Electrocatalysts For Oxygen Reduction Reaction Research Articles

Multiscale Regulation of Ordered PtCu Intermetallic Electrocatalyst for Highly Durable Oxygen Reduction Reaction.

Transforming the Pt-M alloy into an ordered intermetallic is an effective strategy to improve the electrocatalytic activity and stability toward the oxygen reduction reaction (ORR). However, the synthesis of nanosized intermetallics remains challenging. Herein, we report an efficient ORR electrocatalyst, consisting of a monodisperse nanosized PtCu intermetallic on hollow mesoporous carbon spheres (HMCS). As predicted by theoretical calculations, PtCu intermetallics exhibit beneficial electronic structure, with a low theoretical overpotential of 0.33 V and enhanced Cu stability. Resulting from the multiscale modulation of catalyst structure, the O-PtCu/HMCS catalyst delivers a high mass activity of 2.73 A cm-2Pt at 0.9 V and remarkable stability. Identical location transmission electron microscopy (IL-TEM) investigations demonstrate that the rate of carbon corrosion is alleviated on HMCS, which contributes to the long-term durability. This work provides a promising design strategy for an ORR electrocatalyst, and the IL-TEM investigations offer new perspectives for the performance enhancement mechanism.

Boron and Fluorine Co‐Doped Graphene/Few‐Walled Carbon Nanotube Composite as Highly Active Electrocatalyst for Oxygen Reduction Reaction

Functionalization of nanocarbon materials with heteroatoms is of paramount interest as doping of carbon with electron withdrawing groups results in change of electrochemical properties of the potential catalyst. Adding fluorine, as the most electronegative element into the doping process next to boron is expected to have significant effect on the design of novel nanocarbon‐based electrocatalysts. In this paper boron and fluorine co‐doped reduced graphene oxide/few‐walled carbon nanotube (BF‐rGO/FWCNT) catalyst are synthesized via simple and low‐cost direct pyrolysis method using boron trifluoride diethyl etherate (BTDE). Composition analysis confirmed that boron and fluorine have been grafted onto the carbon support. Rotating disk electrode (RDE) measurements revealed that BF‐rGO/FWCNT has remarkable electrocatalytic activity toward the oxygen reduction reaction (ORR) both in alkaline and acid media. The onset potential of the best BF‐rGO/FWCNT catalyst was 50 mV more positive in alkaline and 600 mV more positive in acidic media compared with un‐doped rGO/FWCNT. The half‐wave potential was 100 mV more positive in alkaline media and 700 mV more positive in acidic media in comparison with un‐doped rGO/FWCNT.

A facile synthesis of iron single-atom electrocatalyst for high-performing oxygen reduction reaction and remarkable rechargeable zinc-air battery

Iron-based single-atom catalysts (SACs) are considered to the most promising catalysts to replace Pt for efficient oxygen reduction reaction (ORR). However, the precise synthesis of high-performance SACs and the understanding of their ORR origin remain challenging. In this work, microporous nitrogen-doped carbon with abundant and accessible atomically dispersed N-coordinated Fe sites (Fe-N-C) is prepared by molecular-confined coupling pyrolysis strategy. The Fe-N-C exhibits excellent ORR activities in acid (E1/2 of 0.78 V vs. RHE) and alkaline (E1/2 of 0.91 V vs. RHE) electrolytes. When integrated into a rechargeable aqueous Zinc-air battery (ZAB), both large specific capacity (770 mAh g−1) and high peak power density (240 mW cm−2) are achieved. Remarkably, the as-prepared ZAB presents amazing charge-discharge cycle performance of 1600 h at the large current density, which is 52.5 times of that using Pt/C+RuO2. Furthermore, all-solid-state ZAB delivers ultra-robust cycling stability even under bending. This work may advance a critical step towards the design of rational and controlled preparation of remarkable and ultra-stable catalysts.

Biochar from olive tree twigs and spent malt rootlets as electrodes in Zn-air batteries

Biochars, i.e. porous carbons obtained by pyrolysis of biomass, can act as electrocatalysts for oxygen evolution and oxygen reduction reaction. In the present work, two biochars have been prepared by using materials of completely different biomass origin: olive-tree twigs and spent malt rootlets (brewery wastes). Both biomass species were subjected to pyrolysis under limited oxygen supply and then they were activated by mixing with KOH and pyrolysis again. The obtained biochars were characterized by several techniques in order to determine their structural characteristics and the composition of their active components. Despite their different origin, the two biochars demonstrated similar structural and compositional characteristics thus highlighting the importance of the pyrolysis and activation procedure. Both biochars were used as electrocatalysts in the operation of rechargeable Zn-air batteries, where they also demonstrated similar electrocatalytic capacities with only a small advantage gained by olive-tree-twigs biochar. Compared to bare nanoparticulate carbon (carbon black), both biochars demonstrated a marked advantage towards oxygen evolution reaction.

Impact of Heat Treatment on the Oxygen Reduction Reaction Performance of PtCo/C(N) Electrocatalyst in PEM Fuel Cell

AbstractThe synthesis of efficient and stable Pt alloy catalysts is a major challenge for the commercialization of PEMFC. Herein, we report a PtCo/C(N) electrocatalyst prepared by Na2CO3‐assisted urea liquid‐phase deposition strategy as an efficient cathodic oxygen reduction reaction electrocatalyst, and test its activity and stability in a rotating disc electrode and a single‐cell. The membrane electrode prepared with PtCo/C(N)‐800 °C catalyst has an output voltage of 0.652 V at 2 A/cm2 and a maximum power density of 1.501 W/cm2, which are 36 mV and 81 W/cm2 higher than those of commercial Pt/C catalyst, respectively. In addition, the mass activity and half‐wave potential of PtCo/C(N)‐800 °C are 2.44 times and 50 mV higher than those of commercial Pt/C, respectively. After 5000 voltammetric cycles, its mass activity and half‐wave potential only lose 35 A/gPt and 9 mV, respectively. XPS results show that the binding energy of Pt 4f is positively shifted relative to Pt/C‐TKK, and the d‐band center of Pt decreases, leading to weak chemical interaction between the oxygen‐containing intermediate and the surface of the electrocatalyst, which is conducive to the improvement of the ORR activity and stability of the catalyst.

Synergistic Effect of Electrocatalyst for Enhanced Oxygen Reduction Reaction: Low Pt-Loaded CuPt Alloy Nanoparticles Supported on N-Doped Hierarchical Porous Carbon.

It is challenging to synthesize oxygen reduction reaction (ORR) electrocatalysts that are highly efficient, affordable, and stable for use in proton exchange membrane fuel cells. To address this challenge, we developed a low platinum-loading (only 6.68% wt) ORR catalyst (PtCu1-NC), comprising CuPt nanoparticles (average size: 1.51 nm) supported on the N-doped carbon substrates. PtCu1-NC possesses a high specific surface area of 662 m2 g-1 and a hierarchical porous structure, facilitating efficient mass transfer. The synergistic effect from introduced copper and the electron effect from nitrogen modify the electronic structure of platinum, effectively accelerating the ORR reaction and enhancing stability. Density functional theory calculations demonstrate the catalytic mechanism and further verify the synergistic effect. Electrochemical assessments indicate that PtCu1-NC exhibits specific activity and mass activity 5.3 and 5.6 times higher, respectively, than commercial Pt/C. The half-wave potential is 27 mV more positive than that of commercial Pt/C. The electrochemical active surface area value is 104.3 m2 g-1, surpassing that of Pt/C. Approximately 78% of current is retained after 10,000 s chronoamperometry measurement. These results highlight the effectiveness of alloying in improving the catalyst performance.

Simultaneously Engineering the First and Second Coordination Shells of Single Iron Catalysts for Enhanced Oxygen Reduction.

The atomically dispersed Fe-N4 active site presents enormous potential for various renewable energy conversions. Despite its already remarkable catalytic performance, the local atomic microenvironment of each Fe atom can be regulated to further enhance its efficiency. Herein, a novel conceptual strategy that utilizes a simple salt-template polymerization method to simultaneously adjust the first coordination shell (Fe-N3S1) and second coordination shell (C-S-C, a structure similar to thiophene) of Fe-N4 isolated atoms is proposed. Theoretical studies suggest that this approach can redistribute charge density in the MN4 moiety, lowering the d-band center of the metal site. This weakens the binding of oxygenated intermediates, enhancing oxygen reduction reaction (ORR) activity when compared to only implementing coordination shell regulation. Based on the above discovery, a single Fe atom electrocatalyst with the optimal Fe-N3S1-S active moiety incorporated in nitrogen, sulfur co-doped graphene (Fe-SAc/NSG) is designed and synthesized. The Fe-SAc/NSG catalyst exhibits excellent alkaline ORR activity, exceeding benchmark Pt/C and most Fe-SAc ORR electrocatalysts, as well as superior stability in Zn-air battery. This work aims to pave the way for creating highly active single metal atom catalysts through the localized regulation of their atomic structure.

Direct Synthesis of CuP2 and Cu3P and Their Performance as Electrocatalysts for Hydrogen Evolution, Oxygen Evolution, and Oxygen Reduction Reactions

Copper phosphides are promising materials for energy conversion applications because of their unique electronic structure and controllable composition. Two stoichiometric copper phosphides, CuP2 and Cu3P, were prepared by direct wet-chemical synthesis using red phosphorus. They were characterized by powder X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy. The precursor selection, reaction temperature, time and solvent composition were also studied. CuP2 is the thermodynamically more stable product, but Cu3P is more commonly obtained. This work demonstrated that higher temperature helps in CuP2 formation. More importantly, using more trioctylphosphine oxide helps control the morphology leading to crystal growth along the crystallographic a-axis. CuP2 and Cu3P were tested for hydrogen evolution, oxygen evolution, and oxygen reduction reactions. CuP2 works better for HER in acidic conditions and OER in general, and Cu3P showed better activity than CuP2 for HER and ORR in an alkaline medium. This study has led to a simple approach to the synthesis of CuP2 nanowires.

Adjusting the Operational Potential Window as a Tool for Prolonging the Durability of Carbon-Supported Pt-Alloy Nanoparticles as Oxygen Reduction Reaction Electrocatalysts.

A current trend in the investigation of state-of-the-art Pt-alloys as proton exchange membrane fuel cell (PEMFC) electrocatalysts is to study their long-term stability as a bottleneck for their full commercialization. Although many parameters have been appropriately addressed, there are still certain issues that must be considered. Here, the stability of an experimental Pt-Co/C electrocatalyst is investigated by high-temperature accelerated degradation tests (HT-ADTs) in a high-temperature disk electrode (HT-DE) setup, allowing the imitation of close-to-real operational conditions in terms of temperature (60 °C). Although the US Department of Energy (DoE) protocol has been chosen as the basis of the study (30,000 trapezoidal wave cycling steps between 0.6 and 0.95 VRHE with a 3 s hold time at both the lower potential limit (LPL) and the upper potential limit (UPL)), this works demonstrates that limiting both the LPL and UPL (from 0.6-0.95 to 0.7-0.85 VRHE) can dramatically reduce the degradation rate of state-of-the-art Pt-alloy electrocatalysts. This has been additionally confirmed with the use of an electrochemical flow cell coupled to inductively coupled plasma mass spectrometry (EFC-ICP-MS), which enables real-time monitoring of the dissolution mechanisms of Pt and Co. In line with the HT-DE methodology observations, a dramatic decrease in the total dissolution of Pt and Co has once again been observed upon narrowing the potential window to 0.7-0.85 VRHE rather than 0.6-0.95 VRHE. Additionally, the effect of the potential hold time at both LPL and UPL on metal dissolution has also been investigated. The findings demonstrate that the dissolution rate of both metals is proportional to the hold time at UPL regardless of the applied potential window, whereas the hold time at the LPL does not appear to be as detrimental to the stability of metals.

A Hybrid Hydrogel Approach for the Design of N, S Dual-Doped Porous Carbon Electrocatalyst for Oxygen Reduction Reaction

A Hybrid Hydrogel Approach for the Design of N, S Dual-Doped Porous Carbon Electrocatalyst for Oxygen Reduction Reaction

Designing a MnF2/MnO2 heterostructure for enhanced electrocatalysis in the oxygen reduction reaction

Studying noble-metal-free oxygen reduction reaction (ORR) catalysts is crucial for advancing fuel cells. Manganese dioxide (MnO2) has garnered widespread attention due to its convenient synthesis, low cost, high electrochemical activity, and diverse structures. However, it still faces challenges, such as poor conductivity and relatively lower inherent catalytic activity. In this study, a novel ORR electrocatalyst is introduced by constructing a heterostructure of manganese fluoride (MnF2) and MnO2, referred to as MnF2/MnO2. In a 0.1 M KOH solution, the ORR half-wave potential (E1/2) of MnF2/MnO2 is measured at 0.804 V, surpassing that of the original MnO2 catalyst (0.69 V). Compared to the MnO2 electrocatalyst, the MnF2/MnO2 heterostructure exhibits faster ORR reaction kinetics and a larger electrochemically active surface area. Density functional theory (DFT) calculations confirm that the MnF2/MnO2 heterostructure possesses enhanced intrinsic conductivity, facilitating the rapid transfer of ions of and electrons. Therefore, this study provides a promising pathway for enhancing the ORR catalytic activity of noble-metal-free electrocatalysts through rational heterostructure design.

Cobalt molybdenum di-selenide surface modification: A path to improved trifunctional catalysis via partial oxygenation

Efficient, stable, and cost-effective electrocatalysts for hydrogen evolution, oxygen evolution, and oxygen reduction reactions have been in demand for decades. Recently, layered transition metals (Co, Mo, Ni, and Fe) and chalcogen compounds (S/Se/Te) gained prominence in catalysis and device studies. Density functional theory identified the covalency of Co and Mo, oxygenated bimetallic selenium bond, crystal structure distortions, and adsorption properties as crucial for enhanced electrocatalytic activity. Hybridizing the Co and Mo d-orbitals around the Fermi level of 0.463 eV improves bonding with metal surface-adsorbate intermediates validated by partial density of states. Oxygenated cobalt molybdenum selenide (O-CoMoSe2) (210) exhibited remarkable electrocatalytic properties at various active sites, with Gibbs free energy and theoretical overpotential at an active site of Co = 0.086 eV, 0.41 V, and Se = 0.50 V.

Molecular architectures of iron complexes for oxygen reduction catalysis—Activity enhancement by hydroxide ions coupling

Developing cost-effective and high-performance electrocatalysts for oxygen reduction reaction (ORR) is critical for clean energy generation. Here, we propose an approach to the synthesis of iron phthalocyanine nanotubes (FePc NTs) as a highly active and selective electrocatalyst for ORR. The performance is significantly superior to FePc in randomly aggregated and molecularly dispersed states, as well as the commercial Pt/C catalyst. When FePc NTs are anchored on graphene, the resulting architecture shifts the ORR potentials above the redox potentials of Fe2+/3+ sites. This does not obey the redox-mediated mechanism operative on conventional FePc with a Fe2+-N moiety serving as the active sites. Pourbaix analysis shows that the redox of Fe2+/3+ sites couples with HO- ions transfer, forming a HO-Fe3+-N moiety serving as the ORR active sites under the turnover condition. The chemisorption of ORR intermediates is appropriately weakened on the HO-Fe3+-N moiety compared to the Fe2+-N state and thus is intrinsically more ORR active.

Hollow Ti3C2Tx MXene sphere-based ZIF-67 derived central radiative cobalt-tipped carbon nanotubes electrocatalysts for ORR and OER

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) plays a key role in many renewable energy conversion and storage technologies. As the state-of-the-art ORR and OER electrocatalysts, noble-metal-based electrocatalysts suffer from high price, low earth abundance, single functionality, and poor stability. Developing high performance noble-metal-free ORR and OER bifunctional electrocatalysts as alternatives is highly desirable but remains a significant challenge. In this work, we reported a metal-organic-framework-engaged strategy for the fabrication of central radiative cobalt-tipped N-doped carbon nanotube/hollow Ti3C2Tx sphere composites (h-Ti3C2Tx@Co-NCNT), in which ZIF-67 particles were in situ grown on spherical structure composed of Ti3C2Tx nanosheets constructed with hard template PMMA and then were converted to cobalt-tipped N-doped carbon nanotubes through a pyrolysis process. The hollow Ti3C2Tx nanosheets sphere not only served as conductive scaffolds for the growth of Co-NCNT but also balanced the tradeoff between graphitization of carbon and the surface area. Benefiting from the abundant Co-N/C active sites, reasonably high graphitization of carbon and suitable surface areas, the optimized h-Ti3C2Tx@Co-NCNT manifested comparable ORR (half-wave potential of 0.843 V) and OER (overpotential of 323 mV) activities. In addition, the h-Ti3C2Tx@Co-NCNT assembled zinc-air battery exhibits superior performance beyond commercial Pt/C+RuO2. Certificating this strategy can provide great opportunity for its application in renewable conversion and storage technologies.

Fe[sbnd]N doped carbon materials from oily sludge as electrocatalysts for alkaline oxygen reduction reaction

Alkaline oxygen reduction reaction (ORR) presents an important role for energy conversion technologies and requires the development of an efficient electrocatalyst. Pt-based catalysts provide suitable activity; however, Pt production accessibility and high costs create hurdles to their commercial implementation. Fe coordinated within N-doped carbon materials (FeNC) are a promising alternative due to their high ORR catalytic activity, although the currently commercially available FeNC materials rely on harsh synthetic protocols which can lead to increased environmental impacts. In this work we target this issue by taking advantage of an oily sludge waste currently generated in refineries to synthesize FeNC materials, thus, avoiding the environmental impact caused by the management of this waste. The solid particles within oily sludge, which present a high concentration of C and Fe, were combined by different nitrogen sources and pyrolyzed at high temperatures.The prepared materials present a hierarchical pore structure with surface areas up to 547 m2 g−1. X-ray photoelectron spectroscopy analysis found that the impregnation of N using phenanthroline promotes the formation of pyridinic-N structures, which enhances the ORR performance compared to melamine doping. Additional doping of Fe with phenanthroline results in an ORR mass activity of 1.23 ± 0.04 A gFeNC−1 at 0.9 VRHE, iR-free in a rotating disc electrode (0.1 M KOH). This catalyst also shows a lower relative loss in activity at 0.9 VRHE after 8000 cycles in O2-saturated conditions compared to a commercial FeNC catalyst, PMF D14401, (−63.5 vs −69 %, respectively), demonstrating promise as a cheap and simple route to FeNC catalysts for alkaline ORR.

Construction of imide‐linked covalent organic frameworks with palladium nanoparticles for oxygen reduction reaction

AbstractCovalent organic frameworks (COFs) have been widely employed as electrocatalysts for oxygen reduction reaction (ORR) due to their diverse and tunable skeletons and pores. However, their electrocatalytic activity was limited due to the lack of highly active catalytic sites. In this work, we have first immobilized palladium nanoparticles (NPs) into the crystal, porous, and stable imide‐linked COF for ORR. The newly designed COF had pyridine linkers with imide‐linkages in the frameworks serving as the binding sites to anchor Pd sites, and the high surface area and open pore channels provide fast mass transport pathway to the active Pd sites, which contributed highly active performance in ORR. And the designed catalyst delivered onset potential and the half‐wave potential of COF‐Pd of 0.97 and 0.83 V, with a limited current density of 6.1 mA cm−2, respectively. This work provides us insights into developing high crystalline COFs with metal NPs in electrocatalytic systems.

Optimization and regulation of catalytic activity and stability: Pt–Ni diamond-shaped pearl nanochains with core-shell structure as high-efficient oxygen reduction reaction catalysts

The low utilization efficiency and poor stability of carbon-supported Pt nanoparticles (Pt/C) catalyst are two main problems of proton exchange membrane fuel cells (PEMFC), which can improve the catalytic performance by forming alloys and precisely regulating morphology and structures. Here, we introduced a simple and direct method for synthesizing Pt–Ni diamond-shaped pearl nanochains (Pt–Ni DP-NCs) as efficient electrocatalyst for oxygen reduction reaction (ORR). The alloying with Ni could enhance the catalytic activity, but because of leaching out of Ni during the cathodic reaction process, which causes a poor stability. To achieve the optimal point for both high activity and robust stability, a portion of Ni is selectively etched from Pt–Ni DP-NCs precursor in advance. During the process of de-alloying, Pt atoms with high catalytic activity are exposed to the surface of the nanochain after atomic rearrangement, thus obtaining Pt–Ni etched diamond-shaped pearl nanochains (Pt–Ni EDP-NCs) with 1D core-shell structure, which consisted of Pt–Ni as the core and Pt as the shell. Benefitting from the unique 1D core-shell structure and composition, Pt–Ni EDP-NCs-9 (etched for 9 h) exhibits high catalytic activity and robust stability for ORR. The mass activity of the sample Pt–Ni EDP-NCs-9 is 0.43 A/mgPt, which is 1.65 times higher than that of the Pt–Ni DP-NCs (0.26 A/mgPt), and 2.05 times higher than that of commercial Pt/C (0.21 A/mgPt). In addition, the 1D core-shell structure enables Pt–Ni EDP-NCs to be highly stable, which only lost by 8.6% of mass activity after 10,000 long cycles, whereas Pt–Ni DP-NCs suffers from a 34% loss under the same conditions. This work provides a strategic approach for designing efficient Pt-based catalysts that simultaneously modulate activity and stability.

Boron-alloyed porous network platinum nanospheres for efficient oxygen reduction in proton exchange membrane fuel cells

Alloying (or doping) non-metals with platinum (Pt) is an advanced solution for the development of high-performance Pt-based electrocatalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Herein, we report boron (B)-alloyed Pt nanospheres (B-PtNSs) with a porous network nanostructure by a combination strategy of confinement reduction and post-boronation. B-alloying can induce effective electronic/geometric structures, strong Pt-B coordination, and lowered d-band center to weaken the binding energy of oxygenated intermediates on the Pt surface. The H2-O2 PEMFC with such a B-PtNSs/C as the cathode catalyst can reach a maximum power density of 1.49 W cm−2, about 1.28 times higher than that of Pt/C. After 30,000 voltage cycles in the range of 0.6 ∼ 0.95 V, only a 14.1 % loss of initial peak power density can be observed, while that with Pt/C declines 45.7 %. Non-metals alloying with Pt-based nanostructures can enable high-performance ORR electrocatalysts for their practical application in PEMFCs.

Synergy of porous network nanostructuring and nonmetallic phosphorus alloying for efficient oxygen reduction of platinum

Alloying of nanostructured platinum (Pt)-based electrocatalysts can significantly improve their electrocatalytic performance for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, there are few studies of nonmetals alloyed Pt-based nanostructures for ORR electrocatalysis. Herein, we present a synergy of porous network nanostructuring and nonmetallic phosphorus (P) alloying to engineer the high-performance P-alloyed Pt nanospheres (P-PtNSs) for efficient ORR electrocatalysis. This characteristic porous network nanostructure is crafted through surfactant soft-templates induced confinement growth, and P-alloying is realized by a post-phosphating method. The introduction of P into Pt lattice can not only regulate electronic and geometric structure but also augment electrocatalytic active sites through the contribution of Pt-P bonds. The resultant P-PtNSs/C catalyst shows mass activity and specific activity at 0.90 V, surpassing those of commercial Pt/C catalyst by factors of 2.7 and 5.8, respectively, while also exhibiting superior stability. More importantly, the H2-O2 PEMFC with a P-PtNSs/C cathode exhibits higher current and power densities than one with Pt/C throughout the entire evaluation process, achieving a peak power density of 1.28 W cm−2 at a low Pt loading of 0.1 mgPt cm−2. This study will provide valuable insights into the nonmetals alloying and nanostructuring of Pt-based ORR electrocatalysts.

NiCo2O4/MXene Hybrid as an Efficient Bifunctional Electrocatalyst for Oxygen Evolution and Reduction Reaction

AbstractFor the advancement of electrochemical energy conversion and storage technologies, bifunctional electrocatalysts are crucial for efficiently driving both the oxygen evolution (OER) and reduction reactions (ORR). Cobalt‐based spinel oxides are a class of promising bifunctional electrocatalysts. However their low electrical conductivity and stability may hinder further improvement. A novel composite material composed of NiCo2O4 nanoparticles integrated with emerging two dimensional MXene nanosheets (NiCo2O4/MXene) was developed. The successful integration of NiCo2O4 with MXene brings about a number of attractive structural features. This includes synergistic effects between NiCo2O4 and MXene, highly accessible surface areas, complete exposure of numerous active sites, and excellent electronic conductivity, all of which collectively contribute to the desirability of composite material for OER and ORR. The synthesized NiCo2O4/MXene composite showed extraordinary OER electrocatalytic activity with a lower overpotential of 360 mV at a current density of 10 mA/cm2, and a small Tafel slope of 64 mV/dec compared to NiCo2O4, MXene and NiCo2O4+MXene (physically mixed). Additionally, NiCo2O4/MXene displays an ORR limiting current density of −4 mA/cm2 and exhibited highest onset potential and half wave potential of 0.92 V and 0.72 V vs. RHE, respectively, for the ORR in alkaline media compared to NiCo2O4, MXene and NiCo2O4+MXene (physically mixed).