The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited ...The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited a high formate Faradaic efficiency(FE)of 97.45%(-0.9 V)and a large partial current density of-45.82 mA/cm^(2)(-1.2 V).The good performance benefits from the reconstruction of BiVO_(4)to generate active metal Bi sites,which results in the electron redistribution to boost the OCHO∗formation.In flow cells,near industrial current density of 183.94 mA/cm^(2)was achieved,with the FE of formate above 95%from 20mA/cm^(2)to 180mA/cm^(2).Our work provides a facily synthesized BiVO_(4)precatalyst for CO_(2)electroreduction.展开更多
Exploiting efficient urea oxidation reaction(UOR)and hydrogen evolution reaction(HER)catalysts are significant for energy-saving H2 production through urea-assisted water electrolysis,but it is still challenging.Herei...Exploiting efficient urea oxidation reaction(UOR)and hydrogen evolution reaction(HER)catalysts are significant for energy-saving H2 production through urea-assisted water electrolysis,but it is still challenging.Herein,carbon-encapsulated CoNi coupled with CoNiMoO(CoNi@CN-CoNiMoO)is prepared by solvothermal method and calcination to enhance the activity/stability of urea-assisted water electrolysis at large current density.It exhibits good activity for UOR(E10/1,000=1.29/1.40 V)and HER(E-10/-1000=-45/-245 mV)in 1.0 M KOH+0.5 M urea solution.For the UOR||HER system,CoNi@CN-CoNiMoO only needs 1.58 V at 500 mA cm-2 and shows good stability.Density functional theory calculation suggests that the strong electronic interaction at the interface between NiCo alloy and N-doping-carbon layers can optimize the adsorption/desorption energy of UOR/HER intermediates and accelerate the water dissociation,which can expedite urea decomposition and Volmer step,thus increasing the UOR and HER activity,respectively.This work provides a new solution to design UOR/HER catalysts for H2 production through urea-assisted water electrolysis.展开更多
Developing the high activity,low cost and robust large-current-density-based electrocatalysts is of great significance for the industrial electrolytic water splitting.However,the current range of most reported materia...Developing the high activity,low cost and robust large-current-density-based electrocatalysts is of great significance for the industrial electrolytic water splitting.However,the current range of most reported materials is small,which makes it difficult for them to play their roles in practical applications.Here,a self-supported amorphous FexNi1-xMo O4/IF treated with ammonium fluoride (AF_(0.1)-FNMO/IF) is synthesized by one-step hydrothermal method.With the help of NH4F,AF_(0.1)-FNMO/IF exhibits a vertically cross-linked nanosheet with spherical structure.Electrochemical measurement shows that AF_(0.1)-FNMO/IF affords a large current density ordeal and only need low overpotentials of 289 and 345 m V to reach a current response of 500 m A/cm ^(2)for oxygen evolution reaction and hydrogen evolution reaction,respectively,together with long-time stability (both at 500,1000 and 2000 m A/cm ^(2)) in 1.0 mol/L KOH solution.Using it as bifunctional catalyst for overall water splitting,the current densities of 100,500,1000 and1500 m A/cm ^(2)are achieved at a cell voltage of 1.71,1.88,1.94 and 1.97 V with excellent durability,which is much better than that of most published electrodes.The work provides valuable insight for designing higher activity nickel iron-based molybdate catalysts with large current density.展开更多
The urgent demand for sustainable energy resources has boosted research into highly efficient electrocatalysts for the hydrogen evolution reaction(HER).However,the majority of reported catalysts have only been evaluat...The urgent demand for sustainable energy resources has boosted research into highly efficient electrocatalysts for the hydrogen evolution reaction(HER).However,the majority of reported catalysts have only been evaluated under small current density(10 mA cm^(−2))and acidic conditions.In contrast,the industrial standard of HER requires a substantially higher current density(at least 1000 mA cm^(−2))and favors an alkaline medium.Therefore,increasing efforts on HER electrocatalysts have been shifted to fulfill the requirements for driving HER at large current density with extremely high durability under alkaline conditions,as well as the facile large-scale fabrication of the HER electrocatalysts and electrodes.This review will briefly introduce the features and challenges in industrial HER,including the requirements,benchmark protocols,and parameters,and distinguish the key differences from common lab-level evaluations.Afterward,the recent progress in industrial HER electrocatalysts will be presented,organized mainly by material selections,and will focus on the performance,durability,special fabrication techniques,and brief explanations of mechanisms.Finally,the future outlook and perspectives about industrial HER electrocatalysts are discussed.This review will supply significant insights into the future development of practical HER electrocatalysts.展开更多
Earth-abundant electrocatalysts for large-current-density water splitting under alkaline condition are desirable.Oxygen evolution reaction,which is a bottleneck of the overall water splitting,faces the problems of com...Earth-abundant electrocatalysts for large-current-density water splitting under alkaline condition are desirable.Oxygen evolution reaction,which is a bottleneck of the overall water splitting,faces the problems of complicated reconstruction and deficiency in rational design of active sites.Herein,we report a series of transition metal chalcogenides for alkaline OER.Among them,FeCoNi(S)displayed a low overpotential of 293 m V to deliver a current density of 500 m A cm^(-2),which is in the top level of non-precious metal based OER electrocatalysts.A combination of(ex)in situ characterizations and DFT calculation shows that Ni(Fe,Co)trimetallic oxyhydroxides were the active sites for highly-efficient OER.Furthermore,for FeCoNi(S),when used as a bifunctional catalyst for water splitting,it only required a cell voltage of 1.84 V to deliver~500 m A cm^(-2) with extraordinary long-term stability over 2000 h.This work provides the comprehension of high-efficiency,robust catalysts for OER and overall water splitting at large current densities in alkaline media.展开更多
Developing high performance anode catalysts for oxygen evolution reaction (OER) and hydrazine oxidation reaction (HzOR) at large current density is an efficient pathway to produce hydrogen. Herein, we synthesize a FeW...Developing high performance anode catalysts for oxygen evolution reaction (OER) and hydrazine oxidation reaction (HzOR) at large current density is an efficient pathway to produce hydrogen. Herein, we synthesize a FeWO_(4)-WO_(3) heterostructure catalyst growing on nickel foam (FeWO_(4)-WO_(3)/NF) by a combination of hydrothermal and calcination method. It shows good catalytic activity with ultralow potentials for OER (ζ_(10) = 1.43 V, ζ_(1.000) = 1.56 V) and HzOR (ζ_(10) = −0.034 V, ζ_(1.000) = 0.164 V). Moreover, there is little performance degradation after being tested for _(10)0 h at 1,000 (OER) and _(10)0 (HzOR) mA·cm−2, indicating good stability. The superior performance could be attributed to the wolframite structure and heterostructure: The former provides a high electrical conductivity to ensure the electronic transfer capability, and the later induces interfacial electron redistribution to enhance the intrinsic activity and stability. The work offers a brand-new way to prepare good performance catalysts for OER and HzOR, especially at large current density.展开更多
Highly efficient and stable bifunctional electrocatalysts that can be used for large-current-density electrolysis of alkaline seawater are highly desirable for carbon-neutral economies,but their facile and controllabl...Highly efficient and stable bifunctional electrocatalysts that can be used for large-current-density electrolysis of alkaline seawater are highly desirable for carbon-neutral economies,but their facile and controllable synthesis remains a challenge.Here,self-assembled ultralow Ru,Ni-doped Fe_(2)O_(3) with a lily shaped morphology was synthesized on iron foam(RuNi-Fe_(2)O_(3)/IF)via a facile one-step hydrothermal process,in which the intact lily shaped RuNi-Fe_(2)O_(3)/IF was obtained by adjusting the ratio of Ru/Ni.Benefitting from the Ru/Ni chemical substitution,the as-synthesized RuNi-Fe_(2)O_(3)/IF can act as free-standing dual-function electrodes that are applied to electrocatalysis for the hydrogen evolution(HER)and oxygen evolution reactions(OER)in 1.0 mol L^(-1) KOH,requiring an overpotential of 75.0 mV to drive 100 mA cm^(-2) for HER and 329.0 mV for OER.Moreover,the overall water splitting catalyzed by RuNi-Fe_(2)O_(3)/IF only demands ultralow cell voltages of 1.66 and 1.73 V to drive 100 mA cm^(-2) in 1.0 mol L^(-1) KOH and 1.0 mol L^(-1) KOH seawater electrolytes,respectively.The electrodes show remarkable long-term durability,maintaining current densities exceeding 100 mA cm^(-2) for more than 100 h and thus outperforming the two-electrode system composed of noble catalysts.This work provides an efficient,economical method to synthesize self-standing bifunctional electrodes for large-current-density alkaline seawater electrolysis,which is of significant importance for ecological protection and energy exploitation.展开更多
Within the framework of achieving global carbon neutrality,utilizing electrocatalytic water splitting to produce“green hydrogen”holds significant promise as an effective solution.The strategic development of economi...Within the framework of achieving global carbon neutrality,utilizing electrocatalytic water splitting to produce“green hydrogen”holds significant promise as an effective solution.The strategic development of economic,efficient,and robust anode oxygen evolution reaction(OER)catalysts is one of the imminent bottlenecks for scalable application of electrolyzing water into hydrogen and oxygen,particularly under actual yet harsh operating conditions such as large current density(LCD).In this review,we intend to summarize the advances and challenges in the understanding of the electrocatalytic OER at LCD.Initially,the impact of LCD on the electron transfer,mass transportation efficiency and catalyst stability is identified and summarized.Furthermore,five basic principles for catalyst design,namely the dimension of the materials,surface chemistry,creation of electron transfer pathways,synergy among nano-,micro-,and macroscale structures,and catalyst-support interaction,are systematically discussed.Specifically,the correlation between the synergistic function of the multiscale structures and the catalyst-support interaction is highlighted to direct improvements in catalyst efficiency and durability at the LCD.Finally,an outlook is prospected to further our understanding of these topics and provide related researchers with potential research areas.展开更多
Large-scale green hydrogen production technology,based on the electrolysis of water powered by renewable energy,relies heavily on non-precious metal oxygen evolution reactions(OER)electrocatalysts with high activity a...Large-scale green hydrogen production technology,based on the electrolysis of water powered by renewable energy,relies heavily on non-precious metal oxygen evolution reactions(OER)electrocatalysts with high activity and stability under industrial conditions(6 M KOH,60℃-80℃)at large current density.Here,we construct Fe and Co co-incorporated nickel(oxy)hydroxide(Fe_(2.5)Co_(2.5)Ni_(10)O_(y)H_(z)@NFF)via a multi-metal electrodeposition,which exhibits outstanding OER performance(overpotential:185 mV@10 mA cm^(-2)).Importantly,an overwhelming stability for more than 1100 h at 500 mA cm^(-2)under industrial conditions is achieved.Our combined experimental and computational investigation reveals the surface-reconstructedγ-NiOOH with a high valence state is the active layer,where the optimal(Fe,Co)co-incorporation tunes its electronic structure,changes the potential determining step,and reduces the energy barrier,leading to ultrahigh activity and stability.Our findings demonstrate a facile way to achieve an electrocatalyst with high performance for the industrial production of green hydrogen.展开更多
Electrochemical water splitting is a pivotal technology in the large-scale production of green hydrogen for sus-tainable future energy provisions.Highly active,stable electrocatalysts have been extensively explored,bu...Electrochemical water splitting is a pivotal technology in the large-scale production of green hydrogen for sus-tainable future energy provisions.Highly active,stable electrocatalysts have been extensively explored,but the majority suffer from low current densities and small sizes,rendering them unsuitable for industrial applications.Recently,however,the scalable production of electrocatalysts with high performance at large current densities has made tremendous progress.In this review,the current achievements in developing outstanding large elec-trocatalysts for high-current-density water electrolysis are described in detail.First,we introduce the funda-mentals of water electrolysis,the criteria for performance evaluation,and the requirements for producing electrocatalysts at scale under large current densities.Second,we summarize the key approaches for realizing large-sized electrocatalysts with excellent performance,including electrodeposition,corrosion engineering,and thermal treatment,as well as combinations of these methods.Finally,we offer perspectives on research challenges and propose directions for mass-producing high-performance electrocatalysts with large current densities for water electrolysis,to guide the further industrialization of water-electrolysis catalysts.展开更多
Constructing heterojunction is an effective strategy to develop high-performance non-preciousmetal-based catalysts for electrochemical water splitting(WS).Herein,we design and prepare an N-doped-carbon-encapsulated Ni...Constructing heterojunction is an effective strategy to develop high-performance non-preciousmetal-based catalysts for electrochemical water splitting(WS).Herein,we design and prepare an N-doped-carbon-encapsulated Ni/MoO_(2) nano-needle with three-phase heterojunction(Ni/MoO_(2)@CN)for accelerating the WS under industrial alkaline condition.Density functional theory calculations reveal that the electrons are redistributed at the three-phase heterojunction interface,which optimizes the adsorption energy of H-and O-containing intermediates to obtain the best ΔG_(H*) for hydrogen evolution reaction(HER)and decrease the ΔG value of ratedetermining step for oxygen evolution reaction(OER),thus enhancing the HER/OER catalytic activity.Electrochemical results confirm that Ni/MoO_(2)@CN exhibits good activity for HER(ƞ_(-10)=33 mV,ƞ_(-1000)=267 mV)and OER(ƞ_(10)=250 mV,ƞ_(1000)=420 mV).It shows a low potential of 1.86 V at 1000 mA cm^(−2) for WS in 6.0 M KOH solution at 60℃ and can steadily operate for 330 h.This good HER/OER performance can be attributed to the three-phase heterojunction with high intrinsic activity and the self-supporting nano-needle with more active sites,faster mass diffusion,and bubbles release.This work provides a unique idea for designing high efficiency catalytic materials for WS.展开更多
Developing highly stable electrocatalysts under industry-compatible current densities(>500 mA cm^(-2))in an anion-exchange membrane water electrolyzer(AEMWE)is an enormous challenge for water splitting.Herein,based...Developing highly stable electrocatalysts under industry-compatible current densities(>500 mA cm^(-2))in an anion-exchange membrane water electrolyzer(AEMWE)is an enormous challenge for water splitting.Herein,based on the results of density function theory calculations,a dual heterogeneous interfacial structured NiSe/Fe-Ni(OH)_(2)catalyst was subtly designed and successfully prepared by electrodepositing Fe-doped Ni(OH)_(2)on NiSe-loaded nickel foam(NF).Fe doping-driven heterogeneous structures in NiSe/Fe-Ni(OH)_(2)markedly boost catalytic activity and durability at industrially compatible current densities in single hydrogen and oxygen evolution reactions under alkaline conditions.In particular,NiSe/Fe-Ni(OH)_(2)shows a negligible performance loss at 600 mA cm^(-2)at least 1,000 h for overall water splitting,a distinguished long-term durability acting as AEMWE electrodes at 600 mA cm^(-2)and 1 A cm^(-2)at 85℃for at least 95 h.Owing to Fe doping-induced strong synergetic effect between Ni and Fe,dual heterostructure-promoted charge transfer and redistribution,abundant catalytic active sites,and improvement of stability and durability,a mechanism of Fe doping-driven heterogeneous interfacial structurepromoted catalytic performance was proposed.This study provides a successful example of theory-directed catalyst preparation and pioneers a creative strategy for industry-compatible water splitting at high current density.展开更多
Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/C...Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis(30 s).The OH-from rapid surface hydrolysis of Co_(2)P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site,which may bring out better synergistic effect for alkaline HER.Moreover,the covering of CoRuOH can improve the stability of Co_(2)P for HER.When drives at 100 mA/cm^(2),it only requires overpotential of 81 mV in 1.0 mol/L KOH(25℃).Even at higher current density(1000 mA/cm^(2)),CoRuOH/Co_(2)P/CF can also operate stability for at least 100 h.When coupling with NiFe-LDH/IF in a two-electrode system,the voltage of NiFe-LDH/IF(+)||CoRuOH/Co_(2)P/CF(-)at 1000 mA/cm^(2)is merely 1.77 V with 100 h,demonstrating great potential for water splitting.The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.展开更多
Li-CO_(2)batteries(LCBs)suffer from high overpotentials caused by sluggish CO_(2)reaction kinetics.This work designs a Te-doped Fe_(3)O_(4)(Te-Fe_(3)O_(4))flower-like microsphere catalyst to lower the overpotential an...Li-CO_(2)batteries(LCBs)suffer from high overpotentials caused by sluggish CO_(2)reaction kinetics.This work designs a Te-doped Fe_(3)O_(4)(Te-Fe_(3)O_(4))flower-like microsphere catalyst to lower the overpotential and improve the reversibility of LCBs.Experimental results reveal that Te doping modifies the electronic structure of Fe_(3)O_(4)and reduces the overpotential.The stable Te-O bond between Te and C_(2)O^(2-)_(4)could effectively inhibit the dispro-portionation reaction of the latter,enabling the Te-Fe_(3)O_(4)cathodes to exhibit a remarkable capacity(9485 mAh g^(-1))and a long cycling life(155 cycles)with an overpotential of 1.21 V and an energy efficiency of about 80%at a high current density(2000 mA g^(-1)).Through the interaction between Te and Li_(2)C_(2)O_(4)to inhibit the dispro-portionation reaction,this work successfully achieves long-term cycling of LCBs with low overpotential at high current density.展开更多
Deliberate modulation of the electronic structure via interface engineering is one of promising perspectives to build advanced catalysts for urea oxidation reaction(UOR)at high current densities.However,it still remai...Deliberate modulation of the electronic structure via interface engineering is one of promising perspectives to build advanced catalysts for urea oxidation reaction(UOR)at high current densities.However,it still remains some challenges originating from the intrinsically sluggish UOR dynamics and the high energy barrier for urea adsorption.In response,we report the coupled NiSe_(2)nanowrinkles with Ni_(5)P_(4)nanorods heterogeneous structure onto Ni foam(denoted as NiSe_(2)@Ni_(5)P_(4)/NF)through successive phosphorization and selenization strategy,in which the produced closely contacted interface could provide high-flux electron transfer pathways.Theoretical findings decipher that the fast charge transfer takes place at the interfacial region from Ni_(5)P_(4)to NiSe_(2),which is conducive to optimizing adsorption energy of urea molecules.As expected,the well-designed NiSe_(2)@Ni_(5)P_(4)/NF only requires the low potential of 1.402 V at the current density of 500 mA·cm^(-2).More importantly,a small Tafel slope of 27.6 mV·dec^(-1),a high turnover frequency(TOF)value of 1.037 s^(-1)as well as the prolonged stability of 950 h at the current density of 100 mA·cm^(-2)are also achieved.This study enriches the understanding on the electronic structure modulation via interface engineering and offers bright prospect to design advanced UOR catalysts.展开更多
基金financially supported by the Fundamental Research Funds for the Central Universities of Central South University(No.2022ZZTS0579).
文摘The large current density of electrochemical CO_(2)reduction towards industrial application is challenging.Herein,without strong acid and reductant,the synthesized BiVO_(4)with abundant oxygen vacancies(Ovs)exhibited a high formate Faradaic efficiency(FE)of 97.45%(-0.9 V)and a large partial current density of-45.82 mA/cm^(2)(-1.2 V).The good performance benefits from the reconstruction of BiVO_(4)to generate active metal Bi sites,which results in the electron redistribution to boost the OCHO∗formation.In flow cells,near industrial current density of 183.94 mA/cm^(2)was achieved,with the FE of formate above 95%from 20mA/cm^(2)to 180mA/cm^(2).Our work provides a facily synthesized BiVO_(4)precatalyst for CO_(2)electroreduction.
基金the National Natural Science Foundation of China(22162004)the Excellent Scholars and Innovation Team of Guangxi Universities,the Innovation Project of Guangxi Graduate Education(YCBZ2022038)the High-performance Computing Platform of Guangxi University。
文摘Exploiting efficient urea oxidation reaction(UOR)and hydrogen evolution reaction(HER)catalysts are significant for energy-saving H2 production through urea-assisted water electrolysis,but it is still challenging.Herein,carbon-encapsulated CoNi coupled with CoNiMoO(CoNi@CN-CoNiMoO)is prepared by solvothermal method and calcination to enhance the activity/stability of urea-assisted water electrolysis at large current density.It exhibits good activity for UOR(E10/1,000=1.29/1.40 V)and HER(E-10/-1000=-45/-245 mV)in 1.0 M KOH+0.5 M urea solution.For the UOR||HER system,CoNi@CN-CoNiMoO only needs 1.58 V at 500 mA cm-2 and shows good stability.Density functional theory calculation suggests that the strong electronic interaction at the interface between NiCo alloy and N-doping-carbon layers can optimize the adsorption/desorption energy of UOR/HER intermediates and accelerate the water dissociation,which can expedite urea decomposition and Volmer step,thus increasing the UOR and HER activity,respectively.This work provides a new solution to design UOR/HER catalysts for H2 production through urea-assisted water electrolysis.
基金financially supported by National Natural Science Foundation of China (No. 52174283)Shandong Provincial Natural Science Foundation (No. ZR2020MB044)+1 种基金Innovation Fund Project for Graduate Students of China University of Petroleum (East China) (No. 22CX04026A)the Fundameantal Research Funds for the Central Universities。
文摘Developing the high activity,low cost and robust large-current-density-based electrocatalysts is of great significance for the industrial electrolytic water splitting.However,the current range of most reported materials is small,which makes it difficult for them to play their roles in practical applications.Here,a self-supported amorphous FexNi1-xMo O4/IF treated with ammonium fluoride (AF_(0.1)-FNMO/IF) is synthesized by one-step hydrothermal method.With the help of NH4F,AF_(0.1)-FNMO/IF exhibits a vertically cross-linked nanosheet with spherical structure.Electrochemical measurement shows that AF_(0.1)-FNMO/IF affords a large current density ordeal and only need low overpotentials of 289 and 345 m V to reach a current response of 500 m A/cm ^(2)for oxygen evolution reaction and hydrogen evolution reaction,respectively,together with long-time stability (both at 500,1000 and 2000 m A/cm ^(2)) in 1.0 mol/L KOH solution.Using it as bifunctional catalyst for overall water splitting,the current densities of 100,500,1000 and1500 m A/cm ^(2)are achieved at a cell voltage of 1.71,1.88,1.94 and 1.97 V with excellent durability,which is much better than that of most published electrodes.The work provides valuable insight for designing higher activity nickel iron-based molybdate catalysts with large current density.
基金the National Key R&D Program of China(2021YFA1501101)the National Natural Science Foundation of China/Research Grant Council of Hong Kong Joint Research Scheme(N_PolyU502/21)+4 种基金National Natural Science Foundation of China/Research Grants Council(RGC)of Hong Kong Collaborative Research Scheme(CRS_PolyU504_22)the funding for Projects of Strategic Importance of The Hong Kong Polytechnic University(Project Code:1-ZE2V)Shenzhen Fundamental Research Scheme-General Program(JCYJ20220531090807017)the Natural Science Foundation of Guangdong Province(2023A1515012219)Departmental General Research Fund(Project Code:ZVUL)from The Hong Kong Polytechnic University.
文摘The urgent demand for sustainable energy resources has boosted research into highly efficient electrocatalysts for the hydrogen evolution reaction(HER).However,the majority of reported catalysts have only been evaluated under small current density(10 mA cm^(−2))and acidic conditions.In contrast,the industrial standard of HER requires a substantially higher current density(at least 1000 mA cm^(−2))and favors an alkaline medium.Therefore,increasing efforts on HER electrocatalysts have been shifted to fulfill the requirements for driving HER at large current density with extremely high durability under alkaline conditions,as well as the facile large-scale fabrication of the HER electrocatalysts and electrodes.This review will briefly introduce the features and challenges in industrial HER,including the requirements,benchmark protocols,and parameters,and distinguish the key differences from common lab-level evaluations.Afterward,the recent progress in industrial HER electrocatalysts will be presented,organized mainly by material selections,and will focus on the performance,durability,special fabrication techniques,and brief explanations of mechanisms.Finally,the future outlook and perspectives about industrial HER electrocatalysts are discussed.This review will supply significant insights into the future development of practical HER electrocatalysts.
基金the financial support from the Hunan Provincial Science and Technology Plan Project(No.2020JJ4710)the Hunan Key Laboratory of Two-Dimensional Materials(No.2018TP1010)+1 种基金the postdoctoral research funding plan in Central South University(No.140050022)the support from National Natural Science Foundation of China(No.12004439)。
文摘Earth-abundant electrocatalysts for large-current-density water splitting under alkaline condition are desirable.Oxygen evolution reaction,which is a bottleneck of the overall water splitting,faces the problems of complicated reconstruction and deficiency in rational design of active sites.Herein,we report a series of transition metal chalcogenides for alkaline OER.Among them,FeCoNi(S)displayed a low overpotential of 293 m V to deliver a current density of 500 m A cm^(-2),which is in the top level of non-precious metal based OER electrocatalysts.A combination of(ex)in situ characterizations and DFT calculation shows that Ni(Fe,Co)trimetallic oxyhydroxides were the active sites for highly-efficient OER.Furthermore,for FeCoNi(S),when used as a bifunctional catalyst for water splitting,it only required a cell voltage of 1.84 V to deliver~500 m A cm^(-2) with extraordinary long-term stability over 2000 h.This work provides the comprehension of high-efficiency,robust catalysts for OER and overall water splitting at large current densities in alkaline media.
基金This work is supported by the National Natural Science Foundation of China(No.21872040)the Hundred Talents Program of Guangxi Universities,the Excellent Scholars and Innovation Team of Guangxi Universities,Guangxi Major Projects of Science and Technology(No.GXMPSTAA17202032),Guangxi Ba-Gui Scholars Program.
文摘Developing high performance anode catalysts for oxygen evolution reaction (OER) and hydrazine oxidation reaction (HzOR) at large current density is an efficient pathway to produce hydrogen. Herein, we synthesize a FeWO_(4)-WO_(3) heterostructure catalyst growing on nickel foam (FeWO_(4)-WO_(3)/NF) by a combination of hydrothermal and calcination method. It shows good catalytic activity with ultralow potentials for OER (ζ_(10) = 1.43 V, ζ_(1.000) = 1.56 V) and HzOR (ζ_(10) = −0.034 V, ζ_(1.000) = 0.164 V). Moreover, there is little performance degradation after being tested for _(10)0 h at 1,000 (OER) and _(10)0 (HzOR) mA·cm−2, indicating good stability. The superior performance could be attributed to the wolframite structure and heterostructure: The former provides a high electrical conductivity to ensure the electronic transfer capability, and the later induces interfacial electron redistribution to enhance the intrinsic activity and stability. The work offers a brand-new way to prepare good performance catalysts for OER and HzOR, especially at large current density.
文摘Highly efficient and stable bifunctional electrocatalysts that can be used for large-current-density electrolysis of alkaline seawater are highly desirable for carbon-neutral economies,but their facile and controllable synthesis remains a challenge.Here,self-assembled ultralow Ru,Ni-doped Fe_(2)O_(3) with a lily shaped morphology was synthesized on iron foam(RuNi-Fe_(2)O_(3)/IF)via a facile one-step hydrothermal process,in which the intact lily shaped RuNi-Fe_(2)O_(3)/IF was obtained by adjusting the ratio of Ru/Ni.Benefitting from the Ru/Ni chemical substitution,the as-synthesized RuNi-Fe_(2)O_(3)/IF can act as free-standing dual-function electrodes that are applied to electrocatalysis for the hydrogen evolution(HER)and oxygen evolution reactions(OER)in 1.0 mol L^(-1) KOH,requiring an overpotential of 75.0 mV to drive 100 mA cm^(-2) for HER and 329.0 mV for OER.Moreover,the overall water splitting catalyzed by RuNi-Fe_(2)O_(3)/IF only demands ultralow cell voltages of 1.66 and 1.73 V to drive 100 mA cm^(-2) in 1.0 mol L^(-1) KOH and 1.0 mol L^(-1) KOH seawater electrolytes,respectively.The electrodes show remarkable long-term durability,maintaining current densities exceeding 100 mA cm^(-2) for more than 100 h and thus outperforming the two-electrode system composed of noble catalysts.This work provides an efficient,economical method to synthesize self-standing bifunctional electrodes for large-current-density alkaline seawater electrolysis,which is of significant importance for ecological protection and energy exploitation.
基金support of the Fundamental Research Funds for the Central Universities(Grant No.40120631)National Natural Science Foundation of China(Grant No.52202291)for the support+2 种基金Dr.C.Chen acknowledges the financial support of Natural Science Foundation of Hubei Province(Grant No.2022CFB388)the Natural Science Foundation of Hainan Province of China(Grant No.623MS068)J.Wang thanks Singapore MOE for support of research conducted at the National University of Singapore(Tier 1,A-8000186-01-00).
文摘Within the framework of achieving global carbon neutrality,utilizing electrocatalytic water splitting to produce“green hydrogen”holds significant promise as an effective solution.The strategic development of economic,efficient,and robust anode oxygen evolution reaction(OER)catalysts is one of the imminent bottlenecks for scalable application of electrolyzing water into hydrogen and oxygen,particularly under actual yet harsh operating conditions such as large current density(LCD).In this review,we intend to summarize the advances and challenges in the understanding of the electrocatalytic OER at LCD.Initially,the impact of LCD on the electron transfer,mass transportation efficiency and catalyst stability is identified and summarized.Furthermore,five basic principles for catalyst design,namely the dimension of the materials,surface chemistry,creation of electron transfer pathways,synergy among nano-,micro-,and macroscale structures,and catalyst-support interaction,are systematically discussed.Specifically,the correlation between the synergistic function of the multiscale structures and the catalyst-support interaction is highlighted to direct improvements in catalyst efficiency and durability at the LCD.Finally,an outlook is prospected to further our understanding of these topics and provide related researchers with potential research areas.
基金supported by the Science and Technology Development Fund(FDCT)from Macao SAR(0050/2023/RIB2,0023/2023/AFJ,006/2022/ALC,0111/2022/A2,0105/2023/RIA2)Multi-Year Research Grants(MYRG-GRG2023-00010-IAPME,and MYRG2022-00026-IAPME)from Research&Development Office at University of MacaoShenzhen-Hong Kong-Macao Science and Technology Research Programme(Type C)(SGDX20210823103803017)from Shenzhen.
文摘Large-scale green hydrogen production technology,based on the electrolysis of water powered by renewable energy,relies heavily on non-precious metal oxygen evolution reactions(OER)electrocatalysts with high activity and stability under industrial conditions(6 M KOH,60℃-80℃)at large current density.Here,we construct Fe and Co co-incorporated nickel(oxy)hydroxide(Fe_(2.5)Co_(2.5)Ni_(10)O_(y)H_(z)@NFF)via a multi-metal electrodeposition,which exhibits outstanding OER performance(overpotential:185 mV@10 mA cm^(-2)).Importantly,an overwhelming stability for more than 1100 h at 500 mA cm^(-2)under industrial conditions is achieved.Our combined experimental and computational investigation reveals the surface-reconstructedγ-NiOOH with a high valence state is the active layer,where the optimal(Fe,Co)co-incorporation tunes its electronic structure,changes the potential determining step,and reduces the energy barrier,leading to ultrahigh activity and stability.Our findings demonstrate a facile way to achieve an electrocatalyst with high performance for the industrial production of green hydrogen.
基金supported by the National Natural Science Foundation of China(Grants No.22125903,22439003)National Key R&D Program of China(Grant 2022YFA1504100,2023YFB4005204)Doctoral Research Start-up Fund of Liaoning Province(No.2024-BSBA-36).
文摘Electrochemical water splitting is a pivotal technology in the large-scale production of green hydrogen for sus-tainable future energy provisions.Highly active,stable electrocatalysts have been extensively explored,but the majority suffer from low current densities and small sizes,rendering them unsuitable for industrial applications.Recently,however,the scalable production of electrocatalysts with high performance at large current densities has made tremendous progress.In this review,the current achievements in developing outstanding large elec-trocatalysts for high-current-density water electrolysis are described in detail.First,we introduce the funda-mentals of water electrolysis,the criteria for performance evaluation,and the requirements for producing electrocatalysts at scale under large current densities.Second,we summarize the key approaches for realizing large-sized electrocatalysts with excellent performance,including electrodeposition,corrosion engineering,and thermal treatment,as well as combinations of these methods.Finally,we offer perspectives on research challenges and propose directions for mass-producing high-performance electrocatalysts with large current densities for water electrolysis,to guide the further industrialization of water-electrolysis catalysts.
基金supported by the National Natural Science Foundation of China(21872040,22162004)the Hundred Talents Program of Guangxi Universities,the Excellent Scholars and Innovation Team of Guangxi Universities+1 种基金the Innovation Project of Guangxi Graduate Education(YCBZ2021011)the High-performance Computing Platform of Guangxi University.
文摘Constructing heterojunction is an effective strategy to develop high-performance non-preciousmetal-based catalysts for electrochemical water splitting(WS).Herein,we design and prepare an N-doped-carbon-encapsulated Ni/MoO_(2) nano-needle with three-phase heterojunction(Ni/MoO_(2)@CN)for accelerating the WS under industrial alkaline condition.Density functional theory calculations reveal that the electrons are redistributed at the three-phase heterojunction interface,which optimizes the adsorption energy of H-and O-containing intermediates to obtain the best ΔG_(H*) for hydrogen evolution reaction(HER)and decrease the ΔG value of ratedetermining step for oxygen evolution reaction(OER),thus enhancing the HER/OER catalytic activity.Electrochemical results confirm that Ni/MoO_(2)@CN exhibits good activity for HER(ƞ_(-10)=33 mV,ƞ_(-1000)=267 mV)and OER(ƞ_(10)=250 mV,ƞ_(1000)=420 mV).It shows a low potential of 1.86 V at 1000 mA cm^(−2) for WS in 6.0 M KOH solution at 60℃ and can steadily operate for 330 h.This good HER/OER performance can be attributed to the three-phase heterojunction with high intrinsic activity and the self-supporting nano-needle with more active sites,faster mass diffusion,and bubbles release.This work provides a unique idea for designing high efficiency catalytic materials for WS.
基金supported by the National Natural Science Foundation of China(22162025,22068037)the Youth Innovation Team of Shaanxi Universities+2 种基金the Open and Innovation Fund of Hubei Three Gorges Laboratory(SK232001)the Regional Innovation Capability Leading Program of Shaanxi(2022QFY07-03,2022QFY07-06)the Shaanxi Province Training Program of Innovation and Entrepreneurship for Undergraduates(S202210719108)。
文摘Developing highly stable electrocatalysts under industry-compatible current densities(>500 mA cm^(-2))in an anion-exchange membrane water electrolyzer(AEMWE)is an enormous challenge for water splitting.Herein,based on the results of density function theory calculations,a dual heterogeneous interfacial structured NiSe/Fe-Ni(OH)_(2)catalyst was subtly designed and successfully prepared by electrodepositing Fe-doped Ni(OH)_(2)on NiSe-loaded nickel foam(NF).Fe doping-driven heterogeneous structures in NiSe/Fe-Ni(OH)_(2)markedly boost catalytic activity and durability at industrially compatible current densities in single hydrogen and oxygen evolution reactions under alkaline conditions.In particular,NiSe/Fe-Ni(OH)_(2)shows a negligible performance loss at 600 mA cm^(-2)at least 1,000 h for overall water splitting,a distinguished long-term durability acting as AEMWE electrodes at 600 mA cm^(-2)and 1 A cm^(-2)at 85℃for at least 95 h.Owing to Fe doping-induced strong synergetic effect between Ni and Fe,dual heterostructure-promoted charge transfer and redistribution,abundant catalytic active sites,and improvement of stability and durability,a mechanism of Fe doping-driven heterogeneous interfacial structurepromoted catalytic performance was proposed.This study provides a successful example of theory-directed catalyst preparation and pioneers a creative strategy for industry-compatible water splitting at high current density.
基金financially supported by the National Natural Science Foundation of China(Nos.52174283 and 52274308)。
文摘Cobalt-based phosphides show excellent hydrogen evolution reaction(HER)performance,however,improving the intrinsic activity and stability of it in alkaline electrolyte still remains a challenge.Herein,CoRuOH/Co_(2)P/CF with heterojunction structure was developed by means of molten salt and rapid hydrolysis(30 s).The OH-from rapid surface hydrolysis of Co_(2)P as a hydrogen adsorption site can facilitate the formation of thin CoRuOH layer as a water dissociation site,which may bring out better synergistic effect for alkaline HER.Moreover,the covering of CoRuOH can improve the stability of Co_(2)P for HER.When drives at 100 mA/cm^(2),it only requires overpotential of 81 mV in 1.0 mol/L KOH(25℃).Even at higher current density(1000 mA/cm^(2)),CoRuOH/Co_(2)P/CF can also operate stability for at least 100 h.When coupling with NiFe-LDH/IF in a two-electrode system,the voltage of NiFe-LDH/IF(+)||CoRuOH/Co_(2)P/CF(-)at 1000 mA/cm^(2)is merely 1.77 V with 100 h,demonstrating great potential for water splitting.The implementation of this work provides a new strategy and reference for the further improvement of transition metal phosphides as HER electrocatalysts.
基金supported by the National Natural Science Foundation of China(22162004)the Natural Science Foundation of Guangxi Province(2022JJD120011)the Innovation Project of Guangxi Graduate Education(YCBZ2023012,YCSW2023115,YCBZ2023048).
文摘Li-CO_(2)batteries(LCBs)suffer from high overpotentials caused by sluggish CO_(2)reaction kinetics.This work designs a Te-doped Fe_(3)O_(4)(Te-Fe_(3)O_(4))flower-like microsphere catalyst to lower the overpotential and improve the reversibility of LCBs.Experimental results reveal that Te doping modifies the electronic structure of Fe_(3)O_(4)and reduces the overpotential.The stable Te-O bond between Te and C_(2)O^(2-)_(4)could effectively inhibit the dispro-portionation reaction of the latter,enabling the Te-Fe_(3)O_(4)cathodes to exhibit a remarkable capacity(9485 mAh g^(-1))and a long cycling life(155 cycles)with an overpotential of 1.21 V and an energy efficiency of about 80%at a high current density(2000 mA g^(-1)).Through the interaction between Te and Li_(2)C_(2)O_(4)to inhibit the dispro-portionation reaction,this work successfully achieves long-term cycling of LCBs with low overpotential at high current density.
基金The authors extend their appreciation to the Deanship of Scientific Research at Imam Mohammad Ibn Saud Islamic University(IMSIU)for funding and supporting this work through Research Partnership Program(No.RP-21-09-75).
文摘Deliberate modulation of the electronic structure via interface engineering is one of promising perspectives to build advanced catalysts for urea oxidation reaction(UOR)at high current densities.However,it still remains some challenges originating from the intrinsically sluggish UOR dynamics and the high energy barrier for urea adsorption.In response,we report the coupled NiSe_(2)nanowrinkles with Ni_(5)P_(4)nanorods heterogeneous structure onto Ni foam(denoted as NiSe_(2)@Ni_(5)P_(4)/NF)through successive phosphorization and selenization strategy,in which the produced closely contacted interface could provide high-flux electron transfer pathways.Theoretical findings decipher that the fast charge transfer takes place at the interfacial region from Ni_(5)P_(4)to NiSe_(2),which is conducive to optimizing adsorption energy of urea molecules.As expected,the well-designed NiSe_(2)@Ni_(5)P_(4)/NF only requires the low potential of 1.402 V at the current density of 500 mA·cm^(-2).More importantly,a small Tafel slope of 27.6 mV·dec^(-1),a high turnover frequency(TOF)value of 1.037 s^(-1)as well as the prolonged stability of 950 h at the current density of 100 mA·cm^(-2)are also achieved.This study enriches the understanding on the electronic structure modulation via interface engineering and offers bright prospect to design advanced UOR catalysts.
