Effect of pre-oxidation on the porosity development in a heavy oil fly ash by CO2 activation

The effect of pre-oxidation on the porosity evolution in heavy-oil fly ash subjected to activation with CO₂ has been investigated. After preliminary acid leaching, used to reduce the mineral matter content, the leached fly ash has been oxidised in air at 250 °C for 36 h. Pyrolysis was conducted on the unoxidised and oxidised leached fly ash at 900 °C for 2 h and the resultant chars were activated with CO₂ at 900 °C for different times. The activated samples have been characterised as regards the surface area and the pore volume.The pre-oxidation enhances the porosity development mainly in terms of mesoporosity leading to obtain activated products with higher surface area (about 270 m²/g at a 40% burn-off).     

Effect of pre-oxidation on the porosity development in a heavy oil fly ash by CO2 activation

The effect of pre-oxidation on the porosity evolution in heavy oil fly ash subjected to activation with CO₂ has been investigated. After preliminary acid leaching, used to reduce the mineral matter content, the leached fly ash has been oxidised in air at 250 °C for 36 h. Pyrolysis was conducted on the unoxidised and oxidised leached fly ash at 900 °C for 2 h and the resultant chars were activated with CO₂ at 900 °C for different times. The activated samples have been characterised as regards the surface area and the pore volume.The pre-oxidation enhances the porosity development mainly in terms of mesoporosity leading to obtain activated products with higher surface area (about 270 m²/g at a 40% burn-off).     

Acid modified local clay beads as effective low-cost adsorbent for dynamic adsorption of methylene blue

Locally sourced clay was harnessed to study its adsorptive potential of methylene blue (MB) in wastewater streams. The clay was modified with sulfuric acid and aluminum hydroxide. The raw and modified freeze dried clay bead RHC and MHC were subjected to batch and batch/fixed-bed adsorption studies, respectively. Elemental analysis, morphological structures were determined, and surface area of 19.3 (RHC) and 101.2 (MHC) m²/g were obtained. Langmuir, Freundlich and Redlich–Peterson isotherms models were analyzed and the modification increased adsorption capacity from 58.02 to 223.19 mg/g at 30 °C. The MB adsorption on RHC/MHC was spontaneous, exothermic and obeyed pseudo-second-order model.     

Characteristics of unburned carbons and their application for humic acid removal from water

Two unburned carbons (UCs) were separated from coal fly ash and their physicochemical properties were characterised using N₂ adsorption, XRD, SEM, XPS, FT-IR and potentiometric mass titration. Chemical treatments using HNO₃ and KOH were also conducted on one of the unburned carbons. The adsorption of humic acid from aqueous solution was performed on these untreated and chemically treated UCs. It was found that the UCs showed different porous structure and surface chemical properties, which influenced their adsorption behaviour. UCs exhibited high adsorption capacity for humic acid. After chemical treatment, the textural structure and surface functional groups of the unburned carbon were changed and the adsorption behaviour showed significant difference. Acid treatment did not change the surface area but reduced the functional groups while basic treatment significantly enhanced the surface area in microporous section but still reduced the surface functional groups. Particle size and pH solution will also influence the adsorption capacity. The adsorption will increase with decreasing particle size for humic acid. Higher pH solution will reduce humic acid adsorption on unburned carbon. Ionic strength will also affect humic acid adsorption showing positive effect on adsorption capacity.     

Photocatalytic activity of rubber sheet impregnated with TiO2 particles and its recyclability

The preparation of rubber sheet impregnated with titanium dioxide particles is presented. This method is simple and low cost based on the use of commercial TiO₂ powder directly mixing with rubber latex (60% HA) and distilled water. The morphology and roughness of the sheet surface increased with increasing amount of distilled water. Sheet impregnated with anatase (Imp-An) showed uniform, small grains with dense structure and well surface coverage more than one with P25 (Imp-P25). Their photocatalytic activities were evaluated using methylene blue (MB) as a model organic dye compound. These impregnated sheets could degrade MB solution under UV-light irradiation. Comparing with the commercial TiO₂ samples in powder form (anatase from Carlo Erba and Degussa P25) the efficiencies of photocatalytic degradation of MB fall in the decreasing order as: P25 (powder) > anatase (Carlo Erba) (powder) > Imp-An sheet > Imp-P25 sheet. However, the impregnated sheet has an advantage over the loose powder that the catalyst sheet can be recovered after used and can be reused.     

The effect of alkalinity of Class F PC fly ash on metal release

Thirty-five samples of Class F fly ash from pulverized coal (PC) combustion boilers were leached with deionized water, acetic acid, and sulfuric acid. The release of metal ions from fly ash was related to the pH of the leachant solution and to the alkalinity of the ash. The maximum soluble concentration of the metallic elements was measured when the pH of the leachate was less than 5. Twenty-three of the samples were strongly alkaline and buffered the leachate until the ash was neutralized. The leachate from the other 13 samples became acidic with the addition of less than 1 L of 0.1 N acid. The alkalinity of the ash and the volume of acid required to neutralize it were a function of the Ca concentration.     

Synthesis and photocatalytic performance of hollow sphere particles of SiO2-TiO2 composite of mesocellular foam walls

Hollow Microspheres of SiO₂-TiO₂ photocatalysts whose walls are made up of mesoporous cellular foams were synthesized with the aid of hexane as a swelling agent and P123 as a pore template by an emulsion templating method. Pore structure of materials and crystal phase of titanium oxide was tailored by hydrothermal and calcination temperature during synthesis of samples. The samples were characterized with field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), N₂ adsorption–desorption experiments, X-ray photoelectron spectroscopy (XPS) and X ray diffraction (XRD) techniques. The effect of pore structure and titania phase on photoactivity were evaluated by methylene blue (MB) degradation test under UV light as well. Results showed that hydrothermal temperature during synthesis process has a significant effect on pore and window sizes of mesostructured cellular foam. Interestingly, for the sample hydrothermally treated at higher temperature (130 °C), anatase to rutile transformation was avoided after calcination treatment as high as 800 °C. The highest photocatalytic activity was detected from the sample hydrothermally treated at 130 °C and calcined at 800 °C for which the highest degree of crystallinity and anatase phase as well as enhanced pore connectivity was obtained.     

Freestanding hematite nanofiber membrane for visible-light-responsive photocatalyst

Freestanding mesoporous hematite (α-Fe₂O₃) nanofiber membranes were successfully fabricated by sol–gel electrospinning process using ferratrane precursor for use as a high-performance material for visible-light-responsive photocatalyst. Non-porous nanofiber membranes spun on the heated collector at 300 °C were crystalline α-Fe₂O₃ phase. Upon calcination, pure mesoporous nanofiber membranes were obtained even at a low temperature of 400 °C. The photocatalytic membrane calcined at 400 °C showed the highest efficiency for methylene blue (MB) degradation under visible-light irradiation. The synergetic effects of higher surface area, pore volume and pore diameter promoted the photocatalytic efficiency for MB degradation under visible light. The utilization of photocatalyst in the form of membrane could not only solve the problems of catalyst separation and recovery, but also produce high photodegradation efficiency for both systems without and with hydrogen peroxide even at a catalyst loading as low as 0.04 g/L. No appreciable loss in photocatalytic activity was observed and structural integrity was retained, even after five cycles of photodegradation, which predicted the stability and reusability of these nanofiber membranes for practical use in environmental applications.     

Adsorption of heavy metal ions from aqueous solution by fly ash

The removal characteristics of lead and copper ions from aqueous solution by fly ash were investigated under various conditions of contact time, pH and temperature. The influence of pH of the metal ion solutions on the uptake levels of the metal ions by fly ash were carried out between pH 4 and 12. The level of uptake of Pb²⁺ and Cu²⁺ ions by the fly ash generally increased, but not in a progressive manner, at higher pH values. The effect of temperature on the uptake of Pb²⁺ and Cu²⁺ ions was investigated between 30 °C and 60 °C, the adsorption of being enhanced at the lowest temperature. Rate constants were evaluated in terms of a first-order kinetics. The rate constant, k for uptake of Pb²⁺ and Cu²⁺ ions were 1.77 × 10⁻² s⁻¹ and 2.11 × 10⁻² s⁻¹, respectively. The experimental results underline the potential of coal fly ash for the recovery of metal ions from waste water. The main mechanisms involved in the removal of heavy metal ions from solution were adsorption at the surface of the fly ash and precipitation.     

Photocatalytic activity of porous titania nanocrystals prepared by nanoscale permeation process in supercritical CO2: Effects of supercritical conditions

Porous TiO₂ nanocrystals (PTN) were synthesized using activated carbon templates with supercritical CO₂ by using the nanoscale permeation (NP) process. The photoactivity of PTN was tested by methylene blue (MB) degradation. Compared with the commercially available P-25, all PTN exhibited significant photocatalytic degradation of MB mainly due to their porous structure with high surface area, high hydroxy concentration and small crystalline size. The optimum temperature and pressure are found to be 60 °C and 26 MPa, under which obtained PTN-1 shows the highest photoactivity and slow deactivation for MB degradation after 15 trials.     

A novel synthesis method of hierarchical mesoporous MgO nanoflakes employing carbon nanoparticles as the hard templates for photocatalytic degradation

We describe a novel synthesis method for the preparation of bimodal mesoporous MgO nanoflakes and their application in photocatalytic activity for the degradation of methylene blue dye under UV light irradiation. For this purpose, Mg(OH)₂/carbon nanocomposite was obtained through the precipitation of magnesium hydroxide in the presence of carbon nanoparticles. X-ray diffraction pattern (XRD), scanning electron microscopy (SEM), and transition electron microscopy (TEM) micrographs have shown that this strategy could be successfully used to prepare bimodal mesoporous MgO nanoflakes with two different pore size distributions centered at 3 and 25 nm and a high specific surface area of 216.9 m²/g. Furthermore, the product was used as an adsorbent to remove methylene blue dye from aqueous media. The results confirmed that the photocatalytic activity of the synthesized mesoporous MgO was significantly improved due to the presence of such different pore sizes and high specific surface area resulting in higher adsorption, storage, and degradation of dye molecules.     

Synthesis of a nano-crystalline solid acid catalyst from fly ash and its catalytic performance

The synthesis of nano-crystalline activated fly ash catalyst (AFAC) with crystallite size of 12 nm was carried out by chemical and thermal treatment of fly ash, a waste material generated from coal-burning power plants. Fly ash was chemically activated using sulfuric acid followed by thermal activation at 600 °C. The variation of surface and Physico-chemical properties of the fly ash by activation methods resulted in improved acidity and therefore, catalytic activity for acid catalyzed reactions. The AFAC was characterized by X-ray diffraction, FT-IR spectroscopy, N₂-adsorption–desorption isotherm, scanning electron microscopy, flame atomic absorption spectrophotometry and sulfur content by CHNS/O elemental analysis. It showed amorphous nature due to high silica content (81%) and possessed high BET surface area (120 m²/g). The catalyst was found to be highly active solid acid catalyst for liquid phase esterification of salicylic acid with acetic anhydride and methanol giving acetylsalicylic acid and methyl salicylate respectively. A maximum yield of 97% with high purity of acetylsalicylic acid (aspirin) and a very high conversion 87% of salicylic acid to methyl salicylate (oil of wintergreen) was obtained with AFAC. The surface acidity and therefore, catalytic activity in AFAC was originated by increased silica content, hydroxyl content and higher surface area as compared to fly ash. The study shows that coal generated fly ash can be converted into potential solid acid catalyst for acid catalyzed reactions. Furthermore, this catalyst may replace conventional environmentally hazardous homogeneous liquid acids making an ecofriendly; solvent free, atom efficient, solid acid based catalytic process. The application of fly ash to synthesize a solid acid catalyst finds a noble way to utilize this abundant waste material.     

Adsorption of methylene blue from aqueous solution onto multiporous palygorskite modified by ion beam bombardment: Effect of contact time,temperature, pH and ionic strength

Our previous work has reported that an inorganic nano-network of palygorskite with multiporous structure can be fabricated from rigid nano-rods by ion beam bombardment and has better adsorption capability than nano-rods. Here, this dispersed modified nano adsorbent was characterized by Fourier Transform Infrared (FTIR) spectroscopy and Scanning Electron Microscope (SEM). The adsorption property of methylene blue (MB) onto this adsorbent was investigated. It was found that the adsorption capacity increased with contact time, pH, MB initial concentration, respectively, and then reached an equilibrium. Moreover, the effect of pH on the adsorption was strongly determined by zeta potential. The adsorption kinetics of MB was dominated by the pseudo-second-order reaction model, and the adsorption isotherms fit the Freundlich isotherms better than the Langmuir isotherms. Three temperatures (293 K, 303 K, 313 K) were set for describing the thermodynamic parameters (ΔH^θ, ΔS^θ, and ΔG^θ), which indicated that the adsorption was spontaneous and exothermic. Lastly, the mechanism of the influence of ionic strength on the adsorption was discussed.     

Superior carbon-based CO2 adsorbents prepared from poplar anthers

A series of renewable nitrogen-containing granular porous carbons with developed porosities and controlled surface chemical properties were prepared from poplar anthers. The preparation conditions such as pre-carbonization and activation temperatures and KOH amount significantly influence the structures and chemical compositions of the porous carbons, the CO₂ adsorption capacities of which are highly dependent on their pore structures, surface areas, nitrogen contents and adsorption conditions. The sample with developed microporosity, especially with the pores between 0.43 and 1 nm and high nitrogen content shows high CO₂ adsorption capacity at 1 bar and 25 °C. In contrast, when the adsorption pressure is higher than 5 bar, its CO₂ adsorption capacity is dominated by its surface area, and more accurately by its pore volume. Irrespective of this, if the pressure was decreased to 0.1 bar, its CO₂ capture ability is closely correlated to its nitrogen content but not to its porosity. By optimizing the preparation conditions, a porous carbon with a surface area of 3322 m² g⁻¹ and a CO₂ adsorption capacity as high as 51.3 mmol g⁻¹ at 50 bar and 25 °C was prepared.     

Preparation of mesoporous geopolymer using metakaolin and rice husk ash as synthesis precursors and its use as potential adsorbent to remove organic dye from aqueous solutions

In this work, mesoporous geopolymer was synthesized using a novel and easy synthesis route employing metakaolin and rice husk ash as sources of silica and alumina, and soybean oil as a mesostructure-directing agent. For comparison purposes, a geopolymer sample was produced without the use of oil. The samples were characterized by Fourier transform infrared spectroscopy (FT–IR), X–ray diffraction (XRD), specific surface area, pore volume, average pore size, and pore size distribution (BET and BJH methods). The materials were tested to remove methyl violet 10B dye from aqueous solutions. The results showed that the mesoporous geopolymer presented adsorptive superior behavior compared to the geopolymer prepared without the use of oil, being attributed to its superior pore properties. The adsorption equilibrium was attained within 120 min, and the maximum adsorption capacity of mesoporous geopolymer was 276.9 mg g^–1. Therefore, the mesoporous geopolymer prepared in this work comprises a potential adsorbent, presenting pore intrinsic properties that result in a high adsorption capacity.     

Adsorption studies of methylene blue onto ZnCl2-activated carbon produced from buriti shells (Mauritia flexuosa L.)

The present study reports the preparation of an activated carbon produced from buriti shells (AC_b) using ZnCl₂ as activating agent and its ability to remove methylene blue dye (MB) from aqueous solutions. The obtained AC_b was characterized by N₂ adsorption–desorption isotherms, SEM and FT-IR. The results show that AC_b presents microporous features with BET surface area (S_BET) of 843 m² g⁻¹ and functional groups common in carbonaceous materials. Adsorption studies were carried out and experimental data were fitted to three isotherm models (Langmuir, Freundlich, and Redlich–Peterson) and four kinetic models (pseudo-first order, pseudo-second order, Elovich, and intraparticle diffusion). The isotherm model which best fitted to experimental data was Redlich–Peterson. However, the g parameter of this model indicated that the adsorption of MB onto AC_b occurs according to the mechanism proposed by Langmuir, which showed maximum monolayer adsorption capacity of 274.62 mg g⁻¹. Kinetic studies demonstrated that the Elovich model is suitable to describe the experimental data. Moreover, it was found that the intraparticle diffusion is the limiting step of adsorption process.     

Magnetic porous carbons with high adsorption capacity synthesized by a microwave-enhanced high temperature ionothermal method from a Fe-based metal-organic framework

Magnetic porous carbons with high surface areas were easily synthesized from a Fe-based metal-organic framework (MOF) by a novel microwave-enhanced high temperature ionothermal method. By choosing a Fe-based MOF called MIL-100(Fe) as both a Fe and C precursor and a porous template, and furfuryl alcohol as a second precursor, a series of γ-Fe₂O₃/C composites with strong magnetism were prepared in 3 min by a microwave-enhanced high temperature ionothermal method. Structure, morphology and magnetic property, as well as porosity of the products, were carefully studied by powder X-ray diffraction, X-ray photoelectron spectroscopy, the BET surface area method, thermogravimetry, vibrating sample magnetometry, scanning electron microscopy, and high resolution transmission electron microscopy. The obtained γ-Fe₂O₃/C composites possess both high surface areas and magnetic characteristics. Their adsorption properties were preliminarily tested by the adsorptive removal of methylene blue from aqueous solution. The results suggest that such magnetic carbon composite exhibited high adsorption capacity (303.95 mg g⁻¹) and fast adsorption kinetics, as well as a perfect magnetic separation performance (M_s = 4.12–19.54 emu g⁻¹), for the MB removal from aqueous solution.     

Comparison of removal of bromothymol blue from aqueous solution by multiwalled carbon nanotube and Zn(OH)2 nanoparticles loaded on activated carbon: A thermodynamic study

In this research Zn(OH)₂ nanoparticles loaded on activated carbon (Zn(OH)₂-NPs-AC) as novel adsorbent and raw multiwalled carbon nanotube (MWCNT) were applied for efficient removal of bromothymol blue (BTB). Both adsorbent has been characterized with different techniques such and SEM, XRD and UV–vis spectrometry. Their size was less than 100 nm. In the removal process the variables are pH, temperature, concentration of BTB, amount of adsorbent and contact time that their influence on removal of BTB was optimized using one at a time approach in batch procedure. Adsorptions of BTB on bath adsorbent depend highly on pH. Following the investigation of temperature effect, the thermodynamic parameters including change in entropy, enthalpy and free Gibbs energy were calculated. For both adsorbents, positive value of enthalpy and negative value of ΔG⁰ show routine feasibility of adsorption using energy. At optimum value of variables, the removal processes onto both adsorbent have high adsorption capacity for best fitting model Langmuir, i.e. for Zn(OH)2-NP-AC and 150 mg/g for PAC. The adsorption rates were well explained with pseudo second order and interparticle diffusion model. It is expected that there could an increase in the number of reactive sites due to their expected high volume, pore size and high surface area.     

Self-assembly hydrothermal assisted synthesis of mesoporous anatase in the presence of ethylene glycol

Mesoporous nanocrystalline anatase was prepared hydrothermally employing P123 as structure-directing agent. Ethylene glycol was used as a key synthesis parameter to fine tune the morphology, crystal size and pore size of the resultant mesophases. The incorporation of EG in the synthesis gel resulted in the formation of 1–2 μm sphere-like shapes and led to an increase in the specific surface area from ∼95 to ∼170 m²/g, decrease in the average pore size from ∼11 to ∼4.8 nm, and decrease in the average crystallite size from ∼17 to ∼12 nm. These mesophases were used as photocatalysts for the UV degradation of methylene blue and methyl orange. The mesoporous anatase phases photodegraded MB ∼1.5–3× faster than commercially available P25 and showed limited photocatalytic behavior for methyl orange.     

Characterization of accessible and inaccessible pores in microporous carbons by a combination of adsorption and small angle neutron scattering

We determine the pore size distribution for five activated carbons (comprising carbide derived as well as commercial activated carbon samples) by the interpretation of experimental small angle neutron scattering (SANS) intensity profiles, based on the primary assumption of an infinitely dilute solution of hollow spherical particles. The interpretation yields the pore size distribution of the carbon samples that have predominantly micropore populations (size <20 Å), but not for carbons which have significant mesopore populations of sizes up to 48 Å and high mass fractal degrees. The pore size distribution (PSD) results based on SANS data reveal significant populations of micropores of size <6.1 Å, and mesopores of size >20 Å, which are not present in the PSD results based on adsorption isotherms of either Ar at 87 K or CO₂ 273 K. This inaccessible porosity becomes accessible to CO₂ and Ar on heat treatment, leading to increase in the adsorption based pore volume. However, the surface area does not commensurately increase, indicating the inaccessible microporosity to predominantly comprise surface defects and roughness that are removed on heat treatment or activation. This finding sheds the light onto the evolution of porosity of activated carbons during gasification or post synthesis-treatment.