A novel polyaniline/mesoporous carbon nano-composite electrode for asymmetric supercapacitor

<正>A novel nano-composite of polyaniline/mesoporous carbon(PANI/CMK-3) was prepared with mesoporous carbon(CMK-3) serving as the support.Electrochemical asymmetric capacitors have been successfully designed by using PANI/CMK-3 composite and CMK-3 as positive and negative electrode,respectively.The results showed that the discharge capacity of the asymmetric capacitor could reach 87.4 F/g under the current density of 5 mA/cm~2 and cell voltage of 1.4 V.The energy density of the asymmetric capacitor was up to 23.8 Wh/kg with a power density of 206 W/kg.Furthermore,PANI/CMK-3-CMK-3 asymmetric capacitor using this PANI/CMK-3 nano-composite could be activated quickly and possess high charge-discharge efficiency.     

High-performance supercapacitors of hydrous ruthenium oxide/mesoporous carbon composites

The amorphous hydrous ruthenium oxide/mesoporous carbon composites (denoted as RuO₂·xH₂O/MC), obtained by loading small amount of amorphous hydrous ruthenium oxide nanoparticles ranged from 0.9 to 5.4% by weight of Ru (denoted as RuO₂·xH₂O) on mesoporous carbon (MC), were investigated for the first time and were used for supercapacitors. Electrochemical measurements showed that RuO₂·xH₂O/MC composites not only have an enhanced specific capacitance but also retain the superior rate capability of MC. The RuO₂·xH₂O/MC composite with Ru loading of 3.6 wt% exhibited an increase of the specific capacitance of approximately 57% (from 115 to 181 F/g) at the scan rate of 25 mV s⁻¹ in 0.1 M H₂SO₄ aqueous electrolyte. The specific capacitance based on the mass of RuO₂ was estimated to be 1,527 F/g, by subtracting the contribution from MC in the composite. Cycle performance tests for RuO₂·xH₂O/MC composite (3.6 wt% Ru) showed that approximately 2.8% loss of the total capacitance was observed after 1,000 cycles.     

A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl3/SiO2-templated approach

Molecular nitrogen is relatively inert and the activation of its triple bond is full of challenges and of significance. Hence, searching for an efficiently heterogeneous catalyst with high stability and dispersion is one of the important targets of chemical technology. Here, we report a Ba-K/Ru-MC catalyst with Ru particle size of 1.5–2.5 nm semi-embedded in a mesoporous C matrix and with dual promoters of Ba and K that exhibits a higher activity than the supported Ba-Ru-K/MC catalyst, although both have similar metal particle sizes for ammonia synthesis. Further, the Ba-K/Ru-MC catalyst is more active than commercial fused Fe catalysts and supported Ru catalysts. Characterization techniques such as high-resolution transmission electron microscopy, N₂ physisorption, CO chemisorption, and temperature-programmed reduction suggest that the Ru nanoparticles have strong interactions with the C matrix in Ba-K/Ru-MC, which may facilitate electron transport better than supported nanoparticles.     

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.     

Activated carbon prepared from polyaniline base by K2CO3 activation for application in supercapacitor electrodes

An activated carbon was prepared from a polyaniline base using K₂CO₃ as an activating agent. The morphology, surface chemical composition, and surface area of the as-prepared carbon materials were investigated by scanning electron microscope, X-ray photoelectron spectroscopy, and Brunauer?CEmmett?CTeller measurement, respectively. Electrochemical properties of the as-prepared sample were studied by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy measurements in 6?mol?L^?1 KOH aqueous solution. Compared with the non-activated carbon, activated carbon showed superior capacitive performance. The activation carbon presented a high specific gravimetric capacitance of 210?F?g^?1. The good electrochemical performance of the activated carbon was ascribed to well-developed micropores, high surface area, the presence of nitrogen and oxygen functional groups, and larger pore volume.     

A facile synthesis of hierarchical porous carbon derived from renewable lignin for high-performance supercapacitor

In this work, we proposed a facile one-pot pyrolysis method to conveniently manufacture lignin-derived carbon materials with graded porous construction for use in supercapacitors. The renewable lignin was selected as precursor, while the potassium citrate was used as a pore-forming agent. The properties of the prepared lignin-derived carbon (LAC) and the performance for supercapacitor application were thoroughly evaluated. The LAC at optimal preparation conditions shows a layered porous structure with a large specific surface area of 3174 cm² g⁻¹ and pore volume of 2.796 cm³ g⁻¹, where the specific capacitance reach to 241 F g⁻¹ at 1 A g⁻¹ scan rate in 6 M KOH electrolyte solution. At the same time, the specific capacitance remains at 220 F g⁻¹ even at an excessive scan velocity of 20 A g⁻¹, while the capacitance retention is still close to 91.3%. The capacitance retention rate is stable above 95% after 10,000 charge/discharge cycles, which shows the desired long-time stability. All these results demonstrate the outstanding properties of the new prepared LAC material and the considerable application potential in the field of electrical energy storage.     

Thermal evolution of mesoporous titania prepared by CO2 supercritical extraction

Porous anatase is attractive because of its notable photo-electronic properties. Titania wet gel prepared by hydrolysis of Ti-alkoxide was immersed in the flow of supercritical CO₂ at 60°C and the solvent was extracted (aerogel). Mesoporous TiO₂ consisting of anatase nano-particles, about 5 nm in diameter, have been obtained. Thermal evolution of the microstructure of the aerogel was evaluated by TGA-DTA, N₂ adsorption, TEM and XRD, and discussed in comparison with that of the corresponding xerogel. The diffraction peaks of anatase were found for the as-extracted gel while the xerogel dried at 90°C was amorphous. After calcination at 600°C, the average pore size of the aerogel, about 20 nm in diameter, was 4 times larger than that of the xerogel, and the pore volume, about 0.35 cm³ g⁻¹, and the specific surface area, about 60 m² g⁻¹, were 2 times larger than those of the xerogel. XRD peaks of rutile have been found after calcination at 600°C. The particle sizes of anatase and rutile are about 13 and 25 nm in diameter, respectively. The surface morphology of TiO₂ nano-particles has been discussed in terms of their surface fractal dimensions estimated from the N₂ gas adsorption isotherms.     

超级电容器用中孔炭复合电极材料研究进展

超级电容器是一类利用电化学双电层或电极材料在电极/溶液界面发生的氧化还原反应来存储能量的装置,除兼有常规电容器功率密度大和二次电池能量密度高的特点外,还具有可逆性好和循环寿命长等优点.本文重点介绍了近几年国内外对中孔炭材料、表面官能团修饰中孔炭材料、中孔炭-金属氧化物、中孔炭-导电聚合物等几类电极材料的研究现状;并且展望了超级电容器用中孔炭及其复合电极材料的当前研究热点和发展前景.     

In situ introduction of dispersed metallic Ag nanoparticles into the channels of mesoporous carbon CMK-3

An in situ reduction method has been developed to fabricate metallic Ag nanoparticles inside the channels of mesoporous carbon CMK-3.This approach combines function of the CMK-3 surface by oxidation using HNO_3 with the subsequent absorption of Ag~ . The resultant nanocomposite materials were characterized by nitrogen adsorption,X-ray diffraction,Auger electron spectroscopy and transmission electron microscopy.Compared with the conventional impregnation method,our approach shows that Ag nanoparticles of 2-4 nm can be uniformly incorporated into CMK-3.     

Facile synthesis of ordered magnetic mesoporous gamma-Fe2O3/SiO2 nanocomposites with diverse mesostructures

On the basis of a sol–gel process, a facile, low cost, and one-step approach for preparing ordered magnetic mesoporous γ-Fe₂O₃/SiO₂ nanocomposites by an evaporation-induced self-assembly (EISA) approach is presented. Various mesostructured silica materials (P6mm or Im3m) incorporated with different amounts of iron oxide (n_Si/n_Fe=9/1, 8/2, 7/3, respectively) were synthesized and characterized by XRD, TEM, N₂-sorption analyses, and superconducting quantum interference device (SQUID) magnetometer. The HCl-leaching experiments together with TEM micrographs and nitrogen sorption analysis suggested that most of the γ-Fe₂O₃ domains of several nanometers were embedded in the silica walls, rather than dispersed in the mesopores, which could cause the significant pore clogging reported in some studies. The release behaviors of lysozyme from these magnetic porous nanocomposites were investigated for the possible application of drug targeting and control release. The influence of iron precursors was also studied and a possible mechanism was proposed. The hydrolysis of Fe³⁺ ions under weakly acidic conditions and the induced formation of SiOFe bonds may account for the synthesis of this kind of nanocomposite. These multifunctional nanostructured materials would have a wide range of applications in toxin removal, catalysis, waste remediation, and biological separation as well as novel drug-carrier technologies.     

Efficient 3-aminopropyltrimethoxysilane functionalised mesoporous ceria nanoparticles for CO2 capture

This work described the effect of 3-aminopropyltrimethoxysilane (APTMS) functionalization on the mesoporous ceria nanoparticles (MCNs) toward CO₂ capture. The MCN and APTMS-loaded MCN (APTMS-MCN) were prepared by the sol-gel and impregnation method, respectively. The functionalization of APTMS on the MCN enhanced the CO₂ binding sites which were observed through the formation of carbamate species from the interaction of CO₂ with the NH group. This resulted to the increase of CO₂ adsorption capacity of APTMS-MCN with 10-fold higher than that of pristine MCNs. For MCNs, CO₂ may be adsorbed onto oxygen basic, oxygen vacant, and hydroxyl sites which further formed polydentate, monodentate, bidentate, and hydrogen carbonate species. In addition to these carbonate species, the adsorption of CO₂ on APTMS-MCN has largely occurred through the formation of carbamate species which further enhanced its CO₂ uptake.     

Activated carbon prepared by physical activation of olive stones for the removal of NO2 at ambient temperature

Activated carbon was prepared from olive stones by physical activation using water vapor at 750 °C. Textural, morphology and surface chemistry characterizations were achieved (nitrogen adsorption, SEM, FTIR and TPD–MS). NO₂ adsorption was performed for different inlet gas compositions and temperatures. NO₂ may adsorb directly on the oxygenated surface groups, and can also be reduced to NO. Therefore, a second NO₂ molecule adsorbs on the oxygen left on the carbon surface. TPD performed after NO₂ adsorption showed the presence of various surface groups. The adsorption capacity was about 131 mg/g, which is higher than with several activated carbon prepared from classical lignocellulosic biomass. NO₂ reduction into NO decreased with increasing the inlet oxygen concentration. In contrast, a slight decrease in the NO₂ adsorption capacity was observed with increasing temperature. It seems that the activated carbons prepared from olive stones by steam activation could be used as efficient adsorbents for NO₂ removal.     

Characterization and acidic properties of Al-SBA-15 materials prepared by post-synthesis alumination of a low-cost ordered mesoporous silica

A series of Al-containing SBA-15 type materials with different Si/Al ratio, were prepared by post-synthesis modification of a pure highly ordered mesoporous silica SBA-15 obtained by using sodium silicate as silica source, and amphiphilic block copolymer as structure-directing agent. A high level of aluminum incorporation was achieved, reaching an Si/Al ratio of up to 5.5, without any significant loss in the textural properties of SBA-15. These materials were fully characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ²⁷Al NMR spectroscopy, and N₂ adsorption at 77 K. The acid properties of these materials have been evaluated by NH₃-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FTIR spectroscopy. The effective acidity of these materials was evaluated using two catalytic reactions: 2-propanol dehydrogenation and 1-butene isomerization. The adsorption of basic probe molecules and the catalytic behavior revealed an evolution of the acid properties with the Al content. These studies have shown that the Al-SBA-15 materials contain Brønsted and Lewis acid sites with medium acidity which makes them appropriate to be used as acid catalysts in heterogeneous catalysis, catalytic supports, and adsorbents.     

Extraction of cationic surfactant templates from mesoporous materials by CH(3)OH-modified CO(2) supercritical fluid

Extraction of cationic surfactant templates from MCM-41, MCM-48, SBA-1 and SBA-3 has been conducted using CH₃OH-modified CO₂ supercritical fluid. The supercritical fluid extraction (SFE) has been integrated with thermogravimetry (TG), X-ray diffraction (XRD) and N₂ adsorption-desorption to evaluate extraction efficiency and structural stability of mesoporous materials. Experiments of optimization indicate that the conditions of 90 bar, 85 °C, CH₃OH/CO₂ = 0.1/1.0 ml/min and 3 h are most suitable for the SFE of cationic templates. 76-95% of the cationic templates can be extracted from the mesoporous materials. XRD and N₂ adsorption-desorption studies illustrate that SFE possesses some advantages over calcination in maintaining mesoporous uniformity and structural stability when used to remove templates. The impact of curing on mesoporous structure is also dealt with.     

Construction of label-free electrochemical immunosensor on mesoporous carbon nanospheres for breast cancer susceptibility gene

In this contribution, mesoporous carbon nanospheres (MCN) were used to fabricate a label-free electrochemical immunosensor for breast cancer susceptibility gene (BRCAl). The detection platform was constructed by conjugation of anti-BRCA1 on glassy carbon electrodes which were modified by mesoporous carbon nanospheres–toluidine blue nanocomposite (MCN–TB)/room temperature ionic-liquid (RTIL) composited film. TB was adsorbed onto MCN and acted as a redox probe. The electroactivity of TB was greatly enhanced in the presence of MCN. The good conductivity of MCN and BMIM·BF₄ could promote the electron transfer and thus enhance the detection sensitivity. Moreover, the large surface area of MCN and the protein-binding properties of BMIM·BF₄ could greatly increase the antibody loading. The specific antibody–antigen immunoreaction on the electrode surface resulted in a decrease of amperometric signal of the electrode. Under optimized conditions, the amperometric signal decreased linearly with BRCAl concentration in the range of 0.01–15 ng mL⁻¹ with a low detection limit of 3.97 pg mL⁻¹. The immunosensor exhibits high sensitivity, good selectivity and stability.     

High dispersion Pt nanoparticles using mesoporous carbon support for enhancing conversion efficiency of dye-sensitized solar cells

<正>Mesoporous carbon(MC) with surface area of 380 m~2/g was prepared and employed as the carbon support of Pt catalyst for counter electrode of dye-sensitized solar cells.Pt/MC samples containing 1 wt%Pt were prepared by reducing chloroplatinic acid on MC using wet impregnation.It was found that Pt nanoparticles were uniform in size and highly dispersed on MC supports.The average size of Pt nanoparticles is about 3.4 nm.Pt/MC electrodes were fabricated by coating Pt/MC samples on fluorine-doped tin oxide glass.The overall conversion efficiency of dye-sensitized solar cells with Pt/MC counter electrode is 6.62%,which is higher than that of the cells with conventional Pt counter electrode in the same conditions.     

Fabrication of sulfonated mesoporous carbon by evaporation induced self-assembly/carbonization approach and its supercapacitive properties

Synthesis of functionalized mesoporous carbon by an easy-accessed method is of great importance towards its practical applications.Herein,an evaporation induced self-assembly/carbonization(EISAC) method was developed and applied to the synthesis of sulfonic acid group functionalized mesoporous carbon(SMC).The final mesoporous carbon obtained by EISAC method possesses wormlike mesoporous structure,uniform pore size(3.6 nm),large surface area of 735 m²/g,graphitic pore walls and rich sulfonic acid group.Moreover,the resultant mesoporous carbon achieves a superior electrochemical capacitive performances(216 F/g)to phenolic resin derived mesoporous carbon(OMC,152 F/g)and commercial activated carbon(AC,119 F/g).     

A sensitive amperometric sensor for hydrazine and hydrogen peroxide based on palladium nanoparticles/onion-like mesoporous carbon vesicle

Onion-like mesoporous carbon vesicle (MCV) with multilayer lamellar structure was synthesized by a simply aqueous emulsion co-assembly approach. Palladium (Pd) nanoparticles were deposited on the MCV matrix (Pd/MCV) by chemical reduction of H₂PdCl₄ with NaBH₄ in aqueous media. Pd(X)/MCV (X wt.% indicates the Pd loading amount) nanocomposites with different Pd loading amount were obtained by adjusting the ratio of precursors. The particular structure of the MCV results in efficient mass transport and the onion-like layers of MCV allows for the obtainment of highly dispersed Pd nanoparticles. The introduction of Pd nanoparticles on the MCV matrix facilitates hydrazine oxidation at more negative potential and delivers higher oxidation current in comparison with MCV. A linear range from 2.0 × 10⁻⁸ to 7.1 × 10⁻⁵ M and a low detection limit of 14.9 nM for hydrazine are obtained at Pd(25)/MCV nanocomposite modified glassy carbon (GC) electrode. A nonenzymatic amperometric sensor for hydrogen peroxide based on the Pd(25)/MCV nanocomposite modified GC electrode is also developed. Compared with MCV modified GC electrode, the Pd(25)/MCV nanocomposite modified GC electrode displays enhanced amperometric responses towards hydrogen peroxide and gives a linear range from 1.0 × 10⁻⁷ to 6.1 × 10⁻³ M. The Pd(25)/MCV nanocomposite modified GC electrode achieves 95% of the steady-current for hydrogen peroxide within 1 s. The combination of the unique properties of Pd nanoparticles and the porous mesostructure of MCV matrix guarantees the improved analytical performance for hydrazine and hydrogen peroxide.     

Mechanism of activation of glassy carbon electrodes by cathodic pretreatment

The performance of carbon electrodes depends on the surface pretreatment methods. An exclusively cathodically pretreated glassy carbon electrode (GCE) shows very good activity towards monomeric molybdate(VI) ion adsorption and its reduction. X-ray photoelectron spectroscopy studies reveal the creation of >C–O– surface groups on cathodisation. A strong interaction between the Mo(VI) ion and these >C–O– surface groups with the formation of Mo(V) is responsible for the activation of the cathodically pretreated GCE surface. Received: 5 January 1998 / Accepted: 10 January 1999