Catalyst–Support Interaction in Polyaniline‑Supported Ni_(3)Fe Oxide to Boost Oxygen Evolution Activities for Rechargeable Zn‑Air Batteries

Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.

Boosting Oxygen Evolution Reaction Performance on NiFe‑Based Catalysts Through d‑Orbital Hybridization

Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.

Exciting lattice oxygen of nickel–iron bi-metal alkoxide for efficient electrochemical oxygen evolution reaction

High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.

Valence electronic engineering of superhydrophilic Dy-evoked Ni-MOF outperforming RuO_(2) for highly efficient electrocatalytic oxygen evolution

Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.

Microwave shock motivating the Sr substitution of 2D porous GdFeO_(3) perovskite for highly active oxygen evolution

The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Optimizing 3d spin polarization of CoOOH by in situ Mo doping for efficient oxygen evolution reaction

Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will benefit their quick transition to the next catalysts.Herein,Mo-doped CoOOH was designed as a high-performance model electrocatalyst with durability for 20 h at 10 mAcm−2.Additionally,it had an overpotential of 260 mV(glassy carbon)or 215 mV(nickel foam),which was 78 mV lower than that of IrO_(2)(338 mV).In situ,Raman spectroscopy revealed the transformation process of CoOOH.Calculations using the density functional theory showed that during OER,doped Mo increased the spin-up density of states and shrank the spin-down bandgap of the 3d orbits in the reconstructed CoOOH under the electrochemical activation process,which simultaneously optimized the adsorption and electron conduction of oxygen-related intermediates on Co sites and lowered the OER overpotentials.Our research provides new insights into the methodical planning of the creation of transition-metal oxyhydroxide OER catalysts.

The role of strain in oxygen evolution reaction

The oxygen evolution reaction(OER)is a crucial step in metal-air batteries and water splitting technologies,playing a significant role in the efficiency and achievable heights of these two technologies.However,the OER is a four-step,four-electron reaction,and its slow kinetics result in high overpotentials,posing a challenge.To address this issue,numerous strategies involving modified catalysts have been proposed and proven to be highly efficient.In these strategies,the introduction of strain has been widely reported because it is generally believed to effectively regulate the electronic structure of metal sites and alter the adsorption energy of catalyst surfaces with reaction intermediates.However,strain has many other effects that are not well known,making it an important yet unexplored area.Based on this,this review provides a detailed introduction to the various roles of strain in OER.To better explain these roles,the review also presents the definition of strain and elucidates the potential mechanisms of strain in OER based on the d-band center theory and adsorption volcano plot.Additionally,the review showcases various ways of introducing strain in OER through examples reported in the latest literature,aiming to provide a comprehensive perspective for the development of strain engineering.Finally,the review analyzes the appropriate proportion of strain introduction,compares compressive and tensile strain,and examines the impact of strain on stability.And the review offers prospects for future research directions in this emerging field.

Steering surface reconstruction of hybrid metal oxides for efficient oxygen evolution reaction in water splitting and zinc-air batteries

Surface reconstruction yields real active species in electrochemical oxygen evolution reaction(OER)conditions;however,rationally regulating reconstruction in a targeted manner for constructing highly active OER electrocatalysts remains a formidable challenge.Here,an electrochemical activation strategy with selective etching was utilized to guide the reconstruction process of a hybrid cobalt-molybdenum oxide(CoMoO_(4)/Co_(3)O_(4)@CC)in a favorable direction to improve the OER performance.Both in-situ Raman and multiple ex-situ characterization tools demonstrate that controlled surface reconstruction can be easily achieved through Mo etching,with the formation of a dynamically stable amorphous-crystalline heterostructure.Theoretical calculations together with experimental results reveal that the synergistic effects between amorphous CoOOH and crystalline Co_(3)O_(4) are crucial in enhancing the catalytic performance.Consequently,the reconstructed CoMoO_(4)/Co_(3)O_(4)@CC exhibits a low overpotential of 250 mV to achieve a current density of 10 mA cm^(-2) in 1 M KOH,and more importantly it can be practiced in electrolytic water splitting and rechargeable zinc-air batteries devices,achieving ultra-long stability for over 500 and 1200 h,respectively.This work provides a promising route for the construction of high-performance electrocatalysts.

Rational design of MXene-based vacancy-confined single-atom catalyst for efficient oxygen evolution reaction

Two-dimensional transition metal carbides(MXenes) have been demonstrated to be promising supports for single-atom catalysts(SACs) to enable efficient oxygen evolution reaction(OER).However,the rational design of MXene-based SACs depends on an experimental trial-and-error approach.A theoretical guidance principle is highly expected for the efficient evaluation of MXene-based SACs.Herein,highthroughput screening was performed through first-principles calculations and machine learning techniques.Ti_(3)C_(2)(OH)_(x),V_(3)C_(2)(OH)_(x),Zr_(3)C_(2)(OH)_(x),Nb_(3)C_(2)(OH)_(x),Hf_(3)C_(2)(OH)_(x),Ta_(3)C_(2)(OH)_(x),and W_(3)C_(2)(OH)_(x) were screened out based on their excellent stability.Zn,Pd,Ag,Cd,Au,and Hg were proposed to be promising single atoms anchored in MXenes based on cohesive energy analysis.Hf_(3)C_(2)(OH)_(x) with a Pd single atom delivers a theoretical overpotential of 81 mV.Both moderate electron-deficient state and high covalency of metal-carbon bonds were critical features for the high OER reactivity.This principle is expected to be a promising approach to the rational design of OER catalysts for metal-air batteries,fuel cells,and other OER-based energy storage devices.

Rational Design of Cost-Effective Metal-Doped ZrO_(2)for Oxygen Evolution Reaction

The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stable under OER operating conditions,exhibits inherently poor OER activity from experimental observations.Herein,we doped a series of metal elements to regulate the ZrO_(2)catalytic activity in OER via spin-polarized density functional theory calculations with van der Waals interactions.Microkinetic modeling as a function of the OER activity descriptor(G_(O*)-G_(HO*))displays that 16 metal dopants enable to enhance OER activities over a thermodynamically stable ZrO_(2)surface,among which Fe and Rh(in the form of single-atom dopant)reach the volcano peak(i.e.the optimal activity of OER under the potential of interest),indicating excellent OER performance.Free energy diagram calculations,density of states,and ab initio molecular dynamics simulations further showed that Fe and Rh are the effective dopants for ZrO_(2),leading to low OER overpotential,high conductivity,and good stability.Considering cost-effectiveness,single-atom Fe doped ZrO_(2)emerged as the most promising catalyst for OER.This finding offers a valuable perspective and reference for experimental researchers to design cost-effective catalysts for the industrial-scale OER production.

Surface-neutralization engineered NiCo-LDH/phosphate hetero-sheets toward robust oxygen evolution reaction

Developing highly active oxygen evolution reaction(OER)electrocatalysts with robust durability is essential in producing high-purity hydrogen through water electrolysis.Layered double hydroxide(LDH)based catalysts have demonstrated efficient catalytic performance toward the relatively sluggish OER.By considering the promotion effect of phosphate(Pi)on proton transfer,herein,a facile phosphate acid(PA)surface-neutralization strategy is developed to in-situ construct NiCo-LDH/NiCoPi hetero-sheets toward OER catalysis.OER activity of NiCoLDH is significantly boosted due to the proton promotion effect and the electronic modulation effect of NiCoPi.As a result,the facilely prepared NiCo-LDH/NiCoPi catalyst displays superior OER catalytic activity with a low overpotential of 300 mV to deliver 100 mA cm^(-2)OER and a Tafel slope of 73 mV dec^(-1).Furthermore,no visible activity decay is detected after a 200-h continuous OER operation.The present work,therefore,provides a promising strategy to exploit robust OER electrocatalysts for commercial water electrolysers.

Retaining the self-released chalcogenate at reconstructed cobalt sites by self-transformed carbonate regulation for boosted oxygen evolution

The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction(OER)kinetics.However,it remains a challenge to retain these self-released oxyanions at reconstructed catalysts,hindering its utilization as a tool to develop efficient OER catalysts.Here,we demonstrate a versatile selftransformed carbonate regulation strategy to efficiently retain the self-released chalcogenate at Co oxyhydroxides reconstructed from carbon-incorporated Co selenides under OER conditions.These selftransformed CO_(3)^(2-)can induce electron accumulation and narrow d bond at Co sites to facilitate the Co3d-O 2p orbital hybridization between Co sites and SeO_(x)^(2-)for enhanced SeO_(x)^(2-)retention,which can accelerate the rate-limiting step for^(*)OOH formation during OER.Relative to CoOOH-SeO_(x)^(2-)with limited SeO_(x)^(2-)residues,CoOOH-CO_(3)^(2-)/SeO_(x)^(2-)with elevated SeO_(x)^(2-)retention by CO_(3)^(2-)regulation exhibited a 5.6-fold increase in current density and a remarkable lower Tafel slope towards OER.This strategy paves a rational avenue to design efficient catalysts for electrooxidation reactions through finely regulating self-released oxyanions at reconstructed structures.

Molecular-level proton acceptor boosts oxygen evolution catalysis to enable efficient industrial-scale water splitting

Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy to produce an efficient OER catalyst that can boost industrial-scale water splitting.Molecular-level phosphate(-PO_(4))group is introduced to modify the surface of PrBa_(0.5)Ca_(0.5)Co_(2)O_(5)+δ(PBCC).The achieved catalyst(PO_(4)-PBCC)exhibits significantly enhanced catalytic performance in alkaline media.Based on the X-ray absorption spectroscopy results and density functional theory(DFT)calculations,the PO_(4)on the surface,which is regarded as the Lewis base,is the key factor to overcome the kinetic limitation of the proton transfer process during the OER.The use of the catalyst in a membrane electrode assembly(MEA)is further evaluated for industrial-scale water splitting,and it only needs a low voltage of 1.66 V to achieve a large current density of 1 A cm^(-2).This work provides a new molecular-level strategy to develop highly efficient OER electrocatalysts for industrial applications.

Triphenylphosphine-Assisted Exsolution Engineering on Ruddlesden-Popper Perovskites for Promoting Oxygen Evolution

Metal exsolution engineering has been regarded as a promising strategy for activating intrinsically inert perovskite oxide catalysts toward efficient oxygen evolution reaction.Traditional metal exsolution processes on perovskites are often achieved by using the reducing hydrogen gas;however,this is not effective for the relatively stable phase,such as Ruddlesden-Popper perovskite oxides.To address this issue,triphenylphosphine is proposed to be a reduction promotor for accelerating the reduction and migration of the target metal atoms,aiming to achieve the effective exsolution of metallic species from Ruddlesden-Popper-type parent perovskites.Upon oxygen evolution reaction,these exsolved metallic aggregates are reconstructed into oxyhydroxides as the real active centers.After further modification by lowpercentage iridium oxide nanoclusters,the optimal catalyst delivered an overpotential as low as 305 mV for generating the density of 10 mA cm^(-2),outperforming these reported noble metal-containing perovskite-based alkaline oxygen evolution reaction electrocatalysts.This work provides a potential approach to activate catalytically inert oxides through promoting surface metal exsolution and explores a novel class of Ruddlesden-Poppertype oxides for electrocatalytic applications.

Nano-Au-decorated hierarchical porous cobalt sulfide derived from ZIF-67 toward optimized oxygen evolution catalysis:Important roles of microstructures and electronic modulation

Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.

Suppress oxygen evolution of lithium-rich manganese-based cathode materials via an integrated strategy

Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.

Nickel Sulfide Modified NiCu Nanoalloy with Excellent Oxygen Evolution Reaction Properties Prepared through Electrospinning and Heat Treatment

Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).

Calcium titanate corrosion inhibitor enabling carbon as inert anode for oxygen evolution in molten chlorides

The corrosion inhibition efficacy of titanate(CaTiO_(3))for carbon anodes in molten salts was investigated through various analytical techniques,including linear sweep voltammetry,X-ray diffraction,scanning electron microscopy,and energy dispersion spectroscopy.The results demonstrate that the addition of CaTiO_(3)corrosion inhibitor efficiently passivates the carbon anode and leads to the formation of a dense CaTiO_(3)layer during the electrolysis process in molten CaCl_(2)-CaO.Subsequently,the passivated carbon anode effectively undergoes the oxygen evolution reaction,with an optimal current density for passivation identified at 400 m A/cm^(2).Comprehensive investigations,including CaTiO_(3)solubility tests in molten CaCl_(2)-CaO and numerical modeling of the stability of complex ionic structures,provide compelling evidence supporting“complexation-precipitation”passivation mechanism.This mechanism involves the initial formation of a complex containing TiO_(2)·nCaO by CaTiO_(3)and CaO,which subsequently decomposes to yield CaTiO_(3),firmly coating the surface of the carbon anode.In practical applications,the integration of CaTiO_(3)corrosion inhibitor with the carbon anode leads to the successful preparation of the FeCoNiCrMn high-entropy alloy without carbon contamination in the molten CaCl_(2)-CaO.

Recent advances and key perspectives of in-situ studies for oxygen evolution reaction in water electrolysis

Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.