Heterojunction Electrocatalyst Research Articles

Hydrogen Spillover Mechanism of Superaerophobic NiSe2‐Ni5P4 Electrocatalyst to Promote Hydrogen Evolution in Saline Water

AbstractThe hydrogen spillover mechanism of metal‐supported electrocatalyst can significantly improve HER activity. However, the rational design of binary heterojunction hydrogen spillover electrocatalysts remains a challenge. Here, a NiSe2‐Ni5P4 heterojunction electrocatalyst with superaerophobic structure is synthesized by using a simple substrate self‐derived strategy. Experimental characterization and theoretical calculation reveal the hydrogen spillover mechanism of NiSe2‐Ni5P4 heterogeneous electrocatalyst. NiSe2 and Ni5P4 synergistically promote the adsorption/dissociation of H2O and the adsorption of H*, respectively. The smaller ΔΦ effectively reduced the electron density at the interface, weakening the proton adsorption at the interface and promoting the migration of H* from NiSe2 to Ni5P4. The NiSe2‐Ni5P4 exhibits excellent HER activity in alkaline electrolyte, requiring only a potential of 65, 270 mV to achieve a current density of 10, 500 mA cm−2, respectively, and a stability of up to 200 h. Moreover, the design of NiSe2‐Ni5P4 with superaerophobic structure can reduce the deposition of impurity ions on the electrode surface and avoid Cl− corrosion of the electrode, which results in NiSe2‐Ni5P4 showing better HER activity and stability than commercial Pt/C in brackish water. This study deepens the understanding of hydrogen spillover mechanism of binary heterojunction electrocatalysts, broadens the application of hydrogen production in complex water quality.

Engineering CoO/B heterojunction electrocatalysts for boosting electrocatalytic nitrate reduction to ammonia

Electrocatalytic nitrate reduction to ammonia represents a one-stone-two-birds approach for mitigating nitrate pollution and large-scale ammonia production. However, due to its multiple-electron process, it faces challenges regarding unsatisfactory Faraday efficiency (FE) and ammonia yield rate. Herein, a novel heterojunction electrocatalyst with sub-nanometric cobaltous oxide (CoO) decorated boron (B) nanosheets for electrocatalytic nitrate reduction (NO3RR) is first presented as an efficient electrocatalyst. The CoO/B heterojunction electrocatalyst exhibits a noteworthy NO3RR performance with an ammonia FE and yield rate of 95.41 % and 29.42 mg h-1 mgcat-1, respectively, in alkaline media at −0.4 V vs. reversible hydrogen electrode (RHE), surpassing CoO and B catalysts. Results demonstrated that the synergistic effect of CoO and B enhances the adsorption and activation of NO3−, lowers the formation energy of *NOH and provides sufficient active hydrogen to facilitate hydrogenation, thereby enhancing NO3RR performance. This work presents a novel approach for constructing cost-effective and high-performance NO3RR heterojunction electrocatalysts.

Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott-Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction.

Regulating the adsorption of an intermediate on an electrocatalyst by manipulating the electron spin state of the transition metal is of great significance for promoting the activation of inert nitrogen molecules (N2) during the electrocatalytic nitrogen reduction reaction (eNRR). However, achieving this remains challenging. Herein, a novel 2D/2D Mott-Schottky heterojunction, Co9S8/Nb2CTx-P, is developed as an eNRR catalyst. This is achieved through the in situ growth of cobalt sulfide (Co9S8) nanosheets over a Nb2CTx MXene using a solution plasma modification method. Transformation of the Co spin state from low (t2g 6eg 1) to high (t2g 5eg 2) is achieved by adjusting the interface electronic structure and sulfur vacancy of Co9S8/Nb2CTx-P. The adsorption ability of N2 is optimized through high spin Co(II) with more unpaired electrons, significantly accelerating the *N2→*NNH kinetic process. The Co9S8/Nb2CTx-P exhibits a high NH3 yield of 62.62µg h-1 mgcat. -1 and a Faradaic efficiency (FE) of 30.33% at -0.40V versus the reversible hydrogen electrode (RHE) in 0.1m HCl. Additionally, it achieves an NH3 yield of 41.47µg h-1 mgcat. -1 and FE of 23.19% at -0.60V versus RHE in 0.1m Na2SO4. This work demonstrates a promising strategy for constructing heterojunction electrocatalysts for efficient eNRR.

An Electron-Coupled Co-ZrO2 Nanodot Heterojunction Electrocatalyst with Lewis Acid-Base Site Pairs Enables High Redox Reaction Kinetics of Li-S Batteries.

Using electrocatalysts is effective in solving the slow reaction kinetics of polysulfides in Li-S batteries, but designing stable electrocatalysts with an integrated adsorption-catalysis-desorption system is challenging. Here, we report a stable metal-semiconductor (Co-ZrO2) heterojunction electrocatalyst fabricated by assembling electron-coupled Co-ZrO2 nanodots into macroporous carbon nanofibers. The Co-ZrO2 contact causes interfacial electron enrichment and electron transfer from Co to ZrO2, which creates abundant Lewis-acid sites on Co that can adsorb polysulfides. Simultaneously, the enriched interfacial electrons can activate the S-S bond and boost the catalytic conversion of long-chain polysulfides, while the ZrO2 with Lewis-base sites facilitate the desorption of short-chain polysulfides from the electrocatalyst. Moreover, the nanodot heterojunctions show great chemical stability and high redox reaction kinetics of polysulfides. Li-S batteries show high discharge capacities of 954.5 mA h·g-1 at 0.5 C with a retention of 84.9% over 200 cycles, and 710.2 mA hg-1 at 1 C with a retention of 98.6% over 200 cycles. This study provides an effective strategy for developing active and durable electrocatalysts for Li-S batteries.

Construction of a p-p heterojunction Co3O4/MoS2 electrocatalyst for boosting hydrogen evolution reaction

Building p-p heterojunctions with Fermi level difference, due to the motion of energy levels, band bending, and internal electric field generation, can effectively improve the electronic structure of the interface, enrich the active sites of heterojunctions, and promote the adsorption of reaction intermediates, which is an effective approach to constructing high-performance electrocatalysts. In this study, a Co3O4/MoS2 p-p heterojunction catalyst with nano-particle/nano-flower structure was designed, inducing charge transfer from Co3O4 to MoS2, thereby increasing the negative charge of MoS2, improving *H adsorption through electrostatic interaction, enhancing electrocatalytic kinetics, and reducing reaction overpotential. The catalytic performance of MoS2 for hydrogen evolution reaction was effectively enhanced. In 1 M KOH solution, the current density was 10 mA cm−2, and the overpotential was 156 mV, with good stability after 40 h of operation. This work provides a new direction for the design of p-p heterojunction electrocatalysts and offers more choices for promoting the development of high-performance non-noble metal catalysts.

SnO2/CoTeO3 heterojunction for smartly conducting hydrogen evolution linking to organics electrocatalytic oxidation

As a sustainable energy form, hydrogen can be most practically obtained from electrocatalytic water splitting. The familiar organics can be oxidized to more useful intermediates in chemical industries. Herein, a SnO2/(CoTeO3)2 heterojunction is designed as an electrocatalyst for hydrogen evolution reaction (HER) and organic electrocatalytic oxidation. The heterojunction has good electrocatalytic performances with overpotentials of 281 mV at 10 mA cm−2 in 1 M KOH+0.1 M glycerol, 358 mV at 10 mA cm−2 in 1 M KOH +0.33 M urea, 203 mV in 1 M KOH+0.1 M glucose, and 111 mV for HER in 1 M KOH. The glucose is electrocatalytically oxidized to gluconic acid and formic acid. Density functional theory computation shows the formation of the SnO2/(CoTeO3)2 heterojunction makes the total densities of states of SnO2 move to the Fermi level, which is beneficial for adsorption in the electrocatalysis. This work propagandizes a new avenue for heterojunction electrocatalyst is applied for organics oxidation linking to hydrogen production.

Interfacial Electronic Interactions Between Ultrathin NiFe-MOF Nanosheets and Ir Nanoparticles Heterojunctions Leading to Efficient Overall Water Splitting.

Creating specific noble metal/metal-organic framework (MOF) heterojunction nanostructures represents an effective strategy to promote water electrolysis but remains rather challenging. Herein, a heterojunction electrocatalyst is developed by growing Ir nanoparticles on ultrathin NiFe-MOF nanosheets supported by nickel foam (NF) via a readily accessible solvothermal approach and subsequent redox strategy. Because of the electronic interactions between Ir nanoparticles and NiFe-MOF nanosheets, the optimized Ir@NiFe-MOF/NF catalyst exhibits exceptional bifunctional performance for the hydrogen evolution reaction (HER) (η10 = 15mV, η denotes the overpotential) and oxygen evolution reaction (OER) (η10 = 213mV) in 1.0m KOH solution, superior to commercial and recently reported electrocatalysts. Density functional theory calculations are used to further investigate the electronic interactions between Ir nanoparticles and NiFe-MOF nanosheets, shedding light on the mechanisms behind the enhanced HER and OER performance. This work details a promising approach for the design and development of efficient electrocatalysts for overall water splitting.

Value‐Added Cascade Synthesis Mediated by Paired‐Electrolysis Using an Ultrathin Microenvironment‐Inbuilt Metalized Covalent Organic Framework Heterojunction

AbstractEnergy‐saving and value‐added management in advanced catalysis is highly desirable but is challenged by the limitations of multifunctional catalysts and catalytic modules. Herein, an azo‐linked phthalocyanine‐porphyrin covalent organic framework (COF) with the ultrathin layered nanostructure grown on carbon nanotubes (NiPc‐azo‐H2Pp@CNTs) has been designed and synthesized, which can serve as a highly active and stable bifunctional heterojunction electrocatalyst for selective paired‐electrosynthesis through coupling anodic iodide oxidation reaction and cathodic CO2 conversion. Particularly, the inbuilt local microenvironment conferred by the dihydroporphyrin moieties in COF can act as a proton reservoir to promote the proton relay at the heterojunction interface during the electrocatalytic process. Moreover, through the cascade construction of dual electrocatalytic/organocatalytic modules, the cathode‐generated CO can be further converted to dimethyl carbonate with a yield of 6.21 mmol L−1 h−1, while the anode‐produced iodine can be derived into iodoform on the hundred‐milligram scale. It is worth noting that the value‐added cascade synthesis mediated by paired‐electrolysis using the distinctive and high‐powered electrocatalysts will help advance the sustainable development of industrial intelligent manufacturing.

Highly Stable Mo-NiO@NiFe-Layered Double Hydroxide Heterojunction Anode Catalyst for Alkaline Electrolyzers with Porous Membrane.

Heterostructure catalysts are considered as promising candidates for promoting the oxygen evolution reaction (OER) process due to their strong electron coupling. However, the inevitable dissolution and detachment of the heterostructure catalysts are caused by the severe reconstruction, dramatically limiting their industrial application. Herein, the NiFe-layered double hydroxide (LDH) nanosheets attached on Mo-NiO microrods (Mo-NiO@NiFe LDH) by the preoxidation strategy of the core NiMoN layer are synthesized for ensuring the high catalytic performance and stability. Owing to the enhanced electron coupling and preoxidation process, the obtained Mo-NiO@NiFe LDH exhibits a superlow overpotential of 253 mV to achieve a practically relevant current density of 1000 mA cm-2 for OER with exceptional stability over 1200 h. Notably, the overall water splitting system based on Mo-NiO@NiFe LDH reveals remarkable stability, maintaining the catalytic activity at a current density of 1000 mA cm-2 for 140 h under industrial harsh conditions. Furthermore, the Mo-NiO@NiFe LDH demonstrates outstanding activity and long-term durability in a practical alkaline electrolyzer assembly with a porous membrane, even surpassing the performance of IrO2. This work provides a new sight for designing and synthesizing highly stable heterojunction electrocatalysts, further promoting and realizing the industrial electrocatalytic OER.

Electron regulation of CeO2 on CoP multi-shell hetero-junction micro-sphere towards highly efficient water oxidation

CeO2 has been identified as a significant cocatalyst to enhance the electrocatalytic activity of transition metal phosphides (TMPs). However, the electrocatalytic mechanism by which CeO2 enhances the catalytic activity of TMP remains unclear. In this study, we have successfully developed a unique CeO2-CoP-1–4 multishell microsphere heterostructure catalyst through a simple hydrothermal and calcination process. CeO2-CoP-1–4 exhibits great potential for electrocatalytic oxygen evolution reaction (OER), requiring only an overpotential of 254 mV to achieve a current density of 10 mA cm−2. Moreover, CeO2-CoP-1–4 demonstrates excellent operating durability lasting for 55 h. The presence of CeO2 as a cocatalyst can regulate the microsphere structure of CoP, the resulting multishell microsphere structure can shorten the mass transfer distance, and improve the utilization rate of the active site. Furthermore, in situ Raman and ex situ characterizations, and DFT theoretical calculation results reveal that CeO2 can effectively regulates the electronic structure of Co species, reduces the reaction free energy of rate-limiting step, thus increase the reaction kinetic. Overall, this study provides experimental and theoretical evidence to better comprehend the mechanism and structure evolution of CeO2 in enhancing the OER performance of CoP, offering a unique design inspiration for the development of efficient hollow heterojunction electrocatalysts.

Hydrothermal synthesis of FeCoNi/V3O5 heterojunctions as highly efficient electrocatalysts for the oxygen evolution reaction

To produce green hydrogen in a cost-effective and efficient manner, the research on low-cost, high-performance electrocatalysts is both attractive and challenging. In this study, a heterojunction electrocatalyst containing V3O5 and FeCoNi alloy nanoparticles was introduced. The adsorption and activation of the reactants at the FeCoNi/V3O5 heterointerface are significantly enhanced. The overall performance of the FeCoNi/V3O5 catalyst is excellent, with an OER activity reaching 265 mV at a current density of 10 mA cm−2, nearly 65 mV lower compared to the commercial IrO2 catalyst. Furthermore, it exhibits outstanding durability, remaining stable for 50 h under a constant current density of 100 mA cm−2. Theoretical calculations also revealed a synergistic effect between the FeCoNi alloy (referred to as FeCoNi) nanoparticles and V3O5, thereby enhancing the OER performance, consistent with the experimental findings.

Nitrogen-doped MoO2/Cu heterojunction electrocatalyst for highly efficient alkaline hydrogen evolution reaction

Metal/metal-(hydr)oxide heterojunction has been proposed as an efficient means to enhance the kinetics of alkaline hydrogen evolution reaction (HER). However, the poor electronic conductivity of metal-(hydr)oxides hinders the transport of electrons and the inappropriate electronic structure of the constituent phases would lower the HER activity. Herein, a nitrogen-doped MoO2/Cu heterostructure nanosheets was prepared by a simple hydrothermal and subsequent annealing treatment, acting as a model catalyst for element-doped modified metals/metal-oxides composite towards alkaline HER. Experimental results revealed that the HER catalytic activity of the catalyst was effectively improved by the nitrogen doping and the hetero coupling effect. The obtained N–MoO2/Cu catalyst exhibited a low overpotential of 40 and 363 mV to drive the current densities of 10 and 1000 mA cm−2, respectively, and showed high stability in the constant-current test of 50 h at 10 mA cm−2, 100 mA cm−2 and 1000 mA cm−2. Impressively, the N–MoO2/Cu catalyst coupled with Ni–Fe LDH to assemble an alkaline electrolyzer only require a voltage of 1.49 V to achieve a current density of 10 mA cm−2, and could be actuated by wind power to continuously produce hydrogen.

Identifying the Active Sites in MoSi2@MoO3 Heterojunctions for Enhanced Hydrogen Evolution.

Developing Two-dimensional (2D) Mo-based heterogeneous nanomaterials is of great significance for energy conversion, especially in alkaline hydrogen evolution reaction (HER), however, it remains a challenge to identify the active sites at the interface due to the structure complexity. Herein, the real active sites are systematically explored during the HER process in varied Mo-based 2D materials by theoretical computational and magnetron sputtering approaches first to filtrate the candidates, then successfully combined the MoSi2 and MoO3 together through Oxygen doping to construct heterojunctions. Benefiting from the synergistic effects between the MoSi2 and MoO3, the obtained MoSi2@MoO3 exhibits an unprecedented overpotential of 72mV at a current density of 10mA cm-2. Density functional theory calculations uncover the different Gibbs free energy of hydrogen adsorption (ΔGH*) values achieved at the interfaces with different sites as adsorption sites. The results can facilitate the optimization of heterojunction electrocatalyst design principles for the Mo-based 2D materials.

Vertical Cross-Alignments of 2D Semiconductors with Steered Internal Electric Field for Urea Electrooxidation via Balancing Intermediates Adsorption.

Single-component electrocatalysts generally lead to unbalanced adsorption of OH- and urea during urea oxidation reaction (UOR), thus obtaining low activity and selectivity especially when oxygen evolution reaction (OER) competes at high potentials (>1.5 V). Herein, a cross-alignment strategy of in situ vertically growing Ni(OH)2 nanosheets on 2D semiconductor g-C3N4 is reported to form a hetero-structured electrocatalyst. Various spectroscopy measurements including in situ experiments indicate the existence of enhanced internal electric field at the interfaces of vertical Ni(OH)2 and g-C3N4 nanosheets, favorable for balancing adsorption of reaction intermediates. This heterojunction electrocatalyst shows high-selectivity UOR compared to pure Ni(OH)2, even at high potentials (>1.5 V) and large current density. The computational results show the vertical heterojunction could steer the internal electric field to increase the adsorption of urea, thus efficiently avoiding poisoning of strongly adsorbed OH- on active sites. A membrane electrode assembly (MEA)-based electrolyzer with the heterojunction anode could operate at an industrial-level current density of 200 mA cm-2. This work paves an avenue for designing high-performance electrocatalysts by vertical cross-alignments of active components.

Ag engineered NiFe-LDH/NiFe2O4 Mott-Schottky heterojunction electrocatalyst for highly efficient oxygen evolution and urea oxidation reactions

Efficient and durable electrocatalysts with sufficient active sites and high intrinsic activity are essential for advancing energy-saving hydrogen production technology. In this study, a Mott-Schottky heterojunction electrocatalyst with Ag nanoparticles in-situ grown on NiFe layered double hydroxides (NiFe-LDH)/NiFe2O4 nanosheets (Ag@NiFe-LDH/NiFe2O4) were designed and successfully synthesized through a hydrothermal process and subsequent spontaneous redox reaction. The in-situ growth of metallic Ag on semiconducting NiFe-LDH/NiFe2O4 triggers a strong electron interaction across the Mott-Schottky interface, leading to a significant increase in both the intrinsic catalytic activity and the electrochemical active surface area of the heterojunction electrocatalyst. As a result, the Ag@NiFe-LDH/NiFe2O4 demonstrates impressive oxygen evolution reaction (OER) performance in alkaline KOH solution, achieving a low overpotential of 249 mV at 100 mA cm−2 and a Tafel slope of 42.79 mV dec−1. When the self-supported Ag@NiFe-LDH/NiFe2O4 is coupled with the Pt/C electrocatalyst, the alkaline electrolyzer reaches a current density of 10 mA cm−2 at a cell voltage of only 1.460 V. Furthermore, X-ray photoelectron spectroscopy and in-situ Raman analysis reveal that the Ni(Fe)OOH is the possible active phase for OER in the catalyst. In addition, when employed for UOR catalysis, the Ag@NiFe-LDH/NiFe2O4 also displays intriguing activity with an ultralow potential of 1.389 V at 50 mA cm−2. This work may shed light on the rational design of multiple-phase heterogeneous electrocatalysts and demonstrate the significance of interface engineering in enhancing catalytic performance.

Interfacial engineering of high-performance Fe2P2O7-based electrocatalysts for alkaline exchange membrane fuel cells

Fuel cells promise high energy density and energy conversion efficiency but are plagued by the scarcity of platinum for facilitating the oxygen reduction reaction (ORR). Herein, a facile synthesis of a heterojunction electrocatalyst of ZIF-8 derived carbon (Z8C) supported Fe2P2O7 (Fe2P2O7@Z8C) is reported. The electrocatalyst exhibited higher half-wave potential than the state-of-the-art Pt/C catalyst by more than 33 mV and achieved a peak power density of 152.47 mW cm−2, outperforming the Pt/C-driven cell by ca. 14.5 mW cm−2 in alkaline membrane electrode assemblies under similar operating conditions. X-ray photoelectron and X-ray absorption spectroscopic studies suggested a spontaneous electron redistribution across the heterojunction interface in Fe2P2O7@Z8C. Density functional theory calculations indicated that the electron redistribution may remarkably promote the intrinsic activity of Fe2P2O7@Z8C toward the four-electron ORR pathway. These findings offer an indispensable strategy for rational design of highly efficient and durable non-noble electrocatalysts.

Modulating positive charge sites generations and iron oxidation state transitions in FeP4/CoP/C p-n heterojunction toward efficient oxygen evolution

Promoting the formation of positive charge active sites and high oxidation state FeOOH in the heterojunction electrocatalyst can enhance its intrinsic activity for oxygen evolution reaction (OER). However, the current synthesis methods that can simultaneously achieve both properties remain a great challenge. In this work, a feasible strategy for concurrently promoting the generation of positive charge active sites and high oxidation state metal species by constructing a heterojunction between FeP4 and CoP is proposed. Specifically, the p-n heterojunction between FeP4 and CoP is constructed by pyrolysis of MIL88A@FeCoLDH prepared by introducing Co through cation exchange using MIL88A as a template. The experimental and density functional theory calculation analyses suggest the construction of p-n heterojunction can effectively modulate the electron structure, optimize the d-band center, induce the generation of strong space charge region, and shorten the bond length of Fe-O, thus promoting the formation of positive charge active sites and high active species FeOOH and the adsorption ability of oxygen-containing intermediates for enhancing the OER performance. Benefiting from the synergistic effect between positive charge active sites and FeOOH, the obtained FeP4/CoP/C electrocatalyst exhibits a low overpotential of 258 mV for the OER at a current density of 10 mA cm−2 and superior stability at 20 mA cm−2 for 52 h. This work gives insights into the charge regulation effect in the heterojunction for enhancing the OER catalytic activity and provides a general strategy for designing more efficient oxygen evolution electrocatalysts.

Charge redistribution enabling Ru/W5N4 heterojunction electrocatalyst for highly efficient alkaline hydrogen production

The development of electrocatalysts capable of efficiently catalyzing the alkaline hydrogen evolution reaction (HER) is crucial for driving the advancement of sustainable energy. Herein, by altering the surface state of the support, we transformed the bulk W5N4 into a porous structure and constructed a Ru/W5N4 heterostructure. The transfer of electrons from Ru to W5N4 can optimize the electronic structure of the catalyst, thereby effectively promoting electron transfer, accelerating reaction kinetics, and enhancing the activity of the catalyst. Furthermore, W5N4 can serve as a protective shell to stabilize Ru0, which is regarded as the active center in HER. The resulting Ru/W5N4 exhibits excellent HER activity, requiring only overpotentials of 43 and 156 mV to achieve current densities of −10 and −100 mA cm−2, respectively. This work provides valuable insights into the rational construction of heterostructures to optimize HER performance.

A Mott-Schottky Heterojunction with Strong Chemisorption and Fast Conversion Effects for Room-Temperature Na-S Batteries.

The practical application of the room-temperature sodium-sulfur (RT Na-S) batteries is currently limited by low reversible capacity and serious capacity decay due to the sluggish reaction kinetics and shuttle effect. It is necessary to design a suitable sulfur host integrated with electrocatalysts to realize effective chemisorption and catalysis of sodium polysulfides (NaPSs). Herein, under the guidance of theoretical calculation, the Mott-Schottky heterojunction with a built-in electric field composed of iron (Fe) and iron disulfide (FeS2) components anchored on a porous carbon matrix (Fe/FeS2-PC) is designed and prepared. The enhanced chemisorption effect of Fe, the fast electrocatalytic effect of FeS2, and the fast transfer effect of the built-in electric field within the Fe/FeS2 heterojunction in the cathode of RT Na-S batteries work together to effectively improve the electrochemical performance. As a result, the Fe/FeS2-PC@S cathode exhibits high reversible capacity (815 mAh g-1 after 150 cycles at 0.2 A g-1) and excellent stability (516 mAh g-1 after 600 cycles at 5 A g-1, with only 0.07% decay per cycle). The design of the Fe/FeS2 heterojunction electrocatalyst provides a new strategy for the development of highly stable RT Na-S batteries.

Surface oxygen vacancy engineering of Cr-doped FeNi3/NiFe2O4 Mott-Schottky heterojunction as efficient electrocatalyst for high current density water oxidation

The defect engineering at the surface by filling of oxygen vacancies during OER causing surface reconstruction is considered to be a unique way to boost up intrinsic electrocatalytic activity, especially towards oxygen evolution reaction (OER) mechanism. The present study aimed creation of large number of oxygen vacancies by Cr-doping into FeNi3/NiFe2O4 Mott-Schottky heterojunction electrocatalyst causing much desirable surface engineering and electronic modulation in favour of OER activity. The optimized heterojunction nanoparticles exhibited an excellent catalytic activity with low overpotential of 246 mV at the current density of 20 mA cm−2 with low Tafel slope value of 55 mV dec−1 for OER. Such oxygen vacancy-aided surface reconstruction during OER demonstrated an outstanding durability over 200 h even at high current density of 1000 mA cm−2 in 1 M KOH electrolyte. The surface oxygen vacancy engineering with the help of ex-situ Raman spectroscopy at different anodic potentials reveals the filling of vacancies and generation of MOOH as surface reconstruction of electrocatalyst during OER, also supported by XPS, TEM and EELS analyses.