Use of cellulose-based carbon aerogels as catalyst support for PEM fuel cell electrodes: Electrochemical characterization

New nanostructured carbons have been developed through pyrolysis of organic aerogels, based on supercritical drying of cellulose acetate gels. These cellulose acetate-based carbon aerogels (CA) are activated by CO₂ at 800 °C and impregnated by PtCl₆²⁻; the platinum salt is then chemically or electrochemically reduced. The resulting platinized carbon aerogels (Pt/CA) are characterized with transmission electron microscopy (TEM) and electrochemistry. The active area of platinum is estimated from hydrogen adsorption/desorption or CO-stripping voltammetry: it is possible to deposit platinum nanoparticles onto the cellulose acetate-based carbon aerogel surface in significant proportions. The oxygen reduction reaction (ORR) kinetic parameters of the Pt/CA materials, determined from quasi-steady-state voltammetry, are comparable with that of Pt/Vulcan XC72R. These cellulose acetate-based carbon aerogels are thus promising electrocatalyst support for PEM application.     

Kinetic study of oxygen reduction reaction and PEM fuel cell performance of Pt/TiO2-C electrocatalyst

The electrochemical activity and thermal stability of the Pt/TiO₂-C were evaluated in the oxygen reduction reaction (ORR) in acid medium at different temperatures. The platinum was selectively deposited onto the TiO₂ (E_bg = 2.3 eV) by the photo-irradiation of platinum precursor (Pt⁴⁺→Pt⁰). The Pt/TiO₂-C electrocatalyst prepared was characterized by XRD, TEM/EDS, cyclic and lineal voltammetry techniques. TEM images indicated that platinum nanoparticles (<5 nm) were deposited in agglomerates form around the oxide sites. EDS and XRD results confirm the composition and crystalline structure of Pt/TiO₂-C. The thermal stability and electrochemical activity of the Pt/TiO₂-C for ORR at different temperatures (298–343 K) is higher than Pt/C commercial sample (Pt-Etek). A more favorable apparent enthalpy of activation for Pt/TiO₂-C was greatly influenced by addition of oxide in the catalyst compare to Pt-Etek. Single H₂/O₂ fuel cell performance results of Pt/TiO₂-C show an improvement of the power density with the increase of the temperature.     

Understand the Fe3C nanocrystalline grown on rGO and its performance for oxygen reduction reaction

Transition metal carbide catalysts are the alternative products of traditional noble metal Pt/C in oxygen reduction reaction (ORR). Oleic acid-coated iron oxide nanoparticles (F₃O₄@OA) was prepared by pyrolysis, assembled with reduced graphene oxide (rGO), and carbonized at 800 °C to obtain N doped iron carbide nanoparticles supported rGO (N–Fe₃C/rGO). The particle size of nanocrystals increases significantly with the graphene loading risen can be seen in the transmission electron microscope (TEM) image which roughly distributed around 40 nm. The linear scanning voltammetry (LSV) curve shows the material has an ORR performance equivalent to Pt/C in alkaline media.     

Emergent hierarchical porosity by ZIF-8/GO nanocomposite increases oxygen electroreduction activity of Pt nanoparticles

Hierarchically porous materials are promising as catalyst supports in fuel cells and batteries as they increase overall mass transfer and active site density. In this work, a hierarchically porous catalyst support for oxygen reduction reaction (ORR) in acidic media has been developed by a bottom-up approach. Graphene oxide (GO) was introduced during synthesis conditions of zeolitic imidazolate framework-8 (ZIF-8) to produce hybrid material of ZIF-8/GO. Successful nanocomposite formation was realized by preserved crystallinity and chemical interaction between species as revealed by X-ray diffraction and Fourier transform infrared spectroscopy. Introduction of GO and pyrolysis of resulting hybrid structure causes emergence of disordered meso/macropores with an accompanying increase in pore volume as revealed by N₂ sorption experiments. Pt nanoparticle deposition on pyrolyzed hybrid material by polyol method results in electrocatalyst Pt/NC-1, which shows greatly improved mass activity (182 vs 86 A g⁻¹_Pt) and specific activity (467 vs 186 μA g⁻¹_Pt) at 0.8 V for ORR against reference electrocatalyst Pt/r-GO and improved specific activity against Pt/C.     

Nitrogen doped carbon layer coated platinum electrocatalyst supported on carbon nanotubes with enhanced stability

Enhancement in durability of electrocatalyst is still one of the most important issues in polymer electrolyte fuel cells (PEFCs). Here, we report a structurally coated electrocatalyst supported on carbon nanotubes (CNT), in which platinum (Pt) nanoparticles are coated by nitrogen doped carbon (NC) layers. CNT/NC/Pt/NC shows comparable electrochemical surface area (ECSA) and oxygen reduction reaction (ORR) activity to the non-coated electrocatalyst (CNT/NC/Pt), indicating that NC layer on Pt nanoparticles almost negligibly affects the activities of electrocatalyst; while, CNT/NC/Pt/NC exhibits a higher Pt stability due to the unique structure, in which the Pt nanoparticles are stabilized by the NC layers and Pt aggregation is decelerated proved by TEM measurement. Maximum power density of CNT/NC/Pt/NC reached 604 mW cm^?2 with Pt loading of 0.1 mg_Pt cm^?2, which only decreases by 7% compared to CNT/NC/Pt (650 mW cm^?2). The electrochemical analysis and fuel cell test illustrate that NC layer on Pt nanoparticles enhances the durability without serious deterioration of fuel cell performance.     

Synergy between isolated-Fe3O4 nanoparticles and CNx layers derived from lysine to improve the catalytic activity for oxygen reduction reaction

In order to seek heterogeneous electrocatalyst with efficient catalytic activity for oxygen reduction reaction (ORR), Fe₃O₄-CN_x composite reported in our previous work was studied as electrocatalyst for ORR and showed poor catalytic activity. To improve the catalytic activity, Fe₃O₄-CN_x composite is modified by the CN_x layers derived from lysine through pyrolysis. The physical characterization show that the coral-shaped morphology of the resultant composite (Fe₃O₄-CN_x-Lys) is still retained, while the degree of its graphitic crystalline increases. Besides, Fe₃O₄-CN_x-Lys has 364.7 m² g⁻¹ of surface area with hierarchical porous structure. Electrochemical tests show that the catalytic activity Fe₃O₄-CN_x-Lys for ORR is not only higher than those Fe₃O₄-CN_x, XC-72-Lys derived from lysine and XC-72 Vulcan carbon but also comparable to that of commercial Pt/C (20 wt%).     

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.     

PANI-modified Pt/Na4Ge9O20 with low Pt loadings: Efficient bifunctional electrocatalyst for oxygen reduction and hydrogen evolution

Exploring cost-effective electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) have been a goal in the sustainable hydrogen-based society. Although abundant of alternative materials have been developed, Pt/C remains the most efficient electrocatalyst for the ORR and HER. Nevertheless, improving the stability and reducing Pt loading for Pt-based electrocatalysts are still big challenges. Herein, semiconductor crystals Na₄Ge₉O₂₀ with richer topology structure was chosen as electrocatalyst support, subsequently, the conductive polymer polyaniline (PANI) was decorated on semiconductor Na₄Ge₉O₂₀, low-content Pt nanoparticles (Pt NPs) with the size of 1–3 nm were then uniformly anchored on the surface of Na₄Ge₉O₂₀-PANI to obtain the efficient bifunctional electrocatalyst for ORR and HER in the acidic solution. More importantly, the stability and mass activity of the obtained electrocatalyst 5 wt% Pt/Na₄Ge₉O₂₀-PNAI are significantly higher than that of commercial 20 wt% Pt/C for ORR and HER. It was proposed that the PANI could not only promote the electron transfer from Na₄Ge₉O₂₀ to Pt, but also stabilize the Pt NPs, thus, improving the electrocatalytic activity and stability of 5 wt% Pt/Na₄Ge₉O₂₀-PNAI.     

Fe3C nanoparticles-loaded 3D nanoporous N-doped carbon: A highly efficient electrocatalyst for oxygen reduction in alkaline media

High-performance, non-precious metal electrocatalysts have been widely considered among the most prospective candidates to replace Pt-based electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. Herein, we report a synthetic method, involving templating, polymerization and pyrolysis, that produces catalytically active iron carbide (Fe₃C) nanoparticles-loaded porous N-doped carbon materials from polyaniline- and Fe(III)-modified mesoporous graphitic carbon nitride (g-C₃N₄). We also show that the resulting noble metal-free materials exhibit good electrocatalytic activity for ORR, with good onset and half-wave potentials, in O₂-saturated alkaline solution. The structure, composition, crystallinity, and electrocatalytic activity of these materials are found to depend on the pyrolysis temperature and the specific components in the precursor. In particular, the material obtained by pyrolysis at 1000 °C, named Fe₃C/NC-1000, shows excellent electrocatalytic activity and better performance, in terms of both onset and half-wave potentials, than Pt/C (20 wt% Pt). The material also tolerates the methanol crossover reaction better than Pt/C and shows negligible shift in onset and half-wave potentials to negative values even after use in 3000 cycles of electrocatalysis. This robust, non-noble metal-based carbon material can potentially become a viable alternative to precious metal electrocatalysts for ORR.     

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.     

Oxygen reduction on carbon supported Pt-W electrocatalysts

The catalytic activity of Pt-W electrocatalysts towards oxygen reduction reaction (ORR) was studied. Pt-W/C materials were prepared by thermolysis of tungsten and platinum carbonyl complexes in 1-2 dichloro-benzene during 48 h. The precursors were mixed to obtain relations of Pt:W: 50:50 and 80:20%w, respectively. The Pt carbonyl complex was previously synthesized by bubbling CO in a chloroplatinic acid solution. The synthesized materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry (CV) and a rotating disk electrode (RDE). The results show that both materials (Pt₅₀W₅₀/C and Pt₈₀W₂₀/C) have a crystalline phase associated with metallic platinum and an amorphous phase related with tungsten and carbon. The particle size of the electrocatalysts depends on the relationship between platinum and tungsten. Finally, both materials exhibit catalytic activity for oxygen reduction.     

Oxygen reduction on a Pt70Ni30/C electrocatalyst prepared by the borohydride method in H2SO4/CH3OH solutions

The activity for the oxygen reduction reaction (ORR) on carbon supported Pt–Ni electrocatalysts prepared by reduction of Pt and Ni precursors with NaHB₄ was investigated in sulphuric acid both in the absence and in the presence of methanol and compared with that of a commercial Pt/C electrocatalyst. In methanol-free sulphuric acid solution the Pt₇₀Ni₃₀/C alloy electrocatalyst showed a lower specific activity towards oxygen reduction compared to Pt/C. In O₂-free H₂SO₄ the onset potential for methanol oxidation on Pt₇₀Ni₃₀/C was shifted to more positive potentials, which indicates a lower activity for methanol oxidation than platinum. In the methanol containing electrolyte the higher methanol tolerance of the Pt₇₀Ni₃₀/C electrocatalyst for the ORR was ascribed to the lower activity of the binary electrocatalyst for methanol oxidation, arising from a composition effect.     

Platinum/carbon nanofiber nanocomposite synthesized by electrophoretic deposition as electrocatalyst for oxygen reduction

A platinum/carbon nanofiber (Pt/CNF) nanocomposite with a platinum loading of 15 wt% is prepared by a modified electrophoretic deposition (EPD) method, and the as-grown nanocomposite is used as the electrocatalyst for oxygen reduction reaction (ORR). For comparison, a Pt/CNF composite with 40 wt% platinum loading is prepared by chemical reduction. High resolution transmission electron microscope (HRTEM) images show that the size of platinum nanoparticles formed by EPD is about 1 nm, much smaller than those by chemical reduction (about 3–5 nm). Cyclic voltammetric analysis in a nitrogen saturated electrolyte shows that the electrochemical surface area of electrocatalyst by EPD is larger than that by chemical reduction. Moreover, although the electrocatalyst prepared by chemical reduction has a higher electrochemical capacity, it is less active than that prepared by EPD. Analysis of the electrode kinetics using Tafel plot suggests that the electrocatalyst prepared by EPD provides a strong ORR activity. Cyclic voltammetric measurements at different scan rates confirm that the ORR on the nanocomposites prepared by EPD is a diffusion-controlled process. This work demonstrates that the Pt/CNF composites synthesized by EPD are effective for ORR.     

Carbon nanotube-supported Pt-HxMoO3 as electrocatalyst for methanol oxidation

Carbon nanotube (CNT)-supported platinum modified with H_xMoO₃ (Pt-H_xMoO₃/CNT) was prepared and used as an electrocatalyst for methanol oxidation. In the preparation of this electrocatalyst, a platinum precursor was loaded on CNTs and reduced by sodium borohydride in ethylene glycol, resulting in CNT-supported platinum without modification (Pt/CNT), and then the Pt/CNT was modified with H_xMoO₃ that was formed by hydrolysis and subsequent reduction of ammonium molybdate. The surface morphology, structure and composition of Pt-H_xMoO₃/CNT and Pt/CNT as well as their activity toward methanol oxidation were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive spectrometry (EDS), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), chronoamperometry (CA), chronopentiometry (CP), and electrochemical impedance spectroscopy (EIS). The results, obtained from TEM, XRD, EDS, and FTIR, indicate that the platinum loaded on CNTs has a face-centered cubic structure with particle sizes of 2–5 nm, and the modification of H_xMoO₃ on platinum with an atom ratio of Pt:Mo = 2:1 has little effect on the particle size, distribution and structure of the platinum. The results, obtained from CV, CA, CP, and EIS, show that the Pt-H_xMoO₃/CNT exhibits higher electrocatalytic activity toward methanol oxidation and better carbon monoxide tolerance than Pt/CNT.     

Two-step pyrolytic engineering to form porous nitrogen-rich carbons with a 3D network structure for Zn-air battery oxygen reduction electrocatalysis

It is of great urgency to design inexpensive and high-performance oxygen reduction reaction (ORR) electrocatalysts derived from biowastes as substitutes for Pt-based materials in electrochemical energy-conversion devices. Here we propose a strategy to synthesize three-dimensional (3D) porous nitrogen-doped network carbons to catalyze the ORR from two-step pyrolysis engineering of biowaste scale combined with the use of a ZnCl₂ activator and a FeCl₂ promotor. Electrochemical tests show that the synthesized network carbons have exhibited comparable ORR catalytic activity with a half-wave potential (~0.85 V vs. RHE) and outstanding cyclical stability in comparison to the Pt/C catalyst. Beyond that, a high electron transfer number (~3.8) and a low peroxide yield (<7.6%) can be obtained, indicating a four-electron reaction pathway. The maximum power density is ~68 mW cm^?2, but continuous discharge curves (at a constant potential of ~1.30 V) for 12 h are not obviously declined in Zn-air battery tests using synthesized network carbons as the cathodic catalyst. The formation of 3D porous structures with high BET surface area can effectively expose the surface catalytic sites and promote mass transportation to boost the ORR activity. This work may open a new idea to prepare porous carbon-based catalysts for some important reactions in new energy devices.     

A new durable and high performance platinum supported on Ag–Ni-porous coordination polymer as an anodic DMFC nano-electrocatalyst: DFT and experimental investigation

Due to the poor performance and intermediates poisoning of available catalysts in direct methanol fuel cells (DMFC), the researcher is confronted with a considerable challenge for obtaining modified electrocatalyst. Ag–Ni porous coordination polymer (ANP) as a new electrocatalyst supporter was synthesized by a hydrothermal method. To achieve favorable electrocatalyst for DMFC systems, platinum nanoparticles was deposited upon ANP by an electrochemical method and platinum supported on Ag–Ni porous coordination polymer (Pt-ANP) was formed. Fourier transform infrared spectroscopy (FTIR) analysis ensured correct synthesized of ANP and Pt-ANP. In addition, the morphologies investigation of ANP and Pt-ANP were carried out by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The FE-SEM images indicate that the platinum nanoparticles have been greatly deposited on ANP surface. Electrochemical behaviors of prepared catalyst for methanol oxidation were evaluated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), and chronoamperometry (CA) techniques. Electrochemical cyclic voltammetry tests (CV) indicate that the forward peak current density of Pt-ANP is about 105 mA/cm² which it is 33% more than the forward peak current density of pure Pt catalyst (70.21 mA/cm²). Moreover, electrochemical surface area (ECSA) of Pt-ANP is 26.42 m²/g_Pt. In addition, density functional theory (DFT) computations show that with the deposition of Pt upon ANP, the HOMO-LOMO energy gap of ANP has been decreased which they are suitable for electrochemical reactions. Theoretical results are greatly in accordance with the experiments. Based on the results, Pt-ANP could be a superior electrocatalyst for methanol oxidation.     

Highly dispersed MnO nanoparticles supported on N-doped rGO as an efficient oxygen reduction electrocatalyst via high-temperature pyrolysis

Transition metal-based compounds, due to their excellent ORR catalytic performance under alkaline condition, have recently emerged as one of the most promising alternatives to noble metal-based ORR catalysts. It is worth noting that manganese oxide can take an unique advantage for decomposition of intermediate adsorption products H₂O₂ and can effectively reduce O₂ to OH⁻. However, most research has focused on MnO₂, while attention has rarely been paid to MnO catalysts. In addition, under high-temperature pyrolysis condition, MnO is the most stable manganese oxide but MnO nanoparticles easily agglomerate. Hence, it is very difficult to obtain well-dispersed and small-sized MnO nanoparticles. Herein, on the basis of pre-synthesizing uniformly distributed manganese complexes on the reduced graphene oxide (rGO), we innovatively prepare highly dispersed and small-sized MnO nanoparticles (~3.94 nm) via high-temperature pyrolysis, which are uniformly anchored on N-doped reduced graphene oxide (NrGO) as an efficient oxygen reduction electrocatalyst. The as-obtained MnO/NrGO (1050 °C) electrocatalyst achieves satisfactory onset potential (0.942 V) and half-wave potential (0.820 V) under alkaline condition. And the limiting current density is 4.17 mA cm⁻², which is very close to that of Pt/C (20 wt%, JM). Meanwhile, MnO/NrGO (1050 °C) catalyst presents superior longstanding durability and methanol resistance than Pt/C (JM). This work indicates that high-temperature pyrolysis can improve the purity of manganese oxide, simultaneously the defects of NrGO can reduce particle size of MnO nanoparticles, which are greatly beneficial to improve ORR performance. This work provides a new idea for research of MnO catalysts for ORR in the future.     

Cobalt,sulfur, nitrogen co-doped carbon as highly active electrocatalysts towards oxygen reduction reaction

Rational design of efficient, cost-effective electrocatalyst towards oxygen reduction reaction (ORR) is of vital importance to the wide application of polymer electrolyte membrane fuel cells. In this work, a novel and simple Na₂SO₄-assisted pyrolysis strategy with ZIF-12 as the precursor is reported for the synthesis of cobalt, sulfur, nitrogen, co-doped carbon (termed as CoSNC-xNa₂SO₄-T) materials towards ORR. Different from CoNC-800 derived from pure ZIF-12, with the presence of Na₂SO₄, the derived CoSNC-0.5Na₂SO₄-800 material exhibits layered flake morphology with hierarchical meso-microporous structure. Besides, CoSNC-0.5Na₂SO₄-800 material shows higher content of pyridinic-N and graphitic-N, higher relative intensity of Co-N_x, higher content of carbon defect, as well as larger specific surface area in comparison with CoNC-800, which results in higher activity of CoSNC-0.5Na₂SO₄-800. The CoSNC-0.5Na₂SO₄-800 material displays a half-wave potential of 0.88 V, which is superior to that of commercial Pt/C (half-wave potential being 0.86 V). Moreover, CoSNC-0.5Na₂SO₄-800 demonstrates a better durability compared with Pt/C. The pyrolysis temperature and the amount of Na₂SO₄ are found to affect the physiochemical properties and electrochemical performance of the CoSNC-xNa₂SO₄-T materials. This work not only provides a facile and novel synthesis approach for the preparation of highly active Co, S, N co-doped carbon materials for ORR, but also disclosing the key structure properties for enhancing the performance of these catalysts.     

PtCo incorporated porous carbon nanofiber as a promising oxygen reduction electrocatalyst

Designing oxygen reduction reaction (ORR) catalysts with high activity and long durability is significant for the development of proton exchange membrane fuel cells. Herein, the optimized platinum nanowires are used as templates for inducing growth of cobalt-containing metal-organic framework, deriving uniform nanofibers. After the calcination, the metal ions are transferred into the nitrogen-rich porous carbon, and wrapped by the carbon skeleton to form the PtCo bimetal incorporated nanofibers as high-performance ORR electrocatalyst. The Pt₄Co@NC-900 catalyst yields high specific activity (1.37 mA cm⁻²) in comparison to Pt/C (0.38 mA cm⁻²). The mass activity (MA) of Pt₄Co@NC-900 catalyst is approximately 3.8-fold higher than that of the commercial Pt/C under acidic conditions. After the accelerated durability tests, the Pt₄Co@NC-900 catalyst presents only 16% loss in MA, while Pt/C catalyst retains 73.0% of the initial MA. The improved ORR performance can be ascribed to the synergistic interaction between Co and Pt.     

A dual ligand coordination strategy for synthesizing drum-like Co,N co-doped porous carbon electrocatalyst towards superior oxygen reduction and zinc-air batteries

We herein propose a dual ligand coordination strategy for deriving puissant non-noble metal electrocatalysts to substitute valuable platinum (Pt)-based materials toward oxygen reduction reaction (ORR), a key reaction in metal-air batteries and fuel cells. In brief, cobalt ions are firstly double-coordinated with proportionate 2-methylimidazole (2-MeIm) and benzimidazole (BIm) to obtain drum-like zeolitic imidazolate frameworks (D-ZIFs), which are then carbonized to output the final Co, N co-doped porous carbon (Co–N–PC_D) catalyst inheriting the drum-like morphology of D-ZIFs. The Co–N–PC_D is featured by mesopores and exhibits superb electrocatalytic behavior for ORR. Impressively, the half-wave potential of Co–N–PC_D catalysts is 0.886 V with finer methanol-tolerance and stability than those of commercial Pt/C. Additionally, a zinc-air battery assembled from the Co–N–PC_D displays an open-circuit voltage of 1.413 V, comparable to that of commercial Pt/C (1.455 V), suggesting the potentials of Co–N–PC_D in practical energy conversion devices.