Metal-organic framework as a template for porous carbon synthesis

Porous carbon was synthesized by heating the precursor FA within the pores of MOF-5. The resultant carbon displayed a high specific surface area (BET, 2872 m2.g-1) and important hydrogen uptake (2.6 wt % at 760 Torr, -196 degrees C) as well as excellent electrochemical properties as an electrode material for electrochemical double-layered capacitor (EDLC).     

新型活性炭材料在双电层电容器中的应用研究

以椰壳为原料,利用特定的物理 化学方法在一定条件下制得双电层电容器活性炭电极材料.实验表明,该活性炭经压制成型后制作的双电层电容器,具有大的比电容,文中同时研究了酸处理、二次活化以及电极冷压成型方法对电极性能的影响.     

Enhanced hydrogen storage capacity of high surface area zeolite-like carbon materials

We report the synthesis of zeolite-like carbon materials that exhibit well-resolved powder XRD patterns and very high surface area. The zeolite-like carbons are prepared via chemical vapor deposition (CVD) at 800 or 850 degrees C using zeolite beta as solid template and acetonitrile as carbon precursor. The zeolite-like structural ordering of the carbon materials is indicated by powder XRD patterns with at least two well-resolved diffraction peaks and TEM images that reveal well-ordered micropore channels. The carbons possess surface area of up to 3200 m2/g and pore volume of up to 2.41 cm3/g. A significant proportion of the porosity in the carbons (up to 76% and 56% for surface area and pore volume, respectively) is from micropores. Both TEM and nitrogen sorption data indicate that porosity is dominated by pores of size 0.6-0.8 nm. The carbon materials exhibit enhanced (and reversible) hydrogen storage capacity, with measured uptake of up to 6.9 wt % and estimated maximum of 8.33 wt % at -196 degrees C and 20 bar. At 1 bar, hydrogen uptake capacity as high as 2.6 wt % is achieved. Isosteric heat of adsorption of 8.2 kJ/mol indicates a favorable interaction between hydrogen and the surface of the carbons. The hydrogen uptake capacity observed for the zeolite-like carbon materials is among the highest ever reported for carbon (activated carbon, mesoporous carbon, CNTs) or any other (MOFs, zeolites) porous material.     

Nitrogen‐Doped Porous Graphitic Carbon as an Excellent Electrode Material for Advanced Supercapacitors

An advanced supercapacitor material based on nitrogen‐doped porous graphitic carbon (NPGC) with high a surface area was synthesized by means of a simple coordination–pyrolysis combination process, in which tetraethyl orthosilicate (TEOS), nickel nitrate, and glucose were adopted as porogent, graphitic catalyst precursor, and carbon source, respectively. In addition, melamine was selected as a nitrogen source owing to its nitrogen‐enriched structure and the strong interaction between the amine groups and the glucose unit. A low‐temperature treatment resulted in the formation of a NPGC precursor by combination of the catalytic precursor, hydrolyzed TEOS, and the melamine–glucose unit. Following pyrolysis and removal of the catalyst and porogent, the NPGC material showed excellent electrical conductivity owing to its high crystallinity, a large Brunauer–Emmett–Teller surface area (S_BET=1027 m² g^?1), and a high nitrogen level (7.72 wt %). The unusual microstructure of NPGC materials could provide electrochemical energy storage. The NPGC material, without the need for any conductive additives, showed excellent capacitive behavior (293 F g^?1 at 1 A g^?1), long‐term cycling stability, and high coulombic efficiency (>99.9 % over 5000 cycles) in KOH when used as an electrode. Notably, in a two‐electrode symmetric supercapacitor, NPGC energy densities as high as 8.1 and 47.5 Wh kg^?1, at a high power density (10.5 kW kg^?1), were achieved in 6 M KOH and 1 M Et₄NBF₄‐PC electrolytes, respectively. Thus, the synthesized NPGC material could be a highly promising electrode material for advanced supercapacitors and other conversion devices.     

基于不同前驱体制备的硬碳负极材料的储锂性能

以聚丙烯腈、石油沥青和花生壳为前驱体,在1200℃下碳化制备三种不同的硬碳材料.通过扫描电子显微、X射线衍射、氮气吸附/脱附测试和拉曼光谱等方法探究不同前驱体所制备的硬碳材料的表面形貌和物相结构.通过恒流充放电测试考察了这三种硬碳负极材料的电化学性能.结果表明,花生壳基硬碳的初始放电比容量最高,但首圈库仑效率最低,石油...     

双峰孔分布薄壁中孔碳的便捷制备

以廉价的γ-氧化铝为模板制备薄壁中孔碳材料,且可在制备过程中方便地对碳材料的孔结构、微孔率等参数进行调控.以原位聚合的酚醛树脂为碳源取代蔗糖,简化了制备流程.制得的碳材料不仅可以较好地复制氧化铝模板的孔结构,且比表面积比以蔗糖为碳源的样品显著提高.在此基础上,选用模板堆积孔径与模板自身直径差异较大的长棒状氧化铝为模板,成功地以一种模板、经过一次聚合-碳化过程制备出了具有双峰孔分布(PSD)结构的薄壁碳材料,两个峰分别位于4 nm附近的较小中孔区和13 nm附近的较大中孔区.此外,所得碳材料的比表面积(>1800 m2·g-1)和孔容(>4.5 cm3·g-1)均很高,而微孔率却较低,具有优异的中孔特性.将所得碳材料用作电化学电容器的电极,电容可达200 F·g-1,且当电流密度从0.1 A·g-1升至1.0 A·g-1时,比电容仅衰减10%,表现出良好的电容性能.     

Carbon/λ-MnO2 composites for supercapacitor electrodes

In the present work a composite of carbon with λ-MnO₂ have been synthesized by a simple two-step route. In the first step, to obtain LiMn₂O₄/carbon material, mesoporous activated carbon was impregnated with the solution of precursor metal salts and heated subsequently. As-prepared materials were acid treated which resulted in the formation of λ-MnO₂/carbon. Physical properties, structure and specific surface area of electrode materials were studied by TEM, X-ray diffraction and nitrogen sorption measurements. Voltammetry cycling, galvanostatic charge/discharge and impedance spectroscopy measurements performed in two- and three-electrode cells have been applied in order to measure electrochemical parameters. TEM images confirmed well dispersed λ-MnO₂ particles on the surface of carbon material. The carbon in the composite plays an important role as the surface area enhancing component and a support of pseudocapacitive material. Furthermore, the through-connected porosity serves as a continuous pathway for electrolyte transport. A synergetic effect of the porous carbon framework and of the redox properties of the λ-MnO₂ is at the origin of improvement of specific capacitance values which has been observed for composites after delithiation.     

Synthesis and characterization of chiral benzylic ether-bridged periodic mesoporous organosilicas

The first synthesis of a chiral periodic mesoporous organosilica (PMO) carrying benzylic ether bridging groups is reported. By hydrolysis and condensation of the new designed chiral organosilica precursor 1,4-bis(triethoxysilyl)-2-(1-methoxyethyl)benzene (BTEMEB) in the presence of the non-ionic oligomeric surfactant Brij 76 as supramolecular structure-directing agent under acidic conditions, an ordered mesoporous chiral benzylic ether-bridged hybrid material with a high specific surface area was obtained. The chiral PMO precursor was synthesized in a four-step reaction from 1,4-dibromobenzene as the starting compound. The evidence for the presence of the chiral units in the organosilica precursor as well as inside the PMO material is provided by optical activity measurements.     

Morphology and electrochemical properties of a composite produced by a peroxide method on the basis of tin dioxide and carbon black

Using peroxostannate as a precursor, a composite material based on tin dioxide and carbon black was obtained, in which tin dioxide forms a coating on the surface of carbon black nanoparticles. The synthesized material was characterized by electron microscopy and X-ray powder diffraction analysis, and also the electrochemical characteristics of this material as an anode material for lithium-ion batteries were studied. The material demonstrates good stability and rate performance, which is indicative of the efficiency of the peroxide method for producing promising inexpensive anode materials based on tin dioxide and carbon black.     

Peony pollen derived nitrogen-doped activated carbon for supercapacitor application

Peony pollen is a cheap and readily available biomass material with a relatively high protein content.In this work,it was employed as an N-rich precursor to prepare the nitrogen-doped porous carbon for supercapacitor application.The porous carbon microspheres were prepared through a hydrothermal method and subsequent carbonization process.Notably,ammonium borofruoride and potassium hydroxide were employed respectively as an etchant and an activator to modify the porosity of the materials.The as prepared ANPPCs-700 has a super high BET specific surface area of 824.69 m~2/g.The microstructure,chemical state and electrochemical properties of the product were investigated in detail.The prepared nitrogen-doped carbon microspheres exhibits excellent specific capacity of 209 F/g at a current density of lA/g and remained 92.5% of the initial capacitance after 5000 deep cycles at 5 A/g.     

壳聚糖基多孔碳材料的制备及其超级电容性能

以胶态SiO₂纳米粒子为模板,壳聚糖为碳源,ZnCl₂为活化剂,制备了具有不同比表面积和孔体积的氮掺杂介孔碳。采用多种表征手段对碳材料的微观形貌、比表面积和孔道结构进行了表征,探究了壳聚糖与SiO₂纳米粒子的比例以及ZnCl₂活化剂对碳材料孔体积和比表面积的影响。结果表明,在未使用活化剂时碳材料(CSi-1.75)的孔体积高达4.53 cm³·g^-1,但其比表面积最小(729 m²·g^-1);使用ZnCl₂作为活化剂制备的碳材料(CSi-1.75-Zn)比表面积为1 032 m²·g^-1,但其孔体积下降到1.99 cm³·g^-1,且具有最多的吡啶氮和吡咯氮。在以6.0 mol·L^-1KOH为电解液的三电极体系中,当电流密度为0.5 A·g^-1时,CSi-1.75...     

Magnetic spherical carbon as an efficient adsorbent for the magnetic extraction of phthalate esters from lake water and milk samples

Magnetic spherical carbon was synthesized by a facile hydrothermal carbonization procedure with biomass glucose as the carbon precursor and nanoclusters iron colloid as magnetic precursor. The textures of the as‐prepared magnetic spherical carbon were characterized by nitrogen adsorption–desorption isotherms, X‐ray diffraction, transmission electron microscopy, scanning electron microscopy and vibration sample magnetometry. Results indicated that the magnetic spherical carbon possessed high surface area as well as strong magnetism, which endows the material with good adsorption capability and easy separation properties. To assess its absorption performance, the magnetic spherical carbon was employed as adsorbent for the extraction and preconcentration of phthalate esters from lake water and milk samples before high‐performance liquid chromatographic analysis. Some key parameters that could influence the enrichment efficiency were investigated. Under the optimum conditions, a good linearity was achieved with the linear correlation coefficients higher than 0.9973. The limits of detection (S/N = 3) were 0.05–0.08 ng/mL for lake water and 0.1–0.2 ng/mL for milk samples. The recoveries of the analytes for the method were in the range 80.1–112.6%.     

有序介孔碳的微波快速合成和表面修饰及其负载性能

以低聚合度酚醛树脂为碳源、三嵌段共聚物F127(Mw=12600,PEO106PPO70PEO106)为模板导向剂,以微波辐照替代传统的烘箱热聚合,在常见功率下(400～800W)快速(15～60min)聚合,并高温碳化获得介孔碳。XRD、TEM、低温N2吸脱附等测试表明所得样品具有高度有序的介孔结构,比表面积和孔容分别可达614m2·g-1和0.47cm3·g-1。合成的介孔碳经NaBH4和胶体钯溶液两步修饰处理,表面被活化并沉积了Pd颗粒,导电性和亲水性均得到改善,载Pt的量和分散性明显提高,Pt/C催化剂的电化学活性面积由4m2·g-1增加到29m2·g-1。     

Tuning physical surface properties of tin dioxide nanopowders using zinc oxide as template

With a view to energetic and (opto)electronic applications, tin (IV) oxide (SnO₂) nanoparticles have been successfully prepared at the nanoscale by a templating approach based on the use of zinc (II) oxide (ZnO) as template. The procedure consisted in preparing a mixture of tin precursor and template, subsequently calcined at 650 °C under air to lead to the formation of a SnO₂/ZnO composite material. Finally, the material was washed with an alkali solution to remove the template. The template/tin precursor mass ratio was varied in order to tailor the tin (IV) oxide material, especially with a view to main particle size. The resulting SnO₂ nanomaterials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption and electron microscopy. The tin (IV) oxide nanomaterial exhibited enhanced textural and physical surface properties (particle size, surface area, pore size) correlated to an increasing template/tin precursor mass ratio. For instance, from optimized experimental conditions, the specific surface area and pore volume were heightened twofold, reaching values of 49 m²/g and 0.32 cm³/g, respectively.     

Three-dimensional nano-foam of few-layer graphene grown by CVD for DSSC

We report a robust and direct route to fabricate a three-dimensional nano-foam of few-layer graphene (3D-NFG) with large area coverage via a chemical vapor deposition (CVD) technique. Pyrolysis of polymer/nickel precursor film under a hydrogen environment, simply prepared by spin-coating, leads to the creation of nano-foam in the film and the reduction process of nickel ions. Carbonized-C and the nickel nano-frame formed from the pyrolysis are used as a solid carbon source and as a catalyst for the growth of graphene under CVD conditions, respectively. We investigate the use of 3D-NFG, with the advantage of large surface area and high conductivity, as an alternative to the Pt counter electrode material in dye sensitized solar cells. The excellent properties of 3D-NFG, fabricated in this simple and direct manner, suggest a great potential for interconnected graphene networks in electronic devices and photocatalytic sensors as well as in energy-related materials.     

Fabrication of polyacrylonitrile/lignin-based carbon nanofibers for high-power lithium ion battery anodes

Low-cost carbon nanofibers are fabricated from lignin, the second most abundant raw material in wood after cellulose and polyacrylonitrile mixture as a carbon precursor by electrospinning, followed by suitable heat treatments. As the lignin content in the precursor increases, the carbon nanofibers become thinner, as seen from scanning electron microscopy images. However, their carbon structure and electrochemical performance are found to be very similar, even though surface functional groups on carbon nanofibers are slightly different from each other. For example, in the initial charge (lithium insertion) and discharge (lithium deinsertion) process, the reversible specific capacities of the various carbon nanofibers come from different precursor ratios of lignin and polyacrylonitrile are similar. Even at a fast (7 min) charge and discharge condition, the carbon nanofibers prepared from the lignin-containing precursors show a discharge capacity of 150 mAh g^?1. The lignin-based carbon nanofibers thus show promise for use in high-power lithium ion battery anodes with low price.     

Carbon materials as electrodes for electrosorption of NaCl in aqueous solutions

Different porous carbons (MWCNT, a carbon aerogel, an activated carbon cloth and a chemically activated carbon) were evaluated as electrode material for the electrosorption of NaCl. The results obtained from the chronoamperometric experiments were correlated to the surface area and the size of the pores present in each carbon. These results indicate that all the surfaces are equivalent for the electrosorption process, demonstrating that both, mesopores and micropores, are equally effective. Nevertheless, the kinetics of the process is influenced by the pore size distribution of the carbon, although it is rather fast for all the carbons studied. The chemically activated carbon seems to be the most suitable carbon material for electrosorption of NaCl due to the combination of a high surface area and an appropriate pore size distribution.     

High surface area, mesoporous, glassy alumina with a controllable pore size by nanocasting from carbon aerogels

A strategy to synthesize amorphous, mesoporous alumina by nanocasting has been developed, involving carbon aerogel as a hard template and aluminum nitrate solution as an alumina precursor. The alumina generated exhibits small, transparent granules with a 3-6 mm diameter and has inherited the three-dimensional network structure of the carbon template. The mesopore surface area of the alumina can be as high as 365 m2 g(-1), and the pore volume reaches 1.55 cm3 g(-1) after calcination at 600 degrees C in air for 8 h. The pore parameters can be varied within a certain range by variation of the carbon aerogel template and the loading amount of the alumina precursor. At high loadings, the obtained glassy alumina clearly has a bimodal pore size distribution in the mesopore range.     

Effect of surface area and heteroatom of porous carbon materials on electrochemical capacitance in aqueous and organic electrolytes

A series of porous carbon materials with wide range of specific surface areas and different heteroatom contents had been prepared using polyaniline as carbon precursor and KOH as an activating agent. Effect of surface area and heteroatom of porous carbon materials on specific capacitance was investigated thoroughly in two typical aqueous KOH and organic 1-butyl-3- methylimidazolium tetrafluoroborate/acetonitirle electrolytes. The different trends of capacitance performance were observed in these two electrolytes. Electrochemical analyses suggested that the presence of faradaic interactions on heteroatom-enriched carbon materials in organic environment is less significant than that observed in aqueous electrolytes. Thus, in aqueous electrolyte, a balance between surface area and heteroatom content of activated porous carbon would be found to develop a supercapacitor with high energy density. In organic electrolyte, the capacitance performance of porous carbon is strongly dependent on the surface area. The results may be useful for the design of porous carbon-based supercapacitor with the desired capacitive performance in aqueous and organic electrolytes.     

A study of ion charge transfer on electrochemical behaviors of poly(vinylidene fluoride)-derived carbon electrodes

In this work, porous carbon with a high specific surface area as electrode materials for supercapacitors are obtained by a carbonization process at various temperatures from 700 °C to 1000 °C without activation process using poly(vinylidene fluoride) (PVDF) as a carbon precursor. The electrochemical performance is characterized by cyclic voltammetry and galvanostatic charge–discharge cycling performance using two-electrode system in 6.0 M KOH as an aqueous electrolyte. The results indicate that carbonization temperature significantly affected the specific surface area and pore volume of the PVDF-derived carbons and their capacitive behavior. In particular, the electrochemical performance of the prepared PVDF-derived carbon is determined by both the electric double-layer capacitance and the pseudo-capacitance resulting from the residual surface functional groups on PVDF-derived carbons.