Oxygen Reduction Reaction In Alkaline Solution Research Articles

Engineering of the A-site deficiency in La0.4Sr0.6Co0.7Fe0.2Nb0.1O3-δ perovskites for enhanced elelctrocatalytic oxygen reduction reaction

• Series of (La 0.4 Sr 0.6 ) 1-x Co 0.7 Fe 0.2 Nb 0.1 O 3-δ (LSCFN) perovskites developed. • A-site deficiency enhances electrocatalytic activity for ORR in alkaline solutions. • LSCFN-0.90 with the highest density of vacant A-sites is a much better ORR catalyst. • Used as cathode in aluminum-air batteries. The development of efficient non-noble metal electrocatalysts for the oxygen reduction reaction (ORR) can aid the commercialization of fuel cells and metal-air batteries. Here, we developed a series of La 0.4 Sr 0.6 Co 0.7 Fe 0.2 Nb 0.1 O 3-δ (LSCFN) perovskites by engineering A-site deficiency to enhance their electrocatalytic activity for ORR in alkaline solutions. We found that LSCFN-0.90 with the highest amount of vacant A-sites has a highly oxidative oxygen species (O 2 2− /O − ) and an appropriate Co oxidation state - is a much better ORR catalyst in alkaline solutions compared to those with less vacant A-sites. The enhanced ORR kinetics enabled their use as the cathode catalyst in aluminum-air batteries, which also revealed better electrochemical performances for the catalyst with the highest A-site deficiency. Overall, the results demonstrate that an appropriate A-site cation deficiency in perovskites can enhance the ORR electrocatalytic activity.

Bifunctional Catalytic Activity of γ-NiOOH toward Oxygen Reduction and Oxygen Evolution Reactions in Alkaline Solutions

Nickel oxyhydroxides (NiOOHs) are well-known for their superior activity toward oxygen evolution reaction (OER) in alkaline solutions. However, their activity toward oxygen reduction reaction (ORR) has been largely unexplored. There exist three NiOOH polymorphs: α-, β-, and γ-NiOOH, characterized by different interlayer spacing. Although still debated, γ-NiOOH with a large layer spacing has been indicated as the active phase for OER. Here, a highly crystalline γ-NiOOH was prepared in a carbon matrix by the in situ electrochemical transformation of nickel dithiooxamide Ni(dto) in 1 M KOH solution. The catalyst prepared in this way showed low overpotential not only for OER, but also for ORR in alkaline solutions. The onset potential for ORR is ~0.81 V vs. RHE, and the reaction proceeds via the 2e− transfer pathway. The high OER catalytic activity and relatively low ORR overpotential make this nanocomposite catalyst a good candidate for bifunctional OER/ORR catalyst, stable in alkaline solutions.

MIL-88-Derived N and S Co-Doped Carbon Materials with Supplemental FeSx to Enhance the Oxygen Reduction Reaction Performance

To overcome the drawbacks of the single N-doped carbon materials, the further development of dual-heteroatoms (N and S) co-doped electrocatalysts is highly anticipated. Herein, N, S-doping and Fe-based carbon materials were synthesized by pyrolyzing a metal–organic framework (MIL-88) with the addition of N-/N, and S-containing ligands (chitosan and L-Cysteine) in the case of iron salt. The resulting electrocatalyst heat-treated at 850 °C (FeNSC-850) displays superior oxygen reduction reaction (ORR) performances to MIL-88-850, with an overall electron transfer number of 3.97 and a minor yield of HO2-% (<2.6%). In addition to the comparable activity to commercial Pt/C in catalyzing the ORR in alkaline solution, the FeNSC-850 also shows higher stability, with a slight decline in half-wave potential (∆E1/2 = 15 mV) after 5000-cycle scanning of cyclic voltammetry. In view of the multiple Fe-based active sites, the additional S doping within FeNSC-850 creates more FeSx active sites for boosting the ORR performances in alkaline solution.

Three-dimensional PdAuRu nanospines assemblies for oxygen reduction electrocatalysis

Tailoring morphology and composition of electrocatalysts has a substantial impact on catalytic properties for oxygen reduction reaction (ORR). In this work, trimetallic PdAuRu nanospine assemblies (PdAuRu NSAs) are fabricated via a simple one-step reduction route using DM-970 and KBr used as surfactant and structure directing agent, respectively. The hyperbranched structure has the characteristics of sufficient active sites, accessible transfer channels, and the excellent tolerance towards Ostwald ripening, migration and agglomeration of catalysts. Furthermore, the synergistic effect of Pd, Au and Ru atoms can alter the d-band energy of Pd, weaken the bond energy between the catalyst surface and the adsorbed species, thus changing the electronic structure and optimize the adsorption of oxygen on Pd. When explored for ORR in alkaline solution, the PdAuRu NSAs display superior catalytic activity and stability to commercial Pt/C. This synthesis tactic delivers a feasible route for the preparation of hyperbranched multi-metallic nanomaterials towards various electrocatalytic applications.

Hollow yolk-shell nanoboxes assembled by Fe-doped Mn3O4 nanosheets for high-efficiency electrocatalytic oxygen reduction in Zn-Air battery

The rational design of cost-effective and highly-performance transition metal-based electrocatalysts towards oxygen reduction reaction (ORR) is essentially desirable to realize the commercial applications of metal-air batteries and fuel cells. Herein, Fe-doped Mn3O4 hollow yolk-shell nanoboxes (Fe-Mn3O4 HYSNBs) assembled from ultrathin nanosheets with a thickness of 1.5 nm are fabricated via utilizing KMn[Fe(CN)6] prussian blue analogs as the sacrificed precursor. Choreographed construction of such hybrid hierarchical architecture and composite is responsible to generate substantially active sites and abundant channels for mass diffusion and ion transport. The resultant Fe-Mn3O4 HYSNBs exhibit outstanding electrocatalytic activity and long-term stability, as well as good tolerance to methanol towards ORR in alkaline solution. Theoretical calculation demonstrates that the highly dispersed Fe active sites implanted within ultrathin Mn3O4 nanosheets can effectively regulate electronic structure and ORR intermediates adsorption energy. Moreover, Fe-Mn3O4 HYSNBs display high power density and specific capacity as an air–cathode in Zn-Air batteries, demonstrating outstanding practicability.

Ultrafast fabrication of robust electrocatalyst having Fe/Fe3C and CuNC for enhanced oxygen reduction reaction activity

The search for ultrafast and simple methods to fabricate non-noble metal catalysts to boost electrocatalytic oxygen reduction reaction (ORR) is still ongoing. Herein, we demonstrate a one-step microwave-assisted heating method to prepare copper nitride/iron/iron carbide nanoparticle hybrids (CuNC/Fe/Fe3C/CNT). This ultrafast heating method induces plentiful carbon-wrapped metal and Fe3C nanoparticles that are attached to the surface of CNT and scattered nanosheets. The CuNC/Fe/Fe3C/CNT exhibit a half-wave potential (E1/2) of 0.886 V toward the ORR in alkaline solution, with 220 mV more positive E1/2 than that of CuNC/CNT and Fe/Fe3C/CNT respectively. The activity of as-prepared catalysts is discussed by investigating their structures and compositions and their relationship with the ORR performance. Detailed analysis results disclose that the high activity of the CuNC/Fe/Fe3C/CNT catalysts could be attributed to the interaction of CuNC and Fe/Fe3C species. To be specific, as the electron donor, Fe/Fe3C nanoparticles induce electron localization and promote the formation of Cu (δ + )–NC (0 < δ < 2), therefore leading to the improvement of the ORR performance. This work may offer an ultrafast way to construct efficient catalysts with enhanced ORR performance.

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 (Pmax) of 195 mW cm−2, which is 78% of the Pmax 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-Nx active centres.

Synthesis of N-doped Co@C/CNT materials based on ZIF-67 and their electrocatalytic performance for oxygen reduction

ZIF-67/CNT materials are prepared by using in situ growth method with cobalt nitrate and 2-methylimidazole (2-MI) as raw materials, polyvinyl pyrrolidone (PVP) as complexing agents. A series of N-Co@C/CNT catalysts are prepared through heating ZIF-67/CNT in N2 atmosphere. The effects of additional proportion of CNT on the catalytic performance of N-Co@C/CNT catalysts for oxygen reduction reaction (ORR) are studied. The chemical states of the materials, micro-morphology, elemental composition, and crystalline structure are analyzed by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), and X-ray diffraction (XRD). The results show that polyhedral ZIF-67 has grown on the surfaces of CNTs. After heat treatment, ZIF-67/CNT transforms to N-Co@C/CNT. The particle size of Co is 10–20 nm. N-Co@C/CNT-2.6 shows the best catalytic performance for ORR in alkaline solution with the onset potential of 0.94 V, half-wave-potential of 0.83 V, and limiting diffusion current density of 5.6 mA cm−2. The ORR on N-Co@C/CNT proceeds through a four-electron path and the yield of H2O2 is 12%, which is close to Pt/C. N-Co@C/CNT shows higher methanol-tolerant ability than Pt/C. The addition of CNT makes N-Co@C expose more active sites. CNT plays an important role in connecting different N-Co@C particles and enhancing the electron conductivity. The contents of graphitic nitrogen and pyridine nitrogen in N-Co@C/CNT-2.6 catalysts are 15.8% and 38.6%, respectively, which are higher than those in N-Co@C (7% and 34%).

The study of oxygen reduction reaction on Ge‐doped MoS 2 monolayer based on first principle

Rational design of electrocatalyst for air cathode with high oxygen reduction reaction (ORR) performance is highly demanded. However, current low performance of electrocatalyst remains a big challenge. Herein, the possibility of germanium (Ge)-doped molybdenum disulfide (MoS2) monolayer as a novel electrocatalyst for ORR in alkaline solution was studied based on first principle calculation. The results indicate that oxygen is strongly adsorbed on the surface of Ge-doped MoS2 monolayer. Moreover, a high barrier should be overcome during H2O molecular dissociation and the barrier of dissociation decreases with the number of doped Ge atoms increasing. Based on the calculation of transition state and Gibbs free energy, the triple Ge atoms-doped MoS2 monolayer shows the best activity toward ORR with the lowest rate-determine step barrier of 0.23 eV. Our study may provide a meaningful method for the design of novel MoS2-based electrocatalyst for ORR.

Cobalt Nanoparticles with Narrow Size Distribution Anchored to Flower-Like Carbon Microspheres for Enhanced Oxygen Reduction Catalysis

The development of efficient non-precious ORR electrocatalysts is crucial for the practical applications of fuel cells and metal-air batteries. In this work, a highly active and durable electrocatalyst for oxygen reduction reaction (ORR) was developed. Flower-like carbon microspheres coated with crystalline cobalt nanoparticles (Co@CMS) were successfully synthesized by the carbonization of Co-organic framework (Co-MOF). The Co nanoparticles, with narrow size distribution, are strongly anchored to the carbon support. Co@CMS possesses good catalytic ability for ORR in alkaline solution with a reduction peak potential ( E p, c ) of 0.75 V vs. RHE, which was comparable to Pt/C. The unique 3D porous structure of Co@CMS enhanced the electron transfer and electrolyte diffusion during the ORR. The ORR on Co@CMS is a diffusion-controlled process and follows a 4-electron-transfer mechanism.

Transition metal-containing nitrogen-doped nanocarbon catalysts derived from 5-methylresorcinol for anion exchange membrane fuel cell application

Highly active electrocatalysts for electrochemical oxygen reduction reaction (ORR) were prepared by high-temperature pyrolysis from 5-methylresorcinol, Co and/or Fe salts and dicyandiamide, which acts simultaneously as a precursor for reactive carbonitride template and a nitrogen source. The electrocatalytic activity of the catalysts for ORR in alkaline solution was studied using the rotating disc electrode (RDE) method. The bimetallic catalyst containing iron and cobalt (FeCoNC-at) showed excellent stability and remarkable ORR performance, comparable to that of commercial Pt/C (20 wt%). The superior activity was attributed to high surface metal and nitrogen contents. The FeCoNC-at catalyst was further tested in anion exchange membrane fuel cell (AEMFC) with poly-(hexamethyl-p-terphenylbenzimidazolium) (HMT-PMBI) membrane, where a high value of peak power density (Pmax = 415 mW cm−2) was achieved.

A simple microwave process for the preparation of cobalt oxide nanoparticles supported on carbon nanotubes for electrocatalytic applications

Cobalt oxide nanoparticles supported on multiwalled carbon nanotubes (CoOx/CNTs) were prepared by a facile and rapid solid-state synthesis using microwave irradiation. Thermal decomposition of a cobalt precursor under microwave irradiation leads to the formation of oxides of cobalt in the nanoparticle range (mainly 10–15 nm). X-ray diffraction reveals the existence of crystalline CoO and Co3O4. CoOx/CNTs show superior electrochemical activity towards oxygen reduction reaction (ORR) in alkaline media with a near 4-electron transfer. Initial electrochemical stability tests of the CoOx/CNTs for ORR in alkaline solution under potentiostatic conditions show ~ 88% retention in performance after continuous operation for 6 h. The results on activity and stability of CoOx/CNT catalysts demonstrate that this facile and rapid synthesis might pave the way to a quick and cheap preparation of catalysts for applications in electrochemical energy conversion.

Enhanced cathodic catalytic activity of an N-doped micropore structure obtained through the six-coordinate bond of an EDTA-Ce composite for the oxygen reduction reaction

The development of catalytic materials to increase the efficiency of the oxygen reduction reaction (ORR), which effects an important role in next generation energy storage and conversion systems, is essential but challenging. Electrocatalysts for ORR in alkaline solution, including Ce/N-doped micropore carbon materials (CNMCs), are prepared as nonprecious-metal catalysts from an ethylenediaminetetraacetic acid (EDTA) and cerium (III) nitrate hexahydrate complex. The material obtained via a simple manual synthesis method has a microporous and octahedral structure as a result of six-coordinate bonds between EDTA and Ce metals. The CNMC materials have high surface areas, which advantageous for electrochemical catalysts. Furthermore, the micropore structure positively affects the ORR by allowing three phases (solid/catalyst–liquid/electrolyte–gas/oxygen) to coexist in a wide range. Ultimately, a new cathodic catalyst based on EDTA, which has not been reported thus far, is obtained after the optimal Ce content is determined. The electrocatalytic performance of CNMCs toward the ORR is characterized using a rotating disk electrode (RDE) technique. The RDE results obtained with the CNMCs reveal an onset-potential and half-wave potential similar to those of a Pt/C catalyst. In addition, the CNMCs exhibit good long-term stability and excellent durability. Therefore, these materials may be alternative cathode electrocatalysts in commercial use.

Fabricating carbon nanocages as ORR catalysts in alkaline electrolyte from F127 self-assemble core-shell micelle

In order to reduce the cost of oxygen reduction reaction (ORR) catalyst in fuel cell, polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) three-block copolymer (F127) and Zn(OH)2 were used as carbon resource and morphology retaining agent to prepare porous nanocages for ORR catalyst in alkaline solution. Its composition and microstructure were characterized by X-ray diffraction Raman spectroscopy (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer–Emmett–Teller (BET) method. Electrochemical properties were evaluated in O2 saturated alkaline solution. Results showed the sample obtained at 700 °C (C-700) was composed of porous carbon nanocages with diameter of 50 nm and shell thickness of 4 nm. C-700 had the maximum surface area (1011 m2 g−1) and the best ORR catalytic performance. The main reason is that polypropylene oxide (PPO) group at the lipophilic end begins to decompose at 500 °C, and the polyethylene oxide (PEO) group at the lipophilic end at 700 °C decomposes completely. In O2 saturated 0.1 M KOH solution, C-700's oneset potential, limit current density and half-wave potential, which were 0.89 V, 5.59 mA/cm2@0.45 V and 0.71 V, respectively, were close to that of commercial 20% Pt/C catalyst. It was noted that the oneset potential and half-wave potential of C-700 had barely change, and limit current density attenuated about 87.8% after 2000 CV cycle. The obtained catalyst behaved good catalytic activity and stability for ORR in alkaline solution and a potential application prospect in fuel cells.

Co3+ -Rich Na1.95 CoP2 O7 Phosphates as Efficient Bifunctional Catalysts for Oxygen Evolution and Reduction Reactions in Alkaline Solution.

Implementing sustainable energy conversion and storage technologies is highly reliant on crucial oxygen electrocatalysis, such as the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, the pursuit of low cost, energetic efficient and robust bifunctional catalysts for OER and ORR remains a great challenge. Herein, the novel Na-ion-deficient Na2-x CoP2 O7 catalysts are proposed to efficiently electrocatalyze OER and ORR in alkaline solution. The engineering of Na-ion deficiency can tune the electronic structure of Co, and thus tailor the intrinsically electrocatalytic performance. Among the sodium cobalt phosphate catalysts, the Na1.95 CoP2 O7 (NCPO5) catalyst exhibits the lowest ΔE (EJ10,OER -EJ-1,ORR ) of only 0.86 V, which favorably outperforms most of the reported non-noble metal catalysts. Moreover, the Na-ion deficiency can stabilize the phase structure and morphology of NCPO5 during the OER and ORR processes. This study highlights the Na-ion deficient Na2-x CoP2 O7 as a promising class of low-cost, highly active and robust bifunctional catalysts for OER and ORR.

Polyacrylamide Microspheres-Derived Fe3C@N-doped Carbon Nanospheres as Efficient Catalyst for Oxygen Reduction Reaction.

High-performance non-precious metal catalysts exhibit high electrocatalytic activity for the oxygen-reduction reaction (ORR), which is indispensable for facilitating the development of multifarious renewable energy systems. In this work; N-doped carbon-encapsulated Fe3C nanosphere ORR catalysts were prepared through simple carbonization of iron precursors loaded with polyacrylamide microspheres. The effect of iron precursors loading on the electrocatalytic activity for ORR was investigated in detail. The electrochemical measurements revealed that the N-doped carbon-encapsulated Fe3C nanospheres exhibited outstanding electrocatalytic activity for ORR in alkaline solutions. The optimized catalyst possessed more positive onset potential (0.94 V vs. reversible hydrogen electrode (RHE)), higher diffusion limiting current (5.78 mA cm−2), better selectivity (the transferred electron number n > 3.98 at 0.19 V vs. RHE) and higher durability towards ORR than a commercial Pt/C catalyst. The efficient electrocatalytic performance towards ORR can be attributed to the synergistic effect between N-doped carbon and Fe3C as catalytic active sites; and the excellent stability results from the core-shell structure of the catalysts.

Well-Defined Boron/Nitrogen-Doped Polycyclic Aromatic Hydrocarbons Are Active Electrocatalysts for the Oxygen Reduction Reaction

Top-down synthesized B- and B,N-doped carbons (e.g., graphenes) have been previously reported as catalysts for the oxygen reduction reaction (ORR), with activity superior to Pt electrocatalysts also previously reported in some cases. Such doped carbon materials are, however, chemically complex and contain multiple sites, which complicate the development of structure–activity relationships and subsequent catalyst optimization. Herein, a number of well-defined B- and B,N-doped polycyclic aromatic hydrocarbons (PAHs), prepared by a “bottom-up” approach, are shown to be active catalysts for the ORR in alkaline solution when deposited on carbon electrodes in contrast to the all carbon-based PAH perylene. Six dissimilar B-doped PAHs have been tested on three working electrodes, and the merits of each electrode for assessing ORR catalytic activity have been determined. A boron-doped diamond electrode was found to have the lowest background activity (relative to glassy carbon and highly ordered pyrolytic graphite ) and thus proved optimal for determining the ORR catalytic activity of the PAHs. Of the six B-doped PAHs studied, two PAHs with the highest lowest unoccupied molecular orbital (LUMO) energy were found to be inactive, whereas the other PAHs with lower LUMO energies were found to be active catalysts for the ORR. Doping of two heteroatoms, doubly B-doped and a B,N-codoped PAH containing separate (nonbonded) B and N atoms, was found to lead to the most active ORR catalysts from this set. This suggests that two proximal (separated only by one or two carbons) electrophilic sites improve the ORR activity of doped PAHs. This is the first study, to the best of our knowledge, which uses well-defined doped PAHs as models to identify potential ORR electrocatalytic moieties present in doped carbons; this approach thus enables definitive structure–activity relationships to be developed in this important area.

Restructured Fe−Mn Alloys Encapsulated by N‐doped Carbon Nanotube Catalysts Derived from Bimetallic MOF for Enhanced Oxygen Reduction Reaction

AbstractA set of novel catalysts FeMn/N‐CNTs that partly maintain the core‐shell structure have been prepared successfully by calcination of analogous MOF‐74, which has bimetallic species (Fe and Mn) and a cheap organic ligand (2, 5‐dihydroxylbenzoic acid, DHBA) with melamine as additional nitrogen source. These catalysts exhibit a distinctive microstructure of Fe−Mn alloys surrounded by N‐doped carbon nanotubes (CNTs). Electrochemical methods have been employed to investigate their activity in oxygen reduction reaction (ORR) in alkaline solution. The highest ORR performance of Fe3Mn1/N‐CNTs‐100 shows that the half wave potential is at 0.865 V and the kinetic current density (at 0.9 V) is 1.447 mA cm−2, which are higher than those of commercial Pt/C (0.855 V, 0.946 mA cm−2). In addition, Fe3Mn1/N‐CNTs‐100 is much more durable than commercial Pt/C under the conditions tested. The highly efficient ORR performance may be attributed to the unique microstructure and large surface area with appropriate pore size, as well as to the synergistic effects between the pyridinic N species and the Fe−Nx species that play important roles in ORR in alkaline solution. However, in acid medium, only Fe−Nx species catalyze ORR and pyridinic N species are limited to work as the active sites. This study may prompt others to explore the development of heteroatom‐doped CNTs surrounding particles as efficient catalyst for ORR and fuel cell applications.

A biomass derived nitrogen doped carbon fibers as efficient catalysts for the oxygen reduction reaction

Nitrogen doped carbon nanomaterials are excellent electrode materials and catalysts due to their extraordinary conductivity, prolific structures, and abundant active sites. Herein, two kinds of waste biomass, catkins and Okara were used as precursors for the preparation of novel nitrogen doped carbon fibers via hydrothermal and pyrolysis process. The blend of nitrogen-rich Okara with catkins effectively enhanced the content of doped nitrogen in the product. The as-prepared sample (denoted as NCF900) exhibited a hollow fiber like structure with a diameter of 2 to 5 μm and had abundant highly active sites of pyridinic N and graphitic N, thereby improving its electrocatalytic activity in oxygen reduction reaction (ORR). The typical rotating disk electrode test proved that the NCF900 exhibited a high onset potential (0.82 V vs RHE) and a nearly four-electron pathway for ORR in alkaline solution as well as stronger methanol tolerance and better long-term durability than commercial Pt/C. The green, low cost synthetic method and the excellent ORR catalytic efficiency of NCF900 made it a promising electrocatalytic material for the ORR in fuel cells.

Spherical α-MnO₂ Supported on N-KB as Efficient Electrocatalyst for Oxygen Reduction in Al-Air Battery.

Traditional noble metal platinum (Pt) is regarded as a bifunctional oxygen catalyst due to its highly catalytic efficiency, but its commercial availability and application is often restricted by high cost. Herein, a cheap and effective catalyst mixed with α-MnO2 and nitrogen-doped Ketjenblack (N-KB) (denoted as MnO2-SM150-0.5) is examined as a potential electrocatalyst in oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). This α-MnO2 is prepared by redox reaction between K2S2O8 and MnSO4 in acid conditions with a facile hydrothermal process (named the SM method). As a result, MnO2-SM150-0.5 exhibits a good catalytic performance for ORR in alkaline solution, and this result is comparable to a Pt/C catalyst. Moreover, this catalyst also shows superior durability and methanol tolerance compared with a Pt/C catalyst. It also displays a discharge voltage (~1.28 V) at a discharge density of 50 mA cm−2 in homemade Al–air batteries that is higher than commercial 20% Pt/C (~1.19 V). The superior electrocatalytic performance of MnO2-SM150-0.5 could be attributed to its higher Mn3+/Mn4+ ratio and the synergistic effect between MnO2 and the nitrogen-doped KB. This study provides a novel strategy for the preparation of an MnO2-based composite electrocatalyst.