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.     

One-step complexation and self-template strategy to synthesis bimetal Fe/Mn–N doped interconnected hierarchical porous carbon for enhancing catalytic oxygen reduction reaction

Currently, it is still a challenge in the research of fuel cells and zinc-air battery to use a facile method to prepare efficient and low-cost cathode oxygen reduction reaction (ORR) catalysts to replace the precious metal Pt-based catalyst. Herein, we reported a one-step complexation of ethylenediaminetetraacetic acid disodium (EDTA-2Na) with transition metals (M) and self-template strategy to synthesis an bimetal Fe/Mn–N doped interconnected hierarchical porous carbon material for efficient catalytic ORR. In addition to being a carbon source, EDTA-2Na can very well fix M atoms in the carbon precursory by complexation, which is beneficial for M atoms to be anchored in the carbon structure by N atoms, thus forming the M-N_x catalytic active site. During pyrolysis, meanwhile, Na ions in EDTA-2Na not only acted as self-template to form the interconnected porous structure but also separated M atoms from each other, which also suppressed the aggregation and growth of the M atoms. More importantly, the prepared bimetal Fe/Mn–N doped interconnected hierarchical porous carbon (Fe/Mn–NIHPC) showed better catalytic ORR performance (half-wave potentials of 0.86 V vs. RHE) than those prepared by single metal elements (Fe or Mn). And Fe/Mn–NIHPC also exhibited better catalytic ORR activity and durability, compared with the Pt/C (20 wt%) catalyst.     

Fe–N–Si tri-doped carbon nanofibers for efficient oxygen reduction reaction in alkaline and acidic media

The most ideal substitute for Pt/C to catalyze the oxygen reduction reaction (ORR) is the transition metal and nitrogen co-doped carbon-based material (TM-N-C). However, large particles with low catalytic activity are formed easily for the transition metals during high-temperature carbonization. Herein, PAN nanofibers uniformly distributed with FeCl₃ were coated with SiO₂ and then carbonized to obtain Fe–N–Si tri-doped carbon nanofibers catalyst (Fe–N–Si-CNFs). The SiO₂ can further anchor the Fe atoms, thus preventing agglomeration during the carbonization process. Meanwhile, Si atoms have been doped in CNFs during this process, which is conducive to the further improvement of catalytic performance. The Fe–N–Si-CNFs catalyst has a 3D network structure and a large specific surface area (809.3 m² g⁻¹), which contributes to catalyzing the ORR. In alkaline media, Fe–N–Si-CNFs exhibits superior catalytic performance (E_1/2 = 0.86 V vs. RHE) and higher stability (9.6% activity attenuation after 20000s) than Pt/C catalyst (20 wt%).     

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.     

Manganese coordinated with nitrogen in aligned hierarchical porous carbon for efficient electrocatalytic oxygen reduction reaction in alkaline and acidic medium

A Mn coordinated with N atoms aligned hierarchical porous carbon catalyst is prepared through an inorganic metal salt sublimation doping strategy. Gelatin is served as a carbon source and N source, Ca²⁺ is acted as templates to establish aligned porous structure during carbonization. MnCl₂ sublimates into gas to serve as Mn source after reaching the melting point. This method can effectively avoid the agglomeration of Mn atoms, which is beneficial to form Mn-N_x active sites. The prepared optimal catalyst exhibits a large specific surface area with an aligned hierarchical porous structure. XAFs result demonstrates that Mn coordinates with N atoms to form Mn-N_x configuration in the carbon structure. Notably, it exhibits outstanding catalytic ORR performance with a positive half-wave potential (0.86 V vs. RHE) and excellent durability, superior to Pt/C (20 wt%) catalyst under alkaline medium. Meanwhile, enhanced catalytic ORR performance and stability in an acidic medium are also achieved.     

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.     

ZrO2 anchored core-shell Pt–Co alloy particles through direct pyrolysis of mixed Pt–Co–Zr salts for improving activity and durability in proton exchange membrane fuel cells

Highly active and durable Pt-based catalysts for oxygen reduction reaction (ORR) are very important and necessary for the proton exchange membrane fuel cells (PEMFCs). In this paper, we report the preparation and performance study of ORR catalysts composed of core-shell Pt–Co alloy nanoparticles (NPs) on multi-walled carbon nanotubes (MWCNTs) anchored with ZrO₂ NPs (denoted as Pt–Co–ZrO₂/MWCNTs). Thanks to the unique three-phase structure, the mass activity of Pt–Co–ZrO₂/MWCNTs for ORR at 0.9 V versus reversible hydrogen electrode (RHE) is1577 mA mg_Pt^?1, which is ～6.6-fold higher than that of the commercial Pt/C (238 mA mg_Pt^?1). After 50,000 cycles for durability test, the mass activity of Pt–Co–ZrO₂/MWCNTs for ORR remained 88% of its initial value. In stark contrast, that of Pt/C kept only about 56.3% of its initial value. More importantly, its catalytic performance was fully observed/verified in a H₂-air PEMFC single cell test. When the Pt loading of Pt–Co–ZrO₂/MWCNTs loaded cathode was one fourth of that with commercial Pt/C as the cathode catalyst, comparable cell performance was achieved. More impressively, the MEA with Pt–Co–ZrO₂/MWCNTs underwent only 24.5% degradation in maximum power density after 30,000 accelerated durability tests (ADTs). However, the MEA with Pt/C after 30,000 ADTs exhibited 39.6% performance loss in maximum power density. The enhanced mass activity and catalytic durability of Pt–Co–ZrO₂/MWCNTs could be attributed to the core-shell Pt–Co alloy NPs with Pt-rich surface and the interface effect between Pt–Co alloy NPs and oxygen vacancy-rich ZrO₂ NPs. In addition, this research also provided a solution to the durability issue of cathodes without sacrificing ORR mass activity, which would promote practical application of PEMFCs.     

Preparation of three-dimensional Fe–N co-doped open-porous carbon networks as an efficient ORR electrocatalyst in both alkaline and acidic media

It is of significant importance to construct the low-cost, efficient, and stable carbon-based non-noble metal to replace the noble metal electrocatalyst for oxygen reduction reaction in both alkaline and acidic media. In this work, a straightforward and cost-efficient strategy is reported to synthesize the Fe–N co-doped open-porous carbon materials with three-dimensional (3D) carbon networks structure, high surface areas and multiple actives sites including iron carbide nanoparticles, pyridinic N, and graphitic N using a new kind of Fe-Imace coordinated complex as the precursor and melamine as nitrogen sources by direct pyrolysis. The obtained Fe–N–C 900 catalyst shows excellent oxygen reduction performance in both alkaline (E_onset, 1.014 vs. RHE) and acidic (E_onset, 0.982 V vs. RHE) media, which are better than those of the Pt/C in alkaline (E_onset, 0.986 vs. RHE) and acidic media (E_onset, 0.979 V vs. RHE). Even more important, the stability and methanol tolerance of the Fe–N–C 900 catalyst are much better than that of the Pt/C catalyst in both alkaline and acidic media. All the results demonstrate that the present facile and universal one-step pyrolytic strategy can be used to synthesize catalyst materials as one of the superior non-precious cathode electrocatalysts for fuel cells.     

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.     

Atomically dispersed Co atoms in nitrogen-doped carbon aerogel for efficient and durable oxygen reduction reaction

Developing non-noble-metal-based electrocatalysts as alternatives to replace Pt-based catalysts for oxygen reduction reaction (ORR) is crucial for large scale industrial application of fuel cells. Herein, we report a facile method to synthesize atomically dispersed Co atoms anchored on nitrogen-doped carbon aerogels with a 3D hierarchically porous network structure via F127-assisted pyrolysis of a phenolic resin/Co²⁺ composite and subsequent HCl etching treatment. HRTEM, AC-STEM, XRD, XPS, and Raman spectroscopy measurements demonstrate that Co atoms are homogeneously atomically dispersed on nitrogen-doped carbon aerogels within the porous structure by coordination with pyridinic-N. Among a series of samples, the Co-NCA@F127-1: 0.56 catalyst exhibits an enhanced ORR activity with onset potential (E_onset) of 0.935 V vs. RHE, the high diffusion limiting current density of 5.96 mA cm⁻² at 0.45 V, as well as an excellent resistance to methanol poisoning and good long-term stability in alkaline medium, comparable to the state-of-the-art Pt/C catalyst. This work may provide a novel and ingenious thought in the design and engineering of efficient and robust electrocatalysts based on single transition-metal atoms supported by nitrogen-doped carbon materials.     

Melamine-assisted synthesis of paper mill sludge-based carbon nanotube/nanoporous carbon nanocomposite for enhanced electrocatalytic oxygen reduction activity

Developing efficient and cheap electrocatalysts as substitutes for commercial Pt/C in the oxygen reduction reaction(ORR)is extremely necessary. Herein, paper mill sludge (PMS) was utilized to produce iron, nitrogen and sulfur co-doped carbon nanotube/nanoporous carbon nanocomposite (PMS-CNT/C) by pyrolysis. PMS-CNT/C-b, one of as-prepared PMS-CNT/C exhibited excellent oxygen reduction reaction activity with an onset potential of 0.99 V vs. RHE and half-wave potential of 0.77 V vs. RHE, which was similar to the commercial Pt/C catalyst (onset potential of 0.99 V vs. RHE and half-wave potential of 0.76 V vs. RHE). It had longer-term stability and higher methanol tolerance in alkaline medium than Pt/C. Moreover, the new catalyst also exhibited excellent catalytic performance in neutral solution. The energy output of microbial fuel cells loaded with PMS-CNT/C-b catalyst was also higher than that of commercial Pt/C under neutral condition. The excellent ORR performance of PMS-CNT/C-b was due to the carbon nanotube/nanoporous structure and the synergistic effect of abundant N groups, iron nitrides and thiophene-S. The formation of CNTs in the carbon nanotube/nanoporous carbon nanocomposite was mainly attributed to melamine, which was added into PMS and was at first just considered as a nitrogen source to develop N-doped PMS-based catalysis in this work. The synthesis of paper mill sludge-based carbon nanotube/nanoporous nanocomposite and its excellent ORR activity will make the new catalyst a promising cathodic electrocatalyst alternative for fuel cells.     

Synthesis and electrocatalytic properties of M (Fe,Co),N co-doped porous carbon frameworks for efficient oxygen reduction reaction

The exploitation of high efficiency non-precious metal electrocatalysts towards oxygen reduction reaction (ORR) is great significant for large-scale commercialization of next-generation fuel cells. In this work, we designed and fabricated a series of porous carbazole-based N and M (Co, Fe) doped carbon framework catalysts which were obtained by the pyrolysis of a N-rich hypercrosslinked polymers derived from Friedel–Crafts reaction (abbreviated as TSP-HCP-900) followed by the incorporation of metal into the as-resulted N rich carbon (abbreviated as M-TSP-HCP-900, M = Co, Fe). Based on the high specific surface, excellent porosity, large pyridine nitrogen content and synergistic catalytic effects between the N dopants and metal nanoparticles, the M-TSP-HCP-900 exhibited superior ORR catalytic activity. Among them, the Co-TSP-HCP-900 possesses better electrocatalysis, i.e., a high diffusion limiting current density of 4.74 mA cm^?2, half-wave potential of 0.8 V (vs. RHE, the same below) and onset potential of 0.9 V were found, respectively. In addition, this catalyst also discloses an excellent methanol tolerance, better durability and a biased 4e^? reaction pathway, which are comparable to state-of-the-art Pt/C catalysts. Taking advantage of mentioning above, the M-TSP-HCP-900 may hold great potentials as promising alternative of precious metal catalysts for electrochemical energy conversion and storage.     

The synthesis of Fe/N–C@CNFs and its electrochemical performance toward oxygen reduction reaction

The one-dimensional filamentous carbon nanofibers hold great promise to substitute noble catalysts ascribing to the excellent physicochemical properties, environmentally friendly, easy to prepare, etc. Synthesizing non-noble catalysts with outstanding electro-catalytic activity for oxygen reduction reaction and excellent durability and application in the field of commercialization still exist lots of challenges. Herein, we report a facile synthesis of carbon nanofibers coated with iron doping nitrogen-carbon (Fe/N–C@CNFs) derived from carbon nanofibers coated with polyaniline (PANI@CNFs) via chemical vapor deposition and heat-treatment, which exhibit an outstanding catalytic activity toward oxygen reduction reaction. In detail, the Fe/N–C@CNFs exhibit onset potential of 0.99 V (vs RHE) and half-wave potential of 0.80 V (vs RHE) in 0.1 M KOH solution, indicating superior electrochemical activity for oxygen reduction reaction (ORR). Meantime, the transferred electron number of oxygen reduction reaction was 3.77, suggesting a nearly 4e⁻ transferring process with little intermediate product (H₂O₂). Moreover, the relative current value of carbon nanofibers coated with nitrogen-carbon film (N–C@CNFs) and Fe/N–C@CNFs maintain 89.6% and 88.2% respectively after 40,000 s, exhibiting good stability and durability. This facile and easy method could provide inspiration for synthesizing carbon nanofibers-based (CNFs-based) oxygen reduction reaction catalysts with excellent catalytic activity and good stability.     

Rapeseed meal-based autochthonous N and S-doped non-metallic porous carbon electrode material for oxygen reduction reaction catalysis

The heteroatom-doped porous carbon material as an alternative to commercial Pt/C catalysts in oxygen reduction reaction has attracted extensive attention. In this study, the rapeseed meal-based material (ARM-900) prepared by carbonization with high temperature and activation with ZnCl₂ had a porous structure and was doped with N and S heteroatoms. Compared to commercial Pt/C catalysts (onset potential of 0.95 V vs. RHE and limiting diffusion current of ?5.7 mA cm^?2), ARM-900 demonstrated excellent electrocatalytic performance with an onset potential of 0.98 V vs. RHE and limiting diffusion current of ?8.1 mA cm^?2 in O₂ saturated 0.1 M KOH solution. Meanwhile, ARM-900 had higher durability and more superior methanol tolerance than Pt/C catalyst. The excellent ORR performance of ARM-900 was derived from the formation of abundant pore structure and the doping of the autochthonous N and S heteroatoms. MFCs with ARM-900 as the cathode had the maximum power density of 808 mW/m², which was obviously better than Pt/C (709 mW/m²). This study provided an environment-friendly and effective strategy for the reuse of rapeseed meal and the preparation of N and S-doped non-metallic ORR catalysts.     

Promotional effects of trace Ni on its dual-functional electrocatalysis of Co/N-doped carbon nanotube catalysts for ORR and OER

It is still a great challenge for developing efficient dual-functional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The electrocatalysts are critical to enhance the efficiency of metal-air cells and fuel cells. In this study, a one-pot vapor deposition method was used to realize the synchronously dope of N and Ni (trace) into Co/C to form Co–Ni (trace)/N-doped carbon nanotubes (Co–Ni (trace)/NCNTs). An interesting result is that injecting dicyandiamide (DCD) into Ni foam as a precursor led to the in situ formation of NCNTs, with synchronous doping of trace Ni into Co species. The cooperative effects of the Co–Ni (trace) and N-doped carbon nanotubes resulted in superior dual-functional electrocatalytic performance of Co–Ni (trace)/NCNTs for the ORR (half-wave potential E_1/2 vs. RHE: 0.83 V, electron transfer number n: 3.97) and OER (overpotential vs. RHE: 337 mV at 10 mA cm^?2, Tafel slope: 94.0 mV dec^?1). Moreover, the Co–Ni (trace)/NCNTs catalyst showed excellent stability during 20,000 s of durability testing for both ORR and OER. This study provides a feasible strategy for designing efficient nonnoble metal-catalysts for renewable energy conversion devices.     

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.     

ZIF-8 derived bimetallic Fe–Ni-Nanoporous carbon for enhanced oxygen reduction reaction

The development of highly efficient nοn-nοble meta? catalysts for (ОRR) in PEMFCs is at the heart of the research, yet their performance is not satisfactory. The Fe–N active sites enclosed in carbon matrix are generally agreed to be the most promising active sites for ORR. In view of this, further effort is made to increase the Fe–N active sites. Here we present the fabrication of novel FeNi bimetallic electrоcatalyst obtained from ZIF, which consists of FeNi nanоallоys incorporated in N-doped carbon (FeNi-NC) featuring carbon nanotubes and porous carbon demonstrates outstanding results for ОRR. The Fe–N and Ni–N active sites synergistically enhance the ORR activity of FeNi-NC catalyst. The FeNi-NC showed remarkable performance in KОH with the half-wave and onset potential of 0.89 V and 0.99 V vs RHE, respectively. This catalyst shows exceptional stability in methanol equivalent to Pt/C commercial. The FeNi-NC retained 71%, while Pt/C commercial retained only 59% of its original current density. The exceptional stability and activity might be associated with the interplay among FeNi active sites and N-doped carbon, the distinct nanо-structure made up of porous carbon and carbon nanotubes with a high graphitization degree.     

Sengon wood-derived RGO supported Fe-based electrocatalyst with stabilized graphitic N-bond for oxygen reduction reaction in acidic medium

This work reports utilised of RGO from Sengon wood biomass to support Fe–N–C noble-free catalyst (Fe–N-RGO), while also attempt to investigate the effect of pyrolysis stage on Fe–N-RGO catalysts with four different nitrogen precursors towards the ORR activity in acidic medium. One- and two-step pyrolysis were performed at 900 °C for 1 h and 2 h respectively to produce Fe–N-RGO. This work revealed that two-step pyrolysis was able to remove the volatile components and hence forming more graphitised, stable graphitic-N and Fe-Nx, synergistically improve the ORR activity with highest onset potential of 0.83 V vs RHE and limiting current density of 5.33 mA cm⁻² reported on Fe-Pani-RGO 2py. An increase in the kinetic on Fe-Pani-RGO 2py with Tafel slope of 74 mV/dec operated at 80 °C was reported. The mesoporous structure on RGO increases the stability by 8% and better methanol tolerance when compared to a benchmark Pt/C catalyst.     

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.     

Imidazole polymerized ionic liquid as a precursor for an iron-nitrogen-doped carbon electrocatalyst used in the oxygen reduction reaction

A class of non-precious metal and highly efficient catalysts (Fe–N(PIL)/C) for the oxygen reduction reaction (ORR)were prepared by a two-step reaction involving polymerization and one-pot high-temperature pyrolysis reaction. The characteristics of Fe–N(PIL)/C electrocatalyst samples were investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS). Additionally, the electrocatalytic properties were tested by linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Under alkaline conditions, the Fe–N(PIL)/C catalyst exhibited a 2D-mesoporous structure with prominent catalytic activity. The E_on and E_1/2 reached 1.08 V and 0.93 V (vs. a reversible hydrogen electrode), respectively. The catalyst showed excellent ORR catalytic performance and stability and is superior to a 20 wt% Pt/C catalyst. This could be attributed to its mesoporous structure and the high content of Fe–N activity sites that enable it to carry out a nearly 4e⁻ reaction pathway for the ORR.