Fabrication and application of highly ordered mesoporous Co3O4, NiO, and their metals

Highly ordered mesoporous Co₃O₄, NiO, and their metals were synthesized by nanocasting method using there corresponding mesoporous SBA-15 silica as a template. The obtained porous metal oxides have high surface areas, large pore volume, and a narrow pore size distribution. The N₂-adsorption data for mesoporous metal oxides have provided the BET area of 257.7 m² g⁻¹ and the total pore volume of 0.46 cm³ g⁻¹. The mesoporous metals were employed as a catalyst in the synthesis of (S)-3-pyrrolidinol from chiral (S)-4-chloro-3-hydroxybutyronitrile, and a high yield to (S)-3-pyrrolidinol-salt was obtained on the mesoporous Co metal catalyst.     

BET surface area of carbonaceous adsorbents—Verification using geometric considerations and GCMC simulations on virtual porous carbon models

The applicability of BET model for calculation of surface area of activated carbons is checked by using molecular simulations. By calculation of geometric surface areas for the simple model carbon slit-like pore with the increasing width, and by comparison of the obtained values with those for the same systems from the VEGA ZZ package (adsorbate-accessible molecular surface), it is shown that the latter methods provide correct values. For the system where a monolayer inside a pore is created the ASA approach (GCMC, Ar, T = 87 K) underestimates the value of surface area for micropores (especially, where only one layer is observed and/or two layers of adsorbed Ar are formed). Therefore, we propose the modification of this method based on searching the relationship between the pore diameter and the number of layers in a pore. Finally BET; original and modified ASA; and A, B and C-point surface areas are calculated for a series of virtual porous carbons using simulated Ar adsorption isotherms (GCMC and T = 87 K). The comparison of results shows that the BET method underestimates and not, as it was usually postulated, overestimates the surface areas of microporous carbons.     

Preparation and hydrogen storage of activated rayon-based carbon fibers with high specific surface area

Activated carbon fibers were prepared from rayon-based carbon fibers by two step activations with steam and KOH treatments. Hydrogen storage properties of the activated rayon-based carbon fibers with high specific surface area and micropore volume have been investigated. SEM, XRD and Brunauer-Emmett-Teller (BET) were used to characterize the samples. The adsorption performance and porous structure were investigated by nitrogen adsorption isotherm at 77 K on the base of BET and density functional theory (DFT). The BET specific surface area and micropore volume of the activated rayon-based carbon fibers were 3144 m²/g and 0.744 m³/g, respectively. Hydrogen storage properties of the samples were measured at 77 and 298 K with pressure-composition isotherm (PCT) measuring system based on the volumetric method. The capacities of hydrogen storage of the activated rayon-based carbon fibers were 7.01 and 1.46 wt% at 77 and 298 K at 4 MPa, respectively. Possible mechanisms for hydrogen storage in the activated rayon-based carbon fibers are discussed.     

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.     

A novel method for the assembly of nano-zeolite crystals on porous stainless steel microchannel and then zeolite film growth

A new method that is simple, efficient, and clean was developed for seeding surfaces with a monolayer of covalently bonded zeolite seeds. This method was used to seed the microchannels fabricated on porous stainless steel with NaA nano-zeolites enabling the deposition and growth of defect-free zeolite film. The NaA nano-zeolites were attached to the surface of the stainless steel via alkoxysilane linkers (e.g., 3-chloropropyltrimethoxysilane and 3-aminopropyltrimethoxysilane) grafted on the stainless steel. The NaA zeolite grown on the microchannel by hydrothermal synthesis consists of intergrown, (1 1 1)-oriented pyramidal NaA crystals that completely clad the stainless steel grains. The zeolite cladding the grains grew uniformly until the zeolite layers of neighboring grain impinges, then intergrew to fully bridge the gaps between the grains forming a defect-free film layer. A separation factor of 10,000 and a flux of 0.04 kg m⁻² h⁻¹ were obtained for water pervaporation from a 3 wt% water-benzaldehyde solution at room 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.     

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.     

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.     

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.     

Polymer-templated mesoporous carbons synthesized in the presence of nickel nanoparticles, nickel oxide nanoparticles, and nickel nitrate

Mesoporous carbon composites, containing nickel and nickel oxide nanoparticles, were obtained by soft-templating method. Samples were synthesized under acidic conditions using resorcinol and formaldehyde as carbon precursors, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock co-polymer Lutrol F127 as a soft template and nickel and nickel oxide nanoparticles, and nickel nitrate as metal precursors. In addition, a one set of samples was obtained by impregnation of mesoporous carbons with a nickel nitrate solution followed by further annealing at 400 °C. Wide angle X-ray powder diffraction along with thermogravimetric analysis proved the presence of nickel nanoparticles in the final composites obtained using nickel and nickel oxide nanoparticles, and Ni(NO₃)₂ solution. Whereas, the impregnation of carbons with a nickel nitrate solution followed by annealing at 400 °C resulted in needle-like nickel oxide nanoparticles present inside the composites’ pores. Low-temperature (−196 °C) nitrogen physisorption, X-ray powder diffraction, and thermogravimetric analysis confirmed good adsorption and structural properties of the synthesized nickel-carbon composites, in particular, the samples possessed high surface areas (>600 m²/g), large total pore volumes (>0.50 cm³/g), and maxima of pore size distribution functions at circa 7 nm. It was found that the composites were partially graphitized during carbonization process at 850 °C. The samples are stable in an air environment below temperature of 500 °C. All these features make the synthesized nickel-carbon composites attractive materials for adsorption, catalysis, energy storage, and environmental applications.     

A general and low-cost synthetic route to high-surface area metal oxides through a silica xerogel template

Porous metal oxides with a large surface area are synthesised by means of a procedure based on the templating approach. An inexpensive porous silica xerogel synthesised at moderate temperatures (∼100 °C) in order to preserve the silanol superficial groups was used as template. In a first step, the silica porosity was filled with a concentrated solution containing a metallic salt. Then, the impregnated sample was calcined in air at a temperature of 600 °C. Under these conditions, the metal oxides were synthesised within the confined space provided by the silica pores. Finally, the product was recovered after dissolution of the silica framework in 2 M NaOH solution. The materials obtained by this procedure are made up of aggregates of nanoparticles and/or 3D solid structures containing confined pores. In this work, the synthetic route proposed is illustrated by the preparation of various binary metal oxides (i.e. Fe₂O₃, Cr₂O₃, NiO, CeO₂, Mn₂O₃, Co₂O₃ and Al₂O₃). The BET surface areas measured for these materials are in the range of 100-270 m² g⁻¹. The proposed method is not restricted to the binary metal oxides. It can also be used in the preparation of other inorganic materials such as metal sulphides or mixed metal oxides.     

Novel porous CuO microrods: synthesis,characterization, and their photocatalysis property

Porous copper oxide microrods have been synthesized via calcining copper glycinate monohydrate microrod precursor which was prepared in mild conditions without any template or additive. Several techniques, such as X-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller (BET) N₂ adsorption–desorption analyses, were used to characterize the structure and morphology of the products. Scanning electron microscopy (SEM) analyses show that the precursor consists of a large quantity of uniform rod-like micro/nanostructures with typical lengths in the range of 25–40 µm and diameters in the range of 0.1–0.35 µm. The microrod-like precursors transformed into porous microrod products after calcination at 450 °C in flow air for 2 h. The BET surface area of the porous CuO microrods was calculated to be 8.5 m² g⁻¹. In addition, the obtained porous CuO microrods were used as catalysts to photodegrade rhodamine B (RhB), methyl orange, methylene blue, eosin B, and p-nitrophenol. Compared with commercial CuO powders, the as-prepared porous CuO microrods exhibit superior properties on photocatalytic decomposition of RhB due to their porous hierarchical structures.     

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.     

Removal of naphthalene from petrochemical wastewater streams using carbon nanoporous adsorbent

Ordered mesoporous carbon, OMC, was synthesized using ordered mesoporous silica MCM-48 as hard template, the structural order and textural properties of the synthesized materials were studied by XRD, SEM, and nitrogen adsorption-desorption analysis. Adsorption of naphthalene over various porous adsorbents such as OMC, MCM-48, and commercial activated carbon was studied from solutions with different concentration at ambient temperature (25 ± 2 °C) and pH 7. The adsorption isotherms of naphthalene were in agreement with a Langmuir model, moreover, the uptake capacity of naphthalene followed the order: OMC > commercial activated carbon > mesoporous silica (MCM-48).     

Preparation of activated carbon from Enteromorpha prolifera and its use on cationic red X-GRL removal

Enteromorpha prolifera was pyrolyzed to prepare activated carbon using chemical activation by zinc chloride. The effect of activation parameters such as activation temperature, weight ratio (Enteromorpha prolifera to ZnCl₂), and activation time was investigated. The BET results showed that the surface area and pore volume of activated carbons were achieved as high as 1722 m²/g and 1.11 cm³/g, respectively, in the optimal activation conditions. Batch adsorption studies were carried out to study the adsorption properties of cationic red X-GRL onto activated carbon by varying the parameters like initial solution pH, contact time, and temperature. The kinetic studies showed that the adsorption data followed a pseudo second-order model. The isotherm analysis indicated that the adsorption data could be represented by the Langmuir isotherm model. The Langmuir monolayer adsorption capacity of cationic red X-GRL was estimated as 263.16 mg/g at pH 6.0.     

Hexagonal mesoporous silica modified with 2-mercaptothiazoline for removing mercury from water solution

A method for the attachment of 2-mercaptothiazoline (MTZ) to modified silica gel has been developed. In the first step, a new silylant agent was synthesized, named SiMTZ, by the reaction between MTZ molecule and chloropropyltrimethoxysilane (SiCl). SiMTZ and tetraethylortosilicate were co-condensed in the presence of n-dodecylamine, a neutral surfactant template, to produce a modified ordered hexagonal mesoporous silica named HMTZ. The modified material contained 0.89 ± 0.03 mmol of 2-mercaptothiazoline per gram of silica. FT-IR, FT-Raman, ²⁹Si- and ¹³C-NMR spectra were in agreement with the proposed structure of the modified mesoporous silica in the solid state. HMTZ material has been used for divalent mercury adsorption from aqueous solution at 298 ± 1 K. The series of adsorption isotherms were adjusted to a modified Langmuir equation. The maximum number of moles of mercury adsorbed gave 2.34 ± 0.09 mmol/g of material. The same interaction was followed by calorimetric titration on an isoperibol calorimeter. The HMTZ presented a high capacity for the removal of the contaminant mercury from water. The ΔH and ΔG values for the interaction were determined to be −56.34 ± 1.07 and −2.14 ± 0.11 kJ mol⁻¹. This interaction process was accompanied by a decrease of entropy value (−182 J mol⁻¹ K⁻¹). Thus, the interaction between mercury and HMTZ resulted in a spontaneous thermodynamic system with a high favorable exothermic enthalpic effect.     

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.     

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.