Developing novel oxygen reduction reaction(ORR)catalysts with high activity is urgent for proton exchange membrane fuel cells.Herein,we investigated a group of size-dependent Pt-based catalysts as promising ORR cataly...Developing novel oxygen reduction reaction(ORR)catalysts with high activity is urgent for proton exchange membrane fuel cells.Herein,we investigated a group of size-dependent Pt-based catalysts as promising ORR catalysts by density functional theory calculations,ranging from single-atom,nanocluster to bulk Pt catalysts.The results showed that the ORR overpotential of these Pt-based catalysts increased when its size enlarged to the nanoparticle scale or reduced to the single-atom scale,and the Pt_(38)cluster had the lowest ORR overpotential(0.46 V)compared with that of Pt_(111)(0.57 V)and single atom Pt(0.7 V).Moreover,we established a volcano curve relationship between the ORR overpotential and binding energy of O*(ΔE_(O*),confirming the intermediate species anchored on Pt38cluster with suitable binding energy located at top of volcano curve.The interaction between intermediate species and Pt-based catalysts were also investigated by the charge distribution and projected density of state and which further confirmed the results of volcano curve.展开更多
In the context of the current serious problems related to energy demand and climate change,substantial progress has been made in developing a sustainable energy system.Electrochemical hydrogen-water conversion is an i...In the context of the current serious problems related to energy demand and climate change,substantial progress has been made in developing a sustainable energy system.Electrochemical hydrogen-water conversion is an ideal energy system that can produce fuels via sustainable,fossil-free pathways.However,the energy conversion efficiency of two functioning technologies in this energy system—namely,water electrolysis and the fuel cell—still has great scope for improvement.This review analyzes the energy dissipation of water electrolysis and the fuel cell in the hydrogen-water energy system and discusses the key barriers in the hydrogen-and oxygen-involving reactions that occur on the catalyst surface.By means of the scaling relations between reactive intermediates and their apparent catalytic performance,this article summarizes the frameworks of the catalytic activity trends,providing insights into the design of highly active electrocatalysts for the involved reactions.A series of structural engineering methodologies(including nano architecture,facet engineering,polymorph engineering,amorphization,defect engineering,element doping,interface engineering,and alloying)and their applications based on catalytic performance are then introduced,w让h an emphasis on the rational guidance from previous theoretical and experimental studies.The key scientific problems in the electrochemical hydrogen-water conversion system are outlined,and future directions are proposed for developing advanced catalysts for technologies with high energy-conversion efficiency.展开更多
This work demonstrates the outstanding performance of alloyed Au1 Pt1 nanoparticles on hydrogen oxidation reaction(HOR)in alkaline solution.Due to the weakened hydrogen binding energy caused by uniform incorporation o...This work demonstrates the outstanding performance of alloyed Au1 Pt1 nanoparticles on hydrogen oxidation reaction(HOR)in alkaline solution.Due to the weakened hydrogen binding energy caused by uniform incorporation of Au,the alloyed Au1Pt1/C nanoparticles exhibit superior HOR activity than commercial PtRu/C.On the contrary,the catalytic performance of the phase-segregated Au2Pt1/C and Au1Pt1/C bimetallic nanoparticles in HOR is significantly worse.Moreover,Au1Pt1/C shows a remarkable durability with activity dropping only 4% after 3000 CV cycles,while performance attenuation of commercial PtRu/C is high up to 15% under the same condition.Our results indicate that the alloyed Au1Pt1/C is a promising candidate to substitute commercial PtRu/C for hydrogen oxidation reaction in alkaline electrolyte.展开更多
The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as a...The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as an excellent electrocatalyst for alkaline hydrogen evolution reaction(HER).The welldispersed amorphous TiO_(2)on nanoneedle-like CoP arrays preserves the crystal structure of CoP and changes its electronic structure by interfacial charge transfer.Compared to CoP/NF catalyst,the Ti O_(2)–CoP/NF composite catalyst exhibits high HER activity with an overpotential of 61 mV at 10 mA cm^(-2)and high stability.Importantly,it almost maintains the Volmer step as a rate-determining step(RDS)and the Tafel slope at a wide cathodic potential range showing the fast kinetics under large polarization regions.Theoretical simulations reveal that the combination of TiO_(2)and CoP selectively accelerates the hydrated K+diffusion,regulates the interfacial water orientation to adapt to the subsequent smooth water dissociation,and optimizes*H adsorption/H_(2)desorption.The strengthened coupling of HER multi-scale-processes on transition metal compound composites catalysts is the underlying mechanism for improving HER activity.展开更多
Developing platinum-group-metal(PGM)catalysts possessing strong metal-support interaction and controllable PGM size is urgent for the sluggish oxygen reduction reaction(ORR)in proton-exchange membrane fuel cells.Herei...Developing platinum-group-metal(PGM)catalysts possessing strong metal-support interaction and controllable PGM size is urgent for the sluggish oxygen reduction reaction(ORR)in proton-exchange membrane fuel cells.Herein,we propose an in-situ self-assembled reduction strategy to successfully induce highly-dispersed sub-3nm platinum nanoparticles(Pt NPs)to attach on resin-derived atomic Co coordinated by N-doped carbon substrate(Pt/Co_(SA)-N-C)for ORR.To be specific,the interfacial electron interaction effect,along with a highly robust Co_(SA)-N-C support endow the as-fabricated Pt/Co_(SA)-N-C catalyst with significantly enhanced catalytic properties,i.e.,a mass activity(MA)of 0.719 A/mgPt at 0.9 ViR-free and a reduction of 24.2%in MA after a 20,000-cycles test.Density functional theory(DFT)calculations demonstrate that the enhanced electron interaction between Pt and Co_(SA)-N-C support decreases the dband center of Pt,which is in favor of lowering the desorption energy of ^(*)OH on Pt/Co_(SA)-N-C surface and accelerating the formation of H_(2)O,thus enhance the instinct activity of ORR.Furthermore,the higher binding energy between Pt and Co_(SA)-N-C compared to Pt and C indicates that the migration of Pt has been suppressed,which theoretically explains the improved durability of Pt/Co_(SA)-N-C.Our work offers an enlightenment on constructing composite Pt-based catalysts with multiple active sites.展开更多
The near-surface structure of the Pt-based alloy including the surface and subsurface structures is prominent to their electrocatalytic performance.Modulating the near-surface structure of PtCo intermetallics with sma...The near-surface structure of the Pt-based alloy including the surface and subsurface structures is prominent to their electrocatalytic performance.Modulating the near-surface structure of PtCo intermetallics with small particle size could efficiently optimize the binding force between Pt and oxygen and finally enhance its oxygen reduction reaction(ORR)performance.Here we simultaneously achieve the size controlling and surface modulation of intermetallic nanoparticles(NPs)in a weak-oxidative confined space with abundant uncoordinated oxygen atoms.1–2 atomic layers of concave Pt-rich surface were successfully constructed on 4 nm L1_(0)-PtCo core after removing Co–O species which is derived from the segregation of the subsurface Co to the surface induced by the uncoordinated oxygen atoms.Owing to the elaborate structure,PtCo-1000/C catalyst shows significant improvement in both activity(1.290 A∙mg_(Pt)^(−1)and 1.529 mA∙cm_(Pt)^(−2) at 0.9 V vs.reversible hydrogen electrode(RHE))and stability(85.2%of initial mass activity after accelerated degression tests(ADTs))even the production is scaled up to gram level.Density functional theory calculations suggest that the cave Pt site optimizes the protonation of*O,which finally boosts the ORR performance.展开更多
Metal-nitrogen doped carbon catalysts(M-N/C) with abundantly accessible M-Nxsites, particularly single metal atom M-N/C(SAM-N/C), have been developed as a substitute for expensive Pt-based catalysts.These catalysts ar...Metal-nitrogen doped carbon catalysts(M-N/C) with abundantly accessible M-Nxsites, particularly single metal atom M-N/C(SAM-N/C), have been developed as a substitute for expensive Pt-based catalysts.These catalysts are used to increase the efficiency of otherwise sluggish oxygen reduction reactions(ORR) and hydrogen evolution reactions(HER). However, although the agglomerated metal nanoparticles are usually easy to form, they are very difficult to remove due to the protective surface-coating carbon layers, a factor that significantly hampers SAM-N/C fabrication. Herein, we report a one-step pyrolysis approach to successfully fabricate single cobalt atom Co-N/C(SACo-N/C) by using a Co2+-SCN-coordination compound as the metal precursor. Thanks to the decomposition of Co2+-SCN-compound at lower temperature than that of carbon layer deposition, Co-rich particles grow up to larger ones before carbon layers formation. Even though encapsulated by the carbon layers, it is difficult for the large Co-rich particle to be completely sealed. And thus, it makes the Co atoms possible to escape from incomplete carbon layer, to coordinate with nitrogen atoms, and to form SACo-N/C catalysts. This SACo-N/C exhibits excellent performances for both ORR(half-wave potential of 0.878 V) and HER(overpotential at 10 mA/cm2 of178 m V), and is thus a potential replacement for Pt-based catalysts. When SACo-N/C is integrated into a Zn-O2 battery, battery with high open-circuit voltage(1.536 V) has high peak power density(266 mW/cm2)and large gravimetric energy density(755 mA h/gZn) at current densities of 100 mA/cm2. Thus, we believe that this strategy may offer a new direction for the effective generation of SAM-N/C catalysts.展开更多
Electrocatalytic materials with different morphologies,sizes,and components show different catalytic behavior in various heterogeneous catalytic reactions.It has been proved that the catalytic properties of these mate...Electrocatalytic materials with different morphologies,sizes,and components show different catalytic behavior in various heterogeneous catalytic reactions.It has been proved that the catalytic properties of these materials are strongly influenced by several factors at different levels,including the electrode morphology,reaction channels,three-phase interface,and surface active sites.Recent developments of mesoscience allow one to study the relationship between the apparent catalytic performance of electro-catalytic materials with these factors from different levels.In this review,following a brief introduction of new mesoscience,we summarize the effect of mesoscience on electrocatalytic material design,including modulating the geometric and electronic structures of materials focusing on morphology(particulate,fiber,film,array,monolith,and superlattice),pore structure(microporous,mesoporous,and hierarchical),size(single atoms,nanoclusters,and nanoparticles),multiple components(alloys,heterostructures,and multiple ligands),and crystal structures(crystalline,amorphous,and multiple crystal phases).By evaluating the electrocatalytic performance of catalytic materials tuned at the mesoscale,we paint a picture of how these factors at different levels affect the final system performance and then provide a new direction to better understand and design catalytic materials from the viewpoint of mesoscience.展开更多
基金supported by the National Natural Science Foundation of China(92061125,21978294)Beijing Natural Science Foundation(Z200012)+3 种基金Jiangxi Natural Science Foundation(20212ACB213009)DNL Cooperation Fund,CAS(DNL201921)Self-deployed Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(E055B003)Hebei Natural Science Foundation(B2020103043)。
文摘Developing novel oxygen reduction reaction(ORR)catalysts with high activity is urgent for proton exchange membrane fuel cells.Herein,we investigated a group of size-dependent Pt-based catalysts as promising ORR catalysts by density functional theory calculations,ranging from single-atom,nanocluster to bulk Pt catalysts.The results showed that the ORR overpotential of these Pt-based catalysts increased when its size enlarged to the nanoparticle scale or reduced to the single-atom scale,and the Pt_(38)cluster had the lowest ORR overpotential(0.46 V)compared with that of Pt_(111)(0.57 V)and single atom Pt(0.7 V).Moreover,we established a volcano curve relationship between the ORR overpotential and binding energy of O*(ΔE_(O*),confirming the intermediate species anchored on Pt38cluster with suitable binding energy located at top of volcano curve.The interaction between intermediate species and Pt-based catalysts were also investigated by the charge distribution and projected density of state and which further confirmed the results of volcano curve.
基金We gratefully acknowledge financial support from the National Natural Science Foundation of China(21576032 and 51772037)the Key Program of the National Natural Science Foundation of China(21436003)+1 种基金the Major Research Plan of the National Natural Science Foundation of China(91534205)the National Program on Key Basic Research Project of China(2016YFB0101202).
文摘In the context of the current serious problems related to energy demand and climate change,substantial progress has been made in developing a sustainable energy system.Electrochemical hydrogen-water conversion is an ideal energy system that can produce fuels via sustainable,fossil-free pathways.However,the energy conversion efficiency of two functioning technologies in this energy system—namely,water electrolysis and the fuel cell—still has great scope for improvement.This review analyzes the energy dissipation of water electrolysis and the fuel cell in the hydrogen-water energy system and discusses the key barriers in the hydrogen-and oxygen-involving reactions that occur on the catalyst surface.By means of the scaling relations between reactive intermediates and their apparent catalytic performance,this article summarizes the frameworks of the catalytic activity trends,providing insights into the design of highly active electrocatalysts for the involved reactions.A series of structural engineering methodologies(including nano architecture,facet engineering,polymorph engineering,amorphization,defect engineering,element doping,interface engineering,and alloying)and their applications based on catalytic performance are then introduced,w让h an emphasis on the rational guidance from previous theoretical and experimental studies.The key scientific problems in the electrochemical hydrogen-water conversion system are outlined,and future directions are proposed for developing advanced catalysts for technologies with high energy-conversion efficiency.
基金financially supported by the National Natural Science Foundation of China (Grants no. 21376283, 21436003 and 21576032)
文摘This work demonstrates the outstanding performance of alloyed Au1 Pt1 nanoparticles on hydrogen oxidation reaction(HOR)in alkaline solution.Due to the weakened hydrogen binding energy caused by uniform incorporation of Au,the alloyed Au1Pt1/C nanoparticles exhibit superior HOR activity than commercial PtRu/C.On the contrary,the catalytic performance of the phase-segregated Au2Pt1/C and Au1Pt1/C bimetallic nanoparticles in HOR is significantly worse.Moreover,Au1Pt1/C shows a remarkable durability with activity dropping only 4% after 3000 CV cycles,while performance attenuation of commercial PtRu/C is high up to 15% under the same condition.Our results indicate that the alloyed Au1Pt1/C is a promising candidate to substitute commercial PtRu/C for hydrogen oxidation reaction in alkaline electrolyte.
基金financially supported by the National Key Research and Development Program of China(2021YFB4000301)the National Natural Science Foundation of China(21822803,22090030,and 21576032)。
文摘The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as an excellent electrocatalyst for alkaline hydrogen evolution reaction(HER).The welldispersed amorphous TiO_(2)on nanoneedle-like CoP arrays preserves the crystal structure of CoP and changes its electronic structure by interfacial charge transfer.Compared to CoP/NF catalyst,the Ti O_(2)–CoP/NF composite catalyst exhibits high HER activity with an overpotential of 61 mV at 10 mA cm^(-2)and high stability.Importantly,it almost maintains the Volmer step as a rate-determining step(RDS)and the Tafel slope at a wide cathodic potential range showing the fast kinetics under large polarization regions.Theoretical simulations reveal that the combination of TiO_(2)and CoP selectively accelerates the hydrated K+diffusion,regulates the interfacial water orientation to adapt to the subsequent smooth water dissociation,and optimizes*H adsorption/H_(2)desorption.The strengthened coupling of HER multi-scale-processes on transition metal compound composites catalysts is the underlying mechanism for improving HER activity.
基金financially supported by the Natural Science Foundation of China(Nos.22169005,22209186,22068009 and 22262006)the Science and Technology Support Project of Guizhou Provincial Science and Technology Department(Nos.ZK[2023]050 and[2023]403)+2 种基金the Open Project of Institute of Dualcarbon and New Energy Technology Innovation and Development of Guizhou Province(No.DCRE-2023-06)Youth Innovation Promotion Association,CAS(No.2023343)Self-deployed Projects of Ganjiang Innovation Academy,CAS(No.E355F006).
文摘Developing platinum-group-metal(PGM)catalysts possessing strong metal-support interaction and controllable PGM size is urgent for the sluggish oxygen reduction reaction(ORR)in proton-exchange membrane fuel cells.Herein,we propose an in-situ self-assembled reduction strategy to successfully induce highly-dispersed sub-3nm platinum nanoparticles(Pt NPs)to attach on resin-derived atomic Co coordinated by N-doped carbon substrate(Pt/Co_(SA)-N-C)for ORR.To be specific,the interfacial electron interaction effect,along with a highly robust Co_(SA)-N-C support endow the as-fabricated Pt/Co_(SA)-N-C catalyst with significantly enhanced catalytic properties,i.e.,a mass activity(MA)of 0.719 A/mgPt at 0.9 ViR-free and a reduction of 24.2%in MA after a 20,000-cycles test.Density functional theory(DFT)calculations demonstrate that the enhanced electron interaction between Pt and Co_(SA)-N-C support decreases the dband center of Pt,which is in favor of lowering the desorption energy of ^(*)OH on Pt/Co_(SA)-N-C surface and accelerating the formation of H_(2)O,thus enhance the instinct activity of ORR.Furthermore,the higher binding energy between Pt and Co_(SA)-N-C compared to Pt and C indicates that the migration of Pt has been suppressed,which theoretically explains the improved durability of Pt/Co_(SA)-N-C.Our work offers an enlightenment on constructing composite Pt-based catalysts with multiple active sites.
基金the National Natural Science Foundation of China(Nos.22279082 and 21908148)the Natural Science Foundation of Sichuan(No.2022NSFSC1247)。
文摘The near-surface structure of the Pt-based alloy including the surface and subsurface structures is prominent to their electrocatalytic performance.Modulating the near-surface structure of PtCo intermetallics with small particle size could efficiently optimize the binding force between Pt and oxygen and finally enhance its oxygen reduction reaction(ORR)performance.Here we simultaneously achieve the size controlling and surface modulation of intermetallic nanoparticles(NPs)in a weak-oxidative confined space with abundant uncoordinated oxygen atoms.1–2 atomic layers of concave Pt-rich surface were successfully constructed on 4 nm L1_(0)-PtCo core after removing Co–O species which is derived from the segregation of the subsurface Co to the surface induced by the uncoordinated oxygen atoms.Owing to the elaborate structure,PtCo-1000/C catalyst shows significant improvement in both activity(1.290 A∙mg_(Pt)^(−1)and 1.529 mA∙cm_(Pt)^(−2) at 0.9 V vs.reversible hydrogen electrode(RHE))and stability(85.2%of initial mass activity after accelerated degression tests(ADTs))even the production is scaled up to gram level.Density functional theory calculations suggest that the cave Pt site optimizes the protonation of*O,which finally boosts the ORR performance.
基金supported by the National Natural Science Foundation of China(22209121,21975183,22279150,51825205,and 22088102)Beijing Natural Science Foundation(2222080)the Youth Innovation Promotion Association of the CAS(Y2021011)。
基金supported by the National Key Research and Development Program of China(2016YFB0101202)the National Natural Science Foundation of China(21761162015,91534205,21436003)the Fundamental Research Funds for the Central Universities
文摘Metal-nitrogen doped carbon catalysts(M-N/C) with abundantly accessible M-Nxsites, particularly single metal atom M-N/C(SAM-N/C), have been developed as a substitute for expensive Pt-based catalysts.These catalysts are used to increase the efficiency of otherwise sluggish oxygen reduction reactions(ORR) and hydrogen evolution reactions(HER). However, although the agglomerated metal nanoparticles are usually easy to form, they are very difficult to remove due to the protective surface-coating carbon layers, a factor that significantly hampers SAM-N/C fabrication. Herein, we report a one-step pyrolysis approach to successfully fabricate single cobalt atom Co-N/C(SACo-N/C) by using a Co2+-SCN-coordination compound as the metal precursor. Thanks to the decomposition of Co2+-SCN-compound at lower temperature than that of carbon layer deposition, Co-rich particles grow up to larger ones before carbon layers formation. Even though encapsulated by the carbon layers, it is difficult for the large Co-rich particle to be completely sealed. And thus, it makes the Co atoms possible to escape from incomplete carbon layer, to coordinate with nitrogen atoms, and to form SACo-N/C catalysts. This SACo-N/C exhibits excellent performances for both ORR(half-wave potential of 0.878 V) and HER(overpotential at 10 mA/cm2 of178 m V), and is thus a potential replacement for Pt-based catalysts. When SACo-N/C is integrated into a Zn-O2 battery, battery with high open-circuit voltage(1.536 V) has high peak power density(266 mW/cm2)and large gravimetric energy density(755 mA h/gZn) at current densities of 100 mA/cm2. Thus, we believe that this strategy may offer a new direction for the effective generation of SAM-N/C catalysts.
基金supported by a James Cook Research Fellowship,administered by the Royal Society Te Apārangifunding support from Greg and Kathryn Trounson,the Energy Education Trust of New Zealand,the Mac Diarmid Institute for Advanced Materials and Nanotechnology,the National Key Projects for Fundamental Research and Development of China(2017YFA0206904 and 2017YFA0206900)+1 种基金the National Natural Science Foundation of China(51825205 and 21871279)the Beijing Natural Science Foundation(2191002)。
基金This research work was financially sponsored by the National Key Research and Development Program of China(2016YFB0101202)the Key Program of the National Nature Science Foundation of China(Grant No.91534205,No.21376283 and No.21576032).
文摘Electrocatalytic materials with different morphologies,sizes,and components show different catalytic behavior in various heterogeneous catalytic reactions.It has been proved that the catalytic properties of these materials are strongly influenced by several factors at different levels,including the electrode morphology,reaction channels,three-phase interface,and surface active sites.Recent developments of mesoscience allow one to study the relationship between the apparent catalytic performance of electro-catalytic materials with these factors from different levels.In this review,following a brief introduction of new mesoscience,we summarize the effect of mesoscience on electrocatalytic material design,including modulating the geometric and electronic structures of materials focusing on morphology(particulate,fiber,film,array,monolith,and superlattice),pore structure(microporous,mesoporous,and hierarchical),size(single atoms,nanoclusters,and nanoparticles),multiple components(alloys,heterostructures,and multiple ligands),and crystal structures(crystalline,amorphous,and multiple crystal phases).By evaluating the electrocatalytic performance of catalytic materials tuned at the mesoscale,we paint a picture of how these factors at different levels affect the final system performance and then provide a new direction to better understand and design catalytic materials from the viewpoint of mesoscience.
