Oxygen Electrocatalysts Research Articles

Interface transformation strategy to 1D hierarchically porous carbon with enhanced bifunctional oxygen electrocatalytic performance

Developing efficient oxygen electrocatalysts is considered a key step to advancing renewable energy technologies, especially in fuel cells and metal-air batteries. Herein, an interface transformation strategy is proposed to prepare a one-dimensional cobalt (Co)/nitrogen (N) co-doped porous carbon material (Co/N-PCM). Polydopamine nanotubes (PDA NT) and cobalt phthalocyanine (CoPc) were used as precursors for the controlled formation of Co/N-PCM. Immobilized CoPc molecules on PDA NT formed Co/N-PCM with evenly distributed Co/Co-N-C sites and a hierarchical micro-/mesoporous structure. Theoretical calculations revealed that the electronic modulation of the substrate by Co(111) played a pivotal role in establishing the d-band center of active Co sites on the monatomic Co-N-C layer. The surface-active Co sites provided an optimum adsorption strength between the Co/N-PCM and oxygenated intermediates, leading to significantly enhanced intrinsic oxygen reduction/evolution reaction (ORR/OER) activities. The engineered Co/N-PCM catalyst displayed high activity towards bifunctional oxygen electrocatalysis and delivered outstanding rechargeable zinc-air battery (ZAB) performance.

Pd@CoFe Alloys on N-Doped Carbon Derived from Charred Tissue Paper as Synergistic Bifunctional Oxygen Electrocatalysts

Integrating more active components into a catalyst material could facilitate the development of multifunctional electrocatalysts for energy conversion and storage applications. In this study, we developed a multifunctional electrocatalyst, namely, Pd alloyed with Co-Fe deposited on N-doped mesoporous carbon derived from tissue paper (Pd@Co-Fe/N-TDC). The synergism in Pd@Co-Fe/N-TDC, stemming from the interatomic alloy between Pd and Co-Fe, N-doped mesoporous carbon with defective surfaces, distribution of polyhedral Pd nanoparticles, and strong metal-support interfacial interaction, resulted in significantly high electrocatalytic performance for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Pd@Co-Fe/N-TDC was found to be an efficient bifunctional oxygen electrocatalyst, and this was evidenced by a high onset potential (1.01 V) and kinetic current density (2.6 mA/cm2) for the ORR and by a low overpotential (296 mV) and a low Tafel slope value (38 mV/dec) for the OER, along with a small ΔE of 736 mV. The catalyst also exhibited high durability for both ORR and OER, even after 10000 and 5000 cycles, respectively. Theoretical assessment provides an insight into the synergism of active metal sites in Pd@Co-Fe/N-TDC, which showed its potential for use as a non-Pt electrocatalyst for energy applications.

Supercapacitor Electrodes: Is Nickel Foam the Right Substrate for Active Materials?

Ni foam is an extensively used current collector and substrate in investigations of electrochemically active materials such as supercapacitors and electrocatalysts for oxygen and hydrogen evolution reactions. This material is relatively cheap, porous, and conductive and has a large specific surface area, all of which make it a good substrate. We investigated Ni-Mg ferrites and NiMn2O4 as active materials for electrochemical energy storage. These materials, when loaded on Ni foam, gave promising capacitance values: 172 F/g (at 2 mV/s) for NiMn2O4 in 6 M KOH and 242 F/g (at 2 mV/s) for MgFe2O4 in 3 M KOH. Nevertheless, during the authors' work, many experimental problems occurred. Inconsistencies in the results directed further investigation towards measuring the capacitance of the active materials using GCE and platinum electrodes as substrates to discover if Ni foam was the culprit of the inconsistencies. When non-nickel substrates were used, both NiMn2O4 and MgFe2O4 showed reduced capacitance. Experimental problems associated with the utilization of Ni foam as a substrate for active materials in supercapacitor electrodes are discussed here, combined with other problems already addressed in the scientific literature.

Heterojunction of MXenes and MN4–graphene: Machine learning to accelerate the design of bifunctional oxygen electrocatalysts

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for the development of excellent bifunctional electrocatalysts, which are key functions in clean energy production. The emphasis of this study lies in the rapid design and investigation of 153 MN4–graphene (Gra)/ MXene (M2NO) electrocatalysts for ORR/OER catalytic activity using machine learning (ML) and density functional theory (DFT). The DFT results indicated that CoN4–Gra/Ti2NO had both good ORR (0.37 V) and OER (0.30 V) overpotentials, while TiN4–Gra/M2NO and MN4–Gra/Cr2NO had high overpotentials. Our research further indicated orbital spin polarization and d-band centers far from the Fermi energy level, affecting the adsorption energy of oxygen-containing intermediates and thus reducing the catalytic activity. The ML results showed that the gradient boosting regression (GBR) model successfully predicted the overpotentials of the monofunctional catalysts RhN4–Gra/Ti2NO (ORR, 0.39 V) and RuN4–Gra/W2NO (OER, 0.45 V) as well as the overpotentials of the bifunctional catalyst RuN4–Gra/W2NO (ORR, 0.39 V; OER, 0.45 V). The symbolic regression (SR) algorithm was used to construct the overpotential descriptors without environmental variable features to accelerate the catalyst screening and shorten the trial-and-error costs from the source, providing a reliable theoretical basis for the experimental synthesis of MXene heterostructures.

Screening Spinel Oxide Supports for RuO2 to Boost Bifunctional Electrocatalysts for Advanced Zn–Air Batteries

AbstractThe compositing strategy offers great potential in designing bifunctional oxygen electrocatalysts for Zn–air batteries. Recent reports reveal that the couple of RuO2, serving as a benchmark oxygen evolution reaction (OER) catalyst, with other oxygen reduction reaction (ORR) catalysts is a wise choice to build highly efficient bifunctional electrocatalysts. However, the design criteria for ORR and OER activities of RuO2‐based composite catalysts are still unclear. Herein, a series of transition metal (Fe, Co, Mn, and Ni)‐doped spinel oxides are designed to support RuO2 nanorods for exploring the reaction mechanism. Through advanced technology, it is considered that increasing the content and binding energy of Co3+ and enhancing the oxidation state of Ru4+ is an efficient strategy to promote ORR and OER activities for RuO2/Co‐based spinel oxide composite catalysts. It is found that coupling Mn‐doping Co3O4 (CMO) supports with RuO2 can induce the highest catalytic activities in ORR/OER and excellent performance in rechargeable Zn–air batteries. Operando electrochemical impedance spectroscopy and theoretical calculation further prove the synergistic effect between RuO2 and CMO supports originated from the oxygen overflow to overcome the large barrier for oxygen desorption on RuO2 during OER and oxygen adsorption on CMO supports during ORR.

Bifunctional ligand Co metal-organic framework derived heterostructured Co-based nanocomposites as oxygen electrocatalysts toward rechargeable zinc-air batteries

Rational construction of efficient and robust bifunctional oxygen electrocatalysts is key but challenging for the widespread application of rechargeable zinc-air batteries (ZABs). Herein, bifunctional ligand Co metal–organic frameworks were first explored to fabricate a hybrid of heterostructured CoOx/Co nanoparticles anchored on a carbon substrate rich in CoNx sites (CoOx/Co@CoNC) via a one-step pyrolysis method. Such a unique heterostructure provides abundant CoNx and CoOx/Co active sites to drive oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. Besides, their positive synergies facilitate electron transfer and optimize charge/mass transportation. Consequently, the obtained CoOx/Co@CoNC exhibits a superior ORR activity with a higher half-wave potential of 0.88 V than Pt/C (0.83 V vs. RHE), and a comparable OER performance with an overpotential of 346 mV at 10 mA cm−2 to the commercial RuO2. The assembled ZAB using CoOx/Co@CoNC as a cathode catalyst displays a maximum power density of 168.4 mW cm−2, and excellent charge–discharge cyclability over 250 h at 5 mA cm−2. This work highlights the great potential of heterostructures in oxygen electrocatalysis and provides a new pathway for designing efficient bifunctional oxygen catalysts toward rechargeable ZABs.

Ni-Co ternary nitrides with multiple surface oxides as bifunctional oxygen electrocatalysts for metal-air batteries

The bifunctional non-noble metal catalysts based on the metal nitrides with high activity and high efficiency is very challenging for the development of high-performance metal-air batteries. Herein, a new Ni-Co ternary nitrides anchored on nitrogen-doped carbontubes (denoted as NiCoxN/CNT) is rationally designed by the thermal of corresponding hydroxide/carbontubes at low temperature, following nitridation. The synergistic effect between Ni-Co ternary nitrides (Ni4N, Co5.47N, CoN) effectively regulates the electronic configuration of the active site, thereby optimizing the chemisorption energy of the reaction intermediates, resulting in improved intrinsic catalytic activity. The result shows that NiCoxN/CNT not only exhibits excellent half-wave potential of 0.80 V for ORR but also with a low overpotential of 280 mV for OER at 10 mA cm−2, outperforming those of cobalt mononitride and nickel mononitride. Furthermore, Zn-air batteries assembled with NiCoxN/CNT show a high specific capacity of 826.9 mA h g−1 and excellent cycling stabilities up to 190 h in an aqueous electrolyte. More attractively, when assembled into Mg-air batteries, NiCoxN/CNT cathode realizes high power density of 112.38 mWcm−2. Therefore, the design and construction of multiple TMNs is a new guide to break through the bifunctional catalytic activity.

Revolutionizing Zn-Air batteries with chainmail catalysts: Ultrathin carbon-encapsulated FeNi alloys on N-doped graphene for enhanced oxygen electrocatalysis

The sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) pose significant challenges for the viability of rechargeable Zn-air batteries. Developing efficient, cost-effective, stable, and dual-purpose oxygen electrocatalysts remains a formidable hurdle. In this study, we successfully synthesized a highly promising chainmail catalyst named FeNi@NC, comprising ultrathin carbon shells encapsulating FeNi alloy nanoparticles on N-doped graphene-like nanosheets. The strong synergistic effects between FeNi alloys and N-doped carbon shells result in outstanding bifunctional catalytic activity, particularly in alkaline media. Consequently, Zn-air batteries incorporating FeNi@NC as the catalyst demonstrate exceptional performance, operating reliably at high power density with extended lifespan. Furthermore, computational analyses provided further confirmation of the catalytic activity and revealed that the electron transfer from FeNi alloy nanoparticles to the carbon shells activates the carbon surface, leading to enhanced catalytic performance. This research not only sheds light on the rational design and synthesis of heteroatom-doped carbon materials supporting the growth-constrained transition metal alloys but also offers a practical solution for advancing the application of Zn-air batteries.

Atomically dispersed Mn, N doped the cotton biomass aerogel of carbon fibers as bifunctional oxygen electrocatalyst for long-term rechargeable Zn-air battery

Atomically dispersed Mn, N doped the cotton biomass aerogel of carbon fibers as bifunctional oxygen electrocatalyst for long-term rechargeable Zn-air battery

MnFeNi‐Based Composite as a Case Study of a Bifunctional Oxygen Electrocatalyst under Dynamically Changing Electrode Potentials

AbstractHigh‐performance bifunctional electrocatalysts for the oxygen reduction (ORR) and oxygen evolution reaction (OER) are essential components in energy conversion and storage technologies. Yet, their poor reversibility hinders their applicability. A highly active ORR/OER catalyst, consisting of multiwalled carbon nanotubes‐supported MnFeNiOx nanoparticles, was subjected to sequences of chronoamperometric steps alternating between the ORR, the OER and highly cathodic potentials (Ec). Rotating ring disk electrode methods revealed that applying Ec leads to a small increase in the current and peroxide species yield during the ORR while enhancing substantially the OER. X‐ray absorption spectroscopy showed irreversible changes in the chemical state of MnFeNiOx correlating with its catalytic properties. The complexity of changes that a composite catalyst may undergo under varying potentials, the importance of monitoring product formation, and the convenience of using dynamic electrochemical sequences for the assessment of catalyst reversibility, as well as for the activation and/or restoration of their catalytic properties, are highlighted.

Architecting N-doped Carbon Nanotube-Rich Carbon Nanofibers with Biomimetic Vine-Leaf-Whisker Structure as Robust Bifunctional Electrocatalysts for Rechargeable Zn-Air Batteries.

Efficient and durable bifunctional catalysts toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are urgently desirable but challenging for rechargeable Zn-air batteries (ZABs), especially flexible wearable ZABs. Inspired by the vine-leaf-whisker structure in nature, we proposed a three-dimensional (3D) hierarchical bifunctional catalyst (denoted as Co-Fe-Zn@N-CNT/CNF) consisting of N-doped carbon nanotubes embedded with abundant CoFe alloy nanoparticles, leaf-shaped N-doped carbon nanoflakes, and porous carbon fibers for rechargeable ZABs. The special biomimetic structure provides a large specific surface area, allowing for high exposure of the active site and ensuring fast mass transport/charge transfer. The close combination of CoFe bimetallic alloys and N-doped carbon nanotubes delivers high electrocatalytic activity, while the coexistence of various active sites such as metal nanoparticles (NPs), metal-Nx, doped N species, and their synergistic interactions endows the catalysts with more active sites. As such, the Co-Fe-Zn@N-CNT/CNF catalyst achieves superior bifunctional catalytic activities for the ORR (a half-wave potential of 0.84 V) and the OER (an overpotential of 326 mV at 10 mA cm-2) in alkaline media, comparable to commercial Pt/C and RuO2. Remarkably, both aqueous and solid-state ZABs assembled with Co-Fe-Zn@N-CNT/CNF catalysts as air electrodes demonstrate excellent charging/discharging performance, high peak power density, and robust long-term cycling stability. More interestingly, the flexible ZAB performs well even under bending conditions, displaying satisfactory device stability and mechanical flexibility. This study presents a new collective morphological-composition-structural engineering strategy for exploiting the efficient bifunctional oxygen electrocatalysts, which is of great significance for high-performance rechargeable ZABs and wearable energy storage devices.

Highly Porous Metal-Organic Framework Entrapped by Cobalt Telluride-Manganese Telluride as an Efficient Bifunctional Electrocatalyst.

The electrochemical conversion of oxygen holds great promise in the development of sustainable energy for various applications, such as water electrolysis, regenerative fuel cells, and rechargeable metal-air batteries. Oxygen electrocatalysts are needed that are both highly efficient and affordable, since they can serve as alternatives to costly precious-metal-based catalysts. This aspect is particularly significant for their practical implementation on a large scale in the future. Herein, highly porous polyhedron-entrapped metal-organic framework (MOF)-assisted CoTe2/MnTe2 heterostructure one-dimensional nanorods were initially synthesized using a simple hydrothermal strategy and then transformed into ZIF-67 followed by tellurization which was used as a bifunctional electrocatalyst for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). The designed MOF CoTe2/MnTe2 nanorod electrocatalyst exhibited superior activity for both OER (η = 220 mV@ 10 mA cm-2) and ORR (E1/2 = 0.81 V vs RHE) and outstanding stability. The exceptional achievement could be primarily credited to the porous structure, interconnected designs, and deliberately created deficiencies that enhanced the electrocatalytic activity for the OER/ORR. This improvement was predominantly due to the enhanced electrochemical surface area and charge transfer inherent in the materials. Therefore, this simple and cost-effective method can be used to produce highly active bifunctional oxygen electrocatalysts.

Tip and heterogeneous effects co-contribute to a boosted performance and stability in zinc air battery

The zinc-air battery (ZAB) performance and stability strongly depend on the structure of bifunctional electrocatalyst for oxygen reduction/evolution reaction (ORR/OER). In this work, we combine the tip and heterogeneous effects to construct cobalt/cobalt oxide heterostructure nanoarrays (Co/CoO-NAs). Due to the formed heterostructure, more oxygen vacancies are found for Co/CoO-NAs resulting in a 1.4-fold higher ORR intrinsic activity than commercial carbon supported platinum electrocatalyst (Pt/C) at 0.8 V versus reversible hydrogen electrode (vs. RHE). Moreover, a fast surface reconstruction is observed for Co/CoO-NAs during OER catalysis evidenced by in-situ electrochemical impedance spectroscopy and Raman tests. In addition, the tip effect efficiently lowers the mass transfer resistance triggering a low overpotential of 347 mV at 200 mA cm−2 for Co/CoO-NAs. The strong electronic interplay between cobalt (Co) and cobalt oxide (CoO) contributes to a stable battery performance during 1200 h galvanostatic charge–discharge test at 5 mA cm−2. This work offers a new avenue to construct high-performance and stable oxygen electrocatalyst for rechargeable ZAB.

External Field-Responsive Ternary Non-Noble Metal Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries.

Despite the increasing effort in advancing oxygen electrocatalysts for zinc-air batteries (ZABs), the performance development gradually reaches a plateau via only ameliorating the electrocatalyst materials. Herein, a new class of external field-responsive electrocatalyst comprising Ni0.5Mn0.5Fe2O4 stably dispersed on N-doped Ketjenblack (Ni0.5Mn0.5Fe2O4/N-KB) is developed via polymer-assisted strategy for practical ZABs. Briefly, the activity indicator ΔE is significantly decreased to 0.618V upon photothermal assistance, far exceeding most reported electrocatalysts (generally >0.680V). As a result, the photothermal electrocatalyst possesses comprehensive merits of excellent power density (319mW cm-2), ultralong lifespan (5163 cycles at 25mA cm-2), and outstanding rate performance (100mA cm-2) for liquid ZABs, and superb temperature and deformation adaptability for flexible ZABs. Such improvement is attributed to the photothermal-heating-enabled synergy of promoted electrical conductivity, reactant-molecule motion, active area, and surface reconstruction, as revealed by operando Raman and simulation. The findings open vast possibilities toward more-energy-efficient energy applications.

Efficient and Stable Dual-Active-Site of Core-Shell NiFe-Layered Double Hydroxide Anchored on FeMnON-N-Doped Carbon Nanotubes as Bifunctional Oxygen Electrocatalysts for Zn-Air Batteries

The bifunctional air electrodes with numerous dual-active sites and low cost are desirable to modify the performance of Zn-air batteries (ZABs). Metal–oxygen-nitrogen–carbon substrate (M = Mn, Fe, Ni, etc.) and NiFe-layered double hydroxide (NiFe-LDH) nanosheets are excellent catalysts in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) processes, respectively. Hereby, we investigate a bifunctional electrocatalytic substrate with a 3D core–shell hierarchical architecture by anchoring high OER-active NiFe-LDH on ORR-active FeMnZIF-8@gC3N4-derived FeMnON-N doped carbon nanotubes bamboo like (NiFe-LDH@FeMnON-NC). This nanocomposite has unique features such as robust synergistic effects, high conductivity, balance, and optimization of surface chemical valences of Fe, Mn, and Ni atoms to boost the bifunctional ORR and OER properties and stability in ZABs. The NiFe-LDH@FeMnON-NC nanocomposite not only exhibited superior OER electroactivity with a low onset overpotential of 235 mV (10 mA cm−2) but also had excellent ORR activity with a current density of −5.48 mA cm−2 and onset potential of 1.04 V, which is better than or comparable to those of commercial Pt/C and RuO2. Rechargeable ZABs constructed by bifunctional NiFe-LDH@FeMnON-NC have a peak power density (235.41 mW cm−2), open-circuit potential (OCV) (1.53 V), small discharge/charge band gap of 0.74 V and excellent discharge stability.

Fe3 C/Fe Decorated N-doped Carbon Derived from Tetrabutylammonium tetrachloroferrate Complex as Bifunctional Electrocatalysts for ORR, OER and Zn-Air Batteries in Alkaline Medium.

The emergence of non-precious metal-based robust and economic bifunctional oxygen electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is crucial for the rational design of commercial rechargeable Zn-air batteries (RZAB) with safe energy conversion and storage systems. Herein, a facile strategy to fabricate a cost-efficient, bifunctional oxygen electrocatalyst Fe3 C/Fe decorated N doped carbon (FeC-700, the catalyst prepared at carbinization temperature of 700 °C) with a unique structure has been developed by carbonization of a single source precursor, tetrabutylammonium tetrachloroferrate(III) complex. The ORR and OER activity revealed excellent performance (ΔE=0.77 V) of the FeC-700 electrocatalyst, comparable to commercial Pt/C and RuO2, respectively. The designed temperature-tuneable structure provided sufficiently accessible active sites for the continuous passage of electrons by shortening the mass transfer pathway, leading to extremely durable electrocatalysts with high ECSA and amazing charge transfer performance. Remarkably, the assembled Zn-air batteries with the FeC-700 catalyst as the bifunctional air electrode delivers gratifying charging-discharging ability with an impressive power density of 134 mW cm-2 with a long lifespan, demonstrating prodigious possibilities for practical application.

F Doping-Induced Multicomponent Synergistic Active Site Construction toward High-Efficiency Bifunctional Oxygen Electrocatalysis for Rechargeable Zn-Air Batteries.

The commercialization of rechargeable Zn-air batteries (ZABs) relies on the material innovation to accelerate the sluggish oxygen electrocatalysis kinetics. Due to the differentiated mechanisms of reverse processes, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), rationally integrating dual sites for bifunctional oxygen electrocatalysis is prerequisite yet remains challenging. Herein, multicomponent synergistic active sites within highly graphitic carbon substrate are exquisitely constructed, which is accomplished by fluorine (F) modulation strategy. The incorporation of F dopants facilitates pyridinic N formation for anchoring single metal sites, thus guaranteeing the coexistence of sufficient M-Nx sites and metal nanoparticles toward bifunctional oxygen electrocatalysis. As a result, the optimal catalyst, denoted as F NH2-FeNi-800, outperforms commercial Pt/C+RuO2 with smaller gap between Ej = 10 and E1/2 (ΔE) of 0.63V (vs 0.7V for Pt/C+RuO2), demonstrating its superior bifunctionality. Beyond that, its superiority is validated in homemade rechargeable ZABs. ZABs assembled using F NH2-FeNi-800 as the air cathode delivers higher peak power density (123.8mW cm-2) and long-cycle lifetime (over 660 cycles) in comparison with Pt/C@RuO2 (68.8mW cm-2; 300 cycles). The finding not only affords a highly promising oxygen electrocatalyst, but also opens an avenue to constructing multifunctional active sites for heterogeneous catalysts.

ZIFs-Derived Hollow Nanostructures via a Strong/Weak Coetching Strategy for Long-Life Rechargeable Zn-Air Batteries.

Recently, zeolitic imidazolate frameworks (ZIFs) composites have emerged as promising precursors for synthesizing hollow-structured N-doped carbon-based noble-metal materials with diverse structures and compositions. Here, a strong/weak competitive coordination strategy is presented for synthesizing high-performance electrocatalysts with hollow features. During the competitive coordination process, the cubic zeolitic-imidazole framework-8 (Cube-8)@ZIF-67 with core-shell structures are transformed into Cube-8@ZIF-67@PF/POM with yolk-shell nanostructures employing phosphomolybdic acid (POM) and potassium ferricyanide (PF) as the strong chelator and the weak chelator, respectively. After calcination, the hollow Mo/Fe/Co@NC catalyst exhibits superior performance in both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Interestingly, the Mo/Fe/Co@NC catalyst exhibits efficient electrocatalytic performance for Zn-air batteries (ZABs), with a high power density (≈150mW cm-2) and superior cycling life (≈500h) compared to commercial platinum/carbon (Pt/C) and ruthenium dioxide (RuO2) mixture benchmarks catalysts. In addition, the density functional theory further proves that after the introduction of Mo and Fe atoms, the adsorption energy with the adsorption intermediates is weakened by adjusting the d-band center, thus weakening the reaction barrier and promoting the reaction kinetics of OER. Undoubtedly, this study presents novel insights into the fabrication of ZIFs-derived hollow structure bifunctional oxygen electrocatalysts for clean-energy diverse applications.

The Effect of Ga Incorporation in TiO2/SnO2 Nanoparticle‐Decorated Hierarchical ZSM‐5 Composite as Precious‐Metal‐Free Electrocatalysts for Oxygen Electro‐Reduction

AbstractThe slow nature of oxygen electro‐reduction has become a major obstacle in fuel cell commercialization. Researchers have recently focused on developing efficient electrocatalysts to address this issue. In this study, we investigated the catalytic activity of electrocatalysts based on metal‐incorporated zeolites. We prepared the zeolite socony mobil‐5 (ZSM‐5) zeolite samples hydrothermally and modified them to introduce mesopores and metal nanoparticles. The metal nanoparticles were supported on the hierarchical zeolite socony mobil‐5 (HZSM‐5) support materials by ion‐exchange process. Surface morphology analysis revealed that the pristine material had a smooth surface which became rough upon post‐modification of the material. Hierarchical zeolites showed large surface area and pore volume. The TiSn‐loaded‐HZSM‐5 demonstrated higher catalytic efficiency than other prepared electrocatalysts for ORR. The catalytic efficiency of the synthesized electrocatalysts was in the order TiSn‐HZSM‐5>GaSn‐HZSM‐5>TiGaSn‐HZSM‐5>TiGa‐HZSM‐5 with the onset potential of 0.86, 0.81, 0.80 and 0.78 V respectively. Catalysis is affected by the size, dispersion and electronic state of metal nanoparticles as observed by the catalytic efficiency of the trimetallic electrocatalysts which have low catalytic activity compared to bimetallic counterparts. Bimetallic hierarchical zeolites based electrocatalysts have great potential in catalysis, but there is still room for improvement.

Hydrogel derived N, P co-doped porous defective carbon framework anchored with Co2P nanoparticles as robust electrocatalysts for Zn-air battery

Recently, it is critical but a challenge to exploit economical, high active and stable bifunctional oxygen electrocatalysts for advanced rechargeable Zn-air batteries (ZABs). Herein, a robust ORR/OER electrocatalyst (Co2P/H-NPC) was prepared using Co2P nanoparticles (NPs) anchored on a N,P-doped three-dimensional (3D) hierarchically porous carbon framework with rich defects through carbonizing a hydrogel, involving starch, polyinosinic acid, cobalt(II) acetate and NH4Cl. Co2P NPs and the dual doping of heteroatoms (N and P), as well as the hierarchically porous feature, synergistically endow Co2P/H-NPC with an excellent ORR and OER activities, in terms of positive half-wave potential (0.83 V) and low overpotential (390 mV) at a current density of 10 mA cm−2, respectively. Additionally, the assembled ZAB based on Co2P/H-NPC delivers a peak power density of 120 mW cm−2, and a wonderful discharge-charge cycling stability, indicating good potential for further application in the fields of energy storage and conversion devices.