Surface and adsorptive properties of carbons prepared from biomass

A number of activated carbons were prepared from a locally available by-product, corncobs, under currently established activation schemes. Obtained carbons were characterized by N₂ adsorption at 77 K and the isotherms were analyzed by BET and α_s methods. Steam-activation at 900 °C produced a microporous carbon having the highest S^α of 788 m² g⁻¹, whereas activation with air at 350 °C produced a carbon of S^α = 321 m²/g and possess wider pores. KOH impregnation with char in ratio 1:1 (w/w) and impregnated in the same ratio with the raw material prior to pyrolysis at 700 °C for 1 h, gave CK700, K700 respectively. An additional sample was obtained by oxidizing part of K700 with conc. HNO₃. All three KOH carbons show pore structures much close to char itself which may be due to potassium salt left in pores and is not easily leached with repeated water washings. In addition, KOH is more effective on the precursor itself than on its char of already developed porosity. FT-IR spectra show an increase in oxygen functionalties on the carbon surface as a result of activation process and the bands become stronger in the spectra of the acid-treated sample. The oxidized carbon sample showed relatively higher uptake of Pb²⁺ and MB and its surface chemistry plays the key role in their adsorption, while sharp decrease was observed in the uptake of phenol and mono-nitrophenols from aqueous solutions. An SEM study showed that air activation produce obvious voids reflecting its erosive effect on the external carbon surface.     

An insight into the KOH activation mechanism through the production of microporous activated carbon for the removal of Pb cations

Chemical activation was used through direct mixing of KOH with maize stalks in the smallest amount of water to provide KOH-to-stalk ratios of 33, 50, 66 and 75% by weight. The KOH-treated stalks were carbonized at 700 °C to produce a series of four activated carbons, besides a non-activated sample that was prepared and carbonized at 550 °C. The porous properties of these carbons were characterized by the Langmuir, BET and Dubinin-Radushkevich linear equations as well as both α_s (alpha-s) and t methods based on nitrogen adsorption isotherms. The chemical reactions involved during the impregnation and the carbonization processes for these hydroxide/lignocellulose mixtures have been proposed. Deep insight has been obtained concerning the possible reactions mechanism. The results showed that the KOH ratio was found to be the basic indicator of micoporosity development. The increase in the concentration of KOH much increased the S^α values of the resulting carbons reaching a maximum limit at 66 wt% KOH with S^α of 1684 m²/g and micropore ratio of ∼85% displaying an inverse correlation thereafter. The thermal behaviour and the surface microstructure in addition to the surface functional groups of the maize stalks and their prepared carbons were investigated by TGA, SEM and FTIR. The investigated carbons took up significant amounts of Pb²⁺ ions from aqueous solutions, which are ascribed to both the porosity and surface chemical nature of the adsorbents.     

Optimization of nickel adsorption from aqueous solution by using activated carbon prepared from waste apricot by chemical activation

Waste apricot supplied by Malatya apricot plant (Turkey) was activated by using chemical activation method and K₂CO₃ was chosen for this purpose. Activation temperature was varied over the temperature range of 400-900 °C and N₂ atmosphere was used with 10 °C/min heat rate. The maximum surface area (1214 m²/g) and micropore volume (0.355 cm³/g) were obtained at 900 °C, but activated carbon was predominantly microporous at 700 °C. The resulting activated carbons were used for removal of Ni(II) ions from aqueous solution and adsorption properties have been investigated under various conditions such as pH, activation temperature, adsorbent dosage and nickel concentration. Adsorption parameters were determined by using Langmuir model. Optimal condition was determined as; pH 5, 0.7 g/10 ml adsorbent dosage, 10 mg/l Ni(II) concentration and 60 min contact time. The results indicate that the effective uptake of Ni(II) ions was obtained by activating the carbon at 900 °C.     

Preparation of activated carbons from used tyres by gasification with steam and carbon dioxide

Activated carbons were prepared from waste tyres by gasification with steam and carbon dioxide and their characteristics were investigated. A two-stage activation procedure (pyrolysis at 800 °C in N₂ atmosphere, followed by steam or carbon dioxide activation) was used for the production of activated samples. The effect of the activation temperature (750-900 °C) and the activation time (1-3 h) on the surface characteristics of the prepared carbon was investigated. Carbons produced to different degrees of burn-off were characterized by means of their nitrogen adsorption isotherms at 77 K. In both sets of experiments, the mesopore, micropore volume, and BET surface area increased almost linearly with the degree of activation. For burn-off values lower than 53%, the steam activation produced carbons with a narrower and more extensive microporosity and higher BET and external surface area than the carbon dioxide activation. As the activation proceeds (burn-off > 53%), a strong development of the mesoporosity in the carbons was observed and the micropores size distribution revealed broader micropores, that is, a more heterogeneous distribution.     

Carbon dioxide-activated carbons from almond tree pruning: Preparation and characterization

Activated carbons were prepared from almond tree pruning by non-catalytic and catalytic gasification with carbon dioxide and their surface characteristics were investigated. In both series a two-stage activation procedure (pyrolysis at 800 °C in nitrogen atmosphere, followed by carbon dioxide activation) was used for the production of activated samples. In non-catalytic gasification, the effect of the temperature (650-800 °C for 1 h) and the reaction time (1-12 h at 650 °C) on the surface characteristics of the prepared samples was investigated. Carbons were characterized by means of nitrogen adsorption isotherms at 77 K. The textural parameters of the carbons present a linear relation with the conversion degree until a value of approximately 40%, when they come independent from both parameters studied. The highest surface area obtained for this series was 840 m² g⁻¹. In the catalytic gasification the effect of the addition of one catalyst (K and Co) and the gasification time (2-4 h) on the surface and porosity development of the carbons was also studied. At the same conditions, Co leads to higher conversion values than K but this last gives a better porosity development.     

Effect of combined activation on the preparation of high porous active carbons from granulated post-consumer polyethyleneterephthalate

Activated carbons were prepared from granulated post-consumer PET by combined activation including heat treatment with sulphuric acid (chemical activation) followed by steam activation. The effect of activation time, temperature, impregnation coefficient in the activation process was studied in order to optimize those reception parameters. One of the most important parameter in combined activation of crushed PET was found to be impregnation coefficient. It was defined that the optimal impregnation coefficient is equal 28%. Activation temperature is another variability which has a significant effect on the pore volume evolution. The increasing of activation temperature enhances the surface area and pore volumes of active carbons. The yield of final product which composes of nearly 15% is the factor limited the activation temperature above 800 °C. Textural characteristics of the samples were carried out by performing N₂ adsorption isotherm at −196 °C. The obtained active carbons were mainly micro- and mesoporous and with BET apparent surface areas of up to 1030 m²/g. The adsorption capacity on methylene blue reaches 1.0 mmol/g, the sorption activity on iodine comes to 77%.     

Preparation of activated carbons from cherry stones by activation with potassium hydroxide

Using cherry stones, the preparation of activated carbon has been undertaken in the present study by chemical activation with potassium hydroxide. A series of KOH-activated products was prepared by varying the carbonisation temperature in the 400-900 °C range. Such products were characterised texturally by gas adsorption (N₂, −196 °C), mercury porosimetry, and helium and mercury density measurements. FT-IR spectroscopy was also applied. The carbons prepared as a rule are microporous and macroporous solids. The degree of development of surface area and porosity increases with increasing carbonisation temperature. For the carbon heated at 900 °C the specific surface area (BET) is 1624 m² g⁻¹, the micropore volume is 0.67 cm³ g⁻¹, the mesopore volume is 0.28 cm³ g⁻¹, and the macropore volume is 1.84 cm³ g⁻¹.     

Preparation and characterization of carbons for the retention of halogens in the condenser vacuum system of a thermonuclear plant

Activated carbons were prepared by air and carbon dioxide activation, from almond tree pruning, with the aim of obtaining carbons that reproduce the textural and mechanical properties of the carbons currently used in the filtering system of the condenser vacuum installation of a Thermonuclear Plant (CNA; Central Nuclear de Almaraz in Caceres, Spain), produced from coconut shell. The variables studied in non-catalytic gasification series with air were the temperature (215-270 °C) and the time (1-16 h) and the influence of the addition of one catalyst (Co) and the time (1-2 h) in catalytic gasification. In the case of activation with CO₂, the influence of the temperature (700-950 °C) and the time (1-8 h) was studied. The resulting carbons were characterized in terms of their BET surface, porosity, and pore size distribution. The N₂ adsorption isotherms at 77 K for both series showed a type I behaviour, typical of microporous materials. The isotherms showed that with both gasificant agents the temperature rise produced an increase in the carbon porosity. With regards to the activation time, a positive effect on the N₂ adsorbed volume on the carbons was observed. The best carbons of each series, as well as the CNA (carbon currently used in the CNA), were characterized by mercury porosimetry and iodine solution adsorption isotherms. The results obtained allowed to state that several of the carbons produced had characteristics similar to the carbon that is target of reproduction (which has S_BET of 741 m² g⁻¹, V_mi of 0.39 cm³ g⁻¹ and a iodine retention capacity of 429.3 mg g⁻¹): carbon C (gasification with CO₂ at 850 °C during 1 h), with S_BET of 523 m² g⁻¹, V_mi of 0.33 cm³ g⁻¹ and a iodine retention capacity of 402.5 mg g⁻¹, and carbon D (gasification with CO₂ at 900 °C during 1 h), whose S_BET is 672 m² g⁻¹, V_mi is 0.28 cm³ g⁻¹ and has a iodine retention capacity of 345.2 mg g⁻¹.     

Fabrication of densely distributed Si nanorods by Ar-ion bombardment

For the direct fabrication of densely distributed one dimensional nanostructures on Si substrates, Si (1 0 0) surfaces were bombarded by obliquely incident 3 keV Ar⁺ ions with a simultaneous supply of Mo seed atoms at various temperatures ranging from room temperature to 400 °C. The surface sputtered at room-temperature with Mo seeding was characterized by the nanocones pointing in the direction of the incident ion beam. In addition, they possessed a so-called “web” at their acute-angle side. This web decreased in size with an increase in the sputtering temperature. Thus, the projections fabricated at elevated temperatures were featured by the nanorod-like structure rather than conical structure. With increasing the sputtering temperature, projections decreased in base diameter (from ∼90 nm at 200 °C to ∼50 nm at 400 °C) while they increased in both length (from ∼160 nm at 200 °C to ∼240 nm at 400 °C) and numerical density (from ∼5 × 10⁷ mm⁻² at 200 °C to ∼1.2 × 10⁸ mm⁻² at 400 °C). The controlled fabrication of such densely distributed one dimensional nanoprojections on Si using ion beam technique, we believe, would open up a variety of applications such as nanoelectronics and optoelectronics devices.     

Electrical- and magneto-resistance control for magnetite nanoparticle sinter by regulation of heat treatment temperature

We investigated electrical- and magneto-resistance control in magnetite (Fe₃O₄) nanoparticle sinter (MNPS) by the regulation of heat treatment (HT) temperature. MNPS was produced from hematite (α-Fe₂O₃) nanoparticles (HNP’s) using a deoxidization reaction. The average size of HNP was 30 nm, and HT was carried out between 400 and 800 °C. X-ray diffraction, magnetization, electrical resistivity (ER), and magneto-resistivity (MR) measurements were performed at temperatures ranging from 5 to 300 K. The ER and MR behaviors were considerably different at HT temperatures above and below ∼600 °C. After HT below ∼600 °C, ER followed the Mott-type variable-range-hopping conduction, and MR showed large values over a wide temperature range. After HT above ∼600 °C, ER indicated a Verwey transition near 110 K and MR showed small values, except in the vicinity of the Verwey transition temperature. Changing the HT temperature altered the coupling between adjacent magnetite nanoparticles (MNPs) and affected the crystallinity of MNPS. Below ∼600 °C, ER and MR were dominated by grain-boundary conduction, while above ∼600 °C they were determined by inter-grain conduction. The application of a magnetic field to the grain-boundary region, which had random localized spins, caused a large enhancement in MR.     

Preparation and ozone-surface modification of activated carbon. Thermal stability of oxygen surface groups

The control of the surface chemistry of activated carbon by ozone and heat treatment is investigated. Using cherry stones, activated carbons were prepared by carbonization at 900 °C and activation in CO₂ or steam at 850 °C. The obtained products were ozone-treated at room temperature. After their thermogravimetric analysis, the samples were heat-treated to 300, 500, 700 or 900 °C. The textural characterization was carried out by N₂ adsorption at 77 K, mercury porosimetry, and density measurements. The surface analysis was performed by the Bohem method and pH of the point of zero charge (pH_pzc). It has been found that the treatment of activated carbon with ozone combined with heat treatment enables one to control the acidic-basic character and strength of the carbon surface. Whereas the treatment with ozone yields acidic carbons, carbon dioxide and steam activations of the carbonized product and the heat treatment of the ozone-treated products result in basic carbons; the strength of a base which increases with the increasing heat treatment temperature. pH_pzc ranges between 3.6 and 10.3.     

Synthesis and characterization of activated carbon from asphalt

Asphalt (cheap and available in huge amount in Jordan) was converted into activated carbon powder by chemical treatment with sulphuric and nitric acids at 450 °C. The final product was characterized and found effective as adsorbent material. Its cation exchange capacity reaches 191.2 meq/100-g carbons when treated with 30 wt% acid/asphalt ratio without airflow rate injection and 208 meq/100-g carbons when 6.5 ml air/min was injected into the surface of the asphalt during activation at the same acid/asphalt weight ratio of 30 and temperature 450 °C. The zero point of charge for this product was found to be stable at pH value around 3 in the range of initial pH between 3 and 10.     

Air-activated carbons from almond tree pruning: Preparation and characterization

In this work the results obtained in the preparation and characterization of carbons made from almond tree pruning by non-catalytic and catalytic gasification (using K and Co) with air are analyzed and discussed. The main aim was to obtain high quality activated carbons at the lowest possible cost. The variables studied have been the temperature (190-260 °C) and the time (1-10 h) in non-catalytic gasification and the influence of the catalyst type (K and Co, 1 wt.% referred to cation, at 190 °C and 1 h) and the time (1-4 h) in catalytic gasification with Co at 190 °C. The air flow rate used in all the series was 167 cm³ min⁻¹. In non-catalytic gasification the reaction normalized rate versus the conversion degree was maintained until a conversion value of 10% for the experiment made at 260 °C since, at lower temperatures, this rate drops quickly for low conversion values. The N₂ adsorption isotherms for the carbons of this series resemble type I, although there is an increase of N₂ adsorbed volume at relatively high pressures. A temperature rise produced an increase of the carbon porosity and BET specific surface (116-469 m² g⁻¹). The activation time has a positive effect on the N₂ volume adsorbed by the carbons. The isotherms shapes were similar to those previously commented. A concentration equal to 1 wt.% was used to study the influence of the catalyst type. Under the studied experimental conditions, Co drives to a bigger porosity development than K, although with both catalysts a very similar pore size distribution is obtained. The activation time, in the gasifications catalyzed with Co, gives rise to a very important porosity development in the carbons. This produces a strong increase of the carbon specific surface area with very high values in the 4 h experiment, in which a BET specific surface of 959 m² g⁻¹ was obtained.     

Dielectric relaxations above room temperature in DMPU derived polyaniline film

Dielectric measurements carried out on drop casted from solution of emeraldine base form of polyaniline films in the temperature range 30–300 °C revealed occurrence of two maxima in the loss tangent as a function of temperature. The activation energies corresponding to these two relaxation processes were found to be ∼0.5 eV and ∼1.5 eV. The occurrence of one relaxation peak in the dispersion curve of the imaginary part of the electric modulus suggests the absence of microphase separation in the film. Thermogravimetric analysis and infrared spectroscopic measurements showed that the films retained its integrity up to 300 °C. The dielectric relaxation at higher temperatures with large activation energy of 1.5 eV is attributed to increase in the barrier potential due to decrease in the polymer conjugation as a result of wide amplitude motion of the chain segments well above the glass transition temperature.     

Preparation and textural characterisation of activated carbon from vine shoots (Vitis vinifera) by H3PO4—Chemical activation

An abundant and low-cost agricultural waste as vine shoots (Vitis vinifera) (VS), which is generated by the annual pruning of vineyards, has been used as raw material in the preparation of powder activated carbon (AC) by the method of chemical activation with phosphoric acid. After size reduction, VS were impregnated for 2 h with 60 wt.% H₃PO₄ solution at room temperature, 50 and 85 °C. The three impregnated products were carbonised at 400 °C. The product impregnated at 50 °C was heated either first at 150-250 °C and then at 400 °C or simply at 350-550 °C in N₂ atmosphere. The time of isothermal treatment after each dynamic heating was 2 h. The carbons were texturally characterised by gas adsorption (N₂, −196 °C), mercury porosimetry, and density measurements. FT-IR spectroscopy was also applied. Better developments of surface area and microporosity are obtained when the impregnation of VS with the H₃PO₄ solution is effected at 50 °C and for the products heated isothermally at 200 and 450 °C. The mesopore volume is also usually higher for the products impregnated and heated at intermediate temperatures.     

Dual N/Pb ion-implanted Si: Temperature dependence of the novel shift of the Pb peak under electron beam annealing

(1 0 0) Si was dual ion-implanted with 24 keV N and 7 keV Pb to peak concentrations ∼10 at.%. Implanted samples were then electron beam annealed (EBA) at a peak temperature T for 30 s with T ranging from 100 °C to 900 °C and for 15 s at 1000 °C. Pb profiles were measured using RBS and surfaces characterised by AFM. For T up to 500 °C there was no shift in the profile from the implanted depth ∼10 nm. For higher values of T a striking feature was the large movement of the Pb profile away from the surface without a significant change in width or Pb content. The profile depths were: ∼40 nm for 600 °C, ∼68 nm for 700-900 °C and ∼80 nm for 1000 °C. The response to EBA was found to be strongly dependent on both ion implantation order and Si starting structure. For (1 0 0) Si nanowhiskers formed on the treated surfaces for T = 900 °C and 1000 °C. A model is developed based on the restructuring of the amorphous implanted layer under EBA. It is proposed that a compaction starting at the surface sweeps the Pb before it via a stress interaction as it advances into the Si.     

Effects of carbonization temperature on microstructure and electrochemical performances of phenolic resin-based carbon spheres

Activated phenol resin-based carbon spheres (APCS) electrodes with high double layer capacitance and good rate capability were prepared from phenol resin-based spheres (PS) at different carbonization temperatures prior to KOH activation. The carbonization temperature has a marked effect on both the pore structure and the electrochemical performances of the APCS in 6 M KOH electrolyte. APCS carbonized at 600 °C results in higher specific surface area and larger pore size, and hence higher capacitance and better rate capability. The specific capacitance of the APCS in 6 M KOH aqueous solution can be as high as 282 F g⁻¹. It remains 252 F g⁻¹ as the current density increases to 1000 mA g⁻¹.     

Structural, electrical and optical properties of ZnS films deposited by close-spaced evaporation

ZnS films have been deposited on glass substrates by close-spaced evaporation (CSE) technique. The films were grown at different temperatures in the range, 200-350 °C. The layers have been characterized with X-ray diffractometer (XRD), atomic force microscope (AFM), energy dispersive analysis of X-rays (EDAX) and optical spectrophotometer to evaluate the quality of the layers for photovoltaic applications. The studies showed that the optimum substrate temperature for the growth of ZnS layers was 300 °C. The films grown at these temperatures exhibited cubic structure with nearly stoichiometric composition. The AFM data revealed that the films had nano-sized grains with a grain size of ∼40 nm. The optical studies exhibited direct allowed transition with an energy band gap of 3.61 eV. The other structural and optical parameters such as lattice stress, dislocation density, refractive index and extinction coefficient were also evaluated. The temperature-dependent conductivity measured in the range, 303-523 K showed a change in the conduction mechanism at 120 °C. The activation energy values evaluated using the temperature dependence of electrical conductivity are 7 and 29 meV at low and high temperature regions, respectively.     

Controlling the micropore size of activated carbons for the treatment of fuels and combustion gases

Exclusively microporous activated carbons have been prepared from cork by physical and chemical activation under different conditions. The results show that it is possible to control the pore size of the activated carbons and to obtain materials with narrow micropore size (≥0.69 nm) and high micropore volume (≤0.64 cm³ g⁻¹) equal to or better than the best activated carbon fibres. Higher micropore volumes are generally obtained by chemical activation at higher temperature using dry or potassium hydroxide impregnation. On the other hand, wet or carbonate impregnation, as well as high temperature, or physical activation with CO₂ or H₂O under appropriate conditions, favours low mean pore widths.     

Valence band and band gap photoemission study of (1 1 1) In2O3 epitaxial films under interactions with oxygen, water and carbon monoxide

Synchrotron radiation ultraviolet photoemission experiments at photon energies of 150 and 49 eV were performed on an epitaxial layer of (1 1 1) In₂O₃ with good crystallinity as established by a standard scanning probe and diffraction methods. Valence band (VB) and band gap photoemission spectra were monitored under separate oxygen, water and carbon monoxide exposures (100 L) at different activation temperatures within the range utilized for chemiresistive gas sensors (160-450 °C). Large changes in photoemission response within the whole VB were observed for all gases. Regular shifts of the valence band edge relative to the Fermi energy were found under gas exposures on two kinds of surface (partially reduced or partially oxidized), and are interpreted as changes of surface potential. Treatments in oxygen resulted in upward band bending (∼0.5 eV at T = 320 °C). Regardless of activation temperature, treatments in water resulted in downward band bending, but with small changes (<0.1 eV). Reduction properties of carbon monoxide were observed only at high temperatures of T ? 370 °C. At temperatures of 160 and 250 °C unusual “oxidizing” behavior of CO was observed with upward band bending of ∼0.7 eV (160 °C). Oxidizing and reducing effects of the gas interactions with the (1 1 1) In₂O₃ surface in all cases were accompanied by a corresponding behavior, i.e., a decrease or increase in photoemission response from so-called defect states in the band gap near the top of the valence band. The increases of photoemission within a band gap with maxima at binding energies (BE) of 0.4 (O₂-induced peak) and 1.0 eV (CO-induced peak) were, respectively, found for interactions with O₂ and CO for low temperatures (T = 160 and 250 °C). These responses were ascribed to acceptor-like electronic levels of O₂ and CO chemisorption states, respectively. A definite split of the top VB peak (BE ∼ 4.0 eV) was found under CO dosing at 160 °C. Established knowledge of the CO interaction with the (1 1 1) In₂O₃ surface explains earlier revealed acceptor-like behavior of In₂O₃ film conductivity during CO detection at operational temperatures lower than 250 °C through the formation of acceptor-like electronic levels of adsorbed CO molecules.