Hydrogen production from water electrolysis,in particular from proton exchange membrane water electrolyzers(PEMWE),is a key approach to realizing a carbon-free energy cycle.However,the high anodic potential and strong...Hydrogen production from water electrolysis,in particular from proton exchange membrane water electrolyzers(PEMWE),is a key approach to realizing a carbon-free energy cycle.However,the high anodic potential and strong acid in PEMWE systems pose a major challenge to the stability of electrocatalysts,and the development of efficient and corrosion-resistant catalysts is urgently needed.Currently,iridium(Ir)-based catalysts have gained great attention due to their promising activity and stability,while the extremely low reserves of Ir in the earth seriously hinder the commercialization of PEMWE.Therefore,a systematic understanding of the latest advances in Ir-based catalysts is necessary to guide their rational design to meet the industrial requirements.In this review,the general reaction mechanisms and advanced characterization techniques for mechanism recognition are first introduced.Afterwards,the systematic design strategies and performances of Ir-based catalysts,including metallic Ir,Ir oxides,and Ir-based perovskites,are summarized in detail.Finally,the conclusions,challenges,and prospects for Ir-based electrocatalysts are presented.展开更多
Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nano...Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.展开更多
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 int...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.展开更多
The development of highly active catalyst in pH-neutral media for oxygen evolution reaction(OER)is critical in the field of renewable energy storage and conversion.Nevertheless,the slow kinetics of proton-coupled elec...The development of highly active catalyst in pH-neutral media for oxygen evolution reaction(OER)is critical in the field of renewable energy storage and conversion.Nevertheless,the slow kinetics of proton-coupled electron transfer(PCET)hinders the overall OER efficiency.Herein,we report an ionic liquid(IL)modified CoSn(OH)_(6)nanocubes(denoted as CoS-n(OH)_(6)-IL),which could be prepared through a facile strategy.The modified IL would not change the structural character-istics of CoSn(OH)_(6),but could effectively regulate the local proton activity near the active sites.The CoSn(OH)_(6)-IL exhibited higher intrinsic OER performances than the pristine CoSn(OH)_(6)in neutral media.For example,the current density of CoS-n(OH)_(6)-IL at 1.8 V versus reversible hydrogen electrode(RHE)was about 4 times higher than that of CoSn(OH)_(6).According to the pH-dependent kinetic investigations,operando electrochemical impedance spectroscopic,chemical probe tests,and deuterium kinetic isotope effects,the interfacial layer of IL could be utilized as a proton transfer mediator to promote the proton transfer,which enhances the surface coverage of OER intermediates and reduces the activation barrier.Consequent-ly,the sluggish OER kinetics would be efficiently accelerated.This study provides a facile and effective strategy to facilitate the PCET processes and is beneficial to guide the rational design of OER electrocatalysts.展开更多
Through employing zeolitic imidazolate framework-67(ZIF-67)templates,the straightforward hydrother-mal and electrodeposition methods were applied to synthesize FeOOH@CoMoO_(4)heterostructure attached to the sur-face o...Through employing zeolitic imidazolate framework-67(ZIF-67)templates,the straightforward hydrother-mal and electrodeposition methods were applied to synthesize FeOOH@CoMoO_(4)heterostructure attached to the sur-face of nickel foam(NF).The specific structure of the as-prepared FeOOH@CoMoO_(4)/NF-400s provided pronounced porosity and extensive surface area,enhancing rapid electron transport and exposing abundant active sites to improve catalytic reactions.Furthermore,the introduction of FeOOH,which induces electron transfer from FeOOH to CoMoO_(4),confirms their strong electronic interaction,thereby leading to an accelerated surface catalytic reaction.Consequently,the constructed FeOOH@CoMoO_(4)/NF-400s heterostructure demonstrated exceptional oxygen evolu-tion reaction(OER)activity,requiring an overpotential of 199 mV to deliver the current density of 10 mA·cm^(-2),cou-pled with the superior Tafel slope value of 49.56 mV·dec^(-1)and outstanding stability over 20 h under the current densities of both 10 and 100 mA·cm^(-2).展开更多
The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic...The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic study on isostructural 2D coordination polymers(CPs)based on 1,10-ferrocenediyl-bis(H-phosphinic)acid,with cobalt,manganese,and cadmium metals as electrocatalysts for OER.These polymers were synthesized via a facile solution reaction,yielding crystalline materials with excellent structural integrity.The electrocatalytic performance of CPs composites,prepared with carbon and phosphonium ionic liquid,was evaluated in 0.1 M KOH using a three-electrode system.Notably,the Co-and Cd-based CPs demonstrated exceptional OER activity,achieving an overpotential as low as 236–255 mV at 10 mA cm^(-2),surpassing those of many previously reported CP-based OER catalysts.Furthermore,these materials exhibited high stability over prolonged electrolysis,maintaining their activity without significant degradation.This work not only introduces a new class of ferrocenyl phosphinatebased CPs as highly active and durable OER catalysts but also provides valuable insights into their structureactivity relationships,paving the way for future advancements in electrocatalysis.展开更多
Proton exchange membrane water electrolysis(PEMWE)is a favorable technology for producing highpurity hydrogen under high current density using intermittent renewable energy.The performance of PEMWE is largely determin...Proton exchange membrane water electrolysis(PEMWE)is a favorable technology for producing highpurity hydrogen under high current density using intermittent renewable energy.The performance of PEMWE is largely determined by the oxygen evolution reaction(OER),a sluggish four-electron reaction with a high reaction barrier.Nowadays,iridium(Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution.However,its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application.In this review,we initiate by introducing the current OER reaction mechanisms,namely adsorbate evolution mechanism and lattice oxygen mechanism,with degradation mechanisms discussed.Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced,with merits and potential problems also discussed.The parameters that determine the performance of PEMWE are then introduced,with unsolved issues and related outlooks summarized in the end.展开更多
Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incor...Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incorporating heteroatom strategy via one-step hydrothermal approach to adjust more than one factor of Mn-doped NiFe(oxy)hydroxide(Mn-NiFeOOH/LDH)heterojunction.Mn doping regulates heterojunction morphology(reducing nanoparticles and becoming thinner and denser nanosheets),Ni/Fe ratio and valence states(Ni^(2+),Ni^(3+),and Ni^(3+Δ))of Ni ions.The former could effectively increase surface active sites,and the latter two reduce the content of Fe in the Mnx-NiFeOOH/LDH heterojunction,en-abling more Ni^(2+)convert to Ni^(3+/3+Δ)that have higher intrinsic OER activity.As a result,the first-rank Mn-NiFeOOH/LDH with ultra-low overpotential of 185 mV@20 mA cm^(-2) and 296 mV@500 mA cm^(-2),and the improved OER performance are outdo to those of commercial RuO_(2) catalyst for OER.Moreover,the Mn-NiFeOOH/LDH affords the earliest initial potential(1.392 V vs.RHE),corresponds to a recorded low overpotential(162 mV).Based on the density functional theory(DFT),Mn dopants can alter intermedi-ate adsorption energy and effectively decrease∗OOH’s energy barrier.This research exhibits a feasible strategy to design low cost electrocatalysts and provide new possibilities for future industrialization.展开更多
Rare earth has a unique electronic structure and brings highly anticipated properties in light,electricity,heat and magnetism.Lanthanum is widely distributed among the rare earth elements and has a great potential for...Rare earth has a unique electronic structure and brings highly anticipated properties in light,electricity,heat and magnetism.Lanthanum is widely distributed among the rare earth elements and has a great potential for the electrocatalytic application.This paper reviews the common types and synthesis methods of lanthanum-based catalysts used in the electrocatalytic oxygen evolution reaction,and highlights the optimization of lanthanum-based catalysts.The electronic structure and active sites of the catalysts can be adjusted through atomic doping,interfacial modulation,and structural defects to enhance the OER.Further,the development of lanthanum-based catalyst is envisioned.展开更多
Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction(OER).However,constructing a novel catalysis system with high catalytic activity and precise str...Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction(OER).However,constructing a novel catalysis system with high catalytic activity and precise structures is still a huge challenge due to the tedious procedure of precursor synthesis and anion selection.Here,a bimetallic(FeNi)nanowire self-assembled superstructure was synthesized using the Hoffmann rearrangement method,and then functionalized with four anions(P,Se,S,and O).Notably,the Fe_(3)Se_(4)/Ni_(3)Se_(4) catalyst shows a high conductivity,enhances the adsorption of intermediate products,accelerates the rate-determining step,and consequently results to improved electrocatalytic performance.Using the Fe_(3)Se_(4)/Ni_(3)Se_(4) catalyst exhibits enhanced performance with overpotential of 316mV at 10 mA/cm^(2),in stark contrast to Fe_(2) P/Ni_(2)P(357mV),Fe_(7)S_(8)/NiS(379 mV),and Fe_(3)O_(4)/NiO(464 mV).Moreover,the formation mechanism of superstructure and the relationship between electronegativities and electrocatalytic properties,are elucidated.Accordingly,this work provides an efficient approach to Hoffmann-type coordination polymer catalyst for oxygen evolution towards a near future.展开更多
A thorough understanding of the oxygen evolution reaction(OER)in Mo-based materials is crucial for the advancement of water-splitting technologies.However,the identification of the active phase in Mo-based systems rem...A thorough understanding of the oxygen evolution reaction(OER)in Mo-based materials is crucial for the advancement of water-splitting technologies.However,the identification of the active phase in Mo-based systems remains a subject of debate,largely due to the dissolution of molybdenum oxides in alkaline electrolytes.In this review,we provide a comprehensive overview of recent advances in the application of Mo-based materials for OER in alkaline media,with an emphasis on their diverse roles in catalysis.Various design strategies employed to optimize Mo-based materials are discussed,focusing on how these approaches influence their physicochemical properties and the specific effects of different design perspectives on their OER performance.Additionally,the structure-performance relationship underlying these materials is explored,offering insights into how structural modifications impact catalytic efficiency.Lastly,key challenges for Mo-based materials in OER applications are provided,and future research directions for further improving the efficacy of sustainable water-splitting technologies in alkaline environments are proposed.展开更多
Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-5...Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-53),is successfully prepared via the hydrothermal method.In-situ Raman spectroscopy and electrochemical impedance spectroscopy reveal that the doped Rh accelerates the phase transformation of NiFe-MIL-53 and the in-situ formed Rh@NiFeOOH is the actual active species.More importantly,the enhanced reversibility of electrochemical reconstruction between NiFeOOH and NiFe(OH)_(2)after doping Rh is beneficial for improving the electrochemical stability of the catalyst.X-ray photoelectron spectroscopy spectra show the strong electronic interaction between single-atom Rh and Ni/Fe in Rh@NiFeOOH.Furthermore,theoretical calculations confirm that the integration of single-atom Rh into the NiFeOOH successfully reduces the band gap,regulates the d-band center(εd),accelerates the charge transfer,and optimizes the adsorption behavior of oxygen-containing intermediates,thereby lowering the energy barrier of rate-determining steps.Consequently,the optimized Rh@NiFe-MIL-53 exhibits excellent OER activity(240 mV)with a small Tafel slope of 48.2 mV dec^(-1)and long-term durability(over1270 h at 10 m A cm^(-2)and 110 h at 200 mA cm^(-2)).This work presents a new perspective on designing highly efficient OER electrocatalysts.展开更多
Proton exchange membrane water electrolyzers(PEMWEs)are pivotal for efficient hydrogen production due to their high energy efficiency and ability to operate at high current densities,making them ideally suited for int...Proton exchange membrane water electrolyzers(PEMWEs)are pivotal for efficient hydrogen production due to their high energy efficiency and ability to operate at high current densities,making them ideally suited for integration with renewable energy sources.Cobalt(Co)-based nanomaterials,characterized by diverse oxidation states,tunable electronic spin states,and hybrid orbitals,have emerged as promising non-noble metal alternatives to platinum group catalysts for accelerating the anodic oxygen evolution reaction(OER).Based on their inherent properties,this review provides a comprehensive overview of the latest developments in Co-based nanomaterials for acidic OER.The review begins by introducing the operational principles of PEMWEs,the underlying catalytic mechanisms,and the critical design considerations for OER catalysts.It then explores strategies to enhance the activity and stability of Co-based catalysts for acidic OER in PEMWEs,including the incorporation of corrosion-resistant metals or dispersion on acid-resistant supports to increase active surface area and stability;utilization of geometric structural engineering to improve structural integrity and active site efficiency;the optimization of reaction mechanisms to fine-tune catalytic pathways for enhanced stability and performance.The performance degradation mechanisms and metal leaching analysis for Co-based catalysts in PEMWE are also clarified.Finally,this review not only outlines the key challenges associated with Co-based catalysts for acidic OER but also proposes potential strategies to overcome these limitations,offering a roadmap for future advancements and practical implementation of PEMWE technology.展开更多
Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-...Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-entropy materials,featured with their distinctive multi-component properties,have found extensive application as catalysts in electrochemical energy storage and conversion devices.However,synthesizing nanostructured high-entropy compounds under mild conditions poses a significant challenge due to the difficulty in overcoming the immiscibility of multiple metallic constituents.In this context,the current study focuses on the synthesis of an array of nano-sized high entropy sulfides tailored for OER via a facile precursor pyrolysis method at low temperature.The representative compound,Fe Co Ni Cu Mn Sx,demonstrates remarkable OER performance,achieving a current density of 10 m A/cm^(2) at an overpotential of merely 220 m V and excellent stability with constant electrolysis at 100 m A/cm^(2) for over 400 h.The in-situ formed metal(oxy)hydroxide has been confirmed as the real active sites and its exceptional performance can be primarily attributed to the synergistic effects arising from its multiple components.Furthermore,the synthetic methodology presented here is versatile and can be extended to the preparation of high entropy phosphides,which also present favorable OER performance.This research not only introduces promising non-noble electrocatalysts for OER but also offers a facile approach to expand the family of nano high-entropy materials,contributing significantly to the field of electrochemical energy conversion.展开更多
Shape control of nickel sulfide(NiS_(2))catalysts is beneficial for boosting their catalytic performances,which is vital to their practical application as a class of advanced non-noble electro-catalysts.However,precis...Shape control of nickel sulfide(NiS_(2))catalysts is beneficial for boosting their catalytic performances,which is vital to their practical application as a class of advanced non-noble electro-catalysts.However,precisely controlling the formation kinetics and fabricate ultrathin NiS_(2)nanostructures still remains challenge.Herein,we provide an injection rate-mediated method to fabricate ultrathin NiS_(2)nanocages(HNCs)with hierarchical walls,high-density lattice defects and abundant grain boundaries(GBs).Through mechanism analysis,we find the injection rate determines the concentration of S_(2)−in the steady state and thus control the growth pattern,leading to the formation of NiS_(2)HNCs at slow etching kinetics and NiCo PBA@NiS_(2)frames at fast etching kinetics,respectively.Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions,the high-density lattice defects and GBs that offer abundant unsaturated reaction sites,the NiS_(2)HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER,with overpotential of 255mV to reach 10mA/cm^(2)and a Tafel slope of 27.44mV/dec,surpassing the performances of NiCo PBA@NiS_(2)frames and commercial RuO_(2).展开更多
Neutral oxygen evolution reaction(OER)is a crucial half-reaction for electrocatalytic chemical production under mild condition,but with limited development due to low activity and poor stability.Herein,a tungsten-dope...Neutral oxygen evolution reaction(OER)is a crucial half-reaction for electrocatalytic chemical production under mild condition,but with limited development due to low activity and poor stability.Herein,a tungsten-doped cobalt molybdate(WDCMO)catalyst was synthesized for efficient and durable OER under neutral electrolyte.It is demonstrated that catalyst reconstruction is suppressed by W doping,which stabilizes the Co-O-Mo point-to-point connection in CoMoO_(4) architecture and stimulates to a lower valence state of active sites over the surface phase.Thereby,the surface structure maintains to avoid compound dissolution caused by over-oxidation during OER.Meanwhile,the WDCMO catalyst promotes charge transfer and optimizes*OH intermediate adsorption,which improves reaction kinetics and intrinsic activity.Consequently,the WDCMO electrode exhibits an overpotential of 302 mV at 10 mA cm^(-2) in neutral electrolyte with an improvement of 182 mV compared with CoMoO4 electrode.Furthermore,W doping significantly improves the electrode stability from 50 h to more than 320 h,with a suppressive potential attenuation from 2.82 to 0.29 mV h^(-1).This work will shed new light on designing rational electrocatalysts for neutral OER.展开更多
Developing highly active and stable oxygen evolution reaction(OER)catalysts necessitates the establishment of a comprehensive OER catalyst database.However,the absence of a standardized benchmarking protocol has hinde...Developing highly active and stable oxygen evolution reaction(OER)catalysts necessitates the establishment of a comprehensive OER catalyst database.However,the absence of a standardized benchmarking protocol has hindered this progress.In this work,we present a systematic protocol for electrochemical measurements to thoroughly evaluate the activity and stability of OER electrocatalysts.We begin with a detailed introduction to constructing the electrochemical system,encompassing experimental setup and the selection criteria for electrodes and electrolytes.Potential contaminants originating from electrolytes,cells,and electrodes are identified and their impacts are discussed.We also examine the effects of external factors,such as temperature,magnetic fields,and natural light,on OER measurements.The protocol outlines operational mechanisms and recommended settings for various electrochemical techniques,including cyclic voltammetry(CV),potentiostatic electrochemical impedance spectroscopy(PEIS),Tafel slope analysis,and pulse voltammetry(PV).We summarize existing evaluation methodologies for assessing intrinsic activities and long-term stabilities of catalysts.Based on these discussions,we propose a comprehensive protocol for evaluating OER electrocatalysts’performance.Finally,we offer perspectives on advancing OER catalysts from laboratory research to industrial applications.展开更多
The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vi...The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vital role of noble metals in electrocatalytic activity,this work focuses on the rational synthesis of Ni-noble metal composite nanocatalysts for overcoming the drawbacks of high cost and susceptible oxidized surfaces of noble metals.The inherent catalytic activity is improved by the altered electronic structure and effective active sites of the catalyst induced by the size effect of noble metal clusters.In particular,a series of Ni-noble metal nanocomposites are successfully synthesized by partially introducing noble metal into Ni with porous interfacial defects derived from Ni-Al layered double hydroxide(LDH).The Ni_(10)Pd_(1)nanocomposite exhibits high OER catalytic activity with an overpotential of 0.279 V at 10 m A/cm^(2),surpassing Ni_(10)Ag_(1)and Ni_(10)Au_(1)counterparts.Furthermore,the average diameter of Pd clusters gradually increases from 5.57 nm to 44.44 nm with the increased proportion of doped Pd,leading to the passivation of catalytic activity due to the exacerbated surface oxidation of Pd in the form of Pd^(2+).After optimization,Ni_(10)Pd_(1)delivers significantly enhanced OER and MOR electroactivities and long-term stability compared to that of Ni_(2)Pd_(1),Ni_(1)Pd_(1)and Ni_(1)Pd_(2),which is conducive to the effective utilization of Pd and alleviation of surface oxidation.展开更多
Pyrochlore oxide(Y_(2)Ru_(2)O_(7))has been identified as a promising catalyst for the oxygen evolution reaction(OER)in advanced green energy strategies.However,its electrochemical inertness necessitates the exploratio...Pyrochlore oxide(Y_(2)Ru_(2)O_(7))has been identified as a promising catalyst for the oxygen evolution reaction(OER)in advanced green energy strategies.However,its electrochemical inertness necessitates the exploration of an effective strategy to facilitate electronic modulation.This study proposes a surface modification approach involving the integration of defective NiFe(D-NiFe)nanoparticles onto a Y_(2)Ru_(2)O_(7)(YRO)support(YRO@D-NiFeP/Ru)using a Prussian blue analog(PBA).Numerous cyanide(CN)vacancies are generated through the oxidation treatment of the NiFe PBA grown on the YRO support,yielding a defective PBA precursor(YRO@D-PBA).Subsequent annealing facilitates the transformation to the D-NiFe nanoparticles on the YRO support(YRO@D-NiFeP/Ru),which augments the exposure of Ni3+active sites beneficial for the OER.Moreover,the reduction of Ru cations from YRO results in the exsolution of Ru nanoparticles,which promotes synergistic charge transfer from the nanoparticles to the interior of Y_(2)Ru_(2)O_(7).Consequently,YRO@D-NiFeP/Ru exhibits a remarkable voltage of 1.49 V at 10 mA·cm^(−2) and the lowest Tafel slope of 42.4 mV·dec^(−1).In addition,a Zn–air battery constructed with YRO@D-NiFeP/Ru exhibits an outstanding power density of 136.2 mW·cm^(−2) and high charge–discharge stability,confirming the applicability of YRO@D-NiFeP/Ru in metal-air batteries.展开更多
The study of the oxygen evolution reaction(OER)mechanism is vital for advancing our understanding of this pivotal energy conversion process.This review synthesizes recent advancements in OER mechanism,emphasizing the ...The study of the oxygen evolution reaction(OER)mechanism is vital for advancing our understanding of this pivotal energy conversion process.This review synthesizes recent advancements in OER mechanism,emphasizing the intricate relationship between catalytic mechanisms and catalyst design.This review discusses the connotation and cutting-edge progress of traditional mechanisms such as adsorbate evolution mechanism(AEM)and lattice oxygen mechanism(LOM)as well as emerging pathways including oxide path mechanism(OPM),oxo-oxo coupling mechanism(OCM),and intramolecular oxygen coupling mechanism(IMOC)etc.Innovative research progress on the coexistence and transformation of multiple mechanisms is highlighted,and the intrinsic factors that influence these dynamic processes are summarized.Advanced characterization techniques and theoretical modeling are underscored as indispensable tools for revealing these complex interactions.This review provides guiding principles for mechanism-based catalyst design.Finally,in view of the multidimensional challenges currently faced by OER mechanisms,prospects for future research are given to bridge the gap between mechanism innovation and experimental verification and application.This comprehensive review provides valuable perspectives for advancing clean energy technologies and achieving sustainable development.展开更多
基金supported by the National Natural Science Foundation of China(22202053,22109035,52362031,and 52274297)the start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20083,20084,23068,and 23169)+4 种基金the Hainan Province Science and Technology Special Fund(ZDYF2024SHFZ074)the Collaborative Innovation Center of Marine Science and Technology,Hainan University(XTCX2022HYC04)the specific research fund of The Innovation Platform for Academicians of Hainan Province(YSPTZX202315)the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202307)the Open Fund Project of Key Laboratory of Electrochemical Energy Storage and Energy Conversion in Hainan Province of China(KFKT2023002)。
文摘Hydrogen production from water electrolysis,in particular from proton exchange membrane water electrolyzers(PEMWE),is a key approach to realizing a carbon-free energy cycle.However,the high anodic potential and strong acid in PEMWE systems pose a major challenge to the stability of electrocatalysts,and the development of efficient and corrosion-resistant catalysts is urgently needed.Currently,iridium(Ir)-based catalysts have gained great attention due to their promising activity and stability,while the extremely low reserves of Ir in the earth seriously hinder the commercialization of PEMWE.Therefore,a systematic understanding of the latest advances in Ir-based catalysts is necessary to guide their rational design to meet the industrial requirements.In this review,the general reaction mechanisms and advanced characterization techniques for mechanism recognition are first introduced.Afterwards,the systematic design strategies and performances of Ir-based catalysts,including metallic Ir,Ir oxides,and Ir-based perovskites,are summarized in detail.Finally,the conclusions,challenges,and prospects for Ir-based electrocatalysts are presented.
文摘Sulfur-doped iron-cobalt tannate nanorods(S-FeCoTA)derived from metal-organic frameworks(MOFs)as electrocatalysts were synthesized via a one-step hydrothermal method.The optimized S-FeCoTA was interlaced by loose nanorods,which had many voids.The S-FeCoTA catalysts exhibited excellent electrochemical oxygen evolution reaction(OER)performance with a low overpotential of 273 mV at 10 mA·cm^(-2)and a small Tafel slope of 36 mV·dec^(-1)in 1 mol·L^(-1)KOH.The potential remained at 1.48 V(vs RHE)at 10 mA·cm^(-2)under continuous testing for 15 h,implying that S-FeCoTA had good stability.The Faraday efficiency of S-FeCoTA was 94%.The outstanding OER activity of S-FeCoTA is attributed to the synergistic effects among S,Fe,and Co,thus promoting electron transfer,reducing the reaction kinetic barrier,and enhancing the OER performance.
基金financially supported by the National Natural Science Foundation of China(22309137,22279095)Open subject project State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2023001).
文摘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.
基金supported by the National Natural Science Foundation of China(22209040,22202063).
文摘The development of highly active catalyst in pH-neutral media for oxygen evolution reaction(OER)is critical in the field of renewable energy storage and conversion.Nevertheless,the slow kinetics of proton-coupled electron transfer(PCET)hinders the overall OER efficiency.Herein,we report an ionic liquid(IL)modified CoSn(OH)_(6)nanocubes(denoted as CoS-n(OH)_(6)-IL),which could be prepared through a facile strategy.The modified IL would not change the structural character-istics of CoSn(OH)_(6),but could effectively regulate the local proton activity near the active sites.The CoSn(OH)_(6)-IL exhibited higher intrinsic OER performances than the pristine CoSn(OH)_(6)in neutral media.For example,the current density of CoS-n(OH)_(6)-IL at 1.8 V versus reversible hydrogen electrode(RHE)was about 4 times higher than that of CoSn(OH)_(6).According to the pH-dependent kinetic investigations,operando electrochemical impedance spectroscopic,chemical probe tests,and deuterium kinetic isotope effects,the interfacial layer of IL could be utilized as a proton transfer mediator to promote the proton transfer,which enhances the surface coverage of OER intermediates and reduces the activation barrier.Consequent-ly,the sluggish OER kinetics would be efficiently accelerated.This study provides a facile and effective strategy to facilitate the PCET processes and is beneficial to guide the rational design of OER electrocatalysts.
文摘Through employing zeolitic imidazolate framework-67(ZIF-67)templates,the straightforward hydrother-mal and electrodeposition methods were applied to synthesize FeOOH@CoMoO_(4)heterostructure attached to the sur-face of nickel foam(NF).The specific structure of the as-prepared FeOOH@CoMoO_(4)/NF-400s provided pronounced porosity and extensive surface area,enhancing rapid electron transport and exposing abundant active sites to improve catalytic reactions.Furthermore,the introduction of FeOOH,which induces electron transfer from FeOOH to CoMoO_(4),confirms their strong electronic interaction,thereby leading to an accelerated surface catalytic reaction.Consequently,the constructed FeOOH@CoMoO_(4)/NF-400s heterostructure demonstrated exceptional oxygen evolu-tion reaction(OER)activity,requiring an overpotential of 199 mV to deliver the current density of 10 mA·cm^(-2),cou-pled with the superior Tafel slope value of 49.56 mV·dec^(-1)and outstanding stability over 20 h under the current densities of both 10 and 100 mA·cm^(-2).
文摘The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic study on isostructural 2D coordination polymers(CPs)based on 1,10-ferrocenediyl-bis(H-phosphinic)acid,with cobalt,manganese,and cadmium metals as electrocatalysts for OER.These polymers were synthesized via a facile solution reaction,yielding crystalline materials with excellent structural integrity.The electrocatalytic performance of CPs composites,prepared with carbon and phosphonium ionic liquid,was evaluated in 0.1 M KOH using a three-electrode system.Notably,the Co-and Cd-based CPs demonstrated exceptional OER activity,achieving an overpotential as low as 236–255 mV at 10 mA cm^(-2),surpassing those of many previously reported CP-based OER catalysts.Furthermore,these materials exhibited high stability over prolonged electrolysis,maintaining their activity without significant degradation.This work not only introduces a new class of ferrocenyl phosphinatebased CPs as highly active and durable OER catalysts but also provides valuable insights into their structureactivity relationships,paving the way for future advancements in electrocatalysis.
基金supported by the National Key Research and Development Program of China(No.2022YFB4004100)National Natural Science Foundation of China(Nos.U22A20396,22209168)+1 种基金Natural Science Foundation of Anhui Province(No.2208085UD04)Liaoning Binhai Laboratory(No.LBLF-2023-04),and Shandong Energy Institute(No.SEI U202307).
文摘Proton exchange membrane water electrolysis(PEMWE)is a favorable technology for producing highpurity hydrogen under high current density using intermittent renewable energy.The performance of PEMWE is largely determined by the oxygen evolution reaction(OER),a sluggish four-electron reaction with a high reaction barrier.Nowadays,iridium(Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution.However,its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application.In this review,we initiate by introducing the current OER reaction mechanisms,namely adsorbate evolution mechanism and lattice oxygen mechanism,with degradation mechanisms discussed.Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced,with merits and potential problems also discussed.The parameters that determine the performance of PEMWE are then introduced,with unsolved issues and related outlooks summarized in the end.
基金funding support by the Changsha Natural Science Foundation(grant no.kq2208023)National Natural Scientific Foundation of China(grant no.12074113).
文摘Transition metal(oxy)hydroxides are potential oxygen evolution reaction(OER)electrocatalysts;however,simultaneously modulating multiple factors to enhance their performance is a grand challenge.Here,we report an incorporating heteroatom strategy via one-step hydrothermal approach to adjust more than one factor of Mn-doped NiFe(oxy)hydroxide(Mn-NiFeOOH/LDH)heterojunction.Mn doping regulates heterojunction morphology(reducing nanoparticles and becoming thinner and denser nanosheets),Ni/Fe ratio and valence states(Ni^(2+),Ni^(3+),and Ni^(3+Δ))of Ni ions.The former could effectively increase surface active sites,and the latter two reduce the content of Fe in the Mnx-NiFeOOH/LDH heterojunction,en-abling more Ni^(2+)convert to Ni^(3+/3+Δ)that have higher intrinsic OER activity.As a result,the first-rank Mn-NiFeOOH/LDH with ultra-low overpotential of 185 mV@20 mA cm^(-2) and 296 mV@500 mA cm^(-2),and the improved OER performance are outdo to those of commercial RuO_(2) catalyst for OER.Moreover,the Mn-NiFeOOH/LDH affords the earliest initial potential(1.392 V vs.RHE),corresponds to a recorded low overpotential(162 mV).Based on the density functional theory(DFT),Mn dopants can alter intermedi-ate adsorption energy and effectively decrease∗OOH’s energy barrier.This research exhibits a feasible strategy to design low cost electrocatalysts and provide new possibilities for future industrialization.
基金the National Natural Science Foundation of China(22122113)National Key R&D Program of China(2022YFB3506200).
文摘Rare earth has a unique electronic structure and brings highly anticipated properties in light,electricity,heat and magnetism.Lanthanum is widely distributed among the rare earth elements and has a great potential for the electrocatalytic application.This paper reviews the common types and synthesis methods of lanthanum-based catalysts used in the electrocatalytic oxygen evolution reaction,and highlights the optimization of lanthanum-based catalysts.The electronic structure and active sites of the catalysts can be adjusted through atomic doping,interfacial modulation,and structural defects to enhance the OER.Further,the development of lanthanum-based catalyst is envisioned.
基金supported by the National Natural Science Foundation of China(Nos.52222317,21902144,52225208)the“Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang”(No.2020R01002)+1 种基金the Natural Science Foundation of Zhejiang Province(No.LZ23E020002)the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.RFC2023002).
文摘Anion modification has been considered as a strategy to improve water splitting efficiency upon oxygen evolution reaction(OER).However,constructing a novel catalysis system with high catalytic activity and precise structures is still a huge challenge due to the tedious procedure of precursor synthesis and anion selection.Here,a bimetallic(FeNi)nanowire self-assembled superstructure was synthesized using the Hoffmann rearrangement method,and then functionalized with four anions(P,Se,S,and O).Notably,the Fe_(3)Se_(4)/Ni_(3)Se_(4) catalyst shows a high conductivity,enhances the adsorption of intermediate products,accelerates the rate-determining step,and consequently results to improved electrocatalytic performance.Using the Fe_(3)Se_(4)/Ni_(3)Se_(4) catalyst exhibits enhanced performance with overpotential of 316mV at 10 mA/cm^(2),in stark contrast to Fe_(2) P/Ni_(2)P(357mV),Fe_(7)S_(8)/NiS(379 mV),and Fe_(3)O_(4)/NiO(464 mV).Moreover,the formation mechanism of superstructure and the relationship between electronegativities and electrocatalytic properties,are elucidated.Accordingly,this work provides an efficient approach to Hoffmann-type coordination polymer catalyst for oxygen evolution towards a near future.
基金financially supported by the National Natural Science Foundation of China(52162036 and 22378342)the Key Project of Nature Science Foundation of Xinjiang(2021D01D08)+1 种基金the Major Projects of Xinjiang(2022A01005-4 and 2021A01001-1)the Key Research and Development Project of Xinjiang(2023B01025-1)。
文摘A thorough understanding of the oxygen evolution reaction(OER)in Mo-based materials is crucial for the advancement of water-splitting technologies.However,the identification of the active phase in Mo-based systems remains a subject of debate,largely due to the dissolution of molybdenum oxides in alkaline electrolytes.In this review,we provide a comprehensive overview of recent advances in the application of Mo-based materials for OER in alkaline media,with an emphasis on their diverse roles in catalysis.Various design strategies employed to optimize Mo-based materials are discussed,focusing on how these approaches influence their physicochemical properties and the specific effects of different design perspectives on their OER performance.Additionally,the structure-performance relationship underlying these materials is explored,offering insights into how structural modifications impact catalytic efficiency.Lastly,key challenges for Mo-based materials in OER applications are provided,and future research directions for further improving the efficacy of sustainable water-splitting technologies in alkaline environments are proposed.
基金Natural Science Foundation of China(Grant No.NSFC-22072062,22202098)。
文摘Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-53),is successfully prepared via the hydrothermal method.In-situ Raman spectroscopy and electrochemical impedance spectroscopy reveal that the doped Rh accelerates the phase transformation of NiFe-MIL-53 and the in-situ formed Rh@NiFeOOH is the actual active species.More importantly,the enhanced reversibility of electrochemical reconstruction between NiFeOOH and NiFe(OH)_(2)after doping Rh is beneficial for improving the electrochemical stability of the catalyst.X-ray photoelectron spectroscopy spectra show the strong electronic interaction between single-atom Rh and Ni/Fe in Rh@NiFeOOH.Furthermore,theoretical calculations confirm that the integration of single-atom Rh into the NiFeOOH successfully reduces the band gap,regulates the d-band center(εd),accelerates the charge transfer,and optimizes the adsorption behavior of oxygen-containing intermediates,thereby lowering the energy barrier of rate-determining steps.Consequently,the optimized Rh@NiFe-MIL-53 exhibits excellent OER activity(240 mV)with a small Tafel slope of 48.2 mV dec^(-1)and long-term durability(over1270 h at 10 m A cm^(-2)and 110 h at 200 mA cm^(-2)).This work presents a new perspective on designing highly efficient OER electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(22172063)the Young Taishan Scholars Program(tsqn201812080)+2 种基金the China Scholarship Council(CSC)for scholarship support(202008130132)the Independent Cultivation Program of Innovation Team of Ji’nan City(2021GXRC052)funding from CERCA Programme/Generalitat de Catalunya。
文摘Proton exchange membrane water electrolyzers(PEMWEs)are pivotal for efficient hydrogen production due to their high energy efficiency and ability to operate at high current densities,making them ideally suited for integration with renewable energy sources.Cobalt(Co)-based nanomaterials,characterized by diverse oxidation states,tunable electronic spin states,and hybrid orbitals,have emerged as promising non-noble metal alternatives to platinum group catalysts for accelerating the anodic oxygen evolution reaction(OER).Based on their inherent properties,this review provides a comprehensive overview of the latest developments in Co-based nanomaterials for acidic OER.The review begins by introducing the operational principles of PEMWEs,the underlying catalytic mechanisms,and the critical design considerations for OER catalysts.It then explores strategies to enhance the activity and stability of Co-based catalysts for acidic OER in PEMWEs,including the incorporation of corrosion-resistant metals or dispersion on acid-resistant supports to increase active surface area and stability;utilization of geometric structural engineering to improve structural integrity and active site efficiency;the optimization of reaction mechanisms to fine-tune catalytic pathways for enhanced stability and performance.The performance degradation mechanisms and metal leaching analysis for Co-based catalysts in PEMWE are also clarified.Finally,this review not only outlines the key challenges associated with Co-based catalysts for acidic OER but also proposes potential strategies to overcome these limitations,offering a roadmap for future advancements and practical implementation of PEMWE technology.
基金financially supported by the National Natural Science Foundation of China(Nos.22209183,22225902,U22A20436)the Advanced Talents of Jiangsu University,China(No.23JDG027)。
文摘Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-entropy materials,featured with their distinctive multi-component properties,have found extensive application as catalysts in electrochemical energy storage and conversion devices.However,synthesizing nanostructured high-entropy compounds under mild conditions poses a significant challenge due to the difficulty in overcoming the immiscibility of multiple metallic constituents.In this context,the current study focuses on the synthesis of an array of nano-sized high entropy sulfides tailored for OER via a facile precursor pyrolysis method at low temperature.The representative compound,Fe Co Ni Cu Mn Sx,demonstrates remarkable OER performance,achieving a current density of 10 m A/cm^(2) at an overpotential of merely 220 m V and excellent stability with constant electrolysis at 100 m A/cm^(2) for over 400 h.The in-situ formed metal(oxy)hydroxide has been confirmed as the real active sites and its exceptional performance can be primarily attributed to the synergistic effects arising from its multiple components.Furthermore,the synthetic methodology presented here is versatile and can be extended to the preparation of high entropy phosphides,which also present favorable OER performance.This research not only introduces promising non-noble electrocatalysts for OER but also offers a facile approach to expand the family of nano high-entropy materials,contributing significantly to the field of electrochemical energy conversion.
基金financially supported by National Natural Science Foundation of China (Nos. 21902078, 22279062, 22232004,22072067)the supports from National and Local Joint Engineering Research Center of Biomedical Functional Materialsa project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Shape control of nickel sulfide(NiS_(2))catalysts is beneficial for boosting their catalytic performances,which is vital to their practical application as a class of advanced non-noble electro-catalysts.However,precisely controlling the formation kinetics and fabricate ultrathin NiS_(2)nanostructures still remains challenge.Herein,we provide an injection rate-mediated method to fabricate ultrathin NiS_(2)nanocages(HNCs)with hierarchical walls,high-density lattice defects and abundant grain boundaries(GBs).Through mechanism analysis,we find the injection rate determines the concentration of S_(2)−in the steady state and thus control the growth pattern,leading to the formation of NiS_(2)HNCs at slow etching kinetics and NiCo PBA@NiS_(2)frames at fast etching kinetics,respectively.Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions,the high-density lattice defects and GBs that offer abundant unsaturated reaction sites,the NiS_(2)HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER,with overpotential of 255mV to reach 10mA/cm^(2)and a Tafel slope of 27.44mV/dec,surpassing the performances of NiCo PBA@NiS_(2)frames and commercial RuO_(2).
文摘Neutral oxygen evolution reaction(OER)is a crucial half-reaction for electrocatalytic chemical production under mild condition,but with limited development due to low activity and poor stability.Herein,a tungsten-doped cobalt molybdate(WDCMO)catalyst was synthesized for efficient and durable OER under neutral electrolyte.It is demonstrated that catalyst reconstruction is suppressed by W doping,which stabilizes the Co-O-Mo point-to-point connection in CoMoO_(4) architecture and stimulates to a lower valence state of active sites over the surface phase.Thereby,the surface structure maintains to avoid compound dissolution caused by over-oxidation during OER.Meanwhile,the WDCMO catalyst promotes charge transfer and optimizes*OH intermediate adsorption,which improves reaction kinetics and intrinsic activity.Consequently,the WDCMO electrode exhibits an overpotential of 302 mV at 10 mA cm^(-2) in neutral electrolyte with an improvement of 182 mV compared with CoMoO4 electrode.Furthermore,W doping significantly improves the electrode stability from 50 h to more than 320 h,with a suppressive potential attenuation from 2.82 to 0.29 mV h^(-1).This work will shed new light on designing rational electrocatalysts for neutral OER.
基金supported by the Fundamental Research Funds for the Central Universities(20822041H4082)。
文摘Developing highly active and stable oxygen evolution reaction(OER)catalysts necessitates the establishment of a comprehensive OER catalyst database.However,the absence of a standardized benchmarking protocol has hindered this progress.In this work,we present a systematic protocol for electrochemical measurements to thoroughly evaluate the activity and stability of OER electrocatalysts.We begin with a detailed introduction to constructing the electrochemical system,encompassing experimental setup and the selection criteria for electrodes and electrolytes.Potential contaminants originating from electrolytes,cells,and electrodes are identified and their impacts are discussed.We also examine the effects of external factors,such as temperature,magnetic fields,and natural light,on OER measurements.The protocol outlines operational mechanisms and recommended settings for various electrochemical techniques,including cyclic voltammetry(CV),potentiostatic electrochemical impedance spectroscopy(PEIS),Tafel slope analysis,and pulse voltammetry(PV).We summarize existing evaluation methodologies for assessing intrinsic activities and long-term stabilities of catalysts.Based on these discussions,we propose a comprehensive protocol for evaluating OER electrocatalysts’performance.Finally,we offer perspectives on advancing OER catalysts from laboratory research to industrial applications.
基金support by the National Natural Science Foundation of China(Nos.U20A20123,51874357,22379166)Natural Science Foundation for Distinguished Young Scholars of Hunan Province(No.2022JJ10089)。
文摘The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vital role of noble metals in electrocatalytic activity,this work focuses on the rational synthesis of Ni-noble metal composite nanocatalysts for overcoming the drawbacks of high cost and susceptible oxidized surfaces of noble metals.The inherent catalytic activity is improved by the altered electronic structure and effective active sites of the catalyst induced by the size effect of noble metal clusters.In particular,a series of Ni-noble metal nanocomposites are successfully synthesized by partially introducing noble metal into Ni with porous interfacial defects derived from Ni-Al layered double hydroxide(LDH).The Ni_(10)Pd_(1)nanocomposite exhibits high OER catalytic activity with an overpotential of 0.279 V at 10 m A/cm^(2),surpassing Ni_(10)Ag_(1)and Ni_(10)Au_(1)counterparts.Furthermore,the average diameter of Pd clusters gradually increases from 5.57 nm to 44.44 nm with the increased proportion of doped Pd,leading to the passivation of catalytic activity due to the exacerbated surface oxidation of Pd in the form of Pd^(2+).After optimization,Ni_(10)Pd_(1)delivers significantly enhanced OER and MOR electroactivities and long-term stability compared to that of Ni_(2)Pd_(1),Ni_(1)Pd_(1)and Ni_(1)Pd_(2),which is conducive to the effective utilization of Pd and alleviation of surface oxidation.
基金supported by Korea Institute of Energy Technology Evaluation and Planning(KETEP)grant funded by the Korea government(MOTIE)(No.RS-2024-00398346,ESS BigData-Based O&M and Asset Management Technical Manpower Training)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2024-00350658).
文摘Pyrochlore oxide(Y_(2)Ru_(2)O_(7))has been identified as a promising catalyst for the oxygen evolution reaction(OER)in advanced green energy strategies.However,its electrochemical inertness necessitates the exploration of an effective strategy to facilitate electronic modulation.This study proposes a surface modification approach involving the integration of defective NiFe(D-NiFe)nanoparticles onto a Y_(2)Ru_(2)O_(7)(YRO)support(YRO@D-NiFeP/Ru)using a Prussian blue analog(PBA).Numerous cyanide(CN)vacancies are generated through the oxidation treatment of the NiFe PBA grown on the YRO support,yielding a defective PBA precursor(YRO@D-PBA).Subsequent annealing facilitates the transformation to the D-NiFe nanoparticles on the YRO support(YRO@D-NiFeP/Ru),which augments the exposure of Ni3+active sites beneficial for the OER.Moreover,the reduction of Ru cations from YRO results in the exsolution of Ru nanoparticles,which promotes synergistic charge transfer from the nanoparticles to the interior of Y_(2)Ru_(2)O_(7).Consequently,YRO@D-NiFeP/Ru exhibits a remarkable voltage of 1.49 V at 10 mA·cm^(−2) and the lowest Tafel slope of 42.4 mV·dec^(−1).In addition,a Zn–air battery constructed with YRO@D-NiFeP/Ru exhibits an outstanding power density of 136.2 mW·cm^(−2) and high charge–discharge stability,confirming the applicability of YRO@D-NiFeP/Ru in metal-air batteries.
文摘The study of the oxygen evolution reaction(OER)mechanism is vital for advancing our understanding of this pivotal energy conversion process.This review synthesizes recent advancements in OER mechanism,emphasizing the intricate relationship between catalytic mechanisms and catalyst design.This review discusses the connotation and cutting-edge progress of traditional mechanisms such as adsorbate evolution mechanism(AEM)and lattice oxygen mechanism(LOM)as well as emerging pathways including oxide path mechanism(OPM),oxo-oxo coupling mechanism(OCM),and intramolecular oxygen coupling mechanism(IMOC)etc.Innovative research progress on the coexistence and transformation of multiple mechanisms is highlighted,and the intrinsic factors that influence these dynamic processes are summarized.Advanced characterization techniques and theoretical modeling are underscored as indispensable tools for revealing these complex interactions.This review provides guiding principles for mechanism-based catalyst design.Finally,in view of the multidimensional challenges currently faced by OER mechanisms,prospects for future research are given to bridge the gap between mechanism innovation and experimental verification and application.This comprehensive review provides valuable perspectives for advancing clean energy technologies and achieving sustainable development.
