Influence of surfactants on porous properties of carbon cryogels prepared by sol–gel polycondensation of resorcinol and formaldehyde

The role of surfactants on carbon cryogels is investigated by using three different surfactants, nonionic (SPAN80), cationic (trimethylstearylammonium chloride; C18) and nonionic polymeric fluorinated (FC4430) surfactants. By using different SPAN80 concentrations (10.0, 5.0, 2.5, 1.0 and 0.5 vol.%), double-structure carbon microspheres with S_BET (630–700 m²/g) and V_mes (0.51–0.93 cm³/g) are obtained. Mesoporous carbon cryogels with different S_BET and V_mes are prepared by using C18 with different volume ratios of cyclohexane to water in a C18/water/cyclohexane mixture. Carbon cryogels with S_BET (690–810 m²/g) and V_mes (0.83–1.74 cm³/g) are obtained when cyclohexane is contained in the mixture, on the contrary, when there is no cyclohexane in the mixture, a water-based carbon cryogel with low S_BET (480 m²/g) and V_mes (0.29 cm³/g) is obtained. Carbon cryogels prepared by using C18 have larger mesopore size and broader mesopore size distribution compared with carbon cryogels prepared by using other surfactants. Microcellular (sponge-like) carbon cryogels with mesoporous surface, S_BET (210–660 m²/g) and V_mes (0.37–0.92 cm³/g), are obtained by introducing FC4430 (two concentrations) to two starting RF solutions (C/W=6,45). Low FC4430 concentration leads to carbon cryogels with higher S_BET (610 and 660 m²/g) and narrower mesopore size distributions compared to the high concentration counterpart. Hence, it is found that different surfactant types have interesting effects on morphologies and porous properties of RF carbon cryogels.     

Preparation of granular activated carbon from oil palm shell by microwave-induced chemical activation: Optimisation using surface response methodology

In this study, waste palm shell was used to produce activated carbon (AC) using microwave radiation and zinc chloride as a chemical agent. The operating parameters of the preparation process were optimised by a combination of response surface methodology (RSM) and central composite design (CCD). The influence of the four major parameters, namely, microwave power, activation time, chemical impregnation ratio and particle size, on methylene blue (MB) adsorption capacity and AC yield were investigated. Based on the analysis of variance, microwave power and microwave radiation time were identified as the most influential factors for AC yield and MB adsorption capacity, respectively. The optimum preparation conditions are a microwave power of 1200 W, an activation time of 15 min, a ZnCl₂ impregnation ratio of 1.65 (g Zn/g precursor) and a particle size of 2 mm. The prepared AC under the optimised condition had a BET surface area (S_BET) of 1253.5 m²/g with a total pore volume (V_tot) of 0.83 cm³/g, which 56% of it was contributed to the micropore volume (V_mic).     

Evaluation of CO2 adsorption capacity of electrospun carbon fibers with thermal and chemical activation

The use of urea was investigated as an alternative to the poisonous and expensive NH₃ gas, commonly used for amination of adsorbents. First, we fabricated activated carbon nanofibers (AnFs) by electrospinning of urea‐doped polyacrylonitrile solution (N‐AnF). By increasing the activation temperature, the average specific surface area (S_BET) and micropore volume (V_micro) of pristine nFs improved from 27.3 to 300 m²/g and 0.004 to 0.13 cm³/g, respectively. Upon urea doping, both properties were further enhanced to 542 m²/g and 0.22 cm³/g, respectively. However, with chemical investigation via X‐ray photoelectron spectroscopy, we observed that the urea‐doping incorporated more of less desired quaternary‐N, along with other more basic and desirable N‐functionalities (i.e., nitrile, pyridinic, pyrrolic N) tethered. Based on the eventual CO₂ adsorption results, we realized that average pore diameter (d_avg) is a limiting factor with regard to CO₂ adsorption by AnFs; the lower the d_avg, the better the adsorption. Further examination via adsorption isotherm model fitting showed that CO₂ molecules were homogenously collected in a monolayer pattern. However, three‐parameter model Redlich–Peterson model best fits the experimental data, suggesting that the adsorption is concentration‐driven and that it tends toward Langmuir rather than Freundlich at elevated concentration of CO₂. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45534.     

Alkaline activation of the donbass coals of different ranks

The effect of the rank of coal (C ^daf = 80?95.2%) on the yield and characteristics of activated carbons prepared under the conditions of alkaline activation (800°C, 1 h, Ar) at KOH/coal ratios of 1 g/g was studied. Under these conditions, the ability of coals to form porous materials decreased in the metamorphic series. Grade D coal (C ^daf = 80%) exhibited a maximum activation ability to form a material with S _BET = 1560 m²/g, V _Σ = 0.71 cm³/g, and V _mi = 0.51 cm³/g. A minimum activation ability was found in anthracite (C ^daf = 95.2%), which forms activated carbon with poorly developed porosity (S _BET = 306 m²/g, V _Σ = 0.15 cm³/g, and V _mi = 0.11 cm³/g).     

Activated carbon nanotubes-supported catalyst in fuel cells

The electrochemical property of platinum loaded on activated carbon nanotubes (Pt/ACNTs) was investigated by cyclic voltammograms (CVs) recorded in H₂SO₄ and H₂SO₄/CH₃OH aqueous solutions, respectively. Compared to 0.0046 A/cm² of Pt-loaded on pristine carbon nanotubes (Pt/CNTs) with a S_BET of 164 m²/g and 0.0042 A/cm² of conventional carbon black (Pt/C, Vulcan XC-72) with a S_BET of ∼250 m²/g, a better electrochemical activity (a high current density of 0.0070 A/cm² for weak-H₂ adsorption/desorption) of the Pt/ACNTs with high specific surface area (S_BET) of 830-960 m²/g was obtained. Furthermore, the highest current density of 0.079 A/cm² at 0.65 V in anodic sweep was observed during the methanol oxidation. On the basis of Pt size, utility ratio, and electro-active specific surface area (EAS), the Pt/ACNTs with a high Pt-loading of 50 wt.% exhibited the best electrochemical activity. The present ACNTs may be an excellent support material for electrochemical catalyst in proton exchange membrane and direct methanol fuel cells.     

Preparation of activated carbon derived from Jatropha curcas fruit shell by simple thermo-chemical activation and characterization of their physico-chemical properties

High surface area activated carbons were prepared by simple thermo-chemical activation of Jatropha curcas fruit shell with NaOH as a chemical activating agent. The effects of the preparation variables, which were impregnation ratio (NaOH:char), activation temperature and activation time, on the adsorption capacity of iodine and methylene blue solution were investigated. The activated carbon which had the highest iodine and methylene blue numbers was obtained by these conditions as follows: 4:1 (w/w) NaOH to char ratio, 800 °C activation temperature and 120 min activation time. Characterization of the activated carbon obtained was performed by using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and nitrogen adsorption isotherm as BET. The results present that the activated carbon possesses a large apparent surface area (S_BET = 1873 m²/g) and high total pore volume (1.312 cm³/g) with average pore size diameter of 28.0 Å.     

Preparation and characterization of mesoporous activated carbon from waste tires

Activated carbons were produced from waste tires and their characteristics were investigated. Rubber separated from waste tires was first carbonized at 500 °C in N₂ atmosphere. Next, the obtained chars were activated with steam at 850 °C. As a result, fairly mesoporous activated carbons with mesopore volumes and BET surface areas up to 1.09 cm³/g and 737 m²/g, respectively, were obtained. To further improve the porous properties of the activated carbons, the char was treated with 1 M HCl at room temperature for 1 day prior to steam activation. This treatment increased mesopore volumes and BET surface areas of the activated carbons up to 1.62 cm³/g and 1119 m²/g, respectively. Furthermore, adsorption characteristics of phenol and a dye, Black 5, on the activated carbon prepared via acid treatment were compared with those of a commercial activated carbon in the liquid phase. Although the prepared carbon had a larger micropore volume than the commercial carbon, it showed a slightly lower phenol adsorption capacity. On the other hand, the prepared carbon showed an obviously larger dye adsorption capacity than the commercial carbon, because of its larger mesopore volume.     

Hierarchical porous carbon obtained from animal bone and evaluation in electric double-layer capacitors

Animal bone, an abundant biomass source and high volume food waste, had been converted into a hierarchical porous carbon in a simple two-step sustainable manner to yield a highly textured material. The structures were characterized by nitrogen sorption at 77 K, scanning electron microscopy and X-ray diffraction. The electrochemical measurement in 7 M KOH electrolyte showed that the porous carbon had excellent capacitive performances, which can be attributed to the unique hierarchical porous structure (abundant micropores with the size of 0.5–0.8 and 1–2 nm, mesopores and macropores with the size of 2–10 and 10–100 nm), high surface area (S_BET = 2157 m²/g) and high total pore volume (V_t = 2.26 cm³/g). Its specific capacitance was 185 F/g at a current density of 0.05 A/g. Of special interest was the fact that the porous carbon still maintained 130 F/g even at a high current density of 100 A/g.     

Preparation of ultra-thin PAN-based activated carbon fibers with physical activation

This study elucidates the stabilization and activation in forming activated carbon fibers (ACFs) from ultra-thin polyacrylonitrile (PAN) fibers. The effect of stabilization time on the properties and structure of resultant stabilized fibers was investigated by thermal analysis, X-ray diffraction (XRD), elemental analysis, and scanning electron microscopy (SEM). Stabilization was optimized by the pyrolysis of ultra-thin PAN fibers in air atmosphere at 280°C for 15 min, and subsequent activation in steam at 1000°C for 0.75 to 15 min. Resultant ACFs were characterized by N₂ adsorption at 77 K to evaluate pore parameters, XRD to evaluate structure parameters, and field emission scanning electron microscopy (FESEM) to elucidate surface morphology. The produced ACFs had surface areas of 668–1408 m²/g and a micropore volume to total pore volume ratio from 78 to 88%. Experimental results demonstrate the surface area and micropore volume of 1408 m²/g and 0.687 cm³/g, respectively, following activation at 1000°C for 10 min. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of chars and activated carbons from Saskatchewan lignite

Saskatchewan lignite was used as a precursor to prepare carbonaceous adsorbents for use as SO₂ adsorbent from flue gases. The lignite was carbonized producing char in a fixed bed microreactor system at different temperatures from 350 to 550 ^°C in nitrogen atmosphere. The chars obtained at 475 ^°C for 120 min exhibited the highest micropore surface area (136 m²/g) and volume (0.062 cm³/g) and the smallest median pore diameter (∼ 0.7 nm). Carbon dioxide and steam were used as activating agents. Activation of char at optimum conditions of 650–675 ^°C for 15 min with carbon dioxide and steam resulted in a further increase in micropore surface area (220 and 186 m²/g for CO₂ and steam, respectively) and volume (0.090 and 0.085 cm³/g for CO₂ and steam, respectively). The yield of char was 64 wt.%, while the yields of activated carbon were 60 and 57 wt.% for CO₂ and steam activation, respectively; all based on the mass of original lignite.     

Nanoporosity development in the thermal-shock KOH activation of brown coal

Thermal-shock KOH activation of brown coal (800 °C, KOH/coal ratio 1 g/g) was shown to produce nanoporous activated carbon with more developed surface area than thermally-programmed heating (S_BET up to 1700 vs 1000 m²/g). Increasing the KOH/coal ratio (up to 1 g/g) in the activated mixture increases the total pore volume (0.14–1.0 cm³/g), the micropore volume (0.03–0.71 cm³/g), and also the volume of subnanometer pores (0.01–0.40 cm³/g). Thermal shock produces nanoporosity at lower KOH/coal ratios (0.5-1.0 g/g) than respective low-rate heating KOH activation.     

High power supercapacitors using polyacrylonitrile-based carbon nanofiber paper

Porous carbon nanofiber paper has been obtained by one-step carbonization/activation of PAN-based nanofiber paper at temperatures from 700 to 1000 °C in CO₂ atmosphere. The paper was used as supercapacitor electrode without any binder or percolator. At low temperature, e.g., ?900 °C, nitrogen enriched carbons with a poorly developed specific surface area (S_BET ? 400 m²/g) are obtained. In aqueous electrolytes, these carbons withstand high current loads without a noticeable decrease of capacitance, and the normalized capacitance reaches 67 μF/cm². At 10 s time constant, the values of energy and power densities are 3-4 times higher than for activated carbons (AC) presenting higher specific surface area. By carbonization/activation at 1000 °C, subnanometer pores are developed and S_BET = 705 m²/g. Despite moderate BET specific surface area, the capacitance reaches values higher than 100 F/g in organic electrolyte. At high power densities, the nanofiber paper obtained at 1000 °C outperforms the energy density retention of ACs in organic electrolyte. The high power capability of the carbon nanofiber papers in the two kinds of electrolytes is attributed both to the high intrinsic conductivity of the fibers and to the high diffusion rate of ions in the opened mesopores.     

Preparation and characterization of spherical activated carbons from oil agglomerated bituminous coals for removing organic impurities from water

A new and simple method of producing of spherical activated carbons (SACs) from different bituminous coals, i.e., gas coal, gas-coking coal and orthocoking coal, is presented. Coal agglomerates of spherical shape obtained by oil agglomeration using rapeseed oil and linseed oil, were subjected to carbonization and activation with steam at 850 °C. The SACs prepared from gas-coking coal (hvAb) agglomerates were characterized by the best developed porous structure with surface area S_BET of about 800 m²/g and pore volume of 0.40 cm³/g. The adsorption capacity of the produced SACs was determined in terms of substituted phenolic compounds. The adsorption of 2-chlorophenol (OCP), 4-chlorophenol (PCP) and 4-nitrophenol (PNP) from aqueous solutions was studied under a static conditions on the SAC prepared from gas-coking coal agglomerated using rapeseed oil. At high concentrations of the solute the adsorption behavior of OCP was found to be different in comparison to PCP and PNP. The adsorption of the two last phenolic compounds on the selected SAC is very well described by Langmuir adsorption model. For OCP a two-stepped adsorption isotherm was obtained. The Langmuir isotherm equation fits very well only for the first stage of the OCP adsorption.     

Acid catalyst influence on the polymerization time of polyfurfuryl alcohol and on the porosity of monolithic vitreous carbon

This study compares the influence of different acid catalysts on the polymerization rate of polyfurfuryl alcohol (PFA) precursor and especially on the respective porosity of Monolithic Vitreous Carbon (MVC) produced from that. Five acid catalysts commonly used were compared: p‐toluenesulfonic (PTLS), hydrochloric, sulfuric, nitric, and phosphoric. A fixed molar concentration of catalyst was diluted in PFA resin under room pressure and temperature. The time dependence of PFA resin polymerization was investigated by optical transmittance of PFA films, and the polymerization degree, characterized by ATR spectroscopy and thermogravimetry. MVC samples prepared with the same PFA resin and each catalyst were carbonized up to 1200 °C, under inert atmosphere. MVC porosity was studied by nitrogen adsorption/desorption, and by SEM and optical microscopy. Higher polymerization degree and higher residual mass were obtained with faster catalysts. No direct relation between the polymerization rate and the acid force was observed. PTLS promoted the fastest PFA polymerization process and the sulfuric acid, the slowest one. MVC samples were obtained by slow carbonization. MVC presented low specific surface S_BET from 1.4 to 7.4 m²/g. Nitric acid catalyst contributed the most to micropores formation. Micrometric apparent porosity was smaller for the catalysts having longer polymerizations times, such as phosphoric and sulfuric acid. Phosphoric catalyst corresponded to the lowest porosity in MVC. As the polymerization time increased, the average size of the micrometric surface pores tended to augment. The MVC macroscopic porosity increased with the S_BET increment. Acid catalysts choice exerted a fundamental role on the porosity of MVC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43272.     

Carbon adsorbents from waste ion-exchange resins

A series of activated carbons was prepared from different waste commercial ion-exchange resins and studied by means of adsorption, SEM and IR methods. Samples were additionally washed or washed/frozen. This resulted in increases in micro- and mesoporosity in comparison with initial activated carbons. For some samples, the latter treatment gives enhancement of mesoporosity but reduction of microporosity and vice versa comparing with only washed carbons due to different localization of water droplets in mesopores or micropores. Changes in the morphology of chars and activated samples depended on resin composition and history. Relatively high values of porosity (V_p ≈ 0.4 cm³/g) and specific surface area (S_BET ≈ 600 m²/g) show that activated carbons prepared from waste ion-exchange resins can be utilized for different purposes, especially after additional treatment (such as washing, impregnation by certain compounds and subsequent thermal activation).     

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     

Optimization of mesoporous alumina sol-gel synthesis by Taguchi and response surface methodology

Taguchi method (TM) and response surface methodology (RSM) have been employed to optimize three parameters, including the amounts of P123, the amounts of nitric acid and calcination temperature, in order to define an optimal setting for sol-gel synthesis of high surface area mesoporous alumina powder (MA). Herein, the comparison of the both statistical approaches has been examined and discussed considering the nitrogen adsorption as the response variable because this important character for mesoporous materials is exceedingly sensitive to the synthesis parameters. The BET surface area (S_BET) and pore volume of MA under Taguchi optimal condition were 323.5 m² g⁻¹ and 0.551 cm³ g⁻¹, respectively, by conducting confirmation test. Furthermore, the confirmation test showed high S_BET of MA (363.4 m² g⁻¹), which was in a good agreement with calculated S_BET result (431.25 m² g⁻¹) by a quadratic model under RSM optimal condition. Moreover, 3D response surface plots and 2D contour plots of desirability have been discussed to visualize the influence of input factors on response variable. It is also concluded that RSM shows more appropriate (12.33% higher S_BET than TM) and efficient optimal condition with determining a quadratic function as the relationship between S_BET and synthesis parameters.     

A study of the characteristics of activated carbons produced by steam and carbon dioxide activation of waste tyre rubber

This paper presents a study into the effect of different activation conditions on the porosity and adsorption characteristics of carbon adsorbents produced from waste tyre rubber. For the purpose of this work, three carbon series were produced using different activation temperatures (between 925 and 1100 °C) and oxidising agents (steam or carbon dioxide). Carbons produced to different degrees of burn off were characterised using gas (nitrogen) and liquid phase (phenol, methylene blue and Procion Red H-E2B) adsorption. Total micropore volumes and BET surface areas increased almost linearly with the degree of activation to 0.554 ml/g and 1070 m²/g, respectively, while the development of external surface area was particularly rapid at degrees of activation above 50 wt% burn off. Steam was observed to generate a narrower but more extensive microporosity than carbon dioxide. However, carbon dioxide produced carbons of slightly larger external surface areas. Activation at higher temperatures resulted in pores of slightly larger dimensions, although this was only evident in highly activated samples. Porosity characteristics were reflected in the capacity of the carbons to adsorb species of different molecular size from solution. In this respect, steam-activated carbons presented greater capacities for the adsorption of smaller molecular size compounds (phenol), while carbon dioxide-activated carbons adsorbed larger textile dyes more effectively.     

Functionalisation and chemical characterisation of cellulose-derived carbon aerogels

A series of nitrogen- and oxygen-functionalised carbon aerogels was produced from a carbon aerogel derived from cellulose acetate. Samples were oxidised by H₂O₂ or HNO₃ and/or enriched in nitrogen by reaction with gaseous ammonia or co-heating of the carbon aerogel and melamine. Porosity variations and morphology were monitored using N₂ adsorption and helium pycnometry. The surface chemistry was characterised by elemental analysis, FTIR and XPS spectroscopy, pH of the point of zero charge and acid/base titration. The prepared carbons are mainly mesoporous and show a moderate porosity development (S_BET between 160 and 300 m²/g). The applied chemical methods allow producing a wide range of functionalised carbon aerogels differing in terms of oxygen and nitrogen groups, their distribution and basicity. Both oxidation methods introduce a similar amount of oxygen, while the produced carbons differ in term of their acid/base character. Treatment with ammonia produces the most basic materials, which is partly due to the introduction of basic nitrogen groups, but also to the reduction of the acidic oxygen functionalities.     

Removal of methylene blue from aqueous solution by a carbon-microsilica composite adsorbent

Microsilica, one kind of industrial solid waste material, was utilized firstly to prepare a carbon-microsilica composite adsorbent (CMS). The prepared adsorbent was characterized with XPS, SEM and Gas sorption experiments. The results indicated the SO₃H groups, which are very effective in capturing cationic organic dye, were introduced onto the surface of CMS; the Brunauer-Emmett-Teller (BET) surface area (S _BET ) and total pore volume (V _total ) of CMS reach 51m²/g and 0.045 cm³/g, respectively. Meanwhile, the possibility of the utilization of the adsorbent for removal of methylene blue (MB) from aqueous solution was investigated. The effect of pH, contact time and initial MB concentration for MB removal were studied. Equilibrium data were modeled using the Langmuir, Freundlich and Dubinin-Radushkevich equations to describe the equilibrium isotherms. It was found that data fit to the Langmuir equation better than the Freundlich equation. Maximum monolayer adsorption capacity was calculated at different temperatures (298, 308, and 318 K) reach 251.81, 283.76 and 309.70 mg/g, respectively. It was observed that adsorption kinetics obeys the pseudo-first-order equation.