Entropy-Driven Morphology Regulation of MAX Phase Solid Solutions with Enhanced Microwave Absorption and Thermal Insulation Performance.

Morphology regulation and composition design have proved to be effective strategies for the fabrication of desirable microwave absorbers. However, it is still challenging to precisely control the microstructure and components of MAX phases. Herein, an entropy-driven approach, a transition from irregular grains (low entropy) to sheet structure (high entropy), is proposed to modulate the morphology of MAX phases. The theoretical calculation indicates that the morphology evolution can be ascribed to the enlarged energy difference between (11_00) and (0001) facets. The enriched structural defects and optimized morphologies yield significant dipolar polarization, interfacial polarization, multiple reflections, and scattering, which all enhance the electromagnetic wave absorption performance of (V0.25 Ti0.25 Cr0.25 Mo0.25 )2 GaC. Specifically, its minimum reflection loss can reach up to -47.12 dB at 12.13 GHz, and the optimal effective absorption bandwidth is 4.56 GHz (2.03 mm). Meanwhile, (V0.25 Ti0.25 Cr0.25 Mo0.25 )2 GaC shows also pronounced thermal insulation properties affording it good reliability in the harsh working environment. This work offers a novel approach to designing and regulating the morphology of the high entropy MAX phase, and also presents an opportunity to elucidate the relationship between entropy and electromagnetic wave absorption performance.

Oxidative Cleavage of ß-O-4 Linkage in Lignin via Co Nanoparticles Embedded in 3DNG as Catalyst.

The cleavage of ß-O-4 linkage in lignin is one of the key steps for oxidative conversion of lignin to low-molecular-weight aromatics. Herein, Co nanoparticles embedded in three-dimensional network of nitrogen-doped graphene (Co/NG@3DNG-X) were prepared through an immersion-pyrolysis procedure, in which X denotes the pyrolysis temperature. The detailed characterization of Co/NG@3DNG-X shows that the Co nanoparticles are coated with a few layers of nitrogen-doped graphene (NG) sheets that are further embedded in 3DNG matrix. The catalytic activities of the Co/NG@3DNG-X for the oxidative cleavage of ß-O-4 linkage in lignin model compounds with O2 as oxidant are explored. It is demonstrated that catalytic activities of as-prepared Co/NG@3DNG-X can be tuned by varying the pyrolysis condition, and the Co/NG@3DNG-900 shows the highest catalytic activity, which is attributed to the enriched Co-Nx species, the strong surface basicity, the high specific surface and the mesoporous motif of 3DNG network. More pronouncedly, the Co/NG@3DNG-900 can also effectively catalyze the oxidative cleavage of organosolv lignin, generating certain monomeric aromatics. Additionally, the intrinsic magnetic property of Co nanoparticles makes the Co/NG@3DNG-X be easily recovered from the reaction mixture, and the as-coated thin NG layer can protect Co nanoparticle from oxidation condition, which putting together afford the Co/NG@3DNG-X with good reusability and stability.

Catalytic Oxidation of Veratryl Alcohol Derivatives Using RuCo/rGO Composites.

Chemoselectively oxidizing Cα -OH to C=O has been considered as a key step for the oxidative depolymerization of lignin. In this work, we design and prepare a series of composites of RuCo alloy nanoparticles and reduced graphene oxide (RuCo/rGO) with different Ru to Co ratios and explore their catalytic activities in the oxidation of veratryl alcohol derivatives, which usually serve as the model compounds for studying lignin oxidation. It is illustrated that the Ru to Co ratio determines the morphology and average size of the RuCo alloy nanoparticles on rGO, and the overall catalytic activities of the composites. The RuCo alloy nanoparticles on rGO with Ru to Co ratios of 1 : 0 to 1.2 : 1 show a unique flower-shaped morphology that increases the exposure of the active sites and thus promotes their contact with the substrates. The RuCo/rGO composites exhibit high catalytic activities for the oxidation of Cα -OH to aldehydes at 100 °C for 2 h. Additionally, the Co component affords the RuCo/rGO composites with magnetic properties that make the separation and recovery of the catalyst simple. Given the high catalytic performances and easy recovery, the RuCo/rGO composites would be potentially useful for the depolymerization of lignin.

Hydrolysis of Organophosphorus Agents Catalyzed by Cobalt Nanoparticles Supported on Three-Dimensional Nitrogen-Doped Graphene.

Catalytic chemical degradations and many other methodologies have been explored for the removal and/or degradation of organophosphorus agents (OPs) that are often used as pesticides, nerve agents, and plasticizers. To explore more efficient and recyclable catalysts for the removal and/or degradation of OPs, we fabricate the composites of cobalt nanoparticles and three-dimensional nitrogen-doped graphene (Co/3DNG). We demonstrate that OPs can be hydrolyzed efficiently at ambient temperature by the Co/3DNG. Because of the unique structural and chemical properties of the supporting matrix 3DNG and active species Co-N, the catalytic activities of Co/3DNG composites are much higher than those of bare 3DNG, Co nanoparticles, or the Co nanoparticles physically mixed with 3DNG. We conclude that in the Co/3DNG composites, the interaction between 3DNG and Co stabilizes and distributes well the Co nanoparticles and affords the active catalytic species Co-N.

Flexible micro-supercapacitors assembled via chemically reduced graphene oxide films assisted by a laser printer.

Flexible micro-supercapacitors (MSCs) as power suppliers are important for portable and wearable electronic devices. Despite enormous efforts made, a simple, inexpensive high-throughput technique of graphene-based MSCs is still challenging. In this work, flexible MSCs are fabricated through commercial laser printing of the interdigital configuration of reduced graphene oxide-graphene oxide-reduced graphene oxide (rGO-GO-rGO) where the conductive rGO works as the electrode and the insulated GO serves as the separator. We demonstrate that the as-fabricated MSC devices show high-energy storage capacities, good cyclic stability and remarkable flexibility. The relationship between the geometric parameters (integration level and coverage fraction) and the capacitive performance of the MSCs is studied systematically to build better theoretical guidance for the design of future in-plane MSCs.

Preparation of nitrogen and sulfur co-doped ordered mesoporous carbon for enhanced microwave absorption performance.

Ordered mesoporous carbon nanomaterials (OMCs) co-doped with homogeneous nitrogen and sulfur heteroatoms were prepared by nanocasting with the pyrrole oligomer catalyzed by sulfuric acid as a precursor and ordered mesoporous silica SBA-15 as a hard-template. By multi-technique approach utilization, it was demonstrated that the N and S co-doped OMCs possessed high ordered mesoporous structures, large surface areas and homogeneous distribution of heteroatoms. As a microwave absorber, the as-prepared materials exhibited a minimum reflection loss (RL) of -32.5 dB at the thickness of 2.5 mm and an absorption bandwidth of 3.2 GHz (RL < -10 dB) in X-band (8.2-12.4 GHz). The good microwave absorption performance was mainly originated from the high electrical conductivity induced by the high surface activity and special structures. And microwave energy can be effectively attenuated through multiple reflections and absorptions in complex conductive network. The design strategy in this work would contribute to the production of a lightweight absorber, presenting a strong absorbency and a wide bandwidth in microwave frequency.

Graphene quantum dots enhance anticancer activity of cisplatin via increasing its cellular and nuclear uptake.

Using assistant reagents to improve the pharmaceutical performance of cisplatin (CDDP) has been one of promising strategies. Owing to their extraordinary properties, graphene quantum dots (GQDs) have shown great potentials in biomedical applications. Here we demonstrate that the combination of GQDs with CDDP can effectively enhance the cytotoxicity, cell cycle arrest, and DNA fragmentation that induced by CDDP. We also found that the GQDs improved the interaction of CDDP with DNA. Combing these results with our previous finding that graphene oxide could enhance the permeability of the cells, we believe GQDs improve the pharmaceutical performance of CDDP via first increasing its cellular uptake through improving the cell permeability, and then reinforcing its interaction with DNA once it is inside cells. The remarkable enhancement to CDDP cellular uptake in CDDP resistant cells further specifies that GQDs can increase chemotherapy efficacy of anticancer drugs that are suboptimal due to the drug resistance.

Morphology change and detachment of lipid bilayers from the mica substrate driven by graphene oxide sheets.

Understanding the interaction between graphene oxide (GO) and a lipid membrane is significant for exploring the biocompatibility and cytotoxicity of GO, which is the basis for utilizing GO in the fields of biosensors, bioimaging, drug delivery, antibacterials, and so on. In this article, we monitored the dynamic process of the morphology change and detachment of lipid bilayers on mica substrates prompted by GO sheets by in situ atomic force microscope (AFM) imaging. It was found that the bare lipid bilayer dramatically expanded in height and would be unstable and detachable from the mica substrates as induced by GO. The detached lipid molecules were found to bind to the GO surface. The results also imply that GO is likely to influence the height and stability of the supported lipid bilayers (SLBs) by adsorbing metal ions such as calcium ions that were used to stabilize the bilayer structures on the mica substrate. These findings illustrate a complicated effect of GO on the SLBs and should be helpful in future applications of GO in biotechnology.

Fluorine-Terminated Self-Assembled Monolayers Grafted Graphite Anode Inducing a LiF-Dominated SEI Inorganic Layer for Fast-Charging Lithium-Ion Batteries.

The electrochemical kinetic processes of Li+ ions, including the desolvation of the Li+ ions from the electrolyte to the solid electrolyte interphase (SEI), the transportation of desolvated Li+ ions across the SEI, and the charge transfer at the interface between the SEI and graphite, determine the rate performance and cycling stability of the graphitic anode in lithium-ion batteries (LIBs). In this work, fluorine-terminated self-assembled monolayers were grafted on the surface of spherical graphite particles to regulate the chemical composition and structure of SEI formed on the graphite surface in the presence of conventional ester electrolytes. The comprehensive characterization and first-principles calculation results illustrate that a uniform LiF-dominated SEI film can be generated on the as-functionalized graphite anode due to the carbon-fluorine bonds' cleavage of fluorine-terminated self-assembled monolayers. The LiF-dominated SEI film is particularly beneficial for desolvated lithium-ion transport across the SEI, affording LiCoO2//graphite full cells with substantially enhanced fast-charging capability and cycle stability. This strategy should be potentially useful for modifying other anode materials to regulate the interfacial chemistry between the anode and electrolyte in lithium-ion batteries.

Dual Design on Hierarchically Hollow MoTe2/C with Ion/Electron Channel Engineering for High-Performance Sodium Storage.

Transition-metal tellurides have been investigated as novel anode materials for application in sodium-ion batteries (SIBs) due to their rich active sites and unique and controllable layered nanostructures. However, the weak structural strength and inferior intercalation/deintercalation kinetics inhibit the development of transition-metal tellurides. In this work, MoTe2/C composites with two different hollow nanostructures are designed and prepared. By adjustment of the precursor structure, MoTe2/C-2 exhibits superior sodium-storage performance because of its uniquely hollow nanostructure with self-assembled 2D flexible nanosheets grown on the external surface. MoTe2/C-2 delivers a higher specific capacity (276 mAh g-1 at 0.1 A g-1 after 300 cycles), much more than MoTe2/C-1 (201 mAh g-1 at 0.1 A g-1 after 300 cycles), and exhibits a long-time cycling performance (131 mAh g-1 at 1 A g-1 after 2000 cycles). The excellent sodium-storage performance derived from the rational structure design is beneficial for shortening the ion paths, facilitating the sodiation/desodiation process, and reinforcing the intrinsic structural stability, thus boosting the reaction kinetics and prolonging the cycling life. Meanwhile, the assembled full-cell maintains 101 mAh g-1 at 0.1 A g-1 after 50 cycles and lights an electric watch. The findings provide several new views for preparation of more transition-metal tellurides with multi-ion/electron migration channel engineering.

Solution-processable graphene quantum dots.

This minireview describes recent progress in solution-processable graphene quantum dots (SGQDs). Advances in the preparation, modification, properties, and applications of SGQDs are highlighted in detail. As one of emerging nanostructured materials, possible ongoing research related to the precise control of the lateral size, edge structure and surface functionality; the manipulation and characterization; the relationship between the properties and structure; and interfaces with biological systems of SGQDs have been speculated upon.

Study of the structure and electrical properties of chemically reduced graphene/polyvinyl alcohol composite films.

Thin films of composites of chemically reduced graphene oxide (rGO) and polyvinyl alcohol (PVA) were prepared by simple solution-mixing technique followed by filtration or evaporation. The as-obtained composite rGO/PVA films were characterized by using optical microscope, gloss meter, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The different glossiness of the upper and lower surface of the films prepared by filtration and evaporation, combined with the section SEM images indicated that the thin films have a gradient layered structure, and the distance between the layers increases from the bottom to the top surface of the thin film obtained by filtration, and decreases for the film obtained by evaporation. Such a structure gives the films anisotropic swelling and electrical conduction properties which may find practical applications in electrodes and multifunctional composites.

Removal of organophosphorus agents via atomically dispersed Co on nitrogen-doped graphene: catalytic degradation and adsorption.

In this work, we disperse Co atomically on three-dimensional networks of N-doped graphene (3DNG) through the impregnation of 3DNG with Co(Ac)2·4H2O solution followed by rapid pyrolysis. The structure, morphology and composition of the as-prepared composite, namely ACo/3DNG, are characterized. The atomically dispersed Co and enriched Co-N species afford the ACo/3DNG with unique catalytic activity for hydrolysis of organophosphorus agents (OPs), and the network structure and super-hydrophobic surface of 3DNG ensures excellent physical adsorption capacity. Thus, ACo/3DNG demonstrates good capability for removal of OPs pesticides from water.

Flexible Fluorinated Graphene/Poly(vinyl Alcohol) Films toward High Thermal Management Capability.

Graphene is widely used in heat dissipation, owing to its inherently high in-plane thermal conductivity and excellent mechanical properties. However, its poor cross-plane thermal conductivity limits its use in some electronic applications. The electron distribution of graphene and the interaction with the base material can be greatly altered by introducing F, the most electronegative element, giving fluorinated graphene oxide (FG) with a high thermal conductivity. Herein, FG is prepared by grafting F atoms onto the surface of graphene oxide in a low-temperature solid-phase reaction with poly(vinylidene fluoride) as a fluorine source. This method can effectively avoid the use of dangerous substances such as HF and F2. The FG dispersion and aqueous poly(vinyl alcohol) (PVA) solution are sequentially vacuum-filtered to obtain the FG/PVA composite film. After natural drying and hot-pressing, the thermal conductivity of the N-FG/PVA film is enhanced by the hydrogen bond between F of FG and the hydroxyl group of PVA. The in-plane and cross-plane thermal conductivity of an N-FG/PVA film containing 10.4 wt % FG are 7.13 and 1.42 W m-1 k-1, respectively. The film has a tensile strength of 60 MPa and an elongation at a break of 28%, which is promising for the thermal management of flexible electronic devices.

Vapor-phase derived ultra-fine Bismuth nanoparticles embedded in carbon nanotube networks as anodes for sodium and potassium ion batteries.

Bismuth (Bi) is a promising material as the anode for sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) due to its characteristics such as reasonable price and high theoretical volumetric capacity (3800 mAh cm-3). Nevertheless, considerable drawbacks have hindered the practical applications of Bi, including its relatively low electrical conductivity and inevitable volumetric change during the alloying/dealloying processes. To solve these problems, we proposed a novel design:Bi nanoparticles were synthesized via a single-step low-pressure vapor-phase reaction and embedded onto the surfaces of multi-walled carbon nanotubes (MWCNTs). After being vaporized at 650℃ and 10-5 Pa, Bi nanoparticles less than 10 nm were uniformly distributed in the three-dimensional (3D) MWCNT networks to form a Bi/MWNTs composite. In this unique design, the nanostructured Bi can reduce the risk of structural rupture during cycling, and the structure of the MWCMT network is beneficial in shortening the electron/ion transport path. In addition, MWCNTs can improve the overall conductivity of the Bi/MWCNTs composite and prevent particle aggregation, thus improving the cycling stability and rate performance. As an anode material for SIB, the Bi/MWCNTs composite has demonstrated excellent fast charging performance with a reversible capacity of 254 mAh/g at 20 A/g. A capacity of 221mAhg-1 after cycling at 10 A/g for 8000 cycles has also been achieved for SIB. As an anode material for PIB, the Bi/MWCNTs composite has delivered excellent rate performances with a reversible capacity of 251 mAh/g at 20 A/g. A specific capacity of 270mAhg-1 after cycling at 1Ag-1 for 5000 cycles has also been achieved for PIB.

Assembly of graphene oxide-enzyme conjugates through hydrophobic interaction.

Biochemical and biomedical applications of graphene oxide (GO) critically rely on the interaction of biomolecules with it. It has been previously reported that the biological activity of the GO-enzyme conjugate decreases due to electrostatic interaction between the enzymes and GO. Herein, the immobilization of horseradish peroxidase (HRP) and oxalate oxidase (OxOx) on chemically reduced graphene oxide (CRGO) are reported. The enzymes can be adsorbed onto CRGO directly with a tenfold higher enzyme loading than that on GO, and maximum enzyme loadings reach 1.3 and 12 mg mg(-1) for HRP and OxOx, respectively. Significantly, the more CRGO is reduced, the higher the enzyme loading. The CRGO-HRP conjugates also exhibit higher enzyme activity and stability than GO-HRP. Excellent properties of the CRGO-enzyme conjugates are attributed to hydrophobic interaction between the enzymes and the CRGO. The hydrophobic interaction mode of the CRGO-enzyme conjugates can be applied to other hydrophobic proteins, and thus could dramatically improve the performance of immobilized proteins. The results indicate that CRGO is a potential substrate for efficient enzyme immobilization, and is an ideal candidate as a macromolecule carrier and biosensor.

Hydrated vanadium pentoxide/reduced graphene oxide composite cathode material for high-rate lithium ion batteries.

As well-known, hydrated vanadium pentoxide (V2O5·nH2O) has a larger layer spacing than orthogonal V2O5, which could offer more active sites to accommodate lithium ions, ensuring a high specific capacity. However, the exploration of V2O5·nH2O cathode is limited by its inherently low conductivity and slow electrochemical kinetics, leading to a significant decrease in capability. Herein, we prepared V2O5·nH2O/reduced graphene oxide (rGO) composite with low rGO content (8 wt%) via a simple yet effective dual electrostatic assembly strategy. When used as the cathode material for lithium-ion batteries (LIBs), V2O5·nH2O/rGO manifests a high reversible capacity of 268 mAh g-1 at 100 mA g-1 and especially an excellent rate capability (196 mAh g-1 at 1000 mA g-1 and 129 mA h g-1 at 2000 mA g-1), surpassing those of the V2O5/carbon composites reported in the literatures. Notably, the remarkable performance should be referable to the synergetic effects between one-dimensional V2O5·nH2O nanobelts and two-dimensional rGO nanosheets, which provide a short transport pathway and enhanced electrical conductivity. This strategy opens a new opportunity for designing high-performance cathode material with excellent rate performance for advanced LIBs.

Core-Shell PMIA@PVdF-HFP/Al2O3 Nanofiber Mats In Situ Coaxial Electrospun on LiFePO4 Electrode as Matrices for Gel Electrolytes.

Gel electrolytes show certain advantages over conventional liquid and solid electrolytes, but their mechanical strength and surface adhesion to the electrode remain to be improved. To address the challenges, we design and fabricate herein the core-shell nanofiber mats in situ on the LiFePO4 electrode as matrices for gel electrolytes, in which the core is poly(m-phenylene isophthalamide) (PMIA) nanofiber and the shell are composite of Al2O3 nanoparticles and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP). The mechanical property of the core-shell polymeric nanofiber mats and their surface interaction with LiFePO4 electrode are characterized complementarily using dynamic thermomechanical analysis and scanning electron microscopy. The electrochemical properties of the gel electrolytes based on the as-prepared matrices after being loaded with lithium salt solution are studied systematically on half coin cells. It is found that the ultimate strength of the core-shell PMIA@PVdF-HFP/Al2O3 mat can reach 6.70 MPa, 2 times higher than that of the PVdF-HFP/Al2O3 nanofiber mat. Meanwhile, the shell PVdF-HFP/Al2O3 can ensure manifest surface affinity to the LiFePO4 electrode and enhance lithium-ion conductance. Thus, the as-assembled LiFePO4 half coin cells using PMIA@PVdF-HFP/Al2O3 gel electrolyte show good electrochemical performances, especially the long cycle stability with the capacity retention of 96.6% after 600 cycles under 1C.

Graphene oxide as a matrix for enzyme immobilization.

Graphene oxide (GO), having a large specific surface area and abundant functional groups, provides an ideal substrate for study enzyme immobilization. We demonstrated that the enzyme immobilization on the GO sheets could take place readily without using any cross-linking reagents and additional surface modification. The atomically flat surface enabled us to observe the immobilized enzyme in the native state directly using atomic force microscopy (AFM). Combining the AFM imaging results of the immobilized enzyme molecules and their catalytic activity, we illustrated that the conformation of the immobilized enzyme is mainly determined by interactions of enzyme molecules with the functional groups of GO.

Enhancing the photoelectric conversion of dye-sensitized solar cell via nitrogen-doped nanocrystalline titania electrode.

A high efficient dye-sensitized solar cell (DSC) was fabricated using nitrogen-doped nanocrystalline titania(TiO2) photoanode. X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), X-ray powder diffraction (XRD), zeta potentials, nitrogen adsorption-desorption and elemental analysis experiments were employed to characterize the nitrogen-doped nanocrystalline TiO2 photoanode. An obvious enhancement of the optical absorption in the range of 380-550 nm was observed for nitrogen-doped TiO2, which was attributed to both the substitutional N and the chemisorbed N2 molecules. A conversion efficiency of 9.04% was obtained on the DSC based on nitrogen-doped TiO2 photoanode annealed in a flow of NH3 at 550 degrees C, with an increase of 15.6% improvement in comparison with pure TiO2 (7.82%). The mechanism for the enhanced photovoltaic performance was discussed.