title: Low temperature in situ synthesis and the formation mechanism of various carbon-encapsulated nanocrystals by the electrophilic oxidation of metallocene complexes.
abstract: The core-shell nanostructures have the advantages of combining distinctive properties of varied materials and improved properties over their single-component counterparts. Synthesis approaches for this class of nanostructures have been intensively explored, generally involving multiple steps. Here, a general and convenient strategy is developed for one-step in situ synthesis of various carbon-encapsulated nanocrystals with a core-shell structure via a solid-state reaction of metallocene complexes with (NH4)2S2O8 in an autoclave at 200 °C. A variety of near-spherical and equiaxed nanocrystals with a small median size ranging from 6.5 to 50.6 nm are prepared as inner cores, including Fe7S8, Ni3S4 and NiS, CoS, TiO2, TiO2 and S8, ZrO2, (NH4)3V(SO4)3 and VO2, Fe7S8 and Fe3O4, MoS2 and MoO2. The worm-like carbon shell provides exclusive room for hundreds of nanocrystals separated from each other, preventing nanocrystal aggregation. The synergistic effect of ammonium and a strong oxidizing anion on the electrophilic oxidation of metallocene complexes containing a metal-ligand π bond contributes to the carbon formation at low temperature. It is considered that the cyclopentadienyl ligand in a metallocene complex will decompose into highly reactive straight chain olefinic pieces and the metal-olefin π interaction enables an ordered self-assembly of olefinic pieces on nanocrystals to partially form graphitizable carbon and a core-shell structure. The high capacity, good cycling behavior and rate capability of Fe7S8@C and Ni3S4 and NiS@C electrodes are attributed to the good protection and electrical conductivity of the carbon shell.
authors.affiliation: College of Ocean Science and Engineering, Shanghai Maritime University, Shanghai 201306, People's Republic of China.
authors.forename: Boyang
authors.initials: B
authors.lastname: Liu
authors.forename: Chunhua
authors.initials: C
authors.lastname: Fan
authors.forename: Jianwei
authors.initials: J
authors.lastname: Chen
authors.forename: Junhua
authors.initials: J
authors.lastname: Wang
authors.forename: Zepeng
authors.initials: Z
authors.lastname: Lu
authors.forename: Jiayuan
authors.initials: J
authors.lastname: Ren
authors.forename: Shuaiqin
authors.initials: S
authors.lastname: Yu
authors.forename: Lihua
authors.initials: L
authors.lastname: Dong
authors.forename: Wenge
authors.initials: W
authors.lastname: Li