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Carbon-based polymer brushes (CBPBs) are an important class of functional polymer materials, which synergistically combine the advantageous properties of both carbons and polymers. However, the conventional fabrication procedures of CBPBs involve tedious multistep modification, including preoxidation of carbon substrates, introduction of initiating groups, and subsequent graft polymerization. In this study, a simple yet versatile defect-engineering strategy is proposed for the efficient synthesis of high-grafting-density CBPBs with highly stable CC linkages via free radical polymerization. This strategy involves the introduction and removal of nitrogen heteroatoms in the carbon skeletons via a simple temperature-Fmed heat treatment, leading to the formation of numerous carbon defects (e.g., pentagons, heptagons, and octagons) with reactive C=C bonds in the carbon substrates. The as-proposed methodology enables the facile fabrication of CBPBs with various carbon substrates and polymers. More importantly, the highly grafted polymer chains in the resulting CBPBs are tethered with the carbon skeletons by robust CC bonds, which can endure strong acid and alkali environments. These interesting findings will shed new light on the well-orchestrated design of CBPBs and broaden their applications in various areas with fascinating performances.
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Carbonaceous materials are widely investigated as anodes for potassium-ion batteries (PIBs). However, the inferior rate capability, low areal capacity, and limited working temperature caused by sluggish K-ions diffusion kinetics are still primary challenges for carbon-based anodes. Herein, a simple temperature-programmed co-pyrolysis strategy is proposed for the efficient synthesis of topologically defective soft carbon (TDSC) based on inexpensive pitch and melamine. The skeletons of TDSC are optimized with shortened graphite-like microcrystals, enlarged interlayer spacing, and abundant topological defects (e.g., pentagons, heptagons, and octagons), which endow TDSC with fast pseudocapacitive K-ion intercalation behavior. Meanwhile, micrometer-sized structure can reduce the electrolyte degradation over particle surface and avoid unnecessary voids, ensuring a high initial Coulombic efficiency as well as high energy density. These synergistic structural advantages contribute to excellent rate capability (116 mA h g-1 at 20 C), impressive areal capacity (1.83 mA h cm-2 with a mass loading of 8.32 mg cm-2 ), long-term cycling stability (capacity retention of 91.8% after 1200 h cycling), and low working temperature (-10 °C) of TDSC anodes, demonstrating great potential for the practical application of PIBs.
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Porous carbon nanosheets have the advantages of longitudinal continuity, transverse ultrathin, high specific surface area, and surface atomic activity, as well as the synergistic effect of micro and nanoproperties, so the research on their preparation, structure, and properties has attracted wide attention. A series of ultrathin hierarchical porous carbon nanosheets (HPCNs) is fabricated through carbonization of precursors obtained through the Friedel-Crafts reaction-assisted loading of polystyrene on graphene oxide. Hierarchical pore structures consist of three parts: (1) the micropores (1.3 nm), which were provided by porous polystyrene through the Friedel-Crafts reaction; (2) the mesopores (3.8 nm), which were provided by slab pores from the stack of carbon nanosheets; and (3) the pores (>5 nm) formed from the random stack of carbon nanosheets. Controlling the carbonization time and temperature adds to a prominent increase in specific surface area from 405.8 to 1420 m2 g-1. It was found that excessive carbonization would destroy the hierarchical pore structure. These porous carbon materials were used as cathode materials for lithium-sulfur battery and showed good performance. HPCN/sulfur cathode has good rate performance and cycle performance, and the capacity retention rate is 87% after the current density rises from 1 to 3 C and 91% after 200 cycles.
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Multifunctionalization of microporous polymers is highly desirable but remains a significant challenge, considering that the current microporous polymers are generally hydrophobic and nonresponsive to different environmental stimuli and difficult to be carbonized without damage of their well-defined nanomorphology. Herein, we demonstrate a facile and versatile method to fabricate water-dispersible, pH/temperature responsive and readily carbonizable hairy microporous polymeric nanospheres based on combination of the hyper-cross-linking chemistry with the surface-initiated atom transfer radical polymerization (SI-ATRP). The hyper-cross-linking creates a highly microporous core, whereas the SI-ATRP provides diverse functionalities by surface grafting of hairy functional blocks. The as-prepared materials present multifunctional properties, including sensitive response to pH/temperature, high adsorption capacity toward adsorbates from aqueous solution, and valuable transformation into well-defined microporous carbon nanospheres because of hybrid of carbonizable core and thermo-decomposable protection shell. We hope this strategy could promote the development of both functional microporous polymers and advanced hairy nanoparticles for multipurpose applications.
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Ordered π-columns and open nanochannels found in covalent organic frameworks (COFs) could render them able to store electric energy. However, the synthetic difficulty in achieving redox-active skeletons has thus far restricted their potential for energy storage. A general strategy is presented for converting a conventional COF into an outstanding platform for energy storage through post-synthetic functionalization with organic radicals. The radical frameworks with openly accessible polyradicals immobilized on the pore walls undergo rapid and reversible redox reactions, leading to capacitive energy storage with high capacitance, high-rate kinetics, and robust cycle stability. The results suggest that channel-wall functional engineering with redox-active species will be a facile and versatile strategy to explore COFs for energy storage.
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Formation of a uniform interface between the carbon precursor and the selected template is critical for preparing high-quality nanoporous carbons. It can be accomplished by various templating procedures but still remains a challenge, especially for microporous carbons. A new strategy to fabricate well-defined microporous carbon nanosphere (MCNS) materials via molecular-scale interfacial engineering using an organic/inorganic hybrid molecule as the building block was designed. A commercially available octaphenyl polyhedral oligomeric silsesquioxane was selected as such a building block and transformed into the MCNS products via cross-linking of organic components, followed by carbonization, and subsequent removal of monodispersed silica domains, surrounded by molecular-scale carbon/silica interfaces. The obtained MCNS materials exhibit very large surface area (e.g., 2264 m(2)/g) and fast and selective sorption, and thus demonstrate excellent adsorption and supercapacitance properties. These findings could provide a new benchmark for preparing well-defined nanoporous carbons for various applications.
Asunto(s)
Carbono/química , Nanosferas/química , Compuestos de Organosilicio/química , Adsorción , Nanosferas/ultraestructura , Nanotecnología , Compuestos de Organosilicio/síntesis química , Porosidad , Propiedades de SuperficieRESUMEN
A simple and effective way to introduce micropores into skeleton of carbon aerogel (CA) without damaging its unique 3D mesoporous nanonetwork has been successfully developed by NH3-assisted semicarbonization. During the NH3-assisted semicarbonization process, nitrogen functional groups with high thermo-decomposable ability like pyrrolic/pyridine and pyridinic can be introduced into the semicarbonized aerogel framework by substituting oxygen functional groups with low thermo-decomposable ability like CâO quinone-type groups and then escape from the resultant CA framework during the subsequent carbonization, thus forming abundant micropores inside carbon framework under the circumstance of keeping wonderful stability of mesoporous nanonetwork structure. Compared with the traditional CA without NH3 assistance during semicarbonization, the as-prepared novel CA represents a much higher surface area (1100 vs 620 m(2) g(-1)) and a compatible mesopore structure. Meanwhile, such a NH3 treatment confers many useful nitrogen functional groups on the nanonetwork framework. The novel CA is then used as electrode material of supercapacitors and shows a much higher capacitance and comparable high capacitance retention as compared with the traditional CA.
Asunto(s)
Amoníaco/química , Carbono , PorosidadRESUMEN
Carbonaceous materials are regarded as one of the most promising anodes for potassium-ion batteries (PIBs), but their rate capabilities are largely limited by the slow solid-state potassium diffusion kinetics inside anode and sluggish interfacial potassium ion transfer process. Herein, high-rate and high-capacity PIBs are demonstrated by facile topological defect-regulation of the microstructure of carbon anodes. The carbon lattice of the as-obtained porous carbon nanosheets (CNSs) with abundant topological defects (TDPCNSs) holds relatively high potassium adsorption energy yet low potassium migration barrier, thereby enabling efficient storage and diffusion of potassium inside graphitic layers. Moreover, the topological defects can induce preferential decomposition of anions, leading to the formation of high potassium ion conductive solid electrolyte interphase (SEI) film with decreased potassium ion de-solvation and transfer barrier. Additionally, the dominant sp2-hybridized carbon conjugated skeleton of TDPCNSs enables high electrical conductivity (39.4 S cm-1) and relatively low potassium storage potential. As a result, the as-constructed TDPCNSs anode demonstrates high potassium storage capacity (504 mA h g-1 at 0.1 A g-1), remarkable rate capability (118 mA h g-1 at 40 A g-1), as well as long-term cycling stability.
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The low cycling efficiency and uncontrolled dendrite growth resulting from an unstable and heterogeneous lithium-electrolyte interface have largely hindered the practical application of lithium metal batteries. In this study, a robust all-organic interfacial protective layer has been developed to achieve a highly efficient and dendrite-free lithium metal anode by the rational integration of porous polymer-based molecular brushes (poly(oligo(ethylene glycol) methyl ether methacrylate)-grafted, hypercrosslinked poly(4-chloromethylstyrene) nanospheres, denoted as xPCMS-g-PEGMA) with single-ion-conductive lithiated Nafion. The porous xPCMS inner cores with rigid hypercrosslinked skeletons substantially increase mechanical robustness and provide adequate channels for rapid ionic conduction, while the flexible PEGMA and lithiated Nafion polymers enable the formation of a structurally stable artificial protective layer with uniform Li+ diffusion and high Li+ transference number. With such artificial solid electrolyte interphases, ultralong-term stable cycling at an ultrahigh current density of 10 mA cm-2 for over 9,100 h (>1 year) and unprecedented reversible lithium plating/stripping (over 2,800 h) at a large areal capacity (10 mAh cm-2) have been achieved for lithium metal anodes. Moreover, the protected anodes also show excellent cell stability when paired with high-loading cathodes (~4 mAh cm-2), demonstrating great prospects for the practical application of lithium metal batteries.
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Carbon-based nanomaterials have been regarded as promising non-noble metal catalysts for renewable energy conversion system (e.g., fuel cells and metal-air batteries). In general, graphitic skeleton and porous structure are both critical for the performances of carbon-based catalysts. However, the pursuit of high surface area while maintaining high graphitization degree remains an arduous challenge because of the trade-off relationship between these two key characteristics. Herein, a simple yet efficient approach is demonstrated to fabricate a class of 2D N-doped graphitized porous carbon nanosheets (GPCNSs) featuring both high crystallinity and high specific surface area by utilizing amine aromatic organoalkoxysilane as an all-in-one precursor and FeCl3 ·6H2 O as an active salt template. The highly porous structure of the as-obtained GPCNSs is mainly attributed to the alkoxysilane-derived SiOx nanodomains that function as micro/mesopore templates; meanwhile, the highly crystalline graphitic skeleton is synergistically contributed by the aromatic nucleus of the precursor and FeCl3 ·6H2 O. The unusual integration of graphitic skeleton with porous structure endows GPCNSs with superior catalytic activity and long-term stability when used as electrocatalysts for oxygen reduction reaction and Zn-air batteries. These findings will shed new light on the facile fabrication of highly porous carbon materials with desired graphitic structure for numerous applications.
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A unique hierarchical architecture is successfully constructed in a wormhole-like mesopore structure via a multiple nanocasting route. This novel type of hierarchical porous carbon (HPC) consists of three-dimensional ordered macropores (ca. 150 nm) with interconnecting pore windows, and the walls of these macropores are rich in wormhole-like mesopores (ca. 2.7 nm) and large spherical mesopores (ca. 10 nm), as well as a significant microporosity, presenting a macro-meso-microporous structure with a three-dimensional interconnectivity. Such a hierarchically porous structure may provide fine diffusion pathways for reaction species, which is demonstrated by the experimental result of an enhanced performance in a supercapacitor. For example, with the introduction of a hierarchical porous structure for fast transport and effective access of ions, the as-prepared HPC exhibits a specific capacitance as high as 247 F g(-1), whereas traditional wormhole-like mesoporous carbon has only a specific capacitance of 176 F g(-1).
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A generalized and facile strategy toward 2D hybrid porous carbons (2DHPCs) with various highly active functional species (e.g. Co, B, and P) is developed via 2D molecular brushes as biomimetic building blocks. The resulting 2DHPCs present superior electrochemical energy conversion and storage properties.
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Nitrogen-doped porous carbon spheres have attracted great interest in diversified fields owing to their unique physical and chemical properties. However, the synthesis of nitrogen-doped porous carbon spheres with hierarchical superstructures and refined micropore structures is still a challenge. Herein, we develop a molecular-scale silica templating strategy to prepare nitrogen-doped microporous carbon spheres (MCSSs) with high porosity and a well-defined micropore structure. Octa(aminophenyl) polyhedral oligomeric silsesquioxane is used as a building block in MCSS precursors to provide precise molecular-scale templating and nitrogen doping. The morphology of MCSSs can be easily tuned by choosing the proper solvent. The as-synthesized MCSS with a large surface area (2036 m2 g-1), narrow micropore size distribution, nitrogen doping, and hierarchical geometry can serve as an efficient selective adsorbent for CO2 and organic pollutants. Furthermore, the MCSS decorated with Fe-N-C active sites (MCSS-Fe) shows enhanced electrocatalytic ORR activity in alkaline solution. This novel approach may open a new avenue for controllable fabrication of porous carbon spheres with desired geometry and well-designed pore structure and show potential applications in selective adsorption and catalysis.
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MnO(2) as one of the most promising candidates for electrochemical supercapacitors has attracted much attention because of its superior electrochemical performance, low cost, and environmentally benign nature. In this Letter, we explored a novel route to prepare mesoporous MnO(2)/carbon aerogel composites by electrochemical deposition assisted by gas bubbles. The products were characterized by energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The MnO(2) deposits are found to have high purity and have a mesoporous structure that will optimize the electronic and ionic conductivity to minimize the total resistance of the system and thereby maximize the performance characteristics of this material for use in supercapacitor electrodes. The results of nitrogen adsorption-desorption experiments and electrochemical measurements showed that these obtained mesoporous MnO(2)/carbon aerogel composites had a large specific surface area (120 m(2)/g), uniform pore-size distribution (around 5 nm), high specific capacitance (515.5 F/g), and good stability over 1000 cycles, which give these composites potential application as high-performance supercapacitor electrode materials.
Asunto(s)
Carbono/química , Geles/química , Compuestos de Manganeso/química , Óxidos/química , Adsorción , Electroquímica , Electrodos , Compuestos de Manganeso/síntesis química , Ensayo de Materiales , Nitrógeno/química , Óxidos/síntesis química , Tamaño de la Partícula , Porosidad , Propiedades de SuperficieRESUMEN
Two typical carbon materials (ordered mesoporous carbon and carbon nanotube) were chosen as scaffolds in combination with semiconductor quantum dots (SQDs) for making light-harvesting assemblies. The effects of interfacial morphology on photoelectric performance of the carbon-based heterostructures have been investigated in detail. The enhanced photoresponse shows a strong dependence on the interfacial morphology as a result of direct interfacial contacts between SQDs and carbon materials, which plays a major role in increasing charge generation at the interface and transport pathways for photoinduced electron transfer. The methodology to enhance the photoresponse through tuning interfacial morphology proves to be a potent alternative in fabricating photochemical energy conversion systems.
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Polyaniline (PANI) with carbon aerogel (CA) as conducting filler has been synthesized by an in situ chemical oxidative polymerization method. Scanning electron microscopy, infrared spectra, cyclic voltammetry and X-ray diffraction indicate that the three-dimensional carbon nano-network of CA is entirely buried inside the PANI matrix and its introduction basically does not change the structure of PANI. The electrochemical performances of the as-prepared PANI materials with CA filler are evaluated by means of galvanostatic charge-discharge test, cyclic voltammetry and electrochemical impedance spectroscopy. It is found that the electrochemical performances of PANI are notably improved due to the introduction of CA filler. For example, when operating at a large current density of 50 mA cm(-2), CA-modified PANI with the optimal CA/aniline ratio of 1.0 wt% exhibits a specific capacitance as high as 226 F g(-1), whereas neat PANI has only 89 F g(-1). The CA modification mechanism of PANI has been discussed in detail.
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In this work, kinetics of phase separation in the blends of polystyrene (PS) and poly(vinyl methyl ether) (PVME) was investigated by a simple and sensitive method, i.e., resonance light scattering (RLS) spectroscopy. Owing to the aggregation of chromophores (phenyl rings) in the systems when phase separation occurred, RLS intensities were drastically enhanced and hence acted as a characteristic indicator. At the early stage of phase separation, two different RLS behaviors corresponding to spinodal decomposition (SD) and nucleation and growth (NG) were observed. The Cahn-Hilliard (C-H) linearization theory was found not applicable for kinetics analysis of the scattering data at lambda < 346 nm due to RLS effect near the absorption band. Based on a decomposition reaction model, the apparent activation energy of SD phase separation was estimated by the Arrhenius equation. In view of its simplicity and sensitivity of measurement, affordability and availability of instrument, and wide application range of polymer blends, RLS proved to be an effective means for characterization of microstructural variation in polymer blends.
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In the present paper, we demonstrate the importance of the role of a mass transport pathway (MTP) in wormholelike mesoporous carbon (WMC) through studying the ion diffusion behaviors within two different wormholelike mesopore networks with and without MTP. Our results reveal that the introduction of MTP is very helpful in improving ion diffusion properties. The as-prepared WMC with a MTP of ca. 9.7 nm exhibits notably better electric double layer performance as compared to the conventional WMC without a MTP. For example, even at the quick sweep rate of 50 mV s(-1), the surface specific capacitance of the former is 21.6 microF cm(-2), which is almost 4 times as high as that of the latter (5.5 microF cm(-2)).
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A novel strategy is developed to produce an FeS-FeNC-decorated hierarchical porous N,S-co-doped carbon (FeS-FeNC@NSC) electrocatalyst via introducing volatile FeCl3 into a porphyrin polymer framework followed by carbonization. The synergistic effect between the FeS nanoparticles and FeNC active sites in FeS-FeNC@NSC is beneficial for enhancing the ORR activity.