Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catal...Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catalytic system exhibited a broad substrate scope and excellent regi‐oselectivity, as well as being amenable to gram‐scale synthesis. This MnOx‐N@C catalyst also showed good reusability and was successfully recycled six times without any significant loss of activity.展开更多
Transition metal catalysts M-N-C（M = Co,Fe,Mn） were synthesized by a template-free method by heating meso-tetraphenyl porphyrins（i.e.CoTPP,FeTPPCl,MnTPPCl） precursors.The catalysts were characterized by N2 adsorpt...Transition metal catalysts M-N-C（M = Co,Fe,Mn） were synthesized by a template-free method by heating meso-tetraphenyl porphyrins（i.e.CoTPP,FeTPPCl,MnTPPCl） precursors.The catalysts were characterized by N2 adsorption-desorption,thermogravimetry,high-resolution transmission electron microscopy,and Raman and X-ray photoelectron spectroscopy.The selective oxidation of ethylbenzene with molecular oxygen under a solvent-free condition was carried out to explore the catalytic performance of the M-N-Cs,which exhibited different catalytic performance.That was ascribed to the difference in M（Co,Fe,Mn） and different graphitization degree forming during the heating process,in which M（Co,Fe,Mn） might have different catalytic activity on the formation of the M-N-C catalyst.All the M-N-C composites had remarkable recyclability in the selective oxidation of ethylbenzene.展开更多
Cryptomelane has been widely applied as catalyst in oxidation reactions due to its excellent redox properties and low cost.Here,a novel one-pot hydrothermal synthesis using a potassium permanganate aqueous solution as...Cryptomelane has been widely applied as catalyst in oxidation reactions due to its excellent redox properties and low cost.Here,a novel one-pot hydrothermal synthesis using a potassium permanganate aqueous solution as precursor and ethanol as reducing agent has successfully been developed to obtain cryptomelane nano-oxides.This synthetic route makes it possible to control the amount of potassium incorporated into the structure of the cryptomelane by selecting the appropriate synthesis temperature and ethanol initial concentration.Taking advantage of this approach,the effect of potassium concentration on the structural stability and reducibility of the cryptomelane,which are poorly discussed in the literature,has been studied.We have observed that samples with low content of potassium(~11%)show high conversions of CO to CO2 especially at low temperatures.The lower activity of the samples with high K contents(~16%)can be ascribed to the beneficial effect of K on the structural stability of cryptomelane in detriment of labile oxygen on cryptomelane surface.展开更多
Development of cheap,abundant and noblemetal-free materials as high efficient oxygen reduction electrocatalysts is crucial for future energy storage system. Here,one-dimensional（1D） MnO N-doped carbon nanofibers（Mn...Development of cheap,abundant and noblemetal-free materials as high efficient oxygen reduction electrocatalysts is crucial for future energy storage system. Here,one-dimensional（1D） MnO N-doped carbon nanofibers（MnO-NCNFs） were successfully developed by electrospinning combined with high temperature pyrolysis. The MnO-NCNFs exhibit promising electrochemical performance,methanol tolerance,and durability in alkaline medium. The outstanding electrocatalytic activity is mainly attributed to several issues.First of all,the uniform 1D fiber structure and the conductive network could facilitate the electron transport. Besides,the introduction of Mn into the precursor can catalyze the transformation of amorphous carbon to graphite carbon,while the improved graphitization means better conductivity,beneficial for the enhancement of catalytic activity for oxygen reduction reaction（ORR）. Furthermore,the porous structure and high surface area can effectively decrease the mass transport resistance and increase the exposed ORR active sites,thus improve utilization efficiency and raise the quantity of exposed ORR active sites. The synergistic effect of MnO and NCNFs matrix,which enhances charge transfer,adsorbent transport,and delivers efficiency in the electrolyte solution,ensures the high ORR performance of MnO-NCNFs.展开更多
Tubular nanocomposite with interconnected MnO2 nanoflakes coated on MWCNTs(MWCNTs@MnO2)was fabricated by an aqueous solution method at 80°C.Scanning electron microscopy,X-ray diffraction and galvanostatic charge-...Tubular nanocomposite with interconnected MnO2 nanoflakes coated on MWCNTs(MWCNTs@MnO2)was fabricated by an aqueous solution method at 80°C.Scanning electron microscopy,X-ray diffraction and galvanostatic charge-discharge tests were used to characterize the structures and electrochemical performances of the as-prepared nanocomposite.The capacity reaches 1233.6 mA h g-1 at a current density of 100 mA g-1 for the first discharge,and it can still maintain a capacity of 633.1mA h g-1 after 100 charge-discharge cycles.The results show that MWCNTs with good electrical conductivity as anchors of MnO2 can provide fast electron transport channels for MnO2 in the electrochemical reactions,and the as-prepared MWCNTs@MnO2 nanocomposite is a potential anode material for lithium ion batteries.展开更多
基金supported by the National Basic research Program of China (973 Program,2009CB623505)the National Natural Science Foundation of China (21273225)~~
文摘Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catalytic system exhibited a broad substrate scope and excellent regi‐oselectivity, as well as being amenable to gram‐scale synthesis. This MnOx‐N@C catalyst also showed good reusability and was successfully recycled six times without any significant loss of activity.
基金supported by the National Natural Science Foundation of China (21103045, 1210040, 1103312)State Key Laboratory of Heavy Oil at China University of Petroleum (SKCHOP201504)Key Laboratory of Mineralogy and Metallogeny of the Chinese Academy of Sciences at Guangzhou Institute of Geochemistry(KLMM20150103)~~
文摘Transition metal catalysts M-N-C（M = Co,Fe,Mn） were synthesized by a template-free method by heating meso-tetraphenyl porphyrins（i.e.CoTPP,FeTPPCl,MnTPPCl） precursors.The catalysts were characterized by N2 adsorption-desorption,thermogravimetry,high-resolution transmission electron microscopy,and Raman and X-ray photoelectron spectroscopy.The selective oxidation of ethylbenzene with molecular oxygen under a solvent-free condition was carried out to explore the catalytic performance of the M-N-Cs,which exhibited different catalytic performance.That was ascribed to the difference in M（Co,Fe,Mn） and different graphitization degree forming during the heating process,in which M（Co,Fe,Mn） might have different catalytic activity on the formation of the M-N-C catalyst.All the M-N-C composites had remarkable recyclability in the selective oxidation of ethylbenzene.
基金supported by the Ministry of Science and Innovation of Spain/FEDER Program of the EU(MAT2013-50137-EXP,MAT 2013-40823-R and ENE2017-82451-C3-2-R)~~
文摘Cryptomelane has been widely applied as catalyst in oxidation reactions due to its excellent redox properties and low cost.Here,a novel one-pot hydrothermal synthesis using a potassium permanganate aqueous solution as precursor and ethanol as reducing agent has successfully been developed to obtain cryptomelane nano-oxides.This synthetic route makes it possible to control the amount of potassium incorporated into the structure of the cryptomelane by selecting the appropriate synthesis temperature and ethanol initial concentration.Taking advantage of this approach,the effect of potassium concentration on the structural stability and reducibility of the cryptomelane,which are poorly discussed in the literature,has been studied.We have observed that samples with low content of potassium(~11%)show high conversions of CO to CO2 especially at low temperatures.The lower activity of the samples with high K contents(~16%)can be ascribed to the beneficial effect of K on the structural stability of cryptomelane in detriment of labile oxygen on cryptomelane surface.
基金supported by the National Natural Science Foundation of China (21671096 and 21603094)the Natural Science Foundation of Guangdong Province (2016A030310376)+2 种基金Shenzhen Key Laboratory Project (ZDSYS201603311013489)the Natural Science Foundation of Shenzhen (JCYJ20150630145302231 and JCYJ20150331101823677)the Undergraduate Training Program for Innovation and Entrepreneurship of Guangdong (2016S10)
文摘Development of cheap,abundant and noblemetal-free materials as high efficient oxygen reduction electrocatalysts is crucial for future energy storage system. Here,one-dimensional（1D） MnO N-doped carbon nanofibers（MnO-NCNFs） were successfully developed by electrospinning combined with high temperature pyrolysis. The MnO-NCNFs exhibit promising electrochemical performance,methanol tolerance,and durability in alkaline medium. The outstanding electrocatalytic activity is mainly attributed to several issues.First of all,the uniform 1D fiber structure and the conductive network could facilitate the electron transport. Besides,the introduction of Mn into the precursor can catalyze the transformation of amorphous carbon to graphite carbon,while the improved graphitization means better conductivity,beneficial for the enhancement of catalytic activity for oxygen reduction reaction（ORR）. Furthermore,the porous structure and high surface area can effectively decrease the mass transport resistance and increase the exposed ORR active sites,thus improve utilization efficiency and raise the quantity of exposed ORR active sites. The synergistic effect of MnO and NCNFs matrix,which enhances charge transfer,adsorbent transport,and delivers efficiency in the electrolyte solution,ensures the high ORR performance of MnO-NCNFs.
基金supported by the National Natural Science Foundation of China(Grant Nos.11179038 and 10974073)the Specialized Re-search Fund for the Doctoral Program of Higher Education(Grant No.20120211130005)
文摘Tubular nanocomposite with interconnected MnO2 nanoflakes coated on MWCNTs(MWCNTs@MnO2)was fabricated by an aqueous solution method at 80°C.Scanning electron microscopy,X-ray diffraction and galvanostatic charge-discharge tests were used to characterize the structures and electrochemical performances of the as-prepared nanocomposite.The capacity reaches 1233.6 mA h g-1 at a current density of 100 mA g-1 for the first discharge,and it can still maintain a capacity of 633.1mA h g-1 after 100 charge-discharge cycles.The results show that MWCNTs with good electrical conductivity as anchors of MnO2 can provide fast electron transport channels for MnO2 in the electrochemical reactions,and the as-prepared MWCNTs@MnO2 nanocomposite is a potential anode material for lithium ion batteries.
