γ-MnO2 nanorod-assembled hierarchical micro-spheres with abundant oxygen defects are synthesized by a simple thermal treatment approach as oxygen reduction electrocatalysts for Al(aluminum)-air batteries. The rich ox...γ-MnO2 nanorod-assembled hierarchical micro-spheres with abundant oxygen defects are synthesized by a simple thermal treatment approach as oxygen reduction electrocatalysts for Al(aluminum)-air batteries. The rich oxygen vacancies on the surface of γ-MnO2 are verified by morphology, structure,electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS) results. The oxygen reduction reaction(ORR) electrocatalytic activity of γ-MnO2 is significantly improved by the incoming oxygen vacancies. The γ-MnO2 nanorod-assembled hierarchical micro-spheres calcined under 300 °C in Ar atmosphere show the best ORR performance. The primary Al-air batteries using γ-MnO2 catalysts as the cathode, which demonstrates excellent peal power density of 318 m W cm^(-2) when applying theγ-MnO2 catalysts with optimal amount of oxygen vacancies.展开更多
Carbon supported Pt-Co alloys are among the most promising electrocatalysts towards oxygen reduction reaction(ORR)for the application in low temperature fuel cells and beyond,thus their facile and green synthesis is h...Carbon supported Pt-Co alloys are among the most promising electrocatalysts towards oxygen reduction reaction(ORR)for the application in low temperature fuel cells and beyond,thus their facile and green synthesis is highly demanded.Herein we initially report an alternate aqueous phase one-pot synthesis of such catalysts(containing nominally ca.20 wt.%Pt)based on dimethylamine borane(DMAB)reduction.The as-obtained electrocatalyst(denoted as Pt3Co/C-DMAB)is compared with the ones obtained by NaBH4 and N2H4·H2O reduction(denoted as Pt3Co/C-NaBH4 and Pt3Co/C-N2H4·H2O,respectively)as well as a commercial Pt/C,in terms of the structure and electrocatalytic property.It turns out that Pt3Co/C-DMAB exhibits the highest ORR performance among all the tested samples in an O2-saturated 0.1 mol/L HClO4,with the mass activity(specific activity)ca.4(6)times as large as that for Pt/C.After 10000 cycles of the accelerated degradation test,the half-wave potential for ORR on Pt3Co/C-DMAB decreases only by 4 mV,in contrast to 24 mV for that on Pt/C.Pt3Co/C-NaBH4 or Pt3Co/C-N2H4·H2O shows a specific activity comparable to that for Pt3Co/C-DMAB,but a mass activity similar to that for Pt/C.ICP-AES,TEM,XRD and XPS characterizations indicate that Pt3Co nanoparticles are well-dispersed and alloyed with a mean particle size of ca.3.4±0.4 nm,contributing to the prominent electrocatalytic performance of Pt3Co/C-DMAB.This simple aqueous synthetic route may provide an alternate opportunity for developing efficient practical electrocatalysts for ORR.展开更多
A highly active nitrogen-doped catalyst with a unique red-blood-cell（RBC） like structure is reported for oxygen reduction reaction（ORR）.The catalyst Fe,N-C@carbon-900 was prepared by pyrolysis of the polyaniline（...A highly active nitrogen-doped catalyst with a unique red-blood-cell（RBC） like structure is reported for oxygen reduction reaction（ORR）.The catalyst Fe,N-C@carbon-900 was prepared by pyrolysis of the polyaniline（PANl） and polystyrene（PS） composites with adsorption of ferric ion on the shell of sphere structure at 900℃.Fe,N-C@carbon-900 with a unique RBC-like structure provides plenty of catalytic sites combining the electrical conductivity of the carbon sphere with the catalytic activity of the nitrogen-doped layer.The four-electron reduction pathway is selected for the catalyst Fe,N-C@carbon-900.The catalyst exhibit the ORR E_（onset） at 0.87 V（potentials is versus to reversible hydrogen electrode（RHE））,E_（1/2） at 0.78 V and high diffusion-limiting current density（5.20mA/cm^2）.Furthermore,this work indicates that both N and Fe accounted for high activity of the catalyst Fe,N-C@carbon-900 toward the oxygen reduction process.It is concluded that Fe and N exhibit synergistically promotion in the ORR activity for the catalyst Fe,N-C@carbon-900.We also provide a rational design of electrocatalysts with high ORR activity to further clarify the essential ORR sites of heteroatom doped carbon materials for fuel cells and metal-air battery applications.展开更多
The exploration of high-efficiency,long-durability,and cost-effectiveness transition metal doped carbon materials to replace the commercial Pt/C in oxygen reduction reaction(ORR)is greatly desirable for promoting the ...The exploration of high-efficiency,long-durability,and cost-effectiveness transition metal doped carbon materials to replace the commercial Pt/C in oxygen reduction reaction(ORR)is greatly desirable for promoting the advancement of sustainable energy devices.Herein,the Fe_(3)N and FeCo alloy decorated N-doped carbon hybrid material(denoted Fe_(3)N-FeCo@NC)is prepared and applied as the ORR catalyst,which is derived from the two-step pyrolysis of an intriguing complex consisted of metal-coordinated porous polydopamine(PDA)nanospheres(i.e.,Fe-PDA@Co)and melamine.The resulting Fe_(3)N-FeCo@NC delivers outstanding ORR activity with an onset potential(E_(on))of 1.05 V,a half-wave potential(E_(1/2))of 0.89 V,as well as excellent long-term stability and methanol resistance over Pt/C.Interestingly,the home-made Zn-air battery with Fe_(3)N-FeCo@NC as the air-cathode demonstrates much higher open-circuit voltage(1.50 vs.1.48 V),power density(141 vs.113 mW·cm^(−2))and specific capacity(806.6 vs.660.6 mAh·g^(−1)_(Zn))than those of Pt/C counterpart.Such a remarkable ORR activity of Fe_(3)N-FeCo@NC may stem from the synergistic effect of Fe_(3)N and FeCo active species,the large surface area,the hierarchical porous structure and the exceptional sphere/sheet hybridized architecture.展开更多
基金supported by the National Natural Science Foundation of China (21975163, 51902204)。
文摘γ-MnO2 nanorod-assembled hierarchical micro-spheres with abundant oxygen defects are synthesized by a simple thermal treatment approach as oxygen reduction electrocatalysts for Al(aluminum)-air batteries. The rich oxygen vacancies on the surface of γ-MnO2 are verified by morphology, structure,electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS) results. The oxygen reduction reaction(ORR) electrocatalytic activity of γ-MnO2 is significantly improved by the incoming oxygen vacancies. The γ-MnO2 nanorod-assembled hierarchical micro-spheres calcined under 300 °C in Ar atmosphere show the best ORR performance. The primary Al-air batteries using γ-MnO2 catalysts as the cathode, which demonstrates excellent peal power density of 318 m W cm^(-2) when applying theγ-MnO2 catalysts with optimal amount of oxygen vacancies.
基金supported by the National Basic Research Program of China(973 Program,2015CB932303)the National Natural Science Foundation of China(NSFC)(21733004 and 21473039)the International Cooperation Program of Shanghai Science and Technology Committee(STCSM)(17520711200)~~
文摘Carbon supported Pt-Co alloys are among the most promising electrocatalysts towards oxygen reduction reaction(ORR)for the application in low temperature fuel cells and beyond,thus their facile and green synthesis is highly demanded.Herein we initially report an alternate aqueous phase one-pot synthesis of such catalysts(containing nominally ca.20 wt.%Pt)based on dimethylamine borane(DMAB)reduction.The as-obtained electrocatalyst(denoted as Pt3Co/C-DMAB)is compared with the ones obtained by NaBH4 and N2H4·H2O reduction(denoted as Pt3Co/C-NaBH4 and Pt3Co/C-N2H4·H2O,respectively)as well as a commercial Pt/C,in terms of the structure and electrocatalytic property.It turns out that Pt3Co/C-DMAB exhibits the highest ORR performance among all the tested samples in an O2-saturated 0.1 mol/L HClO4,with the mass activity(specific activity)ca.4(6)times as large as that for Pt/C.After 10000 cycles of the accelerated degradation test,the half-wave potential for ORR on Pt3Co/C-DMAB decreases only by 4 mV,in contrast to 24 mV for that on Pt/C.Pt3Co/C-NaBH4 or Pt3Co/C-N2H4·H2O shows a specific activity comparable to that for Pt3Co/C-DMAB,but a mass activity similar to that for Pt/C.ICP-AES,TEM,XRD and XPS characterizations indicate that Pt3Co nanoparticles are well-dispersed and alloyed with a mean particle size of ca.3.4±0.4 nm,contributing to the prominent electrocatalytic performance of Pt3Co/C-DMAB.This simple aqueous synthetic route may provide an alternate opportunity for developing efficient practical electrocatalysts for ORR.
基金partially supported by National Natural Science Foundation of China(Nos.51273158,21303131)
文摘A highly active nitrogen-doped catalyst with a unique red-blood-cell（RBC） like structure is reported for oxygen reduction reaction（ORR）.The catalyst Fe,N-C@carbon-900 was prepared by pyrolysis of the polyaniline（PANl） and polystyrene（PS） composites with adsorption of ferric ion on the shell of sphere structure at 900℃.Fe,N-C@carbon-900 with a unique RBC-like structure provides plenty of catalytic sites combining the electrical conductivity of the carbon sphere with the catalytic activity of the nitrogen-doped layer.The four-electron reduction pathway is selected for the catalyst Fe,N-C@carbon-900.The catalyst exhibit the ORR E_（onset） at 0.87 V（potentials is versus to reversible hydrogen electrode（RHE））,E_（1/2） at 0.78 V and high diffusion-limiting current density（5.20mA/cm^2）.Furthermore,this work indicates that both N and Fe accounted for high activity of the catalyst Fe,N-C@carbon-900 toward the oxygen reduction process.It is concluded that Fe and N exhibit synergistically promotion in the ORR activity for the catalyst Fe,N-C@carbon-900.We also provide a rational design of electrocatalysts with high ORR activity to further clarify the essential ORR sites of heteroatom doped carbon materials for fuel cells and metal-air battery applications.
基金upported by the National Natural Science Foundation of China(No.52173207)the Natural Science Foundation of Hunan Province(Nos.2022JJ30563,2020JJ5542)the Outstanding Youth Fund Project of Hunan Provincial Department of Education(No.21B0119).
文摘The exploration of high-efficiency,long-durability,and cost-effectiveness transition metal doped carbon materials to replace the commercial Pt/C in oxygen reduction reaction(ORR)is greatly desirable for promoting the advancement of sustainable energy devices.Herein,the Fe_(3)N and FeCo alloy decorated N-doped carbon hybrid material(denoted Fe_(3)N-FeCo@NC)is prepared and applied as the ORR catalyst,which is derived from the two-step pyrolysis of an intriguing complex consisted of metal-coordinated porous polydopamine(PDA)nanospheres(i.e.,Fe-PDA@Co)and melamine.The resulting Fe_(3)N-FeCo@NC delivers outstanding ORR activity with an onset potential(E_(on))of 1.05 V,a half-wave potential(E_(1/2))of 0.89 V,as well as excellent long-term stability and methanol resistance over Pt/C.Interestingly,the home-made Zn-air battery with Fe_(3)N-FeCo@NC as the air-cathode demonstrates much higher open-circuit voltage(1.50 vs.1.48 V),power density(141 vs.113 mW·cm^(−2))and specific capacity(806.6 vs.660.6 mAh·g^(−1)_(Zn))than those of Pt/C counterpart.Such a remarkable ORR activity of Fe_(3)N-FeCo@NC may stem from the synergistic effect of Fe_(3)N and FeCo active species,the large surface area,the hierarchical porous structure and the exceptional sphere/sheet hybridized architecture.
