Single‐, double‐, and triple‐shelled hollow spheres assembled by Co3O4 nanosheets are successfully synthesized through a novel method. The possible formation mechanism of these novel structures was investigated using powder X‐ray diffraction, scanning and transmission electron microscopies, Fourier transform IR, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. Both poly(vinylpyrrolidone) (PVP) soft templates and the formation of cobalt glycolate play key roles in the formation of these novel multishelled hollow structures. When tested as the anode material in lithium‐ion batteries (LIBs), these multishelled microspheres exhibit excellent cycling performance, good rate capacity, and enhanced lithium storage capacity. This superior cyclic stability and capacity result from the synergetic effect of small diffusion lengths in the nanosheet building blocks and sufficient void space to buffer the volume expansion. This facile strategy may be extended to synthesize other transition metal oxide materials with hollow multishelled micro‐/nanostrucutures, which may find application in sensors and catalysts due to their unique structural features.
A new facile route to fabricate N‐doped graphene‐SnO2 sandwich papers is developed. The 7,7,8,8‐tetracyanoquinodimethane anion (TCNQ−) plays a key role for the formation of such structures as it acts as both the nitrogen source and complexing agent. If used in lithium‐ion batteries (LIBs), the material exhibits a large capacity, high rate capability, and excellent cycling stability. The superior electrochemical performance of this novel material is the result from its unique features: excellent electronic conductivity related to the sandwich structure, short transportation length for both lithium ions and electrons, and elastomeric space to accommodate volume changes upon Li insertion/extraction.
Morphological control of organic nanocrystals (ONCs) is important in the fields ranging from specialty chemicals to molecular semiconductors. Although the thermodynamic shape can be readily predicted, most growth morphologies of ONCs are actually determined by kinetic factors and remain poorly understood. On the basis of the reduction of zinc tetraphenylporphyrin perchlorate (ZnTPP(+)ClO(4)(-)) with sodium nitrite (Na(+)NO(2)(-)), we synthesized two series of ONCs of aquozinc tetraphenylporphyrin (ZnTPP·H(2)O), in the presence of either cetyltrimethylammonium bromide (CTAB) or poly(vinyl pyrrolidone) (PVP) as the capping ligands. As the cationic precursors of ZnTPP(+) are separated in the solution phase, smoothly controlled release of ZnTPP·H(2)O building blocks via the reduction reaction facilitates the separation between the nucleation and growth stages during the formation of ONCs and provides a high and tunable supersaturation unavailable by employing conventional crystallization techniques. We found that CTAB mainly serve as the colloidal stabilizer, while selective adhesion of PVP on the {020}s facet alters the crystal habits significantly. In both cases, manipulation of the growth kinetics had been achieved by adjusting the concentration of ZnTPP·H(2)O growth units, and consequently, the supersaturation for the crystallization, thus yielding ONCs with well-controlled sizes and shapes. Remarkably, thermodynamically stable octahedrons have been obtained at high supersaturation in both CTAB and PVP cases.
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