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1.
Currently, metal‐organic frameworks (MOFs) are intensively studied as active materials for electrochemical energy storage applications due to their tunable structure and exceptional porosities. Among them, water stable pillared MOFs with dual ligands have been reported to exhibit high supercapacitor (SC) performance. Herein, the “One‐for‐All” strategy is applied to synthesize both positive and negative electrodes of a hybrid SC (HSC) from a single pillared MOF. Specifically, Ni‐DMOF‐TM ([Ni(TMBDC)(DABCO)0.5], TMBDC: 2,3,5,6‐tetramethyl‐1,4‐benzenedicarboxylic acid, DABCO: 1,4‐diazabicyclo[2.2.2]‐octane) nanorods are directly grown on carbon fiber paper (CFP) (denoted as CFP@TM‐nanorods) with the help of triethylamine and function as the positive electrode of HSC under alkaline electrolyte. Meanwhile, calcinated N‐doped hierarchical porous carbon nanorods (CFP@TM‐NPCs) are produced and utilized as the negative counter‐electrode from a one‐step heat treatment of CFP@TM‐nanorods. After assembling these two electrodes together to make a hybrid device, the TM‐nanorods//TM‐NPCs exhibit a wide voltage window of 1.5 V with a high sloping discharge plateau between 1‐1.2 V, indicating its great potential for practical applications. This as‐described “One‐for‐All” strategy is widely applicable and highly reproducible in producing MOF‐based electrode materials for HSC applications, which shortens the gap between experimental synthesis and practical application of MOFs in fast energy storage.  相似文献   

2.
Lithium metal is an ultimate anode in “next‐generation” rechargeable batteries, such as Li–sulfur batteries and Li–air (Li–O2) batteries. However, uncontrollable dendritic Li growth and water attack have prevented its practical applications, especially for open‐system Li–O2 batteries. Here, it is reported that the issues can be addressed via the facile process of immersing the Li metal in organic GeCl4–THF steam for several minutes before battery assembly. This creates a 1.5 µm thick protection layer composed of Ge, GeOx, Li2CO3, LiOH, LiCl, and Li2O on Li surface that allows stable cycling of Li electrodes both in Li‐symmetrical cells and Li–O2 cells, especially in “moist” electrolytes (with 1000–10 000 ppm H2O) and humid O2 atmosphere (relative humidity (RH) of 45%). This work illustrates a simple and effective way for the unfettered development of Li‐metal‐based batteries.  相似文献   

3.
Hinokitiol (β‐thujaplicin, volatile oil extracted from the wood of Hiba arborvitae [Thujopsis dolabrata var. hondae], cypress family) is a natural preservative, antimicrobial, and chelating agent, used to prevent decay and extend the shelf life of fruits and vegetables. In the present study, we used nonwoven rayon sheets impregnated with hinokitiol to conduct packaging studies. Mature green tomatoes var. “KEK‐1” were packaged under three packaging conditions, ie, modified atmosphere packaging (MAP), MAP + hinokitiol (MH), and perforated film package (as control), and their quality attributes were compared during storage. The packaging materials used were low‐density polyethylene (LDPE) film (40 μm) and fresh sheets of nonwoven rayon impregnated with hinokitiol. O2 in the MAP packaged tomatoes were retained throughout the storage period (3% to 5% O2). Results showed that MH had slightly improved quality attributes throughout the storage period when compared with MAP alone. Expression levels of LeACS, LeADH, and LeTBG4 genes were higher in 5 and 9 days of control when compared with MAP and MH. “KEK‐1” tomatoes had longer shelf life under MAP and MH packaging and maintained the quality at 15°C. Hence, the effect of the MAP with bioactive packaging treatments could be effective in the future application for the extension of shelf life and quality of fruits and vegetables.  相似文献   

4.
While theoretical studies predicted the stability and exotic properties of plumbene, the last group‐14 cousin of graphene, its realization has remained a challenging quest. Here, it is shown with compelling evidence that plumbene is epitaxially grown by segregation on a Pd1?xPbx(111) alloy surface. In scanning tunneling microscopy (STM), it exhibits a unique surface morphology resembling the famous Weaire–Phelan bubble structure of the Olympic “WaterCube” in Beijing. The “soap bubbles” of this “Nano WaterCube” are adjustable with their average sizes (in‐between 15 and 80 nm) related to the Pb concentration (x < 0.2) dependence of the lattice parameter of the Pd1?xPbx(111) alloy surface. Angle‐resolved core‐level measurements demonstrate that a lead sheet overlays the Pd1?xPbx(111) alloy. Atomic‐scale STM images of this Pb sheet show a planar honeycomb structure with a unit cell ranging from 0.48 to 0.49 nm corresponding to that of the standalone 2D topological insulator plumbene.  相似文献   

5.
Fluorescence imaging in the second near‐infrared window (NIR‐II) is a new technique that permits visualization of deep anatomical features with unprecedented spatial resolution. Although attractive, effectively suppressing the interference signal of the background is still an enormous challenge for obtaining target‐specific NIR‐II imaging in the complex and dynamic physiological environment. Herein, dual‐pathological‐parameter cooperatively activatable NIR‐II fluorescence nanoprobes (HISSNPs) are developed whereby hyaluronic acid chains and disulfide bonds act as the “double locks” to lock the fluorescence‐quenched aggregation state of the NIR‐II fluorescence dyes for performing ultrahigh specific imaging of tumors in vivo. The fluorescence can be lit up only when the “double locks” are opened by reacting with the “dual smart keys” (overexpressed hyaluronidase and thiols in tumor) simultaneously. In vivo NIR‐II imaging shows that they reduce nonspecific activitation and achieve ultralow background fluorescence, which is 10.6‐fold lower than single‐parameter activatable probes (HINPs) in the liver at 15 h postinjection. Consequently, these “dual lock‐and‐key”‐controlled HISSNPs exhibit fivefold higher tumor‐to‐normal tissue ratio than “single lock‐and‐key”‐controlled HINPs at 24 h postinjection, attractively realizing ultrahigh specificity of tumor imaging. This is thought to be the first attempt at implementing ultralow background interference with the participation of multiple pathological parameters in NIR‐II fluorescence imaging.  相似文献   

6.
Potassium has its unique advantages over lithium or sodium as a charge carrier in rechargeable batteries. However, progresses in K‐ion battery (KIB) chemistry have so far been hindered by lacking suitable electrode materials to host the relatively large K+ ions compared to its Li+ and Na+ counterparts. Herein, molybdenum disulfide (MoS2) “roses” grown on reduced graphene oxide sheets (MoS2@rGO) are synthesized via a two‐step solvothermal route. The as‐synthesized MoS2@rGO composite, with expanded interlayer spacing of MoS2, chemically bonded between MoS2 and rGO, and a unique nano‐architecture, displays the one of the best electrochemical performances to date as an anode material for nonaqueous KIBs. More importantly, a combined K+ storage mechanism of intercalation and conversion reaction is also revealed. The findings presented indicate the enormous potential of layered metal dichalcogenides as advanced electrode materials for high‐performance KIBs and also provide new insights and understanding of K+ storage mechanism.  相似文献   

7.
Fabrication of a high‐temperature deep‐ultraviolet photodetector working in the solar‐blind spectrum range (190–280 nm) is a challenge due to the degradation in the dark current and photoresponse properties. Herein, β‐Ga2O3 multi‐layered nanobelts with (l00) facet‐oriented were synthesized, and were demonstrated for the first time to possess excellent mechanical, electrical properties and stability at a high temperature inside a TEM studies. As‐fabricated DUV solar‐blind photodetectors using (l00) facet‐oriented β‐Ga2O3 multi‐layered nanobelts demonstrated enhanced photodetective performances, that is, high sensitivity, high signal‐to‐noise ratio, high spectral selectivity, high speed, and high stability, importantly, at a temperature as high as 433 K, which are comparable to other reported semiconducting nanomaterial photodetectors. In particular, the characteristics of the photoresponsivity of the β‐Ga2O3 nanobelt devices include a high photoexcited current (>21 nA), an ultralow dark current (below the detection limit of 10?14 A), a fast time response (<0.3 s), a high Rλ (≈851 A/W), and a high EQE (~4.2 × 103). The present fabricated facet‐oriented β‐Ga2O3 multi‐layered nanobelt based devices will find practical applications in photodetectors or optical switches for high‐temperature environment.  相似文献   

8.
Hollow micro‐/nanostructures are widely explored for energy applications due to their unique structural advantages. The synthesis of hollow structures generally involves a “top‐down” casting process based on hard or soft templates. Herein, a new and generic confinement strategy is developed to fabricate composite hollow fibers. A thin and homogeneous atomic‐layer‐deposition (ALD) Al2O3 layer is employed to confine the pyrolysis of precursor fibers, which transform into metal (or metal oxide)–carbon composite hollow fibers after removal of Al2O3. Because of the uniform coating by ALD, the resultant composite hollow fibers exhibit a hollow interior from heads to ends even if they are millimeter long. V, Fe, Co, and Ni‐based hollow nanofibers, demonstrating the versatility of this synthesis method, are successfully synthesized. Because of the carbon constituent, these composite fibers are particularly useful for energy applications. Herein, the as‐obtained hollow V2O3–C fiber membrane is employed as a freestanding and flexible electrode for lithium‐ion capacitor. The device shows an impressive energy density and a high power density.  相似文献   

9.
Sodium (Na) metal is one of the most promising electrode materials for next‐generation low‐cost rechargeable batteries. However, the challenges caused by dendrite growth on Na metal anodes restrict practical applications of rechargeable Na metal batteries. Herein, a nitrogen and sulfur co‐doped carbon nanotube (NSCNT) paper is used as the interlayer to control Na nucleation behavior and suppress the Na dendrite growth. The N‐ and S‐containing functional groups on the carbon nanotubes induce the NSCNTs to be highly “sodiophilic,” which can guide the initial Na nucleation and direct Na to distribute uniformly on the NSCNT paper. As a result, the Na‐metal‐based anode (Na/NSCNT anode) exhibits a dendrite‐free morphology during repeated Na plating and striping and excellent cycling stability. As a proof of concept, it is also demonstrated that the electrochemical performance of sodium–oxygen (Na–O2) batteries using the Na/NSCNT anodes show significantly improved cycling performances compared with Na–O2 batteries with bare Na metal anodes. This work opens a new avenue for the development of next‐generation high‐energy‐density sodium‐metal batteries.  相似文献   

10.
Popularly utilized oxidation media, via nitric acid/sulfuric acid mixtures, are too corrosive and oxidizing to preserve structural integrity of highly ordered graphitic materials (carbon nanotubes (CNTs) and graphene). Here, for the most commonly used oxidation method, the important advantages of defect/edge‐selective functionalization of carbon materials (CNTs/graphene/graphite) in a polyphosphoric acid (PPA)/phosphorous pentoxide (P2O5) medium are elucidated. The optimized PPA/P2O5 medium is a mild acid that is not only less corrosive than popularly utilized oxidation media, but also has a strong capability to drive Friedel–Crafts acylation by covalently modifying carbon materials. With a broader spectrum of functional groups accessible, the PPA/P2O5‐driven Friedel–Crafts acylation offers more options for tailoring the properties and processing of carbon materials.  相似文献   

11.
An air‐stable transparent conductive film with “quasi‐freestanding” graphene supported on horizontal single walled carbon nanotubes (SWCNTs) arrays is fabricated. The sheet resistance of graphene films stacked via layer‐by‐layer transfer (LBL) on quartz, and modified by 1‐Pyrenebutyric acid N‐hydroxysuccinimide ester (PBASE), is reduced from 273 Ω/sq to about 76 Ω/sq. The electrical properties are stable to heat treatment (up to 200 ºC) and ambient exposure. Organic light‐emitting diodes (OLEDs) constructed of this carbon anode (T ≈ 89.13% at 550 nm) exhibit ≈88% power efficiency of OLEDs fabricated on an ITO anode (low turn on voltage ≈3.1 eV, high luminance up to ≈29 490 cd/m2, current efficiency ≈14.7 cd/A). Most importantly, the entire graphene‐on‐SWCNT hybrid electrodes can be transferred onto plastic (PET) forming a highly‐flexible OLED device, which continues to function without degradation in performance at bending angles >60°.  相似文献   

12.
Periodically hydrogenated graphene is predicted to form new kinds of crystalline 2D materials such as graphane, graphone, and 2D CxHy, which exhibit unique electronic properties. Controlled synthesis of periodically hydrogenated graphene is needed for fundamental research and possible electronic applications. Only small patches of such materials have been grown so far, while the experimental fabrication of large‐scale, periodically hydrogenated graphene has remained challenging. In the present work, large‐scale, periodically hydrogenated graphene is fabricated on Ru(0001). The as‐fabricated hydrogenated graphene is highly ordered, with a √3 × √3/R30° period relative to the pristine graphene. As the ratio of hydrogen and carbon is 1:3, the periodically hydrogenated graphene is named “one‐third‐hydrogenated graphene” (OTHG). The area of OTHG is up to 16 mm2. Density functional theory calculations demonstrate that the OTHG has two deformed Dirac cones along one high‐symmetry direction and a finite energy gap along the other directions at the Fermi energy, indicating strong anisotropic electrical properties. An efficient method is thus provided to produce large‐scale crystalline functionalized graphene with specially desired properties.  相似文献   

13.
The novel application of two‐dimensional (2D) single‐layer ternary chalcogenide nanosheets as “capture‐release” fluorescence‐based biomolecular nanosensors is demonstrated. Fluorescently labeled biomolecular probe is first captured by the ultrathin Ta2NiS5 nanosheets and then released upon adding analyte containing a target biomolecule due to the higher probe‐target affinity. Here, the authors use a nucleic acid probe for the model target biomolecule Plasmodium lactate dehydrogenase, which is an important malarial biomarker. The ultrathin Ta2NiS5 nanosheet serves as a highly efficient fluorescence quencher and the nanosensor developed from the nanosheet is highly sensitive and specific toward the target biomolecule. Apart from the specificity toward the target biomolecule in homogeneous solutions, the developed nanosensor is capable of detecting and differentiating the target in heterogeneous solutions consisting of either a mixture of biomolecules or serum, with exceptional specificity. The simplicity of the “capture‐release” method, by eliminating the need for preincubation of the probe with the test sample, may facilitate further development of portable and rapid biosensors. The authors anticipate that this ternary chalcogenide nanosheet‐based biomolecular nanosensor will be useful for the rapid detection and differentiation of a wide range of chemical and biological species.  相似文献   

14.
Manganese oxides (MnOx) are promising anode materials for lithium ion batteries, but they generally exhibit mediocre performances due to intrinsic low ionic conductivity, high polarization, and poor stability. Herein, yolk–shell nanorods comprising of nitrogen‐doped carbon (N–C) coating on manganese monoxide (MnO) coupled with zinc manganate (ZnMn2O4) nanoparticles are manufactured via one‐step carbonization of α‐MnO2/ZIF‐8 precursors. When evaluated as anodes for lithium ion batteries, MnO@ZnMn2O4/N–C exhibits an reversible capacity of 803 mAh g?1 at 50 mA g?1 after 100 cycles, excellent cyclability with a capacity of 595 mAh g?1 at 1000 mAg?1 after 200 cycles, as well as better rate capability compared with those non‐N–C shelled manganese oxides (MnOx). The outstanding electrochemical performance is attributed to the unique yolk–shell nanorod structure, the coating effect of N–C and nanoscale size.  相似文献   

15.
Structural symmetry is a simple way to quantify the anisotropic properties of materials toward unique device applications including anisotropic transportation and polarization‐sensitive photodetection. The enhancement of anisotropy can be achieved by artificial symmetry‐reduction design. A core–shell SbI3/Sb2O3 nanowire, a heterostructure bonded by van der Waals forces, is introduced as an example of enhancing the performance of polarization‐sensitive photodetectors via symmetry reduction. The structural, vibrational, and optical anisotropies of such core–shell nanostructures are systematically investigated. It is found that the anisotropic absorbance of a core–shell nanowire is obviously higher than that of two single compounds from both theoretical and experimental investigations. Anisotropic photocurrents of the polarization‐sensitive photodetectors based on these core–shell SbI3/Sb2O3 van der Waals nanowires are measured ranging from ultraviolet (UV) to visible light (360–532 nm). Compared with other van der Waals 1D materials, low anisotropy ratio (Imax/Imin) is measured based on SbI3 but a device based on this core–shell nanowire possesses a relatively high anisotropy ratio of ≈3.14 under 450 nm polarized light. This work shows that the low‐symmetrical core–shell van der Waals heterostructure has large potential to be applied in wide range polarization‐sensitive photodetectors.  相似文献   

16.
A method is developed to directly map nanoscale “noise‐source switching” phenomena during the optoelectronic switching of phase‐separated polymer nanocomposites of tetrathiafulvalene (TTF) and phenyl‐C61‐butyric acid methyl ester (PCBM) molecules dispersed in a polystyrene (PS) matrix. In the method, electrical current and noise maps of the nanocomposite film are recorded using a conducting nanoprobe, enabling the mapping of a conductivity and a noise‐source density. The results provide evidence for a repeated modulation in noise sources, a “noise‐source switching,” in each stage of a switching cycle. Interestingly, when the nanocomposite is “set” by a high bias, insulating PS‐rich phases shows a drastic decrease in a noise‐source density which becomes lower than that of conducting TTF‐PCBM‐rich phases. This can be attributed to a trap filling by charge carriers generated from a TTF (donor)–PCBM (acceptor) complex. In addition, when the film is exposed to UV, an optical switching occurs due to chemical reactions which lead to irreversible changes on the noise‐source density and conductivity. The method provides a new insight on noise‐source activities during the optoelectronic switching of polymer nanocomposites and thus can be a powerful tool for basic noise research and applications in organic memory devices.  相似文献   

17.
A mesoporous ZnO/carbon composite is designed for coimmobilization of two oxidoreductases involving a novel “kiwifruit‐assembly” pattern. The coimmobilization of (S)‐carbonyl reductase II‐glucose dehydrogenase on nanoparticles (SCRII–GDHnano) exhibits 40–50% higher specific activity than the free enzyme and significantly improves stabilities of enzymes to heat, pH and solvents. It performs asymmetric catalysis of 75 × 10?3m substrate with a perfect yield of 100% and an excellent enantioselectivity of 99.9% within 1 h. SCRII–GDHnano gives an over 72% yield and 99.9% enantioselectivity after it is reused for ten times. Even with a highly concentrated (400 × 10?3m ) substrate, it shows about 60% yield and 99.9% enantioselectivity within 4 h. SCRII–GDHnano presents 4.5–8.0‐fold higher productivity in 2.0–8.0‐fold shorter reaction time than the free enzyme. This work provides a general, facile, and unique approach for the immobilization of two oxidoreductases and gives high catalytic efficiency, long‐term and good recycling stabilities by triggering radical proton‐coupled electron transfer.  相似文献   

18.
Incorporation of N,S‐codoped nanotube‐like carbon (N,S‐NTC) can endow electrode materials with superior electrochemical properties owing to the unique nanoarchitecture and improved kinetics. Herein, α‐MnS nanoparticles (NPs) are in situ encapsulated into N,S‐NTC, preparing an advanced anode material (α‐MnS@N,S‐NTC) for lithium‐ion/sodium‐ion batteries (LIBs/SIBs). It is for the first time revealed that electrochemical α → β phase transition of MnS NPs during the 1st cycle effectively promotes Li‐storage properties, which is deduced by the studies of ex situ X‐ray diffraction/high‐resolution transmission electron microscopy and electrode kinetics. As a result, the optimized α‐MnS@N,S‐NTC electrode delivers a high Li‐storage capacity (1415 mA h g?1 at 50 mA g?1), excellent rate capability (430 mA h g?1 at 10 A g?1), and long‐term cycling stability (no obvious capacity decay over 5000 cycles at 1 A g?1) with retained morphology. In addition, the N,S‐NTC‐based encapsulation plays the key roles on enhancing the electrochemical properties due to its high conductivity and unique 1D nanoarchitecture with excellent protective effects to active MnS NPs. Furthermore, α‐MnS@N,S‐NTC also delivers high Na‐storage capacity (536 mA h g?1 at 50 mA g?1) without the occurrence of such α → β phase transition and excellent full‐cell performances as coupling with commercial LiFePO4 and LiNi0.6Co0.2Mn0.2O2 cathodes in LIBs as well as Na3V2(PO4)2O2F cathode in SIBs.  相似文献   

19.
Sodium‐ion batteries (SIBs) have been considered as potential candidates for stationary energy storage because of the low cost and wide availability of Na sources. O3‐type layered oxides have been considered as one of the most promising cathodes for SIBs. However, they commonly show inevitable complicated phase transitions and sluggish kinetics, incurring rapid capacity decline and poor rate capability. Here, a series of sodium‐sufficient O3‐type NaNi0.5Mn0.5‐ x Ti x O2 (0 ≤ x ≤ 0.5) cathodes for SIBs is reported and the mechanisms behind their excellent electrochemical performance are studied in comparison to those of their respective end‐members. The combined analysis of in situ X‐ray diffraction, ex situ X‐ray absorption spectroscopy, and scanning transmission electron microscopy for NaNi0.5Mn0.2Ti0.3O2 reveals that the O3‐type phase transforms reversibly into a P3‐type phase upon Na+ deintercalation/intercalation. The substitution of Ti for Mn enlarges interslab distance and could restrain the unfavorable and irreversible multiphase transformation in the high voltage regions that is usually observed in O3‐type NaNi0.5Mn0.5O2, resulting in improved Na cell performance. This integration of macroscale and atomicscale engineering strategy might open up the modulation of the chemical and physical properties in layered oxides and grasp new insight into the optimal design of high‐performance cathode materials for SIBs.  相似文献   

20.
Large‐size ultrathin 2D materials, with extensive applications in optics, medicine, biology, and semiconductor fields, can be prepared through an existing common physical and chemical process. However, the current exfoliation technologies still need to be improved upon with urgency. Herein, a novel and simple “ultrasonic‐ball milling” strategy is reported to effectively obtain high quality and large size ultrathin 2D materials with complete lattice structure through the introduction of moderate sapphire (Al2O3) abrasives in a liquid phase system. Ultimately numerous high‐quality ultrathin h‐BN, graphene, MoS2, WS2, and BCN nanosheets are obtained with large sizes ranging from 1–20 µm, small thickness of ≈1–3 nm and a high yield of over 20%. Utilizing shear and friction force synergistically, this strategy provides a new method and alternative for preparing and optimizing large size ultrathin 2D materials.  相似文献   

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