Enhancement of the methylene blue adsorption rate for ultramicroporous carbon fiber by addition of mesopores

Predominant mesopores were added to pitch-based activated carbon fiber (0.7 nm of average pore width) by Ca(NO₃)₂-impregnated chemical activation. The influence of the concentration of calcium nitrate solution, reactivation temperature and reactivation time on the mesopore development of ACF were examined. The development of mesopores in the reactivated ACF was evidenced by an explicit hysteresis of N₂ adsorption isotherm at 77 K. The pore volume ratio of mesopores to micropores reached to 3-4. The addition of predominant mesopores to ACF enhanced the liquid phase adsorption rate of methylene blue by more than 10 times.     

双电层电容器活性炭电极的优化

通过物理方法对双电层电容器用活性炭电极进行改性实验,探讨了活性炭电极的结构（比表面积、孔径分布、孔容）和性能（比电容、充放电特性）的优化问题.改性后活性炭电极BET比表面积从1739.77 m²•g^-1增至2215.40 m²•g^-1,其中微孔比表面积增幅22％,中孔比表面积增幅35％,孔容积也有20%～30％的增幅量,孔径分布更为合理.优化的活性炭电极结构改善了电极材料的电化学特性,比电容量可达424 F•g^-1,增幅10％.     

Synthesis of activated carbons by chemical activation of new anthracene oil-based pitches and their optimization by response surface methodology

This paper deals with the synthesis of new anthracene oil-based activated carbons by chemical activation with KOH. It focuses on the optimization of the processing conditions involved by means of surface response methodology. A factorial design (2³+3) in one block with four degrees of freedom was used to optimize the process, based on the responses BET surface area, total pore volume, mesopore volume, micropore volume and mol ratio CO:CO₂. The variables measured include KOH to pitch ratio (1:1, 3:1 and 5:1), activation temperature (700 up to 1000 °C) and pitch characteristics. The activation of anthracene oil-based pitch led to activated carbons with BET surface area values of 2880 m² g⁻¹. The factorial design expresses every response factor as a mathematical equation using the experimental variables. The most critical factor for each experiment design response has been identified from the analysis of variance (ANOVA). These mathematical models were also used to obtain the optimum processing conditions for the production of activated carbon with controlled properties. The experimental processing of the optimized activated carbons gave rise to a sample with BET, total pore volume, mesopore volume, micropore volume values which were in good agreement with those predicted by statistical analysis.     

Microporous activated carbon spheres prepared from resole‐type crosslinked phenolic beads by physical activation

Microporous activated carbon spheres (ACSs) with a high specific Brunauer–Emmet–Teller (BET) surface area were prepared from resole‐type spherical crosslinked phenolic beads (PBs) by physical activation. The PBs used as precursors were synthesized in our laboratory through the mixing of phenol and formaldehyde in the presence of an alkaline medium by suspension polymerization. The effects of the gasification time, temperature, and flow rate of the gasifying agent on the surface properties of ACSs were investigated. ACSs with a controllable pore structure derived from carbonized PBs were prepared by CO₂ gasification. Surface properties of ACSs, such as the BET surface area, pore volume, pore size distribution, and pore diameters, were characterized with BET and Dubinin–Reduchkevich equations based on N₂ adsorption isotherms at 77 K. The results showed that ACSs with a 32–88% extent of burn‐off with CO₂ gasification exhibited a BET surface area ranging from 574 to 3101 m²/g, with the pore volume significantly increased from 0.29 to 2.08 cm³/g. The pore size and its distribution could be tailored by the selection of suitable conditions, including the gasification time, temperature, and flow rate of the gasifying agents. The experimental results of this analysis revealed that ACSs obtained under different conditions were mainly microporous. The development of the surface morphology of ACSs was also studied with scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of polymer‐based spherical activated carbons with tailored pore structure

A series of spherical activated carbons (SACs) with different pore structure were prepared from divinylbenzene‐based polymer through CO₂ activation. The effect of activation temperature and retention time on the yield and textural properties of the resulting SACs were studied. The SACs were characterized by N₂ adsorption, X‐ray diffraction, scanning electron microscopy, and aqueous adsorption assays. Either increasing activation temperature or extending retention time decreases the yield of SACs. The BET surface area and pore volume increase with activation temperature and reach a maximum at 1000°C and then decrease at higher activation temperatures. At 1000°C, BET surface area, total pore volume, and mesopore pore volume increase with retention time from 0.5 to 2 h, and meanwhile micropore volume decreases. The micropores are gradually widened into mesopores with increasing activation temperature or extending retention time. SEM and XRD analyses of SAC10 verify the presence of developed porous structure composed of disordered micrographite stacking. Aqueous adsorption assays indicate that SACs have good adsorption capacity for phenol. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hierarchically porous monoliths of carbon and metal oxides with ordered mesopores

Hierarchically porous carbon and metal oxide materials offer great benefits in separations, catalysis and renewable energy. We have here used hierarchically porous silica monoliths with ordered mesopores as hard templates to produce nanocast carbon, Co₃O₄, and NiO monoliths with similar structures. Besides providing the materials with more well-defined physicochemical properties, the ordered mesopore structure also offers an excellent model system for investigating the nanocasting process in detail. The mesopores of the silica monoliths were first infiltrated with furfuryl alcohol or metal nitrate precursor solutions, which subsequently could be thermally converted to carbon or the corresponding metal oxides. After the silica scaffolds have been removed by etching in base solutions, the resulting replica monoliths display macroscopic morphology and macropore structure similar to the original silica template. However, while the carbon and Co₃O₄ materials both display a well-organized nanowire structure, giving rise to high surface area and narrow pore size distribution, the NiO monoliths exhibit a significantly lower surface area and less well-defined mesopore structure implying that only part of the silica mesopores has been replicated. We believe this apparent difference between the two metal oxides is a consequence of differences in mass transport.     

Variation of the pore structure of coal chars during gasification

The variation of the pore structure of several coal chars during gasification in air and carbon dioxide was studied by argon adsorption at 87 K and CO₂ adsorption at 273 K. It is found that the surface area and volume of the small pores (<10 Å) do not change with carbon conversion when the coal char is gasified in air, while those of the larger pores (10-20 Å, 20-50 Å, 50-2500 Å) increase with increase of carbon conversion. However in CO₂ gasification, all the pores in different size ranges increase in surface area and volume with increase of carbon conversion. Simultaneously, the reaction rate normalized by the surface area of the pores >10 Å for air gasification is constant over a wide range of conversion (>20%), while for CO₂ gasification similar results are obtained using the total surface area. However, in the early stages of gasification (<20%) the normalized reaction rate is much higher than that in the later stage of gasification, due to existence of more inaccessible pores in the beginning of gasification. The inaccessibility of the micropores to adsorption at low and ambient temperatures is confirmed by the measurement of the helium density of the coal chars. The random pore model can fit the experimental data well and the fitted structural parameters match those obtained by physical gas adsorption for coal chars without closed pores.     

Effects of activation temperature on the properties and structure of PAN‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of activation temperature of a precursor fiber on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the BET surface area of the PAN‐ACHF and surface area of mesopores in the PAN‐ACHF increased very remarkably and reached 1422 m² g^?1 and 1234 m² g^?1, respectively, when activation temperature is 1000°C. The adsorptions to creatinine and VB₁₂ of PAN‐ACHF were much high and reached 99 and 84% respectively. In PAN‐ACHF which went through the activation at 700°C and 800°C, the micropore filling mainly occurred at low relative pressures, multimolecular layer adsorption occurred with the increasing of relative pressure, and the filling and emptying of the mesopores by capillary condensation occurred at high relative pressures. But in PAN‐ACHF which went through the activation at 900°C, a mass of mesopores resulted in the large pore filling by capillary condensation. The dominant pore sizes of mesopores in PAN‐ACHF are from 2 nm to 5 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3778–3783, 2006     

KOH activation of ordered mesoporous carbons prepared by a soft-templating method and their enhanced electrochemical properties

Ordered mesoporous carbon (COU-2) was synthesized by a soft-templating method. The COU-2 mesoporous carbon was activated by using KOH to improve its porosity. The mesopore size of COU-2 was 5.5 nm and did not change by the KOH activation. But, the BET surface area of COU-2 largely increased from 694 to 1685 m²/g and total pore volume was increased from 0.54 to 0.94 cm³/g after the KOH activation. The large increase of micropore volume is due to the increase of the surface area. Electrochemical cyclic voltammetry measurements were conducted in aqueous (1 M sulfuric acid) and organic (1 M tetraethyl ammonium tetrafluoroborate/polypropylene carbonate) electrolyte solutions. The KOH-activated COU-2 carbon shows superior capacitances over the COU-2 carbon and a commercial microporous carbon both in aqueous and organic electrolyte solutions. These results suggest that the carbons having regularly-interconnected uniform mesopores and micropores in thin pore walls are desirable for the electrodes in electrochemical double-layer capacitors.     

Influence of the textual properties of activated carbon nanofibers on the performance of electric double-layer capacitors

To investigate the relationship between textural properties and electrochemical properties, activated carbon nanofibers were manufactured using an electrospinning process followed by chemical activation using KOH or NaOH. The specific surface area of the KOH-activated carbon nanofibers was higher than that of NaOH-activated carbon nanofibers; however, the total pore volume and mesopore volume of the NaOH-activated carbon nanofibers were greater than those of the KOH-activated carbon nanofibers when the same number of moles of KOH and NaOH were used. The specific capacitances increased as the specific surface area and pore volume of the activated carbon nanofibers were increased. However, the specific capacitance obtained at a high scan rate (50 mV/s) and the retained capacitance of the activated carbon nanofibers increased with increasing total pore and mesopore volume, especially for mesopores with diameters of 2–4 nm.     

Prospective application of carbon-silica derived from SiC-Si sludge as a support for Fe catalysts

A unique carbon-silica (30 wt%) material was prepared by H₂O activation at 700 °C for 8 h with the carbon derived from SiC-Si sludge and the in-situ hydrolysis of the SiCl₄ trapped in the pores of the carbon into silica. The BET surface area of the carbon-silica was 1,750 m²/g and the pore volume by QSDFT was 1.13 cm³/g, 40% of which stemmed from micropores smaller than 2 nm with 60% from mesopores between 2 nm and 50 nm. The activated carbon-silica was loaded with Fe by means of chemical vapor infiltration (CVI) and incipient wetness impregnation (IWI). A hydrogen temperature-programmed reduction test showed that the activated carbon-silica is a prospective support material for Fe catalysts and that the dispersion of Fe in the carbon-silica is higher with CVI than with IWI.     

Effect of HF and NaOH etching on the composition and structure of SiOC ceramics

Porous SiOC ceramics were prepared with tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTES) as sol?gel precursors, and followed by etching with HF and NaOH solution. The microstructure evolution and chemical etching as a function of pyrolysis temperature were investigated. The amorphous carbon increases as rising the temperature from 800 ^oC to 1200 ^oC, and the graphitic carbon increases with further etching by HF and NaOH. However, the effect of pyrolysis temperature on the structure of C is more significant. The hydroxylation reaction and phase separation of SiOC ceramics results in the increase of SiO₄ unit, which reacts with HF and NaOH to form micro- and mesopores. The existence of mesopore after HF etching provides more specific surface area and pore volume. However, NaOH etching produces more micropores, and the contribution of micropores to specific surface area and pore volume is higher than that of mesopores. Although HF and NaOH etching increase the specific surface area of SiOC ceramics, the etching effect of NaOH is superior to that of HF etching, and the carbon-enriched SiOC ceramics are obtained after NaOH etching.     

Binderfree synthesis of high-surface-area carbon electrodes via CO2 activation of resorcinol–formaldehyde carbon xerogel disks: Analysis of activation process

High-surface-area carbon xerogels were prepared in the form of disks via carbonization of precursor resorcinol–formaldehyde (RF) polymer disks and subsequent activation of the resultant RF carbon xerogels by CO₂. RF carbon xerogels allow the preparation of a set of pre-activated carbon disks having different mesopore volumes. Analysis of the relationship between the mesopore volume of the samples and their CO₂ activation efficiency showed that the presence of mesopores is crucial for obtaining a high-surface-area carbon with minimal burn-off of carbon atoms. Activation of an RF carbon disk with a mesopore volume of 1.0 cm³ g⁻¹ up to a burn-off of 81% yielded an activated carbon disk with a high BET surface area of ∼3000 m² g⁻¹. Such disks could be readily used as electrode materials for an electric double layer capacitor without filler or binder addition and exhibited competitive EDLC performance against other electrode materials previously reported.     

Preparation of activated carbons by utilizing solid wastes from palm oil processing mills

Feasibility of producing activated carbons by utilizing solid wastes (extracted flesh fibre and seed shell) from palm oil processing mills was investigated. The effects of activation conditions (CO₂ flow rate, activation temperature and retention time) on the characteristics of the activated carbons, i.e. density, porosity, BET surface area, pore size distribution and surface chemistry were studied. In this study, the optimum conditions for activation were an activation temperature of 800 °C and a retention time of 30 min for fiber or 50 min for shell, which gave the maximum BET surface area. Pore size distribution revealed that the shell-based activated carbons were predominantly microporous whilst fiber activated carbon had predominant mesopores and macropores, suggesting the application of shell and fiber activated carbon as adsorbents for gas-phase and liquid-phase adsorption, respectively. This was confirmed by further gas- and liquid-phase adsorption tests.     

Preparation of porous carbons from thermoplastic precursors and their performance for electric double layer capacitors

Porous carbons with high surface area were successfully prepared from thermoplastic precursors, such as poly(vinyl alcohol) (PVA), hydroxyl propyl cellulose and poly(ethylene terephthalate), by the carbonization of a mixture with MgO at 900 °C in an inert atmosphere. After carbonization the MgO was dissolved out using a diluted sulfuric acid and the carbons formed were isolated. The mixing of the PVA carbon precursor with the MgO precursors (reagent grade MgO, magnesium acetate or citrate) was done either in powder form or in an aqueous solution. The BET surface area of the carbons obtained via solution mixing could reach a very high value, such as 2000 m²/g, without any activation process. The pore structure of the resultant carbons was found to depend strongly on the mixing method; the carbons prepared via solution mixing were rich in mesopores, but those produced via powder mixing were rich in micropores. The size of mesopores was found to be almost the same as that of the MgO particles, suggesting a way of controlling the mesopore size in the resultant carbons. Measurement of capacitance was carried out in 1 mol/L H₂SO₄ electrolyte. The porous carbon with a BET surface area of 1900 m²/g prepared at 900 °C through solution mixing of Mg acetate with PVA showed a fairly high EDLC capacitance, about 250 F/g with a current density of 20 mA/g and 210 F/g with 1000 mA/g. The rate performance was closely related to the mesoporous surface area.     

Preparation and Phosphine Adsorption of Activated Carbon Prepared from Walnut Shells by KOH Chemical Activation

Walnut-shell activated carbons (WSACs) with high surface area and predominant micropore development were prepared by KOH chemical activation. The effects of carbonization temperature, activation temperature, and ratio of KOH to chars on the pore development of WSACs and PH₃ adsorption performance of the modified walnut-shell activated carbons (MWSACs) were studied. Criteria for determining the optimum preparation conditions were pore development of WSACs and PH₃ breakthrough adsorption capacity of MWSAC adsorbents. The result shows that the optimum preparation conditions are a carbonization temperature of 700°C, an activation temperature of 700°C, and a mass ratio of 3. The BET surface area and the micropore volume of the optimal WASC are 1636m²/g and 0.641cm³/g, respectively. The micropore volume percentage of WSAC plays an important role in PH₃ adsorption when there is a slight difference in BET surface areas. High-surface-area WSACs with predominant micropores are suitable for PH₃ adsorption removal. The MWSAC adsorbent owns the biggest PH₃ breakthrough adsorption capacity (284.12mg/g) due to the biggest specific surface area, total pore volume, and micropore volume percentage. The MWSAC adsorbent will be a potential adsorbent for PH₃ adsorption removal from yellow phosphorus tail gas.     

Characterization of accessible and inaccessible pores in microporous carbons by a combination of adsorption and small angle neutron scattering

We determine the pore size distribution for five activated carbons (comprising carbide derived as well as commercial activated carbon samples) by the interpretation of experimental small angle neutron scattering (SANS) intensity profiles, based on the primary assumption of an infinitely dilute solution of hollow spherical particles. The interpretation yields the pore size distribution of the carbon samples that have predominantly micropore populations (size <20 Å), but not for carbons which have significant mesopore populations of sizes up to 48 Å and high mass fractal degrees. The pore size distribution (PSD) results based on SANS data reveal significant populations of micropores of size <6.1 Å, and mesopores of size >20 Å, which are not present in the PSD results based on adsorption isotherms of either Ar at 87 K or CO₂ 273 K. This inaccessible porosity becomes accessible to CO₂ and Ar on heat treatment, leading to increase in the adsorption based pore volume. However, the surface area does not commensurately increase, indicating the inaccessible microporosity to predominantly comprise surface defects and roughness that are removed on heat treatment or activation. This finding sheds the light onto the evolution of porosity of activated carbons during gasification or post synthesis-treatment.     

Preparation of a carbon monolith with hierarchical porous structure by ultrasonic irradiation followed by carbonization, physical and chemical activation

A two-step direct and simple method for the preparation of a hierarchical porous carbon monolith with micropores, mesopores and macropores is described. The two stages give more flexibility in the preparation of a porous carbon monolith. In step I a macroporous interconnected carbon monolith is prepared by ultrasonic irradiation during sol-gel polycondensation. The effects of sol-gel temperature, catalyst concentration and ultrasonic power on the structure of the monolith are investigated. In step II, mesopores are induced in the monolith by Ca(NO₃)₂ impregnation followed by CO₂ activation. The effect of activation temperature is also studied. A hierarchical interconnected carbon monolith with mean pore size diameter of 1.2 μm, BET surface area of 624 m²/g, mesopore volume of 0.38 cm³/g and micropore volume of 0.22 cm³/g has been obtained from Ca(NO₃)₂ impregnation of the macroporous carbon monolith followed by CO₂ activation at 850 °C.     

Effect of pH in preparation and properties of mesoporous sieve from montmorillonite

Mesoporous material with dual mesoporous size distribution had been synthesized with montmorillonite as precursor. The materials exhibited two kinds of mesopores: one is mesopore in interlayers of montmorillonite with mean sizes of 2.9 nm, the other is mesopore out of layers of montmorillonite with mean sizes of 3.9 nm. With the increasing of pH values (8.0–11.0), the specific surface area and pore volume of two kinds of mesopores changed regularly. The samples were characterized by XRD, TEM and Nitrogen adsorption/desorption isotherms. The results indicated that higher pH benefits the synthesis of mesoporous montmorillonite with smaller pore and the TOT of montmorillonite had been present as porous wall.     

干法制备高中孔率生物质成型活性炭

以锯末为原料,氯化锌为活化剂,不添加黏结剂,采用干法混合后直接成型活化制备高中孔率生物质成型活性炭。为考察这种工艺的可行性,通过单因素实验,以亚甲基蓝吸附值为评价指标,考察了盐料比、活化温度、活化时间与成型密度对生物质成型活性炭吸附性能的影响,得出较优工艺条件为:盐料比1.0:1,活化温度950℃,活化时间为60min,成型密度为1.4g·cm^-3。在此工艺条件下制备得到的生物质成型活性炭,其亚甲基蓝吸附值为387mg·g^-1,BET比表面积为2104m²·g^-1,平均孔径为3.11nm,总孔容为1.63cm³·g^-1,中孔孔容为1.17cm³·g^-1,中孔率高达71.8%,初步证明了干法制备高中孔率生物质成型活性炭工艺的可行性。