preparation of biomass-derived bifunctional electrocatalysts for oxygen reduction and evolution reactions

The development of inexpensive and efficient bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is still remained a challenge in wide range of renewable energy technologies. Herein, biomass-derived nitrogen self-doped porous carbon nanosheets (NPCNS) are produced by a facile and green pyrolysis of Euonymus japonicus leaves at controlled temperature and then the nitric acid pickling was carried out to remove the excess metal ingredients. The obtained NPCNS exhibits a hierarchically porous distribution, high BET surface area and uniform nitrogen doping. Electrochemical measurements show that the NPCNS possess a high electrocatalytic activity for both ORR and OER. Among these NPCNS catalysts, the sample carbonized at 900 °C (NPCNS-900) with the highest concentration of pyridinic nitrogen shows the best ORR and OER activity. According to our DFT calculations, the high content of pyridinic nitrogen with the moderate O and OH adsorption energies among the three types of nitrogen should be the critical factor for the efficient catalytic performance of NPCNS-900 toward ORR and OER. This work demonstrates that the facile prepared NPCNS-900 is a potential candidate material with excellent performance in electrocatalytic applications such as fuel cells or metal-air batteries.     

Spherical mesoporous Fe–N–C catalyst for the air cathode of membrane-less direct formate fuel cells

Fe–N–C catalysts with excellent performance regarding the oxygen reduction reaction (ORR) have aroused enormous interest in direct-formate fuel cells (DFFCs). However, their limited mass transfer ability, insufficient ORR active sites, and complex fabrication processes remain significant obstacles to the widespread application of Fe–N–C catalysts. Herein, we propose a simple hydrothermal-annealing method with agarose powders to synthesize a uniform spherical Fe–N–C catalyst (∼3 μm) with well-developed mesopores (Fe/rG@C/H-Agar-900). The resultant Fe/rG@C/H-Agar-900 catalyst possesses rich oxygen-containing functional groups and enhanced interconnected pores, which can significantly boost the content of catalytic sites and facilitate mass transport, resulting in a high content of active sites. In the meantime, the mesopore content of Fe/rG@C/H-Agar-900, which can facilitate the formation of the three-phase gas/electrolyte/catalyst interfaces, was optimized by varying the annealing temperature. As a result, the Fe/rG@C/H-Agar-900 demonstrates a half-wave potential of 0.91 V vs. RHE, nearly four-electron pathway selectivity, excellent durability, and excellent formate tolerance for ORR. Furthermore, when used as the air cathode in membrane-less DFFCs, the Fe/rG@C/H-Agar-900-based device exhibits a remarkable peak power density of 24.5 mW cm⁻², significantly outperforming the 20 wt% commercial Pt/C. This research facilitates the synthesis of an advanced Fe–N–C catalyst and promotes the practical development of membrane-less DFFCs.     

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.     

CoSe nanoparticles prepared by the microwave-assisted polyol method as an alcohol and formic acid tolerant oxygen reduction catalyst

CoSe catalyst supported on nanoporous carbon was synthesized by microwave heating of glycerol solutions of Co(II) acetate and sodium selenite. The electrocatalytic behavior of the CoSe/C for oxygen reduction reaction (ORR) and its tolerance to several alcohols and formic acid were investigated by rotating disk electrode voltammetry and the results were compared with those of Pt/C. The results indicate that CoSe/C is a highly selective electrocatalyst towards ORR and shows a very high degree of tolerance to the presence of formic acid, methanol, ethanol, 2-propanol and ethylene glycol in acid medium. For a 20 wt.% CoSe/C, the onset potential and the magnitude of the current for ORR were almost the same with or without the presence of these fuels. In contrast, the Pt/C catalyst exhibited a mixed potential due to the simultaneous oxidation of the fuels and reduction of oxygen, which in turn caused the onset potential for the ORR to shift cathodically by ca. 500 mV in the presence of these fuels. Electrochemical measurements showed that the synthesized CoSe/C catalyst had a four-electron transfer mechanism for ORR. It is expected that this low cost electrocatalyst with its almost full tolerance and multi-fuel capability can find application in conventional and mixed-reactant fuel cells fueled with low molecular weight alcohols or formic acid.