Oxygen Evolution Reaction Catalytic Performance Research Articles

Solution combustion synthesis of high-entropy metal spinel oxide as oxygen evolution reaction catalyst

High-entropy metal spinel oxide (HEO) is proved to be a promising oxygen evolution reaction (OER) catalyst with high catalytic performance and stability. A short routine synthesis process based on solution combustion synthesis was proposed to prepare (Co0.25Ni0.25Mn0.25Zn0.25)Fe2O4 spinel HEO in this work. During the process, the products were rapidly synthesized and melted due to the high-temperature reaction, and then quickly crystallized on the surface of nickel foam to form a nano-structure coating. With the aid of nano-scale spinel structure, the overpotential of non-activation HEO electrode reaches 276 mV at the current density of 10 mA·cm−2, and after 100 h i-t test, it can be further reduced to 230 mV, which proves the high activity of OER catalysis. The promotion of OER catalytic performance can be attributed to the surface reconstruction caused by the selective element leaching and the boost of oxygen vacancy, leading to the formation of nano-scale flocculation around spinel core after the long-term OER process. This work indicates a special casting process for functional materials and explores the application of rapid crystallization.

Evaluation of HER and OER electrocatalytic activity over RuO2–Fe2O3 nanocomposite deposited on HrGO nanosheets

Electrochemical water-splitting efficiency is determined by both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts. Therefore, designing a bi-functional configuration is essential for an efficient HER and OER catalytic performance under the same experimental conditions. In this study, a novel ionic pentanuclear complex of the type [Ru(dmbpy)3]3[Fe(CN)6]2, where dmbpy = 4,4′-dimethyl-2,2′-bipyridine, has been synthesized and characterized by structural (X-ray), analytical (CHN), and spectral (FT–IR, UV–Vis) methods. Highly reduced graphene oxide nanosheets (HrGO NSs) supported RuO2–Fe2O3 nanocomposite were prepared by an impregnation method using [Ru(dmbpy)3]3[Fe(CN)6]2 as a precursor and HrGO NSs as a support. The RuO2–Fe2O3/HrGO NSs nanocomposite was characterized by means of spectroscopy (XPS, FT–IR, and FT–Raman), surface area (BET/BJH), diffraction (XRD), thermal (TGA), and electron microscopy (TEM and FE–SEM) analyses. The electrocatalytic HER, OER, and overall water-splitting activities of RuO2–Fe2O3/HrGO NSs, RuO2–Fe2O3, RuO2/HrGO, Fe2O3/HrGO, and HrGO in 1 M KOH solution were studied. According to the overpotentials of −239 and 386 mV (vs. RHE) at 10 mA cm−2 current density, the exchange current densities of 0.0641 and 0.389 × 10−4 mA cm−2, the Tafel slopes of 97 and 67 mV dec−1, and the charge-transfer resistance values of 38.57 and 31.5 Ω for HER and OER, respectively, the RuO2–Fe2O3/HrGO NSs nanocomposite possesses bi-functional catalytic capabilities toward both hydrogen and oxygen evolution reactions. The catalytic performance is enhanced by the high surface area, the high number of catalytically active sites, the presence of nanoparticles with different morphologies, and the synergistic interaction between RuO2–Fe2O3 nanoparticles and HrGO nanosheets.

Engineering Ni(OH)x/(Ni, Cu)Se2 heterostructure nanosheet arrays for highly-efficient water oxidation

The development of efficient and inexpensive alkaline oxygen evolution reaction (OER) catalysts is crucial for electrochemical water splitting. Cu-doped NiSe2 has good electrical conductivity and OER activity, but (Ni, Cu)Se2 will dissolve a large amount of Se during the OER process and adsorb on the surface of the catalyst in the form of selenite, which seriously affects its OER stability. Here, heterostructure electrocatalysts composed of crystalline (Ni, Cu)Se2 and amorphous Ni(OH)x are designed. The Ni(OH)x/(Ni, Cu)Se2 exhibits an distinguished catalytic performance for OER, needing only an overpotential of 200 mV at the current density of 10 mA cm−2 with a Tafel slope of 62 mV dec−1 in 1 M KOH. Combining the experimental and theoretical results, electronic interactions at the coupled interface optimize the free energy of the oxygen-containing intermediate and weaken the Ni-*O bond, which leads to enhanced OER activity and stability. This work of amorphous core-shell interface engineering to improve OER activity and stability may provide a strategy for the rational design of advanced non-precious metal electrocatalysts.

Heterointerface engineered NiFe(OH)x/Ni3S2 electrocatalysts to overcome the scaling relationship for ultrahigh-current-density water oxidation

Breaking the scaling relationship of water oxidation is the gateway to obtain an ultrahigh current density at a low potential for greatly improving the water electrolysis efficiency in industrial hydrogen production. Herein, we demonstrate a novel heterointerface engineered NiFe(OH)x/Ni3S2 electrocatalyst to successfully circumvent the scaling relationship of the oxygen evolution reaction (OER), which significantly decreases the difference of the Gibbs free energy of HOO* and HO*(}ΔGhoo*–ΔGho*) from 3.20 to 2.38 eV. To achieve an ultrahigh current density of 2000 mA cm−2, the NiFe(OH)x/Ni3S2 electrocatalyst requires a small overpotential of 310 mV with an ultralow Tafel slope of 20.8 mV dec−1. It can also steadily operate under 1000 mA cm−2 for over 100 h with insignificant activity loss, thus surpassing the state-of-the-art OER catalysts to date. A parallel catalytic mechanism has been disclosed to be responsible for the optimization of the reaction pathway, thus realizing the homogenization of multi-intermediate adsorption energy with extremely elevated OER catalytic performance at ultrahigh current densities. These findings could be a guidance in developing industrial-grade high-performance electrocatalysts for water splitting.

Accelerated oxygen evolution kinetics on hematite by Zn2+ for boosting the photoelectrochemical water oxidation

The sluggish oxygen evolution reaction (OER) kinetics on hematite (α-Fe2O3) has constrained the photoelectrochemical (PEC) performance for water oxidation. Considering the regulatory effect of Zn for electrocatalytic OER, the Zn doped α-Fe2O3 nanowire is successfully prepared and served as the photoanode for PEC water oxidation. The results reveal the theoretical overpotential for the limiting step (from OH* to O*) is decreased by ca. 320 mV after Zn doing, which indicates an incredibly improved catalytic performance of OER. The Zn doped α-Fe2O3 displays PEC performance improvement over the bare α-Fe2O3, photocurrent density increases up to 0.88 mA/cm2(1.23 VRHE, 1 M NaOH), which shows a 44-fold increase than the α-Fe2O3. Meanwhile, the onset potential also shifts negatively by 300 mV, which also agrees well with the decreased OER overpotential. This work provides a deep understanding of the role of Zn in the α-Fe2O3 photoanodes and the strategy could be extended to other photoactive systems.

Ni3Fe nanoparticles encapsulated by N-doped carbon derived from MOFs for oxygen evolution reaction

It has been a hot research topic to look for inexpensive alternative oxygen evolution reaction (OER) catalysts to replace noble metal-based materials due to their scarcity. Transition metals are ideal candidates because of their high abundance, impressive activities, and easy accessibility. However, a facile method leading to improved performance and stability is still needed. Herein, a highly efficient carbon-encapsulated bimetal catalyst derived from Ni-based metal-organic-frameworks (MOF) was successfully prepared through the low-temperature (350 ℃) pyrolysis of Prussian blue analogue (PBA) precursors under H 2 /Ar atmosphere. Cube-structured PBA as template and precursor，parameters during the pyrolysis process including temperature and calcination atmosphere can be tuned to control the structure and properties of the catalysts. Benefiting from the porous three-dimensional (3D) cubic structure and abundant defect-rich amorphous N-doped carbon shell, Ni 3 Fe@NC-350 exhibits excellent OER activity. The as-prepared catalysts exhibited excellent catalytic performance for OER in 1.0 M KOH with an overpotential of 237 mV to achieve 10 mA cm −2 . More importantly, the presented catalyst has an extremely good durability. • A simple low-temperature annealing method was developed to produce alloy encapsulated with N-doping carbon. • The NiFe PBA was employed as nitrogen and carbon source. • The increased activity of OER is due to the synergy of Ni 3 Fe alloy and N-doped carbon layer. • Theoretical calculations revealed that the synergistic effect of NiFe alloy nanoparticles and N-doped carbon layer.

Tuning the Interface of Co1-xS/Co(OH)F by Atomic Replacement Strategy toward High-Performance Electrocatalytic Oxygen Evolution.

The construction of heterostructures is one of the most promising strategies for engineering interfaces of catalysts to perform high-efficiency oxygen evolution reaction (OER). However, accurately tuning heterostructures' interface during operation remains a challenge. Herein, we fabricated the needled-like heterostructure Co1-xS/Co(OH)F supported on flexible carbon fiber cloth via an atomic substitution strategy, in which sulfur atoms are simultaneously grafted into F vacancies after the partial removal of F atoms from Co(OH)F during the electrodeposition, thus achieving the growth of cobalt sulfide on the interface of Co(OH)F. This electrocatalyst with such design exhibits the following advantages: (1) The lattice distortion caused by atomic substitution leads to the increase of active sites; (2) Co1-xS constructed on the surface of Co(OH)F by the atomic replacement strategy optimizes the adsorption (OH-) and desorption (O2) energy in the OER process; (3) the needle-like structure possesses the tip-enhanced local electric field effect. As a result, the Co1-xS/Co(OH)F/CC catalyst exhibits very high OER catalytic performance with an overpotential of 269 mV at a current density of 10 mA cm-2 and a Tafel slope of 71 mV dec-1. The asymmetric electrode shows superior catalytic activity and stability in overall water splitting. The catalytic mechanism of these highly efficient Co1-xS/Co(OH)F/CC catalysts was investigated via DFT theoretical calculations and ex situ characterizations. This atomic substitution strategy displays universality for other transition metal sulfides (metal = Ni, Mn, Cu).

MnOx Film-Coated NiFe-LDH Nanosheets on Ni Foam as Selective Oxygen Evolution Electrocatalysts for Alkaline Seawater Oxidation.

Compared to freshwater electrolysis, seawater electrolysis to produce hydrogen is preferable and more promising, but this technology is plagued by the electrode's corrosion and oxidative reactions of the competitive Cl- ion on the anode. To develop efficient oxygen evolution reaction (OER) catalysts for seawater electrolysis, the ultrathin MnOx film-covered NiFe-layered double-hydroxide nanosheet array is directly assembled on Ni foam (MnOx/NiFe-LDH/NF) by hydrothermal and electrodeposition in turn. This catalyst demonstrates excellent OER-selective activity in alkaline saline electrolytes. In 1 M KOH/0.5 M NaCl and 1 M KOH/seawater electrolytes, MnOx/NiFe-LDH/NF exhibits lower overpotentials at 100 mA cm-2 (η100 values of 265 and 276 mV, respectively) and Tafel slopes (73 and 77 mV decade-1, respectively) than does the NiFe-LDH/NF electrode (η100 values of 298 and 327 mV and Tafel slopes of 91 and 140 mV decade-1, respectively). In alkaline saline solutions, the stability and durability of the former are also better than those of the latter. The good OER selectivity and catalytic performance are attributed to the MnOx overlayer that selectively blocks Cl- anions from approaching catalytic centers, and the good conductivity, fast kinetics, more oxygen vacancies, and abundant active sites of MnOx/NiFe-LDH/NF. The robust stability is due to the enhanced resistance for Cl- corrosion stemming from the MnOx protective film. Hence, MnOx/NiFe-LDH/NF can act as a promising OER electrocatalyst for alkalized natural seawater electrolysis.

Universal strategy of iron/cobalt-based materials for boosted electrocatalytic activity of water oxidation

Low-dimensional cobalt-based materials have proved to be one of the promising catalytic systems for oxygen-evolution reaction (OER). How to develop a facile and universal strategy for significantly improving their catalytic performance is of great significance, but still faces great challenges. Herein, a series of cobalt-based nanowires (CoS2, CoP, CoF2, and Co3O4) are synthesized and used as conceptual examples to explore the universality to enhance their OER catalytic activity. The FeOOH-modified cobalt-based electrocatalysts exhibit significantly improved OER catalytic performance compared to the pristine samples. Especially, the optimal CoS2@FeOOH material delivers the smallest overpotential of 260 mV at 100 mA cm−2, which outperforms most of the reported excellent materials. Notably, the CoP||CoP@FeOOH electrolyzer (1.63 V@30 mA cm−2) delivers higher performance than the CoS2||CoS2@FeOOH electrolyzer (1.72 V@30 mA cm−2) benefiting from the better HER catalytic activity of CoP. In addition, the post-characterizations confirm that the real catalytic structure of those electrocatalysts consists of a surface CoOOH@FeOOH catalytic layer and cobalt-based nanowire core. The Co-Fe catalytic layer provides more active centers for the adsorption and dissociation of water molecules as well as the formation of oxygen, while the nanowire core acts as an electron transport channel to realize better reaction kinetics. Our work not only develops a general strategy to enhance the catalytic activity but also provides new ideas for the facile design of other advanced catalytic materials.

Sr‐Doped Double Perovskite La2CoMnO6 to Promote the Oxygen Evolution Reaction Activity

AbstractDeveloping effective electrocatalysts for oxygen evolution reaction (OER) is crucial for exploring clean fuels. Owing to the flexible structure and unique 3d electron structure, perovskite has been considered as a promising candidate for OER electrocatalyst. Here, we report a range of A‐site partially substituted perovskite obtained via a facile sol‐gel method, La2‐xSrxCoMnO6 (x=0.2, 0.4, 0.6, 0.8, and 1.0, LSCMO‐x). LSCMO‐x has been proved to have better OER performances. Therein, LSCMO‐0.8 shows the best OER catalytic performance among these A‐site partially substituted perovskites. The OER overpotential of LSCMO‐0.8 catalyst is 0.39 V, which is reduced by 80 mV compared to parent perovskite La2CoMnO6 (LCMO, 0.47 V). The experimental studies have shown that LSCMO‐0.8 exhibits a higher content of oxygen vacancies compared with LCMO, which may be the factor for the enhanced OER activity. Meanwhile, it is revealed that Sr doped in the A site can efficiently optimize the eg orbit filling. This work manifests that doping Sr into perovskites appropriately is an effective strategy for the improvement of OER activity.

Constructing Ag modified NiCoSe2 hybrid nanosheet on 3D-nickel foam as a robust oxygen evolution reaction electrocatalyst

Transition metal selenides are promising oxygen evolution reaction (OER) catalysts, and element doping is a strategy to further enhance their catalytic performance. However, the choice of doping elements and methods needs further study. In this work for cobalt selenide, Ni is has been selected for isomorphic doping to NiCoSe2 with silver doped in bulk to obtain Ag–NiCoSe2 nanosheet on NF. The addition of nickel can form a eutectic phase with cobalt to obtain an effective synergistic catalytic effect. The addition of Ag can regulate the adsorption energy of the active site and conductivity. The as-prepared Ag–NiCoSe2/NF has good catalytic performance for OER, and a current density of 100 mA cm−2 can be achieved with only 270 mV. Its catalytic ability is far superior to that of non-Ag-doped NiCoSe2, which is due to the fact that the sheet structure provides more active sites, and the metal doping modulates the electronic configuration, which effectively improves the intrinsic activity. Moreover, Ag–NiCoSe2/NF can maintain a long-term high-efficiency catalytic process for more than 20 h at a current density of 100 mA cm−2. Therefore, this work proves that metal doping is of great significance for improving the catalytic activity of transition metal selenides.

Construction of amorphous CoFeOx(OH)y/MoS2/CP electrode for superior OER performance

Design and direct construction of oxygen evolution reaction (OER) catalyst-based electrode is an efficient route to improve the water splitting reaction. Herein, we proposed a facile route to synthesize and load the composite of amorphous CoFe oxyhydroxide (CoFeOx(OH)y) and MoS2 on the carbon paper by combining a hydrothermal and an electrodeposition process. CoFeOx(OH)y has a special feature of long-range disorder (amorphous phase) and short-range order (crystal phase), which greatly improves the OER catalytic performance of the hybrids. In virtue of the synergistic effect of CoFeOx(OH)y and MoS2, an improved electronic coupling effect occurs, which increases the oxidation state of Co and Fe, and thus enhances OER activity. As-synthesized CoFeOx(OH)y/MoS2/CP (CFOMS/CP) electrode affords excellent electrocatalytic activity and good electrochemical OER stability: A small Tafel slope of 37.9 mV dec−1 (vs. 62.1 mV dec−1 for CoFeOx(OH)y/CP, 120.2 mV dec−1 for RuO2/CP) and low overpotential 242 mV at 10 mA cm−2 (vs. 263 mV for CoFeOx(OH)y/CP, 317 mV for RuO2/CP), as well as a stable running for 25 h.

Effective Controlling of Ni3S2/MoS2 Porous Hollow Spheres on Ni Foam by Non‐ionic Surfactant Micelles for Oxygen Evolution Reaction

AbstractThe hollow sphere structure has attracted various attention in the catalytic field due to its high specific surface. The good dispersion and morphology of hollow spheres are important to provide high active sites. It is a big challenge to control the morphology and distribution of the active materials during synthesis. Serious deformation and uneven distribution of the spheres were usually obtained due to inappropriate templates. A facile one‐step hydrothermal method using micelles of triblock copolymer surfactant P123 was adopted to in‐situ grow Ni3S2/MoS2 porous hollow spheres on Ni foam with uniform distribution. The as‐produced Ni3S2/MoS2 porous hollow spheres have been demonstrated to have excellent oxygen evolution reaction catalytic performance as integrated electrodes. Low overpotentials of 314 mV and 337 mV have been achieved at current densities of 50 mA cm−2 and 100 mA cm−2 with a Tafel slope of 57 mV dec−1 and an excellent long‐term stability, which is better than other Ni‐base material.

Interfacial microenvironment modulation enhancing catalytic kinetics of bimetallic (oxy)hydroxide heterostructures for highly efficient oxygen evolution reaction

Water splitting is a promising hydrogen production technology limited by the slow kinetic oxygen evolution reaction (OER). The development of highly active and robust OER catalysts is in high demand. A series of three-dimensional (3D) self-supported [email protected](OH)2 heterostructures supported on nickel foam are synthesized and used as efficient OER catalysts using a simple hydrothermal method. The benefits of the appropriate 3D nanoflower morphology, the large number of FeOOH nanosheets adhered on the nanoflower surface, the formation of heterogeneous interfaces, and the synergistic effect of Ni(OH)2 and FeOOH significantly improve the OER catalytic performance of the material. The optimal catalyst in 1 M KOH, alkaline artificial seawater (1 M KOH + 1 M NaCl), and alkaline nature seawater (1 M KOH + seawater) require only 285, 286, and 325 mV overpotential, respectively, to achieve 100 mA cm−2 current density and has robust stability. This study contributes to the rational design of interface-engineered heterostructures for seawater splitting by synthesizing high catalytic activity catalysts.

Construction of Core-Shell CoMoO4@γ-FeOOH Nanosheets for Efficient Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) occurs at the anode in numerous electrochemical reactions and plays an important role due to the nature of proton-coupled electron transfer. However, the high voltage requirement and low stability of the OER dramatically limits the total energy converting efficiency. Recently, electrocatalysts based on multi-metal oxyhydroxides have been reported as excellent substitutes for commercial noble metal catalysts due to their outstanding OER activities. However, normal synthesis routes lead to either the encapsulation of excessively active sites or aggregation during the electrolysis. To this end, we design a novel core–shell structure integrating CoMoO4 as support frameworks covered with two-dimensional γ-FeOOH nanosheets on the surface. By involving CoMoO4, the electrochemically active surface area is significantly enhanced. Additionally, Co atoms immerge into the γ-FeOOH nanosheet, tuning its electronic structure and providing additional active sites. More importantly, the catalysts exhibit excellent OER catalytic performance, reducing overpotentials to merely 243.1 mV a versus 10 mA cm−2. The current strategy contributes to advancing the frontiers of new types of OER electrocatalysts by applying a proper support as a multi-functional platform.

Development of a Binder-Free Tetra-Metallic Oxide Electrocatalyst for Efficient Oxygen Evolution Reaction

Water splitting has emerged as a sustainable, renewable and zero-carbon-based energy source. Water undergoes hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) during electrolysis. However, among these half-cell reactions, OER is more energy demanding. Hence, the development of efficient catalysts for speeding up OER is a key for boosting up the commercial viability of electrolyzers. Typical binders like Nafion and PVDF are not preferred for designing commercial electrocatalysts as they can compromise conductivity. Thus, we have designed a novel and cost-effective binder-free tetra-metallic (Co-Cu-Zn-Fe) oxide catalyst that efficiently catalyzes OER. This catalyst was grown over the surface of Fluorine doped tin oxide (FTO) transducer by a facile potentiodynamic method. The structure and morphology of the modified electrode were characterized by X-ray diffraction (XRD), scanning electron microscopy, and energy dispersive X-ray spectroscopy. XRD analysis confirmed the deposition of CoFe2O4 and CuCo2O4 along with alloy formation of Co-Fe and Co-Cu. Similarly, EDX and SEM results show the presence of metals at the surface of FTO in accordance with the results of XRD. Linear scan voltammetry was employed for testing the performance of the catalyst towards accelerating OER in strongly alkaline medium of pH-13. The catalyst demonstrated stunning OER catalytic performance, with an overpotential of just 216 mV at 10 mA cm−2 current density. Moreover, the chronopotentiometric response revealed that the designed catalyst was stable at a potential of 1.80 V for 16 h. Thus, the designed catalyst is the first example of a highly stable, efficient, and inexpensive catalyst that catalyzes OER at the lowest overpotential.

Amorphous Ni-P-S@FeOOH/CC catalyst for high oxygen evolution Activity: Preparation, characterization and modeling

The oxygen evolution reaction (OER) is the key to prepare electrocatalysts for water splitting. Heteroatom doping is an effective way to improve the catalytic performance of OER by modulating the local electronic environment and stimulating the synergy. However, the complicated manufacturing methods have hindered their practical application. Herein, we demonstrate a method based on FeOOH/CC precursor to realize the preparation of Ni-P-S@FeOOH/CC catalyst through fast electrodeposition method. The overpotential of Ni-P-S@FeOOH/CC catalyst is 210 mV (10 mA cm−2), and still has an initial voltage of 97.35 % for 48 h. The surface area analysis shows a higher electrochemically active surface area for the amorphous structure prepared by electrodeposition method. XPS and DFT results show that the co-doping of P and S can stimulate the synergistic effect and the minimum energy of adsorption/desorption in OER process is only 0.83 eV. The strategy shows good prospects for preparing efficient OER pre-catalysts.

Controlled Growth Interface of Charge Transfer Salts of Nickel-7,7,8,8-Tetracyanoquinodimethane on Surface of Graphdiyne

Controlled Growth Interface of Charge Transfer Salts of Nickel-7,7,8,8-Tetracyanoquinodimethane on Surface of Graphdiyne

Magnetic-Field-Induced Strain Enhances Electrocatalysis of FeCo Alloys on Anode Catalysts for Water Splitting

In water splitting, the oxygen evolution reaction (OER) performance of transition metal alloy catalysts needs to be further improved. To solve this problem, the method of an external magnetic field was used to improve the OER catalytic performance of the alloy catalyst. In this paper, FeCo alloys with different composition ratios were prepared by an arc melting method, and OER catalysts with different compositions were obtained by annealing treatment. Under the action of a magnetic field, all three groups of catalysts showed a better catalytic performance than those without a magnetic field. The overpotentials of Fe35Co65, Fe22Co78 and Fe15Co85 at a current density of 20 mA cm−2 were reduced by 12 mV, 6 mV and 2 mV, respectively. It is found that, due to the magnetostrictive properties of FeCo alloys, the catalyst itself will generate strain under the action of a magnetic field, and the existence of strain may be the main reason for the enhanced OER performance of the magnetic field. Therefore, this work provides a new idea for the development of magnetic material catalysts and a magnetic field to improve the performance of catalysts.

Oxygen Vacancy‐Enhanced Ternary Nickel‐Tungsten‐Cerium Metal Alloy‐Oxides for Efficient Alkaline Electrochemical Full Cell Water Splitting Using Anion Exchange Membrane

AbstractAlkaline water electrolysis is an attractive hydrogen generation technology with ultra‐high purity products and zero carbon emissions. However, the sluggish kinetics of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in both electrodes highly limits their applications. Benefiting from the abundant accessible active sites of the ternary alloy‐oxide structure formed on Ni foam directly, NiCeWOx shows superior HER and OER catalytic performances. The NiCeWOx‐2 (Ce/W ratio with 5/95) displays enhanced OER activity with an overpotential of 263 mV, while the NiCeWOx‐1 (Ce/W ratio with 79.8/21.2) shows better performance for alkaline HER with an overpotential of 130 mV at the current density of 10 mA cm−2. The catalysts show significant enhancement in terms of electrochemical reaction kinetics and conductivity compared to its original NiCeOx and NiWOx alloy phase. The efficient HER‐OER electrocatalytic performance is attributed to its unique alloyed oxygen vacancy structure‐property, which facilitates the diffusion of protons/OH− ions and significantly improves the electron conductivity for catalytic reactions. A low cell potential of 1.65 V is obtained at 10 mA cm−2 for NiCeWOx‐1||NiCeWOx‐2 in a full water‐splitting device in 1 M KOH electrolyzer with an anion exchange membrane. Also, NiCeWOx‐1||NiCeWOx‐2 exhibits extreme high stability after 24 h operation. This novel design utilizes low‐cost and robust electrocatalysts and will be useful for large‐scale alkaline water electrolysis.