Walnut-inspired microsized porous silicon/graphene core–shell composites for high-performance lithium-ion battery anodes

Silicon is considered an exceptionally promising alternative to the most commonly used material, graphite, as an anode for next-generation lithium-ion batteries, as it has high energy density owing to its high theoretical capacity and abundant storage. Here, microsized walnut-like porous silicon/reduced graphene oxide (P-Si/rGO) core–shell composites are successfully prepared via in situ reduction followed by a dealloying process. The composites show specific capacities of more than 2,100 mAh·g^?1 at a current density of 1,000 mA·g^?1, 1,600 mAh·g^?1 at 2,000 mA·g^?1, 1,500 mAh·g^?1 at 3,000 mA·g^?1, 1,200 mAh·g^?1 at 4,000 mA·g^?1, and 950 mAh·g^?1 at 5,000 mA·g^?1, and maintain a value of 1,258 mAh·g^?1 after 300 cycles at a current density of 1,000 mA·g^?1. Their excellent rate performance and cycling stability can be attributed to the unique structural design: 1) The graphene shell dramatically improves the conductivity and stabilizes the solid–electrolyte interface layers; 2) the inner porous structure supplies sufficient space for silicon expansion; 3) the nanostructure of silicon can prevent the pulverization resulting from volume expansion stress. Notably, this in situ reduction method can be applied as a universal formula to coat graphene on almost all types of metals and alloys of various sizes, shapes, and compositions without adding any reagents to afford energy storage materials, graphene-based catalytic materials, graphene-enhanced composites, etc.

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Plasmon enhancement for Vernier coupled single-mode lasing from ZnO/Pt hybrid microcavities

It is essential to develop a single mode operation and improve the performance of lasing in order to ensure practical applicability of microlasers and nanolasers.In this paper,two hexagonal microteeth with varied nanoscaled air-gaps of a ZnO microcomb are used to construct coupled whispering-gallery cavities.This is done to achieve a stable single mode lasing based on Vernier effect without requiring any complicated or sophisticated manipulation to achieve positioning with nanoscale precision.Optical gain and the corresponding ultraviolet lasing performance were improved greatly through coupling with localized surface plasmons of Pt nanoparticles.The ZnO/Pt hybrid microcavities achieved a seven-fold enhancement of intensity of single mode lasing with higher sidemode suppression ratio and lower threshold.The mechanism that led to this enhancement has been described in detail.     

A pH-switched mesoporous nanoreactor for synergetic therapy

Zinc oxide nanoparticles (ZnO NPs),as a new type of pH-sensitive drug carrier,have received much attention.ZnO NPs are stable at physiological pH,but can dissolve quickly in the acidic tumor environment (pH ＜ 6) to generate cytotoxic zinc ions and reactive oxygen species (ROS).However,the protein corona usually causes the non-specific degradation of ZnO NPs,which has limited their application considerably.Herein,a new type of pH-sensitive nanoreactor (ZnO-DOX@F-mSiO2-FA),aimed at reducing the non-specific degradation of ZnO NPs,is presented.In the acidic tumor environment (pH ＜ 6),it can release cytotoxic zinc ions,ROS,and anticancer drugs to kill cancer cells effectively.In addition,the fluorescence emitted from fluorescein isothiocyanate (FITC)-labeled mesoporous silica (F-mSiO2) and doxorubicin (DOX) can be used to monitor the release behavior of the anticancer drug.This report provides a new method to avoid the non-specific degradation of ZnO NPs,resulting in synergetic therapy by taking advantage of ZnO NPs-induced oxidative stress and targeted drug release.     

Nanowire encapsulation with polymer for electrical isolation and enhanced optical properties

Light management and electrical isolation are essential for the majority of optoelectronic nanowire (NW) devices.Here,we present a cost-effective technique,based on vapor-phase deposition of parylene-C and subsequent annealing,that provides conformal encapsulation,anti-reflective coating,improved optical properties,and electrical insulation for GaAs nanowires.The process presented allows facile encapsulation and insulation that is suitable for any nanowire structure.In particular,the parylene-C encapsulation functions as an efficient antireflection coating for the nanowires,with reflectivity down to ＜1％ in the visible spectrum.Furthermore,the parylene-C coating increases photoluminescence intensity,suggesting improved light guiding to the NWs.Finally,based on this process,a NW LED was fabricated,which showed good diode performance and a clear electroluminescence signal.We believe the process can expand the fabrication possibilities and improve the performance of optoelectronic nanowire devices.     

Effects of Ge<Superscript>4+</Superscript> acceptor dopant on sintering and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> lead-free piezoceramics

Lead-free (K_0.5Na_0.5)(Nb_1-xGe _x )O₃ (KNN-xGe, where x = 0-0.01) piezoelectric ceramics were prepared by conventional ceramic processing. The effects of Ge⁴⁺ cation doping on the phase compositions, microstructure and electrical properties of KNN ceramics were studied. SEM images show that Ge⁴⁺ cation doping improved the sintering and promoted the grain growth of the KNN ceramics. Dielectric and ferroelectric measurements proved that Ge⁴⁺ cations substituted Nb⁵⁺ ions as acceptors, and the Curie temperature (T_C) shows an almost linear decrease with increasing the Ge⁴⁺ content. Combining this result with microstructure observations and electrical measurements, it is concluded that the optimal sintering temperature for KNN-xGe ceramics was 1020°C. Ge⁴⁺ doping less than 0.4 mol.%can improve the compositional homogeneity and piezoelectric properties of KNN ceramics. The KNN-xGe ceramics with x = 0.2% exhibited the best piezoelectric properties: piezoelectric constant d₃₃ = 120 pC/N, planar electromechanical coupling coefficient k_p = 34.7%, mechanical quality factor Q_m = 130, and tanδ = 3.6%.     

Environmentally benign chitosan as reductant and supporter for synthesis of Ag/AgCl/chitosan composites by one-step and their photocatalytic degradation performance under visible-light irradiation

A novel Ag/AgCl/chitosan composite photocatalyst was successfully prepared by a simple one-step method. During this progress, environmentally benign chitosan not only served as reductant to reduce Ag⁺ to Ag⁰ species, but also acted as supporter for Ag/AgCl nanoparticles. XRD, SEM, EDX, UV-vis DRS and XPS were employed to characterize the as-prepared simples. SEM images of Ag/AgCl/chitosan composites revealed that Ag/AgCl nanoparticles were successfully loaded onto chitosan without obvious aggregation. All Ag/AgCl/chitosan composites exhibited efficient photocatalytic activity for the degradation of rhodamine B (RhB) under visible-light irradiation. The result of photocatalytic degradation experiment indicated that 20% of the mass ratio of AgCl to chitosan was the optimum, and after 40 min photocatalytic reaction, the degradation rate reached about 96%.     

Phosphorus and phosphide nanomaterials for sodium-ion batteries

Sodium-ion batteries have received remarkable attention as next-generation high-performance electrochemical energy storage devices because of their cost effectiveness and the broad geographical distribution of sodium. As a critical component of sodium-ion batteries, anode materials, especially nanostructured anodes, have a significant effect on the electrochemical performance of sodium-ion batteries. Recent research indicates that phosphorus and metal phosphides show great promise as anode candidates for sodium-ion batteries because of their low cost and relatively high theoretical gravimetric and volumetric specific capacities. In this review, we systematically summarize recent research progress on state-of-the-art nanostructured phosphorus and phosphides, including the synthetic strategies, Na-storage mechanisms, and the relationship between the nanostructure and electrochemical performance. Moreover, we present an overview of future challenges and opportunities based on current developments.

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Interest of molecular functionalization for electrochemical storage

Despite great interests in electrochemical energy storage systems for numerous applications, considerable challenges remain to be overcome. Among the various approaches to improving the stability, safety, performance, and cost of these systems, molecular functionalization has recently been proved an attractive method that allows the tuning of material surface reactivity while retaining the properties of the bulk material. For this purpose, the reduction of aryldiazonium salt, which is a versatile method, is considered suitable; it forms robust covalent bonds with the material surface, however, with the formation of multilayer structures and sp³ defects (for carbon substrate) that can be detrimental to the electronic conductivity. Alternatively, non-covalent molecular functionalization based on π–π interactions using aromatic ring units has been proposed. In this review, the various advances in molecular functionalization concerning the current limitations in lithium-ion batteries and electrochemical capacitors are discussed. According to the targeted applications and required properties, both covalent and non-covalent functionalization methods have proved to be very efficient and versatile. Fundamental aspects to achieve a better understanding of the functionalization reactions as well as molecular layer properties and their effects on the electrochemical performance are also discussed. Finally, perspectives are proposed for future implementation of molecular functionalization in the field of electrochemical storage.

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A series of nanoparticles with phase-separated structures by 1,1-diphenylethene controlled one-step soap-free emulsion copolymerization and their application in drug release

A facile one-step approach to synthesize various phase-separated porous, raspberry-like, flower-like, core–shell and anomalous nanoparticles and nanocapsules via 1,1-diphenylethene (DPE) controlled soap-free emulsion copolymerization of styrene (S) with glycidyl methacrylate (GMA), or acrylic acid (AA) is reported. By regulating the mass ratio of S/GMA, transparent polymer solution, porous and anomalous P(S-GMA) particles could be produced. The P(S-GMA) particles turn from flower-like to raspberry-like and then to anomalous structures with smooth surface as the increase of divinylbenzene (DVB) crosslinker. Transparent polymer solution, nanocapsules and core–shell P(S-AA) particles could be obtained by altering the mole ratio of S/AA; anomalous and raspberry-like P(S-AA) particles are produced by adding DVB. The unpolymerized S resulted from the low monomer conversion in the presence of DPE aggregates to form nano-sized droplets, and migrates towards the external surfaces of the GMA-enriched P(S-GMA) particles and the internal bulk of the AA-enriched P(S-AA) particles. The nano-sized droplets function as in situ porogen, porous P(S-GMA) particles and P(S-AA) nanocapsules are produced when the porogen is removed. This novel, facile, one-step method with excellent controllability and reproducibility will inspire new strategies for creating hierarchical phase-separated polymeric particles with various structures by simply altering the species and ratio of comonomers. The drug loading and release experiments on the porous particles and nanocapsules demonstrate that the release of doxorubicin hydrochloride is very slow in weakly basic environment and quick in weakly acidic environment, which enables the porous particles and nanocapsules with promising potential in drug delivery applications.

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Determination of the acidic properties of carboxylated carbocatalysts in an acid-catalyzed ring-opening reaction using kinetic profiling

The acid-catalyzed ring-opening reaction of styrene oxide was used as a probe reaction for evaluating the acidic properties of carboxylated carbocatalysts. Significant discrepancies in the initial reaction rates were normalized using the total number of carboxyl groups, and demonstrated that the average catalytic activities of the carboxyl moieties on the carbocatalysts differed. Comparisons between the apparent activation energy E _a and the pre-exponential factor A, derived from Arrhenius analysis, demonstrated that A varied more significantly, and therefore had a more significant effect on the reaction rates than E _a. The variation in the calculated pKa values of the carboxyl groups was attributed to the electronic effects of the nitro groups. This hypothesis was supported by the temperature programmed desorption profiles of nitrogen monoxide ions.

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