Large‐Scale Fabrication of Core–Shell Structured C/SnO2 Hollow Spheres as Anode Materials with Improved Lithium Storage Performance

Due to the high theoretical capacity as high as 1494 mAh g^?1, SnO₂ is considered as a potential anode material for high‐capacity lithium–ion batteries (LIBs). Therefore, the simple but effective method focused on fabrication of SnO₂ is imperative. To meet this, a facile and efficient strategy to fabricate core–shell structured C/SnO₂ hollow spheres by a solvothermal method is reported. Herein, the solid and hollow structure as well as the carbon content can be controlled. Very importantly, high‐yield C/SnO₂ spheres can be produced by this method, which suggest potential business applications in LIBs field. Owing to the dual buffer effect of the carbon layer and hollow structures, the core–shell structured C/SnO₂ hollow spheres deliver a high reversible discharge capacity of 1007 mAh g^?1 at a current density of 100 mA g^?1 after 300 cycles and a superior discharge capacity of 915 mAh g^?1 at 500 mA g^?1 after 500 cycles. Even at a high current density of 1 and 2 A g^?1, the core–shell structured C/SnO₂ hollow spheres electrode still exhibits excellent discharge capacity in the long life cycles. Consideration of the superior performance and high yield, the core–shell structured C/SnO₂ hollow spheres are of great interest for the next‐generation LIBs.     

Morphology‐Controlled Synthesis of SnO2 Nanotubes by Using 1D Silica Mesostructures as Sacrificial Templates and Their Applications in Lithium‐Ion Batteries

SnO₂ nanotubes with controllable morphologies are successfully synthesized by using a variety of one‐dimensional (1D) silica mesostructures as effective sacrificial templates. Firstly, 1D silica mesostructures with different morphologies, such as chiral nanorods, nonchiral nanofibers, and helical nanotubes, are readily synthesized in aqueous solution by using the triblock copolymer Pluronic F127 and the cationic surfactant cetyltrimethylammonium bromide as binary templates. Subsequently, the obtained 1D silica mesostructures are used as sacrificial templates to synthesize SnO₂ nanotubes with preserved morphologies via a simple hydrothermal route, resulting in the formation of well‐defined SnO₂ nanotubes with different lengths and unique helical SnO₂ nanotubes with a wealth of conformations. It is revealed that both of the short and long SnO₂ nanotubes showed much better performance as anode materials in lithium‐ion batteries than normal SnO₂ nanopowders, which might be related to the hollow structure of the nanotubes that could alleviate the volume changes and mechanical stress during charging/discharging cycling. Moreover, the capacity and cycling performance of short nanotubes, which showed a specific discharge capacity of 468 mAh g^?1 after 30 cycles, are considerably better than those of long nanotubes because of the more robust structure of the short nanotubes.     

Controlled Synthesis of Hollow Cu2‐xTe Nanocrystals Based on the Kirkendall Effect and Their Enhanced CO Gas‐Sensing Properties

This paper develops a facile solution‐based method to synthesize hollow Cu_2‐xTe nanocrystals (NCs) with tunable interior volume based on the Kirkendall effect. Transmission electron microscopy images and time‐dependent absorption spectra reveal the temporal growth process from solid copper nanoparticles to hollow Cu_2‐xTe NCs. Furthermore, the as‐prepared hollow Cu_2‐xTe NCs show enhanced sensitivity for the detection of carbon monoxide (CO), which is often referred to as the “silent killer”. The response and recovery time of the as‐prepared sensor for the detection of 100 ppm CO gas are estimated to be about 21 and 100 s, respectively, which are sufficient to render it a promising candidate for effective CO gas‐sensing applications. Such enhanced performance is achieved owing to the small grain size and large specific area of the hollow nanostructures. Therefore, the obtained hollow NCs based on the Kirkendall effect may have the potential as new functional blocks for high‐performance gas sensors.     

Direct Synthesis of the 2D Copper(II) 5‐Prop‐2‐ynoxyisophthalate MOF: Comment on “Surface Functionalization of Porous Coordination Nanocages Via Click Chemistry and Their Application in Drug Delivery”

Synthesis of metal–organic materials is often dependent on the reaction conditions of suitable solvent/solvent mixture and temperature. A new finding based on a previously described protocol is reported: instead of obtaining metal–organic polyhedra (MOP), a metal–organic framework (MOF) with a 2D layered structure is obtained, following the same reported protocol. The 2D Cu(II)–5‐prop‐2‐ynoxyisophthlate MOF, crystallized in a kagomé‐type structure, is synthesized using different solvent systems at room temperature, as well as under solvothermal (nonhydrothermal) conditions. Under harsh reaction conditions, alkyne functional groups maintain their integrity and the copper does not catalyze the oxidative coupling of the terminal alkyne groups. X‐ray diffraction analyses confirm the structure and phase purity of the product. Based on the present results and the previous work reported by Zhao et al., it seems that two products, namely 0D MOP and 2D MOF, are equally possible when using the same reactants under same reaction conditions. However, the materials obtained in all the trials are MOF instead of MOP. From the structure point of view, there is a difference in connectivity of the initial building units that determines whether the product is MOP or MOF.     

Fabrication of a 3D Hierarchical Sandwich Co9S8/α‐MnS@N–C@MoS2 Nanowire Architectures as Advanced Electrode Material for High Performance Hybrid Supercapacitors

Supercapacitors suffer from lack of energy density and impulse the energy density limit, so a new class of hybrid electrode materials with promising architectures is strongly desirable. Here, the rational design of a 3D hierarchical sandwich Co₉S₈/α‐MnS@N–C@MoS₂ nanowire architecture is achieved during the hydrothermal sulphurization reaction by the conversion of binary mesoporous metal oxide core to corresponding individual metal sulphides core along with the formation of outer metal sulphide shell at the same time. Benefiting from the 3D hierarchical sandwich architecture, Co₉S₈/α‐MnS@N–C@MoS₂ electrode exhibits enhanced electrochemical performance with high specific capacity/capacitance of 306 mA h g^?1/1938 F g^?1 at 1 A g^?1, and excellent cycling stability with a specific capacity retention of 86.9% after 10 000 cycles at 10 A g^?1. Moreover, the fabricated asymmetric supercapacitor device using Co₉S₈/α‐MnS@N–C@MoS₂ as the positive electrode and nitrogen doped graphene as the negative electrode demonstrates high energy density of 64.2 Wh kg^?1 at 729.2 W kg^?1, and a promising energy density of 23.5 Wh kg^?1 is still attained at a high power density of 11 300 W kg^?1. The hybrid electrode with 3D hierarchical sandwich architecture promotes enhanced energy density with excellent cyclic stability for energy storage.     

The Concept of “Noble,Heteroatom‐Doped Carbons,” Their Directed Synthesis by Electronic Band Control of Carbonization,and Applications in Catalysis and Energy Materials

Carbonization of organic compounds with a highest occupied molecular orbital (HOMO) level more positive than 1.3 V practically automatically results in highly sp²‐conjugated, heteroatom‐doped carbons. Due to the stability of the starting compounds, carbon bond formation is restricted to result in morphologies with a surprisingly high local order which as such are noble, i.e., they are hard to oxidize and combust. The work function of electrons in these systems is so positive that the systems usually accept electrons, i.e., they oxidize other matter rather than being oxidized. Such noble, heteroatom‐doped carbons have been proven to be efficient, metal‐free electrocatalysts, but can be also beneficially used in the manufacturing of carbon nanomaterials for energy applications or as highly active, non‐innocent catalytic supports.     

Fabrication of β-Si3N4 whiskers by combustion synthesis with MgSiN2 as additives

β-Si₃N₄ whiskers with diameter of 0.5–2 μm and aspect ratio of 10–15 have been successfully prepared by combustion synthesis under 30–50 atm nitrogen pressure. The addition of MgSiN₂ powder plays a significant role in the growth of β-Si₃N₄ whiskers. The as-prepared products were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).     

Synthesis and Photoluminescence Properties of Eu3+‐Doped Silica@Coordination Polymer Core–Shell Structures and Their Calcinated Silica@Gd2O3:Eu and Hollow Gd2O3:Eu Microsphere Products

The conjugation of Eu³⁺‐doped coordination polymers constructed from Gd³⁺ and isophthalic acid (H₂IPA) with silica particles is investigated for the production of luminescent microspheres. A series of doping ratio‐controlled silica@coordination polymer core–shell spheres is easily synthesized by altering the amounts of metal nodes used in the reactions, where the ratios of Gd³⁺ and Eu³⁺ are 10:0 ( 1a ), 9:1 ( 1b ), 8:2 ( 1c ), 7:3 ( 1d ), 5:5 ( 1e ), and 0:10 ( 1f ). The formation of monodisperse uniform core–shell structures is achieved throughout the entirety of a series. Investigations of the photoluminescence property of the resulting series of silica@coordination polymer core–shell spheres reveal that 20% Eu³⁺‐doped product ( 1c ) has the strongest emission intensity. The subsequent calcination process on the silica@coordination polymer core–shell structures ( 1a ‐ f ) results in the formation of a series of doping ratio‐controlled silica@Gd₂O₃:Eu core–shell microspheres ( 2a ‐ f ) with uniform shell thickness. During the calcination step, the coordination polymers within silica@coordination polymer core–shells are transformed into metal oxides, resulting in silica@Gd₂O₃:Eu core–shell structures. The final etching process on the silica@Gd₂O₃:Eu core–shell microspheres ( 2a ‐ f ) produces a series of hollow Gd₂O₃:Eu microspheres ( 3a ‐ f ) as a result of the elimination of silica cores. The luminescence intensities of silica@Gd₂O₃:Eu core–shell ( 2a ‐ f ) and hollow Gd₂O₃:Eu microspheres ( 3a ‐ f ) also vary depending upon the doping ratio of Eu³⁺ ions.