Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts...Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.展开更多
Integrated electrocatalysts(IECs)containing well-defined functional materials directly grown on the current collector have sparked increasing interest in the fields of electrocatalysis owing to efficient activity,high...Integrated electrocatalysts(IECs)containing well-defined functional materials directly grown on the current collector have sparked increasing interest in the fields of electrocatalysis owing to efficient activity,high stability and the fact that they are easily assembled into devices.Recently,metal organic frameworks(MOFs)provide a promising platform for constructing advanced IECs because of their properties of low cost,large surface area and efficient structural tunability.In this review,the design principles of state-of-the-art IECs based on MOFs are presented,including by hydrothermal/solvothermal,template-directed,electrospinning,electrodeposition and other methods.The high performance of MOF-derived IECs has also been demonstrated in electrocatalytic gasinvolved reactions.This is promising for green energy storage and conversion.The structure-activity relationship and performance improvement mechanism of IECs are uncovered by discussing some in situ technologies for IECs.Finally,we provide an outlook on the challenges and prospects in this booming field.展开更多
Seawater splitting into hydrogen,a promising technology,is seriously limited by the durability and tolerance of electrocatalysts for chlorine ions in seawater at large current densities due to chloride oxidation and c...Seawater splitting into hydrogen,a promising technology,is seriously limited by the durability and tolerance of electrocatalysts for chlorine ions in seawater at large current densities due to chloride oxidation and corrosion.Here,we present a robust and weak-nucleophilicity nickel-iron hydroxide electrocatalyst with excellent selectivity for oxygen evolution and an inert response for chlorine ion oxidation which are key and highly desired for efficient seawater electrolysis.Such a weak-nucleophilicity electrocatalyst can well match with strong-nucleophilicity OH-compared with the weak-nucleophilicity Cl^(-),resultantly,the oxidation of OH-in electrolyte can be more easily achieved relative to chlorine ion oxidation,confirmed by ethylenediaminetetraacetic acid disodium probing test.Further,no strongly corrosive hypochlorite is produced when the operating voltage reaches about 2.1 V vs.RHE,a potential that is far beyond the thermodynamic potential of chlorine ion oxidatio n.This concept and approach to reasonably designing weaknucleophilicity electrocatalysts that can greatly avoid chlorine ion oxidation under alkaline seawater environments can push forward the seawater electrolysis technology and also accelerate the development of green hydrogen technique.展开更多
Rechargeable lithium-oxygen(Li-O_(2))batteries have attracted wide attention due to their high energy density.However,the sluggish cathode kinetics results in high overvoltage and poor cycling performance.Ruthenium(Ru...Rechargeable lithium-oxygen(Li-O_(2))batteries have attracted wide attention due to their high energy density.However,the sluggish cathode kinetics results in high overvoltage and poor cycling performance.Ruthenium(Ru)-based electrocatalysts have been demonstrated to be promising cathode catalysts to promote oxygen evolution reaction(OER).It facilitates decomposition of lithium peroxide(Li_(2)O_(2))by adjusting Li_(2)O_(2) morphologies,which is due to the strong interaction between Ru-based catalyst and superoxide anion(O_(2))intermediate.In this review,the design strategies of Ru-based electrocatalysts are introduced to enhance their OER catalytic kinetics in Li-O_(2) batteries.Different configurations of Ru-based catalysts,including metal particles(Ru metal and alloys),single-atom catalysts,and Ru-loaded compounds with various substrates(carbon materials,metal oxides/sulfides),have been summarized to regulate the electronic structure and the matrix architecture of the Ru-based electrocatalysts.The structure-property relationship of Ru-based catalysts is discussed for a better understanding of the Li_(2)O_(2) decomposition mechanism at the cathode interface.Finally,the challenges of Ru-based electrocatalysts are proposed for the future development of Li-O_(2) batteries.展开更多
The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past...The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for HER.In this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.展开更多
Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such...Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.展开更多
The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electro...The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electrolysers, fuel cells, and metal–air batteries emerge in response to the need for developing sustainable energy carriers, in which the oxygen evolution reaction and the oxygen reduction reaction play key roles. However, both reactions suffer from sluggish kinetics that restricts the reactivity. Therefore, it is vital to probe into the structure of the catalysts to exploit high-performance bifunctional oxygen electrocatalysts. Spinel-type catalysts are a class of materials with advantages of versatility, low toxicity, low expense, high abundance, flexible ion arrangement, and multivalence structure. In this review, we afford a basic overview of spinel-type materials and then introduce the relevant theoretical principles for electrocatalytic activity, following that we shed light on the structure–property relationship strategies for spinel-type catalysts including electronic structure, microstructure, phase and composition regulation,and coupling with electrically conductive supports. We elaborate the relationship between structure and property, in order to provide some insights into the design of spinel-type bifunctional oxygen electrocatalysts.展开更多
Tuning the electronic structure of the electrocatalysts for oxygen evolution reaction(OER)is a promising way to achieve efficient alkaline water splitting for clean energy production(H2).At first,this paper introduces...Tuning the electronic structure of the electrocatalysts for oxygen evolution reaction(OER)is a promising way to achieve efficient alkaline water splitting for clean energy production(H2).At first,this paper introduces the significance of the tuning of electronic structure,where modifying the electronic structure of the electrocatalysts could generate active sites having optimal adsorption energy with OER intermediates,and that could diminish the energy barrier for OER,and that could improve the activity for OER.Later,this paper reviews the tuning of electronic structure along with catalytic performances,synthetic methodologies,chemical properties,and DFT calculations on various nanostructured earth-abundant electrocatalysts for OER in alkaline environment.Further,this review discusses the tuning of the electronic structure of the several nanostructured earth-abundant electrocatalysts including oxide,(oxy)hydroxide,layered double hydroxide,alloy,metal phosphide/phosphate,nitride,sulfide,selenide,carbon containing materials,MOF,core-shell/hetero/hollow structured materials,and materials with vacancies/defects for OER in alkaline environment(including activity:overpotential(η)of ≤200 mV at10 m A cm^(-2);stability:≥100 h;durability:≥5000 cycles).Then,this review discusses the robust stability of the electrocatalysts for OER towards practical application.Moreover,this review discusses the in situ formation of thin layer on the catalyst surface during OER.In addition,this review discusses the influence of the adsorption energy of the OER intermediates on OER performance of the catalysts.Finally,this review summarizes the various promising strategies for tuning the electronic structure of the electrocatalysts to achieve enhanced performance for OER in alkaline environment.展开更多
The pyrolysis under inert atmosphere has been widely used for the synthesis of metal containing heteroatoms doped carbon materials, versatile catalysts for various reactions. However, it is difficult to prevent metal ...The pyrolysis under inert atmosphere has been widely used for the synthesis of metal containing heteroatoms doped carbon materials, versatile catalysts for various reactions. However, it is difficult to prevent metal nanoparticles aggregation during pyrolysis process. Herein, we reported the efficient synthesis of nitrogen doped carbon hollow nanospheres with cobalt nanoparticles (Co NP, ca. 10nm in size) distributed uniformly in the shell via pyrolysis of yolk-shell structured Zn-Co-ZIFs@polydopamine (PDA). PDA acted as both protection layer and carbon source, which successfully prevented the aggregation of cobalt nanoparticles during high-temperature pyrolysis process. The Co NP and N containing carbon (Co NP/NC) hollow nanospheres were active for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), affording overpotential of 430 mV at 10 mA/cm2 for OER in 1 M KOH and comparable half-wave potential to that of Pt/C (0.80V vs RHE) for ORR in 0.1 M KOH. The superior performance of carbon hollow nanospheres for both OER and ORR was mainly attributed to its small metal nanoparticles, N-doping and hollow nanostructure. The protection and confinement effect that originated from PDA coating strategy could be extended to the synthesis of other hollow structured carbon materials, especially the ones with small metal nanoparticles.展开更多
The construction of high-efficiency and low-cost non-noble metal bifunctional electrocatalysts for water electrolysis is crucial for commercial large-scale application of hydrogen energy.Here,we report a novel strateg...The construction of high-efficiency and low-cost non-noble metal bifunctional electrocatalysts for water electrolysis is crucial for commercial large-scale application of hydrogen energy.Here,we report a novel strategy with erbiumdoped NiCoP nanowire arrays in situ grown on conductive nickel foam(Er-NiCoP/NF).Significantly,the developed electrode shows exceptional bifunctional catalytic activity,which only requires overpotentials of 46 and 225 mV to afford a current density of 10 mAcm^(−2) for the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER),respectively.Density functional theory calculations reveal that the appropriate Er incorporation into the NiCoP lattice can significantly modulate the electronic structure with the d-band centers of Ni and Co atoms by shifting to lower energies with respect to the Fermi level,and optimize the Gibbs free energies of HER/OER intermediates,thereby accelerating water-splitting kinetics.When assembled as a solar-driven overall water-splitting electrolyzer,the as-prepared electrode shows a high and stable solar-to-hydrogen efficiency of 19.6%,indicating its potential for practical storage of intermittent energy.展开更多
Water splitting is an effective strategy to produce renewable and sustainable hydrogen energy.Especially,seawater splitting,avoiding use of the limited freshwater resource,is more intriguing.Nowadays,electrocatalysts ...Water splitting is an effective strategy to produce renewable and sustainable hydrogen energy.Especially,seawater splitting,avoiding use of the limited freshwater resource,is more intriguing.Nowadays,electrocatalysts explored for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)using natural seawater or saline electrolyte have been increasingly reported.To better understand the current status and challenges of the electrocatalysts for HER and OER from seawater,we comprehensively review the recent advances in electro-catalysts for seawater splitting.The fundamentals,challenges and possible strategies for seawater splitting are firstly presented.Then,the recently reported electrocatalysts that explored for HER and OER from seawater are summarized and discussed.Finally,the perspectives in the development of high-efficient electrocatalysts for seawater splitting are also proposed.展开更多
Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the o...Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.展开更多
Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coord...Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coordinationmodulated process.Upon pyrolysis,Ag@C strings of Co nanoparticles embedded with three-dimensional porous carbon with beads-on-string hierarchical structures are developed.Due to the advantages of the rich electrochemical active sites of Co-based“beads”and the efficient electron transfer pathways via Ag@C“strings,”the resultant NH_(3)-Ag@C@Co-N-C-700 catalyst shows an improved electrocatalytic activity toward ORR.NH_(3)-Ag@C@Co-N-C-700 shows a high onset potential of 0.99 V versus RHE,a high half-wave potential of 0.88 V versus RHE,and a large limiting current of 5.8 mA cm^(-2),which are better than those of commercial Pt/C electrocatalysts.Additionally,the NH_(3)-Ag@C@Co-N-C-700 catalyst shows high stability and preeminent methanol tolerance,which makes NH_(3)-Ag@C@Co-N-C-700 a promising catalyst for oxygen electrocatalysis in fuel cell applications.展开更多
The hydrogen evolution reaction performance of semiconducting 2H-phase molybdenum disulfide(2H-MoS_(2))presents a significant hurdle in realizing its full potential applications.Here,we utilize theoretical calculation...The hydrogen evolution reaction performance of semiconducting 2H-phase molybdenum disulfide(2H-MoS_(2))presents a significant hurdle in realizing its full potential applications.Here,we utilize theoretical calculations to predict possible functionalized graphene quantum dots(GQDs),which can enhance HER activity of bulk MoS_(2).Subsequently,we design a functionalized GQD-induced in-situ bottom-up strategy to fabricate near atom-layer 2H-MoS_(2) nanosheets mediated with GQDs(ALQD)by modulating the concentration of electron withdrawing/donating functional groups.Experimental results reveal that the introduction of a series of functionalized GQDs during the synthesis of ALQD plays a crucial role.Notably,the higher the concentration and strength of electron-withdrawing functional groups on GQDs,the thinner and more active the resulting ALQD are.Remarkably,the synthesized near atom-layer ALQD-SO_(3)demonstrate significantly improved HER performance.Our GQD-induced strategy provides a simple and efficient approach for expanding the catalytic application of MoS_(2).Furthermore,it holds substantial potential for developing nanosheets in other transition-metal dichalcogenide materials.展开更多
Efficient electrocatalysts are crucial for hydrogen generation from electrolyzing water.Nevertheless,the conventional"trial and error"method for producing advanced electrocatalysts is not only cost-ineffecti...Efficient electrocatalysts are crucial for hydrogen generation from electrolyzing water.Nevertheless,the conventional"trial and error"method for producing advanced electrocatalysts is not only cost-ineffective but also time-consuming and labor-intensive.Fortunately,the advancement of machine learning brings new opportunities for electrocatalysts discovery and design.By analyzing experimental and theoretical data,machine learning can effectively predict their hydrogen evolution reaction(HER)performance.This review summarizes recent developments in machine learning for low-dimensional electrocatalysts,including zero-dimension nanoparticles and nanoclusters,one-dimensional nanotubes and nanowires,two-dimensional nanosheets,as well as other electrocatalysts.In particular,the effects of descriptors and algorithms on screening low-dimensional electrocatalysts and investigating their HER performance are highlighted.Finally,the future directions and perspectives for machine learning in electrocatalysis are discussed,emphasizing the potential for machine learning to accelerate electrocatalyst discovery,optimize their performance,and provide new insights into electrocatalytic mechanisms.Overall,this work offers an in-depth understanding of the current state of machine learning in electrocatalysis and its potential for future research.展开更多
Electrochemical synthesis of H_(2)O_(2) via a selective two-electron oxygen reduction reaction has emerged as an attractive alternative to the current energy-consuming anthraquinone process. Herein, the progress on el...Electrochemical synthesis of H_(2)O_(2) via a selective two-electron oxygen reduction reaction has emerged as an attractive alternative to the current energy-consuming anthraquinone process. Herein, the progress on electrocatalysts for H_(2)O_(2) generation, including noble metal, transition metalbased, and carbon-based materials, is summarized. At first, the design strategies employed to obtain electrocatalysts with high electroactivity and high selectivity are highlighted. Then, the critical roles of the geometry of the electrodes and the type of reactor in striking a balance to boost the H_(2)O_(2) selectivity and reaction rate are systematically discussed. After that, a potential strategy to combine the complementary properties of the catalysts and the reactor for optimal selectivity and overall yield is illustrated. Finally, the remaining challenges and promising opportunities for highefficient H_(2)O_(2) electrochemical production are highlighted for future studies.展开更多
Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realiz...Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realize the storage of renewable energy,for it guarantees the production of value-added chemicals and fuels.Among CO_(2)RR products,formic acid shows great advantages in low energy consumption and high added-value,and thus producing formic acid is generally considered as a profitable line for CO_(2)RR.Bismuth-based electrocatalysts exhibit high formic acid selectivity in CO_(2)RR.Herein,we review the recent progress in bismuth-based electrocatalysts for CO_(2)RR,including material synthesis,performance optimization/validation,and electrolyzers.The effects of morphologies,structure,and composition of bismuth-based electrocatalysts on CO_(2)RR performance are highlighted.Simultaneously,in situ spectroscopic characterization and DFT calculations for reaction mechanism of CO_(2)RR on Bi-based catalysts are emphasized.The applications and optimization of electrolyzers with high current density for CO_(2)RR are summarized.Finally,conclusions and future directions in this field are prospected.展开更多
基金the support from the CIPHER Project(IIID 2018-008)funded by the Commission on Higher Education-Philippine California Advanced Research Institutes(CHED-PCARI)。
文摘Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.
基金supported by National Natural Science Foundation of China(22090031,21922501,22109004)China Postdoctoral Science Foundation(2021M690319)。
文摘Integrated electrocatalysts(IECs)containing well-defined functional materials directly grown on the current collector have sparked increasing interest in the fields of electrocatalysis owing to efficient activity,high stability and the fact that they are easily assembled into devices.Recently,metal organic frameworks(MOFs)provide a promising platform for constructing advanced IECs because of their properties of low cost,large surface area and efficient structural tunability.In this review,the design principles of state-of-the-art IECs based on MOFs are presented,including by hydrothermal/solvothermal,template-directed,electrospinning,electrodeposition and other methods.The high performance of MOF-derived IECs has also been demonstrated in electrocatalytic gasinvolved reactions.This is promising for green energy storage and conversion.The structure-activity relationship and performance improvement mechanism of IECs are uncovered by discussing some in situ technologies for IECs.Finally,we provide an outlook on the challenges and prospects in this booming field.
基金supported by the National Natural Science Foundation of China(NSFC,No.22078052)the Fundamental Research Funds for the Central Universities(DUT22ZD207,DUT22LAB612)。
文摘Seawater splitting into hydrogen,a promising technology,is seriously limited by the durability and tolerance of electrocatalysts for chlorine ions in seawater at large current densities due to chloride oxidation and corrosion.Here,we present a robust and weak-nucleophilicity nickel-iron hydroxide electrocatalyst with excellent selectivity for oxygen evolution and an inert response for chlorine ion oxidation which are key and highly desired for efficient seawater electrolysis.Such a weak-nucleophilicity electrocatalyst can well match with strong-nucleophilicity OH-compared with the weak-nucleophilicity Cl^(-),resultantly,the oxidation of OH-in electrolyte can be more easily achieved relative to chlorine ion oxidation,confirmed by ethylenediaminetetraacetic acid disodium probing test.Further,no strongly corrosive hypochlorite is produced when the operating voltage reaches about 2.1 V vs.RHE,a potential that is far beyond the thermodynamic potential of chlorine ion oxidatio n.This concept and approach to reasonably designing weaknucleophilicity electrocatalysts that can greatly avoid chlorine ion oxidation under alkaline seawater environments can push forward the seawater electrolysis technology and also accelerate the development of green hydrogen technique.
基金the National Natural Science Foundation of China(22325902 and 51671107)Haihe Laboratory of Sustainable Chemical Transformations.
文摘Rechargeable lithium-oxygen(Li-O_(2))batteries have attracted wide attention due to their high energy density.However,the sluggish cathode kinetics results in high overvoltage and poor cycling performance.Ruthenium(Ru)-based electrocatalysts have been demonstrated to be promising cathode catalysts to promote oxygen evolution reaction(OER).It facilitates decomposition of lithium peroxide(Li_(2)O_(2))by adjusting Li_(2)O_(2) morphologies,which is due to the strong interaction between Ru-based catalyst and superoxide anion(O_(2))intermediate.In this review,the design strategies of Ru-based electrocatalysts are introduced to enhance their OER catalytic kinetics in Li-O_(2) batteries.Different configurations of Ru-based catalysts,including metal particles(Ru metal and alloys),single-atom catalysts,and Ru-loaded compounds with various substrates(carbon materials,metal oxides/sulfides),have been summarized to regulate the electronic structure and the matrix architecture of the Ru-based electrocatalysts.The structure-property relationship of Ru-based catalysts is discussed for a better understanding of the Li_(2)O_(2) decomposition mechanism at the cathode interface.Finally,the challenges of Ru-based electrocatalysts are proposed for the future development of Li-O_(2) batteries.
文摘The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy systems.In the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for HER.In this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.
基金financial support from the Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX24_0690)financial support from the National Natural Science Foundation of China (Project No. 22275088, 52101260)+4 种基金the Project of Shuangchuang Scholar of Jiangsu Province (Project No. JSSCBS20210212)the Fundamental Research Funds for the Central Universities (Project No. 30921011203)the Start-Up Grant (Project No. AE89991/340) from Nanjing University of Science and Technologyfinancial support from the Foundation of Jiangsu Educational Committee (22KJB310008)the Senior Talent Program of Jiangsu University (20JDG073)
文摘Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.
基金supported by the Natural Scientific Foundation of China (21825501)National Key Research and Development Program (2016YFA0202500 and 2016YFA0200102)+1 种基金Australian Research Council (DP160103107, FT170100224)Tsinghua University Initiative Scientific Research Program。
文摘The demand for efficient and environmentally-benign electrocatalysts that help availably harness the renewable energy resources is growing rapidly. In recent years, increasing insights into the design of water electrolysers, fuel cells, and metal–air batteries emerge in response to the need for developing sustainable energy carriers, in which the oxygen evolution reaction and the oxygen reduction reaction play key roles. However, both reactions suffer from sluggish kinetics that restricts the reactivity. Therefore, it is vital to probe into the structure of the catalysts to exploit high-performance bifunctional oxygen electrocatalysts. Spinel-type catalysts are a class of materials with advantages of versatility, low toxicity, low expense, high abundance, flexible ion arrangement, and multivalence structure. In this review, we afford a basic overview of spinel-type materials and then introduce the relevant theoretical principles for electrocatalytic activity, following that we shed light on the structure–property relationship strategies for spinel-type catalysts including electronic structure, microstructure, phase and composition regulation,and coupling with electrically conductive supports. We elaborate the relationship between structure and property, in order to provide some insights into the design of spinel-type bifunctional oxygen electrocatalysts.
基金supported by the King Abdullah University of Science and Technology(KAUST)。
文摘Tuning the electronic structure of the electrocatalysts for oxygen evolution reaction(OER)is a promising way to achieve efficient alkaline water splitting for clean energy production(H2).At first,this paper introduces the significance of the tuning of electronic structure,where modifying the electronic structure of the electrocatalysts could generate active sites having optimal adsorption energy with OER intermediates,and that could diminish the energy barrier for OER,and that could improve the activity for OER.Later,this paper reviews the tuning of electronic structure along with catalytic performances,synthetic methodologies,chemical properties,and DFT calculations on various nanostructured earth-abundant electrocatalysts for OER in alkaline environment.Further,this review discusses the tuning of the electronic structure of the several nanostructured earth-abundant electrocatalysts including oxide,(oxy)hydroxide,layered double hydroxide,alloy,metal phosphide/phosphate,nitride,sulfide,selenide,carbon containing materials,MOF,core-shell/hetero/hollow structured materials,and materials with vacancies/defects for OER in alkaline environment(including activity:overpotential(η)of ≤200 mV at10 m A cm^(-2);stability:≥100 h;durability:≥5000 cycles).Then,this review discusses the robust stability of the electrocatalysts for OER towards practical application.Moreover,this review discusses the in situ formation of thin layer on the catalyst surface during OER.In addition,this review discusses the influence of the adsorption energy of the OER intermediates on OER performance of the catalysts.Finally,this review summarizes the various promising strategies for tuning the electronic structure of the electrocatalysts to achieve enhanced performance for OER in alkaline environment.
文摘The pyrolysis under inert atmosphere has been widely used for the synthesis of metal containing heteroatoms doped carbon materials, versatile catalysts for various reactions. However, it is difficult to prevent metal nanoparticles aggregation during pyrolysis process. Herein, we reported the efficient synthesis of nitrogen doped carbon hollow nanospheres with cobalt nanoparticles (Co NP, ca. 10nm in size) distributed uniformly in the shell via pyrolysis of yolk-shell structured Zn-Co-ZIFs@polydopamine (PDA). PDA acted as both protection layer and carbon source, which successfully prevented the aggregation of cobalt nanoparticles during high-temperature pyrolysis process. The Co NP and N containing carbon (Co NP/NC) hollow nanospheres were active for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), affording overpotential of 430 mV at 10 mA/cm2 for OER in 1 M KOH and comparable half-wave potential to that of Pt/C (0.80V vs RHE) for ORR in 0.1 M KOH. The superior performance of carbon hollow nanospheres for both OER and ORR was mainly attributed to its small metal nanoparticles, N-doping and hollow nanostructure. The protection and confinement effect that originated from PDA coating strategy could be extended to the synthesis of other hollow structured carbon materials, especially the ones with small metal nanoparticles.
基金supported by the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University(2019FY003025)the National Natural Science Foundation of China(U2002213 and 51621001)+2 种基金the East-Land Middle-aged and Young Backbone Teacher of Yunnan University(No.C176220200)Yunnan Applied Basic Research Projects(202001BB050006,202001BB050007)the Double-First Class University Plan(C176220100042).
文摘The construction of high-efficiency and low-cost non-noble metal bifunctional electrocatalysts for water electrolysis is crucial for commercial large-scale application of hydrogen energy.Here,we report a novel strategy with erbiumdoped NiCoP nanowire arrays in situ grown on conductive nickel foam(Er-NiCoP/NF).Significantly,the developed electrode shows exceptional bifunctional catalytic activity,which only requires overpotentials of 46 and 225 mV to afford a current density of 10 mAcm^(−2) for the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER),respectively.Density functional theory calculations reveal that the appropriate Er incorporation into the NiCoP lattice can significantly modulate the electronic structure with the d-band centers of Ni and Co atoms by shifting to lower energies with respect to the Fermi level,and optimize the Gibbs free energies of HER/OER intermediates,thereby accelerating water-splitting kinetics.When assembled as a solar-driven overall water-splitting electrolyzer,the as-prepared electrode shows a high and stable solar-to-hydrogen efficiency of 19.6%,indicating its potential for practical storage of intermittent energy.
基金financially supported by Key Research and Development Programme of Shandong Province (2019JZZY010905)National Natural Science Foundation of China (21776146)Taishan Scholar Program of Shandong Province (ts201712046)
文摘Water splitting is an effective strategy to produce renewable and sustainable hydrogen energy.Especially,seawater splitting,avoiding use of the limited freshwater resource,is more intriguing.Nowadays,electrocatalysts explored for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)using natural seawater or saline electrolyte have been increasingly reported.To better understand the current status and challenges of the electrocatalysts for HER and OER from seawater,we comprehensively review the recent advances in electro-catalysts for seawater splitting.The fundamentals,challenges and possible strategies for seawater splitting are firstly presented.Then,the recently reported electrocatalysts that explored for HER and OER from seawater are summarized and discussed.Finally,the perspectives in the development of high-efficient electrocatalysts for seawater splitting are also proposed.
基金partly supported by the National Natural Science Foundation of China(NSFCs,52202050,52122308,21905253,51973200)the China Postdoctoral Science Foundation(2022TQ0286)the Natural Science Foundation of Henan(202300410372)。
文摘Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.
基金Higher Education Discipline Innovation Project,Grant/Award Number:D17007Xinxiang Major Science and Technology Projects,Grant/Award Number:21ZD001+1 种基金Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2022017National Natural Science Foundation of China,Grant/Award Numbers:51872075,51922008,52072114。
文摘Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coordinationmodulated process.Upon pyrolysis,Ag@C strings of Co nanoparticles embedded with three-dimensional porous carbon with beads-on-string hierarchical structures are developed.Due to the advantages of the rich electrochemical active sites of Co-based“beads”and the efficient electron transfer pathways via Ag@C“strings,”the resultant NH_(3)-Ag@C@Co-N-C-700 catalyst shows an improved electrocatalytic activity toward ORR.NH_(3)-Ag@C@Co-N-C-700 shows a high onset potential of 0.99 V versus RHE,a high half-wave potential of 0.88 V versus RHE,and a large limiting current of 5.8 mA cm^(-2),which are better than those of commercial Pt/C electrocatalysts.Additionally,the NH_(3)-Ag@C@Co-N-C-700 catalyst shows high stability and preeminent methanol tolerance,which makes NH_(3)-Ag@C@Co-N-C-700 a promising catalyst for oxygen electrocatalysis in fuel cell applications.
基金This research was supported by Shanghai Pujiang Program(21PJD022)National Natural Science Foundation of China(21901154).
文摘The hydrogen evolution reaction performance of semiconducting 2H-phase molybdenum disulfide(2H-MoS_(2))presents a significant hurdle in realizing its full potential applications.Here,we utilize theoretical calculations to predict possible functionalized graphene quantum dots(GQDs),which can enhance HER activity of bulk MoS_(2).Subsequently,we design a functionalized GQD-induced in-situ bottom-up strategy to fabricate near atom-layer 2H-MoS_(2) nanosheets mediated with GQDs(ALQD)by modulating the concentration of electron withdrawing/donating functional groups.Experimental results reveal that the introduction of a series of functionalized GQDs during the synthesis of ALQD plays a crucial role.Notably,the higher the concentration and strength of electron-withdrawing functional groups on GQDs,the thinner and more active the resulting ALQD are.Remarkably,the synthesized near atom-layer ALQD-SO_(3)demonstrate significantly improved HER performance.Our GQD-induced strategy provides a simple and efficient approach for expanding the catalytic application of MoS_(2).Furthermore,it holds substantial potential for developing nanosheets in other transition-metal dichalcogenide materials.
基金This work was supported by the National Natural Science Foundation of China(Grant No.22008098,52122408)the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.22HASTIT008)+3 种基金the Programs for Science and Technology Development of Henan Province,China(No.222102320065)the Key Specialized Research and Development Breakthrough(Science and Technology)in Henan Province(No.212102210214)the Natural Science Foundations of Henan Province(No.222300420502)the Key Scientific Research Projects of University in Henan Province(No.23B430002).
文摘Efficient electrocatalysts are crucial for hydrogen generation from electrolyzing water.Nevertheless,the conventional"trial and error"method for producing advanced electrocatalysts is not only cost-ineffective but also time-consuming and labor-intensive.Fortunately,the advancement of machine learning brings new opportunities for electrocatalysts discovery and design.By analyzing experimental and theoretical data,machine learning can effectively predict their hydrogen evolution reaction(HER)performance.This review summarizes recent developments in machine learning for low-dimensional electrocatalysts,including zero-dimension nanoparticles and nanoclusters,one-dimensional nanotubes and nanowires,two-dimensional nanosheets,as well as other electrocatalysts.In particular,the effects of descriptors and algorithms on screening low-dimensional electrocatalysts and investigating their HER performance are highlighted.Finally,the future directions and perspectives for machine learning in electrocatalysis are discussed,emphasizing the potential for machine learning to accelerate electrocatalyst discovery,optimize their performance,and provide new insights into electrocatalytic mechanisms.Overall,this work offers an in-depth understanding of the current state of machine learning in electrocatalysis and its potential for future research.
基金supported by the National Natural Science Foundation (22279036)。
文摘Electrochemical synthesis of H_(2)O_(2) via a selective two-electron oxygen reduction reaction has emerged as an attractive alternative to the current energy-consuming anthraquinone process. Herein, the progress on electrocatalysts for H_(2)O_(2) generation, including noble metal, transition metalbased, and carbon-based materials, is summarized. At first, the design strategies employed to obtain electrocatalysts with high electroactivity and high selectivity are highlighted. Then, the critical roles of the geometry of the electrodes and the type of reactor in striking a balance to boost the H_(2)O_(2) selectivity and reaction rate are systematically discussed. After that, a potential strategy to combine the complementary properties of the catalysts and the reactor for optimal selectivity and overall yield is illustrated. Finally, the remaining challenges and promising opportunities for highefficient H_(2)O_(2) electrochemical production are highlighted for future studies.
基金This work was financially supported by grants from the National Key Research and Development Program of China(2021YFA1501504)Natural Science Foundation of China(22172135,22288102,92045302,and 22021001).
文摘Electrocatalytic CO_(2)reduction reaction(CO_(2)RR),driven by clean electric energy such as solar and wind,can not only alleviate environmental greenhouse effect stemming from excessive CO_(2)emissions,but also realize the storage of renewable energy,for it guarantees the production of value-added chemicals and fuels.Among CO_(2)RR products,formic acid shows great advantages in low energy consumption and high added-value,and thus producing formic acid is generally considered as a profitable line for CO_(2)RR.Bismuth-based electrocatalysts exhibit high formic acid selectivity in CO_(2)RR.Herein,we review the recent progress in bismuth-based electrocatalysts for CO_(2)RR,including material synthesis,performance optimization/validation,and electrolyzers.The effects of morphologies,structure,and composition of bismuth-based electrocatalysts on CO_(2)RR performance are highlighted.Simultaneously,in situ spectroscopic characterization and DFT calculations for reaction mechanism of CO_(2)RR on Bi-based catalysts are emphasized.The applications and optimization of electrolyzers with high current density for CO_(2)RR are summarized.Finally,conclusions and future directions in this field are prospected.