One‐Pot Synthesis of Pomegranate‐Structured Fe3O4/Carbon Nanospheres‐Doped Graphene Aerogel for High‐Rate Lithium Ion Batteries

A unique hierarchically nanostructured composite of iron oxide/carbon (Fe₃O₄/C) nanospheres‐doped three‐dimensional (3D) graphene aerogel has been fabricated by a one‐pot hydrothermal strategy. In this novel nanostructured composite aerogel, uniform Fe₃O₄ nanocrystals (5–10 nm) are individually embedded in carbon nanospheres (ca. 50 nm) forming a pomegranate‐like structure. The carbon matrix suppresses the aggregation of Fe₃O₄ nanocrystals, avoids direct exposure of the encapsulated Fe₃O₄ to the electrolyte, and buffers the volume expansion. Meanwhile, the interconnected 3D graphene aerogel further serves to reinforce the structure of the Fe₃O₄/C nanospheres and enhances the electrical conductivity of the overall electrode. Therefore, the carbon matrix and the interconnected graphene network entrap the Fe₃O₄ nanocrystals such that their electrochemical function is retained even after fracture. This novel hierarchical aerogel structure delivers a long‐term stability of 634 mA h g^?1 over 1000 cycles at a high current density of 6 A g^?1 (7 C), and an excellent rate capability of 413 mA h g^?1 at 10 A g^?1 (11 C), thus exhibiting great potential as an anode composite structure for durable high‐rate lithium‐ion batteries.     

Micro‐/Nanostructured Multicomponent Molecular Materials: Design,Assembly, and Functionality

Molecule‐based micro‐/nanomaterials have attracted considerable attention because their properties can vary greatly from the corresponding macro‐sized bulk systems. Recently, the construction of multicomponent molecular solids based on crystal engineering principles has emerged as a promising alternative way to develop micro‐/nanomaterials. Unlike single‐component materials, the resulting multicomponent systems offer the advantages of tunable composition, and adjustable molecular arrangement, and intermolecular interactions within their solid states. The study of these materials also supplies insight into how the crystal structure, molecular components, and micro‐/nanoscale effects can influence the performance of molecular materials. In this review, we describe recent advances and current directions in the assembly and applications of crystalline multicomponent micro‐/nanostructures. Firstly, the design strategies for multicomponent systems based on molecular recognition and crystal engineering principles are introduced. Attention is then focused on the methods of fabrication of low‐dimensional multicomponent micro‐/nanostructures. Their new applications are also outlined. Finally, we briefly discuss perspectives for the further development of these molecular crystalline micro‐/nanomaterials.     

Luminescent Thin Films Enabled by CsPbX3 (X=Cl,Br, I) Precursor Solution

Inorganic cesium lead halide perovskite nanocrystals are candidates for lighting and display materials due to their outstanding optoelectronic properties. However, the dissolution issue of perovskite nanocrystals in polar solvents remains a challenge for practical applications. Herein, we present a newly designed one-step spin-coating strategy to prepare a novel multicolor-tunable CsPbX₃ (X=Cl, Br, I) nanocrystal film, where the CsPbX₃ precursor solution was formed by dissolving PbO, Cs₂CO₃, and CH₃NH₃X into the ionic liquid n-butylammonium butyrate. The as-designed CsPbX₃ nanocrystal films show high color purity with a narrow emission width. Also, the blue CsPb(Cl/Br)₃ film demonstrates an absolute photoluminescence quantum yields (PLQY) of 15.6 %, which is higher than 11.7 % of green CsPbBr₃ and 8.3 % of red CsPb(Br/I)₃ film. This study develops an effective approach to preparing CsPbX₃ nanocrystal thin films, opening a new avenue to design perovskite nanocrystals-based devices for lighting and display applications.     

Reversible Ultra-Slow Crystal Growth of Mixed Lead Bismuth Perovskite Nanocrystals: The Presence of Dynamic Capping

An ultra-slow crystal growth over a period of 24 h of a newly synthesized CH₃NH₃Pb_1/2Bi_1/3I₃ perovskite (MPBI) nanocrystal in non-polar toluene medium is reported here. From several spectroscopic techniques as well as from TEM analysis we found that the size of nanocrystals changes continuously with time, in spite of being capped by the ligands. Using a single molecular spectroscopic technique, we also found that this size change is not due to the stacking of nanocrystals but due to crystal growth. The notable temperature dependence and reversible nature of the nanocrystals growth is explained by the dynamic nature of the capping. The observed temperature-dependent ultra-slow growth is believed to be a pragmatic step towards controlling the size of perovskite NC in a systematic manner.     

Nonclassical Recrystallization

Applications in the fields of materials science and nanotechnology increasingly demand monodisperse nanoparticles in size and shape. Up to now, no general purification procedure exists to thoroughly narrow the size and shape distributions of nanoparticles. Here, we show by analytical ultracentrifugation (AUC) as an absolute and quantitative high-resolution method that multiple recrystallizations of nanocrystals to mesocrystals is a very efficient tool to generate nanocrystals with an excellent and so-far unsurpassed size-distribution (PDI_c=1.0001) and shape. Similar to the crystallization of molecular building blocks, nonclassical recrystallization removes “colloidal” impurities (i.e., nanoparticles, which are different in shape and size from the majority) by assembling them into a mesocrystal. In the case of nanocrystals, this assembly can be size- and shape-selective, since mesocrystals show both long-range packing ordering and preferable crystallographic orientation of nanocrystals. Besides the generation of highly monodisperse nanoparticles, these findings provide highly relevant insights into the crystallization of mesocrystals.     

A Mechanistic Study of the Multiple Roles of Oleic Acid in the Oil-Phase Synthesis of Pt Nanocrystals

Oleic acid (OAc) is commonly used as a surfactant and/or solvent for the oil-phase synthesis of metal nanocrystals but its explicit roles are yet to be resolved. Here, we report a systematic study of this problem by focusing on a synthesis that simply involves heating of Pt(acac)₂ in OAc for the generation of Pt nanocrystals. When heated at 80 °C, the ligand exchange between Pt(acac)₂ and OAc leads to the formation of a Pt^II–oleate complex that serves as the actual precursor to Pt atoms. Upon increasing the temperature to 120 °C, the decarbonylation of OAc produces CO, which can act as a reducing agent for the generation of Pt atoms and thus formation of nuclei. Afterwards, several catalytic reactions can take place on the surface of the Pt nuclei to produce more CO, which also serves as a capping agent for the formation of Pt nanocrystals enclosed by {100} facets. The emergence of Pt nanocrystals further promotes the autocatalytic surface reduction of Pt^II precursor to enable the continuation of growth. This work not only elucidates the critical roles of OAc at different stages in a synthesis of Pt nanocrystals, but also represents a pivotal step forward toward the rational synthesis of metal nanocrystals.     

Direct Conversion of Bulk Metals to Size‐Tailored,Monodisperse Spherical Non‐Coinage‐Metal Nanocrystals

Monodisperse non‐noble metal nanocrystals (NCs) that are highly uniform in shapes and particle size are much desired in various advanced applications, and are commonly prepared by either thermal decomposition or reduction, where reactive organometallic precursors or/and strong reducing agents are mandatory; however, these are usually toxic, costly, or suffer a lack of availability. Bulk Group 12 metals can now be converted into ligand‐protected, highly crystalline, monodisperse spherical metal NCs with precisely controlled sizes without using any precursors and reducers. The method is based on low‐power NIR‐laser‐induced size‐selective layer‐by‐layer surface vaporization. The monodisperse Cd NCs show pronounced deep‐UV (DUV) localized surface plasmon resonance making them highly competitive DUV‐plasmonic materials. This approach will promote appreciably the emergence of a wide range of monodisperse technically important non‐coinage metal NCs with compelling functionalities.     

Photonic Patterns Printed in Chiral Nematic Mesoporous Resins

Chiral nematic mesoporous phenol‐formaldehyde resins, which were prepared using cellulose nanocrystals as a template, can be used as a substrate to produce latent photonic images. These resins undergo swelling, which changes their reflected color. By writing on the films with chemical inks, the density of methylol groups in the resin changes, subsequently affecting their degree of swelling and, consequently, their color. Writing on the films gives latent images that are revealed only upon swelling of the films. Using inkjet printing, it is possible to make higher resolution photonic patterns both as text and images that can be visualized by swelling and erased by drying. This novel approach to printing photonic patterns in resin films may be applied to anti‐counterfeit tags, signage, and decorative applications.