High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-poly...High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.展开更多
Rational design of complex hollow nanostructures offers a great opportunity to construct various functional nanostructures.A novel in situ disassembly-polymerization-pyrolysis approach was developed to synthesize atom...Rational design of complex hollow nanostructures offers a great opportunity to construct various functional nanostructures.A novel in situ disassembly-polymerization-pyrolysis approach was developed to synthesize atomically dispersed Fe single atoms(Fe SAs)and tiny Co nanoparticles(Co NPs)binary sites embedded in double-shelled hollow carbon nanocages(Co NPs/Fe SAs DSCNs)without removing excess templates.The Co NPs/Fe SAs DSCNs displayed excellent bifunctional activity,boosting the realistic rechargeable zinc-air batteries with high efficiency,long-term durability,and reversibility,which is comparable to noble metal catalysts(Pt/C and RuO_(2)).The enhanced catalytic activity should be attributed to as well as the strong interactions between Fe SAs and Co NPs with the nitrogen-doped carbon matrix,the exposure of more active sites,and the high-flux mass transportation.In addition,the confinement effect between the double C–N shells prevented the aggregation and corrosion of metal atoms,thus improving the durability of the Co NPs/Fe SAs DSCNs,further highlighting the structural advantages of carbon nanoreactor.This work provides guidance for further rational design and preparation of complex hollow structure materials with advanced bifunctional air cathodes.展开更多
Designing rational transition-metal/carbon composites with highly dispersed and firmly anchored nanoparticles(NPs)to prevent agglomeration and shedding is crucial for realizing excellent electrocatalytic performances....Designing rational transition-metal/carbon composites with highly dispersed and firmly anchored nanoparticles(NPs)to prevent agglomeration and shedding is crucial for realizing excellent electrocatalytic performances.Herein,a biomass pore-confined strategy based on mesoporous willow catkin is explored to obtain uniformly dispersed CoFe NPs in N-doped carbon nanotubes and hollow carbon fibers(CoFe@N-CNTs/HCFs).The resultant catalyst exhibits enhanced electrocatalytic performance,which affords a half-wave potential of 0.86 V(vs.RHE)with a limited current density of 6.0 mA·cm^(-2)for oxygen reduction reaction and potential of 1.67 V(vs.RHE)at 10 mA·cm^(-2)in 0.1 M KOH for oxygen evolution reaction.When applied to rechargeable zinc-air batteries,a maximum power density of 340 mW·cm^(-2)and long-term cyclic durability over 800 h are achieved.Such superior bifunctional electrocatalytic activities are ascribed to the biocarbon matrix with abundant mesopores and unobstructed hollow channels,CoFe NPs with high dispersion and controllable nanoscale and the hybrid composite with optimized electronic structure.This work presents an effective approach for constraining the size and dispersion of NPs in a low-cost biocarbon substrate,offering valuable insights for designing advanced oxygen electrocatalysts.展开更多
Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bif...Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs.Atomically dispersed metal-nitrogen-carbon(M-N-C)catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis.In this work,general principles for designing atomically dispersed M-N-C are reviewed.Then,strategies aiming at enhancing the bifunctional catalytic activity and stability are presented.Finally,the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined.It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.展开更多
Efficient bifunctional oxygen electrocatalysts for ORR and OER are fundamental to the development of high performance metal-air batteries.Herein,a facile cost-efficient two-step pyrolysis strategy for the fabrication ...Efficient bifunctional oxygen electrocatalysts for ORR and OER are fundamental to the development of high performance metal-air batteries.Herein,a facile cost-efficient two-step pyrolysis strategy for the fabrication of a bifunctional oxygen electrocatalyst has been proposed.The efficient non-preciousmetal-based electrocatalyst,Fe/Fe_(3)C@Fe-N_(x)-C consists of highly curved onion-like carbon shells that encapsulate Fe/Fe_(3)C nanoparticles,distributed on an extensively porous graphitic carbon aerogel.The obtained Fe/Fe_(3)C@Fe-N_(x)-C aerogel exhibited superb electrochemical activity,excellent durability,and high methanol tolerance.The experimental results indicated that the assembly of onion-like carbon shells with encapsulated Fe/Fe_(3)C yielded highly curved carbon surfaces with abundant Fe-Nxactive sites,a porous structure,and enhanced electrocatalytic activity towards ORR and OER,hence displaying promising potential for application as an air cathode in rechargeable Zn-air batteries.The constructed Zn-air battery possessed an exceptional peak power density of~147 mW cm^(-2),outstanding cycling stability(200 cycles,1 h per cycle),and a small voltage gap of 0.87 V.This study offers valuable insights regarding the construction of low-cost and highly active bifunctional oxygen electrocatalysts for efficient air batteries.展开更多
An effective strategy of regulating active sites in bifunctional oxygen electrocatalysts is essentially desired,especially in rechargeable metal-air batteries(RZABs).Herein,a highly efficient electrocatalyst of CoFe a...An effective strategy of regulating active sites in bifunctional oxygen electrocatalysts is essentially desired,especially in rechargeable metal-air batteries(RZABs).Herein,a highly efficient electrocatalyst of CoFe alloys embedded in pyridinic nitrogen enriched N-doped carbon(CoFe/P-NC)is intelligently constructed by pyrolysis strategy.The high concentration of pyridinic nitrogen in CoFe/P-NC can significantly reprogram the redistribution of electron density of metal active sites,consequently optimizing the oxygen adsorption behavior.As expected,the pyridinic nitrogen guarantees CoFe/P-NC providing the low overpotential of the overall oxygen electrocatalytic process(ΔEORR-OER=0.73 V vs.RHE)and suppresses the benchmark electrocatalysts(Pt/C&RuO_(2)).Assembled rechargeable Zn-air battery using CoFe/P-NC demonstrates a promising peak power density of 172.0 mW cm^(-2),a high specific capacity of 805.0 mAh g^(-1)Zn and an excellent stability.This work proposes an interesting strategy for the design of robust oxygen electrocatalysts for energy conversion and storage fields.展开更多
Electrocatalysts for oxygen reduction reactions(ORR)and oxygen evolution reactions(OER)are highly crucial and challenging toward the energy storage and conversion technologies such as fuel cells,metal-air batteries an...Electrocatalysts for oxygen reduction reactions(ORR)and oxygen evolution reactions(OER)are highly crucial and challenging toward the energy storage and conversion technologies such as fuel cells,metal-air batteries and water electrolysis.To replace noble-metal based catalysts and boost catalytic performance of carbon-based materials,we initially develop the nickel,phospho rus,sulfur and nitrogen co-modified mesoporous carbon(NiPS_(3)@NMC)as a bifunctional oxygen electrocatalyst.The perfo rmance for ORR(half-wave potential at 0.90 V)and OER(10 mA cm^(-2)at 1.48 V)surpasses those of Pt/C coupled with IrO_(2)catalysts and most of the non-precious metal based bifunctional electrocatalysts reported in related literature.Moreover,the electrochemical durability is also confirmed by accelerated durability tests(ADTs)and long-term chronoamperometry(CA)tests.We demonstrated that the interfacial effect between NiPS_(3)quantum sheets(QS s)and NMC substrates by thermal activation contributed to the enhanced oxygen electrode bifunctionality with more active sites,due to the electrons-donating from nickel,phosphorus and sulfur elements and relatively enriched pyridinic type N.Such excellent overall performance highlights the potential application of NiPS3 QSs and NMC composites as the materials on energy conversion and storage.展开更多
Fe-nitrogen-carbon(Fe-N-C)-and Co-nitrogen-carbon(Co-N-C)-based electrocatalysts have been widely concerned because of their high OER/ORR activity,low metal cost,and simple preparation.The exploration of Fe-N-C and Co...Fe-nitrogen-carbon(Fe-N-C)-and Co-nitrogen-carbon(Co-N-C)-based electrocatalysts have been widely concerned because of their high OER/ORR activity,low metal cost,and simple preparation.The exploration of Fe-N-C and Co-N-C single atombased catalysts with high activity and stability to overcome the slow kinetics of oxygen reduction and oxygen evolution reactions is also the key to the development of efficient electrolytic water,fuel cells,and rechargeable metal-air batteries.Fe-N-C and Co-N-C single atom-based electrocatalysts have the advantages of a high utilization rate of metal atoms and high electrocatalytic activity,and are ideal catalysts for promoting electrochemical energy conversion and storage.The general principles of designing Fe-N-C and Co-N-C single atom-based electrocatalysts are reviewed in this paper.Then,the strategies to improve the bifunctional catalytic activity and stability are proposed.Finally,the challenges and prospects of Fe-N-C and Co-N-C single atom-based catalysts are well summarized.This review will provide a reference for the directed optimization of Fe-N-C and Co-N-C single atom-based catalysts.展开更多
The rational control of the active site of metal-organic frameworks(MOFs)derived nanomaterials is essential to build efficient bifunctional oxygen reduction/evolution reaction(ORR/OER)catalysts.Accordingly,through des...The rational control of the active site of metal-organic frameworks(MOFs)derived nanomaterials is essential to build efficient bifunctional oxygen reduction/evolution reaction(ORR/OER)catalysts.Accordingly,through designing and constructing a Co_(3)O_(4)-Co heterostructure embedded in Co,N co-doped carbon polyhedra derived(Co_(3)O_(4)-Co@NC)from the in-situ compositions of ZIF-67 and cobalt nanocrystals synthesized by the strategy of in-situ NaBH4 reduction,the dual-active site(Co_(3)O_(4)-Co and Co-N_(x))is synchronously realized in a MOFs derived nanomaterials.The formed Co_(3)O_(4)-Co@NC shows excellent bifunctional electrocatalytic activity with ultra-small potential gap(ΔE=E_(j=10)(OER)–E_(1/2)(ORR))of 0.72 V,which surpasses the commercial Pt/C and RuO_(2) catalysts.The theory calculation results reveal that the excellent bifunctional electrocatalytic activity can be attributed to the charge redistribution of Co of Co-N_(x) induced by the synergistic effects of well-tuned active sites of Co_(3)O_(4)-Co nanoparticle and Co-N_(x),thus optimizing the rate-determining step of the desorption of O_(2)^(*)intermediate in ORR and OH^(*)intermediate in OER.The rechargeable Zn-air batteries with our bifunctional catalysts exhibit superior performance as well as high cycling stability.This simple-effective optimization strategy offers prospects for tuning the active site of MOF derived bifunctional catalyst in electrochemical energy devices.展开更多
Expanding the application scenario for rechargeable batteries is the key to the terminal utilization of renewable energy.Enabling zinc–air batteries at low temperatures is drawing increasing attention,yet the low-tem...Expanding the application scenario for rechargeable batteries is the key to the terminal utilization of renewable energy.Enabling zinc–air batteries at low temperatures is drawing increasing attention,yet the low-temperature working feasibility of zinc–air batteries with noble metalfree electrocatalysts remains indistinct.In this contribution,the low-temperature performances of zinc–air batteries with noble metal-free electrocatalysts are comprehensively investigated.Armed with a representative noble metal-free bifunctional oxygen electrocatalyst,the zinc–air batteries demonstrate satisfactory yet relatively depressed performance at low temperatures,compared with that at room temperatures.The reduced electrolyte conductivity is identified as one of the limiting factors for the reduced low-temperature performance.Furthermore,electrolyte engineering via solvation structure regulation is performed on the zinc–air batteries with noblemetal-free electrocatalysts,where an improved low-temperature performance is achieved.This work reveals the compatibility between noble metal-free electrocatalysts and low-temperature feasibility/low-temperature performance enhancement strategies for zinc–air batteries and affords new opportunities to satisfy low-cost and efficient energy storage at harsh working conditions.展开更多
The commercial application of non-precious metal-based electrocatalysts is not only limited by the intrinsic activity of the catalysts,but also the stability of the catalysts is extremely important.Herein,we fabricate...The commercial application of non-precious metal-based electrocatalysts is not only limited by the intrinsic activity of the catalysts,but also the stability of the catalysts is extremely important.Herein,we fabricated an ultra-stable NiFe armored catalyst(Ar-NiFe/NC)by a simple secondary pyrolysis strategy.The as-obtained Ar-NiFe/NC electrocatalyst exhibits an excellent bifunctional oxygen electrocatalytic performance with an activity indicatorΔE of 0.74 V vs.reversible hydrogen electrode(RHE).More importantly,the Ar-NiFe/NC electrocatalyst also shows a remarkable operational and storage stability.After accelerated durability test(ADT)cycles,no obvious degradation of oxygen electrocatalytic performance could be observed.In addition,the Ar-NiFe/NC electrocatalyst still exhibits an unbated oxygen electrocatalytic performance comparable to fresh catalysts after three months of air-exposed storage.The assembled liquid and flexible quasi-solid-state rechargeable Zn-air batteries with the Ar-NiFe/NC electrocatalyst exhibit impressive performance.The liquid rechargeable Zn-air batteries possess a high open-circuit voltage(OCV)of 1.43 V and a salient peak power density of 146.40 mW·cm^(−2),while the flexible quasi-solid-state rechargeable Zn-air batteries also exhibit an excellent OCV of 1.60 V and an exciting peak power density of 41.99 mW·cm^(−2).展开更多
Rational design and synthesis of bifunctional oxygen electrocatalysts with high activity and stability are key challenges in the development of rechargeable Zn-air batteries(ZABs).In this paper,tungsten carbide(WC)and...Rational design and synthesis of bifunctional oxygen electrocatalysts with high activity and stability are key challenges in the development of rechargeable Zn-air batteries(ZABs).In this paper,tungsten carbide(WC)and Co_(7)Fe_(3)embedded in N,P co-doped hierarchical carbon(WC/Co_(7)Fe_(3)-NPHC)was prepared by using zeolite imidazolate frameworks as precursor.Density functional theory demonstrates that the mutual adjustment among the WC,Co_(7)Fe_(3),and N,P co-doped carbon at the three-phase heterojunction interface makes the catalyst possess moderate adsorption strength,and greatly improves the conductivity and electron transfer rate of the catalyst.As a result,the WC/Co_(7)Fe_(3)-NPHC exhibits a low overall oxygen redox potential difference of 0.72 V,while the ZAB assembled by WC/Co_(7)Fe_(3)-NPHC as an air cathode exhibits ultra-long cycle stability of over 550 h.Futhermore,WC/Co_(7)Fe_(3)-NPHC can keep good charge and discharge stability at different bending angles when applied to flexible solid ZAB.展开更多
基金supported by the Fundamental Research Funds for the Central Universities(No.22120230104).
文摘High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.
基金supported by the National Natural Science Foundation of China(NSFC,No.21774045)。
文摘Rational design of complex hollow nanostructures offers a great opportunity to construct various functional nanostructures.A novel in situ disassembly-polymerization-pyrolysis approach was developed to synthesize atomically dispersed Fe single atoms(Fe SAs)and tiny Co nanoparticles(Co NPs)binary sites embedded in double-shelled hollow carbon nanocages(Co NPs/Fe SAs DSCNs)without removing excess templates.The Co NPs/Fe SAs DSCNs displayed excellent bifunctional activity,boosting the realistic rechargeable zinc-air batteries with high efficiency,long-term durability,and reversibility,which is comparable to noble metal catalysts(Pt/C and RuO_(2)).The enhanced catalytic activity should be attributed to as well as the strong interactions between Fe SAs and Co NPs with the nitrogen-doped carbon matrix,the exposure of more active sites,and the high-flux mass transportation.In addition,the confinement effect between the double C–N shells prevented the aggregation and corrosion of metal atoms,thus improving the durability of the Co NPs/Fe SAs DSCNs,further highlighting the structural advantages of carbon nanoreactor.This work provides guidance for further rational design and preparation of complex hollow structure materials with advanced bifunctional air cathodes.
基金financially supported by the Natural Science Foundation of Shandong Province(No.ZR2022ME218)the National Natural Science Foundation of China(Nos.52102260,52171211 and 52202243)China Postdoctoral Science Foundation(Nos.2022M711545 and 2022M711371)。
文摘Designing rational transition-metal/carbon composites with highly dispersed and firmly anchored nanoparticles(NPs)to prevent agglomeration and shedding is crucial for realizing excellent electrocatalytic performances.Herein,a biomass pore-confined strategy based on mesoporous willow catkin is explored to obtain uniformly dispersed CoFe NPs in N-doped carbon nanotubes and hollow carbon fibers(CoFe@N-CNTs/HCFs).The resultant catalyst exhibits enhanced electrocatalytic performance,which affords a half-wave potential of 0.86 V(vs.RHE)with a limited current density of 6.0 mA·cm^(-2)for oxygen reduction reaction and potential of 1.67 V(vs.RHE)at 10 mA·cm^(-2)in 0.1 M KOH for oxygen evolution reaction.When applied to rechargeable zinc-air batteries,a maximum power density of 340 mW·cm^(-2)and long-term cyclic durability over 800 h are achieved.Such superior bifunctional electrocatalytic activities are ascribed to the biocarbon matrix with abundant mesopores and unobstructed hollow channels,CoFe NPs with high dispersion and controllable nanoscale and the hybrid composite with optimized electronic structure.This work presents an effective approach for constraining the size and dispersion of NPs in a low-cost biocarbon substrate,offering valuable insights for designing advanced oxygen electrocatalysts.
基金This work is supported by the Natural Sciences and Engineering Research Council of Canada(NSERC)Centre Québéco is sur les Materiaux Fonctionnels(CQMF),Fonds de Recherche du Québec-Nature et Technologies(FRQNT)+2 种基金Institut National de la Recherche Scientifique(INRS)This work is also supported by the National Natural Science Foundation of China(21972017)the“Scientific and Technical Innovation Action Plan”Hong Kong,Macao and Taiwan Science&Technology Cooperation Project of Shanghai Science and Technology Committee(19160760600).F.Dong gratefully acknowledges scholarships from the China Scholarship Council(CSC).
文摘Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs.Atomically dispersed metal-nitrogen-carbon(M-N-C)catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis.In this work,general principles for designing atomically dispersed M-N-C are reviewed.Then,strategies aiming at enhancing the bifunctional catalytic activity and stability are presented.Finally,the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined.It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.
基金supported financially by the National Natural Science Foundation of China,China(Grant No.51702180,51572136,91963113,21703116,51372127,51873096)The Scientific and Technical Development Project of Qingdao,China(Grant No.18-2-2-52-jch)+1 种基金The Taishan Scholar Advantage and Characteristic Discipline Team of Eco Chemical Process and TechnologyThe Natural Science Foundation of Hebei Province(B2019204009)。
文摘Efficient bifunctional oxygen electrocatalysts for ORR and OER are fundamental to the development of high performance metal-air batteries.Herein,a facile cost-efficient two-step pyrolysis strategy for the fabrication of a bifunctional oxygen electrocatalyst has been proposed.The efficient non-preciousmetal-based electrocatalyst,Fe/Fe_(3)C@Fe-N_(x)-C consists of highly curved onion-like carbon shells that encapsulate Fe/Fe_(3)C nanoparticles,distributed on an extensively porous graphitic carbon aerogel.The obtained Fe/Fe_(3)C@Fe-N_(x)-C aerogel exhibited superb electrochemical activity,excellent durability,and high methanol tolerance.The experimental results indicated that the assembly of onion-like carbon shells with encapsulated Fe/Fe_(3)C yielded highly curved carbon surfaces with abundant Fe-Nxactive sites,a porous structure,and enhanced electrocatalytic activity towards ORR and OER,hence displaying promising potential for application as an air cathode in rechargeable Zn-air batteries.The constructed Zn-air battery possessed an exceptional peak power density of~147 mW cm^(-2),outstanding cycling stability(200 cycles,1 h per cycle),and a small voltage gap of 0.87 V.This study offers valuable insights regarding the construction of low-cost and highly active bifunctional oxygen electrocatalysts for efficient air batteries.
基金supported by National Natural Science Foundation of China(52302235,52462013)Distinguished Young Scholars of Anhui Provincial Department of Education Research Plan(2022AH020068)+4 种基金Excellent Young Scholars of Anhui Provincial Department of Education Research Plan(2024AH030037)Excellent Young Teacher Training Program of Anhui(YQZD2024024)China Postdoctoral Science Foundation(2023M730891)Natural Science Foundation of Hainan Province(224QN185)State Key Laboratory of Heavy Oil Processing(SKLHOP202202009).
文摘An effective strategy of regulating active sites in bifunctional oxygen electrocatalysts is essentially desired,especially in rechargeable metal-air batteries(RZABs).Herein,a highly efficient electrocatalyst of CoFe alloys embedded in pyridinic nitrogen enriched N-doped carbon(CoFe/P-NC)is intelligently constructed by pyrolysis strategy.The high concentration of pyridinic nitrogen in CoFe/P-NC can significantly reprogram the redistribution of electron density of metal active sites,consequently optimizing the oxygen adsorption behavior.As expected,the pyridinic nitrogen guarantees CoFe/P-NC providing the low overpotential of the overall oxygen electrocatalytic process(ΔEORR-OER=0.73 V vs.RHE)and suppresses the benchmark electrocatalysts(Pt/C&RuO_(2)).Assembled rechargeable Zn-air battery using CoFe/P-NC demonstrates a promising peak power density of 172.0 mW cm^(-2),a high specific capacity of 805.0 mAh g^(-1)Zn and an excellent stability.This work proposes an interesting strategy for the design of robust oxygen electrocatalysts for energy conversion and storage fields.
基金supported financially by the National Natural Science Foundation of China(Nos.51902027,61674019,51976143,61874014,61874013 and 61974011)the National Basic Research of China(No.2015CB932500)+1 种基金the Fundamental Research Funds for the Central Universities(No.2019RC20)the Fund of State Key Laboratory of Information Photonics and Optical Communications(Beijing University of Posts and Telecommunications,P.R.China)。
文摘Electrocatalysts for oxygen reduction reactions(ORR)and oxygen evolution reactions(OER)are highly crucial and challenging toward the energy storage and conversion technologies such as fuel cells,metal-air batteries and water electrolysis.To replace noble-metal based catalysts and boost catalytic performance of carbon-based materials,we initially develop the nickel,phospho rus,sulfur and nitrogen co-modified mesoporous carbon(NiPS_(3)@NMC)as a bifunctional oxygen electrocatalyst.The perfo rmance for ORR(half-wave potential at 0.90 V)and OER(10 mA cm^(-2)at 1.48 V)surpasses those of Pt/C coupled with IrO_(2)catalysts and most of the non-precious metal based bifunctional electrocatalysts reported in related literature.Moreover,the electrochemical durability is also confirmed by accelerated durability tests(ADTs)and long-term chronoamperometry(CA)tests.We demonstrated that the interfacial effect between NiPS_(3)quantum sheets(QS s)and NMC substrates by thermal activation contributed to the enhanced oxygen electrode bifunctionality with more active sites,due to the electrons-donating from nickel,phosphorus and sulfur elements and relatively enriched pyridinic type N.Such excellent overall performance highlights the potential application of NiPS3 QSs and NMC composites as the materials on energy conversion and storage.
基金supported by NSFC(52373215)Sichuan Science and Technology Program(2023NSFSC0086)Fundamental Research Funds for the Central Universities(YJ2021156)。
文摘Fe-nitrogen-carbon(Fe-N-C)-and Co-nitrogen-carbon(Co-N-C)-based electrocatalysts have been widely concerned because of their high OER/ORR activity,low metal cost,and simple preparation.The exploration of Fe-N-C and Co-N-C single atombased catalysts with high activity and stability to overcome the slow kinetics of oxygen reduction and oxygen evolution reactions is also the key to the development of efficient electrolytic water,fuel cells,and rechargeable metal-air batteries.Fe-N-C and Co-N-C single atom-based electrocatalysts have the advantages of a high utilization rate of metal atoms and high electrocatalytic activity,and are ideal catalysts for promoting electrochemical energy conversion and storage.The general principles of designing Fe-N-C and Co-N-C single atom-based electrocatalysts are reviewed in this paper.Then,the strategies to improve the bifunctional catalytic activity and stability are proposed.Finally,the challenges and prospects of Fe-N-C and Co-N-C single atom-based catalysts are well summarized.This review will provide a reference for the directed optimization of Fe-N-C and Co-N-C single atom-based catalysts.
基金The authors acknowledge support from the National Natural Science Foundation of China(No.21875039)Minjiang Professorship(XRC-1677)+1 种基金Fujian province’s high level innovative and entrepreneurial talents(No.50012709)the Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(No.SKLPEE-201814),Fuzhou University.
文摘The rational control of the active site of metal-organic frameworks(MOFs)derived nanomaterials is essential to build efficient bifunctional oxygen reduction/evolution reaction(ORR/OER)catalysts.Accordingly,through designing and constructing a Co_(3)O_(4)-Co heterostructure embedded in Co,N co-doped carbon polyhedra derived(Co_(3)O_(4)-Co@NC)from the in-situ compositions of ZIF-67 and cobalt nanocrystals synthesized by the strategy of in-situ NaBH4 reduction,the dual-active site(Co_(3)O_(4)-Co and Co-N_(x))is synchronously realized in a MOFs derived nanomaterials.The formed Co_(3)O_(4)-Co@NC shows excellent bifunctional electrocatalytic activity with ultra-small potential gap(ΔE=E_(j=10)(OER)–E_(1/2)(ORR))of 0.72 V,which surpasses the commercial Pt/C and RuO_(2) catalysts.The theory calculation results reveal that the excellent bifunctional electrocatalytic activity can be attributed to the charge redistribution of Co of Co-N_(x) induced by the synergistic effects of well-tuned active sites of Co_(3)O_(4)-Co nanoparticle and Co-N_(x),thus optimizing the rate-determining step of the desorption of O_(2)^(*)intermediate in ORR and OH^(*)intermediate in OER.The rechargeable Zn-air batteries with our bifunctional catalysts exhibit superior performance as well as high cycling stability.This simple-effective optimization strategy offers prospects for tuning the active site of MOF derived bifunctional catalyst in electrochemical energy devices.
基金the Key Research and Development Program of Yunnan Province(grant no.202103AA080019)S&T Program of Hebei(grant no.22344402D)+1 种基金National Natural Science Foundation of China(grant no.22109007)Beijing Institute of Technology Research Fund Program for Young Scholars,and the Tsinghua University Initiative Scientific Research Program.
文摘Expanding the application scenario for rechargeable batteries is the key to the terminal utilization of renewable energy.Enabling zinc–air batteries at low temperatures is drawing increasing attention,yet the low-temperature working feasibility of zinc–air batteries with noble metalfree electrocatalysts remains indistinct.In this contribution,the low-temperature performances of zinc–air batteries with noble metal-free electrocatalysts are comprehensively investigated.Armed with a representative noble metal-free bifunctional oxygen electrocatalyst,the zinc–air batteries demonstrate satisfactory yet relatively depressed performance at low temperatures,compared with that at room temperatures.The reduced electrolyte conductivity is identified as one of the limiting factors for the reduced low-temperature performance.Furthermore,electrolyte engineering via solvation structure regulation is performed on the zinc–air batteries with noblemetal-free electrocatalysts,where an improved low-temperature performance is achieved.This work reveals the compatibility between noble metal-free electrocatalysts and low-temperature feasibility/low-temperature performance enhancement strategies for zinc–air batteries and affords new opportunities to satisfy low-cost and efficient energy storage at harsh working conditions.
基金supported by the National Natural Science Foundation of China(No.22102132)the Funds for Basic Scientific Research in Central Universities and the Youth Project of the Natural Science Foundation of Shaanxi Province,China(No.2021JQ-087)+1 种基金Ningbo Natural Science Foundation(No.2021J053)the open research fund of Key Laboratory for Organic Electronics and Information Displays.
文摘The commercial application of non-precious metal-based electrocatalysts is not only limited by the intrinsic activity of the catalysts,but also the stability of the catalysts is extremely important.Herein,we fabricated an ultra-stable NiFe armored catalyst(Ar-NiFe/NC)by a simple secondary pyrolysis strategy.The as-obtained Ar-NiFe/NC electrocatalyst exhibits an excellent bifunctional oxygen electrocatalytic performance with an activity indicatorΔE of 0.74 V vs.reversible hydrogen electrode(RHE).More importantly,the Ar-NiFe/NC electrocatalyst also shows a remarkable operational and storage stability.After accelerated durability test(ADT)cycles,no obvious degradation of oxygen electrocatalytic performance could be observed.In addition,the Ar-NiFe/NC electrocatalyst still exhibits an unbated oxygen electrocatalytic performance comparable to fresh catalysts after three months of air-exposed storage.The assembled liquid and flexible quasi-solid-state rechargeable Zn-air batteries with the Ar-NiFe/NC electrocatalyst exhibit impressive performance.The liquid rechargeable Zn-air batteries possess a high open-circuit voltage(OCV)of 1.43 V and a salient peak power density of 146.40 mW·cm^(−2),while the flexible quasi-solid-state rechargeable Zn-air batteries also exhibit an excellent OCV of 1.60 V and an exciting peak power density of 41.99 mW·cm^(−2).
基金the National Natural Science Foundation of China(Nos.51772162 and 52072197)China Postdoctoral Science Foundation(No.2020M682135)+6 种基金Postdoctoral Applied Research Project of Qingdao,Postdoctoral Innovation Project of Shandong Province(No.202102039)Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)the Natural Science Foundation of Shandong Province(No.ZR2021MB085)Major Scientific and Technological Innovation Project(No.2019JZZY020405)Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant(No.ZR2020ZD09)Taishan Scholar Young Talent Program(No.tsqn201909114).
文摘Rational design and synthesis of bifunctional oxygen electrocatalysts with high activity and stability are key challenges in the development of rechargeable Zn-air batteries(ZABs).In this paper,tungsten carbide(WC)and Co_(7)Fe_(3)embedded in N,P co-doped hierarchical carbon(WC/Co_(7)Fe_(3)-NPHC)was prepared by using zeolite imidazolate frameworks as precursor.Density functional theory demonstrates that the mutual adjustment among the WC,Co_(7)Fe_(3),and N,P co-doped carbon at the three-phase heterojunction interface makes the catalyst possess moderate adsorption strength,and greatly improves the conductivity and electron transfer rate of the catalyst.As a result,the WC/Co_(7)Fe_(3)-NPHC exhibits a low overall oxygen redox potential difference of 0.72 V,while the ZAB assembled by WC/Co_(7)Fe_(3)-NPHC as an air cathode exhibits ultra-long cycle stability of over 550 h.Futhermore,WC/Co_(7)Fe_(3)-NPHC can keep good charge and discharge stability at different bending angles when applied to flexible solid ZAB.
