Electrocatalytic Materials Research Articles

Single Entity Electrocatalysis.

Making a measurement over millions of nanoparticles or exposed crystal facets seldom reports on reactivity of a single nanoparticle or facet, which may depart drastically from ensemble measurements. Within the past 30 years, science has moved toward studying the reactivity of single atoms, molecules, and nanoparticles, one at a time. This shift has been fueled by the realization that everything changes at the nanoscale, especially important industrially relevant properties like those important to electrocatalysis. Studying single nanoscale entities, however, is not trivial and has required the development of new measurement tools. This review explores a tale of the clever use of old and new measurement tools to study electrocatalysis at the single entity level. We explore in detail the complex interrelationship between measurement method, electrocatalytic material, and reaction of interest (e.g., carbon dioxide reduction, oxygen reduction, hydrazine oxidation, etc.). We end with our perspective on the future of single entity electrocatalysis with a key focus on what types of measurements present the greatest opportunity for fundamental discovery.

Electrochemical Stability of MXenes in Water Based on Constant Potential AIMD Simulations.

MXene has been recently explored as promising electrocatalytic materials to accelerate the electrocatalytic process for hydrogen evolution, but their dynamic stability under electrochemical conditions remains elusive. Here we performed first-principle ab initio molecular dynamics calculations to reveal the electrochemical stability of Ti2CTx MXene in different aqueous environments. The results revealed the high vulnerability of the pure and vacancy-defected Ti2CO2 MXene towards water attack, leading to surface oxidation of MXene under neutral electrochemical condition that formed adsorbed oxygen species to Ti and dissociated proton in solution. The surface oxidation of Ti2CO2 could be prevented in the acid condition or in the neutral condition under the negative potential. Differently, the fully F- or OH-functionalized Ti2CF2 and Ti2C(OH)2 as well as the mixed functionalized Ti2C(O0.5OH0.5)2 and Ti2CO1.12F0.88 are highly stable under various electrochemical conditions, which can effectively prevent close contact between water and surface Ti atoms via electronic repulsion or steric hindrance. These findings provide atomic level understanding of the aqueous stability of MXene and provide useful strategies to prevent degradation and achieve highly stable MXenes.

Rational Construction of a 3D Self-Supported Electrode Based on ZIF-67 and Amorphous NiCoP for an Enhanced Oxygen Evolution Reaction.

The development of efficient and Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is an urgent requirement in the field of electrochemical water splitting. The electrocatalytic performance of the OER can be greatly enhanced by the synergistic combination of zeolite imidazolate frameworks (ZIFs) and transition-metal phosphides, both of which individually exhibit promising capabilities in this regard. In this study, a novel amorphous NiCoP deposited on ZIF-67 sheets supported on Ni foam (labeled as NiCoP/ZIF-67/NF) as an OER electrocatalytic material was successfully synthesized using a simple, secure, and time-efficient two-step strategy. The experimental results demonstrate that NiCoP/ZIF-67/NF possesses a large active surface area with abundant active sites. Also, the synergistic effect and interaction between NiCoP and ZIF-67, as well as between Ni and Co within NiCoP, effectively enhance its electrochemical performance under alkaline conditions. Consequently, NiCoP/ZIF-67/NF exhibits outstanding catalytic activity for OER with an overpotential (η) of 175 mV at a current density of 10 mA cm-2 and a long-term stability over 40 h at 20 mA cm-2 in a 1.0 M KOH electrolyte. The corresponding analyses suggest that the real active sites responsible for the OER are identified as NiOOH and CoOOH species within the structure of NiCoP/ZIF-67/NF. Additionally, the catalytic function and stability of ZIF-67 toward the OER under alkaline conditions were also briefly discussed. This work provides a novel catalytic material for the OER along with a facile strategy to fabricate superior, efficient, and noble metal-free catalysts suitable for energy-related applications.

Improved HER activity of Ru nanoparticles decorated MoS2 with S defect

Surface modification of 2H molybdenum disulfide (2H-MoS2) has been found to be one of the most effective approaches for improving the catalytic performance in the hydrogen evolution reaction (HER) process. Here, the metal Ruthenium (Ru) nanoparticles (NPs) could realize synergistically structural and electronic modulations of MoS2 with S-vacancy (SvMoS2). The experiments and first-principles calculations demonstrated S-vacancy could optimize MoS2 sites for the HER. While Ru NPs loaded on SvMoS2 (Ru@SvMoS2), the interaction between Ru and SvMoS2 contribute to improved electrical conductivity of SvMoS2. Thus, Ru@SvMoS2 possess robust electrocatalytic activity with good stability. Furthermore, this study opens a new venue for optimizing electrocatalytic materials with good performance.

The introduction of rich active sites on 0D@2D nanocarbon via light illuminating with high-efficient electrocatalytic H2O2 production

Two-dimensional (2D) carbon-based materials are high-quality electrocatalytic materials with high mass transfer interfaces. However, the intrinsic 2D surfaces often lack of abundant active sites and outstanding electron transport channels. Herein, a 0D@2D nanocarbon material with affluent unsaturated oxygen-containing groups (UOCGSs) active sites and excellent electron channels are constructed via a novel sodium ion-capping and light illuminating strategy. With the aid of the light illuminating, the final 0D@2D product exhibits a superior practical H2O2 production rate of up to 1109 mmol·gcatalyst−1 h−1 with a high level of onset potential 0.78V and 94 % H2O2 selectivity in H-cell. This improved performance arises from the introduction of UOCGSs and excellent charge transfer on the 0D@2D interface. Obviously, this work exhibits a new green stagey for the design of 0D@2D carbon-based structure via light illuminating.

Reactivity and Durability of Covalent Organic Frameworks Derived Co‐Based Hybrid Bifunctional Electrocatalysts for Zinc‐Air Batteries

AbstractDeveloping bifunctional non‐precious metal electrocatalysts of superior reactivity and durability is essential. Herein, we report a class of phthalocyanine‐based covalent organic frameworks as self‐sacrificial precursors derived Co‐based hybrid electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The fabricated Co‐COFs/CNT‐700 catalysts displayed highly efficient ORR properties with a half‐potential of 0.83 V, while its half‐wave potential in alkaline solution at a current density of 10 mA cm−2 is 1.70 V in the OER test, reflecting exceptional OER activity. Moreover, zinc‐air batteries assembled with Co‐COFs/CNT‐700 catalysts exhibit a marginally higher power density (114 mW cm2) than traditional Pt/C−IrO2 batteries in an air atmosphere, along with an enhanced cycling stability (5.1 % potential loss after 65 h). This work may pave a facile and efficient approach for fabricating electrocatalytic materials with controllably introduced metals and heteroatoms.

Electrochemical determination of dopamine by poly (methyl orange) shape memory alloy modified carbon paste electrode

We have successfully prepared 50Ni-30Ti-20Hf shape memory alloy powders using a high-energy planetary ball mill for 20 h by wet milling. The fabricated shape memory alloy powders were characterized by X-ray diffraction (XRD), and scanning electron microscope (SEM) to investigate the phases present and the morphology of the powders respectively. The use of 50Ni-30Ti-20Hf (nitinol) shape memory alloy powders as electro-catalytic materials is a unique and new idea. We are the first researchers to use nitinol powders as dopamine (DA) electrochemical sensors. For better electrochemical oxidation and higher current response of DA, we have electro-polymerized the surface of nitinol-modified carbon paste electrode (MCPE) with methyl orange (MO). Using poly(MO)-NiTiHf-MCPE, we have determined the DA using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) respectively. The calculated active surface area for BCPE, NiTiHf-MCPE, and the poly(MO)-NiTiHf-MCPE were found to be 0.044, 0.089, and 0.098 cm2 respectively. The electro-polymerized nitinol MCPE not only increased the surface area but also increased the electron transfer kinetics. Our results confirmed the participation of 2 electrons and 2 protons in the electrochemical redox reaction.

Self-assembled from monometallic-organic framework to bimetallic-organic framework materials with promoted supercapacitor performance

Designing new metal–organic frameworks (MOFs) materials with definite structure and introducing heterometallic atom is an effective strategy to develop new electrocatalytic and energy storage materials. Herein, one new 3D close-packed type manganese metal–organic frameworks, namely [Mn2(BPTC)(DMSO)2.5] (Mn-MOF) have been constructed from a rigid biphenylic acid with a rigid biphenyl-3,3′,5,5′-tetracarboxylic acid (H4BPTC) ligand under a solvothermal condition. Besides, adopting the metal doping strategy, a series of bimetallic MnM’-MOF (M’=Co, Ni and Cu) crystalline materials has been successfully grown on nickel foam (NF) and were used for supercapacitor electrode material. By contrast, the MnNi-MOF/NF shows a specific capacitance of 3391.7 mF cm−2 at 1 mA‧cm−2 in 1.0 M KOH, which is 1.6 times that of Mn-MOF/NF electrode. It also displays excellent cycle stability to keep 92.6 % of the initial capacity after GCD 20000 cycles. Finally, a hybrid supercapacitor (HSC) made from on the MnNi-MOF electrode and activated carbon (AC) could deliver an energy density of 0.224 mWh cm−2 at a power density of 1.04 mW cm−2, and a high cycle-to-cycle stability with 90.1 % of the primary capacitance over 20,000 cycles. This work not only confirms the potential supercapacitor properties of as-synthesized new Mn-MOF, but also effectively improves the specific capacity and device stability of pure Mn-MOF by introducing different transition metal ions.

Rational Design Strategy for High-Valence Metal-Driven Electronically Modulated High-Entropy Co-Ni-Fe-Cu-Mo (Oxy)Hydroxide as Superior Multifunctional Electrocatalysts.

Creating durable and efficient multifunctional electrocatalysts capable of high current densities at low applied potentials is crucial for widespread industrial use in hydrogen production. Herein, a Co-Ni-Fe-Cu-Mo (oxy)hydroxide electrocatalyst with abundant grain boundaries on nickel foam using a scalable coating method followed by chemical precipitation is synthesized. This technique efficiently organizes hierarchical Co-Ni-Fe-Cu-Mo (oxy)hydroxide nanoparticles within ultrafine crystalline regions (<4nm), enriched with numerous grain boundaries, enhancing catalytic site density and facilitating charge and mass transfer. The resulting catalyst, structured into nanosheets enriched with grain boundaries, exhibits superior electrocatalytic activity. It achieves a reduced overpotential of 199mV at 10mAcm2 current density with a Tafel slope of 48.8mVdec1 in a 1m KOH solution, maintaining stability over 72h. Advanced analytical techniques reveal that incorporating high-valency copper and molybdenum elements significantly enhances lattice oxygen activation, attributed to weakened metal-oxygen bonds facilitating the lattice oxygen mechanism (LOM). Synchrotron radiation studies confirm a synergistic interaction among constituent elements. Furthermore, the developed high-entropy electrode demonstrates exceptional long-term stability under high current density in alkaline environments, showcasing the effectiveness of high-entropy strategies in advancing electrocatalytic materials for energy-related applications.

High-Entropy Materials in Electrocatalysis: Understanding, Design, and Development.

Electrocatalysis is a crucial method for achieving global carbon neutrality, serving as an essential means of energy conversion, and electrocatalyst is crucial in the process of electrocatalysis. Because of the abundant active sites, the multi-component synergistic effect of high-entropy materials has a wide application prospect in the field of electrocatalysis. Moreover, due to the special structure of high-entropy materials, it is possible to obtain almost continuous adsorption energy distribution by regulating the composition, which has attracted extensive attention of researchers. This paper reviews the properties and types of high-entropy materials, including alloys and compounds. The synthesis strategies of high-entropy materials are systematically introduced, and the solid phase synthesis, liquid-phase synthesis, and gas-phase synthesis are classified and summarized. The application of high-entropy materials in electrocatalysis is summarized, and the promotion effect of high-entropy strategy in various catalytic reaction processes is summarized. Finally, the current progress of high-entropy materials, the problems encountered, and the future development direction are reviewed. It is emphasized that the strategy of high flux density functional theory calculation guiding high-entropy catalyst design will be of great significance to electrocatalysis.

Amorphous/crystalline NiFe LDH hierarchical nanostructure for large-current-density electrocatalytic water oxidation

Amorphous structure shows more catalytic active sites but poor conductivity towards oxygen evolution reaction (OER). Herein, we fabricated a novel three-dimensional (3D) self-supported NiFe layered double hydroxides (LDH) catalytic material with amorphous/ crystalline interface, aiming to obtain both excellent catalytic activity and conductivity. This homogeneous hierarchical structure exhibits a high catalytic activity and robustness, giving the industrially required current density of 1000 mA cm−2 at an ultralow overpotential of 359.8 mV with 240-hour stability in 1 M KOH. In-situ electrochemical tests reveal that the amorphous/crystalline interface boosts the intermediates evolution and OER kinetics, which might be ascribed to considerable active sites and fast charge transfer. Moreover, the 3D structure has unique superhydrophilicity and superaerophobicity, which can further accelerate the electrolyte penetration, facilitate the bubbles desorption from the electrode, enhance mass transport, and thus improve OER performance at large current densities. This work provides a feasible way to develop high-performance electrocatalytic material via constructing homogeneous amorphous/crystalline interface.

MOFs-derived CoMn-layered double hydroxide array anchored to Ti3C2Tx MXene nanosheets as efficent catalysts for rechargeable lithium-oxygen batteries

Rechargeable lithium-oxygen batteries (LOBs) are acknowledged as potential candidates for advanced energy storage devices as a result of their considerable theoretical energy densities. Nevertheless, they encounter significant challenges throughout discharging and recharging phases, including the difficult decomposition of Li2O2 products, sluggish reaction kinetics, and limited cycle stability. In this study, an efficient catalyst was synthesized by in situ growth of metal–organic frameworks (MOFs)-derived cobalt manganese layered double hydroxide (CoMn-LDH) array on Ti3C2Tx MXene nanosheets (CoMn-LDH@Ti3C2Tx). The LOBs with CoMn-LDH@Ti3C2Tx cathode demonstrated high discharge specific capacity of 27.61 Ah g−1 at 100 mA g−1 and an extended cycle stability of over 224 cycles at 500 mA g−1. Density functional theory (DFT) computations showed that CoMn-LDH@Ti3C2Tx facilitates electron redistribution, optimising the adsorption energy of intermediates, thereby lowering the energy barriers for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). Consequently, this work presents a multi-level nanostructured catalyst preparation strategy derived from MOFs, offering new insights for the fabrication of efficient electrocatalytic materials.

Electrocatalysis in Solid Oxide Fuel Cells and Electrolyzers.

Interest in energy-to-X and X-to-energy (where X represents green hydrogen, carbon-based fuels, or ammonia) technologies has expanded the field of electrochemical conversion and storage. Solid oxide electrochemical cells (SOCs) are among the most promising technologies for these processes. Their unmatched conversion efficiencies result from favorable thermodynamics and kinetics at elevated operating temperatures (400-900 °C). These solid-state electrochemical systems exhibit flexibility in reversible operation between fuel cell and electrolysis modes and can efficiently utilize a variety of fuels. However, electrocatalytic materials at SOC electrodes remain nonoptimal for facilitating reversible operation and fuel flexibility. In this Review, we explore the diverse range of electrocatalytic materials utilized in oxygen-ion-conducting SOCs (O-SOCs) and proton-conducting SOCs (H-SOCs). We examine their electrochemical activity as a function of composition and structure across different electrochemical reactions to highlight characteristics that lead to optimal catalytic performance. Catalyst deactivation mechanisms under different operating conditions are discussed to assess the bottlenecks in performance. We conclude by providing guidelines for evaluating the electrochemical performance of electrode catalysts in SOCs and for designing effective catalysts to achieve flexibility in fuel usage and mode of operation.

High Entropy Spinel Oxide (AlCrCoNiFe2)O as Highly Active Oxygen Evolution Reaction Catalysts.

The advancement of water electrolyzer technologies and the production of sustainable hydrogen fuel heavily rely on the development of efficient and cost-effective electrocatalysts for the oxygen evolution reaction (OER). High entropy ceramics, characterized by their unique properties, such as lattice distortion and high configurational entropy, hold significant promise for catalytic applications. In this study, we utilized the sol-gel autocombustion method to synthesize high entropy ceramics containing a combination of 3d transition metals and aluminum ((AlCrCoNiFe2)O). We then compared their electrocatalytic performance with other series of synthesized multimetal and monometallic oxides for the OER under alkaline conditions. Our electrochemical analysis revealed that the high entropy ceramics exhibited excellent performance and the lowest charge transfer resistance, Tafel slope (29 mV·dec-1), and overpotential (η10 = 230 mV). These remarkable results can be primarily attributed to the high entropy effect induced by the addition of Al, Cr, Co, Ni, and Fe, which introduces increased disorder and complexity into the material's structure. This, in turn, facilitates more efficient OER catalysis by providing diverse active sites and promoting optimal electronic configurations for the reaction. Furthermore, the strong electronic interactions among the constituent elements in the metallic spinels further enhance their catalytic activity in the initiation of the OER process. Combined with the reduced charge transfer resistance, these factors collectively play pivotal roles in enhancing the OER performance of the electrocatalysts. Overall, our study provides valuable insights into the design and development of high-performance electrocatalysts for sustainable energy applications. By harnessing the high entropy effect and leveraging strong electronic interactions, electrocatalytic materials can be tailored to improve efficiency and stability, thus advancing the progress of clean energy technologies.

Enhanced catalytic performance of M-doped SnS2 (M: Ni, Cu, Fe, and Co) and graphene nanocomposite for oxygen reduction reaction in alkaline media

In this study, the electrocatalytic behavior of tin sulfide doped with various metallic elements (copper, cobalt, nickel, and iron) for the oxygen reduction reaction was investigated. Our findings reveal cobalt as the most effective dopant in enhancing ORR efficiency. The graphene nanosheets were introduced to form a G/Co-SnS2 nanocomposite, which significantly improved ORR performance, surpassing Pt/C in current density. Our findings underscore the positive impact of chemical doping and the synergistic effect of SnS2 with graphene nanosheets, improving the onset potential and facilitating the ORR. Through comprehensive characterization including XRD, XPS, FESEM, and BET analysis, the structural and surface properties of the materials were evaluated. Employing the Rotating Disk Electrode technique, we observed that G/Co-SnS2 exhibited a superior onset potential of 0.88 V vs. RHE and high current density of 6.12 mA cm−2, indicating enhanced ORR facilitation. Furthermore, Electrochemical Impedance Spectroscopy revealed lower resistance in the G/Co-SnS2 nanocomposite compared to other samples, highlighting its enhanced durability. Additionally, G/Co-SnS2 nanocomposite demonstrated significantly enhanced durability in comparison to the costly Pt/C catalyst, further underscoring its potential as a robust alternative for catalyzing the oxygen reduction reaction. These comprehensive characterizations provide insights into the enhanced electrocatalytic performance observed. Overall, this study highlights the promising potential of Co-doped SnS2 in combination with graphene nanosheets for efficient oxygen reduction reactions, opening avenues for advanced electrocatalytic materials in energy applications.

Accelerated Conversion of Polysulfides for Ultra Long-Cycleof Li-S Batteryat High-Rateover Cooperative Cathode Electrocatalystof Ni0.261Co0.739S2/N-Doped CNTs.

Despite the very high theoretical energy density, Li-S batteries still need to fundamentally overcome the sluggish redox kinetics of lithium polysulfides (LiPSs) and low sulfur utilization that limit the practical applications. Here, highly active and stable cathode, nitrogen-doped porous carbon nanotubes (NPCTs) decorated with NixCo1-xS2 nanocrystals are systematically synthesized as multi-functional electrocatalytic materials. The nitrogen-doped carbon matrix can contribute to the adsorption of LiPSs on heteroatom active sites with buffering space. Also, both experimental and computation-based theoretical analyses validate the electrocatalytic principles of co-operational facilitated redox reaction dominated by covalent-site-dependent mechanism; the favorable adsorption-interaction and electrocatalytic conversion of LiPSs take place subsequently by weakening sulfur-bond strength on the catalytic NiOh 2+-S-CoOh 2+ backbones via octahedral TM-S (TM = Ni, Co) covalency-relationship, demonstrating that fine tuning of CoOh 2+ sites by NiOh 2+ substitution effectively modulates the binding energies of LiPSs on the NixCo1-xS2@NPCTs surface. Noteworthy, the Ni0.261Co0.739S2@NPCTs catalyst shows great cyclic stability with a capacity of up to 511 mAh g-1 and only 0.055% decay per cycle at 5.0 C during 1000 cycles together with a high areal capacity of 2.20 mAh cm-2 under 4.61mg cm-2 sulfur loading even after 200 cycles at 0.2 C. This strategy highlights a new perspective for achieving high-energy-density Li-S batteries.

Cyanogel-Induced Facile Synthesis of Palladium Hydride for Electrocatalytic Oxygen Reduction.

Palladium hydride (PdHx) is one of the well-known electrocatalytic materials, yet its synthesis is still a challenge through an energy-efficient and straightforward method. Herein, we propose a new and facile cyanogel-assisted synthesis strategy for the preparation of PdH0.649 at a mild environment with NaBH4 as the hydrogen source. Unlike traditional inorganic Pd precursors, the unique Pd-CN-Pd bridge in Pdx[Pd(CN)4]y ⋅ aH2O cyanogel offers more favourable spatial sites for insertion of H atoms. The characteristic three-dimensional backbone of cyanogel also acts as a support scaffold resulting in the interconnected network structure of PdH0.649. Due to the incorporation of H atoms and interconnected network structure, the PdH0.649 achieves a high half-wave potential of 0.932 V, a high onset potential of 1.062 V, and a low activation energy, as well as a long-term lifetime for oxygen reduction reaction. Theoretical calculation demonstrates a downshift of the d-band centre of Pd in PdH0.649 owing to the dominant Pd-H incorporation that weakens the binding energies of the *OH intermediate species. Zn-air batteries (ZAB) based on PdH0.649 exhibits high power density, competitive open circuit voltage, and good stability, exceeding that of commercial Pt black. This work not only opens up a new avenue for the development of high-efficiency Pt-free catalysts but also provides an original approach and insight into the synthesis of PdHx.

N, S, P tri-doped porous graphene electrocatalyst with excellent oxygen reduction activity for zinc-air battery

The heteroatom-doped graphene has attracted a lot of research due to its excellent physical, chemical and electrochemical properties considered to be the most promising electrocatalytic material for oxygen reduction reaction (ORR). Multi-doping can exert the synergistic effect between different doped heteroatoms and effectively improve the catalytic activity of doped graphene catalysts. N, P, S tri-doped graphene catalysts were prepared by simple and convenient hydrothermal and high-temperature treatment. The experimental results show that different phosphorus sources have a significant impact on the structure and performance of the prepared catalyst materials. The NSP-Gr-1 catalyst shows the high onset potential (1.035 V), half-wave potential (0.79 V) and limiting current density (−5.33 mA cm−2) for ORR. The power density of the zinc-air battery assembled with the NSP-Gr-1 catalyst achieves 163.1 mW cm−2 at 186.7 mA cm−2, which is much higher than the maximum power density of 140.0 mW cm−2 at 190 mA cm−2 for commercial Pt/C. The discharge stability under different current densities is outstanding.

In situ semi-etching of bimetallic LDH nanosheet arrays into FeNi-LDH/MOF to boost oxygen evolution reaction

The inherent sluggish kinetics of water oxidation is the core issue for electrochemical hydrogen production from water splitting. Metal organic frameworks (MOFs) with tunable porous structures, abundant coordination metal centers and large specific surface area are expected as efficient electrocatalysts. In this paper, FeNi-LDH/MOF composite nanostructures were successfully constructed on carbon cloth (CC) through partially converting iron-nickel layered double hydroxide (FeNi-LDH) into FeNi-MOF (NiFe(CN)5NO) by an in-situ semi-etching method. The MOF nanocrystals in this material are in-situ decorated on the surface of FeNi-LDH nanosheets, providing abundant open active sites and mass transfer channels for electrocatalysis. Thanks to the synergistic effect of the LDH and MOF, as well as the exceptional hierarchical architecture, the FeNi-LDH/MOF/CC as a self-supported electrode exhibits distinguished electrocatalytic OER performance, with a low overpotential of 263 mV@100 mA cm−2 and a small Tafel slope of 50.2 mV dec-1 in 1.0 M KOH. In addition, the catalyst exhibits good durability with almost constant current density during 24 h OER test. This work provides an effective way to design high-performance MOFs-based composite electrocatalytic materials.

Hydrothermal synthesis of high-performance cobalt phosphate nanorod architecture as bifunctional electrocatalysts for rechargeable Zn-air batteries and supercapatteries

Transition metal phosphate bifunctional electrocatalysts demonstrate superior oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and capacitive properties owing to their high electrocatalytic and conductive activities. In this report, cobalt phosphate (Co3P2O8) nanorod (NR) electrocatalytic materials were developed via a facile one-step hydrothermal synthesis, followed by an annealing process. The unique NR structures offer superior electrocatalytic activities, continuous and quick electron transport pathways, short ion diffusion lengths, and rich active sites toward rechargeable zinc-air batteries (ZABs) and supercapatteries (SCs). The self-assembled Co3P2O8 NR electrocatalyst revealed higher current density values during the OER and ORR measurements than the commercially available Pt/C and IrO2 materials. The Co3P2O8 NR electrocatalyst exhibited an excellent OER overpotential of 180 mV. The electocatalyst also showed superior onset and half-wave potentials of 0.92 V and 0.80 V, respectively. Moreover, the fabricated Co3P2O8 NRs-based ZAB exhibited better durability than the Pt/C-based ZAB. Significantly, the Co3P2O8 NR electrode demonstrated an excellent specific capacity of 373 mAh g−1 with outstanding cycling stability of 99% after 5000 cycles. Additionally, the fabricated Co3P2O8 NRs//activated carbon SC demonstrated high specific energy and power densities of 25.62 Wh kg−1 and 2953.12 W kg−1, respectively with remarkable cycling stability of 89% after 7000 cycles. Specifically, the practical applicability of the fabricated Co3P2O8 NRs-based ZAB and SC was tested using a blue light-emitting diode nameplate energized by two devices in series. Overall, the catalytic and energy-storage properties of the Co3P2O8 NR material can provide a new pathway for high-energy electrochemical applications.