Coordination Sphere Research Articles

Tuning Proton Affinity on Co−N−C Atomic Interface to Disentangle Activity‐Selectivity Trade‐off in Acidic Oxygen Reduction to H2O2

AbstractIn oxygen reduction reaction to H2O2 via two‐electron pathway (2e− ORR), adsorption strength of oxygen‐containing intermediates determines both catalytic activity and selectivity. However, it also causes activity‐selectivity trade‐off. Herein, we propose a novel strategy through modulating the interaction between protons and *OOH intermediates to break the activity‐selectivity trade‐off for highly active and selective 2e− ORR. Taking the typical cobalt–nitrogen–carbon single‐atom catalyst as an example, boron heteroatoms doped into second coordination sphere of CoN4 (Co1‐NBC) increase proton affinity on catalyst surface, facilitating proton attack on the former oxygen of *OOH and thereby promoting H2O2 formation. As a result, Co1‐NBC simultaneously achieves prominent 2e− ORR activity and selectivity in acid with onset potential of 0.724 V vs. RHE and H2O2 selectivity of 94 %, surpassing most reported catalysts. Furthermore, Co1‐NBC exhibits a remarkable H2O2 productivity of 202.7 mg cm−2 h−1 and a remarkable stability of 60 h at 200 mA cm−2 in flow cell. This work provides new insights into resolving activity‐selectivity trade‐off in electrocatalysis.

Ligand-Directed Valence Band Engineering in Pb2+ Hybrid Crystals: Achieving Dispersive Bands and Shallow Valence Band Maximum.

While crystalline hybrid solids hold great potential as novel semiconductors, most semiconductive hybrids utilize transition metal ions, which inherently limit carrier mobility due to the small band dispersion derived from the d orbitals. The filled s orbitals of post-transition metal ions offer the potential to design dispersed valence bands, but a method to translate the local structure design of these metal ions to valence band engineering is still in development. This study focuses on Pb2+-containing hybrid crystals, developing a simple strategy to control the Pb2+ coordination geometry through the molecular design of azole ligands. By preprogramming the coordination number of Pb2+ with azolate ligands, we succeeded in obtaining an isotropic coordination environment at a higher coordination number, resulting in a dispersed valence band and shallow valence band maximum while having a wide band gap. Detailed analysis of the band structures reveals that the energy levels and symmetry of the molecular orbitals of the anions play important roles in realizing these antinomic properties. This ligand-directed approach achieves both isotropy and covalency in the coordination bond by exploiting the diversity of the molecular orbitals. Our findings provide a foundation for future design strategies to optimize electronic structures in hybrid materials, advancing their application in semiconductive devices.

Trimetallic FeNiCu Atomic Clusters Supported on Carbon Matrix: Highly Active Catalysts for C3H6-SCR of NO.

C3H6-SCR denitrification technology faces catalyst deactivation problems and low catalytic performance at medium-low temperatures. This study utilized the intermetallic synergies to prepare atomic cluster catalysts (FeNiCu/NC) by anchoring Fe-Ni-Cu on a carbon matrix to enhance the C3H6-SCR performance at medium-low temperatures. The synergistic effect of the Fe-Ni-Cu is reflected in the differences in the physicochemical properties of the catalysts, which is proved by several characterization techniques. Results showed that the FeNiCu/NC catalyst had a larger surface area (541.4 m2/g) and there were no metal oxides on the surface of the catalyst but abundant defective sites that anchored Fe/Ni/Cu atoms through N atoms to form M-Nx active sites and atomic clusters. The hollow carbon morphology provides sufficient active sites for C3H6-SCR. The coordination environments of active sites were M-Nx-C, Fe2/FeCu2/FeNi2, Ni3/NiFe/NiCu2, and Cu4/CuFe2/CuNi2, where the synergistic action of trimetal leads to the presence of Fe-Ni-Cu-Nx-C. The synergistic action of the Fe-Ni-Cu significantly improved the C3H6-SCR performance at medium-low temperatures. The FeNiCu/NC exhibited an 81% NO conversion at 150 °C under 2% O2, 15% and 20% higher than FeNi/NC and FeCu/NC catalysts, respectively. Even at 4% O2, the FeNiCu/NC catalyst was active to remove 78% NO and achieve a 93% N2 selectivity at 150 °C and maintained a 100% NO conversion at 300-425 °C. The DRIFTS results demonstrated that NO and C3H6 could combine with active O at metal cluster, M-Nx, or defective oxygen sites to produce various intermediate species, wherein acetates and nitrates were the main active intermediates. Based on the DRIFTS results, a reaction pathway for C3H6-SCR over the FeNiCu/NC catalyst was proposed.

Enhancement of Selective Catalytic Oxidation of Lignin β-O-4 Bond via Orbital Modulation and Surface Lattice Reconstruction.

The orbital modulation and surface lattice reconstruction represent an effective strategy to regulate the interaction between catalyst interface sites and intermediates, thereby enhancing catalytic activity and selectivity. In this study, the crystal surface of Au-K/CeO2 catalyst can undergo reversible transformation by tuning the coordination environment of Ce, which enables the activation of the Cβ-H bond and the oxidative cleavage of the Cβ-O and Cα-Cβ bonds, leading to the cleavage of 2-phenoxy-1-phenylethanol. The t2g orbitals of Au 5d hybridize with the 2p orbitals of lattice oxygen in CeO2 via π-coordination, modulating the coordination environment of Ce 4 f and reconstructing the lattice oxygen in the CeO2 framework, as well as increasing the oxygen vacancies. The interface sites formed by the synergy between Au clusters in the reconstructed Ce-OL1-Au structure and doped K play dual roles. On the one hand, it activates the Cβ-H bond, facilitating the enolization of the pre-oxidized 2-phenoxy-1-phenylethanone. On the other hand, through single-electron transfer involving Ce3+ 4f1 and the adsorption by oxygen vacancies, it enhances the oxidative cleavage of the Cβ-O and Cα-Cβ bonds. This study elucidates the complex mechanistic roles of the structure and properties of Au-K/CeO2 catalyst in the selective catalytic oxidation of lignin β-O-4 bond.

A multichromotropic dinuclear copper(II) complex: Unveiling its structural and spectroscopic properties

A novel dinuclear copper(II) complex, [Cu₂L₂(μ-Cl)₂]Cl₂•4H₂O, was synthesized using a tetradentate hemilabile ligand, 3,3′-((pyridin-2-ylmethyl)azanediyl)dipropanamide (L). The complex was characterized by various spectroscopic techniques, including FT-IR, UV-Vis spectroscopy, elemental analysis, TG-DTA, and conductivity measurements. X-ray crystallography confirmed the formation of the binuclear complex, revealing a dicationic unit with distorted octahedral geometry at the copper centers, bridged by two chloride ions. The coordination environment around each copper ion includes two nitrogen and two oxygen donors from the ligand, along with the bridging chlorides. Notably, the complex exhibits significant chromotropism, including solvatochromism, halochromism, ionochromism, and thermochromism, which are attributed to the Jahn-Teller effect and the flexible coordination environment around the copper centers. Thermal analysis indicates the stability of the complex up to 118°C, with subsequent decomposition occurring in distinct stages. Hirshfeld surface analysis further elucidates the intermolecular interactions within the crystal lattice. Computational studies were conducted using Time Dependent Density Functional Theory (TD-DFT) to gain insights into the nature of the observed chromotropism. The computed absorption spectra closely matched the experimental data, validating the proposed electronic transitions responsible for the chromotropic behavior. The multifaceted chromotropic behavior of this complex highlights its potential applications in sensing technologies and smart materials. The study advances the understanding of chromotropism in metal complexes and provides insights into the design of responsive materials based on transition metal chemistry.

Comparative Analysis of Tetravalent Actinide Schiff Base Complexes: Influence of Donor and Ligand Backbone on Molecular Geometry and Metal Binding.

A series of isostructural early actinide AnIV complexes was synthesized in order to investigate the influence of a conjugated framework in the ligand backbone on An bonding. Therefore, the AnIV complexes [An(pyrophen)2] (An = Th, U, Np, and Pu) with the pure N-donor ligand bis(2-pyrrolecarbonylaldehyde)-o-phenylenediamine referred to as pyrophen, were synthesized and characterized. Solid state analysis via single-crystal X-ray diffraction (SC-XRD) reveals two sets of ligands binding in an almost orthogonal arrangement to the actinide center. For the larger actinides Th and U, the coordination sphere allows for additional coordination by a solvent molecule. Nuclear magnetic resonance spectroscopy (NMR) studies show the presence of highly symmetrical complexes in solution in good agreement with the solvent-free solid structures. While SC-XRD suggests mainly ionic binding, an analysis of paramagnetic NMR contributions and quantum chemical bond analysis hint towards significant covalency in the U, Np, and Pu compounds. This series of An complexes allowed for a thorough structural and theoretical comparison of a conjugated system to a closely related N-donor ligand (pyren)[1] as well as to the mixed N,O Schiff base ligands salophen (conjugated) and salen (non-conjugated).

The Impact of Coordination Distortion on Magnetic Properties of Co (II) Single‐Ion Magnets With Trigonal Prism Coordination Geometry

ABSTRACTTwo Co (II) compounds [Co (abs)2]·2H2O (1) and [Co (pabs)2] (2) (Habs = N‐(pyridine‐2′‐yl methylene)‐2‐aminobenzene sulfonic acid, Hpabs = N‐[(pyridine‐2′‐yl)(phenyl)methylene]‐2‐aminobenzene sulfonic acid) were synthesized by the introduction of sulfonate ligands with different substitutions. Both Co (II) ions are located in a trigonal prism coordination environment with different coordination distortions. Static magnetic studies and theoretical calculations found that easy‐axis magnetic anisotropy is present in both complexes. The contributions of the negative D values are principally derived from the first quartet excited state. Dynamic magnetic investigations uncovered that both compounds have field‐induced single‐ion magnet (SIM) behavior and their magnetic relaxations mainly realize through Raman and direct pathways.

Cyclometalated N-Difluoromethylbenzimidazolylidene Platinum(II) Complexes with Built-in Secondary Coordination Spheres: Photophysical Properties and Bioimaging.

Bidentate Pt(II) complexes with cyclometalated N-heteroarene or N-heterocyclic carbene (NHC) ligands have been extensively studied as phosphorescent emitters over the past two decades. Herein, we introduce a difluoromethyl group (CF2H) into the wingtip of NHCs, where CF2H acts as a lipophilic hydrogen bond (HB) donor. Their cyclometalated Pt(II) complexes show excellent PLQYs (up to 93%) and phosphorescence lifetimes mainly due to the rigid structure with hydrogen bonding between the CF2H group and the adjacent O atom at the β-diketonate ligand. Bioimaging studies demonstrate high cellular uptake efficiency and deep tumor penetration capability of complex 7 in HeLa cells and multicellular tumor spheroids, highlighting their potential as bioimaging probes.

Understanding the Carbyne Formation from C2H2 Complexes.

Nature chooses a high-valent tungsten center at the active site of the enzyme acetylene hydratase to facilitate acetylene hydration to acetaldehyde. However, the reactions of tungsten-coordinated acetylene are still not well understood, which prevents the development of sustainable bioinspired alkyne hydration catalysts. Here we report the reactivity of two bioinspired tungsten complexes with the acetylene ligand acting as a four-: [W(CO)(C2H2)(PymS)2] (1) and a two-electron donor: [WO(C2H2)(PymS)2] (3), with PMe3 as a nucleophile to simulate the enzyme's reactivity (PymS = 4-(trifluoromethyl)-6-methylpyrimidine-2-thiolate). In dichloromethane, compound 1 was found to react to the cationic carbyne [W≡CCH2PMe3(CO)(PMe3)2(PymS)]Cl (2-Cl) while 3 reacts to the vinyl compound [WO(CH═CHPMe3)(PMe3)3(PymS)]Cl (4-Cl). The formation of the latter follows the common rules applied to η2-alkyne complexes, whereas the carbyne formation was not expected due to the challenging 1,2-H shift. To understand these differences in behavior between seemingly similar acetylene complexes, stepwise addition of the nucleophile in various solvents was investigated by synthetic, spectroscopic, and computational approaches. In this manuscript, we describe that only a four-electron donor acetylene complex can react to the carbyne over the η1-vinyl intermediate and that 1,2-H shift can be assisted by an H-transfer reagent (in this case, the decoordinated PymS ligand). Furthermore, to favor the attack of PMe3 at W coordinated acetylene, the metal center needs to be electron-poor and crowded enough to prevent nucleophile coordination. Finally, the intricate role of the anionic PymS ligand in the vicinity of the first coordination sphere models the potential involvement of amino acid residues during acetylene transformations in AH.

Metal-Hydroxide Organic Frameworks for Aqueous Nickel-Zinc Batteries.

Hydroxides exhibit a high theoretical capacity for energy storage by ion release and are often intercalated with anions to enhance the ion migration kinetics. In this study, a series of metal-hydroxide organic frameworks (MHOFs) are synthesized by intercalating aromatic organic linkers into hydroxides using I-M/Ni(OH)2 (where M = Co2+, Cu2+, Mg2+, Fe2+). The coordination environment and layer spacing (1.09 nm) of I-M/Ni(OH)2 are explored by X-ray absorption fine structure and cryo-electron microscopy. The intercalation nanostructure improves the conductivity of the hydroxides and facilitates Zn2+ migration by increasing the interlayer spacing, while enhancing the rate capability and cycling stability. Consequently, the I-Co/Ni(OH)2 material exhibites a satisfactory specific capacity of 0.35 mAh cm-2 at 3 mA cm-2 and a high peak power density of 6.78 mW cm-2. This study offers a novel perspective on the design of intercalated hydroxide and provides new insights into high-performance nickel-zinc batteres.

Toward the Rational Design of an OsM4 Center for Methane Activation: Gas-Phase Result-Derived Neural Network Model.

Gas-phase reactions of [OsBx]+ (x = 1-4) with methane at ambient temperature have been studied by using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. The [OsBx]+ (x = 1-4) cluster ions can undergo dehydrogenation reactions with methane. Comprehensive analysis of the [OsBx]+/CH4 (x = 1-4) system with Os-complexes ([OsCy]+ (y = 1-3) and [OsOz]+ (z = 1-3)) shows that the large polarity of the cluster and the high sum of the pair energies between Os and the ligand in the ETS-NOCV combine to promote the ability of the cluster to activate methane. Cluster polarity may induce heterolytic cleavage of the C-H bond, and the sum of the pair energies of the fragments may reduce the cluster orbital energy to match the methane orbital and improve the cluster stability. The synergistic interplay of these two factors may offer a viable approach for the activation of methane in the condensed phase, which involves modulating the coordination environment of the active sites to enhance the stability and facilitate C-H bond cleavage and the degree of matching with methane orbitals. A nonlinear function is used to extract second-order characteristic features that have a significant impact on the energy difference based on the limited energy difference data of the OsBmCnOlHk units. A neural network model is next designed to predict the reaction barrier for methane conversion by OsM4+ (M = C, N, O, Al, Si, or P) with high accuracy.

Reconstructing the Coordination Environment of Fe/Co Dual-atom Sites towards Efficient Oxygen Electrocatalysis for Zn-Air Batteries.

Dual-atom catalysts with nitrogen-coordinated metal sites embedded in carbon can drive the oxygen reduction and evolution reactions (ORR/OER) in rechargeable zinc-air batteries (ZABs), and the further improvement is limited by the linear scaling relationship of intermediate binding energies in the absorbate evolution mechanism (AEM). Triggering the lattice oxygen mechanism (LOM) is promising to overcome this challenge, but has yet been verified since the lacking of bridge oxygen (O) in the rigid coordination environment of the metal centers. Here, we demonstrate that suitably tailored dual-atom catalysts of FeCo-N-C can undergo out-plane and in-plane reconstruction to form the both axial O and bridge O at the metal centers, and thus activate the LOM pathway. The tailored FeCo-N-C with shortened Fe-N bonds also favor the ORR process, therefore is a promising dual-atom oxygen catalyst. The assembled rechargeable ZABs demonstrate a peak power density of 332 mW cm-2, and exhibit no notable decline after ~ 720 h of continuous cycling.

Modulating RuO2 Electrocatalysis via Introducing Lanthanides for Enhanced Acidic Oxygen Evolution

AbstractThe low activity of ruthenium dioxide (RuO2) and the rapid dissolution of the ruthenium (Ru) site during acid oxygen evolution reaction (OER) at high current density restricts its application in proton exchange membrane (PEM) electrolyzers. In this work, a series of rare‐earth (RE) elements doped RuO2 nanorods is developed as high‐performance OER electrocatalysts. X‐ray absorption spectroscopy suggests that RE doping regulates the local coordination environment around Ru sites, lowers the valance of Ru, and shortens the Ru─O─Ru(M) bond length, which enhances structural stability. Among the RE‐RuO2 samples, Sm‐RuO2 exhibits remarkable performance with a low overpotential of 283 mV to reach 100 mA cm−2 and maintained stability for over 140 h at 10 mA cm−2. Moreover, the PEM electrolyzer using Sm‐RuO2 as the anode can be stably operated at 500 mA cm−2 for 15 h. Electrochemical analysis, X‐ray photoelectron spectroscopy, and in situ Raman spectroscopy show that Sm doping lowers the d‐band center, reduces the adsorption energy of O intermediates to enhance the OER activity, and restrains excessive oxidation of Ru sites while stabilizing lattice oxygen during the OER process, thereby enhancing OER stability. This work offers valuable insights into improving the stability of metal oxide catalysts in acidic electrolytes.

Modulating Coordination Environment of Cobalt-Based Spinel Octahedral Metal Sites to Boost Metal–Oxygen Bond Covalency for Reversible Lithium–Oxygen Batteries

Modulating Coordination Environment of Cobalt-Based Spinel Octahedral Metal Sites to Boost Metal–Oxygen Bond Covalency for Reversible Lithium–Oxygen Batteries

L10-PtCo and L12-Pt3Co Intermetallics for Oxygen Reduction Reaction: The Influence of Composition and Structure on Properties.

Pt-based intermetallics are regarded as highly efficient electrocatalysts for oxygen reduction reaction (ORR). However, Pt-based intermetallics with different Pt: M atomic ratios have different atomic arrangements and crystal structures, which will change the electronic structure and coordination environment of Pt, thus affecting the electrocatalytic activity. In this work, we prepared L12-Pt3Co and L10-PtCo intermetallic catalysts by modulating the molar ratio of Pt and Co precursors using a thermal annealing method. The mass activity (MA) of L10-PtCo is 0.52 A mg-1 Pt at 0.9 V, which is 1.44 times larger than that of L12-Pt3Co (0.36 A mg-1 Pt). In addition, the MA of L10-PtCo decreases by 17.31 % after 10,000 CV cycles, which is smaller than that of L12-Pt3Co (25.00 % loss in MA), showing excellent structural stability. Theoretical calculations reveal that compared to L12-Pt3Co, L10-PtCo has more electrons transferred to the Pt sites, which further optimizes the electronic structure of Pt and reduces the d-band center, leading to the increase of the electrocatalytic performance. This work provides new insights into the study of Pt-based intermetallics with different Pt: M ratios, which is helpful for the screening and preparation of high-performance Pt-based intermetallics.

Inhomogeneous Coordination in High-Entropy O3-Type Cathodes Enables Suppressed Slab Gliding and Durable Sodium Storage.

O3-type layered oxides are highly promising cathodes for sodium-ion batteries (SIBs), however they undergo complex phase transitions and exhibit high sensibility to air, leading to subpar cycling performance and commercial viability. In this work, we report a layered cathode material (NaNi0.29Cu0.1Mg0.05Li0.05Mn0.2Ti0.2Sn0.11O2) with a sate-of-the-art high-entropy compositional design. We unveil that such a configuration featuring inhomogeneous coordination environment of transition metal (TM) elements, can enable enhanced gliding energy (-0.38 vs -0.58 eV) of TMO2 slabs upon desodiation both theoretically and experimentally, which underlies the fundamental origin of the outstanding structural stability of HEO materials. As a consequence, the complex phase transitions (O3-O'3-P3-P'3-P3'-O3') of conventional O3-type cathode have been eliminated, and the as-obtained material demonstrates exceptional structural robustness and integrity with an ultra-long cycle life in a quasi-solid-state cell (maintaining 73.2 % capacity after 1000 cycles at 2 C). Moreover, the material presents satisfactory air stability, with minimal structural and electrochemical degradation when directly exposed to the air. An Ah-scale pouch cell based on the cathode material is constructed, demonstrating a capacity retention of 83.6 % after 500 cycles, signaling substantial promise for commercial applications.

Inhomogeneous Coordination in High‐Entropy O3‐Type Cathodes Enables Suppressed Slab Gliding and Durable Sodium Storage

AbstractO3‐type layered oxides are highly promising cathodes for sodium‐ion batteries (SIBs), however they undergo complex phase transitions and exhibit high sensibility to air, leading to subpar cycling performance and commercial viability. In this work, we report a layered cathode material (NaNi0.29Cu0.1Mg0.05Li0.05Mn0.2Ti0.2Sn0.11O2) with a sate‐of‐the‐art high‐entropy compositional design. We unveil that such a configuration featuring inhomogeneous coordination environment of transition metal (TM) elements, can enable enhanced gliding energy (−0.38 vs −0.58 eV) of TMO2 slabs upon desodiation both theoretically and experimentally, which underlies the fundamental origin of the outstanding structural stability of HEO materials. As a consequence, the complex phase transitions (O3−O′3−P3−P′3−P3′−O3′) of conventional O3‐type cathode have been eliminated, and the as‐obtained material demonstrates exceptional structural robustness and integrity with an ultra‐long cycle life in a quasi‐solid‐state cell (maintaining 73.2 % capacity after 1000 cycles at 2 C). Moreover, the material presents satisfactory air stability, with minimal structural and electrochemical degradation when directly exposed to the air. An Ah‐scale pouch cell based on the cathode material is constructed, demonstrating a capacity retention of 83.6 % after 500 cycles, signaling substantial promise for commercial applications.

Multifunctional Dy3+ Complexes with Triphenylmethanolates: Structural Diversity, Luminescence, and Magnetic Relaxation.

The coordination environment of magneto-luminescent Dy3+-based Single-Molecule Magnets (SMM) is a crucial factor influencing both magnetic and luminescent properties. In this work, we explore how triphenylmethanolate (Ph3CO-), in combination with other ligands, can modulate the structure and, therefore, the magnetic properties of Dy3+-based SMM. Using triphenylmethanolate in combination with THF and pyridine (Py) as co-ligands, we synthesized a series of mononuclear cis-[Dy(OCPh3)2(THF)4][BPh4]·(2,6-Me2C5H3N) (1), trans-Dy(OCPh3)3(THF)2 (2), fac-Dy(OCPh3)3(py)3 (3) and dinuclear [(Ph3CO)Dy(THF){(μ2-Cl)2Li(THF)2}μ2-Cl]2 (4) complexes where the Dy3+ ion presents five- or six-coordinate geometries. Dinuclear compound 4 exhibits a genuine SMM behavior with a relatively high energy barrier of 421 cm-1, while mononuclear complexes 1-3 are field-induced SMM. These complexes also present Dy3+-characteristic luminescence, highlighting their multifunctional character.

Potential-Driven Coordinated Oxygen Migration in an Electrocatalyst for Sustainable H2O2 Synthesis.

Local coordination environment (LCE) manipulation has emerged as a significant approach for modulating the electrocatalytic behavior of low-dimensional nanomaterials. However, challenges persist in accurately identifying active sites and understanding dynamic changes during operation. Here, we underscore the influence of LCE on the electrochemical production of H2O2, utilizing the Pd cluster as a model catalyst. Density functional theory (DFT) calculations illustrate the role of first- and second-coordinated sulfur and oxygen in modulating the binding strength of HOO*. Guided by DFT screening, the as-prepared Pd cluster (Pdx/HMCS) catalyst presents exceptional catalytic performance with a high mass activity of 4.06 A mg-1 at 0.45 V and selectivity above 94%. The Pdx/HMCS catalyst also delivers promising potential for industrial practices with a production rate of 16.3 mol gcat-1 h-1 in flow cell evaluation. Elaborated in situ characterizations confirm that under operation, oxygen migrates from the second coordination sphere (CS) to the first CS to achieve oxygen coverage on the catalyst surface. Such an oxygen migration phenomenon and the optimized first and second coordination environment give rise to the outstanding performance.

Novel large-scale integrated non-precious metal electrodes for efficient and stable oxygen evolution reaction at high current density in 2.5 kW anion exchange membrane water electrolysis

The utilization of non-precious catalysts to substitute precious metal catalysts on anode side under high current density conditions and with long-term resistance is crucial for the implementation of alkaline anion-exchange membrane water electrolysis (AEMWE) applications. To accommodate industrial applications, a combination of chemical solution and electrodeposition was used to construct NiFeCo layered double hydroxide and NiS nanosheet heterostructures on Ni foam (NiFeCo LDH/NiS/NF). Both experiments and theoretical calculations show that the heterogeneous structure reduces the activation energy barrier of the catalytic reaction and provides an appropriate electronic structure. This not only guarantees the exposure of the active site but also adjusts the local coordination environment and chemisorption properties. Consequently, the reduction in energy barrier affects the rate-determining step (RDS) from *O to *OOH, as well as the energy barriers of all four steps in the oxygen evolution reaction (OER). Consequently, the optimized NiFeCo LDH/NiS/NF catalyst demonstrates a low voltage of 288 mV to operate 1.0 A cm−2. Additionally, the catalyst was conducted with commercial Pt/C coated onto carbon paper (Pt/C/CP) for 2 × 2 cm2 AEMWE exhibited 1.63 V cell voltage to attain 1 A cm−2 and operated for 2100 h from 1 A cm−2 to 2.5 A cm−2 (1.69 V to 1.92 V). Further, the catalyst was prepared scalable to 15 × 15 cm2 for application into a 2.5 kW AEMWE device, which required only 1.77 V at 60 °C to catch 1 A cm−2 for 1000 h, which shows extremally promising application for stable AEMWE device.