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1.
The in situ tracking of the pyrolysis of a binary molecular cluster [Zn73-CH3O)6(L)6][ZnLCl2]2 is presented with one brucite disk and two mononuclear fragments (L=mmimp: 2-methoxy-6-((methylimino)-methyl)phenolate) to porous carbon using TG-MS from 30 to 900 °C. Following up the spilled gas product during the decomposed reaction of zinc cluster along the temperature rising, and in conjunction with XRD, SEM, BET and other materials characterization, where three key steps were observed: 1) cleavage of the bulky external ligand; 2) reduction of ZnO and 3) volatilization of Zn. The real-time-dependent phase-sequential evolution of the remaining products and the processing of pore forming template transformation are proposed simultaneously. The porous carbon structure featuring a uniform nano-sized pore distribution synthesized at 900 °C with the highest surface area of 1644 m2 g−1 and pore volume of 0.926 cm3 g−1 exhibits the best known capacitance of 662 F g−1 at 0.5 A g−1.  相似文献   

2.
Sustainable carbon materials have received particular attention in CO2 capture and storage owing to their abundant pore structures and controllable pore parameters. Here, we report high‐surface‐area hierarchically porous N‐doped carbon microflowers, which were assembled from porous nanosheets by a three‐step route: soft‐template‐assisted self‐assembly, thermal decomposition, and KOH activation. The hydrazine hydrate used in our experiment serves as not only a nitrogen source, but also a structure‐directing agent. The activation process was carried out under low (KOH/carbon=2), mild (KOH/carbon=4) and severe (KOH/carbon=6) activation conditions. The mild activated N‐doped carbon microflowers (A‐NCF‐4) have a hierarchically porous structure, high specific surface area (2309 m2 g?1), desirable micropore size below 1 nm, and importantly large micropore volume (0.95 cm3 g?1). The remarkably high CO2 adsorption capacities of 6.52 and 19.32 mmol g?1 were achieved with this sample at 0 °C (273 K) and two pressures, 1 bar and 20 bar, respectively. Furthermore, this sample also exhibits excellent stability during cyclic operations and good separation selectivity for CO2 over N2.  相似文献   

3.
Herein, four new cadmium metal–organic frameworks (Cd–MOFs), [Cd(bib)(bdc)] ( 1 ), [Cd(bbib)(bdc)(H2O)] ( 2 ), [Cd(bibp)(bdc)] ( 3 ), and [Cd2(bbibp)2(bdc)2(H2O)] ( 4 ), have been constructed from the reaction of Cd(NO3)2 ? 4 H2O with 1,4‐benzenedicarboxylate (H2bdc) and structure‐related bis(imidazole) ligands (1,4‐bis(imidazol‐1‐yl)benzene (bib), 1,4‐bis(benzoimidazol‐1‐yl)benzene (bbib), 4,4′‐bis(imidazol‐1‐yl)biphenyl (bibp), and 4,4′‐bis(benzoimidazol‐1‐yl)biphenyl (bbibp)) under solvothermal conditions. Cd–MOF 1 shows a 2D (4,4) lattice with parallel interpenetration, whereas 2 displays an interesting 3D interpenetrating dia network, 3 exhibits an unusual 3D interpenetrating dmp network, and 4 presents a 3D self‐catenated pillar‐layered framework with a Schäfli symbol of [43 ? 63]2 ? [46 ? 616 ? 86]. The structural diversity indicates that the backbone of the bis(imidazole) ligand (including the terminal group and spacer) plays a crucial role in the assembly of mixed‐ligand frameworks. By using the pore‐forming effect of cadmium vapor, for the first time we have utilized these Cd–MOFs as precursors to further prepare porous carbon materials (PCs) in a calcination–thermolysis procedure. These PCs show different porous features that correspond to the topological structures of Cd–MOFs. Significantly, it was found that the specific surface area and capacitance of PCs are tuned by the Cd/C ratio of the MOF. Furthermore, the as‐synthesized PCs were processed with KOH to obtain activated porous carbon materials (APCs) with higher specific surface area and porosity, which greatly promoted the energy‐storage capacity. After full characterization, we found that APC‐bib displays the largest specific surface area (1290 m2 g?1) and total pore volume (1.37 cm3 g?1) of this series of carbon materials. Consequently, APC‐bib demonstrates the highest specific capacitance of 164 F g?1 at a current density of 0.5 A g?1, and also excellent retention of capacitance (≈89.4 % after 5000 cycles at 1 A g?1). Therefore, APC‐bib has great potential as the electrode material in a supercapacitor.  相似文献   

4.
An innovative technique to obtain high‐surface‐area mesostructured carbon (2545 m2 g?1) with significant microporosity uses Teflon as the silica template removal agent. This method not only shortens synthesis time by combining silica removal and carbonization in a single step, but also assists in ultrafast removal of the template (in 10 min) with complete elimination of toxic HF usage. The obtained carbon material (JNC‐1) displays excellent CO2 capture ability (ca. 26.2 wt % at 0 °C under 0.88 bar CO2 pressure), which is twice that of CMK‐3 obtained by the HF etching method (13.0 wt %). JNC‐1 demonstrated higher H2 adsorption capacity (2.8 wt %) compared to CMK‐3 (1.2 wt %) at ?196 °C under 1.0 bar H2 pressure. The bimodal pore architecture of JNC‐1 led to superior supercapacitor performance, with a specific capacitance of 292 F g?1 and 182 F g?1 at a drain rate of 1 A g?1 and 50 A g?1, respectively, in 1 m H2SO4 compared to CMK‐3 and activated carbon.  相似文献   

5.
Carbon‐based supercapacitors are a kind of supercapacitors with very promising applications because of their low cost, good stability and adjustable properties. Simple and rapid syntheses of carbon materials with a high surface area and narrow pore size distribution are of great significance to practical applications of carbon‐based supercapacitors. Here we report a new strategy to synthesize sub‐nanometer porous carbon films (Snp‐CF) via a condensation reaction under mild conditions. Carbon films exhibit a narrow pore size distribution (6.6 Å) and high surface area (508 m2 g?1) after annealing at 700 °C. Snp‐CF‐700 displays a good specific capacity and excellent cycle performance (130 F g?1 after 5000 cycles, 118 % of initial 110 F g?1).  相似文献   

6.
Using the facile method of solvent evaporation, the leonardite fulvic acids (LFA)-based porous carbon microbeads (PCM) have been successfully prepared at ambient pressure, followed by carbonization and KOH activation (a low mass ratio alkali/LFA = 1.5) in an inert atmosphere. The effects of KOH treatment on pore structures and the formation mechanism of the PCM were discussed. The results showed that the sample exhibited remarkable improvement in textural properties. The activated carbon microbeads had high surface area (2269 m2 g?1), large pore volume (1.97 cm3 g?1), and displayed excellent capacitive performances, compared with carbon powder. The porous carbon material electrodes with the “porous core structure” behaved superiorly at a specific capacitance of 320 F g?1 at a current density of 0.05 A g?1 in 6 M KOH electrolyte, which could still remain 193 F g?1 when the current density increased to 100 A g?1. Remarkably, in the 1 M TEABF4/PC electrolyte, the PCM samples could reach 156 F g?1 at 0.05 A g?1, possess an outstanding energy density of 39.50 Wh kg?1, and maintain at 22.05 Wh kg?1 even when the power density rose up to 5880 W kg?1. The balance of structural characteristic and high performance makes the porous carbon microbeads a competitive and promising supercapacitor electrode material.  相似文献   

7.
CO2 capture and conversion are still a favorable way to reduce CO2 in the atmosphere. Herein, we have developed an environmentally friendly, low energy consumption porous activated carbon from vitamin B9 carbonaceous material for CO2 capture and conversion materials. It is demonstrated that the KOH/vitamin B9 carbonaceous material impregnation ratio of 2 is the optimum condition for obtaining porous activated carbons with high specific surface area of 1903 m2g-1, micropore surface area of 710 m2g-1, total pore volume of 1.05 cm3g-1 and micropore volume of 0.38 cm3g-1. Among all the porous activated carbons prepared, the porous activated carbon synthesized with the KOH/vitamin B9 carbonaceous material impregnation ratio of 2 registers the most excellent CO2 capture for 5.41 mmolg?1 at 0 °C/1 bar and 3.66 mmolg?1 at 25 °C/1 bar. They can also effectively catalyze the cycloaddition of CO2 and epoxides under mild conditions (1 bar, 100 °C and 8 h) with a yield of 89–94%. The synthesized porous carbon materials from vitamin B9 is a promising candidate material for CO2 capture and fixation.  相似文献   

8.
Herein, mesoporous sodium vanadium phosphate nanoparticles with highly sp2‐coordinated carbon coatings (meso‐Na3V2(PO4)3/C) were successfully synthesized as efficient cathode material for rechargeable sodium‐ion batteries by using ascorbic acid as both the reductant and carbon source, followed by calcination at 750 °C in an argon atmosphere. Their crystalline structure, morphology, surface area, chemical composition, carbon nature and amount were systematically explored. Following electrochemical measurements, the resultant meso‐Na3V2(PO4)3/C not only delivered good reversible capacity (98 mAh g?1 at 0.1 A g?1) and superior rate capability (63 mAh g?1 at 1 A g?1) but also exhibited comparable cycling performance (capacity retention: ≈74 % at 450 cycles at 0.4 A g?1). Moreover, the symmetrical sodium‐ion full cell with excellent reversibility and cycling stability was also achieved (capacity retention: 92.2 % at 0.1 A g?1 with 99.5 % coulombic efficiency after 100 cycles). These attributes are ascribed to the distinctive mesostructure for facile sodium‐ion insertion/extraction and their continuous sp2‐coordinated carbon coatings, which facilitate electronic conduction.  相似文献   

9.
Nitrogen-containing carbon aerogel was prepared from resorcinol–melamine–formaldehyde (R–M–F) polymer gel precursor. The polymer gel was supercritically dried with CO2, and the carbonization of the resulting polymer aerogel under nitrogen atmosphere at 900 °C yielded the carbon aerogel. The polymer and carbon aerogels were characterized with TG/DTA–MS, low-temperature nitrogen adsorption/desorption (??196 °C), FTIR, Raman, powder XRD and SEM–EDX techniques. The thermal decomposition of the polymer aerogel had two major steps. The first step was at 150 °C, where the unreacted monomers and the residual solvent were released, and the second one at 300 °C, where the species belonging to the polymer network decomposition could be detected. The pyrolytic conversion of the polymer aerogel was successful, as 0.89 at.% nitrogen was retained in the carbon matrix. The nitrogen-doped carbon aerogel was amorphous and possessed a hierarchical porous structure. It had a significant specific surface area (890 m2 g?1) and pore volume (4.7 cm3 g?1). TG/DTA–MS measurement revealed that during storage in ambient conditions surface functional groups formed, which were released upon annealing.  相似文献   

10.
For the first time, hierarchically porous carbon materials with a sandwich‐like structure are synthesized through a facile and efficient tri‐template approach. The hierarchically porous microstructures consist of abundant macropores and numerous micropores embedded into the crosslinked mesoporous walls. As a result, the obtained carbon material with a unique sandwich‐like structure has a relatively high specific surface (1235 m2 g?1), large pore volume (1.30 cm3 g?1), and appropriate pore size distribution. These merits lead to a comparably high specific capacitance of 274.8 F g?1 at 0.2 A g?1 and satisfying rate performance (87.7 % retention from 1 to 20 A g?1). More importantly, the symmetric supercapacitor with two identical as‐prepared carbon samples shows a superior energy density of 18.47 Wh kg?1 at a power density of 179.9 W kg?1. The asymmetric supercapacitor based on as‐obtained carbon sample and its composite with manganese dioxide (MnO2) can reach up to an energy density of 25.93 Wh kg?1 at a power density of 199.9 W kg?1. Therefore, these unique carbon material open a promising prospect for future development and utilization in the field of energy storage.  相似文献   

11.
Hierarchically porous carbon materials with high surface areas are promising candidates for energy storage and conversion. Herein, the facile synthesis of hierarchically porous carbons through the calcination of metal–organic framework (MOF)/chitosan composites is reported. The effects of the chitosan (CS) additive on the pore structure of the resultant carbons are discussed. The corresponding MOF/chitosan precursors could be readily converted into hierarchically porous carbons (NPC‐V, V=1, 2, 4, and 6) with much higher ratios of meso‐/macropore volume to micropore volume (Vmeso‐macro/Vmicro). The derived carbon NPC‐2 with the high ratio of Vmeso‐macro/Vmicro=1.47 demonstrates a high specific surface area of 2375 m2 g?1, and a high pore volume of 2.49 cm3 g?1, as well as a high graphitization degree, in comparison to its counterpart (NPC) without chitosan addition. These excellent features are favorable for rapid ion diffusion/transport, endowing NPC‐2 with enhanced electrochemical behavior as supercapacitor electrodes in a symmetric electrode system, corresponding to a high specific capacitance of 199.9 F g?1 in the aqueous electrolyte and good rate capability. Good cycling stability is also observed after 10 000 cycles.  相似文献   

12.
Porous carbons have been synthesized by a direct carbonization of potassium biphthalate without an activation process. The experimental results demonstrate that the carbonization temperature plays a crucial role in determining the surface area and pore structure as well as the correlative capacitive performance. The carbon-700/800/900 samples display surface areas of 672, 1,023, and 1,380 m2 g?1 and total pore volumes of 0.38, 0.56, and 0.78 cm3 g?1, respectively. The specific capacitances of the carbon-700/800/900 samples are 300.4, 272.3, and 243.4 F g?1, respectively, at a current density of 0.5 A g?1. More importantly, the carbon-900 sample possesses the highest capacitance retention (~98.4 %) even undergoing charge–discharge 10,000 times. The potassium biphthalate used as a carbon source is inexpensive and commercially available, making it promising for the large-scale production of porous carbons as an excellent electrode material for supercapacitors.  相似文献   

13.
Kombucha, a renewable biomass, has been successfully utilized as an accessible carbon source to fabricate kombucha-derived hierarchical porous carbon (KHPC) by KOH direct treatment and in situ activation. The prepared KHPC shows an interconnected hierarchical porous structure, a pore volume of 0.41 cm3 g?1, and a specific surface area of 917 m2 g?1. Due to the multiple synergistic effects of these advantages, the KHPC-3 exhibits a high specific capacitance of 326 F g?1 at a current density of 1 A g?1 in 6 M KOH, good rate capability of 82% retention from 1 to 20 A g?1, and cycling performance with 91.3% retention over 5000 cycles. Moreover, the KHPC-3 symmetric supercapacitor reveals a good energy density of 20.97 Wh kg?1 at a power density of 871.2 W kg?1 and retains 8.08 Wh kg?1 at 6330 W kg?1 in 1 M Na2SO4 electrolyte. Therefore, the KHPC obtained via the simple synthesis process shows great promise as an electrode material in energy storage devices.  相似文献   

14.
High-performance activated carbon for electrochemical double-layer capacitors (EDLC) has been prepared from cation exchange resin by carbonization and subsequent activation with KOH. The activation temperature has a key role in the determination of porous carbon possessing high surface areas, and large pore structures. The porous carbon activated at 700 °C (carbon-700-1:4) has high surface area (2236 m2?g?1) and large total pore volume (1.15 cm3?g?1), which also displays best capacitive performances due to its well-balanced micro- or mesoporosity distribution. In details, specific capacitances of the carbon-700-1:4 sample are 336.5 F?g?1 at a current density of 1 A?g?1 and 331.8 F?g?1 at 2 A?g?1. At high current density as 20 A?g?1, the retention of its specific capacitance is 68.4 %. The carbon-700-1:4 sample also exhibits high performance of energy density (46.7 Wh?kg?1) and long cycle stability (~8.9 % loss after 3,000 cycles). More importantly, due to the amount of waste ion-exchange resins increasing all over the world, the present synthetic method might be adopted to dispose them, producing high-performance porous carbons for EDLC electrode materials.  相似文献   

15.
The cost-effective activated carbons derived from waste Camellia oleifera shell (COS) by ZnCl2 activation method are investigated as the active electrode material in electric double-layer capacitors (EDLCs) for the first time. The activation temperature and ZnCl2/COS impregnation ratio are two key factors affecting the surface area and pore structure of the prepared activated carbons, which accordingly affect their capacitive performances. Electrochemical investigations indicate that the activated carbon (AC-3-600) obtained at the activation temperature of 600 °C and impregnation ratio of 3 shows the maximum specific capacitance of 374 and 266 F?g?1 in 1 mol L?1 H2SO4 and 6 mol L?1 KOH electrolytes at 0.2 A g?1, respectively. The high capacitance of the AC-3-600 is attributed to its high surface area (1,935 m2 g?1), high total pore volume (1.02 cm3 g?1), and especially the large percentage of micropores (735 m2 g?1). Meanwhile, the activated carbon presents good cycle stability in both acid and alkaline electrolytes during 5,000 cycles at a fair current density of 4 A g?1. So, we had reasons to believe that the activated carbons from waste COS by ZnCl2 activation might be one of the innovative carbon electrode materials for EDLCs application.  相似文献   

16.
In this work, the micromolecule l-glutamic acid (Glu) is employed as nitrogen-rich precursor to prepare a novel porous carbon, and ZnCl2 is used as activating agent to improve the surface area and electrochemical performance of the carbon. The nitrogen content of the carbon (Glu-2.5) prepared by Glu and ZnCl2 with a mass ratio of 1:2.5 retains as high as 7.1 % at an activation temperature of 700 °C. The surface area and pore volume of Glu-2.5 are 1007.4 m2 g?1 and 0.57 cm3 g?1, respectively. Glu-2.5 exhibits a high specific capacitance of 330.6 F g?1 in 2 M KOH electrolyte at the current density of 1 A g?1and good cycling stability (89 % retention of capacitance after 5000 charge/discharge cycles). More importantly, the assembled symmetric supercapacitor using Glu-2.5 as electrodes reveals a high energy density (16.7 Wh kg?1) under the power density of 404.7 W kg?1. Owing to its inherent advantages, Glu-2.5 could be a promising and scalable alternative applied to energy storage/conversion.  相似文献   

17.
Two‐dimensional hexagonal boron carbon nitride (BCN) nanosheets (NSs) were synthesized by new approach in which a mixture of glucose and an adduct of boric acid (H3BO3) and urea (NH2CONH2) is heated at 900 °C. The method is green, scalable and gives a high yield of BCN NSs with average size of about 1 μm and thickness of about 13 nm. Structural characterization of the as‐synthesized material was carried out by several techniques, and its energy‐storage properties were evaluated electrochemically. The material showed excellent capacitive behaviour with a specific capacitance as high as 244 F g?1 at a current density of 1 A g?1. The material retains up to 96 % of its initial capacity after 3000 cycles at a current density of 5 A g?1.  相似文献   

18.
Hierarchical porous carbon nanofibers serving as electrode materials are prepared through carbonization and hydrofluoric acid treatment of polyacrylonitrile-based electrospinning involving dual templates. The hierarchical porous structures are synergistically tailored by varying template contents in the spinning solution. The carbon nanofibers prepared from the electrospinning of polyacrylonitrile containing 15/15 wt.% polymethylmethacrylate/tetraethyl orthosilicate exhibit the largest specific surface area (699 m2 g?1) and microporous volume (0.196 cm3 g?1). In 6 M KOH electrolyte, a symmetrical supercapacitor equipped with the hierarchical porous carbon nanofibers demonstrates its high-end specific capacitance of 170 F g?1, superior rate capability, and high-power density output up to 14.7 kW kg?1. Cycling evolution indicates capacitance fading is only 5.8 % of initial capacitance at a current density of 1 A g?1 even after 8,000 cycles. The excellent electrochemical performances of the carbon nanofiber are mainly ascribed to the optimized pore size distributions of both micropores and mesopores and the unique hierarchical pore structures possessed by abundant micropores.  相似文献   

19.
Continuous metal–organic framework‐type Co3(HCOO)6 intergrown films with a one‐dimensional zigzag channel system and pore aperture of 5.5 Å are prepared by secondary growth on preseeded macroporous glass‐frit disks and silicon wafers. The adsorption behavior of CO2 or CH4 single gases on the Co3(HCOO)6 membrane is investigated by in situ IR spectroscopy. It is shown that the isosteric heats of adsorption for CO2 (17.7 kJ mol?1) and CH4 (14.4 kJ mol?1) do not vary with increasing amount of adsorbed gases. The higher value of isosteric heat for CO2 is an indication of the stronger interaction between the CO2 and the Co3(HCOO)6 membrane. The Co3(HCOO)6 membrane is studied by binary gas permeation of CO2 and CH4 at different temperatures (0, 25, and 60 °C). The membrane has CO2/CH4 selectivity with a separation factor higher than 10, which is due to the unique structure and molecular sieving effect. Upon increasing the temperature from 0 to 60 °C, the preferred permeance of CO2 over CH4 is increased from 1.70×10?6 to 2.09×10?6 mol m?2 s?1 Pa?1, while the separation factor for CO2/CH4 shows a corresponding decrease from 15.95 to 10.37. The effective pore size of the Co3(HCOO)6 material combined with the pore shape do not allow the two molecules to pass simultaneously, and once the CO2 molecules are diffused in the micropores, the CH4 is blocked. The supported Co3(HCOO)6 membrane retains high mechanical stability after a number of thermal cycles.  相似文献   

20.
Porous carbon materials with high surface area and different pore structure have been successfully prepared by phenolic resin combined with polyvinyl alcohol (PVA) and KOH as activation agents. The surface morphology, structure, and specific surface area of the carbon materials were studied by scanning electron microscopy, X-ray diffraction, and nitrogen sorption measurement, respectively. Furthermore, the effects of specific surface area, pore structure, and electrolyte on electrochemical properties were investigated by galvanostatic charge–discharge measurement. The results show that KOH–PVA-activated carbon materials display specific capacitance as high as 218 F?g?1 in 30 wt.% KOH aqueous electrolyte, 147 F?g?1 in 1 M LiPF6/(ethylene carbonate (EC) + dimethyl carbonate) (1:1?v/v), and 115 F?g?1 in 1 M Et3MeNBF4/propylene carbonate organic electrolyte, respectively. In addition, the carbon materials demonstrate long-term cycle stability, especially the AK3P-0.30 in aqueous electrolyte and the AK2P-0.30 with excellent rate capability in organic electrolyte. These reveal that the existence of a micro-mesoporous structure of activated carbon is beneficial to store energy in an aqueous supercapacitor and broad pore size distribution of activated carbon is favorable to energy storage in an organic supercapacitor. The carbon materials with pore size distribution in different ranges improve the electrochemical performance of supercapacitor in different electrolytes. A new pore-expand agent (PVA combining with KOH) was used to obtain porous carbons with enhanced properties for supercapacitor.  相似文献   

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