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Lithium‐ion batteries are widely used as reliable electrochemical energy storage devices due to their high energy density and excellent cycling performance. The search for anode materials with excellent electrochemical performances remains critical to the further development of lithium‐ion batteries. Tungsten‐based materials are receiving considerable attention as promising anode materials for lithium‐ion batteries owing to their high intrinsic density and rich framework diversity. This review describes the advances of exploratory research on tungsten‐based materials (tungsten oxide, tungsten sulfide, tungsten diselenide, and their composites) in lithium‐ion batteries, including synthesis methods, microstructures, and electrochemical performance. Some personal prospects for the further development of this field are also proposed.  相似文献   

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In the field of engineering, a crack, inducing enormous mechanical energy concentration at a tip, is considered a typical kind of defect. However, it is found that, to maximize the sensitivity of slit‐based mechanoreceptors, the near‐tip stress field of “risky” crack‐shaped slits is ingeniously used by scorpions to precisely detect the cyclic loads acting on walking legs without the crack nucleation from the flaw‐like tip. As a sophisticated biological mechanoelectrical transducing microsystem, the mechanoreceptor can effectively collect mechanical energy contained in the mechanical signal through antifracture slit allays and then convert the mechanical energy into electrical energy through mechanosensory neuron. The highly efficient mechanoelectrical energy conversion mechanism is theoretically analyzed and experimentally verified in a bioinspired artificial mechanoreceptor. The results demonstrate the potential of basic “design” principles, underlying the slit‐dependent mechanoreceptor, for maximizing the electromechanical conversion efficiency of the industrial mechanoelectrical transducing microsystem such as nanogenerators, ultrasensitive mechanical sensors, self‐powered portable, and wearable electronics.  相似文献   

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Enzyme immobilization is an attractive route for achieving catalytically functional surfaces suitable for both continuous and repeated use. Herein, genetic engineering is used to combine the catalytic ability of a xylanase with the self‐assembly properties of recombinant spider silk, realizing silk materials with enzymatic activity. Under near‐physiological conditions, soluble xylanase‐silk fusion proteins assembled into fibers displaying catalytic activity. Also, a xylanase‐silk protein variant with the silk part miniaturized to contain only the C‐terminal domain of the silk protein formed fibers with catalytic activity. The repertoire of xylanase‐silk formats is further extended to include 2D surface coatings and 3D foams, also being catalytically active, showing the versatile range of possible silk materials. The stability of the xylanase‐silk materials is explored, demonstrating the possibility of storage, reuse, and cleaning with ethanol. Interestingly, fibers can also be stored dried with substantial residual activity after rehydration. Moreover, a continuous enzymatic reaction using xylanase‐silk is demonstrated, making enzymatic batch reactions not the sole possible implementation. The proof‐of‐concept for recombinantly produced enzyme‐silk, herein shown with a xylanase, implies that also other enzymes can be used in similar setups. It is envisioned that the concept of enzyme‐silk can find its applicability in, for example, multienzyme reaction systems or biosensors.  相似文献   

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Photoresponsive hydrogels (PRHs) are soft materials whose mechanical and chemical properties can be tuned spatially and temporally with relative ease. Both photo‐crosslinkable and photodegradable hydrogels find utility in a range of biomedical applications that require tissue‐like properties or programmable responses. Progress in engineering with PRHs is facilitated by the development of theoretical tools that enable optimization of their photochemistry, polymer matrices, nanofillers, and architecture. This review brings together models and design principles that enable key applications of PRHs in tissue engineering, drug delivery, and soft robotics, and highlights ongoing challenges in both modeling and application.  相似文献   

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Highly stable graphene oxide (GO)‐based multilayered ultrathin films can be covalently immobilized on solid supports through a covalent‐based method. It is demonstrated that when (3‐aminopropyl) trimethoxysilane (APTMS), which works as a covalent cross‐linking agent, and GO nanosheets are assembled in an layer‐by‐layer (LBL) manner, GO nanosheets can be covalently grafted on the solid substrate successfully to produce uniform multilayered (APTMS/GO)N films over large‐area surfaces. Compared with conventional noncovalent LBL films constructed by electrostatic interactions, those assembled using this covalent‐based method display much higher stability and reproducibility. Upon thermal annealing‐induced reduction of the covalent (APTMS/GO)N films, the obtained reduced GO (RGO) films, (APTMS/RGO)N, preserve their basic structural characteristics. It is also shown that the as‐prepared covalent (APTMS/RGO)N multilayer films can be used as highly stable source/drain electrodes in organic field‐effect transistors (OFETs). When the number of bilayers of the (APTMS/RGO)N film exceeds 2 (ca. 2.7 nm), the OFETs based on (APTMS/RGO)N electrodes display much better electrical performance than devices based on 40 nm Au electrodes. The covalent protocol proposed may open up new opportunities for the construction of graphene‐based ultrathin films with excellent stability and reproducibility, which are desired for practical applications that require withstanding of multistep post‐production processes.  相似文献   

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Triple‐shape polymers can move from a first shape (A) to a second shape (B) and from there to a third shape (C), where both shape changes are induced by temperature increases. This triple‐shape capability is obtained for multiphase polymer networks after application of a complex thermomechanical programming process, which consists of two steps; these steps create shapes (B) and (A), while shape (C) is defined by the covalent crosslinks of the polymer network. Here, the creation of the triple‐shape capability for an AB polymer network system by a simple one‐step process similar to a conventional dual‐shape programming process is reported. The polymer networks are based on poly(ε‐caprolactone) (PCL) and poly(cyclohexyl methacrylate); favorable compositions for obtaining a triple shape effect have a PCL content between 35 and 60 wt%. This finding substantially facilitates handling of the triple‐shape technology and is an important step toward the realization of potential applications in which more than one shape change is required.  相似文献   

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The application of well‐defined poly(furfuryl glycidyl ether) (PFGE) homopolymers and poly(ethylene oxide)‐b‐poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) block copolymers synthesized by living anionic polymerization as self‐healing materials is demonstrated. This is achieved by thermo‐reversible network formation via (retro) Diels‐Alder chemistry between the furan groups in the side‐chain of the PFGE segments and a bifunctional maleimide crosslinker within drop‐cast polymer films. The process is studied in detail by differential scanning calorimetry (DSC), depth‐sensing indentation, and profilometry. It is shown that such materials are capable of healing complex scratch patterns, also multiple times. Furthermore, microphase separation within PEO‐b‐PFGE block copolymer films is indicated by small angle X‐ray scattering (lamellar morphology with a domain spacing of approximately 19 nm), differential scanning calorimetry, and contact angle measurements.  相似文献   

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Covalently‐crosslinked hydrogels are commonly used as 3D matrices for cell culture and transplantation. However, the crosslinking chemistries used to prepare these gels generally cross‐react with functional groups present on the cell surface, potentially leading to cytotoxicity and other undesired effects. Bio‐orthogonal chemistries have been developed that do not react with biologically relevant functional groups, thereby preventing these undesirable side reactions. However, previously developed biomaterials using these chemistries still possess less than ideal properties for cell encapsulation, such as slow gelation kinetics and limited tuning of matrix mechanics and biochemistry. Here, engineered elastin‐like proteins (ELPs) are developed that crosslink via strain‐promoted azide‐alkyne cycloaddition (SPAAC) or Staudinger ligation. The SPAAC‐crosslinked materials form gels within seconds and complete gelation within minutes. These hydrogels support the encapsulation and phenotypic maintenance of human mesenchymal stem cells, human umbilical vein endothelial cells, and murine neural progenitor cells. SPAAC‐ELP gels exhibit independent tuning of stiffness and cell adhesion, with significantly improved cell viability and spreading observed in materials containing a fibronectin‐derived arginine‐glycine‐aspartic acid (RGD) domain. The crosslinking chemistry used permits further material functionalization, even in the presence of cells and serum. These hydrogels are anticipated to be useful in a wide range of applications, including therapeutic cell delivery and bioprinting.  相似文献   

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Filler aggregation in polymer matrix nanocomposites leads to inhomogeneity in particle distribution and deterioration of mechanical properties. The use of polymer‐grafted nanoparticles (PGNPs) with polymers directly attached to the particle surfaces precludes aggregation of the filler. However, solids composed of PGNPs are mechanically weak unless the grafted chains are long enough to form entanglements between particles, and requiring long grafts limits the achievable filler density of the nanocomposite. In this work, long, entangled grafts are replaced with short reactive polymers that form covalent crosslinks between particles. Crosslinkable PGNPs, referred to as XNPs, can be easily processed from solution and subsequently cured to yield a highly filled yet mechanically robust composite. In this specific instance, silica nanoparticles are grafted with poly(glycidyl methacrylate), cast into films, and crosslinked with multifunctional amines at elevated temperatures. Indentation and scratch experiments show significant enhancement of hardness, modulus, and scratch resistance compared to non‐crosslinked PGNPs and to crosslinked polymer films without nanoparticle reinforcement. Loadings of up to 57 wt% are achieved while yielding uniform films that deform locally in a predominantly elastic manner. XNPs therefore potentially allow for the formulation of robust nanocomposites with a high level of functionality imparted by the selected filler particles.  相似文献   

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Femto‐second laser‐based free‐writing of complex protein microstructures and micropatterns, with sub‐micrometer features and controllability over voxel dimension, morphology, and porosity, is reported. Protein voxels including lines, spots, and micropillars are fabricated. Laser power, exposure time, z‐position, protein and photosensitizer concentrations, but not scanning speed, are important controlling parameters. A lateral fabrication resolution of ≈200 nm is demonstrated in 2D line voxels. 3D spot voxels are ellipsoids with 400 nm lateral and 1.5 μm axial dimensions. An ascending z‐stack scanning method to verify the theoretical axial optical resolution, delineate and enhance the axial fabrication resolution of 3D structures, including square prism and cylinder micropillars, is also reported. The micropillar array presents a simple “write‐and‐seed” and table platform for cell niche studies. Fibroblasts attach to, grow on, and express adhesion to molecules on micropillar arrays without the need of matrix coating. They exhibit a more “3D” morphology comparing with that in 2D monolayer cultures and physiological functions such as matrix deposition. This work presents an important milestone in engineering complex protein microstructures and micropatterns with sub‐micrometer topological features to mimic the native matrix niche for cell‐matrix interaction studies.  相似文献   

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Mo‐based binary oxides (MBOs) and Mo‐based ternary oxides (MTOs) are a research focus because of their widespread applications. The traditional synthesis routes for MBOs and MTOs require high temperature and are time intense. Here, a rapid, facile, and scalable strategy to efficiently fabricate MBOs and MTOs with various morphologies and crystal structures is reported. Only 1 min is required for the whole process and the yield is above 90%. This strategy is the simplest and the fastest method reported and exhibits large potential for application. Furthermore, the as‐synthesized Hx MoO3 nanobelts and NiMoO4·x H2O nanowires display a specific capacitance of 660.3 F g?1 at 2 mV s?1 and a specific capacity of 549 C g?1 at 1 A g?1. In addition, to assemble the Hx MoO3 and NiMoO4·x H2O electrodes together, the solid state hybrid electrolyte is employed to take advantage of MBOs and MTOs. The obtained NiMoO4·x H2O//Hx MoO3 device delivers a specific capacitance of 156 F g?1 at 0.8 A g?1 and an energy density of 55.6 Wh kg?1 at a power density of 640 W kg?1, making it attractive for application as an energy storage material.  相似文献   

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To face the increasing demand of self‐healing hydrogels with biocompatibility and high performances, a new class of cellulose‐based self‐healing hydrogels are constructed through dynamic covalent acylhydrazone linkages. The carboxyethyl cellulose‐graft‐dithiodipropionate dihydrazide and dibenzaldehyde‐terminated poly(ethylene glycol) are synthesized, and then the hydrogels are formed from their mixed solutions under 4‐amino‐DL‐phenylalanine (4a‐Phe) catalysis. The chemical structure, as well as microscopic morphologies, gelation times, mechanical and self‐healing performances of the hydrogels are investigated with 1H NMR, Fourier transform infrared spectroscopy, atomic force microscopy, rheological and compression measurements. Their gelation times can be controlled by varying the total polymer concentration or 4a‐Phe content. The resulted hydrogels exhibit excellent self‐healing ability with a high healing efficiency (≈96%) and good mechanical properties. Moreover, the hydrogels display pH/redox dual responsive sol‐gel transition behaviors, and are applied successfully to the controlled release of doxorubicin. Importantly, benefitting from the excellent biocompatibility and the reversibly cross‐linked networks, the hydrogels can function as suitable 3D culture scaffolds for L929 cells, leading to the encapsulated cells maintaining a high viability and proliferative capacity. Therefore, the cellulose‐based self‐healing hydrogels show potential applications in drug delivery and 3D cell culture for tissue engineering.  相似文献   

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Anchoring-based self-assembly (ASA) has emerged as a material-saving and highly scalable strategy to fabricate charge-transporting monolayers for perovskite solar cells (PSCs). However, the interfacial hole-extraction and electron-blocking performances are highly dependent on the compactness of the ASA monolayers, which has been largely ignored though it is very crucial to the efficiency and stability of PSCs. Here, strategically designed hole-transporting molecules with different anchoring groups are incorporated to investigate the effect of bonding strength on monolayer quality and correlate these with the performance of p-i-n structured PSCs. It is unraveled that the anchoring groups with a stronger bonding strength are advantageous for improving the assembly rate, density, and compactness of ASA monolayer, thus enhancing charge collection and suppressing interfacial recombination. The prototypical PSCs based on optimal ASA monolayer achieve a high power conversion efficiency (PCE) of 21.43% (0.09 cm2). More encouragingly, when enlarging the device area by tenfold, a comparable PCE of 20.09% (1.0 cm2) can be obtained, suggesting that the ASA strategy is practically useful for scaling-up. The robust anchoring of the ASA monolayer also enhances devices stability, retaining 90% of initial PCE after three months. This study provides important insights into the ASA charge-transporting monolayers for efficient and stable PSCs.  相似文献   

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Enhancement of thermopower is achieved by doping the narrow‐band semiconductor Ag6.52Sb6.52Ge36.96Te50 (acronym TAGS‐85), one of the best p‐type thermoelectric materials, with 1 or 2% of the rare earth dysprosium (Dy). Evidence for the incorporation of Dy into the lattice is provided by X‐ray diffraction and increased orientation‐dependent local fields detected by 125Te NMR spectroscopy. Since Dy has a stable electronic configuration, the enhancement cannot be attributed to 4f‐electron states formed near the Fermi level. It is likely that the enhancement is due to a small reduction in the carrier concentration, detected by 125Te NMR spectroscopy, but mostly due to energy filtering of the carriers by potential barriers formed in the lattice by Dy, which has large both atomic size and localized magnetic moment. The interplay between the thermopower, the electrical resistivity, and the thermal conductivity of TAGS‐85 doped with Dy results in an enhancement of the power factor (PF) and the thermoelectric figure of merit (ZT) at 730 K, from PF = 28 μW cm?1 K?2 and ZT ≤ 1.3 in TAGS‐85 to PF = 35 μW cm?1 K?2 and ZT ≥ 1.5 in TAGS‐85 doped with 1 or 2% Dy for Ge. This makes TAGS‐85 doped with Dy a promising material for thermoelectric power generation.  相似文献   

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纳米钛酸锶粉体的特殊液相沉淀法制备   总被引：4，自引：1，他引：4  
以制备纳米钛酸锶粉体为目标,在液相反应胶粒析出机理分析的基础上,通过碳酸铵沉淀途径,采用特殊的快速高强度机械混合液相沉淀法,调控各种工艺条件,例如浓度、pH值、高机械混合强度以及陈化时间等,得到分散性和过滤性均好的碳酸锶和无定形氢氧化氧钛高度混合的纳米粉体前驱体,其粒径为3～4nm(平均3.5nm)。经920℃度焙烧,获得了结晶度好、分散性好、平均粒径56nm的立方相钛酸锶粉体。  相似文献   

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Conventional bone composites consistently fail to mimic the chemical composition and integrated organic/inorganic structure of natural bone, lacking sufficient mechanics as well as inherent osteoconductivity and osteoinductivity. Through a facile surface coating process, the strong adhesive, tannic acid (TA), is adhered to the surface of the natural bone component, hydroxyapatite (HA), with and without the immobilization of in situ formed silver nanoparticles. Residual functional groups available on the immobilized TA substituents are subsequently covalently linked to the citrate‐based biodegradable polymer, poly(octamethylene citrate) (POC), effectively bridging the organic and inorganic phases. Due to the synergistic effects of the tannin and citrate components, the obtained citrate‐based tannin‐bridged bone composites (CTBCs) exhibit vastly improved compression strengths up to 323.0 ± 21.3 MPa compared to 229.9 ± 15.6 MPa for POC‐HA, and possess tunable degradation profiles, enhanced biomineralization performance, favorable biocompatibility, increased cell adhesion and proliferation, as well as considerable antimicrobial activity. In vivo study of porous CTBCs using a lumbar fusion model further confirms CTBCs' osteoconductivity and osteoinductivity, promoting bone regeneration. CTBCs possess great potential for bone regeneration applications while the immobilized TA additionally preserves surface bioconjugation sites to further tailor the bioactivity of CTBCs.  相似文献   

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