Activated carbon from cherry stones by chemical activation: Influence of the impregnation method on porous structure

Cherry stones are utilized as a precursor for the preparation of activated carbons by chemical activation with phosphoric acid (H₃PO₄). The activation process typically consists of successive impregnation, carbonization, and washing stages. Here, several impregnation variables are comprehensively studied, including H₃PO₄ concentration, number of soaking steps, H₃PO₄ recycling, washing of the impregnated material, and previous semi-carbonization. The choice of a suitable impregnation methodology opens up additional possibilities for the preparation of a wide variety of activated carbons with high yields and tailored porous structures. Microporous activated carbons with specific surface areas of ～800 m² g^?1 are produced, in which > 60% of the total pore volume is due to micropores. High surface areas of ～1500 m² g^?1 can be also developed, with micropore volumes being a 26% of the total pore volume. Interestingly, using the same amount of H₃PO₄, either carbons with surface areas of 791 and 337 m² g^?1 or only one carbon with a surface area of 640 m² g^?1 can be prepared. The pore volumes range very widely between 0.07–0.55, 0.01–0.90, and 0.09–0.79 cm³ g^?1 for micropores, mesopores, and macropores, respectively.     

Hydrothermal and conventional H3PO4 activation of two natural bio-fibers

Two phosphoric acid activation procedures; Activation after Hydrothermal Impregnation (recently published) and Activation after Incipient Wetness Impregnation instead of conventional impregnation are analyzed in two natural bio-fiber precursors: banana pseudostem and coconut fiber matting. Both procedures are compared analyzing, in both precursors, the influence that variables such as H₃PO₄/precursor ratio, activation temperature and impregnation time have on the resulting activated carbons (ACs) properties. The work also pays special attention to the mesoporosity development and the application of these ACs to adsorb gasoline vapors.Both H₃PO₄ activation procedures develop activated carbons having suitable activation yields and porosity developments, giving the Activation after Incipient Wetness Impregnation method better results than the Activation after Hydrothermal Impregnation. Both natural bio-fibers are good precursors, rendering the coconut fiber matting better results than the banana pseudostem. The variables studied affect the porosity development, being precursor and H₃PO₄/precursor ratio the variables that most affect. By a suitable selection of these variables, activated carbons having high adsorption capacities (BET above 2500 m² g^?1 and micropore volume above 1.00 cm³ g^?1) and well developed mesoporosity (reaching 1.41 cm³ g^?1), can be prepared. Most of the samples prepared perform very well for adsorbing gasoline vapors, showing a linear relationship with their resulting volumes.     

Removal of chlorinated phenol from aqueous solution utilizing activated carbon derived from papaya (<Emphasis Type="Italic">Carica Papaya</Emphasis>) seeds

Activated carbons (ACs) were prepared from papaya seeds with different dry weight impregnation ratios of zinc chloride (ZnCl₂) to papaya seeds by using a two-stage self-generated atmosphere method. The papaya seeds were first semi-carbonized in a muffle furnace at 300 °C for 1 h and then impregnated with ZnCl₂ before activation at 500 °C for 2 h. Several physical and chemical characteristics such as moisture, ash, pH, functional groups, morphological structure and porosity of prepared ACs were studied and presented here. AC2, with the impregnation ration of 1: 2 (papaya seeds: ZnCl₂), yielded a product that had the highest adsorption capacity, 91.75%, achieved after 180min contact time. The maximum Brunauer, Emmett and Teller (BET) surface area of AC2 was 546m²/g. Adsorption studies indicated that AC2 complied well with the Langmuir isotherm (q _m =39.683mg g^?1) and the pseudo-second-order (q _e =29.36mg g^?1). This indicated that chemisorption was the primary adsorption method for AC2. The intraparticle diffusion model proved that the mechanism of adsorption was separated into two stages: the instantaneous stage and the gradual adsorption stage. Overall, this work demonstrated the suitability of using papaya seeds as a precursor to manufacture activated carbon.     

Microwave treated activated carbon from industrial waste lignin for endosulfan adsorption

BACKGROUND: Disposal of large amounts of recurring industrial waste lignin is a big problem for the paper industries and there is need for a rational alternative to utilize this waste lignin. Thus highly porous activated carbons (ACs) were prepared from lignin using H₃PO₄ as an activating chemical with and without microwave treatment in a self‐generated environment at 600 °C and the influence of different types of impregnation on the adsorption–desorption capacities of endosulfan from a liquid phase was studied. RESULT: The maximum adsorption capacities (X_m) for ACs prepared by a microwave treatment and using a simple impregnation method were 6.2422 mg g^?1 and 3.9557 mg g^?1, respectively. Equilibrium adsorption time determined from kinetic experiments was 5 h and the experimental kinetic data were described by a pseudo‐second‐order rate model. Surface characteristics and desorption patterns showed considerable difference between the two ACs with the microwave treated AC showing less hysteresis, greater X_m and established overall superiority over the other. CONCLUSION: Use of microwave treatment produced more oxygen surface functional groups. Results indicate that surface chemistry of the microwave treated sample is more important than the textural properties for the higher adsorption of endosulfan. The microwave treated sample also resulted in less hysteresis and fewer carbonyl surface groups. Desorption patterns cannot be predicted from adsorption alone. Copyright © 2011 Society of Chemical Industry     

Zirconia with Defined Particle Morphology and Hierarchically Structured Pore System Synthesized via Combined Exo‐ and Endotemplating

Highly porous zirconia with defined particle morphology can be prepared by impregnation of spherical activated carbon as an exotemplate with a zirconia nanoparticle sol. The resulting zirconia spheres show a particle size distribution between 0.2 and 0.4 mm and exhibit high specific surface areas and specific pore volumes up to 104 m²g^–1 and 0.56 cm³g^–1, respectively. Addition of a triblockcopolymer (TBC) as an endotemplate during the synthesis leads to the formation of an additional pore system. The corresponding spherical zirconia products possess a hierarchically structured pore system with a bimodal pore size distribution with maxima at ca. 3 and 20 nm. The relative fraction of pores originating from the endotemplate can be varied by changing the endotemplate content in the zirconia nanoparticle sol. The presence of the TBC also has an influence on the specific surface area and the specific pore volume. Using the ratio of TBC to zirconium of n_TBC/n_Zr = 0.027, a material can be prepared that exhibits a specific surface area and a specific pore volume of 161 m²g^–1 and 0.62 cm³g^–1, respectively. These values are more than twice as high as for zirconia prepared by a conventional precipitation method (68 m²g^–1 and 0.11 cm³g^–1, respectively).     

Preparation of ordered porous carbon from tea by chemical activation and its use in Cr(VI) adsorption

Ordered porous carbon was prepared from a new carbon precursor??the tea leaves, the most widely used beverage worldwide by a chemical activation process. We obtained well developed spherical interlinked meso and micro pores with uniform pore morphology and high surface area from green, black and waste tea by NaOH as well as H₃PO₄ activation process. The carbon obtained from green tea by H₃PO₄ activation had the highest BET surface area of 1,285?m²g^?1 with total pore volume of 0.6243?mL?g^?1. The as prepared porous carbon showed high adsorption efficiency of Cr(VI) adsorption from aqueous solution.     

Ordered mesoporous carbon prepared from triblock copolymer/novolac composites

Ordered mesoporous carbon is synthesized by the organic–organic self-assembly method with novolac as carbon precursor and two kinds of triblock copolymers (Pluronic F127 and P123) as template. The hexagonal structure and a worm-hole structure are observed by TEM. The carbonization temperature is determined by TG and FT-IR. Characterization of physical properties of mesoporous carbon is executed by N₂ absorption–desorption isotherms and XRD. The mass ratios of carbon precursor/template affect the textural properties of mesoporous carbon. The mesoporous carbon with F127/PF of 1/1 has lager surface area (670 m² g^?1), pore size (3.2 nm), pore volume (0.40 cm³ g^?1), smaller microporous surface area (368 m² g^?1) and wall thickness (3.7 nm) compare to that with F127/PF of 0.5/1 (576 m² g^?1, 2.7 nm, 0.29 cm³ g^?1, 409 m² g^?1 and 4.3 nm, respectively). The mesoporous carbon prepared by carbonization at high temperature (700 °C) exhibits lager surface area, lower pore size and pore volume than the corresponding one obtained at 500 °C. The structure and order of the resulting materials are notably affected with types of templates. The mesoporous carbon with P123 as template exhibits worm-hole structure compare to that with F127 as template with hexagonal structure. In general, the pore size of mesoporous carbon with novolac as precursor is smaller than that with resorcinol–formaldehyde as precursor.     

The adsorption kinetics of sodium dodecylbenzenesulfonate on activated carbon. Branched-pore diffusional model revisited and comparison with other diffusional models

Abstract

The adsorption rate of sodium dodecylbenzenesulfonate (SDBS) on three commercial activated carbons (ACs) and an AC synthesized from almond shells was investigated in this study. The mechanisms controlling the overall adsorption rate of SDBS on ACs were found out by using the pore volume and surface diffusion model (PVSDM). The PVSDM showed that the intraparticle diffusion of SDBS in all ACs was mainly attributed to pore volume diffusion and surface diffusion. The surface diffusion coefficient, D_s, in all samples of ACs are influenced by the amount of surfactant adsorbed at equilibrium, q_e, as well as the mean micropore width, L₀. The contribution of surface diffusion to the overall intraparticle diffusion ranged from 45 to 70%, depending on the properties of AC. Moreover, the branched-pore diffusional model was revisited (BPDMR) assuming that the Fick diffusion is the only diffusion mechanism in the macropores and the diffusion in the micropores was represented by the micropore rate coefficient, K_C. Besides, it was proposed that the parameter f representing the mass fraction of SDBS adsorbed on macropores, can be estimated from the textural properties of ACs. Three new strategies were proposed to analyze the experimental data using BPDMR model, and it was demonstrated that the macropore diffusivity in BPDMR is close to the molecular diffusivity of SDBS in water solution. The micropore rate constant, K_C, ranged from 3.90?×?10^?6 to 10.6?×?10^?6 s^?1 and was affected by textural characteristics of ACs. Both models predicted the global adsorption rate of SDBS on ACs satisfactorily.     

Activated carbon from sewage sludge for removal of sodium diclofenac and nimesulide from aqueous solutions

Sludge based activated carbons (ACs) were used to remove selected pharmaceuticals such as diclofenac (DCF) and nimesulide (NM) from aqueous solutions. The powered sewage sludge was mixed with different proportions of ZnCl₂. The mixture was pyrolyzed in a conventional oven using three different temperatures under inert atmosphere. Afterwards, in order to increase the specific surface area and uptake capacity the carbonized materials were acidified with 6mol L^?1 HCl under reflux at 80 °C for 3 hours. The characterization of ACs was achieved by scanning electron microscopy, FTIR, TGA, hydrophobicity index by water, n-heptane vapor adsorption and nitrogen adsorption/desorption curves. The specific surface area (S _BET ) of adsorbents varied between 21.2 and 679.3m²g^?1. According to the water and n-heptane analysis data all ACs had hydrophobic surface. Experimental variables such as pH, mass of adsorbent and temperature on the adsorption capacities were studied. The optimum pH, mass of adsorbent and temperature for adsorption of DCF and NM onto ACs were found to be 7.0 (DCF) and 10.0 (NM), 30mg and 25 °C, respectively. The kinetic adsorption was investigated using general-order, pseudo-first order and pseudo-second order kinetic models, while the general-order model described the adsorption process most suitably. The maximum amounts of DCF and NM adsorbed were 156.7 and 66.4mg g^?1 for sample 1(500-15-0.5), respectively.     

Tuning morphology of mesoporous titanium oxides through fluorinated surfactants-based systems

Four different fluorinated surfactant-based systems were used as template for the synthesis of highly ordered TiO₂ mesoporous materials with large-pore wormhole structures. The calcined materials exhibit large pore diameters (up to 5.9 nm), high surface areas (900–1,180 m² g^?1), pore volumes (0.90–1.25 cm³ g^?1) and thick pore walls (4.6–7.7 nm) depending of the synthesis route. It is established that the self-aggregation behavior of fluorinated amphiphile systems can be manipulate and provides a rich phase behavior to obtain well-organized titania sieves with adjustable pore size and surface topography. By comparison to titania and silica sieves obtained by the same procedure, it can be established that there is a deep interaction between head groups of fluorinated surfactants and Ti(IV)(iPrO)₄ showing that the inorganic precursor has a great influence on the properties of the final materials.     

Preparation and Characterization of Activated Carbon from Eucalyptus Sawdust I. Activated by NaOH

Eucalyptus sawdust was used as a precursor to prepare activated carbon using NaOH as a chemical activation agent. The effect of preparation conditions on the characteristics of the produced activated carbon used as an adsorbent was investigated. The performance of the activated carbon was characterized by N₂ adsorption–desorption isotherms, Brunauer–Emmett–Teller equation, Barett–Joyner–Halenda equation, scanning electron microscopy and Fourier transform infrared analysis. When the eucalyptus sawdust mass was 30.00 g, with particle sizes between 0.25 and 0.42 mm, and the sawdust was heated and charred before activation by NaOH, the optimized conditions for the preparation of activated carbon was found to be as follows: mass ratio of NaOH to eucalyptus sawdust, 1:2; activation time, 30 min; and activation temperature, 700 °C. The Iodine number and BET surface area of the produced activated carbon was 899 and 1.12 × 10³ m² g^?1, respectively, with a 13.3 % yield. Activated carbon exhibits adsorption isotherms of type IV. The total pore volume, micropore volume and average pore diameter were recorded as 0.636, 0.160 cm³ g^?1 and 2.27 nm, respectively. The pore structure of the activated carbon is mainly mesoporous. Carbonyl and hydroxyl groups may also exist on the activated carbon surface.     

A new approach to obtain mesoporous-activated carbon via hydrothermal carbonization of Brazilian Cerrado biomass combined with physical activation for bisphenol-A removal

Abstract

The worrying hydric crisis and the increasing water contamination by emerging pollutants around the world stimulate the development of activated carbons (AC) for the removal of endocrine disruptors, including bisphenol-A (BPA). For this reason, a new approach for the synthesis of AC from hydrochar produced through hydrothermal carbonization (HTC) of Brazilian Cerrado biomass (Magonia pubescens–Sapindaceae) and physical activation using water vapor is highlighted. Compared to the traditional method of physical activation after pyrolysis, HTC was found to be better option to develop the specific surface area, porosity, and yield of the ACs, which presented mesoporous structure and carbon content higher than 80%. The BPA adsorption was evaluated by varying the contact time, BPA concentration, and pH. The Langmuir, Freundlich, and Redlich–Peterson isotherms were used to model the adsorption behavior. In the preliminary test to verify the adsorption efficiency, the AC obtained from hydrochar treated at 180?°C presented better results compared to commercial AC. The BPA adsorption data of the best treated hydrochar correlated well with the pseudo first-order model and the Langmuir isotherm (Q_max = 21.26?mg g^?1). The results of the studies indicated the combination of HTC and physical activation with steam to be an efficient way to prepare an ecologically sound adsorbent for removal of Bisphenol-A from water with lower temperature and without chemical reagents. The ACs obtained can also be potential materials for other applications, such as in the field of catalysis and environmental remediation.     

Worm-hole structured mesoporous carbon monoliths synthesized with amphiphilic triblock copolymer

In the present work, mesoporous carbon monoliths with worm-hole structure had been synthesized through hydrothermal reaction by using amphiphilic triblock copolymer F127 and P123 as templates and resole as carbon precursor. Synthesis conditions, carbonization temperature and pore structure were studied by Fourier transform infrared, thermogravimetric analysis, transmission electron microscopy and N₂ adsorption–desorption. The results indicated that the ideal pyrolysis temperature of the template is 450 °C. The organic ingredients were almost removed after further carbonized at 600 °C and the mesoporous carbon monoliths with worm-hole structure were obtained. The mesoporous carbon synthesized with P123 as single template exhibited larger pore size (6.6 nm), higher specific surface area (747 m² g^?1), lower pore ratio (45.9 %) in comparison with the mesoporous carbon synthesized with F127 as single template (with the corresponding value of 4.9 nm, 681 m² g^?1, 49.6 %, respectively), and also exhibited wider pore size distribution and lower structure regularity. Moreover, the higher mass ratio of template P123/resole induced similar pore size, larger specific surface area and lower pore ratio at the same synthesizing condition. It was also found that the textural structure of mesoporous carbon was affect by calcination atmosphere.     

Tape casting of polysiloxane-derived ceramic with controlled porosity and surface properties

Tape casting has been applied to produce porous hybrid and SiOC ceramic tapes using ceramic precursors and commercially available polysiloxanes as polymeric binders. SiC particles of two different mean sizes (4.5 or 6.5?μm) were used as inert fillers to prevent shrinkage and increase mechanical stability. Macroporosity was adjusted by varying the azodicarbonamide (ADA) content from 0 to 30?wt.%. Decomposition of the polysiloxanes at 600?°C resulted in the generation of micropores with high specific surface area (187–267 m²?g^?1) and a predominant hydrophobic behavior. At 1000?°C mainly meso/macroporosity were observed (SSA: 32–162 m²?g^?1) accompanied by increased hydrophilicity. The influence of ADA content, SiC size, and pyrolysis temperature on open porosity (2.5–37%), average pore size (<0.01–1.76?μm), surface characteristics, and flexural strength (10.5–121?MPa) were investigated. The porous tapes with different surface characteristics and controlled structure are highly promising for applications involving membrane processes, particularly microfiltration systems (0.1–10?μm).     

Decomposition of H2O2 on activated carbon obtained from olive stones

Activated carbons were prepared from olive oil solid wastes by treatment in different schemes: impregnation with H₃PO₄ followed by pyrolysis at 300–700 °C, by steam pyrolysis at 600–700 °C, or by conventional steam activation at 850 °C. Porosity characteristics were determined by analysis of nitrogen adsorption isotherms, and carbons of widely different properties and surface pH values were obtained. Decomposition of H₂O₂ in dilute unbuffered solution was followed by measuring evolved oxygen volumetrically. First‐order kinetics was followed, and the catalytic rate coefficients were evaluated. The carbons tested showed appreciable activity where evolved oxygen attained ≈10% of the stoichiometric amount in 1 h. The degree of decomposition showed inverse dependence on surface area, pore volume and mean pore dimensions. The chemical nature of the surface, rather than the porosity characteristics, was the principal factor in enhancing the disproportionation of H₂O₂ on the activated carbon surface. © 2001 Society of Chemical Industry     

A novel method for production of activated carbon from waste tea by chemical activation with microwave energy

This study presents the production of activated carbon from waste tea. Activated carbons were prepared by phosphoric acid activation with and without microwave treatment and carbonisation of the waste tea under nitrogen atmosphere at various temperatures and different phosphoric acid/precursor impregnation ratios. The surface properties of the activated carbons were investigated by elemental analysis, BET surface area, SEM, FTIR. Prior to heat treatment conducted in a furnace, the mixture of the waste tea and H₃PO₄ was treated with microwave heating. The maximum BET surface area was 1157 m²/g for the sample treated with microwave energy and then carbonised at 350 °C. In case of application of conventional method, the BET surface area of the resultant material was 928.8 m²/g using the same precursor and conditions. According to the Dubinin–Radushkevich (DR) method the micropore surface area for the sample treated with microwave energy was higher than the sample obtained from the conventional method. Results show that microwave heating reasonably influenced the micropore surface area of the samples as well as the BET surface area.The samples activated were also characterised in terms of the cumulative pore and micropore volumes according to the BJH, DR and t-methods, respectively.     

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     

Electrochemical capacitors based on highly porous carbons prepared by KOH activation

Various coal and pitch-derived carbonaceous materials were activated for 5 h at 800 °C using potassium hydroxide and 1:4 component ratio. Porosity development of the resultant activated carbons (ACs) was assessed by N₂ sorption at 77 K and their capability of the charge accumulation in electric double layer was determined using galvanostatic, voltammetric and impedance spectroscopy techniques. ACs produced from different precursors are all microporous in character but differ in terms of the total pore volume (from 1.05 to 1.61 cm³ g⁻¹), BET surface area (from 1900 to 3200 m² g⁻¹) and pore size distribution. Very promising capacitance values, ranging from 200 to 320 F g⁻¹, have been found for these materials operating in acidic 1 mol l⁻¹ H₂SO₄ electrolytic solution. The variations in the electrochemical behavior (charge propagation, self-discharge, frequency response) are considered in relation to the porous texture characteristics, elemental composition but also possible effect of structural ordering due to various precursor materials used. Cycling investigation of all the capacitors has been also performed to compare ability of the charge accumulation for different carbon materials during subsequent cycles.     

Solvothermal polycondensation of novolacs phenolic-resin to nanopowders and their derived activated nanocarbons as efficient adsorbents for water cleaning

Novolacs phenolic-resin (PF) was easily polycondensed into polymeric powders with sizes and morphologies ranging from microspheres to nanoparticles by a simple solvothermal process without adding any crosslinking agent. Activating the highly divided PF powders by CO₂ resulted in nanosize activated carbons with high specific surface area (2092 m² g^?1) and large pore volume (1.33 cm³ g^?1) while preserving a high carbon yield of about 38 wt%. As for adsorption tests, the micropore-dominated activated nanocarbons exhibited fast and high adsorption capabilities towards both Cr(VI) ions and bulky rhodamine B molecules due to their much improved external surface area and the greatly shortened intra-particle diffusion distance. The equilibrium adsorption amounts of Cr(VI) and RB on the activated nanocarbons as estimated by the Langmuir model were 200 and 990 mg g^?1, achieved within an adsorption time of 30 and 360 min, respectively.     

Nanoarchitectonics of Nanoporous Carbon Materials from Natural Resource for Supercapacitor Application

Nanoarchitectonics of nanoporous carbon materials (NCMs) derived from natural resource; Areca Catechu Nut (ACN) with enhanced electrochemical supercapacitance properties is reported. ACN powder is chemically activated in a tubular furnace at 400?°C and the effect of activating agent sodium hydroxide (NaOH), zinc chloride (ZnCl₂) and phosphoric acid (H₃PO₄) on the textural properties, surface functional groups and electrochemical supercapacitance properties was thoroughly examined. We found that ACN derived NCMs are amorphous in nature comprising of macropores, micropores and hierarchical micro- and mesopore architecture depending on the activating agent. Surface area and pore volume are found in the range 25–1985 m² g^?1 and 0.12–3.42 cm³ g^?1, respectively giving the best textural properties for H₃PO₄ activated NCM. Nevertheless, despite the different chemical activating agent used, all the prepared NCMs showed similar oxygen-containing surface functional groups (carboxyl, carboxylate, carbonyl and phenolic groups). The H₃PO₄ activated NCM showed excellent supercapacitance properties giving a high specific capacitance of ca. 342 F g^?1 at a scan rate of 5 mV s^?1 together with the high cyclic stability sustaining capacitance retention of about 97% after 5000 charging/discharging cycles. Electrochemical supercapacitance properties have demonstrated that the ACN derived novel nanoporous carbon material would be a potential material in energy storage application.