Fabrication of Zn-Air Battery with High Output Capacity Under Ultra-Large Current.

Zn-air battery (ZAB) is advocated as a more viable option in the new-energy technology. However, the limited-output capacity at a high current density impedes the driving range in power batteries substantially. Here, a novel heterojunction-based graphdiyne (GDY) and Ag29Cu7 alloy quantum dots (Ag29Cu7 QDs/GDY) for constructing a high-performance aqueous ZAB are fabricated. The as-fabricated ZAB achieves discharge at up to 100 mA cm-2 (the highest value ever reported) along with a remarkable output specific capacity of 786.2 mAh g-1 Zn, which is mainly benefitted from the binary-synergistic effect toward a stable triple-phase interface for air electrode induced by the Ag29Cu7 QDs and GDY in harsh base, together with the decreasing reaction energy barrier and polarization. The results outperform the superior reports discharging at low current and will bring breakthrough progress toward the practical applications of ZAB on large power supply facilities.

Rational Fabrication of Defect-Rich and Hierarchically Porous Fe-N-C Nanosheets as Highly Efficient Oxygen Reduction Electrocatalysts for Zinc-Air Battery.

The rational design of morphology and structure for oxygen reduction reaction (ORR) catalysts still remains a critical challenge. Herein, we successfully construct defect-rich and hierarchically porous Fe-N-C nanosheets (Fe-N-CNSs), by taking advantage of metal-organic complexation and a mesoporous template. Benefiting from the advantages of high density of active sites, fast mass transfer channels, and sufficient reaction area, the optimal Fe-N-CNSs demonstrate satisfactory ORR activity with an excellent half-wave potential of up to 0.87 V, desirable durability, and robust methanol tolerance. Noteworthy, the Fe-N-CNSs based zinc-air battery shows significant performance with a peak power density of 128.20 mW cm-2 and open circuit voltage of 1.53 V, which reveals that the Fe-N-CNSs catalysts present promising practical application prospects. Therefore, we believe that this research will provide guidance for the optimization of Fe-N-C materials.

A Novel Carbon Support: Few-Layered Graphdiyne-Decorated Carbon Nanotubes Capture Metal Clusters as Effective Metal-Supported Catalysts.

Carbon-supported metal nanocatalysts have received substantial attention for heterogeneous catalysis in industry. Hunting for suitable and impactful carbon supports that have strong interactions with metal nanocatalyst is a matter of great urgency. Herein, a well-designed graphdiyne layer decorated on the carbon nanotubes sidewalls (CNT@GDY) serves as a novel carbon support. This unique hybrid structure effectively traps platinum and palladium atomic clusters (Pt/Pd-ACs) with dimensions of 0.65 nm and 1.05 nm uniformly and firmly, forming novel carbon-supported metal nanocatalysts (Pt(Pd)-ACs/CNT @ GDY) for efficient hydrogen generation and aromatic nitroreduction, respectively. The Pt-ACs/CNT@GDY can deliver an HER current density of 10 mA cm-2 with a small overpotential of 23 mV in 0.5 M H2 SO4 , showing a greatly enhanced mass activity, intrinsic activity than the commercial Pt/C catalyst. The Pd-ACs/CNT@GDY also exhibits excellent catalytic activity and a high turnover frequency of 38.0 min-1 for aromatic nitroreduction. The carbon support turns out to possess excellent conductivity, abundant and uniform reactive sites, low redox potential, more negative surface and large specific surface area as well as a strong interaction with ACs, as anticipated in ideal supports, which can be applied in other metal-supported catalysts.

High-Performance Gas Sensor of Polyaniline/Carbon Nanotube Composites Promoted by Interface Engineering.

Inspired by the enhanced gas-sensing performance by the one-dimensional hierarchical structure, one-dimensional hierarchical polyaniline/multi-walled carbon nanotubes (PANI/CNT) fibers were prepared. Interestingly, the simple heating changed the sensing characteristics of PANI from p-type to n-type and n-type PANI and p-type CNTs form p-n hetero junctions at the core-shell interface of hierarchical PANI/CNT composites. The p-type PANI/CNT (p-PANI/CNT) and n-type PANI/CNT (n-PANI/CNT) performed the higher sensitivity to NO2 and NH3, respectively. The response times of p-PANI/CNT and n-PANI/CNT to 50 ppm of NO2 and NH3 are only 5.2 and 1.8 s, respectively, showing the real-time response. The estimated limit of detection for NO2 and NH3 is as low as to 16.7 and 6.4 ppb, respectively. After three months, the responses of p-PANI/CNT and n-PANI/CNT decreased by 19.1% and 11.3%, respectively. It was found that one-dimensional hierarchical structures and the deeper charge depletion layer enhanced by structural changes of PANI contributed to the sensitive and fast responses to NH3 and NO2. The formation process of the hierarchical PANI/CNT fibers, p-n transition, and the enhanced gas-sensing performance were systematically analyzed. This work also predicts the development prospects of cost-effective, high-performance PANI/CNT-based sensors.

Ni-Doped ZnS Nanospheres Decorated with Au Nanoparticles for Highly Improved Gas Sensor Performance.

Novel Ni-doped wurtzite ZnS nanospheres decorated with Au nanoparticles (Au NPs⁻ZnS NSs) have been successfully fabricated using a simple method involving vacuum evaporation followed by an annealing process. This transition metal-doped gas sensor had high responsivity, extremely fast response and recovery time, and excellent selectivity to formaldehyde at room temperature. The response and recovery time are only 29 s and 2 s, respectively. Since ZnS is transformed into ZnO at a high temperature, superior room temperature-sensing performance can improve the stability and service life of the sensor. The improvement in sensing performance could be attributed to the reduced charge-transfer distance resulting from the creation of a local charge reservoir layer, and the catalytic and spillover effect of Au nanoparticles. The rough and porous spherical structure can also facilitate the detection and diffusion of gases. The as-prepared Au NPs⁻ZnS NSs are considered to be an extremely promising candidate material for gas sensors, and are expected to have other potential applications in the future.

Multichannel Discriminative Detection of Explosive Vapors with an Array of Nanofibrous Membranes Loaded with Quantum Dots.

The multichannel fluorescent sensor array based on nanofibrous membranes loaded with ZnS quantum dots (QDs) was created and demonstrated for the discriminative detection of explosives. The synergistic effect of the high surface-to-volume ratio of QDs, the good permeability of nanofibrous membranes and the differential response introduced by surface ligands was played by constructing the sensing array using nanofibrous membranes loaded with ZnS QDs featuring several surface ligands. Interestingly, although the fluorescence quenching of the nanofibrous membranes is not linearly related to the exposure time, the fingerprint of each explosive at different times is very similar in shape, and the fingerprints of the three explosives show different shapes. Three saturated vapors of nitroaromatic explosives could be reliably detected and discriminated by the array at room temperature. This work is the first step toward devising a monitoring system for explosives in the field of public security and defense. It could, for example, be coupled with the technology of image recognition and large data analysis for a rapid diagnostic test of explosives. This work further highlights the power of differential, multichannel arrays for the rapid and discriminative detection of a wide range of chemicals.

Design and synthesis of reversible solid-state photochromic pyrazolones by introducing a pyridine ring.

We demonstrate a new strategy for designing reversibility, fatigue resistance and fluorescence switching materials, which are based on pyrazolone derivatives by introducing a pyridine ring. The reversible "on" and "off" modulation of fluorescence emission was up to 95% in the solid state.

Covalent Organic Frameworks Meet Titanium Oxide.

In order to expand the applicability of materials and improve their performance, the combined use of different materials has increasingly been explored. Among these materials, inorganic-organic hybrid materials often exhibit properties superior to those of single materials. Covalent organic frameworks (COFs) are famous crystalline porous materials constructed by organic building blocks linked by covalent bonds. In recent years, the combination of COFs with other materials has shown interesting properties in diverse fields, and the composite materials of COFs and TiO2 have been investigated more and more. These two outstanding materials are combined through covalent bonding, physical mixing, and other methods and exhibit excellent performance in various fields, including photocatalysis, electrocatalysis, sensors, separation, and energy storage and conversion. In this Review, the current preparation methods and applications of COF-TiO2 hybrid materials are introduced in detail, and their future development and possible problems are discussed and prospected, which is of great significance for related research. It is believed that these interesting hybrid materials will show greater application value as research progresses.

Ru nanoparticles modified Ni3Se4/Ni(OH)2 heterostructure nanosheets: A fast kinetics boosted bifunctional overall water splitting electrocatalyst.

Properly design and manufacture of bifunctional electrocatalysts with superb performance and endurance are crucial for overall water splitting. The interfacial engineering strategy is acknowledged as a promising approach to enhance catalytic performance of overall water splitting catalysts. Herein, the Ru nanoparticles modified Ni3Se4/Ni(OH)2 heterostructured nanosheets catalyst was constructed using a simple two-step hydrothermal process. The experimental results demonstrate that the abundant heterointerfaces between Ru and Ni3Se4/Ni(OH)2 can increase the number of active sites and effectively regulate the electronic structure, greatly accelerating the kinetics of the hydrogen evolution reaction (HER)/oxygen evolution reaction (OER). As a result, the Ru/Ni3Se4/Ni(OH)2/NF catalyst exhibits the low overpotential of 102.8 mV and 334.5 mV at 100 mA cm-2 for HER and OER in alkaline medium, respectively. Furthermore, a two-electrode system composed of the Ru/Ni3Se4/Ni(OH)2/NF requires a battery voltage of just 1.51 V at 10 mA cm-2 and remains stable for 200 h at 500 mA cm-2. This work provides an effective strategy for constructing Ru-based heterostructured catalysts with excellent catalytic activity.

Iodine intercalation-assisted alkali activation constructs coal-based porous carbon for high-performance supercapacitors.

Supercapacitors have the advantages of fast charging and discharging speeds, high power density, long cycle life, and wide operating temperature range. They are widely used in portable electronic equipment, rail transit, industry, military, aerospace, and other fields. The design and preparation of low-cost, high-performance electrode materials still pose a bottleneck that hinders the development of supercapacitors. In this paper, coal was used as the raw material, and the coal-based porous carbon electrode material was constructed using the iodine intercalation-assisted activation method and used for supercapacitors. The CK-700 electrode exhibits excellent charge storage performance in a 6 M potassium hydroxide (KOH) electrolyte, with a maximum specific capacitance of 350 F/g at a current density of 0.5 A/g. In addition, it has an excellent rate performance (310 F/g at 1 A/g) and cycle stability (capacitance retention up to 91.7 % after 30000 cycles). This work provides a method for realizing high-quality, high-yield and low-cost preparation of coal-based porous carbon, and an idea for improving the performance of supercapacitors.

Rational Conversion of Imine Linkages to Amide Linkages in Covalent Organic Frameworks for Photocatalytic Oxidation with Enhanced Photostability.

Covalent organic frameworks (COFs) and their applications in photocatalysis have been extensively studied, but the instability of imine-linked COFs is an important factor limiting their performance. In this work, two imine-linked COFs were successfully converted to amide-linked COFs through post synthetic modification (PSM). The oxidized COFs presented lower binding energy to O2, exhibited higher photocatalytic activity for oxidation of thioethers and coupling of benzylamines with excellent stability. The present work can serve as a reliable reference for the development of novel highly active and stable COF-based photocatalysts.

Iron doping and interface engineering on amorphous/crystalline Fe-NixSy heterostructures toward high-stability and kinetically accelerated water splitting.

It is very important to develop transition metal-based electrocatalysts with excellent activity, high stability and low-cost for overall water splitting. In this work, the Fe-doped NixSy/NF amorphous/crystalline heterostructure nanoarrays (Fe-NixSy/NF) was synthesized by a simple one-step method. The resulting hierarchically structured nanoarrays offer the advantages of large surface area, high structural void fraction and accessible internal surfaces. These advantages not only furnish additional catalytically active sites, but also enhance the stability of the structure and effectively accelerate mass diffusion and charge transport. Experimental and characterization results indicate that Fe doping increases the electrical conductivity of amorphous/crystalline NixSy/NF, and the NiS-Ni3S2 heterojunctions evoke interfacial charge rearrangement and optimize the adsorption free energy of the intermediates, which allows the catalyst to exhibit low overpotential and superior electrocatalytic activity. Especially, the overpotentials of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) of Fe-NixSy/NF at 10 mA cm-2 in an alkaline environment are 102.4 and 230.5 mV, respectively. When applied as a bifunctional catalyst for overall water splitting, it requires only 1.45 V cell voltage to deliver a current density of 10 mA cm-2, which is preferable to the all-noble metal Pt/C || IrO2 electrocatalyst (1.62 mV @ 10 mA cm-2). In addition, Fe-NixSy/NF has excellent stability, and there is no obvious degradation after 96 h continuous operation at a current density of 100 mA cm-2. This work affords insights into the application of doping strategies and crystalline/amorphous synergistic modulation of the electrocatalytic activity of transition metal-based catalysts in energy conversion systems.

Ultrastable Dendrite-Free Potassium Metal Batteries Enabled by Weakly-Solvated Electrolyte.

Potassium (K) metal is considered one of the most promising anodes for potassium metal batteries (PMBs) because of its abundant and low-cost advantages but suffers from serious dendritic growth and parasitic reactions, resulting in poor cyclability, low Coulombic efficiency (CE), and safety concerns. In this work, we report a localized high-concentration electrolyte (LHCE) consisting of potassium bis(fluorosulfonyl)imide (KFSI) in a cosolvent of 1,2-dimethoxyethane (DME) and 1,1,2,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) to solve the problems of PMBs. TTE as a diluent not only endows LHCE with advantages of low viscosity, good wettability, and improved conductivity but also solves the dendrite problem pertaining to K metal anodes. Using the formulation of LHCE, a CE of 98% during 800 cycles in the K||Cu cell and extremely stable cycling of over 2000 h in the K||K symmetric cell are achieved at a current density of 0.1 mA cm-2. In addition, the LHCE shows good compatibility with a Prussian Blue cathode, allowing almost 99% CE for the K||KFeIIFeIII(CN)6 full cell during 100 cycles. This promising electrolyte design realizes high-safety and energy-dense PMBs.

Synergistic Incorporating RuO2 and NiFeOOH Layers onto Ni3 S2 Nanoflakes with Modulated Electron Structure for Efficient Water Splitting.

Synergistic electronic modulations is an effective strategy to develop efficient and stable electrocatalysts for the electrochemical hydrogen production via water splitting. Herein, tremella-like Ni3 S2 @RuO2 and Ni3 S2 @NiFeOOH heterostructures catalysts are constructed on Ni foams (NF) by coupling RuO2 and NiFeOOH on Ni3 S2 nanoflake arrays. The resulting Ni3 S2 @RuO2 /NF electrode exhibits top-level hydrogen evolution reaction electrocatalysis with an extremely low overpotential of 12 mV at 10 mA cm-2 and a Tafel slope of 30.7 mV dec-1 , as well as the as-obtained Ni3 S2 @NiFeOOH/NF electrode with tunable binding energy for OH* intermediates shows remarkable oxygen evolution reaction electrocatalysis with an overpotential of 227 mV at 10 mA cm-2 . The electrolyzer employing Ni3 S2 @RuO2 /NF electrode for cathodic H2 production and Ni3 S2 @NiFeOOH/NF for anodic O2 production merely needs a low voltage of 1.47 V to drive 10 mA cm-2 with excellent durability. The combined theoretical calculation and X-ray photoelectron spectroscopy investigation reveal that heterogeneous configuration can induce electron transfer from Ni3 S2 to RuO2 through NiRu/SRu bonds, and thus tailor the d-band center and optimize the activated H2 O/H* Gibbs free energies for enhanced hydrogen evolution reaction on Ni3 S2 @RuO2 . This study may shed new light on the construction of heterostructures as highest-performing electrocatalysts and offer unique insight into the theory mechanism.

Solid-state photochromic behavior and thermal bleaching kinetics of two novel pyrazolone phenylsemicarbazones.

Two novel photochromic compounds, 1,3-diphenyl-4-benzal-5-hydroxypyrazole 4-phenylsemicarbazone (1 a) and 1,3-diphenyl-4-(4-nitrobenzal)-5-hydroxypyrazole 4-phenylsemicarbazone (2 a), are synthesized and characterized by elemental analysis, mass spectrometry, FTIR spectroscopy, and (1)H NMR spectroscopy. Their properties, including photochromic behavior, fluorescence properties, and thermal bleaching kinetics, are investigated. The results show that the two compounds exhibit improved photochromic performance in coloration and thermal bleaching rates, excellent photostability, high fatigue resistance, and reversible fluorescence switching properties in the solid state in comparison to reported pyrazolone thiosemicarbazones. The thermal bleaching process obeys first-order kinetics. Bleaching of powders at 130 °C is completed within 90 s for 1 b (the colored isomer of 1 a) and 150 s for 2 b (the colored isomer of 2 a). The activation energy for the thermal bleaching process is determined to be 69 and 95 kJ mol(-1) , with frequency factors of 9.5×10(7) and 9.4×10(10) s(-1) for 1 b and 2 b, respectively.

Photochromism of a pyrazolone derivative in crystalline state and in HPMC composite film.

A novel photochromic compound, 1,3-diphenyl-4-(3-chloro-4-fluorobenzal)-5-hydoxypyrazole 4-phenylsemicarbazide (1a), has been synthesized by introducing a phenylsemicarbazide unit. The material exhibits good fatigue resistance and reversible fluorescent switching properties with distinct fluorescence on/off ratio under alternating UV irradiation and heating at 120 °C. For the fabrication of actual application materials, 1a/hydroxypropylmethylcellulose (HPMC) composite film has been successfully fabricated using hydrogel casting method. The 1a/HPMC composite film obtained can also show reversible photochromic reaction under UV irradiation and rapid thermal bleaching properties by heating. The HPMC composite film shows similar good photochromic properties as those of 1 in the crystalline state.

Coaxial spinning fabricated high nitrogen-doped porous carbon walnut anchored on carbon fibers as anodic material with boosted lithium storage performance.

Commercial graphite with low theoretical capacity cannot meet the ever-increasing requirement demands of lithium-ion batteries (LIBs) caused by the rapid development of electric devices. Rationally designed carbon-based nanomaterials can provide a wide range of possibilities to meet the growing requirements of energy storage. Hence, the porous walnut anchored on carbon fibers with reasonable pore structure, N-self doping (10.2 at%) and novel structure and morphology is designed via interaction of inner layer polyethylene oxide and outer layer polyacrylonitrile and polyvinylpyrrolidone during pyrolysis of the obtained precursor, which is fabricated by coaxial electrospinning. As an electrode material, the as-made sample shows a high discharge capacity of 965.3 mA h g-1 at 0.2 A g-1 in the first cycle, retains a capacity of 819.7 mA h g-1 after 500 cycles, and displays excellent cycling stability (475.2 mA h g-1 at 1 A g-1 after 1000 cycles). Moreover, the capacity of the electrode material still keeps 260.5 mA h g-1 at 5 A g-1 after 1000 cycles. Therefore, the obtained sample has a bright application prospect as a high performance anode material for LIBs. Besides, this design idea paves the way for situ N-enriched carbon material with novel structure and morphology by coaxial electrospinning.

Synthesis and properties of a novel photochromic compound with modulated fluorescence in the solid state.

A new photochromic compound, 1,3-diphenyl-4-(3-bromobenzal)-5-hydroxypyrazole 4-phenylsemicarbazone (DP3BrBP-PSC), has been prepared. Its photochromic and thermobleaching behavior, crystal structure, and fluorescent property have been investigated in detail. The results show that the compound exhibits reversible enol-keto photoisomerization due to the intermolecular double-proton transfer, excellent photostability, high fatigue resistance, and remarkable fluorescence.

Reactivity of 2,6-lutidine/BR3 and pyridine/BR3 Lewis pairs (R = F, Me, C6F5): a density functional study.

The reactivity of 2,6-lutidine/BR3 and pyridine/BR3 Lewis pairs (R = F, Me, C6F5) is investigated in detail by quantum chemical calculations. The observed reactivity difference of these pairs is interpreted in terms of the existence of a "frustrated complex" on the potential energy curve for coordination of Lewis acid and base, the profiles of local reactivity descriptors with respect to the bond distance between acid and base centers, and the thermodynamic/kinetic properties of the heterolytic dihydrogen cleavage reaction. The calculated results are shown to account well for the observed reactivity of these Lewis pairs.

N/S co-doped coal-based porous carbon spheres as electrode materials for high performance supercapacitors.

N/S co-doped porous carbon spheres (NSPCSs) were prepared by a simple ultrasonic spray pyrolysis (USP) using the mixed solution of coal oxide and l-cysteine, and without a subsequent activation process. The surface properties of carbon materials have been successfully modified by the concurrent incorporation of N and S. So the capacitive performance of NSPCSs was greatly enhanced. It is used as a supercapacitor electrode to achieve a high specific capacitance of 308 F g-1 at a current density of 1 A g-1 and 90.2% capacitance retention even after 10 000 cycles at 5 A g-1. These numerical results show that the supercapacitors based on coal-based carbon materials have great potential in high performance electrochemical energy storage.