Large breathing effect in ZIF-65(Zn) with expansion and contraction of the SOD cage.

The flexibility and guest-responsive behavior of some metal-organic frameworks (MOFs) indicate their potential in the fields of sensors and molecular recognition. As a subfamily of MOFs, the flexible zeolitic imidazolate frameworks (ZIFs) typically feature a small displacive transition due to the rigid zeolite topology. Herein, an atypical reversible displacive transition (6.4 Å) is observed for the sodalite (SOD) cage in flexible ZIF-65(Zn), which represents an unusually large breathing effect compared to other ZIFs. ZIF-65(Zn) exhibits a stepwise II → III → I expansion between an unusual ellipsoidal SOD cage (8.6 Å × 15.9 Å for II) and a spherical SOD cage (15.0 Å for I). The breathing behavior of ZIF-65(Zn) varies depending on the nature of the guest molecules (polarity and shape). Computational simulations are employed to rationalize the differences in the breathing behavior depending on the structure of the ZIF-65(Zn) cage and the nature of the guest-associated host-guest and guest-guest interactions.

An in-plane supercapacitor obtained by facile template method with high performance Mn-Co sulfide-based oxide electrode.

Designing in-plane supercapacitors with high electrode materials selectivity is an indispensable approach to improve electrochemical performance. In this work, a facile template method was employed to fabricate in-plane supercapacitors. This template method could select any electrochemical active materials as electrode materials of in-plane supercapacitors. Hence, a high electrochemical performance material Mn-Co LDO-2S with optimized metal-sulfur bonds proportion and abundant sulfur vacancies was employed as electrode material of symmetrical in-plane supercapacitor (SPS). SPS exhibits excellent electrochemical performance finally, and has considerable area energy density 55.0µWh cm-2with an area power density of 0.7 mW cm-2. As a result, introducing sulfur atoms and sulfur vacancies are efficient approaches to improve electrode materials' electrochemical performance, and template method that proposed in this work is a promising approach to widen selectivity of in-plane supercapacitors' electrode materials.

Face Recognition Algorithm Based on Multiscale Feature Fusion Network.

A face recognition model based on a multiscale feature fusion network is constructed, aiming to make full use of the characteristics of face and to improve the accuracy of face recognition. In addition, three different scale networks are designed to extract global features of faces. Multiscale cross-layer bilinear features of multiple networks are integrated via introducing a hierarchical bilinear pooling layer. By capturing some of the feature relationships between different levels, the model's ability to extract and distinguish subtle facial features is enhanced. Simultaneously, this study uses layer-by-layer deconvolution to fuse multilayer feature information, to solve the problem of losing some key features when extracting features from multilayer convolutional layers and pooled layers. The experimental results show that compared with the recognition accuracy of traditional algorithms, the recognition accuracy of the algorithm on Yale, AR, and ORL face databases is significantly improved.

Formation of Moiré Superlattices via Surfactant/Nanosheet-Co-mediated Crystallization.

Moiré superlattices (MSLs) of two-dimensional (2D) van der Waals materials have attracted considerable attention in recent years; however, studies of bottom-up growth of twisted MSL structures via solution-processed crystallization are rarely reported. Through facile one-pot solvothermal synthesis, here we demonstrate a nonclassical surfactant/nanosheet-co-mediated crystallization pathway for formation of MSL structures with two models of SnS2 and SnSe2. Our experimental results reveal that attractive interactions between 2D inorganic building blocks and surfactant organic molecules during the initial stage of crystallization are crucial to drive surfactant-covered nanosheets to crystallize into molecule-intercalated nanosheet aggregates. Under the high-pressure condition, further crystallograpic fusion can occur if the reaction time is prolonged, which alters the interactions of adjacent layers during the coalescence of small-grain-size 2D domains due to insertion of foreign molecules, leading to interlayer rotations. This work uncovers an interesting organic-inorganic cocrystallization growth mode and provides a novel pathway for large-scale fabrication of MSLs.

Integrated Battery-Capacitor Electrodes: Pyridinic N-Doped Porous Carbon-Coated Abundant Oxygen Vacancy Mn-Ni-Layered Double Oxide for Hybrid Supercapacitors.

Integrating the battery behavior and supercapacitor behavior in a single electrode to obtain better electrochemical performance has been widely researched. However, there is still a lack of research studies on an integrated battery-capacitor supercapacitor electrode (BatCap electrode). In this work, an integrated BatCap electrode porous carbon-coated Mn-Ni-layered double oxide (Mn-Ni LDO-C) was fabricated successfully using controllable heat treatment of polypyrrole-precoated Mn-Ni-layered double hydroxide (Mn-Ni LDH@PPy). This Mn-Ni LDO-C electrode was grown on Ni foam directly and possessed a hierarchical structure that consisted of a pyridinic N (N-6)-doped porous carbon shell and a Mn-Ni LDO core within abundant oxygen vacancies. Benefiting from the synergistic effect of N-6-doped porous carbon and increased oxygen vacancies, Mn-Ni LDO-C exhibited excellent electrochemical performance. The capacity of Mn-Ni LDO-C reached 2.36 C cm-2 (1478.1 C g-1) at 1 mA cm-2 and remained at 92.1% of the initial capacity after 5000 cycles at a current density of 20 mA cm-2. The aqueous battery-supercapacitor hybrid device Mn-Ni LDO-C//active carbon (Mn-Ni LDO-C//AC) also presented superior cycle stability: it retained 85.3% of the original capacity after 5000 cycles at 2 A g-1. Meanwhile, Mn-Ni LDO-C//AC could work normally under a wider potential window (2.0 V), so that the device held the highest energy density of 78.2 Wh kg-1 at a power density of 499.7 W kg-1 and retained 39.1 Wh kg-1 at the highest power density of 31.3 kW kg-1. Two Mn-Ni LDO-C//AC devices connected in series could light a light-emitting diode (LED) bulb easily and keep the LED brightly illuminated for more than 10 min. In general, this work synthesized an integrated BatCap electrode Mn-Ni LDO-C; the integrated electrode exhibited high electrochemical performance, thus has a promising application prospect in the field of energy storage.

Comparative study on supercapacitive and oxygen evolution reaction applications of hollow nanostructured cobalt sulfides.

Due to the diversity of sulfur valence in cobalt-based sulfides, it is difficult to control the crystal phase and composition of the products during synthesis. Herein, a one-pot hydrothermal method is reported to self-assemble the cobalt sulfides (CoS2, Co9S8and Co3S4) with hollow nanostructures. The whole preparation process is simple and mild, avoiding high temperature calcination. The performances of the three kinds of cobalt sulfide in superior supercapacitors and electrocatalytic oxygen evolution performance applications follow the order of CoS2 > Co9S8 > Co3S4. Further analysis demonstrates that the performance difference in these cobalt sulfides may be attributed to three factors: the presence ofS22-,the coordination environment of Co and the presence of continuous network of Co-Co bonds. The distinctive electrochemical performance of CoS2and Co9S8may help us to better understand the excellent electrochemical activity of metal polysulfides and metal sulfides after doping or alloying. Therefore, this work may provide a reference in understanding and designing the electrode materials for highly efficient applications in the fields of energy storage and conversion.

Monolayer Amorphous Carbon-Bridged Nanosheet Mesocrystal: Facile Preparation, Morphosynthetic Transformation, and Energy Storage Applications.

Self-assembly of nanoscale building units into mesoscopically ordered superstructures opens the possibility for tailored applications. Nonetheless, the realization of precise controllability related specifically to the atomic scale has been challenging. Here, first, we explore the key role of a molecular surfactant in adjusting the growth kinetics of two-dimensional (2D) layered SnS2. Experimentally, we show that high pressure both enhances the adsorption energy of the surfactant sodium dodecylbenzene sulfonate (SDBS) on the SnS2(001) surface at the initial nucleation stage and induces the subsequent oriented attachment (OA) growth of 2D crystallites with monolayer thickness, leading to the formation of a monolayer amorphous carbon-bridged nanosheet mesocrystal. It is notable that such a nanosheet-coalesced mesocrystal is metastable with a flowerlike morphology and can be turned into a single crystal via crystallographic fusion. Subsequently, direct encapsulation of the mesocrystal via FeCl3-induced pyrrole monomer self-polymerization generates conformal polypyrrole (PPy) coating, and carbonization of the resulting nanocomposites generates Fe-N-S-co-doped carbons that are embedded with well-dispersed SnS/FeCl3 quantum sheets; this process skillfully integrated structural phase transformation, pyrolysis graphitization, and self-doping. Interestingly, such an integrated design not only guarantees the flowerlike morphology of the final nanohybrids but also, more importantly, allows the thickness of petalous carbon and the size of the nanoconfined particles to be controlled. Benefiting from the unique structural features, the resultant nanohybrids exhibited the brilliant electrochemical performance while simultaneously acting as a reliable platform for exploring the structure-performance correlation of a Li-ion battery (LIB).

Field-Free Spin-Orbit Torque Switching of Perpendicular Magnetization by the Rashba Interface.

Current-induced spin-orbit torques (SOTs) enable efficient electrical manipulation of the magnetization in heterostructures with a perpendicular magnetic anisotropy through the Rashba effect or spin-Hall effect. However, in conventional SOT-based heterostructures, an in-plane bias magnetic field along the current direction is required for the deterministic switching. Here, we report that the field-free SOT switching can be achieved by introducing a wedged oxide interface between a heavy metal and a ferromagnet. The results demonstrate that the field-free SOT switching is determined by a current-induced perpendicular effective field (Hzeff) originating from the interfacial Rashba effect due to the lateral structural symmetry-breaking introduced by the wedged oxide layer. Furthermore, we show that the sign and magnitude of Hzeff exhibit a significant dependence on the interfacial oxygen content, which can be controlled by the inserted oxide thickness. Our findings provide a deeper insight into the field-free SOT switching by the interfacial Rashba effect.

Porous Co3O4/SnO2 quantum dot (QD) heterostructures with abundant oxygen vacancies and Co2+ ions for highly efficient gas sensing and oxygen evolution reaction.

Porous Co3O4/SnO2 quantum dot (QD) heterojunctions with a strong synergistic effect are successfully synthesized in this paper. Owing to the strong synergistic effect between Co3O4 and SnO2QDs, Co3O4/SnO2QD heterostructures possess more Co2+ ions for a faster Co2+/Co0 redox reaction in the process of sensing of reducing gases and electrochemical reactions, and more oxygen vacancies for more active sites and reduced charge transfer resistance on the surface. These advantages are demonstrated to significantly enhance the gas sensitivity to xylene and greatly improve the catalysis for the oxygen evolution reaction (OER). As a catalyst for the OER, Co3O4/SnO2QD (1 : 1) heterostructures exhibit the highest current density, lowest onset potential, largest active surface area and remarkable durability in alkaline electrolytes. The sensitivity of Co3O4/SnO2QD (1 : 1) heterostructures to 100 ppm xylene is almost 10 times higher than that of pure Co3O4 nanosheets and 3 times higher than that of SnO2QDs. In addition, Co3O4/SnO2QD (1 : 1) heterostructure sensors exhibit excellent gas selectivity, long-term stability and markedly high response to low concentrations of xylene at low operating temperatures.

Facile preparation of a TiO2 quantum dot/graphitic carbon nitride heterojunction with highly efficient photocatalytic activity.

In this article, mechanical grinding, an effortless and super-effective synthetic strategy, is used to successfully synthesize a TiO2 quantum dot (TiO2QD)/graphitic carbon nitride (g-C3N4) heterostructure. X-ray photoelectron spectroscopy results together with transmission electron microscopy reveal the formation of the TiO2QD/g-C3N4 heterostructure with strong interfacial interaction. Because of the advantages of this characteristic, the prepared heterostructure exhibits excellent properties for photocatalytic wastewater treatment. Notably, the optimum photocatalytic activity of the TiO2QD/g-C3N4 heterostructure is nearly 3.4 times higher than that of the g-C3N4 nanosheets used for the photodegradation of rhodamine B pollutant. In addition, the stability and possible degradation mechanism of the TiO2QD/g-C3N4 heterojunction are studied in detail. This method may stimulate an effective approach to synthesizing QD-sensitized semiconductor materials and facilitate their application in environmental protection.

A combined experimental-computational investigation on water adsorption in various ZIFs with the SOD and RHO topologies.

We synthesized a series of seven zeolitic imidazolate frameworks (ZIFs), namely ZIF-8, ZIF-90, SIM-1, MAF-6, ZIF-25, ZIF-93 and ZIF-97. Then we investigated the adsorption behavior of water for each ZIF via a combined experimental-computational method. We focused on the van der Waals (vdW) and electrostatic contributions to their water adsorption capacity. The results showed that the vdW interactions were negligible and that electrostatic interactions played a dominant role. Moreover, we studied the effects of topology in the [Zn(almeIm)2] system with the same linker, 4-methylimidazole-5-carbaldehyde (almeIm). We found that SIM-1 with a smaller pore size and higher density exhibited greater water adsorption at low relative pressures, and in contrast, ZIF-93 with a larger pore size and lower density had significantly higher adsorption capacity at high relative pressures.

Probing sub-nano level molecular packing and correlated positron annihilation characteristics of ionic cross-linked chitosan membranes using positron annihilation spectroscopy.

Chitosan, CS, cross-linked with bivalent palladium has shown enhanced mechanical and thermal properties depending on the transformation of the structure at a microscopic scale. In the present study, CS directly cross-linked by palladium cation membranes (CS-cr-PM) was prepared through a solution-casting method. Mobility of chitosan chains were greatly reduced after crosslinking, making a great reduction in the swelling ratio studied by a water-swelling degree measurement, which led to an improvement in molecular chain rigidity. In order to investigate the chain packing at the molecular level in the ionic cross-linked CS system, the structure of chemically-crosslinked CS is investigated by means of the combined use of wide angle X-ray diffraction (WAXD) and infrared measurements, and a combination of positron annihilation lifetime spectroscopy (PALS) and simultaneous coincidence Doppler broadening (CDB) spectroscopy offers coherent information on both the free-volume related sub-nano level molecular packing and the chemical surrounding of free volume nanoholes in CS-cr-PM as a function of palladium salt loading. The variations in the free volume size and size distribution have been determined through the ortho-positronium (o-Ps) lifetime and its lifetime distribution. The studies showed that a strong interaction between CS molecules and palladium cations results in the change in crystallinity in formed CS-cr-PM leading to variational chain packing density. Meanwhile, significant inhibition effects on positronium formation due to doping are observed, which could be interpreted in terms of the existence of chloride ions. Applications of positron annihilation spectroscopy to study the microstructure and correlated positron annihilation characteristics of an ionic cross-linked CS system are systematically discussed.

Facile Synthesis of Co9Se8 Quantum Dots as Charge Traps for Flexible Organic Resistive Switching Memory Device.

Uniform Co9Se8 quantum dots (CSQDs) were successfully synthesized through a facile solvothermal method. The obtained CSQDs with average size of 3.2 ± 0.1 nm and thickness of 1.8 ± 0.2 nm were demonstrated good stability and strong fluorescence under UV light after being easily dispersed in both of N,N-dimethylformamide (DMF) and deionized water. We demonstrated the flexible resistive switching memory device based on the hybridization of CSQDs and polyvinylpyrrolidone (PVP) (CSQDs-PVP). The device with the Al/CSQDs-PVP/Pt/poly(ethylene terephthalate) (PET) structure represented excellent switching parameters such as high ON/OFF current ratio, low operating voltages, good stability, and flexibility. The flexible resistive switching memory device based on hybridization of CSQDs and PVP has a great potential to be used in flexible and high-performance memory applications.

High-performance photodetectors and enhanced photocatalysts of two-dimensional TiO2 nanosheets under UV light excitation.

Due to the large surface area-to-volume ratio and rapid electron transfer, two-dimensional (2D) TiO2 nanosheets with ultrathin thicknesses are synthesized by using a bottom-up strategy and these self-assembled nanosheet (NS)-based photocatalysts and photodetectors were explored for the first time. The influence of calcination temperature on microstructures and photocatalytic activity of TiO2 nanosheets were discovered and presented. The as-obtained TiO2 nanosheets were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) analysis, Fourier transform infrared (FTIR) spectroscopy, UV-vis spectrophotometry, and X-ray photoelectron spectroscopy (XPS). The following heat treatment process induced phase evolution from rutile to anatase. The TiO2 nanosheets calcined at 500 °C exhibited the best activity for photo-degradation of organic dyes under UV light irradiation. The obtained photodetector exhibits excellent performance with a high photocurrent to dark current ratio and fast response and recovery times. Additionally, we demonstrated that the device may have potential applications in the future low-power optoelectronics system.

Surfactant-free Synthesis of CuO with Controllable Morphologies and Enhanced Photocatalytic Property.

A green synthesis for nanoleave, nanosheet, spindle-like, rugby-like, dandelion-like and flower-like CuO nanostructures (from 2D to 3D) is successfully achieved through simply hydrothermal synthetic method without the assistance of surfactant. The morphology of CuO nanostructures can be easily tailored by adjusting the amount of ammonia and the source of copper. By designing a time varying experiment, it is verified that the flower- and dandelion-like CuO structures are synthesized by the self-assembly and Ostwald ripening mechanism. Structural and morphological evolutions are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-visible diffuse reflectance spectra. Additionally, the CuO nanostructures with different morphologies could serve as a potential photocatalyst on the photodecomposition of rhodamine B (RhB) aqueous solutions in the presence of H2O2 under visible light irradiation.

Structural Phase Transition Effect on Resistive Switching Behavior of MoS2 -Polyvinylpyrrolidone Nanocomposites Films for Flexible Memory Devices.

The 2H phase and 1T phase coexisting in the same molybdenum disulfide (MoS2 ) nanosheets can influence the electronic properties of the materials. The 1T phase of MoS2 is introduced into the 2H-MoS2 nanosheets by two-step hydrothermal synthetic methods. Two types of nonvolatile memory effects, namely write-once read-many times memory and rewritable memory effect, are observed in the flexible memory devices with the configuration of Al/1T@2H-MoS2 -polyvinylpyrrolidone (PVP)/indium tin oxide (ITO)/polyethylene terephthalate (PET) and Al/2H-MoS2 -PVP/ITO/PET, respectively. It is observed that structural phase transition in MoS2 nanosheets plays an important role on the resistive switching behaviors of the MoS2 -based device. It is hoped that our results can offer a general route for the preparation of various promising nanocomposites based on 2D nanosheets of layered transition metal dichalcogenides for fabricating the high performance and flexible nonvolatile memory devices through regulating the phase structure in the 2D nanosheets.

Synthesis of multi-shelled ZnO hollow microspheres and their improved photocatalytic activity.

Herein, we report an effective, facile, and low-cost route for preparing ZnO hollow microspheres with a controlled number of shells composed of small ZnO nanoparticles. The formation mechanism of multiple-shelled structures was investigated in detail. The number of shells is manipulated by using different diameters of carbonaceous microspheres. The products were characterized by X-ray powder diffraction, scanning electron microscopy, and transmission electron microscopy. The as-prepared ZnO hollow microspheres and ZnO nanoparticles were then used to study the degradation of methyl orange (MO) dye under ultraviolet (UV) light irradiation, and the triple-shelled ZnO hollow microspheres exhibit the best photocatalytic activity. This work is helpful to develop ZnO-based photocatalysts with high photocatalytic performance in addressing environmental protection issues, and it is also anticipated to other multiple-shelled metal oxide hollow microsphere structures.