This paper uses the generalised gradient approximation based on density functional theory to analyse the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C20F20 （M = Sc...This paper uses the generalised gradient approximation based on density functional theory to analyse the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C20F20 （M = Sc-Ni）. The geometric optimization shows that the cage centre is the most stable position for M, forming the structure named as M@C20F20-4. The inclusion energy, zero-point energy, and energy gap calculations tell us that Ni@C20F20-4 should be thermodynamically and kinetically stablest. M@C20F20-4 （M = Sc-Co） possesses high magnetic moments varied from 1 to 6 μB, while Ni@C20F20-4 is nonmagnetic. The Ni-C bond in Ni@C20F20-4 contains both the covalent and ionic characters.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
Electrical contact materials are generally Ag-or Cu-based composites and play a critical role in ensuring the reliability and efficiency of electrical equipments and electronic instruments.The MAX(M is an early transi...Electrical contact materials are generally Ag-or Cu-based composites and play a critical role in ensuring the reliability and efficiency of electrical equipments and electronic instruments.The MAX(M is an early transition metal,A is an element from III or IV main groups,and X is carbon or/and nitrogen)phase ceramics display a unique combination of properties and may serve as an ideal reinforcement phase for electrical contact materials.The biological materials evolved in nature generally exhibit three-dimensional(3D)interpenetrating-phase architectures,which may offer useful inspiration for the architectural design of electrical contact materials.Here,a series of bi-continuous Ag-Ti_(3)SiC_(2) MAX phase composites with high ceramic contents exceeding 50 vol.%and having micron-and ultrafine-scaled 3D interpenetrating-phase architectures,wherein both constituents were continuous and mutually interspersed,were exploited by pressureless infiltration of Ag melt into partially sintered Ti_(3)SiC_(2) scaffolds.The mechanical and electrical properties as well as the friction and wear performance of the composites were investigated and revealed to be closely dependent on the ceramic contents and characteristic structural dimensions.The composites exhibited a good combination of properties with high hardness over 2.3 GPa,high flexural strength exceeding 530 MPa,decent fracture toughness over 10 MPa·m^(1/2),and good wear resistance with low wear rate at an order of 10^(-5)mm^(3)/(N·m),which were much superior compared to the counterparts made by powder metallurgy methods.In particular,the hardness,electrical conductivity,strength,and fracture toughness of the composites demonstrated a simultaneous improvement as the structure was refined from micron-to ultrafine-scales at equivalent ceramic contents.The good combination of properties along with the facile processing route makes the Ag-Ti_(3)SiC_(2)3D interpenetrating-phase composites appealing for electrical contact applications.展开更多
基金Project supported by the Research Starting Foundation of Hohai University (Grant No. 2084/40801130)the Natural Science Foundation of Hohai University (Grant Nos. 2008431211 and 2008430311)+2 种基金the Excellent Innovation Personal Support Plan of Hohai Universitythe Basic Scientific Research Foundation of National Centralthe Special Foundation of the Natural Natural Science (Grant No. 10947132)
文摘This paper uses the generalised gradient approximation based on density functional theory to analyse the geometric structure and properties of the 3d transition metal atom doped endohedral fullerene M@C20F20 （M = Sc-Ni）. The geometric optimization shows that the cage centre is the most stable position for M, forming the structure named as M@C20F20-4. The inclusion energy, zero-point energy, and energy gap calculations tell us that Ni@C20F20-4 should be thermodynamically and kinetically stablest. M@C20F20-4 （M = Sc-Co） possesses high magnetic moments varied from 1 to 6 μB, while Ni@C20F20-4 is nonmagnetic. The Ni-C bond in Ni@C20F20-4 contains both the covalent and ionic characters.
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supports from the National Key R&D Program of China(No.2020YFA0710404)the National Natural Science Foundation of China(No.52173269),the KC Wong Education Foundation(No.GJTD-2020-09)the Liaoning Revitalization Talents Program,and the Youth Innovation Promotion Association CAS(No.2019191).
文摘Electrical contact materials are generally Ag-or Cu-based composites and play a critical role in ensuring the reliability and efficiency of electrical equipments and electronic instruments.The MAX(M is an early transition metal,A is an element from III or IV main groups,and X is carbon or/and nitrogen)phase ceramics display a unique combination of properties and may serve as an ideal reinforcement phase for electrical contact materials.The biological materials evolved in nature generally exhibit three-dimensional(3D)interpenetrating-phase architectures,which may offer useful inspiration for the architectural design of electrical contact materials.Here,a series of bi-continuous Ag-Ti_(3)SiC_(2) MAX phase composites with high ceramic contents exceeding 50 vol.%and having micron-and ultrafine-scaled 3D interpenetrating-phase architectures,wherein both constituents were continuous and mutually interspersed,were exploited by pressureless infiltration of Ag melt into partially sintered Ti_(3)SiC_(2) scaffolds.The mechanical and electrical properties as well as the friction and wear performance of the composites were investigated and revealed to be closely dependent on the ceramic contents and characteristic structural dimensions.The composites exhibited a good combination of properties with high hardness over 2.3 GPa,high flexural strength exceeding 530 MPa,decent fracture toughness over 10 MPa·m^(1/2),and good wear resistance with low wear rate at an order of 10^(-5)mm^(3)/(N·m),which were much superior compared to the counterparts made by powder metallurgy methods.In particular,the hardness,electrical conductivity,strength,and fracture toughness of the composites demonstrated a simultaneous improvement as the structure was refined from micron-to ultrafine-scales at equivalent ceramic contents.The good combination of properties along with the facile processing route makes the Ag-Ti_(3)SiC_(2)3D interpenetrating-phase composites appealing for electrical contact applications.
