Tuning interface mechanism of FeCo alloy embedded N,S-codoped carbon substrate for rechargeable Zn-air battery

The interface mechanism between catalyst and carbon substrate has been the focus of research.In this paper,the FeCo alloy embedded N,S co-doped carbon substrate bifunctional catalyst(FeCo/S-NC)is obtained by a simple one-step pyrolysis strategy.The experimental results and density functional theory(DFT)calculation show that the formation of FeCo alloy is conducive to promoting electron transfer,and the introduction of S atom can enhance the interaction between FeCo alloy and carbon substrate,thus inhibiting the migration and agglomeration of particles on the surface of carbon material.The FeCo/SNC catalysts show outstanding performance for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).FeCo/S-NC shows a high half-wave potential(E_(1/2)=0.8823 V)for ORR and a low overpotential at 10 mA cm^(-2)(E_(j=10)=299 mV)for OER.In addition,compared with Pt/C+RuO_(2) assembled Zn-air battery(ZAB),the FeCo/S-NC assembled ZAB exhibits a larger power density(198.8 mW cm^(-2)),a higher specific capacity(786.1 mA h g_(zn)~(-1)),and ultra-stable cycle performance.These results confirm that the optimized composition and the interfacial interaction between catalyst and carbon substrate synergistically enhance the electrochemical performance.

Synergism of preintercalated manganese ions and lattice water in vanadium oxide cathodes for high-capacity and long-life Zn-ion batteries

Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.

Disordered Structure and Reversible Phase Transformation from K-Birnessite to Zn-Buserite Enable High-Performance Aqueous Zinc-lon Batteries

The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from structural degradation during the long-term cycling process,leading to capacity fading.In this study,a Co-doped dMO composite with reduced graphene oxide(GC-dMO)is developed using a simple cost-effective hydrothermal method.The degree of disorderness increases owing to the hetero-atom doping and graphene oxide composites.It is demonstrated that layered dMO and GC-dMO undergo a structural transition from K-birnessite to the Zn-buserite phase upon the first discharge,which enhances the intercalation of Zn^(2+)ions,H_(2)O molecules in the layered structure.The GC-dMO cathode exhibits an excellent capacity of 302 mAh g^(-1)at a current density of 100 mAg^(-1)after 100 cycles as compared with the dMO cathode(159 mAhg^(-1)).The excellent electrochemical performance of the GC-dMO cathode owing to Co-doping and graphene oxide sheets enhances the interlayer gap and disorderness,and maintains structural stability,which facilitates the easy reverse intercalation and de-intercalation of Zn^(2+)ions and H_(2)O molecules.Therefore,GC-dMO is a promising cathode material for large-scale aqueous ZIBs.

Boric Acid-Assisted Pyrolysis for High-Loading Single-Atom Catalysts to Boost Oxygen Reduction Reaction in Zn-Air Batteries

The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.

Temperature inversion enables superior stability for low-temperature Zn-ion batteries

It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing point and high ionic conductivity is proposed.Combined with molecular dynamics simulation and multi-scale interface analysis(time of flight secondary ion mass spectrometry threedimensional mapping and in-situ electrochemical impedance spectroscopy method),the temperature independence of the V_(2)O_(5)cathode and Zn anode is observed to be opposite.Surprisingly,dominated by the solvent structure of the designed electrolyte at low temperatures,vanadium dissolution/shuttle is significantly inhibited,and the zinc dendrites caused by this electrochemical crosstalk are greatly relieved,thus showing an abnormal temperature inversion effect.Through the disclosure and improvement of the above phenomena,the designed Zn||V_(2)O_(5)full cell delivers superior low-T performance,maintaining almost 99%capacity retention after 9500 cycles(working more than 2500 h)at-20°C.This work proposes a kind of electrolyte suitable for low-T ZIBs and reveals the inverse temperature dependence of the Zn anode,which might offer a novel perspective for the investigation of low-T aqueous battery systems.

Heteroatom anchors Fe-Mn dual-atom catalysts with bi-functional oxygen catalytic activity for low-temperature rechargeable flexible Zn-air batteries

M-N-C(M=Fe,Co,Ni,etc.) catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts.But it is still a challenge to further increase the active site density.This article constructs the high-efficiency FeMn-N/S-C-1000 catalyst to realize ORR/OER bifunctional catalysis by hetero-atom,bimetal(Fe,Mn) doped simultaneously strategy.When evaluated it as bi-functional electro-catalysts,FeMn-N/S-C-1000 exhibits excellent catalytic activity(E_(1/2)=0.924 V,E_(j=10)=1.617 V) in alkaline media,outperforms conventional Pt/C,RuO_(2) and most non-precious-metal catalysts reported recently,Such outstanding performance is owing to N,S co-coordinated with metal to form multi-types of single atom,dual atom active sites to carry out bi-catalysis.Importantly,nitrite poison test provides the proof that the active sites of FeMn-N/S-C are more than that of single-atom catalysts to promote catalytic reactions directly.To better understand the local structure of Fe and Mn active sites,XAS and DFT were employed to reveal that FeMn-N_5/S-C site plays the key role during catalysis.Notably,the FeMn-N/S-C-1000 based low-temperature rechargeable flexible Zn-air also exhibits superior discharge performance and extraordinary durability at-40℃.This work will provide a new idea to design diatomic catalysts applied in low-temperature rechargeable batteries.

Hierarchical CoFe@N-Doped Carbon Decorated Wood Carbon as Bifunctional Cathode in Wearable Zn-Air Battery

Rechargeable Zn-air batteries(ZAB)have drawn extensive attention due to their eco-friendliness and safety.However,the lack of high-performance and low-cost oxygen redox reactions(OER and ORR)catalysts has become one of the main stumbling blocks in their development.Herein,we successfully fabricate a CoFe nanobubble encapsulated in nitrogen-doped carbon nanocage on wood carbon support(CoFe@NC/WC)via pyrolysis of a novel Prussian blue analog(PBA)/spruce precursor.The hierarchical CoFe@NC/WC catalyst exhibits an excellent potential difference of 0.74 V between the OER potential at 10 mA cm^(-2)and half-wave potential of ORR in 0.1 M KOH,comparable to recently reported preeminent electrocatalysts.Further,CoFe@NC/WC shows outstanding electrochemical performance in liquid ZAB,with a peak power density of 138.9 mW cm^(-2)and a specific capacity of 763.5 mAh g^(-1).More importantly,a bacterial cellulose nanofiber reinforced polyacrylic acid(BC-PAA)hydrogel electrolyte shows ultrahigh tensile-breaking stress of 1.58 MPa.In conjunction with the as-prepared CoFe@NC/WC catalyst,BC-PAA-based wearable ZAB displays impressive rechargeability and foldability,and can power portable electronics,such as electronic timer and mobile phone,in bent states.This work provides a new approach toward high-activity and low-cost catalysts for ZAB.

Growth and inhibition of zinc anode dendrites in Zn-air batteries:Model and experiment

Zinc(Zn)-air batteries are widely used in secondary battery research owing to their high theoretical energy density,good electrochemical reversibility,stable discharge performance,and low cost of the anode active material Zn.However,the Zn anode also leads to many challenges,including dendrite growth,deformation,and hydrogen precipitation self-corrosion.In this context,Zn dendrite growth has a greater impact on the cycle lives.In this dissertation,a dendrite growth model for a Zn-air battery was established based on electrochemical phase field theory,and the effects of the charging time,anisotropy strength,and electrolyte temperature on the morphology and growth height of Zn dendrites were studied.A series of experiments was designed with different gradient influencing factors in subsequent experiments to verify the theoretical simulations,including elevated electrolyte temperatures,flowing electrolytes,and pulsed charging.The simulation results show that the growth of Zn dendrites is controlled mainly by diffusion and mass transfer processes,whereas the electrolyte temperature,flow rate,and interfacial energy anisotropy intensity are the main factors.The experimental results show that an optimal electrolyte temperature of 343.15 K,an optimal electrolyte flow rate of 40 ml·min^(-1),and an effective pulse charging mode.

Recent progress of self-supported air electrodes for flexible Zn-air batteries

Smart wearable devices are regarded to be the next prevailing technology product after smartphones and smart homes,and thus there has recently been rapid development in flexible electronic energy storage devices.Among them,flexible solid-state zinc-air batteries have received widespread attention because of their high energy density,good safety,and stability.Efficient bifunctional oxygen electrocatalysts are the primary consideration in the development of flexible solid-state zinc-air batteries,and self-supported air cathodes are strong candidates because of their advantages including simplified fabrication process,reduced interfacial resistance,accelerated electron transfer,and good flexibility.This review outlines the research progress in the design and construction of nanoarray bifunctional oxygen electrocatalysts.Starting from the configuration and basic principles of zinc-air batteries and the strategies for the design of bifunctional oxygen electrocatalysts,a detailed discussion of self-supported air cathodes on carbon and metal substrates and their uses in flexible zinc-air batteries will follow.Finally,the challenges and opportunities in the development of flexible zinc-air batteries will be discussed.

Fe-N_(x) sites coupled with core-shell FeS@C nanoparticles to boost the oxygen catalysis for rechargeable Zn-air batteries

The development of efficient single-atom catalysts(SACs) for the oxygen reduction reaction(ORR)remains a formidable challenge,primarily due to the symmetric charge distribution of metal singleatom sites(M-N_(4)).To address such issue,herein,Fe-N_(x) sites coupled synergistic catalysts fabrication strategy is presented to break the uniform electronic distribution,thus enhancing the intrinsic catalytic activity.Precisely,atomically dispersed Fe-N_(x) sites supported on N/S-doped mesoporous carbon(NSC)coupled with FeS@C core-shell nanoparticles(FAS-NSC@950) is synthesized by a facile hydrothermal reaction and subsequent pyrolysis.Due to the presence of an in situ-grown conductive graphitic layer(shell),the FeS nanoparticles(core) effectively adjust the electronic structure of single-atom Fe sites and facilitate the ORR kinetics via short/long-range coupling interactions.Consequently,FAS-NSC@950displays a more positive half-wave potential(E_(1/2)) of 0.871 V with a significantly boosted ORR kinetics(Tafel slope=52.2 mV dec^(-1)),outpacing the commercial Pt/C(E_(1/2)=0.84 V and Tafel slope=54.6 mV dec^(-1)).As a bifunctional electrocatalyst,it displays a smaller bifunctional activity parameter(ΔE) of 0.673 V,surpassing the Pt/C-RuO_(2) combination(ΔE=0.724 V).Besides,the FAS-NSC@950-based zincair battery(ZAB) displays superior power density,specific capacity,and long-term cycling performance to the Pt/C-Ir/C-based ZAB.This work significantly contributes to the field by offering a promising strategy to enhance the catalytic activity of SACs for ORR,with potential implications for energy conversion and storage technologies.

Enhanced bifunctional oxygen electrochemical catalytic performance using La-doped CoFe_(2)O_(4)spinel supported by 3D-G for Zn-air batteries

The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphene(3D-G),where La can facilitate electron transfer from Co to Fe,leading to increased electron cloud density in Fe and improved catalytic performance.The redshift of the G peak in the Raman spectra indicates the interaction between theπbond of 3D-G and d orbitals in La_(0.2)CoFe_(1.8)O_(4).La_(0.2)CoFe_(1.8)/3D-G exhibits superior ORR performance(E_(1/2)=0.86 V vs.RHE)and OER performance(E_(j=10)=1.55 V vs.RHE)to CoFe_(2)O_(4)/3D-G(E_(1/2)=0.831 V vs.RHE,E_(j=10)=1.603 V vs.RHE).Furthermore,it demonstrates excellent bifunctional oxygen catalytic performance while maintaining high power density and stability in liquid zinc-air batteries(ZABs)and flexible ZABs(F-ZABs).This work presents a viable strategy for utilizing rare earth element doped spinels to enhance oxygen catalyst and ZABs performance.

超声处理对可降解Zn-0.5Sr合金组织及腐蚀性能的影响

以Zn-0.5Sr合金为对象,研究了不同超声功率(0、300、600、900 W)对Zn-0.5Sr合金显微组织及腐蚀性能的影响.结果表明:Zn-0.5Sr合金经过超声处理后,铸态组织中SrZn13相由粗大的多边形转变为细小的块状,与未处理的合金相比较,对合金进行600 W超声处理后,合金的电化学腐蚀速率由2.078±0.141 mm/a增加至5.747±0.390 mm/a.当超声功率为600 W时,Zn-0.5Sr合金15、30 d的浸泡腐蚀速度分别为0.090±0.0021、0.074±0.0019 mm/a,是未经超声处理的1.88、1.95倍.

退火工艺对Mg-4.0Zn-0.8Zr合金组织与性能的影响

采用金相显微镜、扫描电镜、拉伸试验、浸泡腐蚀试验等手段,研究了不同温度退火对热轧态Mg-4.0Zn-0.8Zr合金组织、力学性能和耐腐蚀性能的影响。结果表明:热轧态Mg-4.0Zn-0.8Zr合金晶粒沿着轧制方向被拉长。320℃退火合金组织仍保持热轧态纤维状形貌,360℃退火合金再结晶完全,晶粒为均匀的等轴晶,退火温度再升高,合金晶粒均匀性变差。随着退火温度的升高,合金的抗拉强度不断下降,伸长率先升高后降低,腐蚀速率先降低后升高。360℃退火的合金伸长率最高,为22.1%,腐蚀速率最低,为0.24 mm/a,其抗拉强度为250.4 MPa。

热处理对Mg-3Sn-2Al-1Zn-5Li合金耐蚀性能的影响

对Mg-3Sn-2Al-1Zn-5Li合金进行了不同方式的热处理。利用电化学测试研究了不同热处理状态合金在3.5%NaCl溶液中的腐蚀电化学行为,并通过扫描电镜、能谱以及X射线衍射分析了合金腐蚀形貌及腐蚀产物的成分。结果表明:经固溶处理和时效处理后,合金的耐蚀性能有所提高,并且固溶态的Mg-3Sn-2Al-1Zn-5Li合金有着最佳的耐蚀性能;合金的腐蚀特征为丝状腐蚀,腐蚀产物主要为Mg(OH)_(2)。

国产Zn-5%Al-混合稀土合金镀层高钒封闭索丝耐久性研究

以国家速滑馆首次应用的国产Zn-5%Al-混合稀土合金镀层高钒封闭索丝为研究对象,对其使用性能、基本特性及耐久性等进行研究。采用了国家速滑馆内部高空索体实际服役环境处的大气暴露试验方式,综合考虑索在加工安装过程中易产生的损伤,对索丝试件进行了划痕、刮擦、焊点的预制缺陷设计,研究了含预制缺陷的国产Zn-5%Al-稀土合金镀层高钒封闭索丝在真实使用环境中的大气腐蚀行为规律,并采用力学性能测试研究了索丝在服役环境大气腐蚀作用下的力学性能变化规律及不同缺陷对力学性能的影响。结果表明,加工安装过程中在索丝表面合金镀层产生的划痕、刮擦、焊点等损伤,会破坏合金镀层的完整性。大气暴露试验和力学性能试验中,三类缺陷对索丝金属镀层防大气腐蚀性能和单丝抗拉强度均有负面影响,其中焊点缺陷影响最大,单丝抗拉强度下降约40%。

可生物降解Zn-2Ag-0.04Mg合金生物相容性及体内骨再生能力的动物实验研究

目的:采用动物实验的方式,分析可生物降解Zn-2Ag-0.04Mg合金生物相容性及体内骨再生能力。方法:将30只实验兔随机均分为Zn支架组、Zn-2Ag支架组和Zn-2Ag-0.04Mg支架组(每组10只),建立兔股骨缺损模型后,分别使用不同材料的支架固定,术后6周及术后6个月,取出部分大白兔股骨,使用Micro-CT对股骨远端入口周围直径为3 mm的区域进行扫描和三维重建,分析支架体内成骨性能,使用X线观察局部骨缺损愈合情况,并观察股骨组织学情况。结果:入组实验兔实验中未出现异常行为及死亡现象,伤口均愈合良好,无感染及渗出情况出现;二维和三维显微CT结果显示,Zn-2Ag-0.04Mg支架组的新生骨明显多于Zn支架组,Zn-2Ag-0.04Mg合金支架组的骨体积更大(P<0.05);Zn-2Ag-0.04Mg支架组的成骨指数也高于Zn支架组(P<0.05);术后6个月时,Zn-2Ag-0.04Mg组的支架比Zn组或Zn-2Ag组小(P<0.05);肝脏、肾脏和心脏的HE染色未检测到任何异常,证实了Zn-2Ag-0.04Mg合金支架的生物安全性。结论:Zn-2Ag-0.04Mg支架具有良好的生物相容性和体内骨再生能力,具有较好的临床应用前景。

An in-depth understanding of improvement strategies and corresponding characterizations towards Zn anode in aqueous Zn-ions batteries

Combining the unique advantages of aqueous electrolytes and metallic Zn anode, rechargeable aqueous Zn-ion batteries(ZIBs) are of great promise for large-scale energy storage applications due to their inherent high safety, low cost, and environmental friendliness. As the essential component of ZIBs, Zn metal anode suffers from severe dendrite formation and inevitable side reactions(e.g. corrosion and hydrogen evolution)in aqueous electrolytes, which leads to low Coulombic efficiency and inferior cycling stability, impeding their large-scale applications. To be compatible with satisfactory aqueous ZIBs, Zn anode has been modified from various perspectives and focus areas. Herein, based on their intrinsic characteristics, we review the related improvement strategies for Zn anode, including interphase, substrate, and bulk design, so as to achieve an in-depth understanding of Zn anode optimization. Furthermore, the timely summary of characterization methods for Zn anodes are also performed for the first time, from both thermodynamic and kinetics perspectives, which is particularly helpful for beginners to understand the complicated characterizations and employ suitable methods. Finally, certain noteworthy points are put forward for subsequent investigation of aqueous ZIBs. It is expected that this review will enlighten researchers to explore more efficient optimization strategies for Zn anode in aqueous electrolytes.

In situ formation of self-antistacking FeCoO_(x) on N-doped graphene:A 3D-on-2D nanoarchitecture for long-life Zn-air batteries

Before the practical application of rechargeable Zn-air batteries(ZABs),a critical issue regarding the inherent slow reaction kinetics of the oxygen reduction(ORR)and oxygen evolution(OER)must be addressed.Here,we fabricate a cost-effective bifunctional oxygen electrocatalyst with a self-antistacking structure,where three-dimensional(3D)Fe-Co bimetallic oxide particles(FeCoO_(x))are directly grown on 2D N-doped graphene(NG).The in situ grown FeCoO_(x)particles can alleviate the NG interlaminar restacking,ensuring abundant channels for diffusion of O_(2)/OH−species,while the NG allows rapid electron flow.Benefiting from this self-antistacking 3D-on-2D structure and synergetic electrocatalysis,FeCoO_(x)@NG demonstrated excellent activity for both ORR and OER(ΔE=0.78 V),which is superior to that of the binary mixtures of Pt/C and RuO_(2)(ΔE=0.83 V).A homemade ZAB with 20%-FeCoO_(x)@NG delivers a specific capacity of 758.9 mAh g^(−1),a peak power density of 215 mW cm^(−2),and long-term cyclability for over 400 h.These research results suggest that designing a bimetallic oxide/N-doped carbon 3D-on-2D nanoarchitecture using an in situ growth strategy is an attractive and feasible solution to overcome electrocatalytic problems in ZABs.

Hierarchically porous Co@N-doped carbon fiber assembled by MOF-derived hollow polyhedrons enables effective electronic/mass transport:An advanced 1D oxygen reduction catalyst for Zn-air battery

Developing advanced oxygen reduction reaction(ORR)electrocatalysts with rapid mass/electron transport as well as conducting relevant kinetics investigations is essential for energy technologies,but both still face ongoing challenges.Herein,a facile approach was reported for achieving the highly dispersed Co nanoparticles anchored hierarchically porous N-doped carbon fibers(Co@N-HPCFs),which were assembled by core-shell MOFs-derived hollow polyhedrons.Notably,the unique one-dimensional(1D)carbon fibers with hierarchical porosity can effectively improve the exposure of active sites and facilitate the electron transfer and mass transfer,resulting in the enhanced reaction kinetics.As a result,the ORR performance of the optimal Co@N-HPCF catalysts remarkably outperforms that of commercial Pt/C in alkaline solution,reaching a limited diffusion current density(J)of 5.85 m A cm^(-2)and a half-wave potential(E_(1/2))of 0.831 V.Particularly,the prepared Co@N-HPCF catalysts can be used as an excellent air-cathode for liquid/solid-state Zn-air batteries,exhibiting great potentiality in portable/wearable energy devices.Furthermore,the reaction kinetic during ORR process is deeply explored by finite element simulation,so as to intuitively grasp the kinetic control region,diffusion control region,and mixing control region of the ORR process,and accurately obtain the relevant kinetic parameters.This work offers an effective strategy and a reliable theoretical basis for the engineering of first-class ORR electrocatalysts with fast electronic/mass transport.

Vacancy-modified bimetallic FeMoS_(x)/CoNiP_(x) heterostructure array for efficient seawater splitting and Zn-air battery

The development of highly efficient OER catalysts with superior durability for seawater electrolysis and Zn-air battery is important but challenging.Herein,the vacancy-modified heterostructured bimetallic Fe Mo S_(x)/Co Ni P_(x)OER electrocatalyst is exploited.Benefiting from the electron redistribution and reaction kinetics modulation resulting from vacancy introduction and heterojunction formation,it yields ultralow OER overpotentials of 196,276,303 m V in 1 M KOH and 197,318,348 m V in 1 M KOH+seawater at 10,500,1000 m A cm^(-2),respectively,surviving 600 h at 800 m A cm^(-2)without obvious decay.Further,FeMoS_(x)/CoNiP_(x)-based Zn-air battery not only affords the high peak power density of 214.5 m W cm^(-2)but also exhibits the small voltage gap of 0.698 V and long lifetime of 500 h at 10 m A cm^(-2),overmatching overwhelming majority of reported advanced catalysts.It is revealed experimentally that the OER process on rationally designed Fe Mo S_(x)/Co Ni P_(x)follows the adsorbate evolution mechanism and the ratedetermining step shifts from^(*)OOH formation in individual building blocks to^(*)OOH deprotonation process in FeMoS_(x)/CoNiP_(x),providing the directly proof of how the vacancy introduction and heterojunction formation affect the reaction kinetics.