Electrocatalytic Water Oxidation Research Articles

Lewis acid sites in hollow cobalt phytate micropolyhedra promote the electrocatalytic water oxidation.

The acid-base microenvironment of the metal center is crucial for constructing advanced oxygen evolution reaction (OER) electrocatalysts. However, the correlation between acidic site and OER performance remains unclear for cobalt-based catalysts. Herein, Lewis acid sites in hollow cobalt phytate micropolyhedra (M-CoPA, M = Cu, Sr) were synthesized by a cation-exchange strategy, and their OER performances were studied systematically. Experimentally, Lewis acid Cu2+ sites with stronger Lewis acidity exhibited superior intrinsic activity and long-term stability in alkaline electrolytes. The spectroscopic and electrochemical studies show Lewis acid sites in hollow cobalt phytate micropolyhedra can modulate the electronic distribution of the adjacent cobalt center and further optimize the adsorption strength of oxygenated species. This study figures out the effect of Lewis acid sites on the OER kinetics and provides an effective way to develop high-efficiency electrocatalysts for energy conversion systems.

Two Co(II) Isostructural Bifunctional MOFs via Mixed-Ligand Strategy: Syntheses, Crystal Structure, Photocatalytic Degradation of Dyes, and Electrocatalytic Water Oxidation

The solvothermal reactions involving cobalt ions with 5-methylisophthalic acid (H2MIP) and 1,3-bis(2-methylimidazol)propane (BMIP) yielded two cobalt(II) organic frameworks: {[Co4(MIP)4(BMIP)3]·1/2DMA}n (SNUT-31) and {[Co4(MIP)4(BMIP)3]·(EtOH)2·H2O]}n (SNUT-32) where DMA represents N,N-dimethylacetamide and EtOH signifies ethyl alcohol. Single-crystal X-ray diffraction analyses reveal that SNUT-31 and SNUT-32 possess an isomorphic structure, featuring a unique 2-fold interpenetration of 3D frameworks in a parallel manner. Notably, both SNUT-31 and SNUT-32 demonstrate remarkable performance in electrocatalytic oxygen evolution reactions and exhibit exceptional photocatalytic degradation capabilities against a model comprising three distinct dyes: rhodamine B, methyl orange, and methyl blue.

Mo-Doped α-MnO2 for Enhanced Electrocatalytic Water Oxidation.

Manganese is a key metal involved in the catalysis of natural photosynthesis. Thus, the investigation of Mn-based electrocatalysts for water oxidation is of high importance. This work reports the doping of Mo into α-MnO2 nanorods to improve the water oxidation performance. The doping of Mo can transform the microstructure of α-MnO2 from nanorods into nanosphere superstructures. As a dopant, Mo expands the α-MnO2 lattice to result in a decrease in the average oxidation state of Mn and the generation of oxygen vacancies, which are beneficial to water oxidation catalysis. Under optimized doping, the overpotential of 2.34 wt.% Mo/α-MnO2 is reduced by 80 mV (at 10 mA/cm2) compared with pure α-MnO2.

Interface Synergistic Effect of NiFe-LDH/3D GA Composites on Efficient Electrocatalytic Water Oxidation.

Currently, NiFe-LDH exhibits an excellent oxygen evolution reaction (OER) due to the interaction of the two metal elements on the layered double hydroxide (LDH) platform. However, such interaction is still insufficient to compensate for its poor electrical conductivity, limited number of active sites and sluggish dynamics. Herein, a feasible two-step hydrothermal strategy that involves coupling low-conductivity NiFe-LDH with 3D porous graphene aerogel (GA) is proposed. The optimized NiFe-LDH/GA (1:1) produced possesses a 257 mV (10 mA cm-2) overpotential and could operate stably for 56 h in an OER. Our investigation demonstrates that the NiFe-LDH/GA has a three-dimensional mesoporous structure, and that there is synergistic interaction between LDH and GA and interfacial reconstruction of NiOOH. Such an interface synergistic coupling effect promotes fast mass transfer and facilitates OER kinetics, and this work offers new insights into designing efficient and stable GA-based electrocatalysts.

Self-Etching Synthesis of Superhydrophilic Iron-Rich Defect Heterostructure-Integrated Catalyst with Fast Oxygen Evolution Kinetics for Large-Current Water Splitting.

Developing catalysts with rich metal defects, strong hydrophilicit, and extensive grain boundaries is crucial for enhancing the kinetics of electrocatalytic water oxidation and facilitating large-current water splitting. In this study, we utilized pH-controlled etching and gas-phase phosphating to synthesize a flower-like Ni2P-FeP4-Cu3P modified nickel foam heterostructure catalyst. This catalyst features pronounced hydrophilicity and a high concentration of Fe defects. It exhibits low overpotentials of 156 mV and 210 mV at current densities of 10 and 100 mA cm-2 respectively, and maintains stability for up to 200 h at 100 mA cm-2 with only 7.3% degradation, showcasing outstanding electrocatalytic water oxidation performance. Furthermore, when integrated into a Ni2P-FeP4-Cu3P/NF||Pt-C/NF electrolyzer, it achieves excellent overall water splitting performance, reaching current densities of 10 and 400 mA cm-2 at just 1.47 V and 1.73 V, respectively, and operates stably for 60 h at 500 mA cm-2 with minimal degradation. Analysis indicates that high-valence oxyhydroxides/phosphides of Ni, Fe, and Cu act as the primary active species. The presence of abundant Fe defects enhances electron transfer, strong hydrophilicity improves electrolyte contact, and numerous grain boundaries synergistically modulate the activation energy between active sites and oxygen-containing intermediates, significantly improving the kinetics of water oxidation.

Voltage-Driven Molecular Photoelectrocatalysis of Water Oxidation.

Molecular photocatalysis and photoelectrocatalysis have been widely used to conduct oxidation-reduction processes ranging from fuel generation to electroorganic synthesis. We recently showed that an electrostatic potential drop across the double layer contributes to the driving force for electron transfer (ET) between a dissolved reactant and a molecular catalyst immobilized directly on the electrode surface. In this article, we report voltage-driven molecular photoelectrocatalysis with a prevalent homogeneous water oxidation catalyst, (bpy)Cu (II), which was covalently attached to the carbon surface and exhibited photocatalytic activity. The strong potential dependence of the photooxidation current suggests that the electrostatic potential drop across the double layer contributes to the driving force for ET between a water molecule and the excited state of surface-bound (bpy)Cu (II). Scanning electrochemical microscopy (SECM) was used to analyze the products and determine the faradaic efficiencies for the generation of oxygen and hydrogen peroxide. Unlike electrocatalytic water oxidation by (bpy)Cu (II) in the dark, which produces only O2, the voltage-driven photooxidation includes an additional 2e- pathway generating H2O2. DFT calculations show that the applied voltage and the presence of light can alter the activation energy for the rate-determining water nucleophilic attack steps, thereby increasing the reaction rate of photo-oxidation of water and opening the 2e- pathway. These results suggest a new route for designing next-generation hybrid molecular photo(electro)catalysts for water oxidation and other processes.

Selenate-based heterojunction with cobalt–nickel paired site for electrocatalytic oxidation of 5-hydroxymethylfurfural coupling water splitting to produce hydrogen

It is very appealing that 5-hydroxymethylfurfural (HMF) is electrocatalytical oxidized as 2,5-furandicarboxylic acid (FDCA) linking to non-classical cathodic hydrogen (H2) production. However, the electrocatalysts for electrocatalytic HMF oxidative reaction (e-HMFOR) have been facing low Faradaic efficiency (FE) and high water splitting voltage. Herein, we propose a strategy of the NiSeO3@(CoSeO3)4 heterojunction by constructing a Co-Ni paired site, where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site, thus giving the NiSeO3@(CoSeO3)4 heterojunction superior electrocatalytic performances for e-HMFOR and water splitting. By optimizing conditions, the NiSeO3@(CoSeO3)4 heterojunction has high conversion of 99.7%, high selectivity of 99.9%, and high FE of 98.4% at 1.3 V, as well as low cell voltage of 1.31 V at 10 mA cm−2 in 1 M KOH + 0.1 M HMF. This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H2 in an economical manner.

Novel electrocatalyst with abundant oxygen vacancies enabling efficient two-electron water oxidation reaction for H2O2 synthesis

In the realm of electrocatalytic two-electron water oxidation reaction, the quest for efficient and selective catalysts poses a significant challenge in balancing productivity and activity, hindering the decentralized generation of hydrogen peroxide (H2O2) through electrochemical means. Addressing this hurdle, our study introduces a novel approach to crafting an effective and stable electrocatalyst for the two-electron water oxidation reaction (2e-WOR). Through the synthesis of magnesium stannite tungstate from a mixture of MgSnO3 and WO3, the engineer of a material with abundant oxygen vacancies is crucial for catalytic activity. This catalyst demonstrates exceptional performance, ascribed to its distinctive oxygen vacancies proximal to the active center Sn and electronic modulation by tungsten. Notably, Mg1-xSnWO6-x700 exhibits a remarkably low overpotential of 70 mV at 10 mA cm−2, coupled with a high faradic efficiency of 84 % for 2e- WOR at 2.6 V vs. RHE, maintaining consistent performance over 35 h. Furthermore, the formation of oxygen vacancies and the associated electronic transfer underscore the novelty and promise of our material in advancing the field of two-electron WOR. In sum, our electrocatalyst presents a cost-efficient and selective solution for water oxidation, offering potential avenues for enhancing H2O2 production.

Coordination Stabilization of Fe by Porphyrin‐Intercalated NiFe‐LDH Under Industrial‐Level Alkaline Conditions for Long‐Term Electrocatalytic Water Oxidation

AbstractThe durable and economic electrocatalysts with high current density under industrial alkaline conditions are critical for advancing the industrial production of hydrogen energy by water electrolysis. The industrial highly alkaline electrolyte exacerbates the Fe dissolution of NiFe layered double hydroxide (NiFe‐LDH), leading to the dramatic degradation of stability and activity. The NiFe‐LDH intercalated Tetrakis(4‐carboxyphenyl)porphyrin (TCPP) (NiFe‐TCPP), 1,4,7,10‐Tetraazacyclododecane‐1,4,7,10‐tetraacetic acid (DOTA) (NiFe‐DOTA) and CO32− (NiFe‐CO3) are fabricated respectively for electrocatalytic water oxidation under industrial alkaline conditions. In 10 m KOH, compared to NiFe‐DOTA (335.0 mV) and NiFe‐CO3 (499.2 mV), the resultant NiFe‐TCPP exhibits the lowest overpotentials of 290.2 mV at 1000 mA cm−2. The NiFe‐TCPP also operates continuously for 1000 h at 500 mA cm−2 with near‐zero attenuation. The theoretical and experimental studies reveal that the strong coordination between conjugated carboxylate ligand TCPP and Fe of the laminate inhibits the Fe leaching by increasing the dissolution energy barriers to 4.29 eV and improving the self‐healing ability, thus enhancing the stability. Furthermore, the charge redistribution induced by the strong coordination optimizes the d‐band centers (‐2.81 eV) and decreases the reaction energy barriers (1.47 eV), thereby increasing the catalytic activity.

A Proton-Conductive Co(II)-Polyoxometalate Acts as a Precatalyst for Efficient Electrocatalytic Water Oxidation.

A cobalt(II)-containing polyoxometalate, [H3O]5[{Co(H2O)4}3{Na(H2O)4}W12O42]·3H2O (Co-POM), has been isolated in a one-step facile aqueous synthesis and characterized unambiguously using single-crystal X-ray crystallography along with routine spectral analysis. The paratungstate cluster anion [W12O42]12- coordinates with {CoII(H2O)4}2+ and {Na(H2O)4}+ complex cations resulting in the formation of the water-insoluble Co-POM compound having three-dimensional (3-D) extended structure. Motivated by the protonated water molecules existing as the counter cations in Co-POM, herein, we demonstrate the detailed proton conductivity studies of the Co-POM, reaching a value of 1.04 × 10-2 S cm-1 at 80 °C and 98% relative humidity (RH). The temperature- and humidity-dependent proton conductivity in Co-POM is governed by Grotthus mechanism with Ea = 0.25 eV. In addition, we examined the electrochemical behavior of Co-POM, in an alkaline borate buffer where it is found to be electrochemically unstable and acts as a precatalyst (and not a true catalyst) for oxygen evolution reaction (OER). We also discuss the "post-mortem" analysis of the postelectrolysis sample to identify the active species which turns out to be a cobalt oxide material (Co3O4) incorporating small amounts of tungsten. Thus, in the present electrocatalysis work, the Co-POM molecule transforms into an efficient water oxidation catalyst (WOC).

A Novel Banana-Shaped Mixed-Metal Co/Fe Polyoxometalate Cluster.

The synthesis and characterization of a Co/Fe mixed-metal banana-shaped polyoxometalate with the formula [(Co2.5Fe0.5(H2O)PW9O34)2(PW6O26)]16- (Co5Fe) is reported. This transition-metal-substituted polyoxometalate readily assembles from its components in a one-pot reaction and crystallizes in the monoclinic space group P21/c. The structure of Co5Fe can be considered a double sandwich composed by two B-α-{Co2.5Fe0.5PW9O40} Keggin units, in which one coordinatively saturated octahedral metal position is equally occupied by Co(II) and Fe(III) ions with a 50% of site occupancy. These Keggin units are linked via a hexalacunary Keggin unit {PW6O26}. Single crystal X-ray diffraction and magnetic measurements support the proposed atom arrangement within the crystal structure. Magnetic measurements of these double trimeric unit {Co2.5Fe0.5O13}2 show a combination of antiferromagnetic interaction, the presence of spin frustration, and the first-order spin-orbit coupling Co(II) ions. Electrocatalytic water oxidation measurements show that Co5Fe displays low stability in both homogeneous and heterogeneous conditions. This is evidenced by the constant increase on the catalytic currents over time together with the appearance of polyoxometalate-derived electrode-bound species that can be responsible for the observed catalytic activity.

Controlled formation of CoOOH/Co(III)-MOF active phase for boosting electrocatalytic alkaline water oxidation

Surface reconstituted metal-organic frameworks (MOFs) offer appealing properties for electrocatalysis due to their unique structural and compositional advantages. In this work, a controlled potential-induced reconstruction of a two-dimensional cobalt metal-organic framework for boosting oxygen evolution reaction in alkaline media is reported. The current MOF is shown to undergo a partial structural transformation that generates a heterogeneous system, where the original MOF coexists with an oxyhydroxide phase. In fact, the potential-induced stabilization of Co(III) metal centers in the MOF is crucial for delaying its full degradation in alkaline media. This partial retention of the Co(III)MOF phase in the so-derived heterogeneous catalyst has been demonstrated to be decisive for boosting the alkaline electrocatalytic oxygen evolution reaction (OER), displaying superior OER activity in terms of both thermodynamic and kinetic merits compared to the benchmark IrO2 and RuO2 electrocatalysts and the prototypical cobalt (oxy)hydroxides, with a Tafel slope of 52 mV dec−1 and a turnover frequency (TOF) of 6.8 s−1 at 450 mV. Remarkably, the generated final product is stable, exhibiting high robustness and long durability for long-term OER electrolysis. This work provides new insight into the impact of the reconstruction of a MOF for alkaline OER under typical electrochemical conditions, which ultimately benefits the rational design of MOF-based catalysts with high electrocatalytic activity for oxidation reactions.

Construction of Mesoporous Aluminosilicate Thin Films on ITO Electrodes for Immobilizing a Cationic Ru(II) Water Oxidation Catalyst

Aluminosilicate (Al‐SiO2) thin films with vertically aligned mesochannels were successfully synthesized on ITO electrodes and employed for the immobilization of a cationic Ru(II) water oxidation catalyst without requiring linker groups. Optimal synthesis conditions yielded uniform mesoporous Al‐SiO2 films with tunable Al content, high surface area (568 m2/g), 3.94 nm pore size, and 155 nm thickness. Electrochemical studies confirmed the presence of the immobilized Ru complex undergoing diffusion‐controlled Ru(III/II) and Ru(IV/III) electron transfer. The Ru loading reached 4.71 nmol/cm2 at Si/Al = 9.6, with higher Al content enhancing loading amounts via cation exchange. The Ru‐modified electrode exhibited high electrocatalytic water oxidation activity, achieving 75.3% Faradaic efficiency and a turnover number of 298.6 for O2 evolution for 1 hour. This work provides a new approach to construct porous environments on an electrode surface to immobilize positively charged transition‐metal complexes as catalysts, offering potential applications in the development of electrocatalytic systems for energy conversion.

Multicomponent Interface and Electronic Structure Engineering in Ir-Doped CoMO4-Co(OH)2 (M = W and Mo) Enable Promoted Oxygen Evolution Reaction.

The core principles of multicomponent interface and electronic structure engineering are essential in designing high-performance catalysts for the oxygen evolution reaction (OER). However, combining these aspects within a catalyst is a significant challenge. In this investigation, a novel approach involving the development of hybrid Ir-doped CoMO4-Co(OH)2 (M = W and Mo) hollow nanoboxes was introduced, enabling remarkably efficient water oxidation electrocatalysis. Constructed from ultrathin nanosheet-assembled hollow nanoboxes, these structures boast a wealth of active centers for intermediate species, which in turn enhance both charge transfer and mass transport capabilities. Moreover, the compelling electronic and synergistic effects arising from the interaction between CoMO4 and Co(OH)2 significantly bolster OER electrocatalysis by facilitating efficient electron transfer. The introduction of Ir atoms serves to strategically adjust the electronic structure, fine-tune its electronic state, and operate as active centers to enhance OER electrocatalysis, thus diminishing the overpotential. This configuration results in Ir-CoWO4-Co(OH)2 and Ir-CoMoO4-Co(OH)2 exhibiting impressively low overpotentials of 252 and 261 mV, respectively, to 10 mA cm-2. Utilized in conjunction with the Pt/C catalyst in a two-electrode system for overall water splitting, a mere 1.53 V cell potential is needed to achieve the desired 10 mA cm-2 current density.

Surface reconstruction of defect-engineered MIL-88@Fe2O3 p-n heterojunction for enhanced electrocatalytic water and urea oxidation

Defective p-n heterojunction engineering has been under the spotlighted as a promising strategy for electrochemical oxygen evolution reaction (OER) and urea oxidation reaction (UOR). Still, it remains a great challenge how to use the space-charge region of p-n heterojunction to study the regulation mechanism of the p-n heterogeneous interface and vacancy defects on the incomplete self-reconstruction from pristine materials to (oxy)hydroxides. Herein, NH2-MIL-88b(Fe)/α-Fe2O3 p-n heterojunction with rich oxygen vacancies (denoted as p-n MIL-88@Fe2O3-OV) has been prepared using a simple one-step solvothermal method. The prepared catalyst exhibits promising electrocatalytic performance for OER and UOR, requiring low potentials of 1.50 and 1.35 V to reach the current density of 10 mA cm−2, respectively. The combined in-situ/ex-situ experimental and theoretical investigations unveil that p-n heterojunction engineering can not only facilitate charge transfer from n-type α-Fe2O3 to p-type NH2-MIL-88b(Fe) (denoted as MIL-88) and generate abundant oxygen vacancies, but also appreciably trigger phase transformation of MIL-88 into active FeOOH. The reconstructed FeOOH/α-Fe2O3 heterojunction optimizes the bonding strength towards key oxygen-containing intermediates and boosts the intrinsic activity. This work provides new insight into the self-reconstruction effect in the p-n heterojunction for enhancing the OER and UOR catalytic activity.

Engineering MOF@LDH heterojunction with strong interfacial built-in electric field towards enhanced electrocatalytic water oxidation

Guiding the dynamic reconstruction of the oxygen evolution reaction (OER) is crucial for realizing the industrial application of hydrogen production through water electrolysis. In this study, we have intricately designed a built-in electric field (BIEF) between MIL-88B(Fe) and layered double hydroxide (LDH) with an adjusted work function difference. This design drives an asymmetric interfacial electron distribution, enhancing electron accumulation at the Fe sites within MIL-88B(Fe) and electron-deficient LDHs. Consequently, this setup promotes the surface dynamic reconstruction of LDHs into highly active oxyhydroxides, while simultaneously slowing down the rapid dissolution of Fe during OER operation. This optimization improves the adsorption/desorption of oxygen intermediates, ensuring a sustained high OER activity during long-term electrochemical operation. As expected, the optimal MIL-88B(Fe)@NiCo LDH configuration demonstrates a remarkably low overpotential of only 279 mV at 10 mA cm−2, maintaining operational stability for 70 h. This research significantly advances our understanding of the dynamic reconstruction of MOF@LDH heterojunctions and introduces a straightforward strategy for engineering BIEF to guide this process effectively.

Correlating crystallinity regulation in spinel oxides and catalytic activity in electrocatalytic water oxidation

Recently, the electro-Fenton (EF) process by coupling cathodic two-electron oxygen reduction reaction (2e- ORR) with anodic oxygen evolution reaction (OER) has emerged as a potentially viable technology, while the sluggish OER is the main bottleneck. As promising OER catalysts, the amorphous and crystal phases of spinel oxides display high activities and electrical conductivity, respectively. Efforts to produce amorphous/crystal spinel oxides have progressed slowly, and how an amorphous/crystal structure benefits the catalytic performances remains elusive. Herein, Fe-doped NiCo2O4 (Fe-NiCo2O4) was used as a model catalyst to explore the effect mechanism of crystallinity controlled by annealing temperature on OER performance. The results display that the Fe-NiCo2O4 obtained at 300 ℃ shows amorphous/crystal structure, which facilitates the active site exposure and the charge transfer, leading to superior OER activity and catalytic stability. Based on the crystallinity regulation of OER catalysts, we propose an anodic optimized strategy to upgrade the EF-related processes by effectively providing O2 produced in the anode.

Teaching Undergraduate Students Heterogeneous Electrocatalytic Water Oxidation Using Cyclic Voltammetry and Python Simulation

Undergraduate students are motivated and engaged to persist in STEM by learning skills to combat climate change and reduce carbon dioxide (CO2) generation. Water electrolysis is not only an important process to produce the clean energy source hydrogen (H2), but also a classical reaction discussed in the undergraduate chemistry curriculum.In this talk, we will discuss our efforts of developing an upper division laboratory to teach undergraduate students basic concepts in electrochemistry via the heterogeneous anodic electrocatalytic water oxidation in water electrolysis.1Both experimental work and simulation practices with Python were implemented in this laboratory. Key concepts including chemical reversibility, electrochemical reversibility and kinetics of heterogeneous charge transfer were introduced to students in the learning outcomes. The integrated experience of mini lectures, hands-on experience of materials preparation and electrochemical characterizations along with the simulations helped enhance students’ learning. Additionally, the experience of using Python simulations motivates students to learn programming, which will help prepare them for the workforce and other STEM careers. Chem. Educ. 2023, 100, 8, 3036–3043

Encapsulating Nickel-Iron Alloy Nanoparticles in a Polysilazane-Derived Microporous Si-C-O-N-Based Support to Stimulate Superior OER Activity.

The in situ confinement of nickel (Ni)-iron (Fe) nanoparticles (NPs) in a polymer-derived microporous silicon carboxynitride (Si-C-O-N)-based support is investigated to stimulate superior oxygen evolution reaction (OER) activity in an alkaline media. Firstly, we consider a commercial polysilazane (PSZ) and Ni and Fe chlorides to be mixed in N,N-dimethylformamide (DMF) and deliverafter overnight solvent reflux a series of Ni-Fe : organosilicon coordination polymers. The latter are then heat-treated at 500 °C in flowing argon to form the title compounds. By considering a Ni : Fe ratio of 1.5, face centred cubic (fcc) NixFey alloy NPs with a size of 15-30 nm are in situ generated in a porous Si-C-O-N-based matrixdisplaying a specific surface area (SSA) as high as 237 m2 ⋅ g-1. Hence, encapsulated NPs are rendered accessible to promote electrocatalytic water oxidation. An OER overpotential as low as 315 mV at 10 mA ⋅ cm-2 is measured. This high catalytic performance (considering that the metal mass loading is as low as 0.24 mg cm-2) is rather stable as observed after an activation step; thus, validating our synthesis approach. This is clearly attributed to both the strong NP-matrix interaction and the confinement effect of the matrix as highlighted through post mortem microscopy observations.

Ultrasonic-assisted Fenton reaction inducing surface reconstruction endows nickel/iron-layered double hydroxide with efficient water and organics electrooxidation

Nickel/iron-layered double hydroxide (NiFe-LDH) tends to undergo an electrochemically induced surface reconstruction during the water oxidation in alkaline, which will consume excess electric energy to overcome the reconstruction thermodynamic barrier. In the present work, a novel ultrasonic wave-assisted Fenton reaction strategy is employed to synthesize the surface reconstructed NiFe-LDH nanosheets cultivated directly on Ni foam (NiFe-LDH/NF-W). Morphological and structural characterizations reveal that the low-spin states of Ni2+ (t2g6eg2) and Fe2+ (t2g4eg2) on the NiFe-LDH surface partially transform into high-spin states of Ni3+ (t2g6eg1) and Fe3+ (t2g3eg2) and formation of the highly active species of NiFeOOH. A lower surface reconstruction thermodynamic barrier advantages the electrochemical process and enables the NiFe-LDH/NF-W electrode to exhibit superior electrocatalytic water oxidation activity, which delivers 10 mA cm−2 merely needing an overpotential of 235 mV. Besides, surface reconstruction endows NiFe-LDH/NF-W with outstanding electrooxidation activities for organic molecules of methanol, ethanol, glycerol, ethylene glycol, glucose, and urea. Ultrasonic-assisted Fenton reaction inducing surface reconstruction strategy will further advance the utilization of NiFe-LDH catalyst in water and organics electrooxidation.