Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction.The surface reconstruction has been widely observed in perovskite catalysts,and the reconstruction degree has ...Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction.The surface reconstruction has been widely observed in perovskite catalysts,and the reconstruction degree has been often correlated with the activity enhancement.Here,a systematic study on the roles of Fe substitution in activation of perovskite LaNiO_(3)is reported.The substituting Fe content influences both current change tendency and surface reconstruction degree.LaNi_(0.9)Fe_(0.1)O_(3)is found exhibiting a volcano-peak intrinsic activity in both pristine and reconstructed among all substituted perovskites in the LaNi_(1-x)Fe_(x)O_(3)(x=0.00,0.10,0.25,0.50,0.75,1.00)series.The reconstructed LaNi_(0.9)Fe_(0.1)O_(3)shows a higher intrinsic activity than most reported NiFe-based catalysts.Besides,density functional theory calculations reveal that Fe substitution can lower the O 2p level,which thus stabilize lattice oxygen in LaNi0.9Fe0.1O3 and ensure its long-term stability.Furthermore,it is vital interesting that activity of the reconstructed catalysts relied more on the surface chemistry rather than the reconstruction degree.The effect of Fe on the degree of surface reconstruction of the perovskite is decoupled from that on its activity enhancement after surface reconstruction.This finding showcases the importance to customize the surface chemistry of reconstructed catalysts for water oxidation.展开更多
Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the...Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the leaching of the in‐situ catalyst and promote the reconstruction of dynamic surface for the oxygen evolution reaction(OER).The chlorine doping can reduce the possibility of triggering in‐situ cobalt oxidation and chlorine leaching,leading to a transformation of the surface chlorine doped LaCoO_(3)(Cl‐LaCoO_(3))into an intricate amorphous(oxygen)hydroxide phase.And thus,Cl‐LaCoO_(3)nanocrystals shows an ultralow overpotential of 342 mV at the current density of 10 mA cm^(–2)and Tafel slope of 76.2 mV dec–1.Surface reconstructed Cl‐LaCoO_(3)is better than many of the most advanced OER catalysts and has proven significant stability.This work provides a new prospect for designing a high‐efficiency electrocatalyst with optimized perovskite‐structure in renewable energy system.展开更多
The benefits of perovskite oxides include their low cost,customizable composition,ordered atomic structure,and extremely flexible electronic structure.They are the ideal substitute for precious metal catalysts in vari...The benefits of perovskite oxides include their low cost,customizable composition,ordered atomic structure,and extremely flexible electronic structure.They are the ideal substitute for precious metal catalysts in various electrocatalytic reactions.However,the initial activity of perovskite oxides is often quite limited,which is extremely related to their crystal structure and electronic structure.In this regard,component regulation is the simplest and most effective strategy to increase their stability and catalytic activity.In this review,we briefly outline the recent progress in the modulating component of perovskite oxides to enhance their catalytic properties.The outline was categorized according to the sites in the ABO3-type perovskite structure,including A-site,B-site,and O-site regulation.Finally,potential research directions aimed at modulating of perovskite oxide constituents are discussed.展开更多
The development of e cient earth-abundant electrocatalysts for oxygen reduction, oxygen evolution, and hydrogen evolution reactions(ORR, OER, and HER) is important for future energy conversion and energy storage devic...The development of e cient earth-abundant electrocatalysts for oxygen reduction, oxygen evolution, and hydrogen evolution reactions(ORR, OER, and HER) is important for future energy conversion and energy storage devices, for which both rechargeable Zn–air batteries and water splitting have raised great expectations. Herein, we report a single-phase bimetallic nickel cobalt sulfide((Ni,Co)S_2) as an e cient electrocatalyst for both OER and ORR. Owing to the synergistic combination of Ni and Co, the(Ni,Co)S_2 exhibits superior electrocatalytic performance for ORR, OER, and HER in an alkaline electrolyte, and the first principle calculation results indicate that the reaction of an adsorbed O atom with a H_2O molecule to form a *OOH is the potential limiting step in the OER. Importantly, it could be utilized as an advanced air electrode material in Zn–air batteries, which shows an enhanced charge–discharge performance(charging voltage of 1.71 V and discharge voltage of 1.26 V at 2 mA cm^(-2)), large specific capacity(842 mAh g_(Zn)^(-1) at 5 mA cm^(-2)), and excellent cycling stability(480 h). Interestingly, the(Ni,Co)S_2-based Zn–air battery can e ciently power an electrochemical water-splitting unit with(Ni,Co)S_2 serving as both the electrodes. This reveals that the prepared(Ni,Co)S_2 has promising applications in future energy conversion and energy storage devices.展开更多
The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal‐air battery devices.Herein,an efficient liquid exfoliation strategy was designed for pro...The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal‐air battery devices.Herein,an efficient liquid exfoliation strategy was designed for producing silk‐like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn‐air batteries.Because of the unique silk‐like morphology and interface nanocrystal structure,they can catalyze the oxygen evolution reaction(OER)efficiently with a low overpotential of 233 mV at j=10 mA cm?2.This is an improvement from the recently reported catalysts in 1.0 M KOH.Meanwhile,the oxygen reduction reaction(ORR)activity of the silk‐like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half‐wave potential of 640 mV.In addition,the reversible oxygen electrode activity of the silk‐like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V,based on the potential of the OER and ORR.Further,the homemade rechargeable Zn‐air batteries using FeS2/NiS2 hybrid nanocrystals as the air‐cathode displayed a high open‐circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h.The solid Zn‐air batteries exhibited an excellent rechargeable performance for 15 h.This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.展开更多
Exploring efficient oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)electrocatalysts is crucial for developing water splitting devices.The composition and structure of catalysts are of great importan...Exploring efficient oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)electrocatalysts is crucial for developing water splitting devices.The composition and structure of catalysts are of great importance for catalytic performance.In this work,a heterogeneous Ru modified strategy is engineered to improve the catalytic performance of porous NiCo_(2)O_(4)nanosheets(NSs).Profiting from favorable elements composition and optimized structure property of decreased charge transfer barrier,more accessible active sites and increased oxygen vacancy concentration,the Ru-NiCo_(2)O_(4)NSs exhibits excellent OER activity with a low overpotential of 230 mV to reach the current density of 10 mA/cm^(2)and decent durability.Furthermore,Ru-NiCo_(2)O_(4)NSs show superior HER activity than the pristine NiCo_(2)O_(4)NSs,as well.When assembling Ru-NiCo_(2)O_(4)NSs couple as an alkaline water electrolyzer,a cell voltage of 1.60 V can deliver the current density of 10 mA/cm^(2).This work provides feasible guidance for improving the catalytic performance of spinel-based oxides.展开更多
Achieving high activity and stability oxygen evolution reaction(OER) catalysts to optimize the efficiency of metal-air battery, water splitting and other energy conversion devices, remains a formidable challenge.Herei...Achieving high activity and stability oxygen evolution reaction(OER) catalysts to optimize the efficiency of metal-air battery, water splitting and other energy conversion devices, remains a formidable challenge.Herein, we demonstrate the metallic porous nanowires arrays with abundant defects via nitrogen and copper codoped CoS1.97 nanowires(N-CuCoS1.97 NWs). The N-CuCoS1.97 NWs can serve as an excellent OER self-supported electrode with an overpotential of 280 mV(j = 10 m A cm-2) and remarkable long-term stability. The X-ray absorption near-edge structure(XANES) and X-ray photoelectron spectrum(XPS) measurements confirmed the surface lattice oxygen created on the N-CuCoS1.97 NWs during OER. Then, the density function theory(DFT) results evident that lattice oxygen constructed surface of N-CuCoS1.97 NWs has more favorable OER energetic profiles and absorption for reaction intermediate. More importantly,the flexible and wearable Zn-air battery fabricated by the N-CuCoS1.97 NWs shows excellent rechargeable and mechanical stability, which can be used in portable mobile device.展开更多
Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performan...Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.展开更多
Oxygen evolution reaction(OER)in acid media has been intensively studied recently for its important role in proton exchange membrane electrolyzers.CeO_(2)-based nanomaterials have been widely used in various applicati...Oxygen evolution reaction(OER)in acid media has been intensively studied recently for its important role in proton exchange membrane electrolyzers.CeO_(2)-based nanomaterials have been widely used in various applications for their redox properties,oxygen vacancy,and surface activity.CeO_(2)-based nanocatalysts also exhibit superior catalytic performance in OER in acid media.Herein,we fabricated a highly effi cient catalytic interface between IrO x and CeO_(2)(IrO x/CeO_(2)),which showed a boosting OER activity with an overpotential of 217 mV at the current density of 10 mA/cm 2 and long-term stability for 10 h in 0.5 mol/L H_(2)SO_(4),which were better than those of many reported catalysts.The in situ diff erential electrochemical mass spectrometry results demonstrated that IrO x/CeO_(2)and the commercial IrO 2(IrO 2-com)followed the adsorbate evolution mechanism,whereas the pure CeO_(2)surface followed the lattice oxygen oxidation mechanism under the same conditions for OER.These indicated that the interface of IrO x and CeO_(2)improved mass transfer effi ciency and reactivity,which also prevented the lattice oxygen evolution in the CeO_(2)structure and protected the whole structure.This work fi nds a new way for OER in acid media catalyzed by CeO_(2)-based nanocatalysts and promotes the design strategy for other CeO_(2)-based nanostructures.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR)has received great attention in the past few decades as a promising process for reducing CO_(2) emissions and producing high-value chemicals.However,the rational desi...Electrochemical CO_(2) reduction reaction(CO_(2)RR)has received great attention in the past few decades as a promising process for reducing CO_(2) emissions and producing high-value chemicals.However,the rational design of catalysts for CO_(2)RR continues to represent a significant challenge;hence,it is essential to understand the structure-property relationship and how catalysts facilitate CO_(2) conversion.Herein,the tetrahedral site occupancy and octahedral site occupancy of spinel CuAl_(2)O_(4) were modulated by constructing CuAl_(2)O_(4)/CeO_(2) heterointerface,and the effect on CO_(2)RR performance was further investigated.In this work,we demonstrated that the octahedral site occupancy increases after constructing CuAl_(2)O_(4)/CeO_(2) heterointerface,leading to a significant improvement in the catalyst’s ability to absorb and activate CO_(2) and enhance *CO coverage.Meanwhile,the unique oxyphilic property of CeO_(2) enhances OH coverage and maintains the local pH on the catalyst surface.Ultimately,CuAl_(2)O_(4)/CeO_(2) achieved 70.4%multi-carbon(C_(2+))products Faraday efficiency(FE)in the flow cell and operated stably for over 35 h at a current density of 200 mA·cm^(−2) under 1 M KOH.CuAl_(2)O_(4)/CeO_(2) exhibits completely different CO_(2)RR performance compared to pure CuAl_(2)O_(4),providing new insights into accurate regulation of spinel structure.展开更多
The electronic and crystal structures of catalysts are crucial for designing novel oxygen reduction reactions(ORR)catalysts.In recent years,heterojunction catalysts have occupied a very important position in emerging ...The electronic and crystal structures of catalysts are crucial for designing novel oxygen reduction reactions(ORR)catalysts.In recent years,heterojunction catalysts have occupied a very important position in emerging catalysts.In heterojunction catalysts,the generation of lattice strain at the heterophase boundary can affect the catalytic properties.In this article,we regulate the strain effects by modulating the proportion of LaMnO_(3)and Mn_(3)O_(4),and it was revealed that there is a facilitating relationship between the 4e-ORR process and tensile strain,while compressive strain plays the opposite role.This is attributed to the stretched bond length reducing the covalency of the Mn-O bond,promoting the consumption of OOH^(*)intermediates and enhancing the reversible stability of the structure.In situ attenuated total reflection infrared(ATR-IR)measurements were applied to investigate the mechanism for the consumption of intermediate,confirming the strain effects of heterojunction is a key factor in influencing the catalytic performance.展开更多
With the rapid consumption of fossil fuels and the resulting environmental problems,researchers are working to find sustainable alternative energy and energy storage and conversion methods.Transition metal sulfur comp...With the rapid consumption of fossil fuels and the resulting environmental problems,researchers are working to find sustainable alternative energy and energy storage and conversion methods.Transition metal sulfur compounds have attracted extensive attention due to their excellent electrical conductivity,low cost,adjustable components and good electrocatalytic performance.As an alternative to noble metal catalysts,they have emerged as a promising electrocatalyst.However,their low catalytic activity and poor stability limit their large-scale practical applications.Rare earth elements,known as industrial vitamins,are widely used in various fields due to their special redox properties,oxygen affinity and electronic structure.Therefore,the construction of rare earth promoted transition metal sulfides is of far-reaching significance for the development of catalysts.Here,we review the applications of various rare earth promoted transition metal sulfides in energy storage and conversion in recent years,which focuses on three ways in rare earth promoted transition metal sulfide,including doping,interfacial modification engineering and structural facilitation.As well,these materials are used in electrochemical reactions such as OER,HER,ORR,CO_(2)RR,and so on,in order to explore the important role of rare earth in the field of electrocatalysis,the future challenges and opportunities.展开更多
Herein,we prepared a bimetallic layered double hydroxide(FeCo LDH)featuring a dandelion-like structure.Anchoring of CeO_(2)onto FeCo LDH produced interfaces between the functionalizing CeO_(2)and the parent LDH.Compar...Herein,we prepared a bimetallic layered double hydroxide(FeCo LDH)featuring a dandelion-like structure.Anchoring of CeO_(2)onto FeCo LDH produced interfaces between the functionalizing CeO_(2)and the parent LDH.Comparative electrochemical studies were carried out.Onset potential,overpotential,and Tafel slope point to the superior oxygen-evolving performance of CeO_(2)-FeCo LDH with respect to FeCo LDH,therefore,demonstrating the merits of CeO_(2)functionalization.The electronic structures of Fe,Co,and Ce were analyzed by X-ray photoelectron spectroscopy(XPS)and electron energy loss spectroscopy(EELS)from which the increase of Co^(3+)and the concurrent lowering of Ce^(4+)were established.With the use of CeO_(2)-FeCo LDH,accelerated formation at a sizably reduced potential of Co-OOH,one of the key intermediates preceding the release of O_(2)was observed by in situ Raman spectroscopy.We now have the atomic-level and location-specific evidence,the increase of the active Co^(3+)across the interface to correlate the enhanced catalytic performance with CeO_(2)functionalization.展开更多
Interfacial nanostructured materials have stimulated extensive interests in the research areas of green energy production and conversion due to their unique structures and performance.These interfacial crystalline str...Interfacial nanostructured materials have stimulated extensive interests in the research areas of green energy production and conversion due to their unique structures and performance.These interfacial crystalline structures with rich intrinsic defects,such as oxygen vacancies,adatoms,grain bounda-ries,and substitutional impurities,have led to unique activities in a variety of catalytic reactions.The rational design and engineering development of the interfaces provide an attractive way to optimize the catalytic performance and finally improve the efficiency of energy conversion and storage.Herein,a comprehensive overview of interfacial inorganic nanostructures and their electrocatalytic applications are summarized,and some future challenge and opportunity have also been proposed.展开更多
基金funded by the National Key R&D Program of China(2021YFA1501101)the National Natural Science Foundation of China(No.22471103,22425105,22201111,21931001,22221001,and 22271124)+5 种基金Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)the Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province(2019ZX-04)the 111 Project(B20027)as well as the National Natural Science Foundation of Gansu Province(22JR5RA470)the Fundamental Research Funds for the Central Universities(lzujbky-2023-eyt03)supported by the Agency for Science,Technology and Research(A*STAR)MTC Individual Research Grants(IRG)M22K2c0078.
文摘Water splitting hinges crucially on the availability of electrocatalysts for the oxygen evolution reaction.The surface reconstruction has been widely observed in perovskite catalysts,and the reconstruction degree has been often correlated with the activity enhancement.Here,a systematic study on the roles of Fe substitution in activation of perovskite LaNiO_(3)is reported.The substituting Fe content influences both current change tendency and surface reconstruction degree.LaNi_(0.9)Fe_(0.1)O_(3)is found exhibiting a volcano-peak intrinsic activity in both pristine and reconstructed among all substituted perovskites in the LaNi_(1-x)Fe_(x)O_(3)(x=0.00,0.10,0.25,0.50,0.75,1.00)series.The reconstructed LaNi_(0.9)Fe_(0.1)O_(3)shows a higher intrinsic activity than most reported NiFe-based catalysts.Besides,density functional theory calculations reveal that Fe substitution can lower the O 2p level,which thus stabilize lattice oxygen in LaNi0.9Fe0.1O3 and ensure its long-term stability.Furthermore,it is vital interesting that activity of the reconstructed catalysts relied more on the surface chemistry rather than the reconstruction degree.The effect of Fe on the degree of surface reconstruction of the perovskite is decoupled from that on its activity enhancement after surface reconstruction.This finding showcases the importance to customize the surface chemistry of reconstructed catalysts for water oxidation.
文摘Rationally manipulating the in‐situ formed catalytically active surface of catalysts remains a great challenge for a highly efficient water electrolysis.Here,we report a cationic oxidation method which can adjust the leaching of the in‐situ catalyst and promote the reconstruction of dynamic surface for the oxygen evolution reaction(OER).The chlorine doping can reduce the possibility of triggering in‐situ cobalt oxidation and chlorine leaching,leading to a transformation of the surface chlorine doped LaCoO_(3)(Cl‐LaCoO_(3))into an intricate amorphous(oxygen)hydroxide phase.And thus,Cl‐LaCoO_(3)nanocrystals shows an ultralow overpotential of 342 mV at the current density of 10 mA cm^(–2)and Tafel slope of 76.2 mV dec–1.Surface reconstructed Cl‐LaCoO_(3)is better than many of the most advanced OER catalysts and has proven significant stability.This work provides a new prospect for designing a high‐efficiency electrocatalyst with optimized perovskite‐structure in renewable energy system.
基金acknowledge support from the National Natural Science Foundation of China(Nos.21922105,21931001,22201111,and 22271124)the National Key R&D Program of China(2021YFA1501101)+4 种基金the National Natural Science Foundation of Gansu Province(22JR5RA470)the Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province(2019ZX-04)the 111 Project(B20027).We also acknowledge support from the Fundamental Research Funds for the Central Universities(lzujbky-2021-sp62)the support of the Natural Science Foundation of China(NSFC)(No.21771156)the Early Career Scheme(ECS)fund(Grant PolyU253026/16P)from the Research Grant Council(RGC)in Hong Kong.
文摘The benefits of perovskite oxides include their low cost,customizable composition,ordered atomic structure,and extremely flexible electronic structure.They are the ideal substitute for precious metal catalysts in various electrocatalytic reactions.However,the initial activity of perovskite oxides is often quite limited,which is extremely related to their crystal structure and electronic structure.In this regard,component regulation is the simplest and most effective strategy to increase their stability and catalytic activity.In this review,we briefly outline the recent progress in the modulating component of perovskite oxides to enhance their catalytic properties.The outline was categorized according to the sites in the ABO3-type perovskite structure,including A-site,B-site,and O-site regulation.Finally,potential research directions aimed at modulating of perovskite oxide constituents are discussed.
基金supported by the National Natural Science Foundation of China (Grant Nos. 11474137 and 11674143)Program for Changjiang Scholars and Innovative Research Team in University (IRT 16R35)+1 种基金the Fundamental Research Funds for the Central Universities (Grant Nos. LZUMMM2018017, lzujbky-2018-121)the support of Ministry of Education (MOE2016-T2-2-138,Singapore),for research conducted at the National University of Singapore
文摘The development of e cient earth-abundant electrocatalysts for oxygen reduction, oxygen evolution, and hydrogen evolution reactions(ORR, OER, and HER) is important for future energy conversion and energy storage devices, for which both rechargeable Zn–air batteries and water splitting have raised great expectations. Herein, we report a single-phase bimetallic nickel cobalt sulfide((Ni,Co)S_2) as an e cient electrocatalyst for both OER and ORR. Owing to the synergistic combination of Ni and Co, the(Ni,Co)S_2 exhibits superior electrocatalytic performance for ORR, OER, and HER in an alkaline electrolyte, and the first principle calculation results indicate that the reaction of an adsorbed O atom with a H_2O molecule to form a *OOH is the potential limiting step in the OER. Importantly, it could be utilized as an advanced air electrode material in Zn–air batteries, which shows an enhanced charge–discharge performance(charging voltage of 1.71 V and discharge voltage of 1.26 V at 2 mA cm^(-2)), large specific capacity(842 mAh g_(Zn)^(-1) at 5 mA cm^(-2)), and excellent cycling stability(480 h). Interestingly, the(Ni,Co)S_2-based Zn–air battery can e ciently power an electrochemical water-splitting unit with(Ni,Co)S_2 serving as both the electrodes. This reveals that the prepared(Ni,Co)S_2 has promising applications in future energy conversion and energy storage devices.
基金supported by the National Basic Research Program of China(21571089,21503102,51571125)the Fundamental Research Funds for the Central Universities(lzujbky-2016-k02,lzujbky-2018-k08,lzujbky-2017-it42)~~
文摘The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal‐air battery devices.Herein,an efficient liquid exfoliation strategy was designed for producing silk‐like FeS2/NiS2 hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn‐air batteries.Because of the unique silk‐like morphology and interface nanocrystal structure,they can catalyze the oxygen evolution reaction(OER)efficiently with a low overpotential of 233 mV at j=10 mA cm?2.This is an improvement from the recently reported catalysts in 1.0 M KOH.Meanwhile,the oxygen reduction reaction(ORR)activity of the silk‐like FeS2/NiS2 hybrid nanocrystals showed an onset potential of 911 mV and a half‐wave potential of 640 mV.In addition,the reversible oxygen electrode activity of the silk‐like FeS2/NiS2 hybrid nanocrystals was calculated to be 0.823 V,based on the potential of the OER and ORR.Further,the homemade rechargeable Zn‐air batteries using FeS2/NiS2 hybrid nanocrystals as the air‐cathode displayed a high open‐circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h.The solid Zn‐air batteries exhibited an excellent rechargeable performance for 15 h.This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.
基金support from the National Natural Science Foundation of China(Nos.21922105 and 21931001)the National Key R&D Program of China(2021YFA1501101)+4 种基金the Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province(No.2019ZX-04)the 111 Project(No.B20027)support by the Fundamental Research Funds for the Central Universities(Nos.lzujbky-2021-pd04,lzujbky-2021-sp41,lzujbky-2021-it12 and lzujbky-2021-37)support of the China Postdoctoral Science Foundation(No.2021M691375)the China National Postdoctoral Program for Innovative Talents(No.BX20200157)。
文摘Exploring efficient oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)electrocatalysts is crucial for developing water splitting devices.The composition and structure of catalysts are of great importance for catalytic performance.In this work,a heterogeneous Ru modified strategy is engineered to improve the catalytic performance of porous NiCo_(2)O_(4)nanosheets(NSs).Profiting from favorable elements composition and optimized structure property of decreased charge transfer barrier,more accessible active sites and increased oxygen vacancy concentration,the Ru-NiCo_(2)O_(4)NSs exhibits excellent OER activity with a low overpotential of 230 mV to reach the current density of 10 mA/cm^(2)and decent durability.Furthermore,Ru-NiCo_(2)O_(4)NSs show superior HER activity than the pristine NiCo_(2)O_(4)NSs,as well.When assembling Ru-NiCo_(2)O_(4)NSs couple as an alkaline water electrolyzer,a cell voltage of 1.60 V can deliver the current density of 10 mA/cm^(2).This work provides feasible guidance for improving the catalytic performance of spinel-based oxides.
基金support from the NSFC (Nos. 21571089, 21503102, 51571125)the Fundamental Research Funds for the Central Universities (lzujbky-2016-k02, lzujbky-2018-k08 and lzujbky-2017-it42)+1 种基金Shanghai Pujiang Program (15PJ1400500)Shanghai “Chen Guang” project (14CG02)
文摘Achieving high activity and stability oxygen evolution reaction(OER) catalysts to optimize the efficiency of metal-air battery, water splitting and other energy conversion devices, remains a formidable challenge.Herein, we demonstrate the metallic porous nanowires arrays with abundant defects via nitrogen and copper codoped CoS1.97 nanowires(N-CuCoS1.97 NWs). The N-CuCoS1.97 NWs can serve as an excellent OER self-supported electrode with an overpotential of 280 mV(j = 10 m A cm-2) and remarkable long-term stability. The X-ray absorption near-edge structure(XANES) and X-ray photoelectron spectrum(XPS) measurements confirmed the surface lattice oxygen created on the N-CuCoS1.97 NWs during OER. Then, the density function theory(DFT) results evident that lattice oxygen constructed surface of N-CuCoS1.97 NWs has more favorable OER energetic profiles and absorption for reaction intermediate. More importantly,the flexible and wearable Zn-air battery fabricated by the N-CuCoS1.97 NWs shows excellent rechargeable and mechanical stability, which can be used in portable mobile device.
基金funded by the National Natural Science Foundation of China (NSFC) (Nos. 22221001, 22201115, 21931001, and 21922105)the Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province (2019ZX–04)+3 种基金the 111 Project (B20027)by the Fundamental Research Funds for the Central Universities (lzujbky-2023-eyt03)support Natural Science Foundation of Gansu Providence (22JR5RA540)Gansu Province Youth Science and Technology Talent Promotion Project (GXH202220530-02)。
文摘Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.
基金funded by the National Key R&D Program of China(2021YFA1501101)the National Natural Science Foundation of China(NSFC)(Nos.21931001 and 21922105)+5 种基金the Special Fund Project of Guiding Scientifi c and Technological Inno-vation Development of Gansu Province(No.2019ZX-04)the 111 Project(B20027)“Innovation Star”of Outstanding Graduate Students in Gansu Province(No.2023CXZX-083)as well as by the Fundamental Research Funds for the Central Universities(Nos.lzu-jbky-2021-pd04,lzujbky-2021-sp41,and lzujbky-2021-it12)Jie Yin acknowledges the support of the China Postdoctoral Science Founda-tion(No.2021M691375)the China National Postdoctoral Program for Innovative Talents(No.BX20200157).
文摘Oxygen evolution reaction(OER)in acid media has been intensively studied recently for its important role in proton exchange membrane electrolyzers.CeO_(2)-based nanomaterials have been widely used in various applications for their redox properties,oxygen vacancy,and surface activity.CeO_(2)-based nanocatalysts also exhibit superior catalytic performance in OER in acid media.Herein,we fabricated a highly effi cient catalytic interface between IrO x and CeO_(2)(IrO x/CeO_(2)),which showed a boosting OER activity with an overpotential of 217 mV at the current density of 10 mA/cm 2 and long-term stability for 10 h in 0.5 mol/L H_(2)SO_(4),which were better than those of many reported catalysts.The in situ diff erential electrochemical mass spectrometry results demonstrated that IrO x/CeO_(2)and the commercial IrO 2(IrO 2-com)followed the adsorbate evolution mechanism,whereas the pure CeO_(2)surface followed the lattice oxygen oxidation mechanism under the same conditions for OER.These indicated that the interface of IrO x and CeO_(2)improved mass transfer effi ciency and reactivity,which also prevented the lattice oxygen evolution in the CeO_(2)structure and protected the whole structure.This work fi nds a new way for OER in acid media catalyzed by CeO_(2)-based nanocatalysts and promotes the design strategy for other CeO_(2)-based nanostructures.
基金funded by the National Key R&D Program of China(No.2021YFA1501101)the National Natural Science Foundation of China(Nos.22425105,22221001,22271124,22471103,22201111,and 22401120)+5 种基金the 111 Project(No.B20027)the Young Elite Scientists Sponsorship Program by Chinese Association for Science and Technology(CAST,No.2023QNRC001).support from the Science and Technology Major Plan of Gansu Province(Nos.24ZD13GA015,23ZDGA012,and 23ZDKA014)the Natural Science Foundation key project of Gansu Province(No.24JRRA394)the National Natural Science Foundation of Gansu Province(No.23JRRA1135)the Fundamental Research Funds for the Central Universities(No.lzujbky-2023-pd06)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR)has received great attention in the past few decades as a promising process for reducing CO_(2) emissions and producing high-value chemicals.However,the rational design of catalysts for CO_(2)RR continues to represent a significant challenge;hence,it is essential to understand the structure-property relationship and how catalysts facilitate CO_(2) conversion.Herein,the tetrahedral site occupancy and octahedral site occupancy of spinel CuAl_(2)O_(4) were modulated by constructing CuAl_(2)O_(4)/CeO_(2) heterointerface,and the effect on CO_(2)RR performance was further investigated.In this work,we demonstrated that the octahedral site occupancy increases after constructing CuAl_(2)O_(4)/CeO_(2) heterointerface,leading to a significant improvement in the catalyst’s ability to absorb and activate CO_(2) and enhance *CO coverage.Meanwhile,the unique oxyphilic property of CeO_(2) enhances OH coverage and maintains the local pH on the catalyst surface.Ultimately,CuAl_(2)O_(4)/CeO_(2) achieved 70.4%multi-carbon(C_(2+))products Faraday efficiency(FE)in the flow cell and operated stably for over 35 h at a current density of 200 mA·cm^(−2) under 1 M KOH.CuAl_(2)O_(4)/CeO_(2) exhibits completely different CO_(2)RR performance compared to pure CuAl_(2)O_(4),providing new insights into accurate regulation of spinel structure.
基金supported by the National Key R&D Program of China(2021YFA1501101)the National Natural Science Foundation of China(22425105,22221001,22271124,22471103,22201111)+3 种基金the 111 Project(B20027)the Young Elite Scientists Sponsorship Program by China Association for Science and Technology(CAST)(2023QNRC001)support from the Science and Technology Major Plan of Gansu Province(24ZD13GA015,23ZDGA012,23ZDKA014)the Natural Science Foundation Key Project of Gansu Province(24JRRA394)。
文摘The electronic and crystal structures of catalysts are crucial for designing novel oxygen reduction reactions(ORR)catalysts.In recent years,heterojunction catalysts have occupied a very important position in emerging catalysts.In heterojunction catalysts,the generation of lattice strain at the heterophase boundary can affect the catalytic properties.In this article,we regulate the strain effects by modulating the proportion of LaMnO_(3)and Mn_(3)O_(4),and it was revealed that there is a facilitating relationship between the 4e-ORR process and tensile strain,while compressive strain plays the opposite role.This is attributed to the stretched bond length reducing the covalency of the Mn-O bond,promoting the consumption of OOH^(*)intermediates and enhancing the reversible stability of the structure.In situ attenuated total reflection infrared(ATR-IR)measurements were applied to investigate the mechanism for the consumption of intermediate,confirming the strain effects of heterojunction is a key factor in influencing the catalytic performance.
基金support from the National Natural Science Foundation of China(Nos.21922105,21931001 and 22271124)the National Key R&D Program of China(2021YFA1501101)+2 种基金Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province(2019zX-04)the 111 Project(B20027)support by the Fundamental Research Funds for the Central Universities(lzujbky-2021-pd04,Izujbky-2021-it12 and Izujbky-2021-37).
文摘With the rapid consumption of fossil fuels and the resulting environmental problems,researchers are working to find sustainable alternative energy and energy storage and conversion methods.Transition metal sulfur compounds have attracted extensive attention due to their excellent electrical conductivity,low cost,adjustable components and good electrocatalytic performance.As an alternative to noble metal catalysts,they have emerged as a promising electrocatalyst.However,their low catalytic activity and poor stability limit their large-scale practical applications.Rare earth elements,known as industrial vitamins,are widely used in various fields due to their special redox properties,oxygen affinity and electronic structure.Therefore,the construction of rare earth promoted transition metal sulfides is of far-reaching significance for the development of catalysts.Here,we review the applications of various rare earth promoted transition metal sulfides in energy storage and conversion in recent years,which focuses on three ways in rare earth promoted transition metal sulfide,including doping,interfacial modification engineering and structural facilitation.As well,these materials are used in electrochemical reactions such as OER,HER,ORR,CO_(2)RR,and so on,in order to explore the important role of rare earth in the field of electrocatalysis,the future challenges and opportunities.
基金This work was financially supported by Shenzhen Nobel Prize Scientists Laboratory Project(No.C17213101)Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)+6 种基金Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(No.2018B030322001)China Postdoctoral Science Foundation(No.2018M642133,X.Y.Z.)Post-doctorate Scientific Research Fund for staying(coming to)Shenzhen(No.K21217502,X.Y.Z.)the National Natural Science Foundation of China(No.21671096,Z.G.L.)Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials(No.ZDSYS20200421111401738,Z.G.L.)The authors also acknowledge the assistance of Southern University of Science and Technology Core Research Facilities(SUSTech CRF)Key Laboratory of Energy Conversion and Storage Technologies(Southern University of Science and Technology).
文摘Herein,we prepared a bimetallic layered double hydroxide(FeCo LDH)featuring a dandelion-like structure.Anchoring of CeO_(2)onto FeCo LDH produced interfaces between the functionalizing CeO_(2)and the parent LDH.Comparative electrochemical studies were carried out.Onset potential,overpotential,and Tafel slope point to the superior oxygen-evolving performance of CeO_(2)-FeCo LDH with respect to FeCo LDH,therefore,demonstrating the merits of CeO_(2)functionalization.The electronic structures of Fe,Co,and Ce were analyzed by X-ray photoelectron spectroscopy(XPS)and electron energy loss spectroscopy(EELS)from which the increase of Co^(3+)and the concurrent lowering of Ce^(4+)were established.With the use of CeO_(2)-FeCo LDH,accelerated formation at a sizably reduced potential of Co-OOH,one of the key intermediates preceding the release of O_(2)was observed by in situ Raman spectroscopy.We now have the atomic-level and location-specific evidence,the increase of the active Co^(3+)across the interface to correlate the enhanced catalytic performance with CeO_(2)functionalization.
基金This work is supported by the National Natural Science Foundation of China （Nos. 11474137 and 11674143）, and Program for Changjiang Scholars and Innovative Research Team in University （IRT 16R35）. J. W. thanks for the support of MOE （MOE2016-T2-2-138） for research conducted at the National University of Singapore.
基金the National Natural Science Foundation of China(NSFC)(Nos.21931001,21922105,21571089)the Fundamental Research Funds for the Central Uni-versities(lzujbky-2018-k08,lzujbky-2019-it10,lzujbky-2018-it40 and Izujbky-2017-it42)+1 种基金Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province(2019ZX-04)As alumni of Lanzhou University,all authors wish to dedicate this work to Lanzhou University on the occasion of its 110th anniversary.
文摘Interfacial nanostructured materials have stimulated extensive interests in the research areas of green energy production and conversion due to their unique structures and performance.These interfacial crystalline structures with rich intrinsic defects,such as oxygen vacancies,adatoms,grain bounda-ries,and substitutional impurities,have led to unique activities in a variety of catalytic reactions.The rational design and engineering development of the interfaces provide an attractive way to optimize the catalytic performance and finally improve the efficiency of energy conversion and storage.Herein,a comprehensive overview of interfacial inorganic nanostructures and their electrocatalytic applications are summarized,and some future challenge and opportunity have also been proposed.
