Hydrogen Evolution Research Articles

Interfacial Engineering of MoS2@CoS2 Heterostructure Electrocatalysts for Effective pH-Universal Hydrogen Evolution Reaction.

The practical utilization of the hydrogen evolution reaction (HER) necessitates the creation of electrocatalysts that are both efficient and abundant in earth elements, capable of operating effectively within a wide pH range. However, this objective continues to present itself as an arduous obstacle. In this research, we propose the incorporation of sulfur vacancies in a novel heterojunction formed by MoS2@CoS2, designed to exhibit remarkable catalytic performances. This efficacy is attributed to the advantageous combination of the low work function and space charge zone at the interface between MoS2 and CoS2 in the heterojunction. The MoS2@CoS2 heterojunction manifests outstanding hydrogen evolution activity over an extensive pH range. Remarkably, achieving a current density of 10 mA cm-2 in aqueous solutions 1.0 M KOH, 0.5 M H2SO4, and 1.0 M phosphate-buffered saline (PBS), respectively, requires only an overpotential of 48, 62, and 164 mV. The Tafel slopes for each case are 43, 32, and 62 mV dec-1, respectively. In this study, the synergistic effect of MoS2 and CoS2 is conducive to electron transfer, making the MoS2@CoS2 heterojunction show excellent electrocatalytic performance. The synergistic effects arising from the heterojunction and sulfur vacancy not only contribute to the observed catalytic prowess but also provide a valuable model and reference for the exploration of other efficient electrocatalysts. This research marks a significant stride toward overcoming the challenges associated with developing electrocatalysts for practical hydrogen evolution applications.

Graphite sheet-supported bimetallic RhNi thin film alloys for enhanced and durable hydrogen evolution in acidic environments

Noble metal-based materials are excellent catalysts for hydrogen production from water electrolysis, but their high cost and limited availability hinder widespread use. However, precious metals can be effectively utilized in catalysts by forming alloys with low-cost 3d transition metals, thereby reducing the need for precious metals, while enhancing the performance. In this study, aerosol-assisted chemical vapor deposition was employed to deposit bimetallic rhodium-nickel (RhNi) alloy thin films on a graphite sheet for hydrogen evolution reaction (HER) catalysis in a 0.5 M H2SO4 solution. Thin-film morphological patterns were significantly changed as the deposition time varied from 45 to 135 min. The RhNi alloy fabricated for 90 min outperformed its counterparts, displaying lower overpotential of 40 and 197 mV at 10 and 1000 mA cm−2, small Tafel kinetics (54 mV dec−1), high conductivity (0.57 Ω) and large electrochemical surface area (3312 cm2), and extended stability (48 h) compared to pure Rh metal and other reported catalysts. The superior HER performance arises from the synergistic effects between Rh and Ni metals, coupled with a uniform layer of spherical particles that enhance conductive properties and reaction rates by providing maximized active sites on graphite surface. This work provides valuable guidelines for efficiently preparing highly active and durable thin-film electrocatalyst within short time span and applying directly in fuel cell for hydrogen production.

Surface cyano groups optimize the charge transfer of poly heptazine imide for enhanced photocatalytic H2 evolution

Surface functionalization has been considered as an effective strategy to manipulate charge separation of carbon nitride and therefore to largely improve the photocatalytic H2 evolution efficiency. Poly heptazine imide (PHI) is a new class of crystalline carbon nitride frameworks that exhibits remarkable photocatalytic performance for hydrogen evolution. To further improve the H2 evolution performance of PHI and explore the reaction mechanism, ammonium thiocyanate was used as a precursor for the synthesis of poly heptazine imide at elevated temperatures under molten salt conditions. The optimized PHI with an abundance of surface cyano groups shows a significantly enhanced photocatalytic performance for H2 evolution, which is 4.3 times that on pristine PCN. Most importantly, the surface cyano group adjusts the electron intensity of the polymeric framework, enhances the light absorbance, reduces the bandgap, and improves the charge separation efficiency. The synthetic technique also could be applied to other sulfur-containing precursors for the synthesis of PHI frameworks with excellent hydrogen evolution production performance.

Two-step fabrication of hierarchical Ni(OH)2@NiCo2O4 core-shell nanoneedle array for highly efficient decoupled water splitting

The temporal and spatial segregation of the hydrogen and oxygen evolution reactions (HER and OER) are essential for advancing membrane-free electrolysis technology in H2 production through water splitting. This investigation employed a two-step fabrication approach to craft a three-dimensional self-supporting buffered electrode. This method involved utilizing a Ni(OH)2@NiCo2O4 core-shell nanoneedle array as the active material and nickel foam (NF) as the substrate. Remarkably, the H2 production at the cathode displayed remarkable efficiency, maintaining an uninterrupted operation duration of 1500 s at a current of 100 mA. Simultaneously, the Ni(OH)2@NiCo2O4 mediator on the anodic electrode underwent oxidation during this process, leading to the generation of its respective oxidized state, accompanied by a noteworthy operating voltage of 1.50 V. Afterwards, the second step of the OER involved the recovery of the buffered electrode and the generation of O2 at an operational voltage of 0.46 V, with the O2-production duration being equivalent to that of the first step in the HER process. Interestingly, the revival process of the buffered electrode in the second step can also be coupled with zinc sheets, thereby constructing a battery. During the discharge process of the battery, the regeneration of the buffered electrode was achieved, and this discharge process could also provide a power supply for the first step of H2-evolution. Therefore, this decoupled water electrolysis system presents a promising avenue for facilitating the effective transformation of renewable sources into hydrogen.

Surface-Grafted Single-Atomic Pt-Nx Complex with a Precisely Regulating Coordination Sphere for Efficient Electron Acceptor-Inducing Interfacial Electron Transfer.

Based on the electron-withdrawing effect of the Pt(bpy)Cl2 molecule, a simple post-modification amide reaction was firstly used to graft it onto the surface of NH2-MIL-125, which formed a highly efficient electron acceptor that induced the conversion of the photoinduced charge migration pathway from internal BDC→TiOx migration to external BDC→PtNx migration, significantly improving the efficiency of photoinduced electron transfer and separation. Furthermore, precise control over the first coordination sphere of Pt single atoms was achieved using further post-modification with additional bipyridine to investigate the effect of Pt-Nx coordination numbers on reaction activity. The as-synthesized NML-PtN2 exhibited superior photocatalytic hydrogen evolution activity of 7.608 mmol g-1 h-1, a remarkable improvement of 225 and 2.26 times compared to pristine NH2-MIL-125 and NML-PtN4, respectively. In addition, the superior apparent quantum yield of 4.01% (390 nm) and turnover frequency of 190.3 h-1 (0.78 wt% Pt SA; 129 times compared to Pt nanoparticles/NML) revealed the high solar utilization efficiency and hydrogen evolution activity of the material. And macroscopic color changes caused by the transition of carrier migration paths was first observed. It holds profound significance for the design of MOF-Molecule catalysts with efficient charge carrier separation and precise regulation of single-atom coordination sphere.

Self-assembly of NiFe-LDH@Ni3S2 sub-nanosheets catalyst for overall water splitting

The development of water splitting catalysts for generating high-purity hydrogen in large-scale is still facing challenges in terms of improving efficiency and stability. Herein, Ni3S2-coated NiFe layered double hydroxides sub-nanosheets with a hierarchical heterostructure (NiFe-LDH@Ni3S2) were prepared on nickel foam (NF) by a strategy of continuous hydrothermal synthesis. The introduction of S2− broke the hydrogen bonds between NiFe-LDH layers and separated into sub-nanosheets with a thickness of only about 1 nm, which enlarged the active areas of NiFe-LDH@Ni3S2/NF by a factor of 5.7. The coexisting charge channels Ni-O-Ni and Ni-S-Ni in the material enhanced the electrochemical activity, resulting in the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) overpotentials as low as 179 mV and 116 mV at 10 mA cm−2 in 1.0 M KOH. Moreover, after a 50-hour chronopotentiometry test at 50 mA cm−2, the overpotential for OER and HER decreased only 0.013 V and 0.059 V, respectively. Furthermore, under the conditions of simulating industrial hydrogen production with an electrolyte of 6.0 M KOH and a temperature of 75 °C, after a 140-hour test for durability, the current density decreased only 0.75% at the cell voltage of 1.70 V.

Defective Tungsten Oxides with Stacking Faults for Proton Exchange Membrane Green-Hydrogen Generation.

Defects can introduce atomic structural modulation and tailor performance of materials. Herein, it demonstrates that semiconductor WO3 with inert electrocatalytic behavior can be activated through defect-induced tensile strains. Structural characterizations reveal that when simply treated in Ar/H2 atmosphere, oxygen vacancies will generate in WO3 and cause defective structures. Stacking faults are found in defects, thus modulating electronic structure and transforming electrocatalytic-inert WO3 into highly active electrocatalysts. Density functional theory (DFT) calculations are performed to calculate *H adsorption energies on various WOx surfaces, revealing the oxygen vacancy composition and strain predicted to optimize the catalytic activity of hydrogen evolution reaction (HER). Such defective tungsten oxides can be integrated into commercial proton exchange membrane (PEM) electrolyser with comparable performance toward Pt-based PEM. This work demonstrates defective metal oxides as promising non-noble metal catalysts for commercial PEM green-hydrogen generation.

The Bell-Evans-Polanyi relation for hydrogen evolution reaction from first-principles

The versatile Bell-Evans-Polanyi (BEP) relation stipulates the kinetics of a reaction in terms of thermodynamics. Herein, we establish the BEP relation for the hydrogen evolution reaction (HER) from fundamental electrochemical principles leveraging the Butler-Volmer relation for a one-step, one-electron process and the transition state theory. Based on first-principles investigations of HER mechanisms on fourteen metal electrodes, we firmly justify the BEP relation solely using an easy-to compute hydrogen adsorption free energy and universal electrochemical constants.

High yield electrosynthesis of oxygenates from CO using a relay Cu-Ag co-catalyst system

As a sustainable alternative to fossil fuel-based manufacture of bulk oxygenates, electrochemical synthesis using CO and H2O as raw materials at ambient conditions offers immense appeal. However, the upscaling of the electrosynthesis of oxygenates encounters kinetic bottlenecks arising from the competing hydrogen evolution reaction with the selective production of ethylene. Herein, a catalytic relay system that can perform in tandem CO capture, activation, intermediate transfer and enrichment on a Cu-Ag composite catalyst is used for attaining high yield CO-to-oxygenates electrosynthesis at high current densities. The composite catalyst Cu/30Ag (molar ratio of Cu to Ag is 7:3) enables high efficiency CO-to-oxygenates conversion, attaining a maximum partial current density for oxygenates of 800 mA cm−2 at an applied current density of 1200 mA cm−2, and with 67 % selectivity. The ability to finely control the production of ethylene and oxygenates highlights the principle of efficient catalyst design based on the relay mechanism.

Surface‐Grafted Single‐Atomic Pt‐Nx Complex with a Precisely Regulating Coordination Sphere for Efficient Electron Acceptor‐Inducing Interfacial Electron Transfer

Based on the electron‐withdrawing effect of the Pt(bpy)Cl2 molecule, a simple post‐modification amide reaction was firstly used to graft it onto the surface of NH2‐MIL‐125, which formed a highly efficient electron acceptor that induced the conversion of the photoinduced charge migration pathway from internal BDC→TiOx migration to external BDC→PtNx migration, significantly improving the efficiency of photoinduced electron transfer and separation. Furthermore, precise control over the first coordination sphere of Pt single atoms was achieved using further post‐modification with additional bipyridine to investigate the effect of Pt‐Nx coordination numbers on reaction activity. The as‐synthesized NML‐PtN2 exhibited superior photocatalytic hydrogen evolution activity of 7.608 mmol g−1 h−1, a remarkable improvement of 225 and 2.26 times compared to pristine NH2‐MIL‐125 and NML‐PtN4, respectively. In addition, the superior apparent quantum yield of 4.01% (390 nm) and turnover frequency of 190.3 h−1 (0.78 wt% Pt SA; 129 times compared to Pt nanoparticles/NML) revealed the high solar utilization efficiency and hydrogen evolution activity of the material. And macroscopic color changes caused by the transition of carrier migration paths was first observed. It holds profound significance for the design of MOF‐Molecule catalysts with efficient charge carrier separation and precise regulation of single‐atom coordination sphere.

Understanding the Activation Mechanism of RhCrOx Cocatalysts for Hydrogen Evolution with Nanoparticulate Electrodes.

Mixed oxides of Rh-Cr (RhCrOx), containing Rh3+ and Cr3+ cations, are commonly used as cocatalysts for the hydrogen evolution reaction (HER) on particulate photocatalysts. The precise physicochemical mechanisms of the HER at the catalytic sites of these oxides are not well understood. In this study, model cocatalyst electrodes, composed of nanoparticulate RhCrOx, were fabricated to investigate the physicochemical mechanisms of the HER. Electroanalytical and X-ray photoelectron spectroscopic measurements revealed that nanoparticulate RhCrOx produces reduced Rh (Rh0) species by maintaining an electrode potential more negative than 0.03 V versus the reversible hydrogen electrode (VRHE). This results in significant enhancement of the HER activity. The catalytic activity for the HER stems from the reduced Rh species, and the inclusion of Cr3+ (CrOx) aided in the electron transfer process at the solid/liquid interface, resulting in a higher current density during the HER. To achieve a solar-to-hydrogen efficiency of over 3%, the conduction band minimum of the particulate photocatalyst should be positioned more negatively than -0.10 VRHE. Moreover, the formation of electron trap states at potentials more positive than 0.03 VRHE should be avoided. This study highlights the importance of understanding the catalytic sites on metal oxide cocatalysts. Moreover, it offers a design strategy for enhancing the efficiency of photocatalytic water splitting.

Air-Stable and Low-Cost High-Voltage Hydrated Eutectic Electrolyte for High-Performance Aqueous Aluminum-Ion Rechargeable Battery with Wide-Temperature Range.

Aqueous aluminum-ion batteries (AAIBs) are considered as a promising alternative to lithium-ion batteries due to their large theoretical capacity, high safety, and low cost. However, the uneven deposition, hydrogen evolution reaction (HER), and corrosion during cycling impede the development of AAIBs, especially under a harsh environment. Here, a hydrated eutectic electrolyte (AATH40) composed of Al(OTf)3, acetonitrile (AN), triethyl phosphate (TEP), and H2O was designed to improve the electrochemical performance of AAIBs in a wide temperature range. The combination of molecular dynamics simulations and spectroscopy analysis reveals that AATH40 has a less-water-solvated structure [Al(AN)2(TEP)(OTf)2(H2O)]3+, which effectively inhibits side reactions, decreases the freezing point, and extends the electrochemical window of the electrolyte. Furthermore, the formation of a solid electrolyte interface, which effectively inhibits HER and corrosion, has been demonstrated by X-ray photoelectron spectroscopy, X-ray diffraction tests, and in situ differential electrochemical mass spectrometry. Additionally, operando synchrotron Fourier transform infrared spectroscopy and electrochemical quartz crystal microbalance with dissipation monitoring reveal a three-electron storage mechanism for the Al//polyaniline full cells. Consequently, AAIBs with this electrolyte exhibit improved cycling stability within the temperature range of -10-50 °C. This present study introduces a promising methodology for designing electrolytes suitable for low-cost, safe, and stable AAIBs over a wide temperature range.

Integrated Heterogeneous Engineering with the Vacancy Defect of Porous CoPv-MoxPv Nanosheets for an Accelerated Hydrogen Evolution Reaction.

Electrochemical water splitting is a possible way of realizing sustainable and clean hydrogen production but is challenging, because a highly active and durable electrocatalyst is essential. In this work, we integrated heterogeneous engineering and vacancy defect strategies to design and fabricate a heterostructure electrocatalyst (CoPv-MoxPv/CNT) with abundant phosphorus vacancies attached to carbon nanotubes (CNTs). The vacancy defects enabled the optimization of the electronic structure; thereby, the electron-rich low-valent metal sites enhanced the ability of nonmetallic P to capture proton H. Meanwhile, the heterogeneous interface between bimetallic phosphides and CNTs realized rapid electron transfer. In addition, the Co, Mo, and P active species in the electrocatalytic process exposed increased amounts of active sites featuring porous nanosheet structures, which facilitated the adsorption of reaction intermediates and thus enhanced the hydrogen evolution reaction performance. In particular, the optimized CoPv-MoxPv/CNT catalyst possesses an overpotential of 138 mV at a current density of 10 mA cm-2 and long-term stability for 24 h. This work offers insights and possibilities for the engineering and exploration of transition metal-based electrocatalysts through combining multiple synergistic strategies.

Analyzing the Active Site and Predicting the Overall Activity of Alloy Catalysts.

As one of the potential catalysts, disordered solid solution alloys can offer a wealth of catalytic sites. However, accurately evaluating their activity localization structure and overall activity from each individual site remains a formidable challenge. Herein, an approach based on density functional theory and machine learning was used to obtain a large number of sites of the Pt-Ru alloy as the model multisite catalyst for the hydrogen evolution reaction. Subsequently, a series of statistical approaches were employed to unveil the relationship between the geometric structure and overall activity. Based on the radial frequency distribution of metal elements and the distribution of ΔGH, we have identified the surface and subsurface sites occupied by Pt and Ru, respectively, as the most active sites. Particularly, the concept of equivalent site ratio predicts that the overall activity is highest when the Ru content is 20-30%. Furthermore, a series of Pt-Ru alloys were synthesized to validate the proposed theory. This provides crucial insights into understanding the origin of catalytic activity in alloys and thus will better guide the rational development of targeted multisite catalysts.

Ethylene Glycol Co‐Solvent Enables Stable Aqueous Ammonium‐Ion Batteries with Diluted Electrolyte

AbstractAqueous ammonium‐ion batteries (AAIBs) are considered as one of the most promising technologies for large scale energy storage applications, due to their intrinsic safety, environmental friendliness and low cost. Nevertheless, the practical application of AAIBs is impeded by hydrogen evolution reaction (HER) occurring in diluted aqueous electrolyte. Highly concentrated electrolytes can improve electrochemical stability but lead to higher costs and increased hydrolysis of NH4+. In this work ethylene glycol (EG) is proposed as co‐solvent, which can act as H‐bond modulating agent, to increase the stability of AAIBs with diluted electrolytes. The perturbation of water H‐bond network regulated by EG is proved by spectroscopic methods, while the suppressed HER is confirmed by differential electrochemical mass spectrometry (DEMS) results. As a result, full cells with 3,4,9,10‐perylenebis(dicarboximide) (PTCDI) anode and FeFe(CN)6 (FeHCF) cathode and EG‐added electrolyte exhibit stable cycling performance with capacity retention of 77% after 1950 cycles.

Size engineering of porous CuWO4–CuO heterojunction for enhanced hydrogen evolution in alkaline media

Constructing electrocatalysts with heterogeneous interfaces is of great significance for improving the performance of electrocatalytic hydrogen production. In this work, CuWO4·2H2O–CuO (P-CWOC) was synthesized by hydrothermal method, and spherical porous CuWO4–CuO (CWOC) was obtained through annealing treatment. The size of CuWO4–CuO can be controlled from 72 to 221 nm by regulating the supersaturation of the solution. Among them, CuWO4–CuO with a particle size of 72 nm (CWOC-72) possesses the most oxygen vacancies and the largest specific surface area. The W atom in the heterostructure of CuWO4 and CuO can affect the electronic structure of Cu atoms, and the presence of oxygen vacancies is beneficial for increasing the surface oxygen affinity of the composite material. Benefitting from the largest number of oxygen vacancies and the largest specific surface area, the CWOC-72 own the best catalytic performance compared to the other four catalysts. The overpotential at a current density of 10 mA cm−2 is 121 mV, and the Tafel slope is 70 mV·dec−1. Its excellent stability was confirmed by chronoamperometry, in-situ XRD, and in-situ Raman spectroscopy, and its alkaline HER performance is superior to most CuO-based catalysts.

Effects of Intrinsic Defects in Pt-Based Carbon Supports on Alkaline Hydrogen Evolution Reaction.

Carbon material has widely been utilized in the synthesis of efficient carbon-supported Pt (Pt/C) catalysts, in which the structural properties greatly influence the electrocatalytic performances of Pt/C catalysts. However, the effects of intrinsic defects in carbon supports on the performance of the alkaline hydrogen evolution reaction (HER) have not been systematically investigated. Herein, porous carbon supports with different degrees of intrinsic defects were prepared by a simple template-assisted strategy, and the resulting samples were systematically studied by various analytical methods. The results suggested that the presence of abundant intrinsic defects (vacancy and topological defects) in the carbon support was advantageous in terms of favoring the dispersion and anchoring of Pt species, promoting electron transfer between Pt atoms and the carbon support, and tuning the electronic states of Pt species. These features improved the HER performance of Pt/C catalysts. Compared to the nontemplate-assisted carbon-supported Pt catalyst (Pt/NTC) with an overpotential of 178 mV, the optimized template-assisted carbon-supported Pt catalyst (Pt/TC) exhibited a lower overpotential of 58 mV at 10 mA cm-2. Besides, the Pt/TC catalyst displayed better HER durability than the Pt/NTC catalyst owing to its strong metal-support interaction. The DFT calculations confirmed the important role played by intrinsic defects (vacancy and topological defects) in stabilizing Pt atoms, with Pt-C3 coordination identified as the most favorable structure for improving the HER performance of Pt. Overall, novel insights on the significant contribution of intrinsic defects in porous carbon supports on the HER performances of Pt/C catalysts were provided, useful for future design and fabrication of advanced carbon-supported catalysts or other carbon-based electrode materials.

Stabilizing Zn/electrolyte Interphasial Chemistry by a Sustained‐release Drug Inspired Indium‐chelated Resin Protective Layer for High‐areal‐capacity Zn//V2O5 Batteries

For zinc‐metal batteries, the instable chemistry at Zn/electrolyte interphasial region results in severe hydrogen evolution reaction (HER) and dendrite growth, significantly impairing Zn anode reversibility. Moreover, an often‐overlooked aspect is this instability can be further exacerbated by the interaction with dissolved cathode species in full batteries. Here, inspired by sustained‐release drug technology, an indium‐chelated resin protective layer (Chelex‐In), incorporating a sustained‐release mechanism for indium, is developed on Zn surface, stabilizing the anode/electrolyte interphase to ensure reversible Zn plating/stripping performance throughout the entire lifespan of Zn//V2O5 batteries. The sustained‐release indium onto Zn electrode promotes a persistent anticatalytic effect against HER and fosters uniform heterogeneous Zn nucleation. Meanwhile, on the electrolyte side, the residual resin matrix with immobilized iminodiacetates anions can also repel H2O and detrimental anions (SO42‐ and polyoxovanadate ions dissolved from V2O5 cathode) outside the electric double layer. This dual synergetic regulation on both electrode and electrolyte sides culminates a more stable interphasial environment, effectively enhancing Zn anode reversibility in practical high‐areal‐capacity full battery systems. Consequently, the bio‐inspired Chelex‐In protective layer enables an ultralong lifespan of Zn anode over 2800 h, which is also successfully demonstrated in ultrahigh areal capacity Zn//V2O5 full batteries (4.89 mAh cm‐2).

P-Block Antimony-Copper Single-Atom Alloys for Selective Nitrite Electroreduction to Ammonia.

Electrocatalytic reduction of NO2- to NH3 (NO2RR) offers an effective method for alleviating NO2- pollution and generating valuable NH3. Herein, a p-block single-atom alloy, namely, isolated Sb alloyed in a Cu substrate (Sb1Cu), is explored as a durable and high-current-density NO2RR catalyst. As revealed by the theoretical calculations and operando spectroscopic measurements, we demonstrate that Sb1 incorporation can not only hamper the competing hydrogen evolution reaction but also optimize the d-band center of Sb1Cu and intermediate adsorption energies to boost the protonation energetics of NO2--to-NH3 conversion. Consequently, Sb1Cu integrated in a flow cell achieves an outstanding NH3 yield rate of 2529.4 μmol h-1 cm-2 and FENH3 of 95.9% at a high current density of 424.2 mA cm-2, as well as a high durability for 100 h of electrolysis.

Environmentally benign synthesis and characterization of Bi2O3‐Sb2O3 nanocomposite: Investigation of its potential as electrode material in energy storage and generation applications

A shift to alternate energy sources is needed at the present time to address rising environmental concerns. The current research work aims to use a chemical‐free and green route to synthesize nanocomposite for their application as an electrode in the generation as well as storage of energy. Subsequently, the green synthesis of Bi2O3‐Sb2O3 nanocomposite was carried out using the leaf extract of Amaranthus viridis. The synthesized nanocomposite revealed a well‐arranged pattern of spherical nanoparticles with a crystal size of 29.43 nm and a band gap value of 2.5 eV. The hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) potentials of Bi2O3‐Sb2O3 were studied through linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS), whereas the energy storage studies were performed using cyclic voltammetry (CV) and galvanostatic charge discharge (GCD) techniques. The synthesized nanomaterial showed promising results for HER with an overpotential value of 205 mV as compared with OER, where an overpotential value of 450 mV was observed. However, excellent cyclic stability was witnessed for both reactions up to 1000 cycles. CV studies revealed an outstanding capacitance value of 348 F/g at a scan rate of 2 mV/s, whereas a specific capacitance of 269.5 F/g at a current density of 0.5 A/g was observed using GCD. The 15 h of electrode stability further endorsed the potential of synthesized material for energy‐based applications.