Molecular-Based Design of Microporous Carbon Nanosheets

Microporous carbons afford high surface areas, large pore volumes, and good conductivity, and are fascinating over a wide range of applications. Traditionally synthesized microporous carbon materials usually suffer from some limitations, such as poor accessibility and slow mass transport of molecules due to the micrometer-scale diffusion pathways and space confinement imposed by small pore sizes. Two-dimensional microporous carbon materials, denoted as microporous carbon nanosheets (MCNs), possess nanoscale thickness, which allows fast mass and heat transport along the z axis; thus overcoming the drawbacks of their bulk counterparts. Herein, recent breakthroughs in the synthetic strategies for MCNs are summarized. Three typical methods are discussed in detail with several examples: pyrolysis of organic precursors with 2D units, a templating method that uses wet chemistry, and the molten salt method. Among them, molecular-based assembly of MCNs in the liquid phase shows more controllable morphology, thickness, and pore size distribution. Finally, challenges in this research area are discussed to inspire future explorations.     

Self-Healable Polyelectrolytes with Mechanical Enhancement for Flexible and Durable Supercapacitors

The practical application of advanced personalized electronics is inseparable from flexible, durable, and even self-healable energy storage devices. However, the mechanical and self-healing performance of supercapacitors is still limited at present. Herein, highly transparent, stretchable, and self-healable poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA)/poly(vinyl alcohol) (PVA)/LiCl polyelectrolytes were facilely prepared by one-step radical polymerization. The cooperation of PAMPSA and PVA significantly increased the mechanical and self-healing capacity of the polyelectrolyte, which exhibited superior stretchability of 938 %, stress of 112.68 kPa, good electrical performance (ionic conductivity up to 20.6 mS cm⁻¹), and high healing efficiency of 92.68 % after 24 h. After assembly with polypyrrole-coated single-walled carbon nanotubes, the resulting as-prepared supercapacitor had excellent electrochemical properties with high areal capacitance of 297 mF cm⁻² at 0.5 mA cm⁻² and good rate capability (218 mF cm⁻² at 5 mA cm⁻²). Besides, after cutting in two the supercapacitor recovered 99.2 % of its original specific capacitance after healing for 24 h at room temperature. The results also showed negligible change in the interior contact resistance of the supercapacitor after ten cutting/healing cycles. The present work provides a possible solution for the development of smart and durable energy storage devices with low cost for next-generation intelligent electronics.     

Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).     

Ab initio and Monte Carlo studies of phase transitions and magnetic properties of YCrO3: Heisenberg model

By using the density functional theory (DFT) and Monte Carlo simulations (MCS) with the Heisenberg model, we have studied magnetic properties of the bulk perovskite YCrO₃. The exchange couplings of the Heisenberg model and the magnetic anisotropy are investigated. The 110 direction in the crystalline structure of the compound has shown the minimum energy, it is the easy magnetic direction. Using Monte Carlo simulations, the magnetizations behavior, the effects of system parameters and the critical exponents of the compound YCrO₃ are implemented. It is shown that the bulk perovskite YCrO₃ belongs to the 3D Heisenberg universality class.     

A Shell-by-Shell Approach for Synthesis of Mesoporous Multi-Shelled Hollow MOFs for Catalytic Applications

Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi-shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell-by-shell soft-templating protocol has been devised to fabricate highly uniform multi-shelled hollow cobalt-imidazole-based MOF (ZIF-67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base-metal bifunctional catalysts for one-pot oxidation-Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have.     

Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes

The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g^?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g^?1 for the CNOs/Ppy bilayer (electrochemical deposition).     

Radial breathing-mode frequency of elastically confined spherical nanoparticles subjected to circumferential magnetic field

Knowledge of the vibrational properties of nanoparticles is of fundamental interest since it is a signature of their morphology, and it can be utilized to characterize their physical properties. In addition, the vibration characteristics of the nanoparticles coupled with surrounding media and subjected to magnetic field are of recent interest. This paper develops an analytical approach to study the radial breathing-mode frequency of elastically confined spherical nanoparticles subjected to magnetic field. Based on Maxwell's equations, the nonlocal differential equation of radial motion is derived in terms of radial displacement and Lorentz's force. Bessel functions are used to obtain a frequency equation. The model is justified by a good agreement between the results given by the present model and available experimental and atomic simulation data. Furthermore, the model is used to elucidate the effect of nanoparticle size, the magnetic field and the stiffness of the elastic medium on the radial breathing-mode frequencies of several nanoparticles. Our results reveal that the effects of the magnetic field and the elastic medium are significant for nanoparticle with small size.     

Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals

We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by ¹H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases.     

Yolk‐Shell Porous Microspheres of Calcium Phosphate Prepared by Using Calcium L‐Lactate and Adenosine 5′‐Triphosphate Disodium Salt: Application in Protein/Drug Delivery

A facile and environmentally friendly approach has been developed to prepare yolk‐shell porous microspheres of calcium phosphate by using calcium L ‐lactate pentahydrate (CL) as the calcium source and adenosine 5′‐triphosphate disodium salt (ATP) as the phosphate source through the microwave‐assisted hydrothermal method. The effects of the concentration of CL, the microwave hydrothermal temperature, and the time on the morphology and crystal phase of the product are investigated. The possible formation mechanism of yolk‐shell porous microspheres of calcium phosphate is proposed. Hemoglobin from bovine red cells (Hb) and ibuprofen (IBU) are used to explore the application potential of yolk‐shell porous microspheres of calcium phosphate in protein/drug loading and delivery. The experimental results indicate that the as‐prepared yolk‐shell porous microspheres of calcium phosphate have relatively high protein/drug loading capacity, sustained protein/drug release, favorable pH‐responsive release behavior, and a high biocompatibility in the cytotoxicity test. Therefore, the yolk‐shell porous microspheres of calcium phosphate have promising applications in various biomedical fields such as protein/drug delivery.