Design and Synthesis of Multifunctional Drug Carriers Based on Luminescent Rattle‐Type Mesoporous Silica Microspheres with a Thermosensitive Hydrogel as a Controlled Switch

A novel approach for the fabrication of multifunctional microspheres integrating several advantages of mesoporous, luminescence, and temperature responses into one single entity is reported. First, the hollow mesoporous silica capsules are fabricated via a sacrificial template route. Then, Gd₂O₃:Eu³⁺ luminescent nanoparticles are incorporated into the internal cavities to form rattle‐type mesoporous silica nanocapsules by an incipient‐wetness impregnation method. Finally, the rattle‐type capsules serve as a nanoreactor for successfully filling temperature‐responsive hydrogel via photoinduced polymerization to form the multifunctional composite microspheres. The organic–inorganic hybrid microspheres show a red emission under UV irradiation due to the luminescent Gd₂O₃:Eu³⁺ core. The in vitro cytotoxicity tests show that the samples have good biocompatibility, which indicates that the nanocomposite could be a promising candidate for drug delivery. In addition, flow cytometry and confocal laser scanning microscopy (CLSM) confirm that the sample can be effectively taken up by SKOV3 cells. For in vitro magnetic resonance imaging (MRI), the sample shows the promising spin‐lattice relaxation time (T₁) weighted effect and could potentially apply as a T₁‐positive contrast agent. This composite drug delivery system (DDS) provides a positive temperature controlled “on‐off”drug release pattern and the drug, indomethacin (IMC), is released fast at 45 °C (on phase) and completely shut off at 20 °C (off phase). Meanwhile Gd₂O₃:Eu³⁺ plays an important role as the luminescent tag for tracking the drug loading and release process by the reversible luminescence quenching and recovery phenomenon. These results indicate that the obtained multifunctional composite has the potential to be used as a smart DDS for biomedical applications.     

Simple Synthesis of Hollow Tin Dioxide Microspheres and Their Application to Lithium‐Ion Battery Anodes

Hollow tin dioxide (SnO₂) microspheres were synthesized by the simple heat treatment of a mixture composed of tin(IV ) tetrachloride pentahydrate (SnCl₄·5H₂O) and resorcinol–formaldehyde gel (RF gel). Because hollow structures were formed during the heat treatment, the pre‐formation of template and the adsorption of target precursor on template are unnecessary in the current method, leading to simplified synthetic procedures and facilitating mass production. Field‐emission scanning electron microscopy (FE‐SEM) images showed 1.7–2.5 μm sized hollow spherical particles. Transmission electron microscopy (TEM) images showed that the produced spherical particles are composed of a hollow inner cavity and thin outer shell. When the hollow SnO₂ microspheres were used as a lithium‐battery anode, they exhibited extraordinarily high discharge capacities and coulombic efficiency. The reported synthetic procedure is straightforward and inexpensive, and consequently can be readily adopted to produce large quantities of hollow SnO₂ microspheres. This straightforward approach can be extended for the synthesis of other hollow microspheres including those obtained from ZrO₂ and ZrO₂/CeO₂ solid solutions.     

Fast and Reversible Li Ion Insertion in Carbon‐Encapsulated Li3VO4 as Anode for Lithium‐Ion Battery

Carbon‐encapsulated Li₃VO₄ is synthesized by a facile environmentally benign solid‐state method with organic metallic precursor VO(C₅H₇O₂)₂ being chosen as both V and carbon sources yielding a core–shell nanostructure with lithium introduced in the subsequent annealing process. The Li₃VO₄ encapsulated with carbon presents exceeding rate capability (a reversible capability of 450, 340, 169, and 106 mAh g^?1 at 0.1 C, 10 C, 50 C, and 80 C, respectively) and long cyclic performance (80% capacity retention after 2000 cycles at 10 C) as an anode in lithium‐ion batteries. The superior performance is derived from the structural features of the carbon‐encapsulated Li₃VO₄ composite with oxygen vacancies in Li₃VO₄, which increase surface energy and could possibly serve as a nucleation center, thus facilitating phase transitions. The in situ generated carbon shell not only facilitates electron transport, but also suppresses Li₃VO₄ particle growth during the calcination process. The encouraging results demonstrate the significant potential of carbon encapsulated Li₃VO₄ for high power batteries. In addition, the simple generic synthesis method is applicable to the fabrication of a variety of electrode materials for batteries and supercapacitors with unique core–shell structure with mesoporous carbon shell.     

Textured Tubular Nanoparticle Structures: Precursor‐Templated Synthesis of GaN Sub‐micrometer Sized Tubes

Porous and sub‐micrometer tubes made of textured GaN nanoparticles have been synthesized by an in situ chemical reaction and characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) and Raman spectroscopies. The in situ reaction involves thermal decomposition and nitridation of 1D gallium oxyhydroxide (GaOOH) at temperatures in the range of 700–900 °C. The 1D shape of the precursor GaOOH is maintained in the resultant GaN tubes. The GaN nanocrystals (estimated to be about 15 nm in size) are found to be highly oriented with respect to each other in the tube structure, with the [110] GaN direction parallel to the tube axis. The growth mechanism of the tube structure has also been studied. β‐Ga₂O₃ is found to be an intermediate phase between the starting GaOOH precursor and the final GaN product. The growth mechanism involves decomposition of GaOOH, which produces β‐Ga₂O₃ tubes with hollow interiors, and nitridation of β‐Ga₂O₃, which leads to growth of textured GaN nanocrystals. Based on the growth mechanism, tubular structures with either quasi‐circular or rectangular cross section are selectively synthesized by controlling the heating rate and calcination temperature. This in situ chemical reaction method provides a new route for synthesizing 1D hollow nanostructures.     

3D Hierarchical Co3O4 Twin‐Spheres with an Urchin‐Like Structure: Large‐Scale Synthesis,Multistep‐Splitting Growth,and Electrochemical Pseudocapacitors

Novel, 3D hierarchical Co₃O₄ twin‐spheres with an urchin‐like structure are produced successfully on the large scale for the first time by a solvothermal synthesis of cobalt carbonate hydroxide hydrate, Co(CO₃)_0.5(OH)·0.11H₂O, and its subsequent calcination. The morphology of the precursor, which dominates the structure of the final product, evolves from nanorods to sheaf‐like bundles, to flower‐like structures, to dumbbell‐like particles, and eventually to twin‐spheres, accompanying a prolonged reaction time. A multistep‐splitting growth mechanism is proposed to understand the formation of the 3D hierarchical twin‐spheres of the precursor, based on the time effect on the morphologies of the precursor. The 3D hierarchical Co₃O₄ twin‐spheres are further used as electrode materials to fabricate supercapacitors with high specific capacitances of 781, 754, 700, 670, and 611 F g^?1 at current densities of 0.5, 1, 2, 4, and 8 A g^?1, respectively. The devices also show high charge‐discharge reversibility with an efficiency of 97.8% after cycling 1000 times at a current density of 4 A g^?1.     

MoSe2‐Covered N,P‐Doped Carbon Nanosheets as a Long‐Life and High‐Rate Anode Material for Sodium‐Ion Batteries

MoSe₂ grown on N,P‐co‐doped carbon nanosheets is synthesized by a solvothermal reaction followed with a high‐temperature calcination. This composite has an interlayer spacing of MoSe₂ expanded to facilitate sodium‐ion diffusion, MoSe₂ immobilized on carbon nanosheets to improve charge‐transfer kinetics, and N and P incorporated into carbon to enhance its interaction with active species upon cycling. These features greatly improve the electrochemical performance of this composite, as compared to all the controls. It presents a specific capacity of 378 mAh g^?1 after 1000 cycles at 0.5 A g^?1, corresponding to 87% of the capacity at the second cycle. Ex situ Raman spectra and high‐resolution transmission electron microscopy images confirm that it is element Se, rather than MoSe₂, formed after the charging process. The interaction of the active species with modified carbon is simulated using density functional theory to explain this excellent stability. The superior rate capability, where the capacity at 15 A g^?1 equals ≈55% of that at 0.5 A g^?1, could be associated with the significant contribution of pseudocapacitance. By pairing with homemade Na₃V₂(PO₄)₃/C, this composite also exhibits excellent performances in full cells.     

Uniform Rattle‐type Hollow Magnetic Mesoporous Spheres as Drug Delivery Carriers and their Sustained‐Release Property

A novel kind of rattle‐type hollow magnetic mesoporous sphere (HMMS) with Fe₃O₄ particles encapsulated in the cores of mesoporous silica microspheres has been successfully fabricated by sol–gel reactions on hematite particles followed by cavity generation with hydrothermal treatment and H₂ reduction. Such a structure has the merits of both enhanced drug‐loading capacity and a significant magnetization strength. The prepared HMMSs realize a relatively high storage capacity up to 302 mg g^?1 when ibuprofen is used as a model drug, and the IBU–HMMS system has a sustained‐release property, which follows a Fick's law.     

Inverted Organic Solar Cells with Sol–Gel Processed High Work‐Function Vanadium Oxide Hole‐Extraction Layers

For large‐scale and high‐throughput production of organic solar cells (OSCs), liquid processing of the functional layers is desired. We demonstrate inverted bulk‐heterojunction organic solar cells (OSCs) with a sol–gel derived V₂O₅ hole‐extraction‐layer on top of the active organic layer. The V₂O₅ layers are prepared in ambient air using Vanadium(V)‐oxitriisopropoxide as precursor. Without any post‐annealing or plasma treatment, a high work function of the V₂O₅ layers is confirmed by both Kelvin probe analysis and ultraviolet photoelectron spectroscopy (UPS). Using UPS and inverse photoelectron spectroscopy (IPES), we show that the electronic structure of the solution processed V₂O₅ layers is similar to that of thermally evaporated V₂O₅ layers which have been exposed to ambient air. Optimization of the sol gel process leads to inverted OSCs with solution based V₂O₅ layers that show power conversion efficiencies similar to that of control devices with V₂O₅ layers prepared in high‐vacuum.     

Fabrication of Hollow Inorganic Microspheres by Chemically Induced Self‐Transformation

Two contrasting approaches, involving either polymer‐mediated or fluoride‐mediated self‐transformation of amorphous solid particles, are described as general routes to the fabrication of hollow inorganic microspheres. Firstly, calcium carbonate and strontium tungstate hollow microspheres are fabricated in high yield using sodium poly(4‐styrenesulfonate) as a stabilizing agent for the formation and subsequent transformation of amorphous primary particles. Transformation occurs with retention of the bulk morphology by localized Ostwald ripening, in which preferential dissolution of the particle interior is coupled to the deposition of a porous external shell of loosely packed nanocrystals. Secondly, the fabrication process is extended to relatively stable amorphous microspheres, such as TiO₂ and SnO₂, by increasing the surface reactivity of the solid precursor particles. For this, fluoride ions, in the form of NH₄F and SnF₂, are used to produce well‐defined hollow spheroids of nanocrystalline TiO₂ and SnO₂, respectively. Our results suggest that the chemical self‐transformation of precursor objects under morphologically invariant conditions could be of general applicability in the preparation of a wide range of nanoparticle‐based hollow architectures for technological and biomedical applications.     

Yolk–Shell Structured FeP@C Nanoboxes as Advanced Anode Materials for Rechargeable Lithium‐/Potassium‐Ion Batteries

Maintaining structural stability and alleviating the intrinsic poor conductivity of conversion‐type reaction anode materials are of great importance for practical application. Introducing void space and a highly conductive host to accommodate the volume changes and enhance the conductivity would be a smart design to achieve robust construction; effective electron and ion transportation, thus, lead to prolonged cycling life and excellent rate performance. Herein, uniform yolk–shell FeP@C nanoboxes (FeP@CNBs) with the inner FeP nanoparticles completely protected by a thin and self‐supported carbon shell are synthesized through a phosphidation process with yolk–shell Fe₂O₃@CNBs as a precursor. The volumetric variation of the inner FeP nanoparticles during cycling is alleviated, and the FeP nanoparticles can expand without deforming the carbon shell, thanks to the internal void space of the unique yolk–shell structure, thus preserving the electrode microstructure. Furthermore, the presence of the highly conductive carbon shell enhances the conductivity of the whole electrode. Benefiting from the unique design of the yolk–shell structure, the FeP@CNBs manifests remarkable lithium/potassium storage performance.     

Template‐Free Preparation of Hollow Sb2S3 Microspheres as Supports for Ag Nanoparticles and Photocatalytic Properties of the Constructed Metal–Semiconductor Nanostructures

A simple and convenient Ostwald ripening route to the morphology‐ and phase‐controlled preparation of hollow Sb₂S₃ microspheres is developed. The hollow spheres are clusters of smaller microspheres if orange amorphous Sb₂S₃ colloid is used as the precursor, whereas, if starting from the yellow precursor, the products are regular hollow spheres. By selecting appropriate experimental conditions for ripening, the phase of the hollow Sb₂S₃ microspheres can be controlled. Amorphous and orthorhombic hollow spheres are prepared by ripening the colloidal precursors at ambient temperature and in an autoclave, respectively. The closed shell of hollow Sb₂S₃ spheres can be easily eroded by hydrochloric acid to form an open structure. By the in situ reduction of adsorbed Ag⁺ on the surface and interior of the hollow spheres, Ag nanoparticles are introduced into them, to form functional metal–semiconductor composites, the weight content of which is controlled by regulating the concentration of the Ag⁺ source and the adsorption time. The composite structures composed of Ag nanoparticles and hollow Sb₂S₃ spheres exhibit a remarkably enhanced absorption covering the UV and visible regions of the electromagnetic spectrum. A study of the photocatalytic properties of the composite structures demonstrates that exposure to both UV and visible light enables them to induce the rapid decomposition of 2‐chlorophenol. The degradation rate increases with a larger weight content of Ag in the composite structure.     

Nanostructured Vanadium Oxide Electrodes for Enhanced Lithium‐Ion Intercalation

This article summarizes our most recent studies on improved Li⁺‐intercalation properties in vanadium oxides by engineering the nanostructure and interlayer structure. The intercalation capacity and rate are enhanced by almost two orders of magnitude with appropriately fabricated nanostructures. Processing methods for single‐crystal V₂O₅ nanorod arrays, V₂O₅·n H₂O nanotube arrays, and Ni/V₂O₅·n H₂O core/shell nanocable arrays are presented; the morphologies, structures, and growth mechanisms of these nanostructures are discussed. Electrochemical analysis demonstrates that the intercalation properties of all three types of nanostructure exhibit significantly enhanced storage capacity and rate performance compared to the film electrode of vanadium pentoxide. Addition of TiO₂ to orthorhombic V₂O₅ is found to affect the crystallinity, microstructure, and possible interaction force between adjacent layers in V₂O₅, and subsequently leads to enhanced Li⁺‐intercalation properties in V₂O₅. The amount of water intercalated in V₂O₅ is found to have a significant influence on the interlayer spacing and electrochemical performance of V₂O₅·n H₂O. A systematic electrochemical study has demonstrated that the V₂O₅·0.3 H₂O film has the optimal water content and exhibits the best Li⁺‐intercalation performance.     

Synthesis of Uniquely Structured SnO2 Hollow Nanoplates and Their Electrochemical Properties for Li‐Ion Storage

A new mechanism for the transformation of nanostructured metal selenides into uniquely structured metal oxides via the Kirkendall effect, which results from the different diffusion rates of metal and Se ions and O₂ gas, is proposed. SnSe nanoplates are selected as the first target material and transformed into SnO₂ hollow nanoplates by the Kirkendall effect. SnSe‐C composite powder, in which SnSe nanoplates are attached or stuck to amorphous carbon microspheres, transforms into several tens of SnO₂ hollow nanoplates by a thermal oxidation process under an air atmosphere. Core–shell‐structured SnSe‐SnSe₂@SnO₂, SnSe₂@SnO₂, Se‐SnSe₂@SnO₂, and Se@SnO₂ and yolk–shell‐structured Se@void@SnO₂ intermediates are formed step‐by‐step during the oxidation of the SnSe nanoplates. The uniquely structured SnO₂ hollow nanoplates have superior cycling and rate performance for Li‐ion storage. Additionally, their discharge capacities at the 2nd and 600th cycles are 598 and 500 mA h g^‐1, respectively, and the corresponding capacity retention measured from the 2nd cycle is as high as 84%.     

Rational Construction of a Functionalized V2O5 Nanosphere/MWCNT Layer‐by‐Layer Nanoarchitecture as Cathode for Enhanced Performance of Lithium‐Ion Batteries

Vanadium pentoxide (V₂O₅) has received considerable attention owing to its potential application in energy storage with high specific capacity (294 mAh g^?1). However, the development of V₂O₅ cathodes has been limited by the intrinsically low electrical conductivity and slow electrochemical kinetics resulting in a significant capacity decay. In this article, in order to overcome the issues, V₂O₅ nanospheres and multiwalled carbon nanotubes (MWCNTs) are used to fabricate layer‐by‐layer composited paper as the cathode, which is prepared via electrostatic interaction and vacuum filtration by alternating the positively charged V₂O₅ nanospheres and the negatively charged terminated MWCNT solutions. As a result, the V₂O₅ nanospheres are closely intercalated between the adjacent MWCNT layers leading to minimize the disadvantage voids and enhance the overall conductivity of the composited electrode, which exhibits an enhanced cycling durability as well as improved rate capability.     

A Green and Facile Way to Prepare Granadilla‐Like Silicon‐Based Anode Materials for Li‐Ion Batteries

A yolk‐shell‐structured carbon@void@silicon (CVS) anode material in which a void space is created between the inside silicon nanoparticle and the outer carbon shell is considered as a promising candidate for Li‐ion cells. Untill now, all the previous yolk‐shell composites were fabricated through a templating method, wherein the SiO₂ layer acts as a sacrificial layer and creates a void by a selective etching method using toxic hydrofluoric acid. However, this method is complex and toxic. Here, a green and facile synthesis of granadilla‐like outer carbon coating encapsulated silicon/carbon microspheres which are composed of interconnected carbon framework supported CVS nanobeads is reported. The silicon granadillas are prepared via a modified templating method in which calcium carbonate was selected as a sacrificial layer and acetylene as a carbon precursor. Therefore, the void space inside and among these CVS nanobeads can be formed by removing CaCO₃ with diluted hydrochloric acid. As prepared, silicon granadillas having 30% silicon content deliver a reversible capacity of around 1100 mAh g^?1 at a current density of 250 mA g^?1 after 200 cycles. Besides, this composite exhibits an excellent rate performance of about 830 and 700 mAh g^?1 at the current densities of 1000 and 2000 mA g^?1, respectively.     

Inside Front Cover: One‐Pot Synthesis and Hierarchical Assembly of Hollow Cu2O Microspheres with Nanocrystals‐Composed Porous Multishell and Their Gas‐Sensing Properties (Adv. Funct. Mater. 15/2007)

On p. 2766, Qinshan Zhu and co‐workers report on multishell hollow Cu₂O microspheres that are synthesized by a facile and one‐pot solvothermal route. A two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ are formed first followed by reduction to Cu₂O by glutamic acid, leads to the special multishell and hollow microstructures. Interestingly, a Cu₂O gas sensor fabricated with the multishell microspheres shows a much higher sensitivity to ethanol than solid Cu₂O microspheres. Hierarchical assembly of hollow microstructures is of great scientific and practical value and remains a great challenge. This paper presents a facile and one‐pot synthesis of Cu₂O microspheres with multilayered and porous shells, which were organized by nanocrystals. The time‐dependent experiments revealed a two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ were formed first due to the Ostwald ripening and then reduced by glutamic acid, the resultant Cu₂O nanocrystals were deposited on the hollow intermediate microspheres and organized into finally multishell structures. The special microstructures actually recorded the evolution process of materials morphologies and microstructures in space and time scales, implying an intermediate‐templating route, which is important for understanding and fabricating complex architectures. The Cu₂O microspheres obtained were used to fabricate a gas sensor, which showed much higher sensitivity than solid Cu₂O microspheres.     

Phthalocyanine‐Based 2D Conjugated Metal‐Organic Framework Nanosheets for High‐Performance Micro‐Supercapacitors

2D conjugated metal‐organic frameworks (2D c‐MOFs) are emerging as a novel class of conductive redox‐active materials for electrochemical energy storage. However, developing 2D c‐MOFs as flexible thin‐film electrodes have been largely limited, due to the lack of capability of solution‐processing and integration into nanodevices arising from the rigid powder samples by solvothermal synthesis. Here, the synthesis of phthalocyanine‐based 2D c‐MOF (Ni₂[CuPc(NH)₈]) nanosheets through ball milling mechanical exfoliation method are reported. The nanosheets feature with average lateral size of ≈160 nm and mean thickness of ≈7 nm (≈10 layers), and exhibit high crystallinity and chemical stability as well as a p‐type semiconducting behavior with mobility of ≈1.5 cm² V^?1 s^?1 at room temperature. Benefiting from the ultrathin feature, the nanosheets allow high utilization of active sites and facile solution‐processability. Thus, micro‐supercapacitor (MSC) devices are fabricated mixing Ni₂[CuPc(NH)₈] nanosheets with exfoliated graphene, which display outstanding cycling stability and a high areal capacitance up to 18.9 mF cm^?2; the performance surpasses most of the reported conducting polymers‐based and 2D materials‐based MSCs.     

“Ship‐in‐a‐Bottle” Growth of Noble Metal Nanostructures

Noble metal nanostructures are grown inside hollow mesoporous silica microspheres using “ship‐in‐a‐bottle” growth. Small Au seeds are first introduced into the interior of the hollow microspheres. Au nanorods with synthetically tunable longitudinal plasmon wavelengths and Au nanospheres are obtained through seed‐mediated growth within the microspheres. The encapsulated Au nanocrystals are further coated with Pd or Pt shells. The microsphere‐encapsulated bimetallic core/shell nanostructures can function as catalysts. They exhibit high catalytic performance and their stability is superior to that of the corresponding unencapsulated core/shell nanostructures in the catalytic oxidation of o‐phenylenediamine with hydrogen peroxide. Therefore, these hollow microsphere‐encapsulated metal nanostructures are promising as recoverable and efficient catalysts for various liquid‐phase catalytic reactions.     

Monodisperse Hollow Supraparticles via Selective Oxidation

A novel and general strategy to fabricate monodisperse hollow supraparticles (SPs) via selective chemical oxidation is developed. Core‐shell SPs made of semiconductor nanocrystals (NCs) are first obtained by an in situ assembly method. Subsequently, the cores can be selectively removed by preferential oxidation with dilute H₂O₂, resulting in formation of monodisperse hollow SPs. The structural parameters of the products, such as size, shell thickness, and composition, are tailored easily. The hollow structures achieved from CdSe/CdS core‐shell SPs possess high fluorescence quantum yields and a large Stokes shift, the latter is remarkably different from that of conventional organic dyes and quantum dots. In addition to simple hollow structures, rattle‐type nanostructures composed of semiconductor SPs or noble metal‐semiconductor hybrids are also prepared, exemplifying the versatility of the proposed strategy.     

Unusual Formation of ZnCo2O4 3D Hierarchical Twin Microspheres as a High‐Rate and Ultralong‐Life Lithium‐Ion Battery Anode Material

A facile two‐step strategy involving a polyol method and subsequent thermal annealing treatment is successfully developed for the large‐scale preparation of ZnCo₂O₄ various hierarchical micro/nanostructures (twin mcrospheres and microcubes) without surfactant assistance. To the best of our knowledge, this is the first report on the synthesis of ZnCo₂O₄ mesoporous twin microspheres and microcubes. More significantly, based on the effect of the reaction time on the morphology evolution of the precursor, a brand‐new crystal growth mechanism, multistep splitting then in situ dissolution recrystallization accompanied by morphology and phase change, is first proposed to understand the formation of the 3D twin microshperes, providing new research opportunity for investigating the formation of novel micro/nanostructures. When evaluated as anode materials for lithium‐ion batteries (LIBs), ZnCo₂O₄ hierarchical microstructures exhibit superior capacity retention, excellent cycling stability at the 5 A g^?1 rate for 2000 cycles. Surprisingly, the ZnCo₂O₄ twin microspheres show an exceptionally high rate capability up to the 10 A g^?1 rate. It should be noted that such super‐high rate performance and cycling stability at such high charge/discharge rates are significantly higher than most work previously reported on ZnCo₂O₄ micro/nanostructures and ZnCo₂O₄‐based heterostructures. The ZnCo₂O₄ 3D hierarchical micro/nanostructures demonstrate the great potential as negative electrode materials for high‐performance LIBs.