Multi-metal electrocatalyst with crystalline/amorphous structure for enhanced alkaline water/seawater hydrogen evolution.

The development of well-defined nanomaterials as non-noble metal electrocatalysts has broad application prospect for hydrogen generation technology. Recently, multi-metal electrocatalysts for hydrogen evolution reaction (HER) have attracted extensive attention due to their high catalytic performance arising from the synergistic effect of multi-metal interaction. However, most multi-metal catalysts suffer from the limited synergistic effect because of poor interfacial compatibility between different components. Here, a novel multi-metal catalyst (Ni/MoO2@CoFeOx) nanosheet with a crystalline/amorphous structure is demonstrated, which shows high HER activity. Ni/MoO2@CoFeOx exhibits an ultra-low overpotential of 18, 39, and 93 mV at 10 mA cm-2 in alkaline water, alkaline seawater and natural seawater, respectively, which outperformances most of the state-of-the-art non-noble metal compounds. In addition, the catalyst shows exceptional stability under 500 mA cm-2 in alkaline solution. In-situ Raman and other advanced structural characterization confirms the excellent catalytic activity is mainly contributed by: (1) the strong synergistic effect of multi-metal components provides multiple active sites in the catalytic process; (2) the crystalline/amorphous interface in Ni/MoO2@CoFeOx boosts the catalytically active sites and structure stability; (3) the crystalline phase enhances the intrinsic conductivity greatly; and (4) the amorphous phase provides abundant unsaturated sites for improved intrinsic catalytic activity. This work provides a feasible way to design electrocatalyst with high activity and stability for practical applications.

Facile formation of Zn-incorporated NiFe layered double hydroxide as highly-efficient oxygen evolution catalyst.

Electrochemical water splitting is the primary method to produce green hydrogen, which is considered an efficient alternative to fossil fuels for achieving carbon neutrality. For meeting the increasing market demand for green hydrogen, high-efficiency, low-cost, and large-scale electrocatalysts are crucial. In this study, we report a simple spontaneous corrosion and cyclic voltammetry (CV) activation method to fabricate Zn-incorporated NiFe layered double hydroxide (LDH) on commercial NiFe foam, which shows excellent oxygen evolution reaction (OER) performance. The electrocatalyst achieves an overpotential of 565 mV and outstanding stability of up to 112 h at 400 mA cm-2. The active layer for OER is shown to be ß-NiFeOOH according to the results of in-situ Raman. Our findings suggest that the NiFe foam treated by simple spontaneous corrosion has promising industrial applications as a highly efficient OER catalyst.

Chiral Frustrated Lewis Pair@Metal-Organic Framework as a New Platform for Heterogeneous Asymmetric Hydrogenation.

Asymmetric hydrogenation, a seminal strategy for the synthesis of chiral molecules, remains largely unmet in terms of activation by non-metal sites of heterogeneous catalysts. Herein, as demonstrated by combined computational and experimental studies, we present a general strategy for integrating rationally designed molecular chiral frustrated Lewis pair (CFLP) with porous metal-organic framework (MOF) to construct the catalyst CFLP@MOF that can efficiently promote the asymmetric hydrogenation in a heterogeneous manner, which for the first time extends the concept of chiral frustrated Lewis pair from homogeneous system to heterogeneous catalysis. Significantly, the developed CFLP@MOF, inherits the merits of both homogeneous and heterogeneous catalysts, with high activity/enantio-selectivity and excellent recyclability/regenerability. Our work not only advances CFLP@MOF as a new platform for heterogeneous asymmetric hydrogenation, but also opens a new avenue for the design and preparation of advanced catalysts for asymmetric catalysis.

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.

Facile Synthesis of Graphene with Fast Ion/Electron Channels for High-Performance Symmetric Lithium-Ion Capacitors.

With the battery-type anode and capacitor-type cathode, lithium-ion capacitors (LICs) are expected to exhibit both high energy and high power density but suffer from the mismatch of the electrode reaction kinetics and capacity. Herein, to alleviate the mismatch between the two electrodes and synergistically enhance the energy/power density, we design a method of microwave irradiation reduction to prepare graphene-based electrode material (MRPG/CNT) with fast ion/electron pathway. The three-dimensional structure of CNT intercalation to graphene inhibits the restacking of graphene sheets and improves the conductivity of the electrode material, resulting a rapid ion and electron diffusion channel. Due to its specific properties, MRPG/CNT materials can be used as both anode and cathode electrodes of LICs at the same time. As anode, MRPG/CNT shows a high capacity of 1200 mAh g-1 as well as high rate performance. As cathode, MRPG/CNT displays a high capacity of 108 mAh g-1 and the capacity retention of 100% after 8000 cycles. Coupling the prelithiated MRPG/CNT anode with MRPG/CNT cathode gives a full-graphene-based symmetric LIC, which achieves a high energy density of 232.6 Wh kg-1 at 226.0 W kg-1, 111.2 Wh kg-1 at the ultrahigh power density of 45.2 kW kg-1, and superior capacity retention of 86% after 5000 cycles. The structure design of this electrode provides a new strategy for alleviating the mismatch of LIC electrodes and constructing high-performance symmetrical LICs.

Oxidized-Polydopamine-Coated Graphene Anodes and N,P Codoped Porous Foam Structure Activated Carbon Cathodes for High-Energy-Density Lithium-Ion Capacitors.

As a tradeoff between supercapacitors and batteries, lithium-ion capacitors (LICs) are designed to deliver high energy density, high power density, and long cycling stability. Owing to the different energy storage mechanisms of capacitor-type cathodes and battery-type anodes, engineering and fabricating LICs with excellent energy density and power density remains a challenge. Herein, to alleviate the mismatch between the anode and cathode, we ingeniously designed a graphene with oxidized-polydopamine coating (LG@DA1) and N,P codoped porous foam structure activated carbon (CPC750) as the battery-type anode and capacitor-type cathode, respectively. Using oxidized-polydopamine to stabilize the structure of graphene, increase layer spacing, and modify the surface chemical property, the LG@DA1 anode delivers a maximum capacity of 1100 mAh g-1 as well as good cycling stability. With N,P codoping and a porous foam structure, the CPC750 cathode exhibits a large effective specific surface area and a high specific capacity of 87.5 mAh g-1. In specific, the present LG@DA1//CPC750 LIC showcases a high energy density of 170.6 Wh kg-1 and superior capacity retention of 93.5% after 2000 cycles. The success of the present LIC can be attributed to the structural stability design, surface chemistry regulation, and enhanced utilization of effective active sites of the anode and cathode; thus, this strategy can be applied to improve the performance of LICs.

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).

Sand-Milling Fabrication of Screen-Printable Graphene Composite Inks for High-Performance Planar Micro-Supercapacitors.

Rational engineering and simplified production of printable graphene inks are essential for building high-energy and flexible graphene micro-supercapacitors (MSCs). However, few graphene-based MSCs show impressive areal capacitance and energy density, especially based on additive-manufacturing, cost-effective, and printable inks. Herein, a new-style and solution-processable graphene composite ink is ingeniously formulated for scalable screen printing MSCs. More importantly, the as-formulated inks consist of interwoven two-dimensional graphene and activated carbon nanofillers, which are delaminated by one-step sand-milling turbulent flow exfoliation. Notably, embedding the activated carbon nanoplatelets into graphene layers drastically boosts the electrochemical performance of screen-printed micro-supercapacitors (denoted as Gr/AC-MSCs), such as an outstanding areal capacitance of 12.5 mF cm-2 (about 20 times than pure graphene). The maximum energy density, maximum power density, and exceptional cyclability are 1.07 µW h cm-2, 0.004 mW cm-2, and 88.1% after 5000 cycles, respectively. As such, the as-printed MSCs on paper display high resolution and pronounced energy-storage performance. Furthermore, the packaged and optimized Gr/AC-MSCs showcase remarkable mechanical flexibility even under highly folded and excellent water resistance, maintaining 91.8% capacitance retention after being washed for 90 min. The versatile methodology highlights the promise of graphene and analogous 2D nanosheet functional inks for scalable fabrication of flexible energy-storage devices.

Boosting the Electrochemical Performance of Graphene-Based On-Chip Micro-Supercapacitors by Regulating the Functional Groups.

The on-chip system-compatible power supply shows a high demand for the rapid development of miniaturization devices, such as wireless sensors, remote detecting devices, etc. Moreover, the ever-increasing trends of multifunctionalities and long-term working conditions of such devices raise a high-performance standard for the power supply. Herein, the high-performance electrochemical energy storage micro-supercapacitors (MSCs) are obtained with a metal current collector-free symmetric graphene-based planar structure, in which the functional group of graphene was regulated extensively via fully compatible microfabrication techniques of blue-violet (BV) laser exposure and air plasma treatment. BV laser exposure enhanced the electrical conductivity by reducing the substantial functional groups. Furthermore, the wettability and active sites are tuned by air plasma treatment, thus creating a slightly functional group onto the graphene surface. The resulting reduced graphene oxide (RGO) shows a very low resistance down to 27.2 Ω sq-1, ensuring its superb electron conductivity for fast electron transfer during the electrochemical reactions. The electrochemical performance measurements reveal an areal capacitance as high as 21.86 mF cm-2, which delivers a power density of 5 mW cm-2 with an energy density of 2.49 µWh cm-2. Moreover, it shows superior long-term stability with 99% retention after 10 000 cycles, which is beyond that of most of the reported graphene-based all-solid-state MSCs.

Effect of Aromatic Petroleum Resin on Damping Properties of Polybutyl Methacrylate.

The damping properties of polybutyl methacrylate (PBMA)/aromatic petroleum resin (C9) composite were investigated in this work. In particular, a trace of styrene (St) was introduced to copolymerize with PBMA to improve the compatibility between C9 and matrix. The structure of the copolymer, P(BMA-co-St), was characterized by FTIR and 1HNMR. The P(BMA-co-St)/C9 composites were tested by differencial scanning calorimetry (DSC), scanning electron microscopy (SEM) and dynamical mechanical analysis (DMA). DSC curves of all P(BMA-co-1wt%St)/C9 composites expressed only one glass transition temperature (Tg). SEM images showed that C9 had good compatibility with the matrix after St was introduced. DMA curves indicated that the addition of C9 had a positive effect on the damping properties of PBMA. The loss tangent (tanδ) peak moved to a higher temperature with the increment content of C9, and the effective damping temperature range increased significantly. The influence of aromatic resin C9 and aliphatic resin (C5) on PBMA damping performance was compared. It was further shown that C9 with benzene ring effectively improved the damping performance of PBMA.

Effect of Phenolic Resin Oligomer Motion Ability on Energy Dissipation of Poly (Butyl Methacrylate)/Phenolic Resins Composites.

Poly (butyl methacrylate) (PBMA) was blended with a series of phenolic resins (PR) to study the effect of PR molecular weight on dynamic mechanical properties of PBMA/PR composites. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) found a similar variation of glass transition temperature (Tg). The maximum loss peak (tanδmax) improved in all PBMA/PR blends compared with the pure PBMA. However, tanδmax reduced as the molecular weight increased. This is because PR with higher molecular weight is more rigid in the glass transition zone of blends. The hydrogen bonding between PBMA and PR was characterized by Fourier transform infrared spectroscopy (FTIR). Lower molecular weight PR formed more hydrogen bonds with the matrix and it had weaker temperature dependence. Combined with the results from DMA, we studied how molecular weight affected hydrogen bonding and thus further affected tanδmax.

Effect of Graphene Oxide Modified with Organic Amine on the Aging Resistance, Rolling Loss and Wet-skid Resistance of Solution Polymerized Styrene-Butadiene Rubber.

Graphene oxide (GO) was modified by p-phenylenediamine (PPD), aiming at improving the wet-skid resistance and reduce the rolling loss of solution polymerized styrene-butadiene rubber (SSBR). PPD with amino groups enabled GO to obtain anti-aging function. The structure of modified GO (PPD-GO) was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Raman spectroscopy. Mechanical tests showed that the mechanical properties of SSBR before and after aging were improved by adding PPD-GO. The results of thermogravimetric-differential scanning calorimeter synchronization analysis (TGA-DSC) indicated that SSBR/PPD-GO obtained good thermo-oxidative stability. The dynamic mechanical analysis (DMA) of SSBR composites showed that the mechanical loss factor (tanδ) peak moved to high temperature with the content of PPD-GO. The tanδ values of SSBR composites showed that it had a good effect on improving the wet-skid resistance and reducing the rolling loss of SSBR by adjusting the content of PPD-GO. In particular, with the addition of 4 phr GO, SSBR was effectively improved in mechanical properties, aging resistance, wet-skid resistance and low rolling loss.

Effect of Nitrogen-Doped Graphene Oxide on the Aging Behavior of Nitrile-Butadiene Rubber.

Nitrogen-doped graphene oxide (GO), namely, NG, was prepared by o-phenylenediamine (OPD) grafting onto GO. The structure and morphology of NG were characterized by FITR, XRD, SEM, EDS, Raman spectroscopy, and TGA. OPD was linked to the GO surface by covalent bonds, and the absorption peak of the C=N bond in the phenazine structure was identified in the FITR spectra. The aging resistance properties of nitrile-butadiene rubber (NBR)-NG composites was investigated by mechanical testing, before and after aging. The resistance of the NBR/NG composites with the addition of 3 phr NG fillers was the highest. The aging mechanism was investigated by TGA-DSC, DMA, equilibrium swelling testing, and ATR-FTIR. The results showed that NG could effectively inhibit chain cross-linking in NBR.

Robust and Antibacterial Polymer/Mechanically Exfoliated Graphene Nanocomposite Fibers for Biomedical Applications.

With the increasing demand for composites of multifunctional and integrated performance, graphene-based nanocomposites have been attracting increasing attention in biomedical applications because of their outstanding physicochemical properties and biocompatibility. High product yields and dispersion of graphene in the preparation process of graphene-based nanocomposites have long been a challenge. Further, the mechanical properties and biosafety of final nanocomposites are very important for real usage in biomedical applications. Here, we presented a novel high-throughput method of graphene on mechanical exfoliation in a natural honey medium, and a yield of ∼91% of graphene nanoflakes can be easily achieved with 97.76% of single-layer graphenes. The mechanically exfoliated graphene (MEG) can be well-dispersed in the poly(vinyl alcohol) (PVA) matrix. The PVA/MEG nanocomposite fibers are obtained by gel spinning and stretched 20 times. As a candidate for monofilament sutures, the PVA/MEG nanocomposite fibers with 0.3 wt % of MEG have an ultrahigh ultimate tensile strength of 2.1 GPa, which is far higher than that of the neat PVA fiber (0.75 GPa). In addition, the PVA/MEG nanocomposite fibers also have antibacterial property, low cytotoxicity, and other properties. On the basis of the above-mentioned properties, the effects of a common surgical suture and PVA/MEG nanocomposite fibers on wound healing are evaluated. As a result, the wounds treated with PVA/MEG nanocomposite fibers with 0.3 wt % of MEG show the best healing after 5 days of surgery. It is possible that this novel surgical suture will be available in the market relying on the gentle, inexpensive method of obtaining nonoxidized graphene and the simple process of obtaining nanocomposite fibers.

A facile synthesis of reduced holey graphene oxide for supercapacitors.

Hydroxyl radicals (˙OH) generated from a UV/O3 solution reaction is used to efficiently etch graphene oxide nanosheets under moderate conditions. Reduced holey graphene oxide is directly used as a supercapacitor electrode material and exhibits high specific capacitance (224 F g-1 at a current density of 1 A g-1) and high volumetric capacitance (up to 206 F cm-3).

[The design and experiment of multi-parameter water quality monitoring microsystem based on MOEMS microspectrometer].

Aiming at the monitoring and protecting of water resource environment, a multi-parameter water quality monitoring microsystem based on microspectrometer was put forward in the present paper. The microsystem is mainly composed of MOEMS microspectrometer, flow paths system and embedded measuring & controlling system. It has the functions of self-injecting samples and detection regents, automatic constant temperature, self -stirring, self- cleaning and samples' spectrum detection. The principle prototype machine of the microsystem was developed, and its structure principle was introduced in the paper. Through experiment research, it was proved that the principle prototype machine can rapidly detect quite a few water quality parameters and can meet the demands of on-line water quality monitoring, moreover, the principle prototype machine has strong function expansibility.

Developmental distribution of reelin-positive cells and their secreted product in the rodent spinal cord.

To date, only sympathetic and parasympathetic preganglionic neurons are known to migrate abnormally in reeler mutant spinal cord. Reelin, the large extracellular matrix protein absent in reeler, is found in wild-type neurons bordering both groups of preganglionic neurons. To understand better Reelin's function in the spinal cord, we studied its developmental expression in both mice and rats. A remarkable conservation was found in the spatiotemporal pattern of Reelin in both species. Numerous Reelin-expressing cells were found in the intermediate zone, except for regions containing somatic and autonomic motor neurons. A band of Reelin-positive cells filled the superficial dorsal horn, whereas only a few immunoreactive cells populated the deep dorsal horn and dorsal commissure. High levels of diffuse Reelin product were detected in the lateral marginal and ventral ventricular zones in both rodent species. This expression pattern was detected at all segmental spinal cord levels during embryonic development and remained detectable at lower levels throughout the first postnatal month. To discriminate between the cellular and secreted forms of Reelin, brefeldin A was used to block secretion in organotypic cultures. Such perturbations revealed that the high levels of secreted Reelin in the lateral marginal zone were derived from varicose axons of more medially located Reelin-positive cells. Thus, the laterally located secreted Reelin product may normally prevent the preganglionic neurons from migrating too far medially. Based on the strong evolutionary conservation of Reelin expression and its postnatal detection, Reelin may have other important functions in addition to its role in neuronal migration.