Development of activated carbon from vine shoots by physical and?chemical activation methods. Some insight into activation mechanisms

Activated carbons (ACs) are prepared from vine shoots (VS) by the method of physical activation in air, CO₂ and steam atmospheres and by the method of chemical activation with H₃PO₄, ZnCl₂ and KOH aqueous solutions. The ACs were characterized texturally by N₂ adsorption at −196 °C, mercury porosimetry, and density measurements. The method of chemical activation has been proved to be more effective than the method of physical activation to prepare ACs with a well-developed porosity. ACs with high micro- and mesopore volumes are prepared with ZnCl₂ and H₃PO₄. Using ZnCl₂, the volume of micropores is 0.62 cm³ g⁻¹ and the volume of mesopores is 0.81 cm³ g⁻¹. A greater development of macroporosity is obtained by KOH activation. The volume of macropores is as high as 1.13 cm³ g⁻¹ for the resulting AC. Yield of the process of preparation of the ACs is low for the method of chemical activation. Some insights into the performance of the activating agents in the activation process are provided.     

Effect of pore characteristics on electrochemical capacitance of activated carbons

Activated carbons (ACs) for electric double layer capacitors (EDLCs) were fabricated from waste tea leaves, activated with the pore-forming substances ZnCl₂ then, carbonized at high-temperature in N₂ atmosphere. The surface texture and porosity of the ACs were determined using transmission electron micros-copy and N₂ adsorption/desorption studies. The surface area of the 20 wt % ZnCl₂ treated sample was found to be 1029 m²g^?1 and had a distribution of micropores and mesopores. The electrochemical properties of the ACs were evaluated by using cyclic voltammetry and galvanostatic charge-discharge studies. ACs from waste tea leaves exhibited excellent specific capacitance as high as 196 F g^?1 in the 0.1 M Na₂SO₄ neutral electrolyte, with rectangular-like cyclic voltammetry curves at a cell potential of 1.5 V and good cyclability with a capacitance retention of 95% at a high current density of 100 mA g^?1 for 2000 cycles. The results show that the pore texture properties and specific surface area of ACs are dominated by changing carbonization temperature and the amount of activating agent ZnCl₂. The electrochemical performance is influenced mainly by surface area, but the pore size distribution becomes a dominating factor for specific capacitance of a carbon electrode material when the pore structure is in range of micropores/mesopores.     

Adsorption of oxygen-containing aromatics used in petrochemical,pharmaceutical and food industries by means of lignin based active carbons

The adsorption processes of three aromatic chemicals onto activated carbons (ACs) from aqueous solutions have been studied. Eucalyptus kraft lignin obtained from cellulose industry as a residual biomass has been used to prepare activated carbons by physical activation with CO₂. The influences of the activation time on the surface areas and pore volumes of the ACs were analyzed. The physicochemical properties and the surface chemical structure of the adsorbents have been studied by means of N₂ and CO₂ adsorption, ultimate analysis, XPS, TPD and SEM. XPS and TPD spectra of the ACs have suggested the presence of aromatic rings and carbon-oxygen functional groups in the solid surfaces. The potential use of the ACs for the removal of acetaminophen (paracetamol), salicylic acid and benzoic acid has been investigated at different pH, temperature and contact time. The adsorption equilibrium data have been correlated to Langmuir isotherm model. The thermodynamic study has been developed, the values of ΔH, ΔG, and ΔS have been calculated and they indicated that the processes are endothermic for acetaminophen and exothermic for salicylic and benzoic acids. The analysis of the kinetic experiments showed that the effective diffusivities are low; 10⁻¹² to 10⁻¹¹ cm²/s, and they are the corresponding to intraparticle mass transfer, which appears as the controlling step for the net adsorption processes.     

Equilibrium,kinetics and thermodynamics study of phenols adsorption onto activated carbon obtained from lignocellulosic material (<Emphasis Type="Italic">Eucalyptus Globulus labill</Emphasis> seed)

Activated carbon was prepared from lignocellulosic material (Eucalyptus Globulus labill seed) by chemical activation with ZnCl₂ at two different concentrations (10 and 25 % m/v) named ACS25 and ACS10. The textural characteristics of the activated carbons (ACs) were determined by N₂ adsorption isotherms; these exhibit B.E.T. surface areas of 250 and 300 m² g^?1 for ACS25 and ACS10, respectively, with micropore volume contents of 0.140 and 0.125 cm³ g^?1 in the same order. In addition, the FTIR and Boehm methods were conducted for the chemical characterisation of ACs, where many groups with basic character were found, which favours the adsorption of phenols. The prepared carbonaceous adsorbents were used in the adsorption of wide pollutants monosubstituted phenol derivatives: phenol, 4-nitrophenol and 4-chlorophenol. The effect of temperature on the thermodynamics, kinetic and equilibrium of phenols adsorption on ACs was thoroughly examined. The adsorption kinetics adjusted properly for a pseudo-second-order kinetic model. However, the Elovich model (chemisorption) confirms that phenols adsorption did not occur via the sharing of electrons between the phenolic ring and basal plane of ACs because is not properly adjusted, so the process is given by physisorption. The thermodynamic parameters [i.e. Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°)] were also evaluated. The overall adsorption process was exothermic and spontaneous in nature. The values found in the thermodynamic study, confirm that the adsorption process corresponds to a clearly physical process.     

Influence of KMnO4 oxidation on the electrochemical performance of pitch-based activated carbons

In this work, activated carbons (ACs) are obtained from petroleum pitch by the combination of a chemical treatment with different potassium permanganate (KMnO₄) amounts, i.e., 0, 0.5, 1.0, and 2.0 g, and a chemical activation with KOH at a constant KOH/pitch ratio of 3/1. The effects of the chemical activating agent on the surface morphology and porosity are evaluated with scanning electron microscopy and N₂ adsorption isotherms at 77 K, respectively. The specific surface area of the pitch-based ACs is increased with increasing the amount of KMnO₄ pre-treatment and showed the highest value of 2,334 m² g^?1 at 2 g of KMnO₄ amount. The electrochemical performance of AC electrodes is examined by cyclic voltammetry and galvanostatic charge/discharge characteristics in 6 M KOH electrolyte. Among the prepared ACs, 2.0 K-ACs possesses a specific capacitance as high as 237 F g^?1 and showed excellent electrochemical performance due to its suitable porous structure and low interface resistance.     

Surface structural and energetic heterogeneity of carbon materials prepared from corn grains using steam and H3PO4‐steam activations

The porous activated carbons (ACs) were prepared from corn grains through physical (steam) and chemical–physical (H₃PO₄‐steam) activations. The effects of steam activation temperature (700–900 °C) on pore development, surface roughness, and energetic heterogeneity were investigated in both activations. Also, the effect of prior carbonization on H₃PO₄‐steam activation was studied. The physical properties, surface fractal dimensions, and adsorption energy distributions of ACs were determined from nitrogen adsorption–desorption isotherm data. Both physical and chemical–physical activations show that the AC with higher surface area, relatively smoother surface, and energetically heterogeneous surface could be produced at a maximum steam activation temperature (900 °C). Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and characterization of activated carbon from bagasse fly ash

Activated carbons from bagasse fly ash (BFA) were prepared by one step chemical activation using ZnCl₂ as activating agent, or combination method of chemical with CO₂ physical activation (physicochemical activation). The development of porosity was studied in correlation with the method of activation, activation temperature, and also the chemical weight ratio. A typical sample by the combination method at 600 °C and weight ratio of ZnCl₂:BFA = 2 exhibited micropore volume of 0.528 cc/g, mesopore volume of 0.106 cc/g and surface area of 1200 m²/g. For determining the adsorption capacity of the carbon samples in solutions, phenol and methylene blue equilibrium adsorption experiments were conducted. The properties and adsorption capacity of the synthesized activated carbons has been compared to commercial activated carbon (Norit^® SX Plus).     

Hydrothermal modification of carbon adsorbents

The effects of high-pressure autoclave treatments on porous structure and surface properties were studied for a variety of activated carbons (AC, synthetic and produced from plum stones) treated with water vapour, hydrogen peroxide (10–50%) or 10% aqueous ammonia solution at relatively low temperatures (250, 350, 400^○C). Surface and structural parameters of modified ACs were determined using nitrogen, water, ammonia and benzene adsorption isotherms. It was found that the effects of AC modification resulting in changes in their porous structure and surface chemistry depend on the kind of initial ACs, modifier type and concentration of modifier and treatment temperature. At the same conditions synthetic ACs are modified to a larger extent than ACs prepared using natural raw materials. Repeated treatment of a given carbon intensifies changes in its porous structure.     

Preparation of active carbons from corn stalk for butanol vapor adsorption

Active carbons(ACs) were prepared through chemical activation of biochar from whole corn stalk(WCS)and corn stalk pith(CSP) at varying temperatures using potassium hydroxide as the activating agent. ACs were characterized via pore structural analysis and scanning electron microscopy(SEM). These adsorbents were then assessed for their adsorption capacity for butanol vapor. It was found that WCS activated at900 °C for 1 h(WCS-900) had optimal butanol adsorption characteristics. The BET surface area and total pore volume of the WCS-900 were 2330 m2/g and 1.29 cm3/g, respectively. The dynamic adsorption capacity of butanol vapor was 410.0 mg/g, a 185.1% increase compared to charcoal-based commercial AC(143.8 mg/g).     

Calorimetric evaluation of activated carbons modified for phenol and 2,4-dinitrophenol adsorption

Two commercial activated carbons with differences in their superficial chemistry, one granular and the other pelletised, were modified for use in phenol and 2,4-dinitrophenol adsorption. In this paper, changes to the activated carbon surface will be evaluated from their immersion calorimetry in water and benzene, and they will then be compared with Area BET, chemical parameters, micropore size distributions and hydrophobicity factors of the modified activated carbons. The activated carbons were modified using 60 % solutions of phosphoric acid (H₃PO₄), nitric acid (HNO₃), zinc chloride (ZnCl₂) and potassium hydroxide (KOH); the activated carbon/solution ratio was 1:3 and impregnation was conducted 291 K for a period of 72 h before samples were washed until a constant pH was obtained. Water immersion calorimetry showed that the best results were obtained from activated carbons modified with nitric acid, which increased from ?10.6 to ?29.8 J g^?1 for modified granular activated carbon, and ?30.9 to ?129.3 J g^?1 for pelletised activated carbon. Additionally, they showed the best results in phenol and 2.4-dititrophenol adsorption. Those results indicate that impregnation with nitric acid under the employed conditions could generate a greater presence of oxygenated groups on their surface, which favours hydrogen bond formation and the increased adsorption of polar compounds. It should also be noted that immersion enthalpy in benzene for modified activated carbon with nitric acid is the method with the lowest value, which is consistent with the increased presence of polar groups on its surface. Regarding hydrophobicity factors, it was observed that granular carbons modified with nitric acid and potassium hydroxide have the lowest ratios, indicating greater interaction with water.     

Transformation of Residual Açai Fruit (Euterpe oleracea) Seeds into Porous Adsorbent for Efficient Removal of 2,4-Dichlorophenoxyacetic Acid Herbicide from Waters

Brazil’s production and consumption of açai pulp (Euterpe oleracea) occur on a large scale. Most of the fruit is formed by the pit, which generates countless tons of residual biomass. A new purpose for this biomass, making its consumption highly sustainable, was presented in this study, where activated carbon (AC) was produced with zinc chloride for later use as an adsorbent. AC carbon formed by carbon and with a yield of 28 % was satisfactorily used as an adsorbent in removing the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Removal efficiency was due to the highly porous surface (Vp = 0.467 cm³ g⁻¹; Dp = 1.126 nm) and good surface área (SBET = 920.56 m² g⁻¹). The equilibrium data fit the Sips heterogeneous and homogeneous surface model better. It was observed that the increase in temperature favored adsorption, reaching a maximum experimental capacity of 218 mg g⁻¹ at 328 K. The thermodynamic behavior indicated a spontaneous, favorable, and endothermic behavior. The magnitude of the enthalpy of adsorption was in agreement with the physical adsorption. Regardless of the herbicide concentration, the adsorbent displayed fast kinetics, reaching equilibrium within 120 min. The linear driving force (LDF) model provided a strong statistical match to the kinetic curves. AC with zinc chloride (ZnCl₂), created from leftover açai biomass, is a potential alternative as an adsorbent for treating effluents containing 2,4-D.     

活性炭孔隙结构对催化氧化脱除单质汞的影响

研究活性炭在硫化氢存在条件下催化氧化脱除煤气中单质汞的吸附机理和探讨提高其吸附能力的方法,在模拟煤气气氛下对3种活性炭和一种活性焦进行汞的吸附性能实验,并进一步分析活性炭(焦)的孔隙结构。用BET方程处理N₂等温吸附数据,计算比表面积;用HK法进行微孔分析;用BJH法计算中孔孔径分布。结果表明,硫化氢被催化氧化后,生成吸附在活性炭孔壁上的活性硫促进了对汞的吸附;随着活性炭微孔和中孔体积的增大,活性炭对汞的吸附能力得到提高。     

Chemical modification of activated carbon monoliths for CO2 adsorption

The development of materials with potential application for CO₂ capture is a topic of great scientific interest. Activated carbons (AC) can be conveniently used as CO₂ adsorbents thanks to their microporous structure and tunable chemical properties. In this work, two AC honeycomb monoliths were synthesized starting from African palm stones through activation either with H₃PO₄ or with ZnCl₂ solution. Surface functionalization was performed in order to add nitrogen groups, aiming at an enhancement of CO₂ adsorption capacity. This chemical modification was performed either with ammonia in gas phase or a with 30 % ammonium hydroxide aqueous solution on both AC monolith samples. The original and modified monoliths were characterized by N₂ adsorption at 77 K, infrared spectroscopy, Boehm titration, and immersion calorimetry in benzene and water. CO₂ adsorption on both raw and functionalized AC monoliths was evaluated in volumetric equipment at a temperature of 273 K and until 1 bar, and adsorption capacity ranging between 120 and 220 mg_CO2 g _AC ^?1 was obtained. The experimental results indicated that both methods of chemical modification determined an increase in the content of superficial nitrogen groups and thus an increase in CO₂ adsorption capacity, the treatment with ammonium hydroxide being slightly preferable.     

Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

孔结构对活性炭吸附水溶液中铅离子的影响

选取三种表面化学性质相近的活性炭(AC),通过等温吸附实验考察活性炭对水溶液中铅离子的吸附性能,利用扫描电子显微镜(SEM)观察活性炭的表面微观形貌,通过低温(77 K)液氮吸附测定活性炭的比表面积和孔容,并分别以密度泛函理论(DFT)和Barrett-Joyner-Halenda (BJH)法计算微孔和中孔的孔径分布.结果表明:选用的三种活性炭AC1、AC2、AC3在比表面积和总孔容上呈依次下降的趋势,但表面开放孔均匀分布的AC2,具有最高的饱和吸附量,孔结构类似颗粒堆积孔的AC3,具有与表面开放孔分布集中的AC1相近的饱和吸附量;通过对孔结构与吸附量的关联分析可知,在活性炭吸附铅离子的过程中, 0.4-0.6 nm的孔是有效吸附孔, 10.5-20.6 nm、20.6-55.6 nm、5.2-10.5 nm三个区间的孔则会对吸附产生阻碍作用.     

Effects of activation conditions on the structural and adsorption characteristics of pinecones derived activated carbons

This study was conducted to understand and optimize the activation process for the production of a low-cost activated carbon (AC) using a renewable and plentiful biomass waste, pinecones. This was achieved by tracking the changes in porous structure, surface chemistry and adsorption properties of the AC produced using different activating agents, activation temperatures, holding times and heating rates. Generally, produced ACs were predominantly microporous with small external surface area and were different in terms of H/C and O/C ratios. Study of Pb²⁺ cations adsorption on these samples proved the high affinity of the pinecones derived ACs to this cation. The best adsorption behaviour was recognized in sample prepared by impregnation with H₃PO₄ at weight ratio of 2, then heating at 400?°C for 2?h at 5?°C/min heating rate. This sample possessed the highest BET surface area (1335 m²/g). The adsorption process obeyed the pseudo-first-order and Freundlich model slightly better than the pseudo-second-order kinetics and Langmuir model. The high Langmuir maximum adsorption capacity of 418?mg/g supports the applicability of the produced AC for the removal of Pb²⁺ cations from wastewater.     

Microporous Activated Carbon from Pisum sativum Pods Using Various Activation Methods and Tested for Adsorption of Acid Orange 7 Dye from Water

Highlights

• •Pisum sativum pods was used for producing porous activated carbon materials.
• •Two chemical methods and two gases were used in the activation processes.
• •Higher performances were achieved by applying ZnCl₂ and CO₂ for activation.
• •The products exhibited large surface areas and high AO7 dye adsorption performances.
• •RMS study of the AO7 dye removal by produced material was reported.

AbstractThis work demonstrates the preparation of high-surface-area activated carbon (AC) from Pisum sativum pods using ZnCl₂ and KOH as activating agents. The influence of CO₂ and N₂ gases during the carbonization process on the porosity of AC were studied. The highest specific surface area of AC was estimated at 1300 to 1500 m²/g, which presented characteristics of microporous materials. SEM micrographs revealed that chemical activation using an impregnation reagent ZnCl₂ increases the porosity of the AC, which in turn leads to an increase in the surface area, and the SEM image showed that particle size diameter ranged between 48.88 and 69.95 nm. The performance of prepared AC for adsorption of Acid Orange 7 (AO7) dye was tested. The results showed that the adsorption percentage by AC (2.5 g/L) was equal to 94.76% after just 15 min, and the percentage of removal increased to be ~100% after 60 min. The maximum adsorption capacity was 473.93 mg g⁻¹. A Langmuir model (LM) shows the best-fitted equilibrium isotherm, and the kinetic data fitted better to the pseudo-second-order and Film diffusion models. The removal of AO7 dye using AC from Pisum sativum pods was optimized using a response factor model (RSM), and the results were reported.     

Preparation and characterization of activated carbon from cotton stalks in a two-stage process

Activated carbons are prepared from cotton stalks by chemical activation with ZnCl₂, H₂SO₄ and physical activation using CO₂ and steam-CO₂ mixture for temperatures of 750, 850 and 900 °C. The effects of activation temperature and duration time, impregnation concentration of agent, impregnation times, and physical activating agent are examined. These materials are characterized by adsorption/desorption of N₂ to determine the BET areas, thermogravimetric analysis (TG, DTA), FTIR and scanning electron microscopy (SEM). ZnCl₂ under CO₂ atmosphere was found more effective than H₂SO₄ as a chemical reagent under identical conditions in terms of porosity development. The maximum BET surface area is found to be 2053 m²/g for active carbons produced with ZnCl₂ activation under CO₂ atmosphere.     

Synthesis of Nanostructured Carbon through Ionothermal Carbonization of Common Organic Solvents and Solutions

A combination of ionothermal synthesis and hot‐injection techniques leads to novel nanocarbons made from organic solvents. Controlled addition of commonly used organic solvents into a hot ZnCl₂ melt gives rise to spherical, sheetlike, and branched nanofibrous carbon nanoparticles with surprisingly high carbon efficiency. When heteroatom‐containing solvents were used, the doping levels reach up to 14 wt. % nitrogen and 13 wt. % sulfur. Materials with high surface areas and large pore volumes of solvent carbons as high as 1666 m² g^?1 and 2.80 cm³ g^?1 in addition to CO₂ adsorption capacities of 4.13 mmol g^?1 at 273 K and 1 bar can be obtained. The new method works not only for pure carbon materials, but was also extended for the synthesis of carbon/inorganic nanocomposites. ZnS@C, Ni@C, and Co@C were successfully prepared with this straightforward procedure. The obtained Ni@C nanocomposites perform well in the electrocatalytic water oxidation, comparable with commercial noble‐metal catalysts.     

Preparation of activated carbon from sawdust by zinc chloride activation

A series of activated carbons were prepared from sawdust by zinc chloride activation in different operation conditions. The effects of operation parameters such as impregnation ratio, activation temperature and time on the adsorption properties of activated carbons were measured and analyzed in order to optimize these operation conditions. The experimental results show that under the experimental circumstances studied, both the yield and the adsorption for iodine and methylene blue of activated carbon can reach a relatively higher value in the chemical activation process with the impregnation ratio of 100% ZnCl₂/sawdust in the activation temperature of 500 °C carbonized for 60–90 minutes which are the optimum activation conditions in making wood activated carbon. The most important operation parameter in chemical activation with zinc chloride was found to be the impregnation ratio.