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1.
Microporous nitrogen‐rich carbon fibers (HAT‐CNFs) are produced by electrospinning a mixture of hexaazatriphenylene‐hexacarbonitrile (HAT‐CN) and polyvinylpyrrolidone and subsequent thermal condensation. Bonding motives, electronic structure, content of nitrogen heteroatoms, porosity, and degree of carbon stacking can be controlled by the condensation temperature due to the use of the HAT‐CN with predefined nitrogen binding motives. The HAT‐CNFs show remarkable reversible capacities (395 mAh g?1 at 0.1 A g?1) and rate capabilities (106 mAh g?1 at 10 A g?1) as an anode material for sodium storage, resulting from the abundant heteroatoms, enhanced electrical conductivity, and rapid charge carrier transport in the nanoporous structure of the 1D fibers. HAT‐CNFs also serve as a series of model compounds for the investigation of the contribution of sodium storage by intercalation and reversible binding on nitrogen sites at different rates. There is an increasing contribution of intercalation to the charge storage with increasing condensation temperature which becomes less active at high rates. A hybrid sodium‐ion capacitor full cell combining HAT‐CNF as the anode and salt‐templated porous carbon as the cathode provides remarkable performance in the voltage range of 0.5–4.0 V (95 Wh kg?1 at 0.19 kW kg?1 and 18 Wh kg?1 at 13 kW kg?1).  相似文献   

2.
Silica aerogels are amongst the lightest mesoporous solids known and well recognized for their superinsulating properties, but the weak mechanical properties of the inorganic network structure has often narrowed their field of application. Here, the inherent brittleness of dried inorganic gels is tackled through the elaboration of a strong mesoporous silica aerogel interpenetrated with a silylated nanocellulosic scaffold. To this avail, a functionalized scaffold is synthesized by freeze‐drying an aqueous suspension of nanofibrillated cellulose (NFC)—a bio‐based nanomaterial mechanically isolated from renewable resources—in the presence of methyltrimethoxysilane sol. The silylated NFC scaffold displays a high porosity (>98%), high flexibility, and reduced thermal conductivity (λ) compared with classical cellulosic structures. The polysiloxane layer decorating the nanocellulosic scaffold is exploited to promote the attachment of the mesoporous silica matrix onto the nanofibrillated cellulose scaffold (NFCS), leading to a reinforced silica hybrid aerogel with improved thermomechanical properties. The highly porous (>93%) silica‐NFC hybrids displays meso‐ and macroporosity with pore diameters controllable by the NFCS mass fraction, reduced linear shrinkage, improved compressive properties (55% and 126% increase in Young's modulus and tensile strength, respectively), while maintaining superinsulating properties (λ ≤ 20 mW (m K)–1). This study details a new direction for the synthesis of multiscale hybrid silica aerogel structures with tailored properties through the use of alkyltrialkoxysilane prefunctionalized nanocellulosic scaffolds.  相似文献   

3.
Nanocast carbon monoliths exhibiting a three‐ or four‐modal porosity have been prepared by one‐step impregnation, using silica monoliths containing a bimodal porosity as the scaffold. Combined volume and surface templating, together with the controlled synthesis of the starting silica monoliths used as the scaffold, enables a flexible means of pore‐size control on several length scales simultaneously. The monoliths were characterized by nitrogen sorption, scanning electron microscopy, transmission electron microscopy, and mercury porosimetry. It is shown that the carbon monoliths represent a positive replica of the starting silica monoliths on the micrometer length scale, whereas the volume‐templated mesopores are a negative replica of the silica scaffold. In addition to the meso‐ and macropores, the carbon monoliths also exhibit microporosity. The different modes of porosity are arranged in a hierarchical structure‐within‐structure fashion, which is thought to be optimal for applications requiring a high surface area in combination with a low pressure drop over the material.  相似文献   

4.
Extended porous silica films with thicknesses in the range of 60 to 130 μm and pores on both the meso‐ and macroscale have been prepared by simultaneously using porous membrane templates and amphiphilic supramolecular aggregates as porogens. The macropore size is determined by the cellulose acetate or polyamide membrane structure and the mesopores by the chosen ethylene‐oxide‐based molecular self‐assembly (block copolymer or non‐ionic surfactants). Both the template and the porogen are removed during an annealing step leaving the amorphous silica material with a porous structure that results from sol–gel chemistry occurring in the aqueous domains of the amphiphilic liquid‐crystalline phases and casting of the initial template membrane. The surface area and total pore volume of the inorganic films vary from 473 to 856 m2 g–1, and 0.50 to 0.73 cm3 g–1, respectively, depending on the choice of template and porogen. The combined benefits of both macro‐ and mesopores can potentially be obtained in one film. Such materials are envisaged to have applications in areas of large molecule (biomolecule) separation and catalysis. Enhanced gas and liquid flow rates through such membranes, due to the presence of the larger pores, also makes them attractive as supports for other catalytic materials.  相似文献   

5.
A new class of bifunctional periodic mesoporous organosilicas (PMOs) composed of organosilicate building blocks with two different silicon sites have been synthesized from the single‐source bifunctional organosilica precursors tris(triethoxysilylethyl)ethoxysilane and bis(triethoxysilylethyl)diethoxysilane, respectively denoted MT3‐PMO and DT2‐PMO. The synthesis of these PMOs is achieved by the co‐assembly of a triblock‐copolymer Pluronic P123 template with the bifunctional organosilica precursor under acid‐catalyzed and inorganic‐salt‐assisted conditions. After template removal through solvent extraction, the MT3‐PMO and DT2‐PMO so obtained show well‐ordered mesopores and display large pore diameters (6–7 nm) and pore volumes (0.6–0.8 cm3 g–1) with a narrow pore‐size distribution and high surface areas (700–800 m3 g–1).  相似文献   

6.
By employing commercial poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) block copolymers as templates in near‐neutral aqueous solutions in the absence of organic cosolvents, unilamellar siliceous vesicles and nanofoams with ultrahigh pore volumes (> 3 cm3 g–1) are successfully synthesized. At controlled pH, a tubular micelle → unilamellar vesicle → nanofoam structural transformation is observed by increasing the reaction temperature. It is proposed that the siliceous vesicles are synthesized via a co‐operative block‐copolymer vesicle templating approach, while the siliceous nanofoams are obtained by the fusion of vesicles at increased ionic strength. Compared to literature methods to synthesize siliceous vesicles and foams, our method is convenient, cheap, and produces a high yield. Siliceous nanofoams synthesized by using our approach show superior bioimmobilization capacity over other porous materials for biomolecules with large molecular weight.  相似文献   

7.
A facile approach of solvent‐evaporation‐induced coating and self‐assembly is demonstrated for the mass preparation of ordered mesoporous carbon‐silica composite monoliths by using a polyether polyol‐based polyurethane (PU) foam as a sacrificial scaffold. The preparation is carried out using resol as a carbon precursor, tetraethyl orthosilicate (TEOS) as a silica source and Pluronic F127 triblock copolymer as a template. The PU foam with its macrostructure provides a large, 3D, interconnecting interface for evaporation‐induced coating of the phenolic resin‐silica block‐copolymer composites and self‐assembly of the mesostructure, and endows the composite monoliths with a diversity of macroporous architectures. Small‐angle X‐ray scattering, X‐ray diffraction and transmission electron microscopy results indicate that the obtained composite monoliths have an ordered mesostructure with 2D hexagonal symmetry (p6m) and good thermal stability. By simply changing the mass ratio of the resol to TEOS over a wide range (10–90%), a series of ordered, mesoporous composite foams with different compositions can be obtained. The composite monoliths with hierarchical macro/mesopores exhibit large pore volumes (0.3–0.8 cm3 g?1), uniform pore sizes (4.2–9.0 nm), and surface areas (230–610 m2 g?1). A formation process for the hierarchical porous composite monoliths on the struts of the PU foam through the evaporation‐induced coating and self‐assembly method is described in detail. This simple strategy performed on commercial PU foam is a good candidate for mass production of interface‐assembly materials.  相似文献   

8.
Novel carbon materials derived from metal‐organic frameworks (MOFs) have attracted much attention, but the commonly inevitable inward contraction during the carbonization process has restricted their structural variety and applications. In this work, a novel rigid‐interface induced outward contraction approach is reported for synthesizing hollow mesoporous carbon nanocubes (HMCNCs) by using ZIF‐8 nanocubes as precursors. HMCNCs exhibit a cubic morphology with the particle sizes slightly larger than ZIF‐8 nanocubes. Due to the unique outward contraction process, uniform carbon nanocubes with a hollow cavity, an outer microporous shell, and an inner mesoporous wall are simultaneously formed with a large pore size (25 nm), high surface area (1085.7 m2 g?1), high porosity (3.77 cm3 g?1), and high nitrogen content (12.2%). When used as a cathode material for Li–SeS2 batteries, the HMCNCs deliver a stable capacity of 812.6 mA h g?1 at 0.2 A g?1 after 100 cycles and an outstanding rate capability (455.1 mA h g?1 at 5.0 A g?1). The findings may pave the way for the construction of distinctive MOF‐derived carbon materials for various applications.  相似文献   

9.
Hierarchical porous carbon (HPC, DUT‐106) with tailored pore structure is synthesized using a versatile approach based on ZnO nanoparticles avoiding limitations present in conventional silica hard templating approaches. The benefit of the process presented here is the removal of all pore building components by pyrolysis of the ZnO/carbon composite without any need for either toxic/reactive gases or purification of the as‐prepared hierarchical porous carbon. The carbothermal reduction process is accompanied by an advantageous growing of distinctive micropores within the thin carbon walls. The resulting materials show not only high internal porosity (total pore volume up to 3.9 cm3 g?1) but also a large number of electrochemical reaction sites due to their remarkably high specific surface area (up to 3060 m2 g?1), which renders them particularly suitable for the application as sulfur host material. Applied in the lithium‐sulfur battery, the HPC/sulfur composite exhibits a capacity of >1200 mAh g?1‐sulfur (>750 mAh g?1 electrode) at a high sulfur loading of ≥ 3 mg cm?2 as well as outstanding rate capability. In fact, this impressive performance is achieved even using a low amount of electrolyte (6.8 μl mg?1 sulfur) allowing for further weight reduction and maintenance of high energy density on cell level.  相似文献   

10.
Capacitive deionization (CDI) is a competent water desalination technique offering an appropriate route to obtain clean water. However, a rational designed structure of the electrode materials is essentially required for achieving high CDI performance. Here, a novel sponge‐templated strategy is developed for the first time to prepare graphene sheets with high specific surface area and suitable pore size distribution. Sponge is used as the support of graphene oxide to prevent the restack of graphene sheets, as well as to suppress the agglomerate during the annealing process. Importantly, the as‐fabricated graphene sheets possess high specific surface area of 305 m2 g?1 and wide pore size distribution. Ultrahigh CDI performance, a remarkable electrosorptive capacity of 4.95 mg g?1, and siginificant desorption rate of 25 min, is achieved with the sponge‐templated prepared graphene electrodes. This work provides an effective solution for the synthesis of rational graphene architectures for general applications in CDI, energy storage and conversion.  相似文献   

11.
Aqueous dual‐ion batteries (DIBs) are promising for large‐scale energy storage due to low cost and inherent safety. However, DIBs are limited by low capacity and poor cycling of cathode materials and the challenge of electrolyte decomposition. In this study, a new cathode material of nitrogen‐doped microcrystalline graphene‐like carbon is investigated in a water‐in‐salt electrolyte of 30 m ZnCl2, where this carbon cathode stores anions reversibly via both electrical double layer adsorption and ion insertion. The (de)insertion of anions in carbon lattice delivers a high‐potential plateau at 1.85 V versus Zn2+/Zn, contributing nearly 1/3 of the capacity of 134 mAh g?1 and half of the stored energy. This study shows that both the unique carbon structure and concentrated ZnCl2 electrolyte play critical roles in allowing anion storage in carbon cathode for this aqueous DIB.  相似文献   

12.
Nanometer‐sized surfactant‐templated materials are prepared in the form of stable suspensions of colloidal mesoporous silica (CMS) consisting of discrete, nonaggregated particles with dimensions smaller than 200 nm. A high‐yield synthesis procedure is reported based on a cationic surfactant and low water content that additionally enables the adjustment of the size range of the individual particles between 50 and 100 nm. Particularly, the use of the base triethanolamine (TEA) and the specific reaction conditions result in long‐lived suspensions. Dynamic light scattering reveals narrow particle size distributions in these suspensions. Smooth spherical particles with pores growing from the center to the periphery are observed by using transmission electron microscopy, suggesting a seed‐growth mechanism. The template molecules could be extracted from the nanoscale mesoporous particles via sonication in acidic media. The resulting nanoparticles give rise to type IV adsorption isotherms revealing typical mesopores and additional textural porosity. High surface areas of over 1000 m2 g–1 and large pore volumes of up to 1 mL g–1 are obtained for these extracted samples.  相似文献   

13.
Hybrid nanomaterials with tailored functions, consisting of self‐assembled peptides, are intensively applied in nanotechnology, tissue engineering, and biomedical applications due to their unique structures and properties. Herein, a peptide‐mediated biomimetic strategy is adopted to create the multifunctional 3D graphene foam (GF)‐based hybrid minerals. First, 2D peptide nanosheets (PNSs), obtained by self‐assembling a motif‐specific peptide molecule (LLVFGAKMLPHHGA), are expected to exhibit biofunctionality, such as the biomimetic mineralization of hydroxyapatite (HA) minerals. Subsequently, the noncovalent conjugation of PNSs onto GF support is utilized to form 3D GF‐PNSs hybrid scaffolds, which are suitable for the growth of HA minerals. The fabricated biomimetic 3D GF‐PNSs‐HA minerals exhibit adjustable shape, superlow weight (0.017 g cm?3), high porosity (5.17 m2 g?1), and excellent biocompatibility, proving potential applications in both bone tissue engineering and biomedical engineering. To the best of the authors' knowledge, it is the first time to combine 2D PNSs and GF to fabricate 3D organic–inorganic hybrid scaffold. Further development of these hybrid GF‐PNSs scaffolds can potentially lead to materials used as matrices for drug delivery or bone tissue engineering as proven via successful 3D scaffold formation exhibiting interconnected pore‐size structures suitable for vascularization and medium transport.  相似文献   

14.
One of the major challenges to develop high‐performance lithium–oxygen (Li–O2) battery is to find effective cathode catalysts and design porous architecture for the promotion of both oxygen reduction reactions and oxygen evolution reactions. Herein, the synthesis of mesoporous carbon nanocubes as a new cathode nanoarchitecture for Li–O2 batteries is reported. The oxygen electrodes made of mesoporous carbon nanocubes contain numerously hierarchical mesopores and macropores, which can facilitate oxygen diffusion and electrolyte impregnation throughout the electrode, and provide sufficient spaces to accommodate insoluble discharge products. When they are applied as cathode catalysts, the Li–O2 cells deliver discharge capacities of 26 100 mA h g?1 at 200 mA g?1, which is much higher than that of commercial carbon black catalysts. Furthermore, the mesoporous nanocube architecture can also serve as a conductive host structure for other highly efficient catalysts. For instance, the Ru functionalized mesoporous carbon nanocubes show excellent catalytic activities toward oxygen evolution reactions. Li–O2 batteries with Ru functionalized mesoporous carbon nanocube catalysts demonstrate a high charge/discharge electrical energy efficiency of 86.2% at 200 mA g?1 under voltage limitation and a good cycling performance up to 120 cycles at 400 mA g?1 with the curtaining capacity of 1000 mA h g?1.  相似文献   

15.
Hollow carbon materials are considered promising sulfur reservoirs for lithium–sulfur batteries owing to their internal void space and porous conductive shell, providing high loading and utilization of sulfur. Since the pores in carbon materials play a critical role in the infusion of sulfur, access of the electrolyte, and the passage of lithium polysulfides (LPSs), the creation and tuning of hierarchical pore structures is strongly required to improve the electrochemical properties of sulfur/porous carbon composites, but remains a major challenge. Herein, a “brain‐coral‐like” mesoporous hollow carbon nanostructure consisting of an in situ‐grown N‐doped graphitic carbon nanoshell (NGCNs) matrix and embedded CoS2 nanoparticles as an efficient sulfur host is presented. The rational synthetic design based on metal–organic framework chemistry furnishes unusual multiple porosity in a carbon scaffold with a macrohollow in the core and microhollows and mesopores in the shell, without the use of any surfactant or template. The CoS2@NGCNs/S composite electrode facilitates high sulfur loading (75 wt%), strong adsorption of LPSs, efficient reaction kinetics, and stable cycle performance (903 mAh g?1 at 0.1 C after 100 cycles), derived from the synergetic effects of the dual hollow features, chemically active CoS2, and the conductive and mesoporous N‐doped carbon matrix.  相似文献   

16.
Heteroatom modification represents one of the major areas of carbon materials' research in electrical energy storage. However, the influence of heteroatomic state evolution on electrochemical properties remains an elusive topic. Herein, thiophene‐2,5‐dicarboxylic acid is chemically activated to prepare O,S‐diatomic hybrid carbon material (OS–C). The heteroatoms and carbon matrix coexist in the form of C?O/C? O and C? S/S? S bonds, which introduce porous networks to the partially graphitized carbon skeleton and provide abundant active sites for better ion absorption. Moreover, the heteroatoms and carbon matrix are bridged to establish stable pseudocapacitive functional groups like quinoid unit and disulfide bonds, which can be electrochemically converted into benzenoid units and mercaptan anions through Faradaic reactions to further improve the reversible capacity. Combined with the detailed kinetic exploration and in situ investigation of the electrochemical impedance spectra, the energy storage mechanism for lithium/sodium is proposed in the following steps: Faradaic reactions at a higher potential range, energy storage at active sites, and ions intercalation on the graphitized parts in the low‐voltage states. Greatly, the electrode can store lithium up to the capacity of ≈700 mAh g?1, while also delivering ≈330 mAh g?1 of sodium storage, providing lifetimes in excess of thousands of cycles.  相似文献   

17.
The battery shape is a critical limiting factor affecting foreseeable energy storage applications. In particular, deformable metal–air battery systems can offer low cost, low flammability, and high capacity, but the fabrication of such metal–air batteries remains challenging. Here, it is shown that a shape‐reconfigurable‐material approach, in which the deformable components composed of micro‐ and nanoscale composites are assembled, is suitable for constructing polymorphic metal–air batteries. By employing an aluminum foil and an adhesive carbon composite placed on a cellulose scaffold as a substrate, an aluminum–air battery that can be deformed to an unprecedented high level, e.g., via expanding, folding, stacking, and crumpling, can be realized. This significant deformability results in a specific capacity of 128 mA h g?1 (496 mA h g?1 per cell; based on the mass of consumed aluminum) and a high output voltage (10.3 V) with 16 unit battery cells connected in series. The resulting battery can endure significant geometrical distortions such as 3D expanding and twisting, while the electrochemical performance is preserved. This work represents an advancement in deformable aluminum–air batteries using the shape‐reconfigurable‐material concept, thus establishing a paradigm for shape‐reconfigurable batteries with exceptional mechanical functionalities.  相似文献   

18.
A sonochemical method has been successfully used in order to incorporate MnO2 nanoparticles inside the pore channels of CMK‐3 ordered mesoporous carbon. Modification of the intrachannel surfaces of CMK‐3 to make them hydrophilic enables KMnO4 to readily penetrate the pore channels. At the same time, the modification changes the surface reactivity, enabling the formation of MnO2 nanoparticles inside the pores of CMK‐3 by the sonochemical reduction of metal ions. The resultant structures were characterized by X‐ray diffraction (XRD), nitrogen adsorption, and transmission electron microscopy (TEM). CMK‐3 with 20 wt.‐% loading of MnO2 inside CMK‐3 delivered an improved discharge performance of 223 mA h g–1 at a relatively high rate of 1 A g–1. Almost no decrease in specific capacity is observed for the second cycle, and a discharge capacity of more than 165 mA h g–1 is retained after 100 cycles. This is attributed to the nanometer‐sized MnO2 formed inside CMK‐3 and the high surface area of the mesopores (3.1 nm) in which the MnO2 nanoparticles are formed.  相似文献   

19.
An oxidation‐resistant and elastic mesoporous carbon, graphene mesosponge (GMS), is prepared. GMS has a sponge‐like mesoporous framework (mean pore size is 5.8 nm) consisting mostly of single‐layer graphene walls, which realizes a high electric conductivity and a large surface area (1940 m2 g?1). Moreover, the graphene‐based framework includes only a very small amount of edge sites, thereby achieving much higher stability against oxidation than conventional porous carbons such as carbon blacks and activated carbons. Thus, GMS can simultaneously possess seemingly incompatible properties; the advantages of graphitized carbon materials (high conductivity and high oxidation resistance) and porous carbons (large surface area). These unique features allow GMS to exhibit a sufficient capacitance (125 F g?1), wide potential window (4 V), and good rate capability as an electrode material for electric double‐layer capacitors utilizing an organic electrolyte. Hence, GMS achieves a high energy density of 59.3 Wh kg?1 (material mass base), which is more than twice that of commercial materials. Moreover, the continuous graphene framework makes GMS mechanically tough and extremely elastic, and its mean pore size (5.8 nm) can be reversibly compressed down to 0.7 nm by simply applying mechanical force. The sponge‐like elastic property enables an advanced force‐induced adsorption control.  相似文献   

20.
Nitrogen‐rich porous carbons (NPCs) are the leading cathode materials for next‐generation Zn–air and Li–S batteries. However, most existing NPC suffers from insufficient exposure and harnessing of nitrogen‐dopants (NDs), constraining the electrochemical performance. Herein, by combining silica templating with in situ texturing of metal–organic frameworks, a new bifunctional 3D nitrogen‐rich carbon photonic crystal architecture of simultaneously record‐high total pore volume (13.42 cm3 g?1), ultralarge surface area (2546 m2 g?1), and permeable hierarchical macro‐meso‐microporosity is designed, enabling sufficient exposure and accessibility of NDs. Thus, when used as cathode catalysts, the Zn–air battery delivers a fantastic capacity of 770 mAh gZn?1 at an unprecedentedly high rate of 120 mA cm?2, with an ultrahigh power density of 197 mW cm?2. When hosting 78 wt% sulfur, the Li–S battery affords a high‐rate capacity of 967 mAh g?1 at 2 C, with superb stability over 1000 cycles at 0.5 C (0.054% decay rate per cycle), comparable to the best literature value. The results prove the dominant role of highly exposed graphitic‐N in boosting both cathode performances.  相似文献   

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