The synthesis of phenanthroline and bipyridine based ligand for the preparation of Fe-Nx/C type electrocatalyst for oxygen reduction

In this study, we synthesized a nitrogen rich compound (FPPHA) as the precursor of oxygen reduction reaction (ORR) catalysts, which was prepared based on 1,10-phenanthroline-5-amine and 2,2’-bipyridyl-5,5’-dialdehyde. The FPPHA-Fe complex was formed and be loaded on the carbon powder to form the FPPHA-Fe/C composite catalyst. The pyrolysis of the FPPHA-Fe/C composite was conducted at different temperatures, including 700 °C, 800 °C, and 900 °C, and the resultant pyrolyzed materials were designated to FPPHA-Fe/C-700, FPPHA-Fe/C-800, FPPHA-Fe/C-900, respectively. The physical characteristics of the catalysts were examined by powder X-ray diffraction (PXRD), Brunauer–Emmett–Teller analysis, X-ray photoelectron spectrometer (XPS) and scanning electron microscopy (SEM) etc. The ORR performance of the composite catalysts were evaluated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), and rotating ring disk electrodes (RRDE) in an alkaline solution. The results suggested that the pyrolysis process has a positive effect on the ORR activity of the catalysts, and among the catalysts the Fe-FPPHA/C-800 had the most preferable performance, which reduces oxygen through a predominantly four electron pathway with an average electron transfer number of 3.86 and an average hydrogen peroxide yield of 6.7%.     

Fe3C nanoparticles decorated Fe/N codoped graphene-like hierarchically carbon nanosheets for effective oxygen electrocatalysis

Hierarchically porous carbon sheets decorated with transition metal carbides nanoparticles and metal-nitrogen coordinative sites have been proposed as the promising non-precious metal oxygen electrocatalysts. In this work, we demonstrate a facile and low-cost strategy to in situ form Fe/N codoped hierarchically porous graphene-like carbon nanosheets abundant in Fe-N_x sites and Fe₃C nanoparticles (Fe–N/C) from pyrolyzing chestnut shell precursor. The as-prepared Fe–N/C samples with abundant Fe-N_x sites and Fe₃C nanoparticles show superior electrocatalytic activity to oxygen reduction reaction (ORR) in the alkaline medium as well as high stability and methanol tolerance due to the integration of multi-factors: the high content of Fe-N_x active sites, the coexistence of Fe₃C, the unique hierarchically porous structure and high conductivity of carbon matrix. The optimal Fe–N/C-2-900 sample exhibits a more positive half-wave potential (−0.122 V vs. Ag/AgCl (3 M) reference electrode) than commercial 20 wt% Pt/C catalyst. This study provides a facile approach to synthesize Fe₃C nanoparticles decorated Fe/N co-doped hierarchically porous carbon materials for effective oxygen electrocatalyst.     

Iron-gelatin aerogel derivative as high-performance oxygen reduction reaction electrocatalysts in microbial fuel cells

Currently, precious based materials are known as highly efficient and widely used catalysts for oxygen reduction reaction (ORR). The expensive price and scarce resource of precious metals have stimulated researchers to explore low-cost and high-performance non-precious metal catalysts. Gelatin is a promising precursor to prepare cost-effective and high-performance catalysts because of abundant micropores and nitrogen self-doping sites after pyrolysis. Herein, we developed a new highly active ORR catalyst (G/C–Fe-2) containing Fe–N coordination sites and Fe/Fe₃C nanoparticles. G/C–Fe-2 exhibited excellent ORR electrocatalytic activity (onset potential: 0.21 V, and limiting current density:7.36 mA cm^?2) and high-performance in air-cathode MFCs (Output voltage: 660 mV, and maximum power density: 560 mW m^?2). It is significant for synthesizing low-cost and high-activity ORR electrocatalysts through this strategy.     

S,N co-doped graphene quantum dots decorated TiO2 and supported with carbon for oxygen reduction reaction catalysis

Sluggish kinetics and catalyst instability in oxygen reduction reaction are the central issues in fuel cell and metal-air battery technologies. For that, highly active, stable, and low-cost non-platinum based electrocatalysts for oxygen reduction reaction are an immediate requirement in fuel cell and metal-air battery technologies. A new composite (S,N-GQD/TiO₂/C-800) is synthesized, made of sulfur (S) and nitrogen (N) co-doped graphene quantum dot (GQD) with TiO₂. This composite is supported on carbon on heating at 800 °C under N₂ atmosphere and is explored for oxygen reduction reaction (ORR) catalyst. The synthesized composite S,N-GQD/TiO₂/C-800, shows outstanding catalytic activity with an onset potential of 0.91 V and a half-wave potential of 0.82 V vs. RHE, an alkaline medium. The Tafel slope of the catalyst is 61 mV dec^?1. The catalyst is an excellent methanol tolerant and shows good stability in an alkaline medium. The excellent ORR activity of S,N-GQD/TiO₂/C-800 is ascribed to well-built interactivity between the S,N-GQD/TiO₂, and the carbon support. The unique structure offers advantages, with outstanding electrical conductivity, high surface area, and excellent charge transfer kinetics between the doped GQD and TiO₂ interface and subsequently from the carbon surface to the S,N-GQD/TiO_2.     

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.     

Iron and cobalt containing electrospun carbon nanofibre-based cathode catalysts for anion exchange membrane fuel cell

The use of Pt-based cathode catalyst materials hinders the widespread application of anion exchange membrane fuel cells (AEMFCs). Herein, we present a non-precious metal catalyst (NPMC) material based on pyrolysed Fe and Co co-doped electrospun carbon nanofibres (CNFs). The prepared materials are studied as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts in alkaline and acidic environments. High activity towards the ORR in alkaline solution indicated the suitability of the prepared NPMCs for the application at the AEMFC cathode. In the AEMFC test, the membrane-electrode assembly bearing a cathode with the nanofibre-based catalyst prepared with the ionic liquid (IL) (Fe/Co/IL–CNF–800b) showed the maximum power density (P_max) of 195 mW cm⁻², which is 78% of the P_max obtained with a commercial Pt/C cathode catalyst. Such high ORR electrocatalytic activity was attributed to the unique CNF structure, high micro-mesoporosity, different nature of nitrogen species and metal-N_x active centres.     

Cr2O3 nanoparticles boosting Cr–N–C for highly efficient electrocatalysis in acidic oxygen reduction reaction

Transition metal–nitrogen–carbon (M–N–C) catalysts have attracted significant attention for catalyzing oxygen reduction reactions (ORR). In this study, a porous Cr₂O₃@Cr–N–C catalyst with a small amount of Cr₂O₃ nanoparticles loaded on the surface of Cr–N₄–C nanomaterials was prepared using synergistic heat treatment (SHT) method with zeolite imidazole frameworks (ZIFs) as precursors. TEM and spherical aberration-corrected TEM results demonstrated the presence of hollow morphologies, Cr₂O₃ nanoparticles and atomic-level Cr distribution in Cr₂O₃@Cr–N–C. XPS, XRD and XAFS analysis indicated the coexistence of Cr₂O₃ nanoparticles and Cr–N₄ sites which were believed to act as active centers for ORR. In 0.1 M HClO₄, this material showed outstanding ORR catalytic activity with a half-wave potential of 0.78 V that was 40 mV higher than the traditional heat treatment derived Cr–N–C. It also revealed relatively low Tafel slope of 52.2 mV dec^?1; 4-electron pathway; remarkable stability and long-term durability. The improved ORR performance is mainly attributed to the synergy between Cr–N₄ active center and Cr₂O₃ nanoparticle. The SHT strategy reported here provides a new route to prepare highly efficient non-precious metal M?N–C catalysts with greater ORR activity and stability in acidic environments.     

Highly efficient PtCo nanoparticles on Co–N–C nanorods with hierarchical pore structure for oxygen reduction reaction

Developing platinum-based nanoparticles on carbon catalysts with high activity and stability for oxygen reduction reaction (ORR) is of great significance for the practical application of fuel cells. Herein, a synchronous strategy of preparing nano-sized PtCo supported on atomic Co and N co-doped carbon nanorods (PtCo/Co–N–C NR) was developed to replace the conventional method of impregnating Pt sources into ready-made carbon materials, in which metal-organic frameworks (MOFs) with Co and Zn ions of rhombic dodecahedron were first prepared using 2-methylimidazole as building block and then their morphology was transformed into porous nanorods via the reduction of Co ions to Co–B–O complex in the MOFs by NaBH₄; subsequently, Pt was deposited on the Co–Zn MOF nanorods through the displacement reaction of PtCl₆^2- and metallic Co and coordination between MOF and PtCl₆^2-; after pyrolysis and acid-leaching process, highly dispersed PtCo/Co–N–C NR was obtained. Attributed to its unique characteristics of hierarchical pore structure, uniform PtCo alloy nanoparticles with the average size of 7.0 nm and strong supporting interaction effect, the catalyst exhibits high ORR activity and stability with the mass activity of 577.0 mA mg^?1_Pt and specific activity of 1.4 mA cm^?2 at 0.9 V vs RHE in 0.1 M HClO₄, which is about 3.6 times and 3.5 times high than that of commercial Pt/C catalyst respectively. This strategy would provide a flexible route to develop highly active and stable ORR electrocatalysts with various morphologies for optimizing the exposure of active sites.     

One-step carbonization of ZIF-8 in Mn-containing ambience to prepare Mn,N co-doped porous carbon as efficient oxygen reduction reaction electrocatalyst

Economical and efficient non-noble metal catalysts should be developed practically, instead of commercial Pt/C for fuel cells. In this paper, manganese, nitrogen co-doped porous carbon (Mn–N–C) was synthesized to catalyze oxygen reduction reaction (ORR) through the one-step carbonization of ZIF-8 in the Mn-containing (MnCl₂) atmosphere. During the carbonization process, MnCl₂ gas was captured with ZIF-8 and then transformed into uniform Mn–N active sites distributed in the porous carbon materials. The Mn–N–C catalyst exhibited plentiful porous structures, large specific surface areas, high graphitization and conductivity, which contributed to the transfer and transport of charge and exposed more active sites. The Mn–N–C catalyst exhibited superior catalytic ability in alkaline and acidic solutions. Half-wave potential of the Mn–N–C could reach 0.88 and 0.73 V in 0.1 M KOH and 0.5 M H₂SO₄, respectively. In addition, the Mn–N–C catalyst showed a prominent stability after the stability test of 18,000 s. Excellent electrochemical performance and endurance make the Mn–N–C expect to be an effective ORR catalyst to build high-performance fuel cells.     

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.     

Preparation of iron and nitrogen co-doped carbon material Fe/N-CCM-T for oxygen reduction reaction

In this paper, iron and nitrogen co-doped carbon material with nanotube structure (Fe/N-C_CM-T) was synthesized by pyrolyzing a mixture of Fe salt, chitosan and melamine and displayed high electrocatalytic performance for oxygen reduction reaction (ORR). The structure of the Fe/N-C_CM-T was characterized and their ORR performance in alkaline media was investigated by linear sweep voltammetry, cyclic voltammetry and chronoamperometry. Fe/N-C_CM-T displayed better ORR performance than other carbon materials like Fe/N-C_C-800. The Fe/N-C_CM-800 with a large surface area (302.5 m²/g) especially exhibited the best ORR electrocatalytic performance among the prepared carbon materials, which was also proved by its similar Tafel slope (76 mV decade^?1) to Pt/C catalyst (74 mV decade^?1). Fe/N-C_CM-800 showed similar ORR activity as commercial Pt/C catalyst, but superior tolerance to methanol and stability. Such high ORR performance of the Fe/N-C_CM-T can be attributed to its nanotube structure, high specific surface area (SSA), high graphitic-N and pyridinic-N contents.     

Effect of synthesis method on the oxygen reduction performance of Co–N–C catalyst

In recent years, Co, N co-doped carbon (Co–N–C) materials as oxygen reduction reaction (ORR) catalysts have attracted great attention because of their good ORR stability as well as decent activity. Co-doped zeolitic imidazolate framework-8 (Co@ZIF-8) as the precursor for synthesizing Co–N–C has attracted great interest recently. Co@ZIF-8 synthesis method may affect the properties of the as-synthesized Co@ZIF-8 precursors, which will surely affect the properties and ORR performance of Co@ZIF-8-derived Co–N–C catalysts. Herein, three methods, viz. room-temperature stirring method, reflux method, and hydrothermal method, were used to synthesize Co@ZIF-8 precursors. Physical characterization shows that the synthesis method has a great influence on the textural properties, composition, and graphitization degree of the as-synthesized Co–N–C catalysts. Electrochemical characterization shows that Co–N–C-R synthesized with reflux method exhibits an onset potential (E_onset) of 0.905 V, a half-wave potential (E_1/2) of 0.792 V and a limiting current density (J_L) of 5.85 mA cm^?2 in acidic media, which are higher than those of Co–N–C–S (E_onset = 0.870 V, E_1/2 = 0.770 V, J_L = 4.71 mA cm^?2) and Co–N–C–H (E_onset = 0.892 V, E_1/2 = 0.785 V, J_L = 4.68 mA cm^?2) synthesized with room-temperature stirring method and hydrothermal method, respectively. The better ORR activity observed on Co–N–C-R can be attributed to its larger graphitization degree and larger mesopore volume. Catalytic stability test shows that Co–N–C-R has negligible activity loss after 5000 potential cycles. This work demonstrates that reflux method is a more suitable method for synthesizing Co–N–C catalysts for ORR.     

An efficient Co-N/C electrocatalyst for oxygen reduction facilely prepared by tuning cobalt species content

Transition metal and nitrogen co-doped carbon catalysts for the oxygen reduction reaction (ORR) have emerged as promising candidates to replace the expensive platinum catalysts but still remain a great challenge. Herein, a novel and efficient nitrogen-doped carbon material with metal cobalt co-dopant (Co–N/C) has been prepared by pyrolyzing porphyrin-based covalent organic polymer where Co is anchored. The optimized 10%-Co-N/C catalyst through facilely and efficiently tuning the cobalt content is carefully characterized by XRD, Raman, XPS, SEM and TEM for composition and microstructure analysis. This catalyst with only 0.56% Co exhibits an excellent ORR catalytic activity with a positive half-wave potential of 0.816 V (vs. RHE) in 0.1 M KOH solution, which is comparable to that of commercial Pt/C (20 wt%). Notably, the 10%-Co-N/C catalyst displays better electrochemical stability with only a loss of 5.1% of its initial current density in chronoamperometric measurement and also gives rise to stronger methanol tolerance than Pt/C. The good ORR catalytic behaviour for this catalyst may be attributed to the dispersion of the Co-N_X active sites via adjusting the contents of cobalt species in porous organic framework.     

In-situ synthesis of N/S co-doped Cu-based graphene-like nanosheets as high efficiency electrocatalysts for oxygen reduction reaction

Heteroatom-doped transition metal electrocatalysts supported on carbon materials are widely-recognized as the promising catalysts for oxygen reduction reaction (ORR). Here, we describe the one-pot method of preparing the Cu-based PAT₁-Cu_x/KB catalyst with Cu/N/S doped graphene-like nanosheets. For the obtained catalyst, Cu²⁺ ions catalyzed the polymerized 2-aminothiazole organic monomers into nanosheet and simultaneously in-situ doped Cu, N, S atoms into the carbon matrix. The amount of Cu²⁺ ions affected the geometry structure, as well as the formation of Cu–N structure and C–S–C bond of PAT₁-Cu_x/KB catalyst. Cu₂S crystals with ORR catalytic ability were also generated in the catalysts. The Cu–N structure in the catalyst regulates the d-electron density of inert copper through the synergistic effect of electronic connection between copper and nitrogen atoms. N and S doped in the carbon skeleton changes the spin density and charge distribution of near carbon atoms. Therefore, PAT₁-Cu_0.33/KB catalyst with graphene-like nanosheets, Cu–N structure, C–S–C bond, and Cu₂S crystals exhibits excellent activities with E_1/2 = 0.84 V and high limit-current density of 5.25 mA cm⁻² for ORR.     

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.     

A metal-organic framework-derived Fe–N–C electrocatalyst with highly dispersed Fe–Nx towards oxygen reduction reaction

Metal and nitrogen co-doped catalysts have been promising alternatives to platinum group metal (PGM) catalysts for oxygen reduction reaction (ORR) over the past few decades. Herein, we have synthesized an efficient Fe–N–C catalyst by the co-calcination of NH₂-MIL-101@PDA and melamine. The best Fe–N–C shows a positive half-wave potential of 0.844 V, which is 14 mV higher than that of Pt/C catalyst, as well as superior methanol resistance and long-term durability in alkaline electrolyte. In addition, Fe–N–C also exhibits pronounced catalytic activity and a direct 4e⁻ reaction pathway in acid electrolyte. We ascribed the excellent ORR performance of Fe–N–C to its crumpled structure, large specific surface area (584.6 m² g⁻¹) and high content of Fe-Nx sites (1.22 at. %). This study provides a simple way for the fabrication of excellent PGM-free ORR catalysts.     

An improved Stӧber method towards iron and nitrogen co-doped porous carbon spheres for oxygen reduction reaction in alkaline media

The significant progress of non-precious metal cathodic electrocatalytic materials is impressive in electrochemical energy conversion application. Here, iron and nitrogen co-doped porous carbon spheres (Fe/N-PCS) have been designed via 3-aminophenol/formaldehyde (APF) resin spheres as carbon precursor, ferric nitrate as iron source, colloidal silica as template and tetramethylguanidine as catalyst by the improved Stöber method. Fe/N-PCS possesses uniform spherical morphology, abundant mesoporous shape and high surface area and exhibits higher oxygen reduction reaction (ORR) electrocatalytic activity (E_1/2, 0.838 V vs. RHE) compared with the Pt/C (E_1/2, 0.827 V vs. RHE) in alkaline media. In addition, the methanol tolerance and catalytic stability of Fe/N-PCS are greater than commercial Pt/C catalyst. The outstanding ORR behavior of Fe/N-PCS mainly benefits from the iron and nitrogen elements synergistic effect, pyridinic N and the spherical porous structure enabling plenty of active sites exposed. This method is prospective for preparation of highly efficient cathodic ORR electrocatalyst.     

One-step prepared prussian blue/porous carbon composite derives highly efficient Fe–N–C catalyst for oxygen reduction

Preparation of high-efficiency oxygen reduction reaction (ORR) catalysts with abundant and inexpensive biomass materials have been a hot research topic. We use nitrogen-rich lentinus edodes and potassium ferrate (K₂FeO₄) to simultaneously activate the carbon material and prepare prussian blue (PB), and a porous carbon composite (PB/C) containing PB is synthesized. Finally, using ammonium chloride (NH₄Cl) as a nitrogen source to further synthesize a Fe–N–C catalyst (PB/CN₁T₈₀₀) containing a trace amount of Fe for ORR. Results show that the prepared PB/CN₁T₈₀₀ catalyst forms a coral-like structure, which mainly contains mesopores and possesses a large specific surface area of approximately 1582 m² g⁻¹. Moreover, the onset potential of PB/CN₁T₈₀₀ is 0.95 V, and the half-wave potential is 0.83 V, which are consistent with those of commercial Pt/C. Thus the PB/CN₁T₈₀₀ material is an ORR catalyst with excellent performance. This work provides a basis for simple and efficient conversion of rich biomass into PB/porous carbon composites to prepare highly efficient catalysts.     

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.     

Carbon supported Pt-Y electrocatalysts for the oxygen reduction reaction

Carbon supported Pt₃Y (Pt₃Y/C) and PtY (PtY/C) were investigated as oxygen reduction reaction (ORR) catalysts. After synthesis via reduction by NaBH₄, the alloy catalysts exhibited 10-20% higher mass activity (mA mg_Pt⁻¹) than comparably synthesized Pt/C catalyst. The specific activity (μA cm_Pt⁻²) was 23 and 65% higher for the Pt₃Y/C and PtY/C catalysts, respectively, compared to Pt/C. After annealing at 900 °C under a reducing atmosphere, Pt₃Y/C-900 and PtY/C-900 catalysts showed improved ORR activity; the Pt/C and Pt/C-900 (Pt/C catalyst annealed at 900 °C) catalysts exhibited specific activities of 334 and 393 μA cm_Pt⁻², respectively, while those of the Pt₃Y/C-900 and PtY/C-900 catalysts were 492 and 1050 μA cm_Pt⁻², respectively. X-ray diffraction results revealed that both the Pt₃Y/C and PtY/C catalysts have a fcc Pt structure with slight Y doping. After annealing, XRD showed that more Y was incorporated into the Pt structure in the Pt₃Y/C-900 catalyst, while the PtY/C-900 catalyst remained unchanged. Although these results suggested that the high ORR activity of the PtY/C-900 catalyst did not originate from Pt-Y alloy formation, it is clear that the Pt-Y system is a promising ORR catalyst which merits further investigation.