Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Her...Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.展开更多
Low-cost catalysts with high activity are in immediate demand for energy storage and conversion devices.In this study,polyvinyl pyrrolidone was used as a complexing agent to synthesize La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)...Low-cost catalysts with high activity are in immediate demand for energy storage and conversion devices.In this study,polyvinyl pyrrolidone was used as a complexing agent to synthesize La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3)(LSCF)perovskite oxide.The obtained porous layered LSCF has a large specific surface area of 23.74 m^(2)/g,four times higher than that prepared by the traditional sol-gel method(5.08 m^(2)/g).The oxygen reduction reaction activity of the oxide in 0.1 mol/L KOH solution was studied using a rotating ring-disk electrode.In the tests,the initial potential of 0.88 V(vs.reversible hydrogen electrode)and the limiting diffusion current density of 5.02 mA/cm^(2)were obtained at 1600 r/min.Therefore,higher catalytic activity and stability were demonstrated,compared with the preparation of LSCF perovskite oxide by the traditional method.展开更多
A red-blood-cell-like nitrogen-doped porous carbon catalyst with a high nitrogen content(9.81%)and specific surface area(631.46 m^2/g)was prepared by using melamine cyanuric acid and glucose as sacrificial template an...A red-blood-cell-like nitrogen-doped porous carbon catalyst with a high nitrogen content(9.81%)and specific surface area(631.46 m^2/g)was prepared by using melamine cyanuric acid and glucose as sacrificial template and carbon source,respectively.This catalyst has a comparable onset potential and a higher diffusion-limiting current density than the commercial 20 wt%Pt/C catalyst in alkaline electrolyte.The oxygen reduction reaction mechanism catalyzed by this catalyst is mainly through a 4e pathway process.The excellent catalytic activity could origin from the synergistic effect of the in-situ doped nitrogen(up to 9.81%)and three-dimensional(3D)porous network structure with high specific surface area,which is conducive to the exposure of more active sites.It is interesting to note that the catalytic activity of oxygen reduction strongly depends on the proportion of graphic N rather than the total N content.展开更多
Rational design and synthesis of non-precious-metal catalyst plays an important role in improving the activity and stability for oxygen reduction reaction(ORR)but remains a major challenge.In this work,we used a facil...Rational design and synthesis of non-precious-metal catalyst plays an important role in improving the activity and stability for oxygen reduction reaction(ORR)but remains a major challenge.In this work,we used a facile approach to synthesize iron nanoparticles encapsulated in nitrogen-doped porous carbon materials(Fe@N-C)from functionalized metal-organic frameworks(MOFs,MET-6).Embedding Fe nanoparticles into the carbon skeleton increases the graphitization degree and the proportion of graphitic N as well as promotes the formation of mesopores in the catalyst.The Fe@N-C-30 catalyst showed the excellent ORR activity in alkaline solutions(E^(0)=0.97 V vs.RHE,E1/2=0.89 V vs.RHE).Moreover,the Fe@N-C-30 catalyst exhibited better methanol resistance and long-term stability when compared to commercial Pt/C.The superior ORR performance could be attributed to the combination of high electrochemical surface area,relative high portion of graphitic-N,unique porous structures and the synergistic effect between the encapsulated Fe particles and the N-doped carbon layer.This work provides a promising method to construct efficient non-precious-metal ORR catalyst through MOFs.展开更多
基金supported by National Natural Science Foundation of China(No.523B2070,No.52225606).
文摘Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.
基金Project(20192BAB216015)supported by the Science and Technology Program of Jiangxi Province,ChinaProjects(GJJ180464,GJJ171499)supported by the Science and Technology Program of Education Department of Jiangxi Province,China+2 种基金Project(jxxjbs17057)supported by the Scientific Research Foundation of Jiangxi University of Science and Technology,ChinaProject([2018]50)supported by the Key R&D Programs of Science and Technology Project of Ganzhou City,ChinaProject([2017]179)supported by the Science and Technology Project of Ganzhou City,China。
文摘Low-cost catalysts with high activity are in immediate demand for energy storage and conversion devices.In this study,polyvinyl pyrrolidone was used as a complexing agent to synthesize La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3)(LSCF)perovskite oxide.The obtained porous layered LSCF has a large specific surface area of 23.74 m^(2)/g,four times higher than that prepared by the traditional sol-gel method(5.08 m^(2)/g).The oxygen reduction reaction activity of the oxide in 0.1 mol/L KOH solution was studied using a rotating ring-disk electrode.In the tests,the initial potential of 0.88 V(vs.reversible hydrogen electrode)and the limiting diffusion current density of 5.02 mA/cm^(2)were obtained at 1600 r/min.Therefore,higher catalytic activity and stability were demonstrated,compared with the preparation of LSCF perovskite oxide by the traditional method.
基金Projects(21571189,21771062)supported by the National Natural Science Foundation of ChinaProjects(2016TP1007,2017TP1001)supported by the Hunan Provincial Science and Technology Plan,China+1 种基金Project(150110005)supported by the Fundamental Research and Innovation Project for Postgraduate of Hunan Province,ChinaProjects(2016CL04,2017CL17)supported by the Opening Project of Material Corrosion and Protection Key Laboratory of Sichuan Province,China
文摘A red-blood-cell-like nitrogen-doped porous carbon catalyst with a high nitrogen content(9.81%)and specific surface area(631.46 m^2/g)was prepared by using melamine cyanuric acid and glucose as sacrificial template and carbon source,respectively.This catalyst has a comparable onset potential and a higher diffusion-limiting current density than the commercial 20 wt%Pt/C catalyst in alkaline electrolyte.The oxygen reduction reaction mechanism catalyzed by this catalyst is mainly through a 4e pathway process.The excellent catalytic activity could origin from the synergistic effect of the in-situ doped nitrogen(up to 9.81%)and three-dimensional(3D)porous network structure with high specific surface area,which is conducive to the exposure of more active sites.It is interesting to note that the catalytic activity of oxygen reduction strongly depends on the proportion of graphic N rather than the total N content.
基金supported by the National Natural Science Foundation of China(Grants 22002121,22172121)the National Undergraduate Training Program for Innovation and Entrepreneurship(Grant S202210656087).
文摘Rational design and synthesis of non-precious-metal catalyst plays an important role in improving the activity and stability for oxygen reduction reaction(ORR)but remains a major challenge.In this work,we used a facile approach to synthesize iron nanoparticles encapsulated in nitrogen-doped porous carbon materials(Fe@N-C)from functionalized metal-organic frameworks(MOFs,MET-6).Embedding Fe nanoparticles into the carbon skeleton increases the graphitization degree and the proportion of graphitic N as well as promotes the formation of mesopores in the catalyst.The Fe@N-C-30 catalyst showed the excellent ORR activity in alkaline solutions(E^(0)=0.97 V vs.RHE,E1/2=0.89 V vs.RHE).Moreover,the Fe@N-C-30 catalyst exhibited better methanol resistance and long-term stability when compared to commercial Pt/C.The superior ORR performance could be attributed to the combination of high electrochemical surface area,relative high portion of graphitic-N,unique porous structures and the synergistic effect between the encapsulated Fe particles and the N-doped carbon layer.This work provides a promising method to construct efficient non-precious-metal ORR catalyst through MOFs.
