Fe-N-C catalysts are widely considered as promising non-precious-metal candidates for electrocatalytic oxygen reduction reaction(ORR),Yet despite their high catalytic activity through rational modulation,challenges re...Fe-N-C catalysts are widely considered as promising non-precious-metal candidates for electrocatalytic oxygen reduction reaction(ORR),Yet despite their high catalytic activity through rational modulation,challenges remain in their low site density and unsatisfactory mass transfer structure.Herein,we present a structural engineering approach employing a soft-template coating strategy to fabricate a hollow and hierarchically porous N-doped carbon framework anchored with atomically dispersed Fe sites(FeNCh) as an efficient ORR catalyst.The combination of hierarchical porosity and high exterior surface area is proven crucial for exposing more active sites,which gives rise to a remarkable ORR performance with a half-wave potential of 0.902 V in 0.1 m KOH and 0.814 V in 0.1 m HClO_(4),significantly outperforming its counterpart with solid structure and dominance of micropores(FeNC-s).The mass transfer property is revealed by in-situ electrochemical impedance spectroscopy(EIS) measurement.The distribution of relaxation time(DRT) analysis is further introduced to deconvolve the kinetic and mass transport processes,which demonstrates an alleviated mass transport resistance for FeNC-h,validating the effectiveness of structural engineering.This work not only provides an effective structural engineering approach but also contributes to the comprehensive mass transfer evaluation on advanced electrocatalyst for energy conversion applications.展开更多
The effect of defect density on the modulation of incident laser waves is investigated. First, based on the actual defect distribution in the subsurface of fused silica, a three-dimensional （3D） grid model of defect...The effect of defect density on the modulation of incident laser waves is investigated. First, based on the actual defect distribution in the subsurface of fused silica, a three-dimensional （3D） grid model of defect sites is constructed. The 3D finite-difference time-domain method is developed to solve the Maxwell equations. Then the electrical field intensity in the vicinity of the defect sites in the subsurface of fused silica is numerically calculated. The relationships between the maximal electrical field intensity in fused silica and the geometry of the defect sites are given. The simulated results reveal that the modulation becomes more remarkable with an increase of the defect density. In addition, the effect of the distribution mode of defects on modulation is discussed. Meanwhile, the underlying physical mechanism is analyzed in detail.展开更多
In light of the percentage of Earth’s cloud coverage, heterogeneous ice nucleation in clouds is the most important global-scale pathway. More recent parameterizations of ice nucleation processes in the atmosphere are...In light of the percentage of Earth’s cloud coverage, heterogeneous ice nucleation in clouds is the most important global-scale pathway. More recent parameterizations of ice nucleation processes in the atmosphere are based on the concept of ice nucleation active surface site density (<i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;">). It is usually assumed that </span><i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;"> is independent of time and aerosol size distribution, </span><i><span style="font-family:Verdana;">i.e.</span></i><span style="font-family:Verdana;"> that the surface properties of aerosols of the same species do not vary with size. However, the independence of </span><i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;"> on aerosol size for every species has been questioned. This study presents the results of ice nucleation processes of ATD laboratory-generated aerosol (particle diameters of 0 - 3 μm). Ice nucleation in the condensation mode was performed in a Dynamic Filter Processing Cham- ber at temperatures of </span><span style="font-family:;" "=""><span style="font-family:Verdana;"><span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">-</span></span><span style="font-family:Verdana;">18<span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">°</span>C and </span><span style="font-family:Verdana;"><span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">-</span></span><span><span style="font-family:Verdana;">22<span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">°</span>C, with a saturation ratio with respect to water of 1.02. Results show that </span><i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;"> increased by lowering the nucleation temperature, and was also dependent on the particle size. The </span><i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;"> of particles collected on the filters, after a 0.5 μm D</span><sub><span style="font-family:Verdana;">50</span></sub><span style="font-family:Verdana;"> cut-off cyclone, resulted statistically higher with respect to the values obtained from the particles collected on total filters. The results obtained suggest the need for further investigation of </span><i><span style="font-family:Verdana;">n</span></i><sub><span style="font-family:Verdana;">s</span></sub><span style="font-family:Verdana;"> dependence of same composition aerosol particles with a view to support weather and climate predictions.</span></span></span>展开更多
Rational design of Fe and N co-doped carbon catalysts(FeNCs), one promising non-precious cathode catalyst, is critical to commercialization of proton exchange membrane fuel cells. The atomic Fe site density of Fe-NCs ...Rational design of Fe and N co-doped carbon catalysts(FeNCs), one promising non-precious cathode catalyst, is critical to commercialization of proton exchange membrane fuel cells. The atomic Fe site density of Fe-NCs is critical to improve catalytic currents approaching industrial levels. One recent research proposes a template-guided strategy to break the limit of Fe site density, and greatly promotes the fuel cell performance.展开更多
Iron-nitrogen-carbon(Fe-N-C)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)have seriously been hindered by their poor ORR performance of Fe-N-C due to the low active site...Iron-nitrogen-carbon(Fe-N-C)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)have seriously been hindered by their poor ORR performance of Fe-N-C due to the low active site density(SD)and site utilization.Herein,we reported a melamine-assisted vapor deposition approach to overcome these hindrances.The melamine not only compensates for the loss of nitrogen caused by high-temperature pyrolysis but also effectively etches the carbon substrate,increasing the external surface area and mesoporous porosity of the carbon substrate.These can provide more useful area for subsequent vapor deposition on active sites.The prepared 0.20Mela-FeNC catalyst shows a fourfold higher SD value and site utilization than the FeNC without the treatment of melamine.As a result,0.20Mela-FeNC catalyst exhibits a high ORR activity with a half-wave potential(E_(1/2))of 0.861 V and 12-fold higher ORR mass activity than the FeNC in acidic media.As the cathode in a H_(2)-O_(2)PEMFCs,0.20Mela-FeNC catalyst demonstrates a high peak power density of 1.30 W cm^(-2),outstripping most of the reported Fe-N-C catalysts.The developed melamine-assisted vapor deposition approach for boosting the SD and utilization of Fe-N-C catalysts offers a new insight into high-performance ORR electrocatalysts.展开更多
The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a ...The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.展开更多
Structural collapse and aggregation during the annealing process are the key obstacles for MOF-derived electrocatalysts,which will lead to a decrease in the active site density and stability of the electrocatalyst.The...Structural collapse and aggregation during the annealing process are the key obstacles for MOF-derived electrocatalysts,which will lead to a decrease in the active site density and stability of the electrocatalyst.The atomic layer deposition(ALD)technique can form dense and uniform thin films wrapping any complex 3D structure due to the self-limiting surface chemistry reactions.Herein,we developed a confinement strategy based on the ALD technique to prepare a durable Fe2Ni MIL 88-derived electrocatalyst(NiFe/NC@Al_(2)O_(3)-2).Due to the protection of the Al_(2)O_(3) layer deposited by the ALD technique,the asprepared catalyst retained the original rod-like structure of MIL 88 after the annealing process.With the confinement effect of the Al_(2)O_(3) nanolayer,the optimized NiFe/NC@Al_(2)O_(3)-2 exhibited remarkable electrocatalytic properties in the oxygen evolution reaction(OER)with low overpotentials of 270 and 391 mV at 10 and 100 mA cm^(-2),respectively.Furthermore,the catalyst obtained an excellent durability over 100 hours at a high current density of 50 mA cm^(-2),which is superior to those of many previously reported NiFe-based electrocatalysts.The ALD-assisted confinement strategy highlights a novel method to synthesize structure-and morphology-retained MOF-derived catalysts with excellent activity and stability at high current densities.展开更多
The surface acidity of synthetic amorphous AI hydroxide was determined by acid/base titration with several complementary methods including solution analyses of the reacted solutions and XRD characterization of the rea...The surface acidity of synthetic amorphous AI hydroxide was determined by acid/base titration with several complementary methods including solution analyses of the reacted solutions and XRD characterization of the reacted solids. The synthetic specimen was characterized to be the amorphous material showing four broad peaks in XRD pattern. XRD analyses of reacted solids after the titration experiments showed that amorphous AI hydroxide rapidly transformed to crystalline bayerite at the alkaline condition （pH〉10）. The solution analyses after and during the titration Ksp=^aAl^3＋/aH^＋^3 ,was 10^10.3. The amount of consumption of added acid or base during the titration experiment was attributed to both the protonation/deprotonation of dissolved AI species and surface hydroxyl group. The surface acidity constants, surface hydroxyl density and specific surface area were estimated by FITEQL 4.0.展开更多
Fe-N-C catalysts represent very promising cathode catalysts for polymer electrolyte fuel cells,owing to their outstanding activity for the oxygen reduction reaction(ORR),especially in alkaline media.In this review,we ...Fe-N-C catalysts represent very promising cathode catalysts for polymer electrolyte fuel cells,owing to their outstanding activity for the oxygen reduction reaction(ORR),especially in alkaline media.In this review,we summarize recent advances in the design and synthesis of Fe-N-C catalysts rich in highly dispersed FeNx active sites.Special emphasis is placed on emerging strategies for tuning the electronic structure of the Fe atoms to enhance the ORR activity,and also maximizing the surface concentration of FeNx sites that are catalytically accessible during ORR.While great progress has been made over the past 5 years in the development of Fe-N-C catalyst for ORR,significant technical obstacles still need to be overcome to enable the large-scale application of Fe-N-C materials as cathode catalysts in real-world fuel cells.展开更多
Zn-air batteries(ZABs)as a potential energy conversion system suffer from low power density(typically≤200 mW·cm^(−2)).Recently,three-dimensional(3D)integrated air cathodes have demonstrated promising performance...Zn-air batteries(ZABs)as a potential energy conversion system suffer from low power density(typically≤200 mW·cm^(−2)).Recently,three-dimensional(3D)integrated air cathodes have demonstrated promising performance over traditional twodimensional(2D)plane ones,which is ascribed to enriched active sites and enhanced diffusion,but without experimental evidence.Herein,we applied a bubble pump consumption chronoamperometry(BPCC)method to quantitatively identify the gas diffusion coefficient(D)and effective catalytic sites density(ρEC)of the integrated air cathodes for ZABs.Furthermore,the D andρEC values can instruct consequent optimization on the growth of Co embedded N-doped carbon nanotubes(CoNCNTs)on carbon fiber paper(CFP)and aerophilicity tuning,giving 4 times D and 1.3 timesρEC over the conventional 2D Pt/C-CFP counterparts.As a result,using the CoNCNTs with half-wave potential of merely 0.78 V vs.RHE(Pt/C:0.89 V vs.RHE),the superaerophilic CoNCNTs-CFP cathode-based ZABs exhibited a superior peak power density of 245 mW·cm^(−2) over traditional 2D Pt/C-CFP counterparts,breaking the threshold of 200 mW·cm^(−2).This work reveals the intrinsic feature of the 3D integrated air cathodes by yielding exact D andρEC values,and demonstrates the feasibility of BPCC method for the optimization of integrated electrodes,bypassing trial-and-error strategy.展开更多
基金National Natural Science Foundation of China (Nos. 22078242 and U20A20153)Applied Basic Research Program of Yunnan Province (Nos. 202101BE070001-032 and 202101BH070002)。
文摘Fe-N-C catalysts are widely considered as promising non-precious-metal candidates for electrocatalytic oxygen reduction reaction(ORR),Yet despite their high catalytic activity through rational modulation,challenges remain in their low site density and unsatisfactory mass transfer structure.Herein,we present a structural engineering approach employing a soft-template coating strategy to fabricate a hollow and hierarchically porous N-doped carbon framework anchored with atomically dispersed Fe sites(FeNCh) as an efficient ORR catalyst.The combination of hierarchical porosity and high exterior surface area is proven crucial for exposing more active sites,which gives rise to a remarkable ORR performance with a half-wave potential of 0.902 V in 0.1 m KOH and 0.814 V in 0.1 m HClO_(4),significantly outperforming its counterpart with solid structure and dominance of micropores(FeNC-s).The mass transfer property is revealed by in-situ electrochemical impedance spectroscopy(EIS) measurement.The distribution of relaxation time(DRT) analysis is further introduced to deconvolve the kinetic and mass transport processes,which demonstrates an alleviated mass transport resistance for FeNC-h,validating the effectiveness of structural engineering.This work not only provides an effective structural engineering approach but also contributes to the comprehensive mass transfer evaluation on advanced electrocatalyst for energy conversion applications.
基金Project supported by the Fundamental Research Funds for the Central Universities, China (Grant No. ZYGX2010J045)the National Natural Science Fundation of China and the China Academy of Engineering Physics United Foundation (NSFA) (Grant No. 11076008)
文摘The effect of defect density on the modulation of incident laser waves is investigated. First, based on the actual defect distribution in the subsurface of fused silica, a three-dimensional （3D） grid model of defect sites is constructed. The 3D finite-difference time-domain method is developed to solve the Maxwell equations. Then the electrical field intensity in the vicinity of the defect sites in the subsurface of fused silica is numerically calculated. The relationships between the maximal electrical field intensity in fused silica and the geometry of the defect sites are given. The simulated results reveal that the modulation becomes more remarkable with an increase of the defect density. In addition, the effect of the distribution mode of defects on modulation is discussed. Meanwhile, the underlying physical mechanism is analyzed in detail.
文摘In light of the percentage of Earth’s cloud coverage, heterogeneous ice nucleation in clouds is the most important global-scale pathway. More recent parameterizations of ice nucleation processes in the atmosphere are based on the concept of ice nucleation active surface site density (<i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;">). It is usually assumed that </span><i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;"> is independent of time and aerosol size distribution, </span><i><span style="font-family:Verdana;">i.e.</span></i><span style="font-family:Verdana;"> that the surface properties of aerosols of the same species do not vary with size. However, the independence of </span><i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;"> on aerosol size for every species has been questioned. This study presents the results of ice nucleation processes of ATD laboratory-generated aerosol (particle diameters of 0 - 3 μm). Ice nucleation in the condensation mode was performed in a Dynamic Filter Processing Cham- ber at temperatures of </span><span style="font-family:;" "=""><span style="font-family:Verdana;"><span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">-</span></span><span style="font-family:Verdana;">18<span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">°</span>C and </span><span style="font-family:Verdana;"><span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">-</span></span><span><span style="font-family:Verdana;">22<span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">°</span>C, with a saturation ratio with respect to water of 1.02. Results show that </span><i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;"> increased by lowering the nucleation temperature, and was also dependent on the particle size. The </span><i><span style="font-family:Verdana;">n</span><sub><span style="font-family:Verdana;">s</span></sub></i><span style="font-family:Verdana;"> of particles collected on the filters, after a 0.5 μm D</span><sub><span style="font-family:Verdana;">50</span></sub><span style="font-family:Verdana;"> cut-off cyclone, resulted statistically higher with respect to the values obtained from the particles collected on total filters. The results obtained suggest the need for further investigation of </span><i><span style="font-family:Verdana;">n</span></i><sub><span style="font-family:Verdana;">s</span></sub><span style="font-family:Verdana;"> dependence of same composition aerosol particles with a view to support weather and climate predictions.</span></span></span>
文摘Rational design of Fe and N co-doped carbon catalysts(FeNCs), one promising non-precious cathode catalyst, is critical to commercialization of proton exchange membrane fuel cells. The atomic Fe site density of Fe-NCs is critical to improve catalytic currents approaching industrial levels. One recent research proposes a template-guided strategy to break the limit of Fe site density, and greatly promotes the fuel cell performance.
基金granted by the National Natural Science Foundation of China(22172134,22288102)the National Key Research and Development Program of China(2017YFA0206500)
文摘Iron-nitrogen-carbon(Fe-N-C)catalysts for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)have seriously been hindered by their poor ORR performance of Fe-N-C due to the low active site density(SD)and site utilization.Herein,we reported a melamine-assisted vapor deposition approach to overcome these hindrances.The melamine not only compensates for the loss of nitrogen caused by high-temperature pyrolysis but also effectively etches the carbon substrate,increasing the external surface area and mesoporous porosity of the carbon substrate.These can provide more useful area for subsequent vapor deposition on active sites.The prepared 0.20Mela-FeNC catalyst shows a fourfold higher SD value and site utilization than the FeNC without the treatment of melamine.As a result,0.20Mela-FeNC catalyst exhibits a high ORR activity with a half-wave potential(E_(1/2))of 0.861 V and 12-fold higher ORR mass activity than the FeNC in acidic media.As the cathode in a H_(2)-O_(2)PEMFCs,0.20Mela-FeNC catalyst demonstrates a high peak power density of 1.30 W cm^(-2),outstripping most of the reported Fe-N-C catalysts.The developed melamine-assisted vapor deposition approach for boosting the SD and utilization of Fe-N-C catalysts offers a new insight into high-performance ORR electrocatalysts.
基金Natural Science Foundation of Xinjiang Uygur Autonomous Region,Grant/Award Number:2023D01C11National Natural Science Foundation of China,Grant/Award Numbers:22369019,U2003216+2 种基金Special Projects on Regional Collaborative Innovation-SCO Science and Technology Partnership Program,International Science and Technology Cooperation Program,Grant/Award Number:2022E01020Tianshan Talent Training Program,Grant/Award Number:2023TSYCLJ0019National Key Research and Development Program of China,Grant/Award Numbers:2022YFB4101600,2022YFB4101601。
文摘The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.
基金supported by the National Natural Science Foundation of China(21706090,51772135 and 51872124)the Ministry of Education of China(6141A02022516)+4 种基金the Natural Science Foundation of Guangdong Province(2014A030306010)the Natural Science Foundation of Guangzhou(201904010049)Jinan University(88016105)the Open Experimental Project by GETRC of Graphene-like Materials and Products(202001)the Fundamental Research Foundation for the Central Universities(21617326 and 11619103).
文摘Structural collapse and aggregation during the annealing process are the key obstacles for MOF-derived electrocatalysts,which will lead to a decrease in the active site density and stability of the electrocatalyst.The atomic layer deposition(ALD)technique can form dense and uniform thin films wrapping any complex 3D structure due to the self-limiting surface chemistry reactions.Herein,we developed a confinement strategy based on the ALD technique to prepare a durable Fe2Ni MIL 88-derived electrocatalyst(NiFe/NC@Al_(2)O_(3)-2).Due to the protection of the Al_(2)O_(3) layer deposited by the ALD technique,the asprepared catalyst retained the original rod-like structure of MIL 88 after the annealing process.With the confinement effect of the Al_(2)O_(3) nanolayer,the optimized NiFe/NC@Al_(2)O_(3)-2 exhibited remarkable electrocatalytic properties in the oxygen evolution reaction(OER)with low overpotentials of 270 and 391 mV at 10 and 100 mA cm^(-2),respectively.Furthermore,the catalyst obtained an excellent durability over 100 hours at a high current density of 50 mA cm^(-2),which is superior to those of many previously reported NiFe-based electrocatalysts.The ALD-assisted confinement strategy highlights a novel method to synthesize structure-and morphology-retained MOF-derived catalysts with excellent activity and stability at high current densities.
文摘The surface acidity of synthetic amorphous AI hydroxide was determined by acid/base titration with several complementary methods including solution analyses of the reacted solutions and XRD characterization of the reacted solids. The synthetic specimen was characterized to be the amorphous material showing four broad peaks in XRD pattern. XRD analyses of reacted solids after the titration experiments showed that amorphous AI hydroxide rapidly transformed to crystalline bayerite at the alkaline condition （pH〉10）. The solution analyses after and during the titration Ksp=^aAl^3＋/aH^＋^3 ,was 10^10.3. The amount of consumption of added acid or base during the titration experiment was attributed to both the protonation/deprotonation of dissolved AI species and surface hydroxyl group. The surface acidity constants, surface hydroxyl density and specific surface area were estimated by FITEQL 4.0.
基金support from the Ministry of Business,Innovation and Employment for a Catalyst Fund grant(MAUX 1609)the University of Auckland Faculty Research Development Fund,the MacDiarmid Institute for Advanced Materials and Nanotechnology,and a generous Philanthropic donation from Greg and Kathryn Trounson.The authors are also grateful for financial support from the National Key Projects for Fundamental Research and Development of China(2017YFA0206904,2017YFA0206900)+1 种基金the National Natural Science Foundation of China(51825205,51772305,21871279)the Beijing Natural Science Foundation(2191002).
文摘Fe-N-C catalysts represent very promising cathode catalysts for polymer electrolyte fuel cells,owing to their outstanding activity for the oxygen reduction reaction(ORR),especially in alkaline media.In this review,we summarize recent advances in the design and synthesis of Fe-N-C catalysts rich in highly dispersed FeNx active sites.Special emphasis is placed on emerging strategies for tuning the electronic structure of the Fe atoms to enhance the ORR activity,and also maximizing the surface concentration of FeNx sites that are catalytically accessible during ORR.While great progress has been made over the past 5 years in the development of Fe-N-C catalyst for ORR,significant technical obstacles still need to be overcome to enable the large-scale application of Fe-N-C materials as cathode catalysts in real-world fuel cells.
基金supported by the National Natural Science Foundation of China(Nos.21935001 and 22379005)the Beijing Natural Science Foundation(No.Z210016)+3 种基金the National Key Research and Development Program of China(No.2018YFA0702002)Xinjiang Youth Science and Technology Top Talent Project(No.2022TSYCCX0053)Xinjiang Key Research and Development Project(No.2022B01003-2)the Fundamental Research Funds for the Central Universities,and the long-term subsidy mechanism from the Ministry of Finance and the Ministry of Education of PRC.
文摘Zn-air batteries(ZABs)as a potential energy conversion system suffer from low power density(typically≤200 mW·cm^(−2)).Recently,three-dimensional(3D)integrated air cathodes have demonstrated promising performance over traditional twodimensional(2D)plane ones,which is ascribed to enriched active sites and enhanced diffusion,but without experimental evidence.Herein,we applied a bubble pump consumption chronoamperometry(BPCC)method to quantitatively identify the gas diffusion coefficient(D)and effective catalytic sites density(ρEC)of the integrated air cathodes for ZABs.Furthermore,the D andρEC values can instruct consequent optimization on the growth of Co embedded N-doped carbon nanotubes(CoNCNTs)on carbon fiber paper(CFP)and aerophilicity tuning,giving 4 times D and 1.3 timesρEC over the conventional 2D Pt/C-CFP counterparts.As a result,using the CoNCNTs with half-wave potential of merely 0.78 V vs.RHE(Pt/C:0.89 V vs.RHE),the superaerophilic CoNCNTs-CFP cathode-based ZABs exhibited a superior peak power density of 245 mW·cm^(−2) over traditional 2D Pt/C-CFP counterparts,breaking the threshold of 200 mW·cm^(−2).This work reveals the intrinsic feature of the 3D integrated air cathodes by yielding exact D andρEC values,and demonstrates the feasibility of BPCC method for the optimization of integrated electrodes,bypassing trial-and-error strategy.
