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1.
A novel pyridine-containing metal-organic framework (MOF, [Zn(bpdc)DMA]·DMF, bpdc = 2,2′-bipyridine-5,5′-dicarboxylate) was directly carbonized at different temperature to produce nitrogen-doped porous carbons (NPCs). The as-prepared porous carbons, NPC800 (obtained at 800 °C) and NPC1000 (obtained at 1000 °C), were characterized by scanning electron microscopy, X-ray powder diffraction, N2 sorption isotherms, and X-ray photoelectron spectroscopy (XPS). The results from elemental analysis and XPS confirmed that the pyridine groups in MOF served as nitrogen sources to produce NPCs, and NPC800 possessed the higher nitrogen content than NPC1000. N2 sorption data demonstrated that NPC800 exhibited the larger specific surface area and pore volume than NPC1000. The capacitive properties of NPC800 and NPC1000 were investigated in KOH aqueous electrolyte by cyclic voltammetry and galvanostatic charge–discharge curves. NPC800 showed the higher specific capacitance (226.6 F g?1 at 1 A g?1) than NPC1000 and retained 178.0 F g?1 even at a high current density up to 10 A g?1. It was found that the donation of N species to capacitance was more than the role of porosity in view of their synergetic effect.  相似文献   

2.
Microporous amorphous hydrophobic silica materials with well‐defined pores were synthesized by replication of the metal–organic framework (MOF) [Cu3(1,3,5‐benzenetricarboxylate)2] (HKUST‐1). The silica replicas were obtained by using tetramethoxysilane or tetraethoxysilane as silica precursors and have a micro–meso binary pore system. The BET surface area, the micropore volume, and the mesopore volume of the silica replica, obtained by means of hydrothermal treatment at 423 K with tetraethoxysilane, are 620 m2g?1, 0.18 mL g?1, and 0.55 mL g?1, respectively. Interestingly, the silica has micropores with a pore size of 0.55 nm that corresponds to the pore‐wall thickness of the template MOF. The silica replica is hydrophobic, as confirmed by adsorption analyses, although the replica has a certain amount of silanol groups. This hydrophobicity is due to the unique condensation environment of the silica precursors in the template MOF.  相似文献   

3.
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   

4.
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   

5.
A porous carbon designated as MOF‐5‐C was prepared by directly carbonizing a metal–organic framework (MOF‐5). The morphology and microstructure of MOF‐5‐C were characterized by scanning electron microscopy, N2 adsorption, and powder X‐ray diffraction. The MOF‐5‐C retained the original porous structures of MOF‐5, and showed a high Brunauer–Emmett–Teller surface area (1808 m2 g?1) and large pore volume (3.05 cm3 g?1). To evaluate its adsorption performance, the MOF‐5‐C was used as an adsorbent for the solid‐phase extraction of four phthalate esters from bottled water, peach juice, and soft drink samples followed by high‐performance liquid chromatographic analysis. Several parameters that could affect the extraction efficiencies were investigated. Under the optimum conditions, a good linearity was achieved in the concentration range of 0.1–50.0 ng mL?1 for bottled water sample and 0.2–50.0 ng mL?1 for peach juice and soft drink samples. The limits of detection of the method (S/N = 3) were 0.02 ng mL?1 for bottled water sample, and 0.04–0.05 ng mL?1 for peach juice and soft drink samples. The results indicated that the MOF‐5‐C exhibited an excellent adsorption capability for trace levels of phthalate esters, and it could be a promising adsorbent for the preconcentration of other organic compounds.  相似文献   

6.
Porous carbon anodes with a controllable Vmes/Vmic ratio were synthesized through the self‐assembly of poly(benzoxazine‐co‐resol) and the simultaneous hydrolysis of tetraethyl orthosilicate (TEOS) followed by carbonization and removal of silica. The Vmes/Vmic ratio of the carbon can be controlled in the range of approximately 1.3–32.6 through tuning the amount of TEOS. For lithium‐ion battery anodes, a correlation between the electrochemical performance and Vmes/Vmic ratio has been established. A high Vmes/Vmic ratio in porous carbons is favorable for enhancing the accessibility of Li ions to active sites provided by the micropores and for achieving good lithium storage performance. The obtained porous carbon exhibits a high reversible capacity of 660 mAh g?1 after 70 cycles at a current density of 100 mA g?1. Moreover, at a high current density of 3000 mA g?1, the capacity still remains at 215 mAh g?1, showing a fast charge‐discharge potential. This synthesis method relying on modified benzoxazine chemistry with the hydrolysis of TEOS may provide a new route for the development of mesoporous carbon‐based electrode materials.  相似文献   

7.
A three‐dimensional (3D) hierarchical MOF‐on‐reduced graphene oxide (MOF‐on‐rGO) compartment was successfully synthesized through an in situ reduced and combined process. The unique properties of the MOF‐on‐rGO compartment combining the polarity and porous features of MOFs with the high conductivity of rGO make it an ideal candidate as a sulfur host in lithium–sulfur (Li‐S) batteries. A high initial discharge capacity of 1250 mAh g?1 at a current density of 0.1 C (1.0 C=1675 mAh g?1) was reached using the MOF‐on‐rGO based electrode. At the rate of 1.0 C, a high specific capacity of 601 mAh g?1 was still maintained after 400 discharge–charge cycles, which could be ascribed to the synergistic effect between MOFs and rGO. Both the hierarchical structures of rGO and the polar pore environment of MOF retard the diffusion and migration of soluble polysulfide, contributing to a stable cycling performance. Moreover, the spongy‐layered rGO can buffer the volume expansion and contraction changes, thus supplying stable structures for Li‐S batteries.  相似文献   

8.
Nanoporous carbons (NPCs) have large specific surface areas, good electrical and thermal conductivity, and both chemical and mechanical stability, which facilitate their use in energy storage device applications. In the present study, highly graphitized NPCs are synthesized by one‐step direct carbonization of cobalt‐containing zeolitic imidazolate framework‐67 (ZIF‐67). After chemical etching, the deposited Co content can be completely removed to prepare pure NPCs with high specific surface area, large pore volume, and intrinsic electrical conductivity (high content of sp2‐bonded carbons). A detailed electrochemical study is performed using cyclic voltammetry and galvanostatic charge–discharge measurements. Our NPC is very promising for efficient electrodes for high‐performance supercapacitor applications. A maximum specific capacitance of 238 F g?1 is observed at a scan rate of 20 mV s?1. This value is very high compared to previous works on carbon‐based electric double layer capacitors.  相似文献   

9.
A facile and sustainable procedure for the synthesis of nitrogen‐doped hierarchical porous carbons with a three‐dimensional interconnected framework (NHPC‐3D) was developed. The strategy, based on a colloidal crystal‐templating method, utilizes nitrogenous dopamine as the precursor due to its unique properties, including self‐polymerization under mild alkaline conditions, coating onto various surfaces, a high carbonization yield, and well‐preserved nitrogen doping after heat treatment. The obtained NHPC‐3D possesses a high surface area of 1056 m2 g?1, a large pore volume of 2.56 cm3 g?1, and a high nitrogen content of 8.2 wt %. The NHPC‐3D is implemented as the electrode material of a supercapacitor and exhibits a specific capacitance as high as 252 F g?1 at a current density of 2 A g?1. The device also shows a high capacitance retention of 75.7 % at a higher current density of 20 A g?1 in aqueous electrolyte due to a sufficient surface area for charge accommodation, reversible pseudocapacitance, and minimized ion‐transport resistance, as a result of the advantageous interconnected hierarchical porous texture. These results showcase NHPC‐3D as a promising candidate for electrode materials in supercapacitors.  相似文献   

10.
Nitrogen‐doped species (NDs) are theoretically accepted as a determinant of the catalytic activity of metal‐free N‐doped carbon (NC) catalysts for oxygen reduction reaction (ORR). However, direct relationships between ND type and ORR activity have been difficult to extract because the complexity of carbon matrix impairs efforts to expose specific NDs. Herein, we demonstrate the fabrication of a 3D hierarchically porous NC catalyst with micro‐, meso‐, and macroporosity in one structure, in which sufficient exposure and availability of inner‐pore catalytic sites can be achieved due to its super‐high surface area (2191 cm2 g?1) and interconnected pore system. More importantly, in‐situ formation of graphitic‐N species (GNs) on the surface of NC stimulated by KOH activation enables us to experimentally reveal the catalytic nature of GNs for ORR, which is of great significance for the design and development of advanced metal‐free NC electrocatalysts.  相似文献   

11.
Designing and preparing porous materials without using any templates is a challenge. Herein, single‐nozzle electrospinning technology coupled with post pyrolysis is applied to prepare cobalt nanoparticles embedded in N‐doped carbon nanofibers with a hierarchical pore structure (HP‐Co‐NCNFs). The resultant HP‐Co‐NCNFs have lengths up to several millimeters with an average diameter of 200 nm and possess abundant micro/meso/macropores on both the surface and within the fibers. Such a microstructure endows the surface area as high as 115 m2 g?1. When used as an electrocatalyst for the oxygen reduction reaction (ORR), the HP‐Co‐NCNFs exhibit outstanding electrochemical performance in terms of activity, methanol tolerance, and durability. The hierarchically porous structure and high surface area can effectively decrease the mass transport resistance and increase the exposed ORR active sites. The sufficient amount of exposed ORR active sites along with accessible transport channel and enhanced electrical conductivity may be responsible for the good electrocatalytic performance.  相似文献   

12.
A strategy called ultramicroporous building unit (UBU) is introduced. It allows the creation of hierarchical bi‐porous features that work in tandem to enhance gas uptake capacity and separation. Smaller pores from UBUs promote selectivity, while larger inter‐UBU packing pores increase uptake capacity. The effectiveness of this UBU strategy is shown with a cobalt MOF (denoted SNNU‐45) in which octahedral cages with 4.5 Å pore size serve as UBUs. The C2H2 uptake capacity at 1 atm reaches 193.0 cm3 g?1 (8.6 mmol g?1) at 273 K and 134.0 cm3 g?1 (6.0 mmol g?1) at 298 K. Such high uptake capacity is accompanied by a high C2H2/CO2 selectivity of up to 8.5 at 298 K. Dynamic breakthrough studies at room temperature and 1 atm show a C2H2/CO2 breakthrough time up to 79 min g?1, among top‐performing MOFs. Grand canonical Monte Carlo simulations agree that ultrahigh C2H2/CO2 selectivity is mainly from UBU ultramicropores, while packing pores promote C2H2 uptake capacity.  相似文献   

13.
Porous forms of pectin, a major industrial waste biomass polysaccharide, have been prepared by aqueous phase expansion routes (SBET>200 m2 g?1; Vpore>0.80 cm3 g?1). It was demonstrated that the aqueous phase acidity crucially influenced the properties of the porous pectin form. Preparation route selection allows direction of material textural and morphological properties, thought to be the result of polysaccharide configuration, and methyl ester group hydrolysis, believed to alter the lowest energy accessible metastable polysaccharide state during gel recrystallisation. The resulting low density amorphous powders or mouldable monoliths (ρpowder ~0.20 g cm?3/ρmonolith ~0.07 g cm?3) can be directly transformed by thermal carbonisation into low density mesoporous carbonaceous materials (e.g. ρ ~0.27 g cm?3 (Tp=550 °C)), which possess textural and nanoscale material morphology reflective of the porous pectin precursor employed. Acidic gelation promotes methyl ester groups hydrolysis of the polysaccharide structure, generating carbons with unusual interdigitated rod‐like nanoscale morphology. Importantly, the materials presented herein are produced directly from the parent porous pectin material, without the need for additive catalyst (or template) to yield highly mesoporous products (e.g. Vmeso≥0.45 cm3 g?1; polydispersity (PD)>10 nm), with accessible tuneable functionally rich surfaces. Due to the high mesoporosity (>85 %), materials have potential application in chromatography, heterogeneous catalysis and large molecule adsorption strategies.  相似文献   

14.
Highly ordered mesoporous three‐dimensional Ia3d silica (KIT‐6) with different pore diameters has been synthesized by using pluronic P123 as surfactant template and n‐butanol as cosolvent at different synthesis temperatures in a highly acidic medium. The materials were characterized by XRD and N2 adsorption. The synthesis temperature plays a significant role in controlling the pore diameter, surface area, and pore volume of the materials. The material prepared at 150 °C, KIT‐6‐150, has a large pore diameter (11.3 nm) and a high specific pore volume (1.53 cm3 g?1). We also demonstrate immobilization of lysozyme, which is a stable and hard protein, on KIT‐6 materials with different pore diameters. The amount of lysozyme adsorbed on large‐pore KIT‐6 is extremely large (57.2 μmol g?1) and is much higher than that observed for mesoporous silicas MCM‐41, SBA‐15, and KIT‐5, mesoporous carbons, and carbon nanocages. The effect of various parameters such as buffer concentration, adsorption temperature, concentration of the lysozyme, and the textural parameter of the adsorbent on the lysozyme adsorption capacity of KIT‐6 was studied. The amount adsorbed mainly depends on solution pH, ionic strength, adsorption temperature, and pore volume and pore diameter of the adsorbent. The mechanism of adsorption on KIT‐6 under different adsorption conditions is discussed. In addition, the structural stability of lysozyme molecules and the KIT‐6 adsorbent before and after adsorption were investigated by XRD, nitrogen adsorption, and FTIR spectroscopy.  相似文献   

15.
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   

16.
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   

17.
Porous carbons (PC) were prepared from a waste biomass named chestnut shell via a two‐step method involving carbonization and KOH activation. The morphology, pore structure and surface chemical properties were investigated by scanning electron microscopy (SEM), N2 sorption, Raman spectroscopy, X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The carbons have been evaluated as the electrode materials for supercapacitors by a two‐electrode system in 6 mol/L KOH electrolyte. Benefiting from the porous texture, high surface area and high oxygen content, the PCs derived from chestnut shell have exhibited high specific capacitance of 198.2 (PC‐1), 217.2 (PC‐2) and 238.2 F·g?1 (PC‐3) at a current density of 0.1 A·g?1, good rate capability of 55.7%, 56.6% and 54.9% in a range of 0.1–20 A·g?1 and high energy density of 5.6, 6.1 and 6.7 Wh·kg?1, respectively. This is believed to be due to electric double layer capacitance induced by the abundant micropores and extra pseudo‐capacitance generated by oxygen‐containing groups. At a power density of 9000 Wh·kg?1, the energy density is 3.1, 3.5 and 3.7 Wh·kg?1 for PC‐1, PC‐2 and PC‐3, respectively, demonstrating the potential of the carbons derived from chestnut shells in energy storage devices.  相似文献   

18.
A unique hybrid, TiO2–B nanosheets/anatase nanocrystals co‐anchored on nanoporous graphene sheets, can be synthesized by a facile microwave‐induced in situ reduction–hydrolysis route. The as‐formed nanohybrid has a hierarchically porous structure, involving both mesopores of approximately 4 nm and meso‐/macropores of 30–60 nm in the graphene sheets, and a large surface area. Importantly, electrodes composed of the nanohybrid exhibit superior rate capability (160 mA h g?1 at ca. 36 C; 154 mA h g?1 at ca. 72 C) and excellent cyclability. The synergistic effects of conductive graphene with numerous nanopores and the pseudocapacitive effect of ultrafine TiO2–B nanosheets and anatase nanocrystals endow the hybrid a superior rate capability.  相似文献   

19.
A microporous La–metal‐organic framework (MOF) has been synthesized by the reaction of La(NO3)3 ? 6 H2O with a ligand 4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐p‐aminobenzoate (TATAB) featuring three carboxylate groups. Crystal structure analysis confirms the formation of 3D MOF with hexagonal micropores, a Brunauer–Emmett—Teller (BET) surface area of 1074 m2 g?1 and high thermal and chemical stability. The CO2 adsorption capacities are 76.8 cm3 g?1 at 273 K and 34.6 cm3 g?1 at 293 K, a highest measured CO2 uptake for a Ln–MOFs.  相似文献   

20.
A metal–organic framework (NPC‐6) with an NbO topology based on a piperazine ring‐bridged diisophthalate ligand was synthesized and characterized. The incorporated piperazine group leads to an enhanced adsorption affinity for CO2 in NPC‐6, in which the CO2 uptake is 4.83 mmol g?1 at 293 K and 1 bar, ranking among the top values of CO2 uptake on MOF materials. At 0.15 bar and 293 K, the NPC‐6 adsorbs 1.07 mmol g?1 of CO2, which is about 55.1 % higher than that of the analogue MOF NOTT‐101 under the same conditions. The enhanced CO2 uptake combined with comparable uptakes for CH4 and N2 leads to much higher selectivities for CO2/CH4 and CO2/N2 gas mixtures on NPC‐6 than on NOTT‐101. Furthermore, an N‐alkylation is used in the synthesis of the PDIA ligand, leading to a much lower cost compared with that in the synthesis of ligands in the NOTT series, as the former does not require a palladium‐based catalyst and borate esters. Thus, we conclude that NPC‐6 is a promising candidate for CO2 capture applications.  相似文献   

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