Introducing catalytically-active Fe and N into carbon materials results in promising FeNC catalysts for oxygen reduction reaction. However, the doped Fe and N species are frequently subject to heavy loss in a traditio...Introducing catalytically-active Fe and N into carbon materials results in promising FeNC catalysts for oxygen reduction reaction. However, the doped Fe and N species are frequently subject to heavy loss in a traditional carbonization process owing to Fe agglomeration and evaporation of N-contained small molecules. Besides, pyrolysis may make materials sintering which embeds a large number of active sites in the bulk phase and impedes direct exposure of reactive centers to the reactants. We here report that when calcinations, the addition of ZnCl2, an ordinary salt with very wide melting temperature range well covering the carbonization process of the precursor iron porphyrin, can significantly enhance the doping level of the active species and simultaneously create highly porous structures for FeNC catalysts. The obtained FeNC demonstrates ultrahigh catalytic activities even significantly better than Pt/C in oxygen reduction reaction.展开更多
Through in situ redox deposition and growth of MnO2 nanostructures on hierarchically porous carbon （HPC）, a MnOR/HPC hybrid has been synthesized and employed as cathode catalyst for non-aqueous Li-O2 batteries. Owin...Through in situ redox deposition and growth of MnO2 nanostructures on hierarchically porous carbon （HPC）, a MnOR/HPC hybrid has been synthesized and employed as cathode catalyst for non-aqueous Li-O2 batteries. Owing to the mild synthetic conditions, MnO2 was uniformly distributed on the surface of the carbon support, without destroying the hierarchical porous nanostructure. As a result, the as-prepared MnO2/HPC nanocomposite exhibits excellent Li-O2 battery performance, including low charge overpotential, good rate capacity and long cycle stability up to 300 cycles with controlling capacity of 1,000 mAh·g^-1. A combination of the multi-scale porous network of the shell-connected carbon support and the highly dispersed MnO2 nanostructure benefits the transportation of ions, oxygen and electrons and contributes to the excellent electrode performance.展开更多
Electrocatalytic reduction of CO_2 is a promising route for energy storage and utilization. Herein we synthesized SnO_2 nanosheets and supported them on N-doped porous carbon (N-PC) by electrodeposition for the first ...Electrocatalytic reduction of CO_2 is a promising route for energy storage and utilization. Herein we synthesized SnO_2 nanosheets and supported them on N-doped porous carbon (N-PC) by electrodeposition for the first time. The SnO_2 and N-PC in the SnO_2@N-PC composites had exellent synergistic effect for electrocatalytic reduction of CO_2 to HCOOH. The Faradaic efficiency of HCOOH could be as high as 94.1% with a current density of 28.4 mA cm-2 in ionic liquid-MeCN system. The reaction mechanism was proposed on the basis of some control experiments. This work opens a new way to prepare composite electrode for electrochemical reduction of CO_2.展开更多
Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embed...Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon （Pd@CMK-3） has been prepared by a strategy involving immersion, ammonia- hydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd（0） and Pd（I1） species co-exist and were embedded in the matrix of the porous carbon （CMK-3）. The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency （TOF） could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 ℃. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.展开更多
Developing efficient metal-free bi-functional electrocatalysts is required to reduce costs and improve the slow oxygen reduction reaction （ORR） and oxygen evo- lution reaction （OER） kinetics in electrochemical sys...Developing efficient metal-free bi-functional electrocatalysts is required to reduce costs and improve the slow oxygen reduction reaction （ORR） and oxygen evo- lution reaction （OER） kinetics in electrochemical systems. Porous N-doped carbon nanotubes （NCNTs） were fabri- cated by KOH activation and pyrolysis of polypyrrole nanotubes. The NCNTs possessed a large surface area of more than 1,000 m2 g-1. NCNT electrocatalysts, particu- larly those annealed at 900 ℃, exhibited excellent ORR electrocatalytic performance. Specifically, they yielded a more positive onset potential, higher current density, and long-term operation stability in alkaline media, when compared with a commercially available 20 wt% Pt/C catalyst. This resulted from the synergetic effect between the dominant pyridinic/graphitic-N species and the porous tube structures. The NCNT electrocatalyst also exhibited good performance for the OER. The metal-free porous nitrogen-doped carbon nanomaterials were prepared from low cost and environmentally friendly precursors. They are potential alternatives to Pt/C catalysts, for electrochemical energy conversion and storage.展开更多
Chemical conversion of carbon dioxide(CO2)to value-added useful chemicals like cyclic carbonates represents one potential solution to climate warming.Here,a kind of porous organic polymer(HAT-TP)with large surface are...Chemical conversion of carbon dioxide(CO2)to value-added useful chemicals like cyclic carbonates represents one potential solution to climate warming.Here,a kind of porous organic polymer(HAT-TP)with large surface area and excellent carbon dioxide uptake capacity is prepared via a condensation reaction to introduce hexaazatriphenylene(HAT)units into triptycene(TP)-based microporous polymer.HAT-TP can coordinate with zinc ions,and the resulting polymer(Zn/HAT-TP)can be utilized as an efficient recyclable catalyst for chemical conversion of CO2 into cyclic carbonates with epoxides.展开更多
文摘Introducing catalytically-active Fe and N into carbon materials results in promising FeNC catalysts for oxygen reduction reaction. However, the doped Fe and N species are frequently subject to heavy loss in a traditional carbonization process owing to Fe agglomeration and evaporation of N-contained small molecules. Besides, pyrolysis may make materials sintering which embeds a large number of active sites in the bulk phase and impedes direct exposure of reactive centers to the reactants. We here report that when calcinations, the addition of ZnCl2, an ordinary salt with very wide melting temperature range well covering the carbonization process of the precursor iron porphyrin, can significantly enhance the doping level of the active species and simultaneously create highly porous structures for FeNC catalysts. The obtained FeNC demonstrates ultrahigh catalytic activities even significantly better than Pt/C in oxygen reduction reaction.
文摘Through in situ redox deposition and growth of MnO2 nanostructures on hierarchically porous carbon （HPC）, a MnOR/HPC hybrid has been synthesized and employed as cathode catalyst for non-aqueous Li-O2 batteries. Owing to the mild synthetic conditions, MnO2 was uniformly distributed on the surface of the carbon support, without destroying the hierarchical porous nanostructure. As a result, the as-prepared MnO2/HPC nanocomposite exhibits excellent Li-O2 battery performance, including low charge overpotential, good rate capacity and long cycle stability up to 300 cycles with controlling capacity of 1,000 mAh·g^-1. A combination of the multi-scale porous network of the shell-connected carbon support and the highly dispersed MnO2 nanostructure benefits the transportation of ions, oxygen and electrons and contributes to the excellent electrode performance.
基金supported by the National Natural Science Foundation of China (21673248, 21533011)the National Key Research and Development Program of China (2017YFA0403102)Chinese Academy of Sciences (QYZDY-SSW-SLH013)
文摘Electrocatalytic reduction of CO_2 is a promising route for energy storage and utilization. Herein we synthesized SnO_2 nanosheets and supported them on N-doped porous carbon (N-PC) by electrodeposition for the first time. The SnO_2 and N-PC in the SnO_2@N-PC composites had exellent synergistic effect for electrocatalytic reduction of CO_2 to HCOOH. The Faradaic efficiency of HCOOH could be as high as 94.1% with a current density of 28.4 mA cm-2 in ionic liquid-MeCN system. The reaction mechanism was proposed on the basis of some control experiments. This work opens a new way to prepare composite electrode for electrochemical reduction of CO_2.
文摘Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon （Pd@CMK-3） has been prepared by a strategy involving immersion, ammonia- hydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd（0） and Pd（I1） species co-exist and were embedded in the matrix of the porous carbon （CMK-3）. The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency （TOF） could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 ℃. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.
基金This work was supported by the National Nat- ural Science Foundation of China （51273008, 51473008）, and the National Basic Research Program of China （2012CB933200）.
文摘Developing efficient metal-free bi-functional electrocatalysts is required to reduce costs and improve the slow oxygen reduction reaction （ORR） and oxygen evo- lution reaction （OER） kinetics in electrochemical systems. Porous N-doped carbon nanotubes （NCNTs） were fabri- cated by KOH activation and pyrolysis of polypyrrole nanotubes. The NCNTs possessed a large surface area of more than 1,000 m2 g-1. NCNT electrocatalysts, particu- larly those annealed at 900 ℃, exhibited excellent ORR electrocatalytic performance. Specifically, they yielded a more positive onset potential, higher current density, and long-term operation stability in alkaline media, when compared with a commercially available 20 wt% Pt/C catalyst. This resulted from the synergetic effect between the dominant pyridinic/graphitic-N species and the porous tube structures. The NCNT electrocatalyst also exhibited good performance for the OER. The metal-free porous nitrogen-doped carbon nanomaterials were prepared from low cost and environmentally friendly precursors. They are potential alternatives to Pt/C catalysts, for electrochemical energy conversion and storage.
基金supported by the National Natural Science Foundation of China (21875079 and 21672078)
文摘Chemical conversion of carbon dioxide(CO2)to value-added useful chemicals like cyclic carbonates represents one potential solution to climate warming.Here,a kind of porous organic polymer(HAT-TP)with large surface area and excellent carbon dioxide uptake capacity is prepared via a condensation reaction to introduce hexaazatriphenylene(HAT)units into triptycene(TP)-based microporous polymer.HAT-TP can coordinate with zinc ions,and the resulting polymer(Zn/HAT-TP)can be utilized as an efficient recyclable catalyst for chemical conversion of CO2 into cyclic carbonates with epoxides.
