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.     

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.     

Preparation of activated carbon from a renewable bio-plant of Euphorbia rigida by H2SO4 activation and its adsorption behavior in aqueous solutions

The use of activated carbon obtained from Euphorbia rigida for the removal of a basic textile dye, which is methylene blue, from aqueous solutions at various contact times, pHs and temperatures was investigated. The plant material was chemically modified with H₂SO₄. The surface area of chemically modified activated carbon was 741.2 m² g⁻¹. The surface characterization of both plant- and activated carbon was undertaken using FTIR spectroscopic technique. The adsorption process attains equilibrium within 60 min. The experimental data indicated that the adsorption isotherms are well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity of activated carbon was 114.45 mg g⁻¹ at 40° C. The adsorption kinetics of methylene blue obeys the pseudo-second-order kinetic model and also followed by the intraparticle diffusion model up to 60 min. The thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated to estimate the nature of adsorption. The activation energy of the system was calculated as 55.51 kJ mol⁻¹. According to these results, prepared activated carbon could be used as a low-cost adsorbent to compare with the commercial activated carbon for the removal textile dyes from textile wastewater processes.     

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.     

High surface area thermally stabilized porous iron oxide/silica nanocomposites via a formamide modified sol-gel process

Iron oxide/silica (Fe:Si as 1:10 atomic ratio) composite materials have been prepared by calcination for 3 h at different temperatures (400-900 °C) of xerogel precursor obtained via a formamide modified sol-gel process. The process involved TEOS and iron(III) nitrate, nitric acid and formamide. Genesis of the composite materials from the xerogel precursor has been investigated by TGA, DSC, FTIR, XRD, SEM and EDX. Results indicated that all the calcined composites are mainly composed of amorphous iron oxide dispersed as finely divided particles in amorphous silica matrixes. Nitrogen adsorption/desorption isotherms revealed a reversible type I of isotherms indicative of microporosity. However, high S_BET surface area and microsporosity were observed for the calcined composite materials (e.g. S_BET = 625 m² g⁻¹, and S_αs = 556 m² g⁻¹ for the composite calcined at 400 °C). Formation of the porous texture was discussed in terms of the action of formamide, which enhanced strengthening of the silica gel network during evaporation of the more volatile components within the composite body during the drying process.     

Preparation and characterization of activated carbon produced from pomegranate seeds by ZnCl2 activation

In this study, pomegranate seeds, a by-product of fruit juice industry, were used as precursor for the preparation of activated carbon by chemical activation with ZnCl₂. The influence of process variables such as the carbonization temperature and the impregnation ratio on textural and chemical-surface properties of the activated carbons was studied. When using the 2.0 impregnation ratio at the carbonization temperature of 600 °C, the specific surface area of the resultant carbon is as high as 978.8 m² g⁻¹. The results showed that the surface area and total pore volume of the activated carbons at the lowest impregnation ratio and the carbonization temperature were achieved as high as 709.4 m² g⁻¹ and 0.329 cm³ g⁻¹. The surface area was strongly influenced by the impregnation ratio of activation reagent and the subsequent carbonization temperature.     

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.     

Influence of carbon structure on performance of electrode material for electric double-layer capacitor

An isotropic pitch and an anisotropic pitch with similar softening point were chosen to be precursors for activated carbons (ISO and ANISO, respectively). Chemical activations with same conditions were carried out and the effects of microstructure of precursors on characteristics of activated carbons were discussed. Isotropic pitch with more noncrystallite carbon atoms or edge carbon atoms on the microstructural defects had more reactive ability and more pores were manufactured through sufficient chemical activation. Electric double-layer capacitors (EDLC) were made with the two activated carbons as electrode materials and 1 M Et₄NBF₄/PC as the electrolyte. The performance of EDLC with the ISO has higher specific capacitance (43.5 F g⁻¹) than the ANISO (21.3 F g⁻¹) and has better power performance and lower resistance than the latter.     

Removal of nickel(II) ions from aqueous solutions using the natural clinoptilolite and preparation of nano-NiO on the exhausted clinoptilolite

The natural zeolite tuff (clinoptilolite) from a Serbian deposit has been studied as adsorbent for Ni(II) ions from aqueous solutions. Its sorption capacity at 298 K varies from 1.9 mg Ni g⁻¹ (for the initial solution concentration of 100 mg Ni dm⁻³) to 3.8 mg Ni g⁻¹ (for C₀ = 600 mg Ni dm⁻³) and it increases 3 times at 338 K. The sorption is best described by the Sips isotherm model. The sorption kinetics follows the pseudo-second-order model, the activation energies being 7.44, 5.86, 6.62 and 6.63 kJ mol⁻¹ for C₀ = 100, 200, 300 and 400 mg Ni dm⁻³, respectively. The sorption involves a film diffusion, an intra-particle diffusion, and a chemical cation-exchange between the Na⁺ ions of clinoptilolite and the Ni²⁺ ions. The sorption is endothermic (ΔH° being 37.9, 33.4, 30.0, 27.7 and 24.3 kJ mol⁻¹ for C₀ = 100, 200, 300, 400 and 600 mg Ni dm⁻³, respectively) and spontaneous in the 298-338 K temperature range. Thermal treatment of the Ni(II)-loaded clinoptilolite results in the formation of spherical nano-NiO particles of approx. 5 nm in diameter which are randomly dispersed in the clinoptilolite lattice.     

Variable-temperature FT-IR studies on the thermodynamics of carbon dioxide adsorption on a faujasite-type H-Y zeolite

Adsorption of carbon dioxide on a faujasite-type H-Y zeolite (Si:Al = 2.6:1) was studied by variable-temperature (200-290 K range) infrared spectroscopy. Adsorbed CO₂ molecules interact with the Brønsted acid Si(OH)Al groups located inside the zeolite supercage, bringing about a characteristic bathochromic shift of the O-H stretching mode from 3645 cm⁻¹ (free OH group) to 3540 cm⁻¹ (hydrogen-bonded CO₂ adsorption complex). Simultaneously, the asymmetric (ν₃) mode of adsorbed CO₂ is observed at 2353 cm⁻¹. From the observed variation of the integrated intensity of the 3645 and 2353 cm⁻¹ IR absorption bands upon changing temperature, corresponding values of standard adsorption enthalpy and entropy were found to be ΔH° = −28.5(±1) kJ mol⁻¹ and ΔS° = −129(±10) J mol⁻¹ K⁻¹. Comparison with the reported values of ΔH° for CO₂ adsorption on other zeolites is briefly discussed.     

Preparation of activated carbon from cherry stones by chemical activation with ZnCl2

Cherry stones (CS), an industrial product generated abundantly in the Valle del Jerte (Cáceres province, Spain), were used as precursor in the preparation of activated carbon by chemical activation with ZnCl₂. The influence of process variables such as the carbonisation temperature and the ZnCl₂:CS ratio (impregnation ratio) on textural and chemical-surface properties of the products obtained was studied. Such products were characterised texturally by adsorption of N₂ at −196 °C, mercury porosimetry and density measurements. Information on the surface functional groups and structures of the carbons was provided by FT-IR spectroscopy. Activated carbon with a high development of surface area and porosity is prepared. When using the 4:1 impregnation ratio, the specific surface area (BET) of the resultant carbon is as high as 1971 m² g⁻¹. The effect of the increase in the impregnation ratio on the porous structure of activated carbon is stronger than that of the rise in the carbonisation temperature, whereas the opposite applies to the effect on the surface functional groups and structures.     

Heat treatment effects on microstructure and magnetic properties of Mn-Zn ferrite powders

Mn-Zn ferrite powders (Mn_0.5Zn_0.5Fe₂O₄) were prepared by the nitrate-citrate auto-combustion method and subsequently annealed in air or argon. The effects of heat treatment temperature on crystalline phases formation, microstructure and magnetic properties of Mn-Zn ferrite were investigated by X-ray diffraction, thermogravimetric and differential thermal analysis, scanning electron microscopy and vibrating sample magnetometer. Ferrites decomposed to Fe₂O₃ and Mn₂O₃ after annealing above 550 °C in air, and had poor magnetic properties. However, Fe₂O₃ and Mn₂O₃ were dissolved after ferrites annealing above 1100 °C. Moreover, the 1200 °C annealed sample showed pure ferrite phase, larger saturation magnetization (M_s=48.15 emu g⁻¹) and lower coercivity (H_c=51 Oe) compared with the auto-combusted ferrite powder (M_s=44.32 emu g⁻¹, H_c=70 Oe). The 600 °C air annealed sample had the largest saturation magnetization (M_s=56.37 emu g⁻¹) and the lowest coercivity (H_c=32 Oe) due to the presence of pure ferrite spinel phase, its microstructure and crystalline size.     

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.     

Porous LiNi0.75Co0.25O2 microspheres prepared via a hydrothermal process as cathode material for lithium ion batteries

Porous LiNi_0.75Co_0.25O₂ microspheres are successfully prepared by a simple hydrothermal process by using H[Ni_0.75Co_0.25OOH]₃ and LiOH as starting materials in the presence of urea for the first time. The synthesized samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (S_BET), and electrochemical performance. The synthesized LiNi_0.75Co_0.25O₂ has a good electrochemical performance with an initial discharge capacity of 169.3 mA g⁻¹ and good capacity retention of 96.7% after 50 cycles at 0.2 C (25 mA g⁻¹). The electrochemical lithium ion insertion/extraction process is quite reversible even at 5 C. Furthermore, the structure in the charge-discharge process is stable and the impedance increased slowly during cycling.     

Preparation and characterization of iodine-doped mesoporous TiO2 by hydrothermal method

Iodine-doped mesoporous TiO₂ (I/TiO₂) was prepared by hydrothermal method, using tetrabutyl titanate as precursor, potassium iodate as iodine sources. The as-prepared I/TiO₂ catalysts were characterized by UV-vis, XRD, TEM, BET, TG/DTA, XPS and photoluminescence (PL) spectroscopy. Production of OH radicals on the I/TiO₂ surface was detected by the PL technique using terephthalic acid as a probe molecule. The effects of hydrothermal reaction temperature, calcination temperature and iodine doping content on the structure and properties of the catalysts were investigated. The results showed that iodine-doped TiO₂ calcinated at 300 °C have good anatase crystal. The optimal hydrothermal conditions have been determined to be that reaction temperature 120 °C, calcinated temperature 300 °C and added 1.16 mmol iodine dopants. The average particle size of I/TiO₂ synthesized under optimal condition (I-3 sample) is about 3.9 nm. The I-3 photocatalyst contains 100% anatase crystalline phase of TiO₂. BET specific surface area of I-3 sample is184.8 m² g⁻¹ and is 3.67 times that of pure TiO₂ (50.37 m² g⁻¹). Iodine in I/TiO₂ catalyst mainly exists in the form of I₂, and photoactivity of I/TiO₂ catalyst in visible light comes from photosensitize of I₂. I/TiO₂ catalysis shows very high efficiency for the degradation of phenol under visible light.     

VPO catalysts synthesized on substrates with modified activated carbons

VPO catalysts were prepared on oxidized and unoxidized activated carbons differing in initial porous structure. Carbons were oxidized under relatively soft (30% H₂O₂, 200 °C) and hard (50% H₂O₂, 350 °C) conditions. Carbon modification was carried out hydrothermally in a traditional autoclave (HTT) or a microwave reactor (MWT). The synthesis was also carried out under hydrothermal (HTS or MWS) conditions. V₂O₅ and NH₄VO₃ were used as precursors. The samples are characterized by diversified porous structure at S_BET = 732-1617 m²/g and V_por = 0.44-0.90 cm³/g, as well as various degree of VPO crystallinity. Possibility of preparation of the VPO catalysts under ecologically appropriate conditions, i.e. in aqueous solutions, was shown.     

Comparative study of electrochemical capacitance of multi-walled carbon nanotubes before and after chopping

In the work, short multi-walled carbon nanotubes (S-CNTs) were synthesized by chopping conventional μm-long multi-walled carbon nanotubes (L-CNTs) under ultrasonication in H₂SO₄/HNO₃ mixed acids. A comparative electrochemical investigation performed in 6 M KOH solution demonstrated that a specific capacitance (SC) of ca. 14.6 μF cm⁻² was delivered by the S-CNTs with the specific surface area (SSA) of 207 m² g⁻¹, much larger than that of ca. 10.1 μF cm⁻² for the L-CNTs with the SSA of 223 m² g⁻¹, the reason for which was that S-CNTs with two open ends, due to good ion penetrability, provided more entrances for electrolyte ions to access the inner surface easily through their shorter inner pathway so as to enhance their SSA utilization and geometric SC. The surface structure disruption of S-CNTs, owing to ultrasonication and oxidation during chopping process, deteriorated their electronic conductivity and resulted in an inferior power property in contrast to L-CNTs.     

Influence of B2O3 to the inhomogeneous broadening and spectroscopic properties of Er/Yb codoped fluorophosphate glasses

In a three-components fluorophosphate glass system, the introduction of H₃BO₃ brings some valuable influence to the spectroscopic and thermal properties of the glasses. With H₃BO₃ increases from 2 to 20 mol%, Ω₆, S_ed4I13/2, FWHM, T_g and fluorescence lifetime change from 3.21×10⁻²⁰ cm², 1.77×10⁻²⁰ cm², 45 nm, 480 °C and 8.8 ms to 4.66×10⁻²⁰ cm², 2.11×10⁻²⁰ cm², 50 nm, 541 °C and 7.4 ms, respectively. σ_abs, σ_emi, FWHM×τ_f×σ_emi has a maximum when H₃BO₃ is 11 mol%. T_g and T_x−T_g increases with H₃BO₃ introduction. Results showed that in fluorophosphate glasses, proper amount of B₂O₃ can be used as a modifier to suppress upconversion and improve spectroscopic properties, broadband property and crystallization stability of the glasses while keeps the fluorescence lifetime relatively high.     

Cationic starch as a precursor to prepare porous activated carbon for application in supercapacitor electrodes

Three activated carbons (ACs) for the electrodes of supercapacitor were prepared from cationic starch using KOH, ZnCl₂ and ZnCl₂/CO₂ activation. The BET surface area, pore volume and pore size distribution of the ACs were evaluated using density functional theory method, based on N₂ adsorption isotherms at 77 K. The surface morphology was characterized with SEM. Their electrochemical performance in prototype capacitors was determined by galvanostatic charge/discharge characteristics and cyclic voltammetry, and compared with that of a commercial AC, which was especially prepared for use in supercapacitors. The KOH-activated starch AC presented higher BET surface area (3332 m² g⁻¹) and larger pore volume (1.585 cm³ g⁻¹) than those of the others, and had a different surface morphology. When used for the electrodes of supercapacitors, it exhibited excellent capacitance characteristics in 30 wt% KOH aqueous electrolytes and showed a high specific capacitance of 238 F g⁻¹ at 370 mA g⁻¹, which was nearly twice that of the commercial AC.     

Highly active Ce1−xCuxO2 nanocomposite catalysts for the low temperature oxidation of CO

A series of Ce_1−xCu_xO₂ nanocomposite catalysts with various copper contents were synthesized by a simple hydrothermal method at low temperature without any surfactants, using mixed solutions of Cu(II) and Ce(III) nitrates as metal sources. These bimetal oxide nanocomposites were characterized by means of XRD, TEM, HRTEM, EDS, N₂ adsorption, H₂-TPR and XPS. The influence of Cu loading (5-25 mol%) and calcination temperature on the surface area, particle size and catalytic behavior of the nanocomposites have been discussed. The catalytic activity of Ce_1−xCu_xO₂ nanocomposites was investigated using the test of CO oxidation reaction. The optimized performance was achieved for the Ce_0.80Cu_0.20O₂ nanocomposite catalyst, which exhibited superior reaction rate of 11.2 × 10⁻⁴ mmol g⁻¹ s⁻¹ and high turnover frequency of 7.53 × 10⁻² s⁻¹ (1% CO balanced with air at a rate of 40 mL min⁻¹, at 90 °C). No obvious deactivation was observed after six times of catalytic reactions for Ce_0.80Cu_0.20O₂ nanocomposite catalyst.