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.     

Influence of preparation conditions on porous structures of olive stone activated by H3PO4

An olive factory residue was used as a precursor in the preparation of granular activated carbon by chemical activation with H₃PO₄. Effects of final activation temperature, time, and H₃PO₄ concentration used in the impregnation stage on the porous development were investigated. SO₂ adsorption experiments were also performed for some of the activated carbon samples to represent their adsorption performance. Activation at low temperature represented that micropores were developed first at early stages of the temperatures. Mesoporosity developed at around 250 °C, enhanced up to 400 °C, and then started to decrease due to possibly shrinking of pores. The optimum temperature for olive stone was found to be around 400 °C on the basis of total pore volume and BET surface area. It was clearly demonstrated that H₃PO₄ concentration used in the impregnation stage was not only effective for development of surface area and pore volumes but also an effective tool for tailoring the pore structure and size distribution.     

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.     

Adsorption Characteristics of Microporous Carbons from Apricot Stones Activated by Phosphoric Acid

Crushed apricot stone shells were impregnated with varying H₃PO₄ acid concentrations (20–50 wt%), followed by carbonisation at 573–773 K. The products were characterised by nitrogen gas adsorption. Analysis of the nitrogen isotherms by the DR and α_s methods proved that most of the obtained carbons are highly microporous, with high surface areas (⩾1000 m² g^-1) and very low mesoporosity. Increasing acid concentration, at 573 and 673 K, increases surface area and pore volume, whereas at 733 K a small decrease in both parameters appears at higher H₃PO₄ concentrations. Whole apricot stones produce activated carbon of inferior porous characteristics. Development of the extensive pore structure was described in light of the effect of H₃PO₄ on the lignocellulosic mataerial during carbonisation.     

Preparation, characterization and Methylene Blue adsorption of phosphoric acid activated carbons from globe artichoke leaves

Activated carbons were prepared by the pyrolysis of artichoke leaves impregnated with phosphoric acid at 500 °C for different impregnation ratios: 100, 200, 300 wt.%. Materials were characterized for their surface chemistry by elemental analysis, “Boehm titrations”, point of zero charge measurements, infrared spectroscopy, as well as for their porous and morphological structure by Scanning Electron Microscopy and nitrogen adsorption at 77 K. The impregnation ratio was found to govern the porous structure of the prepared activated carbons. Low impregnation ratios (~ 100 wt.%) led to essentially microporous and acidic activated carbons whereas high impregnation ratios (> 100 wt.%) gave essentially microporous-mesoporous carbons with specific surface areas as high as 2038 m²·g^− 1, pore volume as large as 2.47 cm³·g^− 1, and a slightly acidic surface. The prepared activated carbons were studied for their adsorption isotherms of Methylene Blue at pH = 3 and pH = 9. The supermicroporous structure of the material produced at 200 wt.% H₃PO₄ ratio was found to be appropriate for an efficient adsorption of this dye controlled by dispersive and electrostatic interactions depending on the amount of oxygen at the surface.     

Synthesis of High Surface Area MgAl2O4 Nanopowder as Adsorbent for Leather Dye Removal

Abstract

MgAl₂O₄ nanopowder has been prepared by alkoxides hydrolysis with further calcination at temperature of 700°C. The adsorption of a leather dye, Direct Black 38, onto this material was investigated. The sample was characterized by X-ray-diffraction (XRD), N₂ adsorption–desorption isotherm and Fourier transform infrared spectroscopy. The results showed that sample present a pure phase, and the average nanocrystal size of 8 nm, the BET surface area is about 206.5 m² · g^?1 and total pore volume is about 1.44 cm³ · g^?1. Adsorption kinetics data were modeled by film and pore diffusion model. The experimental isotherm was described by the Langmuir model. MgAl₂O₄ nanopowder presented a great removal efficiency of leather dye by adsorption process, with a maximum adsorption capacity of 833 mg of dye per gram of adsorbent.     

Activated carbon from sugar cane bagasse by carbonization in the presence of inorganic acids

Dried ground bagasse, impregnated with 50% inorganic acids and carbonized at 500°C, showed the sequence H₃PO₄ > H₂SO₄ > HCl > HNO₃, with respect to the efficiency of activation. Treatment with phosphoric acid of various concentrations (30–50 wt%) was followed by carbonization at 300–500°C for 3 h. Pore structure parameters were determined from the low-temperature adsorption of nitrogen, by applying the BET and α_s methods. Activated carbons obtained at low temperatures are essentially microporous with a low degree of mesoporosity. At higher temperatures products of higher surface area and total pore volume with developed mesoporosity and low microporosity are formed. An increase in the period of carbonization leads to a small decrease in both surface area and pore volume. Activated carbons with surface areas > 1000 m² g^?1 and mean pore dimensions around 2·0 nm, suitable for various purposes, are thus obtained.     

Physical and chemical properties of carbons synthesized from xylan, cellulose, and Kraft lignin by H3PO4 activation

Physical and chemical properties of activated carbons produced from commercial xylan, cellulose, and Kraft lignin by H₃PO₄ activation at various process conditions were studied. The results show that the more reactive the precursor under acidic conditions, the easier the porosity development, particularly mesoporosity. In addition, Boehm titration and Fourier Transform Infrared Spectroscopy (FTIR) characterization results demonstrated that the functional groups on the surfaces of these carbons consist of both temperature-sensitive and temperature-insensitive components. The temperature-sensitive component is primarily caused by the hydrolysis of raw materials under acidic conditions at low temperature, and the reaction between activation mixture and oxygen in the process of activation, particularly at low impregnation ratio. These surface groups decompose at high temperature. The temperature-insensitive contribution is mainly composed of phosphorus-containing groups arising from the reaction of H₃PO₄ (or pyro- and polyphosphoric acids) with precursor, and carbonyl-containing groups. This part of surface functional group is stable, even at high activation temperatures. This study also confirmed that the nature of precursor, impregnation ratio between H₃PO₄ and precursor, and activation temperature are important factors affecting the properties of final activated carbon products.     

Coconut kernel-derived activated carbon as electrode material for electrical double-layer capacitors

Carbonization of milk-free coconut kernel pulp is carried out at low temperatures. The carbon samples are activated using KOH, and electrical double-layer capacitor (EDLC) properties are studied. Among the several samples prepared, activated carbon prepared at 600 °C has a large surface area (1,200 m² g^?1). There is a decrease in surface area with increasing temperature of preparation. Cyclic voltammetry and galvanostatic charge–discharge studies suggest that activated carbons derived from coconut kernel pulp are appropriate materials for EDLC studies in acidic, alkaline, and non-aqueous electrolytes. Specific capacitance of 173 F g^?1 is obtained in 1 M H₂SO₄ electrolyte for the activated carbon prepared at 600 °C. The supercapacitor properties of activated carbon sample prepared at 600 °C are superior to the samples prepared at higher temperatures.     

Preparation and pore characterization of activated carbon from Ma bamboo (Dendrocalamus latiflorus) by H3PO4 chemical activation

High specific surface area activated carbon materials have been produced from the naturally occurring Ma bamboo (Dendrocalamus latiflorus) using phosphoric acid (H₃PO₄) as the activating agent. The effects of different sizes of raw materials, H₃PO₄ concentrations, and activation temperatures on the specific surface area, pore morphology, and mass yield of activated carbon are presented. A high specific surface area for activated carbon derived from Ma bamboo was achieved under the optimized conditions of 45 wt% H₃PO₄ impregnation concentration, activation temperature of 400 °C, and a holding time of 120 min. Chemical activation of Ma bamboo by H₃PO₄ is a useful technique for obtaining activated carbon with desired pore size distributions and pore morphologies from low cost precursors and at low activation temperatures.     

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.     

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.     

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     

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.     

Spherical microporous/mesoporous activated carbon from pulping black liquor

BACKGROUND: A simple and effective method with environmental and economic benefits has been developed to produce spherical lignin and spheroidal microporous/mesoporous activated carbon from pulping black liquor. RESULTS: Spherical lignin with regular size of about 100 nm was obtained at 90 °C after 8 h treatment at pH 2. Pyrolysis of spherical lignin was impregnated with H₃PO₄ producing spheroidal microporous/mesoporous activated carbon with high apparent Brunauer–Emmett–Teller (BET) surface area of 1972 m² g^?1 and high carbon content of 68.0 wt% at 700 °C with impregnation ratio of 1:7. CONCLUSION: The process was inexpensive, sustainable, environment‐friendly and suitable for large‐scale production. Copyright © 2011 Society of Chemical Industry     

The effect of mechanical grinding on the mesoporosity of steam‐activated palm kernel shell activated carbons

BACKGROUND: Palm kernel shell activated carbon (OPSA) produced by steam gasification at high temperatures generally results in high surface areas of 1146 to 1600 m² g^?1, attributed to the high volume of micropores (0.43 to 0.56 cm³ g^?1). The mesoporosity of naturally occurring activated carbons is observed to increase with decreasing particle size. Mechanical grinding was therefore performed to investigate its effect on the mesoporosity and microporosity of OPSA. RESULTS: Mechanical grinding had a strong effect on mesopore volume and average pore diameter, with an increase in mesopore volume from 47 to 66% as particle size decreases. Interestingly, no significant effect on the micropore fraction was observed in ground OPSA particles. CONCLUSIONS: The mechanically ground OPSA particles possessed dual adsorption capabilities due to the high microporosity and moderate mesoporosity contained in the structures. This results in interesting porosity behaviour of palm kernel shell activated carbons and the potential to provide materials of distinct sorption capacities with minimal treatment. Copyright © 2009 Society of Chemical Industry     

KOH-activated depleted fullerene soot for electrochemical double-layer capacitors

Nanostructured activated carbons for electrochemical double-layer capacitors were synthesized from depleted fullerene soot (DFS) via KOH activation. The structural and textural properties of the activated DFS were studied using transmission electron microscopy, X-ray diffraction, and nitrogen sorption. Activated DFS with high specific surface areas (SSAs) of up to 2,153 m² g^?1 and narrow pore size distributions (PSDs) was obtained by controlling the KOH/DFS ratio. The activated DFS exhibited excellent capacitive behavior, with a high specific capacitance of 250 F g^?1 at a current density of 50 mA g^?1 in a 6 M KOH electrolyte, and a high rate performance, with a capacitance retention of up to 80 % at a high scan rate of 200 mV s^?1. Moreover, the activated DFS samples exhibited good electrochemical stability; high capacitance retention ratios of >90 % were obtained at a current density of 2,000 mA g^?1 for 5,000 cycles with cell voltages of 0.9 and 1.0 V in a two-electrode system. The high electrochemical performance can be attributed to high SSAs, narrow PSDs, and nanoscale particle sizes, which facilitate the formation of electrochemical double layers and rapid ion diffusion.     

Textural Characterization of Activated Carbons Prepared from Oil-palm Stones Pre-treated with Various Impregnating Agents

Activated carbons with relatively high densities and well-developed porosities were prepared from oil-palm stones which were pre-treated with different types of impregnating agents (ZnCl₂, H₃PO₄ or KOH). The benefits derived from impregnation in terms of higher BET surface areas were generally in the following order: 20% ZnCl₂ > 40% H₃PO₄ > 10% KOH. The textural properties such as density and total porosity, overall yield, BET and micropore surface areas and pore size distributions of the activated carbon were related to the concentration of the impregnating solution and the activation conditions (activation temperature and hold time). For the highest BET surface area obtained in this study, the optimum conditions for CO₂ activation were found to be at an activation temperature of 750°C for 1 hour from oil-palm stones pre-treated with 20% ZnCl₂ for 24 hours. Pore size distribution suggests the application of oil-palm-stone activated carbons as gas-phase adsorbents for air pollution control.     

SYNTHESIS OF ACTIVATED CARBON FROM JATROPHA SEED COAT AND APPLICATION TO ADSORPTION OF IODINE AND METHYLENE BLUE

This article provides evidence that jatropha seed coat residues can be used as a carbon source for preparing activated carbons that have good adsorption properties for iodine and methylene blue. Activated carbons were prepared using three different methods of activation, physical, chemical, and physico-chemical, for a range of activation temperatures (600°, 700°, 800°, and 900°C) and activation hold times (1, 2, and 3 h). The highest BET surface area (1479 m² g^?1) and the highest iodine adsorption (1511 mg g^?1) were obtained with physico-chemical activation at a temperature of 900°C and a hold time of 2 h. This activated carbon gave higher BET surface area and iodine adsorption than commercial activated carbon (1169.1 m² g^?1 and 1076 mg g^?1). The activated carbons prepared by physico-chemical activation at 900°C and 2 h were then tested for adsorption of methylene blue at a range of concentrations of methylene blue (100, 200, 300, 400, and 500 mg L^?1). It was found that a Langmuir isotherm gave a better fit (R ² = 0.999) to the observed adsorptions than a Freundlich isotherm (R ² = 0.884). For the adsorption kinetics, a pseudo-second-order model gave a better fit (R ² > 0.998, Δq _e  = 3.7%) than a pseudo-first-order model (R ² ≈ 0.95, Δq _e  = 85.6%). These results suggest that chemisorption is the rate-controlling step for the adsorption of methylene blue. The experimental results show that jatropha seed coat is a lignocellulosic waste precursor for preparation of activated carbon that is an alternative source for preparation of commercial-grade activated carbons.     

Activated Carbon Preparation from Lignin by H3PO4 Activation and Its Application to Gas Separation

Activated carbons were produced from corn straw lignin using H₃PO₄ as activating agent. The optimal activation temperature for producing the largest BET specific surface area and pore volume of carbon was 500 °C. The maximum BET specific surface area and pore volume of the resulting carbon were 820 m²g^–1 and 0.8 cm³g^–1, respectively. The adsorption isotherm model based on the Toth equation together with the Peng‐Robinson equation of state for the determination of gas phase fugacity provide a satisfactory representation of high pressure CO₂, CH₄ and N₂ adsorption. The kinetic adsorption results show that the breakthrough difference between CO₂ and CH₄ is not obvious, indicating that its kinetic separation performance is limited.