Cathodic Reduction Research Articles

ELECTROCHEMICAL REDUCTION OF CADMIUM IONS FROM ETHYLENE GLYCOL ELECTROLYTE

The work is devoted to the study of the process of cathodic reduction of Cd ions from anhydrous ethylene glycol electrolyte. The mechanism of the process of cadmium reduction was studied by taking linear and cyclic potentiodynamic polarization curves. The influence of cadmium chloride concentration, potential sweep rate and temperature on the process of electrochemical deposition of cadmium ions was studied. With an increase in the concentration of cadmium in the electrolyte, the rate of its release at the cathode increases. Precipitates of good quality are obtained at current densities of 25 mA/sm2. It has been established that the cadmium deposition potential almost does not change with increasing potential sweep rate. The dependence of cadmium electrodeposition from ethylene glycol electrolyte on temperature was studied, which made it possible to establish the optimal deposition temperature, which was 363–373 K, and to conclude that the deposition process is controlled by electrochemical polarization. The diffusion coefficient of cadmium ions to the cathode surface has been calculated

Immobilization of iron phthalocyanine on MOF-derived N-doped carbon for promoting oxygen reduction in zinc-air battery

Functional carbon nanomaterials play a crucial role in the cathodic oxygen reduction reaction (ORR) for sustainable fuel cells and metal-air batteries. In this study, we propose an effective approach to immobilize iron phthalocyanines (FePc) by employing a porous N-doped carbon material, denoted as NC-1000, derived from a sheet-shaped coordination polymer. The resulting NC-1000 possesses substantial porosity and abundant pore defects. The nitrogen sites within NC-1000 not only facilitate FePc adsorption but also optimize the electron distribution at the Fe-N site.The FePc@NC-1000 composite material exhibits a significant number of active centers in the form of Fe-N4 moieties, showcasing satisfactory ORR activity. Specifically, it demonstrates an onset potential of 0.99 V, a positive half-wave potential of 0.86 V, a large limiting current of 5.96 mA cm−2, and a small Tafel slope of 44.41 mV dec-1. Additionally, theoretical calculations and experimental results confirm the favorable performance and durability of zinc-air batteries assembled using FePc@NC-1000, thereby highlighting their considerable potential for practical applications. Overall, this study provides a comprehensive exploration of the enhanced catalytic performance and increased stability of metal–organic framework-derived functional carbon nanomaterials as cost-effective, efficient, and stable catalysts for the ORR.

Enhancing Electrochemical CO2 Reduction on Perovskite Oxide for Solid Oxide Electrolysis Cells through In Situ A-Site Deficiencies and Surface Carbonate Deposition Induced by Lithium Cation Doping and Exsolution.

Solid oxide electrolysis cells (SOECs) hold enormous potential for efficient conversion of CO2 to CO at low cost and high reaction kinetics. The identification of active cathodes is highly desirable to promote the SOEC's performance. This study explores a lithium-doped perovskite La0.6- x Lix Sr0.4 Co0.7 Mn0.3 O3-δ (x = 0, 0.025 0.05, and 0.10) material with in situ generated A-site deficiency and surface carbonate as SOEC cathodes for CO2 reduction. The experimental results indicate that the SOEC with the La0.55 Li0.05 Sr0.4 Co0.7 Mn0.3 O3-δ cathode exhibits a current density of 0.991 A cm-2 at 1.5V/800°C, which is an improvement of ≈30% over the pristine sample. Furthermore, SOECs based on the proposed cathode demonstrate excellent stability over 300 h for pure CO2 electrolysis. The addition of lithium with high basicity, low valance, and small radius, coupled with A-site deficiency, promotes the formation of oxygen vacancy and modifies the electronic structure of active sites, thus enhancing CO2 adsorption, dissociation process, and CO desorption steps as corroborated by the experimental analysis and the density functional theory calculation. It is further confirmed that Li-ion migration to the cathode surface forms carbonate and consequently provides the perovskite cathode with an impressive anti-carbon deposition capability, as well as electrolysis activity.

FeNC Catalysts with High Catalytic Activity and Stability for Oxygen Reduction Reaction

Although Pt-based catalysts have been considered as the most effective electrocatalyst for the cathodic oxygen reduction reaction (ORR) of direct methanol fuel cells (DMFCs), they still suffer from the drawbacks of high cost, poor long-term stability and methanol/ CO poisoning effects. Thus, developing low-cost ORR catalysts with high efficiency, durability and antipoisoning ability is of paramount importance. Herein, a series of non-noble metal FeNC materials are prepared through a facile pyrolysis process and used as the electrocatalysts toward ORR in alkaline electrolyte. Results show that the Fe0.50NC-800-1h catalyst pyrolyzed at 800 ºC for 1 h with the mass ratio of Fe(NO3)3•6H2O to melamine being 0.50 exhibits the highest catalytic performance among the as-prepared FeNC catalysts. The half-wave potential of ORR is ca. 0.81 V, which is only 38 mV lower than that on the noble metal Pt/C catalyst. Besides, it also displays higher stability and methanol tolerance than Pt/C. There is almost no change in the current during the chronoamperometric test when methanol is added in the electrolyte whereas significant decrease is found on Pt/C catalyst. This study of FeNC catalysts provides new insights on understanding the ORR mechanism and suggests a promising strategy to develop low-cost and highly efficient non-noble metal electrocatalysts for ORR.

An Integrated Electrochemical System for Synergistic Cathodic Nitrate Reduction and Anodic Sulfite Oxidation.

Electrochemical reduction of nitrate has broad application prospects. However, in traditional electrochemical reduction of nitrate, the low value of oxygen produced by the anodic oxygen evolution reaction and the high overpotential limit its application. Seeking a more valuable and faster anodic reaction to form a cathode-anode integrated system with nitrate reaction can effectively accelerate the reaction rate of the cathode and anode, and improve the utilization of electrical energy. Sulfite, as a pollutant after wet desulfurization, has faster reaction kinetics in its oxidation reaction compared to the oxygen evolution reaction. Therefore, this study proposes an integrated cathodic nitrate reduction and anodic sulfite oxidation system. The effect of operating parameters (cathode potential, initial NO3--N concentration, and initial SO32--S concentration) on the integrated system was studied. Under the optimal operating parameters, the nitrate reduction rate in the integrated system reached 93.26% within 1 h, and the sulfite oxidation rate reached 94.64%. Compared with the nitrate reduction rate (91.26%) and sulfite oxidation rate (53.33%) in the separate system, the integrated system had a significant synergistic effect. This work provides a reference for solving nitrate and sulfite pollution, and promotes the application and development of electrochemical cathode-anode integrated technology.

Direct Nanoscale Visualization of the Electric-Field-Induced Aging Dynamics of MAPbI3 Thin Films.

Perovskite solar cells represent the most attractive emerging photovoltaic technology, but their practical implementation is limited by solar cell devices' low levels of operational stability. The electric field represents one of the key stress factors leading to the fast degradation of perovskite solar cells. To mitigate this issue, one must gain a deep mechanistic understanding of the perovskite aging pathways associated with the action of the electric field. Since degradation processes are spatially heterogeneous, the behaviors of perovskite films under an applied electric field should be visualized with nanoscale resolution. Herein, we report a direct nanoscale visualization of methylammonium (MA+) cation dynamics in methylammonium lead iodide (MAPbI3) films during field-induced degradation, using infrared scattering-type scanning near-field microscopy (IR s-SNOM). The obtained data reveal that the major aging pathways are related to the anodic oxidation of I- and the cathodic reduction of MA+, which finally result in the depletion of organic species in the channel of the device and the formation of Pb. This conclusion was supported by a set of complementary techniques such as time-of-flight secondary ion mass spectrometry (ToF-SIMS), photoluminescence (PL) microscopy, scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) microanalysis. The obtained results demonstrate that IR s-SNOM represents a powerful technique for studying the spatially resolved field-induced degradation dynamics of hybrid perovskite absorbers and the identification of more promising materials resistant to the electric field.

Radical-Based Convergent Paired Electrolysis.

Electrochemistry offers a sustainable platform for discovering reactions involving single-electron transfer (SET) that generates highly reactive and synthetically versatile radical species. Compared with photochemistry similarly specializing in SET which requires expensive photocatalysts, electrochemistry employs low-cost electricity to drive the electron flow. Paired electrolysis makes use of both half-reactions, thus obviating the need for sacrificial reactions and maximizing the atom and energy economy. In convergent paired electrolysis, anodic oxidation and cathodic reduction occur simultaneously to generate two intermediates, which are then coupled to furnish the product. It represents a distinctive approach to challenging redox-neutral reactions. However, the gap between the two electrodes makes it hard for a reactive intermediate to come across the other coupling partner. This concept article summarizes recent state-of-the-art advances on radical-based convergent paired electrolysis, which adopted different strategies to overcome the difficulty.

Alternative approach for the growth of a TiB2/TiC multilayer on M2 steel using the duplex method: Cathodic arc physical vapor deposition and cathodic reduction and thermal diffusion boriding

An alternative approach for producing a hard TiB2/TiC multilayer on M2 high-speed steel was introduced by combining cathodic arc physical vapor deposition (CA-PVD) and cathodic reduction and thermal diffusion-based boriding (CRTD-Bor). In this regard, the CRTD-Bor process was applied on CA-PVD Ti-deposited M2 steel and the effects of boriding parameters (i.e., temperatures and durations) on multilayer growth were examined. During boriding, Ti coating on the substrate was converted into Ti-borides on the top surface and a TiC layer was simultaneously formed at the interface of the Ti deposit and the steel matrix. The growth of boride and carbide phases was found to obey the parabolic law. The pre-exponential factors (K0) and the activation energy (Q) values were calculated as 7.50 × 10−9 m2/s and 146.10 kJ/mol for TiB2 growth and 1.81 × 10−7 m2/s and 187.31 kJ/mol for TiC formations, respectively. Additionally, empirical equations for estimating the thicknesses of TiB2 and TiC layers were derived. The penetration depth-dependent hardness measurements revealed the TiB2 layer hardness as 41 ± 5 Gpa, which decreased gradually toward the TiB region (24 ± 2 GPa) and fell to 13 ± 1 GPa in the Ti-rich area. The hardness then increased to 20 ± 1 GPa with the contribution of the TiC layer adjacent to the substrate. This multilayer coating exhibited −5.5 to −4.5 GPa compressive stress and good adhesions (HF1) to the substrates. Also, the results of tribological tests indicated a sevenfold increase in wear resistance under dry sliding conditions.

Efficient ammonia removal promoted in a bifunctional system constructed with NiCu–S/DSA electrodes

Currently, the treatment of ammonia in wastewater, one of the main causes of eutrophication in water bodies, has received widespread attention. In this work, a novel electrocatalytic bifunctional system was constructed to achieve efficient degradation of ammonia. It consists of Ni1Cu0.25-S/DSA electrodes with both anode and cathode, which is prepared by a combination of electrodeposition and electrochemical tuning strategies. The crystalline phases and oxidation states of the nano-textured particulate metal oxides were determined by using a series of physical characterizations. The Ni1Cu0.25-S/DSA electrode with the best electrocatalytic performance was screened by electrochemical analysis, which has good stability and reliability when processing ammonia nitrogen. The efficiency of electrodes for ammonia removal was verified by running denitrification of synthetic and real wastewater. The results showed that the NH4+-N removal efficiency could approach up to 99%. Kinetically, compared with the monofunctional system, the bifunctional system obtained a higher NH4+-N degradation rate of 45.5 mg L−1 h−1, increased the rate of N2 generation by more than 10 times, and reduced the rate of NO3−-N and NO2−-N generation by one-third on average. The possible reaction mechanism of anodic ammonia oxidation and cathodic nitrate reduction in the bifunctional system was proposed.

Transition metal sulfide/oxide nanoflowers decorated on poly (aniline-2-sulfonic acid) modified polyacrylamide derived carbon cathode catalyst for bioenergy generation in microbial fuel cells

Microbial fuel cells (MFCs) are promising carbon-free energy devices with the potential to harvest power and treat wastewater simultaneously, which is crucial to meet the emerging energy challenges. Despite the high theoretical power output, the performance of MFCs is dependent on the cathodic oxygen reduction reaction (ORR) to generate electricity. Herein, a hybrid nanostructure of nickel-cobalt sulfide (NiCo2S4) nanosheets over NiCo2O4 nanoflowers on in-situ nitrogen and sulfur-doped carbon (NSC) is prepared by direct pyrolysis. Deposition of NiCo2S4 nanosheets improves the effective contact with the electrolyte and increases the catalytic sites for ORR. NiCo2S4/NiCo2O4@NSC shows an oxygen reduction peak at 0.150 V, limiting current of -0.093 mA, close to -0.107 mA for Pt/C and generates optimal power density of 831.74 mW m−2 comparable to Pt/C (857.92 mW m−2) and higher than NiCo2O4@NSC (665.86 mW m−2), NSC (650.28 mW m−2) and NC (485.98 mW m−2) air cathodes. This could be attributed to the high degree of graphitization, appropriate N and S content, a synergistic effect between the metal species and the heteroatoms, and better catalytic surface area utilization. The results suggest that M-N-S-based carbons could be potential cathodes for microbial fuel cells and similar energy devices.

Enhanced oxygen reduction upon Ag-Fe-doped polyacrylonitrile@UiO-66-NH2 nanofibers to improve power-generation performance of microbial fuel cells

Microbial fuel cells (MFCs) have great potential as a new energy technology that utilizes microorganisms to produce electrical energy by decomposing organic matter. A cathode catalyst is key to achieving an accelerated cathodic oxygen reduction reaction (ORR) in MFCs. We prepared a Zr-based metal organic-framework-derived silver-iron co-doped bimetallic material based on electrospun nanofibers by promoting the in situ growth of UiO-66-NH2 on polyacrylonitrile (PAN) nanofibers and named it as CNFs-Ag/Fe-m:n doped catalyst (m:n were 0, 1:1, 1:2, 1:3, and 2:1, respectively). Experimental results combined with density functional theory (DFT) calculations reveal that a moderate amount of Fe doped in CNFs-Ag-1:1 reduces the Gibbs free energy in the last step of the ORR. This indicates that Fe doping improves the performance of the catalytic ORR, and MFCs equipped with CNFs-Ag/Fe-1:1 exhibit a maximum power density of 737. 45 mW m−2, significantly higher than that obtained for MFCs using commercial Pt/C (457.99 mW m−2).

A high-performance and anti-sulfur poisoning oxygen reduction reaction catalysts derive from molybdenum-doping on PtCo alloy nanoparticles surface

During the operation of fuel cell vehicles, sulfur dioxide (SO2) as a primary air pollutant can be transported to the cathode of the fuel cell with the air, leading to poisoning of the cathodic Pt-based catalyst, and subsequently, causing performance degradation and even shutdown. Therefore, there is an urgent need for SO2-tolerant Pt-based catalysts to mitigate poisoning in the cathodic oxygen reduction reaction (ORR). Herein, we report a carbon-supported Mo doped PtCo alloy catalyst with high-performance and anti-sulfur poisoning, termed as Mo-PtCo/C. Detailed investigations demonstrate that the Co in PtCo alloy nanoparticles (NPs) greatly promote ORR activity but do little to improve the SO2-tolerance. However, the PtCo alloy NPs doped with Mo not only exhibit a higher ORR activity, but also a superior SO2 poisoning resistance and a superior recovery performance. The optimal Mo-PtCo/C catalyst demonstrates a high initial mass activity of 871.0 mA mgPt−1, which is higher than that of the PtCo/C catalyst (initial value=558.8 mA mgPt−1) and 6.6 times higher than that of the commercial Pt/C (20 wt.% Pt, initial value=174.6 mA mgPt−1), along with a low mass activity loss of 36.19% after SO2 poisoning, which is much lower than 82.4% of the PtCo/C catalyst and 81.3% of the commercial Pt/C. More importantly, it is revealed that MoO3 formed on the PtCo NPs surface after Mo doping helps to reduce the electrooxidation potentials of SO2 to the operating potential of the fuel cell, thereby markedly boosting SO2-tolerance. Furthermore, the fuel cells test also confirmed that MoO3 improved the SO2-tolerance of the Mo-PtCo/C catalysts.

Decoupling ∗H supply for industrial nitrate electroreduction coupled with glycerol oxidation

Industrial-level ammonia electroproduction from nitrate is significant for modern society but remains a challenge. In this issue of Chem Catalysis, Shao and co-workers report an economically feasible electrochemical system of cathodic nitrate reduction coupled with anodic glycerol oxidation using a bifunctional carbon [email protected] catalyst, which decouples ∗H generation and NOX− hydrogenation at different sites.

A mini review of electrocatalytic upgrading of carbohydrate biomass—System, path, and optimization

AbstractUpgrading carbohydrate biomass is a promising process to convert low‐value carbohydrate feedstocks into high‐value chemicals and fuels, which is critical for the development of a sustainable and renewable society. Among the various carbohydrate conversion technologies, electrocatalytic methods have gained increasing research interest due to their mild reaction conditions and easy accessibility. Moreover, electrocatalytic methods utilize water as a green and abundant source of hydrogen and oxygen for either reduction reactions on the cathode or oxidation reactions on the anode. In recent years, significant progress has been made in this field, with the establishment of various systems aimed at enhancing the electrocatalytic conversion of carbohydrates. In this review, recent technologies and results of electrocatalytic conversion of carbohydrates are summarized in two parts: anodic electrocatalytic oxidation (cellulose, 5‐hydroxymethylfurfural [HMF], glucose, and 2‐furfural) and cathodic electrocatalytic reduction (glucose, HMF, and 2‐furfural). Furthermore, future outlooks for improving this field are also proposed.

Simultaneous Generation of H2O2 and Formate by Co‐Electrolysis of Water and CO2 over Bifunctional Zn/SnO2 Nanodots

AbstractHydrogen peroxide (H2O2) and formate are important chemicals used in various chemical manufacturing industries. One promising approach for the simultaneous production of these chemicals is coupling anodic two‐electron water oxidation with cathodic CO2 reduction in an electrolyzer using nonprecious bifunctional electrocatalysts. Herein, we report an innovative hybrid electrosynthesis strategy using Zn‐doped SnO2 (Zn/SnO2) nanodots as bifunctional redox electrocatalysts to achieve Faradaic efficiencies of 80.6 % and 92.2 % for H2O2 and formate coproduction, respectively, along with excellent stability for at least 60 h at a current density of ≈150 mA cm−2. Through a combination of physicochemical characterizations, including operando attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), isotope labeling mass spectrometry (MS)/1H NMR and quasi‐in situ electron paramagnetic resonance (EPR), with density functional theory (DFT) calculations, we discovered that the Zn dopant facilitates the coupling of *OH intermediates to promote H2O2 production and optimizes the adsorption of *OCHO intermediates to accelerate formate formation. Our findings offer new insights into designing more efficient bifunctional electrocatalyst‐based pair‐electrosynthesis system for the coproduction of H2O2 and formate feedstocks.

Simultaneous Generation of H2 O2 and Formate by Co-Electrolysis of Water and CO2 over Bifunctional Zn/SnO2 Nanodots.

Hydrogen peroxide (H2 O2 ) and formate are important chemicals used in various chemical manufacturing industries. One promising approach for the simultaneous production of these chemicals is coupling anodic two-electron water oxidation with cathodic CO2 reduction in an electrolyzer using nonprecious bifunctional electrocatalysts. Herein, we report an innovative hybrid electrosynthesis strategy using Zn-doped SnO2 (Zn/SnO2 ) nanodots as bifunctional redox electrocatalysts to achieve Faradaic efficiencies of 80.6 % and 92.2 % for H2 O2 and formate coproduction, respectively, along with excellent stability for at least 60 h at a current density of ≈150 mA cm-2 . Through a combination of physicochemical characterizations, including operando attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), isotope labeling mass spectrometry (MS)/1 H NMR and quasi-in situ electron paramagnetic resonance (EPR), with density functional theory (DFT) calculations, we discovered that the Zn dopant facilitates the coupling of *OH intermediates to promote H2 O2 production and optimizes the adsorption of *OCHO intermediates to accelerate formate formation. Our findings offer new insights into designing more efficient bifunctional electrocatalyst-based pair-electrosynthesis system for the coproduction of H2 O2 and formate feedstocks.

A novel triple-conductive cathode with high efficiency and stability for protonic ceramic fuel cells

The sluggish kinetics of cathodic oxygen reduction reaction is one of the key barriers to the development of protonic ceramic fuel cells (PCFCs), while the appearance of triple-conductive material reported in recent years has brought a new dawn for the commercialization of PCFCs. These materials need to have excellent hydration ability and water tolerance to expand the active sites and prolong the operation lifespan. Herein, a highly efficient and stable cathode material, BaCo0.4Fe0.4Zr0.1Sc0.1O3-δ (BCFZSc) with cubic perovskite structure, is proposed for PCFCs. Electrical conductivity relaxation measurements reveal that the oxygen surface exchange coefficient of BCFZSc can reach the value of 1.8 × 10−3 cm s−1 at 700 °C, almost an order of magnitude larger than those of most reported cathodes. Applying BCFZSc as cathode, single cell exhibits an excellent peak power density of 1.334 W cm−2 with a small polarization resistance of 0.044 Ω cm2 at 700 °C, and a decent durability over 150 h at 600 °C is demonstrated. This research highlights that BCFZSc is a promising candidate for PCFCs cathode.

Nano-flower like CoFe-layered double hydroxide@reduced graphene oxide with efficient oxygen reduction reaction for high-power air-cathode microbial fuel cells

Microbial fuel cells (MFCs) are “self-sufficient” renewable energy sources that utilize the redox processes inherent in microbial metabolism to generate an electrical potential. However, the cathodic region of these fuel cells typically utilizes an oxygen reduction reaction (ORR) operating at high overpotential and slow reaction kinetics significantly, restricting the power generation capacity of MFCs. Herein, to improve the cathodic reduction efficiency, we synthesized CoFe-layered double hydroxides (LDH) on partially-reduced graphene oxide (p-rGO) via electrostatic interaction. In contrast to pure CoFe-LDH, CoFe-LDH@p-rGO composite possessed a three-dimensional uniform porous nanoflower-like morphology, giving the catalyst a high surface area for efficient catalysis. The proportions of CoFe-LDH to p-rGO were optimized to minimize layer stacking through strong π-π bond and van der Waals force, maximizing the overal electron transfer numbers n (3.66), with the lowest charge transfer resistance Rct (38.5 Ω). As a result, this novel catalyst combined the rich Co/Fe metal center catalytic active sites and interlayer structure of CoFe-LDH, with the high electrical conductivity of p-rGO to accelerate the electron transfer rate of ORR. Air-cathode microbial fuel cell (ACMFC) utilizing CoFe-LDH@p-rGO catalyst showed comparable output voltage of 423 mV to Pt/C catalyst, and a comparably high-power density of 204 mW m−2. This work provides a new path towards development of nanostructured non-noble metal catalysts for the optimization of oxygen reduction reaction in high-power ACMFCs.

Structure Dynamics of Carbon-Supported Platinum-Neodymium Nanoalloys during the Oxygen Reduction Reaction

Platinum-rare earth nanoalloys have been predicted to be promising proton exchange membrane fuel cell (PEMFC) electrocatalysts for the cathodic oxygen reduction reaction (ORR). However, their implementation in PEMFCs is limited by the challenge of their preparation as carbon-supported nanostructures. Consequently, the practical structure–activity–stability trends for this class of nanoalloys remain largely unexplored. Herein, carbon-supported Pt–Nd nanoalloys as ORR electrocatalysts are described. The physical chemistry of selected electrocatalysts was extensively investigated by means of combined ex situ and operando techniques, which reveal the unique structural dynamics of Pt–Nd nanoalloys in a simulated PEMFC cathode environment. The experimental observations, supported by theoretical calculations, indicate that after initial significant structural modification in the early stage of operation, the ORR activity is mediated in the longer term by surface compressive strain rather than charge transfer between Pt and Nd. Such key operando structure–activity–stability relations underpin further optimization of carbon-supported Pt-rare earth nanoalloys as fuel cell cathode catalysts.

Iron single Atom–Iron nanoparticles dual-deposited nitrogen-doped graphene hybrid as an innovative catalyst to enhance the oxygen reduction reaction

The fabrication of an effective electrocatalyst for cathodic oxygen reduction reaction (ORR) is important to enhance the performance of fuel cell applications. Here, we prepared a novel hybrid material based on the combination of iron single atoms–small iron nanoparticles homogeneously distributed on the surface of nitrogen-doped graphene nanosheets (FeSA-FeNPs/NG). The achieved FeSA–FeNPs/NG material exhibited high catalytic ORR behaviors with high positive values of +0.94 V and +0.81 V for onset potential and half-wave potential, respectively, as well as the remarkable stability with 90% retention of initial current over an operation period of 15 000 s), superior to commercial Pt/C in 0.1 M KOH medium. In addition, the material favored a four-electron reaction pathway along with good methanol crossover tolerance towards ORR. The outstanding catalytic performance could be attributed to the formation of a unique microporous nanoarchitecture owning large specific surface area of 103.63 m2 g−1 and high conductivity, which create rich active sites and fast charge transfer ability, thus effectively accelerating the adsorption and catalyzation processes to convert oxygen reactant to product during ORR. These findings suggest a novel route for the synthesis of potential catalysts exhibiting excellent efficiency and cost effectiveness for fuel cell industries.