Bifunctional Electrocatalysts Research Articles

Phosphorus Defect Mediated Electron Redistribution to Boost Anion Exchange Membrane‐Based Alkaline Seawater Electrolysis

AbstractIt is of essential importance to design bifunctional electrocatalysts with excellent performance for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in seawater splitting. Herein, an approach for manipulating electron redistribution in NiCoP treated by P defect (Pv) engineering (NiCoPv@NF) is presented, exhibiting excellent catalytic activities and stability toward HER/OER in alkaline seawater solution. The Pv reduces the surface electrooxidation reconfiguration energy barrier, making it easier to drive the local conversion of crystals to active oxy(hydroxide) in OER. In addition, the Ni site of NiCoPv and the Co site of NiCoOOH are the active sites for HER and OER processes, respectively. In situ generated PO43− adsorbed on the catalyst surface causes spatial repulsion, preventing Cl− corrosion in seawater electrolysis. The seawater AEM electrolyzer using NiCoPv@NF couple achieves excellent performance of high activity (2.43 V at 500 mA cm−2) and long‐term durability (500 mA cm−2 over 110 h). The working efficiency of AEM in 1.0 M KOH is as high as 77.0% at 100 mA cm−2 with the price of per GGE H2 as low as $ 0.87.

Construction of structurally engineered NiCo2O4 nanostructures as a bifunctional electrocatalyst for high-performance overall water splitting

The development of low-cost and highly efficient bifunctional electrocatalysts for overall water splitting is a challenging but urgent goal. Herein, nickel cobaltite (NiCo2O4) with different morphologies was developed for electrocatalytic overall water splitting. Encouragingly, the NiCo2O4 nanoneedle arrays required competitive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials of 106 and 310 mV to achieve a density of 10 mA cm−2 (j10) in KOH media, respectively. Furthermore, the as-made nanoneedle electrocatalyst employed as both anode and cathode, which displayed a low voltage of 1.67 Vto attain j10, with satisfactory durability for 50 h. The nanoneedle morphology not only improves the electrochemical active surface area, but also helpful to boost the charge transfer ability of NiCo2O4 and control the adsorption of reaction intermediates in water splitting. These results demonstrate the feasibility of the NiCo2O4 nanostructure by altering the active sites using morphology to develop the electrocatalytic activity of the materials.

Stimulus of Work Function on Electron Transfer Process of Intermetallic Nickel-Antimonide Toward Bifunctional Electrocatalyst for Overall Water Splitting.

Engineering the intermetallic nanostructures as an effective bifunctional electrocatalyst for hydrogen and oxygen evolution reactions (HER and OER) is of great interest in green hydrogen production. However, a few non-noble metals act as bifunctional electrocatalysts, exhibiting terrific HER and OER processes reported to date. Herein the intermetallic nickel-antimonide (Ni─Sb) dendritic nanostructure via cost-effective electro-co-deposition method is designed and their bifunctional electrocatalytic property toward HER and OER is unrevealed. The designed Ni─Sb delivers a superior bifunctional activity in 1mKOH electrolyte, with a shallow overpotential of ≈119mV at -10mA for HER and ≈200mV at 50mA for OER. The mechanism behind the excellent bifunctional property of Ni─Sb is discussed via "interfacial descriptor" with the aid of Kelvin probe force microscopy (KPFM). This study reveals the rate of electrocatalytic reaction depends on the energy required for electron and proton transfer from the catalyst's surface. It is noteworthy that the assembled Ni─Sb-90 electrolyzer requires only a minuscule cell voltage of ≈1.46V for water splitting, which is far superior to the art of commercial catalysts.

Exploring Flower-Structured Bifunctional VCu Layered Double Hydroxide and its Nanohybrid with g-C3N4for Electrochemical and Photoelectrochemical Seawater Electrolysis.

Seawater electrolysis holds great promise for sustainable green hydrogen generation, but its implementation is hindered by high energy consumption and electrode degradation. Two dimensional (2D) layered double hydroxide (LDH) exhibits remarkable stability, high catalytic activity, and excellent corrosion resistance in the harsh electrolytic environment. The synergistic effect between LDH and seawater ions enhances the oxygen evolution reaction, enabling efficient and sustainable green hydrogen generation. Here, we report a synthesis of low cost, novel 2D Vanadium Copper (VCu) LDH first time in the series of LDH's as a highly efficient bifunctional electrocatalyst. The electrochemical (EC) and photoelectrochemical (PEC) study of VCu LDH and VCu LDH/Graphite Carbon Nitride (g-C3N4) nanohybrid was performed in 0.5 M H2SO4 (acidic), 1 M KOH (basic), 0.5 M NaCl (artificial seawater), 0.5 M NaCl + 1 M KOH (artificial alkaline seawater), real seawater and 1 M KOH + real seawater (alkaline real seawater) electrolyte medium. It was found that VCu LDH shows a remarkable lower overpotential of 72 mV hydrogen evolution reaction (HER) and 254 mV oxygen evolution reaction (OER) at current density of 10 mA/cm2 under alkaline real seawater electrolysis exhibiting bifunctional activity and also showing better stability.

Lattice-matched spinel/layered double hydroxide 2D/2D heterojunction towards large-current-density overall water splitting

It is fascinating and challenging to construct earth-abundant first-row transition metal-based bifunctional electrocatalysts for large-scale hydrogen production via water electrolysis. Here we report a progressive conversion from spinel nanosheets to layered double hydroxide (LDH) nanosheets through the preferential dissolution of alternated layers in spinel. This process enables the formation of a lattice-matched and chemically bonded edge-to-edge spinel/LDH 2D/2D heterojunction. Significant charge redistribution at the 2D/2D heterointerface accelerates water dissociation kinetics and optimize adsorption energy of hydrogen- and oxygen-containing intermediates. The synthesized CoFe2O4/CoFe-LDH 2D/2D heterojunction demonstrates exceptional performance in the hydrogen evolution reaction, achieving an overpotential of 337 mV at a high current density of 1000 mA cm−2, surpassing previously reported non-noble metal-based spinels and LDHs. Furthermore, its oxygen evolution reaction performance is comparable to that of typical spinel and LDH catalysts. The in-depth insights can guide rational interfacial engineering of heterogeneous catalysts for energy and environmental applications.

Shifting the Oxygen-Evolution Reaction Pathway via Cation Engineering to Activate Lattice Oxygen in Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) as promising electrocatalysts have been widely studied, but their performance is limited by conductivity and coordinating saturation. This study proposes a cationic (V) modification strategy and evaluates its effect on the electrocatalytic performance of CoFe-MOF nanosheet arrays. The optimal V-CoFe-MOF/NF electrocatalyst exhibits excellent oxygen-evolution reaction (OER)/hydrogen-evolution reaction (HER) performance (231 mV at 100 mA cm-2/86 mV at 10 mA cm-2) in alkaline conditions, with its OER durability exceeding 400 h without evident degradation. Furthermore, as a bifunctional electrocatalyst for water splitting, a small cell voltage is achieved (1.60 V at 10 mA cm-2). The practicability of the catalyst is further evaluated by membrane electrode assembly (MEA), showing outstanding activity (1.53 V at 10 mA cm-2) and long-term stability (at 300 mA cm-2). Moreover, our results reveal the apparent reconstruction properties of V-CoFe-MOF/NF in alkaline electrolytes, where the partially dissolved V promotes the formation of more active β-MOOH. The mechanism study shows the OER mechanism shifts to a lattice oxygen oxidation mechanism (LOM) after V doping, which directly avoids complex multistep adsorption mechanism and reduces reaction energy. This study provides a cation mediated strategy for designing efficient electrocatalysts.

Heterointerface-Rich Ni3N/WO3 Hierarchical Nanoarrays for Efficient Glycerol Oxidation-Assisted Alkaline Hydrogen Evolution.

Glycerol oxidation-assisted water electrolysis has emerged as a cost-effective way of co-producing green hydrogen and HCOOH. Still, preparing highly selective and stable nickel-based metal electrocatalysts remains a challenge. Herein, heterostructure Ni3N/WO3 nanosheet arrays of bifunctional catalysts with large specific surface areas loaded on nickel foam (denoted as Ni3N/WO3/NF) were synthesized. This catalyst was for glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER) with excellent catalytic performance, a voltage saving of 267 mV compared to oxygen evolution reaction (OER), and a HER overpotential of 104 mV at 100 mA cm-2. The cell voltage in the assembled GOR//HER hybrid electrolysis system reaches 100 mA cm-2 at 1.50 V, 296 mV lower than the potential required for overall water splitting. This work demonstrates that replacing GOR with OER using a cost-effective and highly active Ni-based bifunctional electrocatalyst can make hybrid water electrolysis an energy-efficient, sustainable, and green strategy for hydrogen production.

Ruthenium Nanoclusters and Single Atoms on α-MoC/N-Doped Carbon Achieves Low-input/Input-free Hydrogen Evolution via Decoupled/Coupled Hydrazine Oxidation.

The hydrazine oxidation-assisted H2 evolution method promises low-input and input-free hydrogen production. However, developing high-performance catalysts for hydrazine oxidation (HzOR) and hydrogen evolution (HER) is challenging. Here, we introduce a bifunctional electrocatalyst α-MoC/N-C/RuNSA, merging ruthenium (Ru) nanoclusters (NCs) and single atoms (SA) into cubic α-MoC nanoparticles-decorated N-doped carbon (α-MoC/N-C) nanowires, through electrodeposition. The composite showcases exceptional activity for both HzOR and HER, requiring -80 mV and -9 mV respectively to reach 10 mA cm-2. Theoretical and experimental insights confirm the importance of two Ru species for bifunctionality: NCs enhance the conductivity, and its coexistence with SA balances the H adsorption for HER and facilitates the initial dehydrogenation during the HzOR. In the overall hydrazine splitting (OHzS) system, α-MoC/N-C/RuNSA excels as both anode and cathode materials, achieving 10 mA cm-2 at just 64 mV. The zinc hydrazine (Zn-Hz) battery assembled with α-MoC/N-C/RuNSA cathode and Zn foil anode can exhibit 96% energy efficiency, as well as temporary separation of hydrogen gas during the discharge process. Therefore, integrating Zn-Hz with OHzS system enables self-powered H2 evolution, even in hydrazine sewage. Overall, the amalgamation of NCs with SA achieves diverse catalytic activities for yielding multifold hydrogen gas through advanced cell-integrated-electrolyzer system.

Synergistic Ru/RuO2 heterojunctions stabilized by carbon coating as efficient and stable bifunctional electrocatalysts for acidic overall water splitting

Synergistic Ru/RuO2 heterojunctions stabilized by carbon coating as efficient and stable bifunctional electrocatalysts for acidic overall water splitting

Ruthenium Nanoclusters and Single Atoms on α‐MoC/N‐Doped Carbon Achieves Low‐input/Input‐free Hydrogen Evolution via Decoupled/Coupled Hydrazine Oxidation

The hydrazine oxidation‐assisted H2 evolution method promises low‐input and input‐free hydrogen production. However, developing high‐performance catalysts for hydrazine oxidation (HzOR) and hydrogen evolution (HER) is challenging. Here, we introduce a bifunctional electrocatalyst α‐MoC/N‐C/RuNSA, merging ruthenium (Ru) nanoclusters (NCs) and single atoms (SA) into cubic α‐MoC nanoparticles‐decorated N‐doped carbon (α‐MoC/N‐C) nanowires, through electrodeposition. The composite showcases exceptional activity for both HzOR and HER, requiring ‐80 mV and ‐9 mV respectively to reach 10 mA cm‐2. Theoretical and experimental insights confirm the importance of two Ru species for bifunctionality: NCs enhance the conductivity, and its coexistence with SA balances the H adsorption for HER and facilitates the initial dehydrogenation during the HzOR. In the overall hydrazine splitting (OHzS) system, α‐MoC/N‐C/RuNSA excels as both anode and cathode materials, achieving 10 mA cm‐2 at just 64 mV. The zinc hydrazine (Zn‐Hz) battery assembled with α‐MoC/N‐C/RuNSA cathode and Zn foil anode can exhibit 96% energy efficiency, as well as temporary separation of hydrogen gas during the discharge process. Therefore, integrating Zn‐Hz with OHzS system enables self‐powered H2 evolution, even in hydrazine sewage. Overall, the amalgamation of NCs with SA achieves diverse catalytic activities for yielding multifold hydrogen gas through advanced cell‐integrated‐electrolyzer system.

Fe-Doped Ni/Co-Based Selenide Hierarchical Nanosheet Arrays as Self-Supporting Bifunctional Electrocatalysts for Overall Water Splitting

Fe-Doped Ni/Co-Based Selenide Hierarchical Nanosheet Arrays as Self-Supporting Bifunctional Electrocatalysts for Overall Water Splitting

Machine Learning-Assisted Study of RENxC6-x-Doped Graphene as Potential Electrocatalysts for Oxygen Electrode Reactions.

In the application of renewable energy, the oxidation-reduction reaction (ORR) and oxygen evolution reaction (OER) are two crucial reactions. Single-atom catalysts (SACs) based on metal-doped graphene have been widely employed due to their high activity and high atom utilization efficiency. However, the catalytic activity is significantly influenced by different metals and local coordination, making it challenging to efficiently screen through either experimental or density functional theory (DFT) calculations. To address this issue, this study employed a combination of DFT calculations and machine learning (DFT-ML) to investigate rare earth-modified carbon-based (RENxC6-x) electrocatalysts. Based on computational data from 75 catalysts, we trained two ML models to capture the underlying patterns of physical properties and overpotential. Subsequently, the candidate catalysts were screened, leading to the discovery of four ORR catalysts, nine OER catalysts, and five bifunctional electrocatalysts, all of which were thoroughly validated for their stability. Lastly, by integrating the ML models with the SHAP analysis framework, we revealed the influence of atomic radius, Pauling electronegativity, and other features on the catalytic activity. Additionally, we analyzed the physicochemical properties of potential catalysts through DFT calculations. The revolutionary DFT-ML approach provides a crucial driving force for the design and synthesis of potential catalysts in subsequent studies.

Unique ping-pong daisy-like catalysts: Efficient overall hydrolysis catalysis driven by vanadium-doped Fe2P and Co3(PO4)2 nanosheet composites

Balancing catalytic activity and durability remains a challenge in the development of high performance, inexpensive and durable electrocatalysts. In this study, fully hydrolyzed composite catalyst V–Fe2P@Co3(PO4)2/NF with ping-pong daisy-like morphology was synthesized using conventional hydrothermal and chemical vapor deposition (CVD) processes. In alkaline electrolyte, V–Fe2P@Co3(PO4)2/NF showed excellent electrochemical performance, achieving a current density of 10 mA cm−2 when the driving overpotentials for the hydrogen production reaction (HER) and oxidation reaction (OER) were 56 mV and 178 mV, respectively. Meanwhile, V–Fe2P@Co3(PO4)2/NF demonstrated good durability in terms of both HER and OER stability. Furthermore, the driving voltage required for the electrolyser assembled with V–Fe2P@Co3(PO4)2/NF as the electrode is lower than that of the RuO2/NF||Pt/C/NF electrode, both of which have driving voltages of 1.503 and 1.562 V (10 mA cm−2), respectively. Meanwhile, it achieves a Faraday efficiency of 95%. This study offers a feasible solution towards synthesizing and applying bifunctional water decomposition electrocatalysts.

Dopant induced hollow Ni2P nanocrystals regulate dehydrogenation kinetics for highly efficient solar-driven hydrazine assisted H2 production

Replacing kinetically sluggish oxygen evolution reaction (OER) with a thermodynamically favorable hydrazine oxidation reaction (HzOR) to produce hydrogen has emerged as a more energy-efficient alternative than water splitting. However, the lack of promising bifunctional electrocatalysts hinders its scalable applications. Here, we report a colloidal synthesis of Mn-dopant induced hollow Ni2P nanocrystals (NCs) using a heat-up approach, which act as superior bifunctional electrocatalysts for both HzOR (55 mV at 10 mA/cm2) and hydrogen evolution reaction (HER, 192 mV at 50 mA/cm2). The two-electrode electrolyzer requires a low cell voltage of 59 mV to achieve 10 mA/cm2 and a current density of ∼ 50.4 mA/cm2 to reach 0.5 V. Theoretical studies unraveled that Mn-doping regulates the electronic structure of Ni2P and optimizes the H* adsorption/desorption and dehydrogenation kinetics. When integrated with a Si photovoltaic device, the bifunctional hollow Mn-doped Ni2P NCs enabled solar-driven hydrazine assisted H2 production with a ∼ 14.6 % efficiency.

Boosting electrocatalytic hydrogen generation from water splitting with heterostructured MoS2/NiFe2O4 composite in alkaline media

Design and synthesis of earth-abundant and robust bifunctional electrocatalysts have been greatly sought for commercialization of the technology for clean and renewable energy and replacement of the energy equipment based on fossil fuels. In this work, a facile hydrothermal approach is used to synthesize MoS2/NiFe2O4-based nanocomposite as a novel electrocatalyst for alkaline water splitting. Surface analysis was conducted using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Benefiting from the synergy of lamellar MoS2 and crystalline NiFe2O4, the obtained MoS2/NiFe2O4 composite shows excellent hydrogen evolution reaction (η10 = 190 mV, η50 = 279 mV) and oxygen evolution reaction (OER) (η50 = 350 mV, η100 = 360 mV) activity with high TOF (0.01 s−1@190 mV for HER and 0.24 s−1 @360 mV for OER) and displays good electrochemical stability. Explicitly, the electrocatalyst requires a cell voltage of 1.69 V to drive overall water splitting at a current density of 10 mA cm−2. Density functional theory (DFT) results demonstrated that the MoS2/NiFe2O4 composite electrocatalyst has smaller hydrogen adsorption free energy (|ΔGH*|) than pristine MoS2 and NiFe2O4, which demonstrates the effective adsorption and cleavage of water on the catalyst surface. This work thus presents an approach for the synthesis and rational design of metal oxide/metal sulfide hybrids as an electrocatalyst with high performance for overall water splitting.

Heterogeneous Ni-Boride/Phosphide Anchored Amorphous B-C Layer for Overall Water Electrocatalysis.

The rational design of efficient and economical bifunctional electrocatalysts remained a challenge for overall water electrolysis. In this work, the Ni-boride/ phosphide particles anchored amorphous B-doped carbon layer with hierarchical porous characteristics in Ni foam (Ni3P/Ni3B/B-C/NF) was fabricated for overall water splitting. The Boroncarbide (B4C) power was filled and fixed in the NF interspace through the electroplating and electroless plating, and then annealed in vacuum high temperature. The amorphous B-C layer derived from the B4 C not only speeded up the electron transport, but also cooperate with Ni-boride/phosphide to enhance the electrocatalytic activity for HER and OER synergistically. Furthermore, the hierarchical porous architecture of Ni3P/Ni3B/B-C/NF increased space utilization to load more active materials. The self-supported Ni3P/Ni3B/B-C/NF electrode possessed a low overpotential of 212 and 280 mV to deliver 100 mA cm-2 for HER and OER, respectively, and high stability for 48 h. In particular, the electrolyzer constituted with the Ni3P/Ni3B/B-C/NF bifunctional electrocatalyst only required a voltage of 1.59 V at 50 mA cm-2 for water electrocatalysis under alkaline medium, and demonstrated long-term stability for 48 h. This study provides a new technical path for the development of bifunctional of transition metal borides to promote the application of hydrogen production from water splitting.

Electron Manipulation and Surface Reconstruction of Bimetallic Iron-Nickel Phosphide Nanotubes for Enhanced Alkaline Water Electrolysis.

Developing high-efficiency and stable bifunctional electrocatalysts for water splitting remains a great challenge. Herein, NiMoO4 nanowires as sacrificial templates to synthesize Mo-doped NiFe Prussian blue analogs are employed, which can be easily phosphorized to Mo-doped Fe2xNi2(1-x)P nanotubes (Mo-FeNiP NTs). This synthesis method enables the controlled etching of NiMoO4 nanowires that results in a unique hollow nanotube architecture. As a bifunctional catalyst, the Mo-FeNiP NTs present lower overpotential and Tafel slope of 151.3 (232.6) mV at 100 mA cm-2 and 76.2 (64.7) mV dec-1 for HER (OER), respectively. Additionally, it only requires an ultralow cell voltage of 1.47 V to achieve 10 mA cm-2 for overall water splitting and can steadily operate for 200 h at 100 mA cm-2. First-principles calculations demonstrate that Mo doping can effectively adjust the electron redistribution of the Ni hollow sites to optimize the hydrogen adsorption-free energy for HER. Besides, in situ Raman characterization reveals the dissolving of doped Mo can promote a rapid surface reconstruction on Mo-FeNiP NTs to dynamically stable (Fe)Ni-oxyhydroxide layers, serving as the actual active species for OER. The work proposes a rational approach addressed by electron manipulation and surface reconstruction of bimetallic phosphides to regulate both the HER and OER activity.

Nickel-hydroxide decorated trimanganese-tetroxide nanorods supported on graphene as bifunctional electrocatalyst for metal–air batteries

Manganese oxide, such as Mn3O4, is one of promising material as electrocatalyst in air–cathode for metal–air battery due to low cost, high catalytic activity and good stability. Although pure Mn3O4 material exhibits excellent catalytic activity to ORR, it is severely limited by its intrinsically low conductivity and high over-potential toward OER. In this work, the hybrid materials of nickel-hydroxide-decorated nanorods of trimanganese-tetroxide supported on reduced-graphene have been prepared by one-step hydrothermal method. The composite materials are used as bifunctional cathode catalysts to ORR/OER, and investigated by the technologies of rotating disk electrode and metal–air batteries. The results indicate that the hybrid material of Mn-Ni/rGO use as catalyst in air–cathode for Al/Zn–air battery has good catalytic activity. Based on analysis of scanning electron microscope and X-ray photoelectron spectroscopy, the composite material shows good performance owing to the improvement of conductivity supported on graphene, more Mn4+ on the surface of hybrid material, the coexistence of Mn3+/Mn4+ redox couple, and the synergism between nickel-hydroxide and graphene.

In situ electrodeposited Zn-doped CoNiS as an efficient and stable electrocatalyst for overall water splitting in neutral media

Zinc-doped cobalt nickel sulfides coupled with polypyrrole hollow nanospheres grown on carbon paper (Zn-CoNiS/PHS/CP) were developed by unipolar pulse electrodeposition (UPED) method as efficient and stable electrocatalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and overall water splitting in neutral media for the first time. With abundant active sites intrigued by moderate Zn doping, the optimized Zn10-CoNiS delivers improved catalytic performance with small overpotentials of 213 mV and 414 mV to achieve the current densities of 10 mA cm−2 for HER and OER respectively, and outstanding long-term stability. The water electrolyzer device with Zn10-CoNiS as both anode and cathode delivers a current density of 10 mA cm−2 at a cell voltage of 1.896 V in neutral media. The low charge transfer resistance of Zn-CoNiS and confinement effect of 2D Ni9S8/Co9S8 nanosheets on 0D ZnS nanodots endow the bifunctional electrocatalysts with efficient activity and high stability, providing a competitive candidate for green hydrogen production.

Multifunctional carbon armor: Synchronously improving oxygen reaction kinetics, mass transfer dynamics, and robustness of transition metal alloy based hybrid catalyst

Construction of robust protective cover on delicate active sites is a frequently-used scheme to enhance the durability of air-cathode catalyst working in harsh environment, thus the lifespan of rechargeable Zinc-air batteries (ZABs). Paradoxically, this would degrade the activity due to the constricted accessibility of active sites to reactants. Herein, carbon nanotubes with abundant mesoporous defects and Fe-N4 species were elaborately designed to be multifunctional protective armor to encapsulate Ni3Fe nano-alloys (Ni3Fe@CNTs/Fe-N4) for bifunctional oxygen electrocatalyst. In/ex-situ spectroscopy analysis and theoretical calculations reveal that the constructed mesoporous carbon defects effectively facilitate the multiphase mass transfer and the oxygen evolution reaction kinetics via strong electrons coupling with packaged Ni3Fe nano-alloys. Meanwhile, the synchronously introduced Fe-N4 moieties could serve as oxygen reduction active sites. Thus, the obtained Ni3Fe@CNTs/Fe-N4 hybrid electrocatalyst simultaneously exhibits remarkable bifunctional catalytic activity (E1/2=0.86/Ej=10=1.59 V vs RHE) and durability over 450 h in the chronoamperometric test at 1.59 V, endowing the assembled Zn-air batteries (ZABs) with a high power density (150 mW cm−2) and lifespan (307 h), much better than that employing benchmark Pt/C+RuO2 mixed catalyst. This work demonstrates an innovative design route for the multifunctional armor to concurrently enhance the durability, activity and robustness of air-cathode-catalyst for ZABs.