Single-step pyrolysis for producing magnetic activated carbon from tucumã (Astrocaryum aculeatum) seed and nickel(II) chloride and zinc(II) chloride. Application for removal of nicotinamide and propanolol.

The present research describes the synthesis of new nanomagnetic activated carbon material with high magnetization, and high surface area prepared in a single pyrolysis step that is used for the carbonization, activation, and magnetization of the produced material. The pyrolysis step of tucumã seed was carried out in a conventional tubular oven at 600 °C under N2-flow. It was prepared three magnetic carbons MT-1.5, MT-2.0, MT-2.5, that corresponds to the proportion of biomass: ZnCl2 always 1:1 and varying the proportion of NiCl2 of 1.5, 2.0, and 2.5, respectively. These magnetic nanocomposites were characterized by Vibrating Sample Magnetometer (VSM), X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, hydrophobic/hydrophilic balance, CHN/O elemental analysis, modified Boehm titration, N2 adsorption-desorption isotherms; and pHpzc. All the materials obtained presented Ni particles with an average crystallite size of less than 33 nm. The MT-2.0 was employed for the removal of nicotinamide and propranolol from aqueous solutions. Based on Liu isotherm, the Qmax was 199.3 and 335.4 mg g-1 for nicotinamide and propranolol, respectively. MT-2.0 was used to treat simulated pharmaceutical industry effluents attaining removal of all organic compounds attaining up to 99.1 % of removal.

Removal of amoxicillin from simulated hospital effluents by adsorption using activated carbons prepared from capsules of cashew of Para.

High-surface-area activated carbons were prepared from an agroindustrial residue, Bertholletia excelsa capsules known as capsules of Para cashew (CCP), that were utilized for removing amoxicillin from aqueous effluents. The activated carbons were prepared with the proportion of CCP:ZnCl2 1:1, and this mixture was pyrolyzed at 600 (CCP-600) and 700 °C (CCP700). The CCP.600 and CCP.700 were characterized by CHN/O elemental analysis, the hydrophobic/hydrophilic ratio, FTIR, TGA, Boehm titration, total pore volume, and surface area. These analyses show that the adsorbents have different polar groups, which confers a hydrophilic surface. The adsorbents presented surface area and total pore volume of 1457 m2 g-1 and 0.275 cm3 g-1 (CCP.600) and 1419 m2 g-1 and 0.285 cm3 g-1 (CCP.700). The chemical and physical properties of the adsorbents were very close, indicating that the pyrolysis temperature of 600 and 700 °C does not bring relevant differences in the physical and chemical properties of these adsorbents. The adsorption data of kinetics and equilibrium were successfully adjusted to Avrami fractional-order and Liu isotherm model. The use of the adsorbents for treatment of simulated hospital effluents, containing different organic and inorganic compounds, showed excellent removals (up to 98.04% for CCP.600 and 98.60% CCP.700). Graphical abstract.

Conversion of Eragrostis plana Nees leaves to activated carbon by microwave-assisted pyrolysis for the removal of organic emerging contaminants from aqueous solutions.

Eragrostis plana Nees leaves, abundant lignocellulosic biomass, was used as carbon source for preparation of activated carbon, by using microwave-assisted pyrolysis and chemical activation. The novel activated carbon (MWEPN) was characterised by FTIR, CHN elemental analysis, Boehm's titration method, TGA, SEM, N2 adsorption/desorption curves and pH of the point of zero charge (pHpzc). Afterwards, the adsorbent was successfully employed for adsorption of the two emerging contaminants (caffeine and 2-nitrophenol). The results indicated that MWEPN had a predominantly mesoporous structure with a high surface area of 1250 m2 g-1. FTIR analysis indicated the presence of carbonyl, hydroxyl and carboxylic groups on the surface of MWEPN. The Boehm analysis showed the existence of the high amount of acid moieties on the surface of activated carbon. Adsorption kinetic indicated that the system followed the Avrami fractional order at the optimal pH of 7. The equilibrium time was attained at 30 min. The Liu isotherm model better described the isothermal data. Based on the Liu isotherm, the maximum sorption capacities (Qmax) of caffeine and 2-nitrophenol adsorbed onto activated carbon at 25 °C were 235.5 and 255.8 mg g-1, respectively.

Eragrostis plana Nees as a novel eco-friendly adsorbent for removal of crystal violet from aqueous solutions.

Eragrostis plana Nees (EPN) was used as new and eco-friendly adsorbent for the removal of crystal violet dye (CV) from aqueous solution. Specific surface area (BET), scanning electron microscopy (SEM), infrared spectroscopy (ATR-FTIR), point of zero charge (pHPZC), and modified Boehm titration method were used to characterize the EPN material. The effects of initial pH of solution, adsorbent mass, contact time and initial dye concentration, and temperature were studied in batch adsorption mode. Kinetic data were evaluated by pseudo-first-order and pseudo-second-order models. The result exhibited that pseudo-second-order model well described the adsorption kinetics of CV onto EPN. Langmuir, Freundlich, and Sips isotherm models were used for analysis of the isothermal data. The equilibrium data of adsorption of CV onto EPN was better fitted with the Sips isotherm. Based on the Sips isotherm model, the maximum adsorption capacity was 76.20 ± 1.20 mg g-1 at 333 K. A high desorption of CV from EPN was obtained using 1.00 mol L-1 of CH3COOH as eluent. The thermodynamic data indicated that the adsorption was spontaneous, endothermic, and physical process. EPN can be used as alternative adsorbent to remove CV from aqueous solution.

Effects of first-row transition metals and impregnation ratios on the physicochemical properties of microwave-assisted activated carbons from wood biomass.

First-row transition metals (Co, Ni, Cu and Zn) were successfully used in the preparation of activated carbons from wood biomass via microwave-assisted irradiation. Physical-chemical properties of the produced materials (MWAC) were studied by nitrogen adsorption-desorption curves, SEM, FTIR, UV-vis DRS and synchronous fluorescence spectroscopy, CHN elemental analysis, TGA/DTG, pHzpc, hydrophobic properties, and total acidity and basicity groups. Results showed that the metals were bound successfully in different amounts with surface functional groups of the wood biomass through ion exchange and surface complexation interaction during the impregnation step. Zn2+ and Cu2+ formed the most complexes. MWAC impregnated with Zn2+ showed higher pore volumes and surface areas, followed by Cu2+, Co2+ and Ni2+, independently of the ratio used. As the metal : biomass ratio was increased from 0.5 to 2, the surface area of MWAC increased from 300 to 620m2g-1 for Co-MC, 260 to 381m2g-1 for Ni-MC, 449 to 765m2g-1 for Cu-MC and from 572 to 1780m2g-1 for Zn-MC. The samples showed high values of carbon contents and oxygen-containing groups. An adsorption experiment revealed that samples prepared using ZnCl2 showed the highest sorption capacities (qe) for the tested adsorbates, followed by CuCl2, CoCl2 and NiCl2. These results matched with the surface areas and pore volumes trends, which were found to follow atomic number and melting point trends-Ni(II)bisphenol A>hydroquinone>4-nitro phenol>2-naphtol>paracetamol>caffeine>resorcinol.

Microwave-assisted activated carbon from cocoa shell as adsorbent for removal of sodium diclofenac and nimesulide from aqueous effluents.

Microwave-induced chemical activation process was used to prepare an activated carbon from cocoa shell for efficient removal of two anti-inflammatories, sodium diclofenac (DFC) and nimesulide (NM), from aqueous solutions. A paste was obtained from a mixture of cocoa shell and inorganic components; with a ratio of inorganic: organic of 1 (CSC-1.0). The mixture was pyrolyzed in a microwave oven in less than 10 min. The CSC-1.0 was acidified with a 6 mol L(-1) HCl under reflux to produce MWCS-1.0. The CSC-1.0 and MWCS-1.0 were characterized using FTIR, SEM, N2 adsorption/desorption curves, X-ray diffraction, and point of zero charge (pHpzc). Experimental variables such as initial pH of the adsorbate solutions and contact time were optimized for adsorptive characteristics of MWCS-1.0. The optimum pH for removal of anti-inflammatories ranged between 7.0 and 8.0. The kinetic of adsorption was investigated using general order, pseudo first-order and pseu do-second order kinetic models. The maximum amounts of DCF and NM adsorbed onto MWCS-1.0 at 25 °C are 63.47 and 74.81 mg g(-1), respectively. The adsorbent was tested on two simulated hospital effluents. MWCS-1.0 is capable of efficient removal of DCF and NM from a medium that contains high sugar and salt concentrations.

Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: Kinetic, equilibrium, and thermodynamic studies.

Activated (AC-PW) and non-activated (C-PW) carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the equilibrium using C-PW and AC-PW as adsorbents was 5 and 4h at 298 K, respectively. The fractionary-order kinetic model provided the best fit to experimental data compared with other models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption experiments ranging from 298 to 323 K.

Metal nanoparticle/ionic liquid/cellulose: new catalytically active membrane materials for hydrogenation reactions.

Transition metal-containing membrane films of 10, 20, and 40 µm thickness were obtained by the combination of irregularly shaped nanoparticles with monomodal size distributions of 4.8 ± 1.1 nm (Rh(0)) and 3.0 ± 0.4 nm (Pt(0)) dispersed in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI·(NTf)(2)) with a syrup of cellulose acetate (CA) in acetone. The Rh(0) and Pt(0) metal concentration increased proportionally with increases in film thickness up to 20 µm, and then the material became metal saturated. The presence of small and stable Rh(0) or Pt(0) nanoparticles induced an augmentation in the CA/IL film surface areas. The augmentation of the IL content resulted in an increase of elasticity and decrease in tenacity and toughness, whereas the stress at break was not influenced. The introduction of IL probably causes an increase in the separation between the cellulose macromolecules that results in a higher flexibility, lower viscosity, and better formability of the cellulose material. The nanoparticle/IL/CA combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The nanoparticle/IL/cellulose acetate film membranes display higher catalytic activity (up to 7353 h(-1) for the 20 µm film of CA/IL/Pt(0)) and stability than the nanoparticles dispersed only in the IL.

Application of Brazilian pine-fruit shell as a biosorbent to removal of reactive red 194 textile dye from aqueous solution kinetics and equilibrium study.

The Brazilian pine-fruit shell (Araucaria angustifolia) is a food residue, that was used as biosorbent for the removal of non-hydrolyzed reactive red 194 (NRR) and hydrolyzed reactive red 194 (HRR) forms from aqueous solutions. Chemical treatment of Brazilian pine-fruit shell (PW), with chromium (Cr-PW), with acid (A-PW), and with acid followed by chromium (Cr-A-PW) were also tested as alternative biosorbents for the removal of NRR and HRR from aqueous effluents. It was observed that the treatment of the Brazilian pine-fruit shell with chromium (Cr-PW and Cr-A-PW) leaded to a remarkable increase in the specific surface area and average porous volume of these biosorbents when compared to unmodified Brazilian pine-fruit shell (PW). The effects of shaking time, biosorbent dosage and pH on biosorption capacity were studied. In acidic pH region (pH 2.0) the biosorption of NRR and HRR were favorable. The contact time required to obtain the equilibrium was 24h at 25 degrees C. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. For NRR reactive dye the equilibrium data were best fitted to the Sips isotherm model using PW and A-PW as biosorbents, and Redlich-Peterson isotherm model using Cr-PW and Cr-A-PW as biosorbents. For HRR reactive dye the equilibrium data were best fitted to the Sips isotherm model using PW, A-PW and Cr-A-PW and the Redlich-Peterson isotherm model for Cr-PW as biosorbent.

Methylene blue biosorption from aqueous solutions by yellow passion fruit waste.

The yellow passion fruit (Passiflora edulis Sims. f. flavicarpa Degener) (YPFW) a powdered solid waste, was tested as biosorbent for the removal of a cationic dye, methylene blue (MB), from aqueous solutions. Adsorption of MB onto this low-cost natural adsorbent was studied by batch adsorption at 25 degrees C. The effects of shaking time, biosorbent dosage and pH on adsorption capacity were studied. In alkaline pH region the adsorption of MB was favorable. The contact time required to obtain the maximum adsorption was 48 h at 25 degrees C. Four kinetic models were tested, being the adsorption kinetics better fitted to pseudo-first order and ion exchange kinetic models. The ion exchange and pseudo-first order constant rates were 0.05594 and 0.05455 h(-1), respectively. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account the analysis of the normal distribution of the residuals (difference of q(measured)-q(model)), the data were best fitted to Sips isotherm model. The maximum amount of MB adsorbed on YPFW biosorbent was 44.70 mg g(-1).

Supported ionic liquid phase rhodium nanoparticle hydrogenation catalysts.

Rh(0) nanoparticles (ca. 4 nm) dispersed in an ionic liquid (1-n-butyl-3-methylimidazolium tetrafluoroborate) were immobilized within a silica network, prepared by the sol-gel method. The effect of the sol-gel catalyst (acid or base) on the encapsulated ionic liquid and Rh(0) content, on the silica morphology and texture, and on the catalyst alkene hydrogenation activity was investigated. The Rh(0) content in the resulting xerogels (ca. 0.1 wt% Rh/SiO(2)) was shown to be independent of the sol-gel process. However, acidic conditions afforded higher contents of encapsulated ionic liquid and xerogels with larger pore diameters, which in turn might be responsible for the higher catalyst activity in hydrogenation of the alkenes.

Adsorption of Cu(II) on Araucaria angustifolia wastes: determination of the optimal conditions by statistic design of experiments.

Wastes of Araucaria angustifolia (named pinhão) natural (PW) and also loaded with Congo red (CRP) were tested as low-cost adsorbents for Cu(II) removal from aqueous solutions. In order to reduce the total number of experiments to achieve the best conditions of the batch adsorption procedure, three sets of statistical designs of experiments were carried-out for each adsorbent. Initially, a full 2(4) factorial design for each adsorbent with two central points (18 experiments) were performed, to optimize the following factors: mass of adsorbent (m), pH, time of contact (t) and initial metallic ion concentration (Co). These results indicated that almost all the main factors and its interactions were significant. It was verified for both adsorbents, that a mass of 30.0mg leaded to higher Cu(II) uptake and that the best pH for Cu(II) adsorption was 5.6. In order to continue the batch adsorption optimization of the systems, a central composite surface analysis design with two factors (Co, t) containing 13 experiments, divided in to four cube points, four axial points and five centre points was carried-out for each adsorbent. By performing these two sets of statistical design of experiments, the best conditions for Cu(II) uptake using pinhão wastes (PW) and pinhão wastes loaded with Congo red (CRP) using batch adsorption system, where: m=30.0mg of adsorbent; pH 5.6; t=2.5h. After optimizing the batch adsorption system by statistical design of experiments, isotherms for Cu(II) uptake using PW and CRP were performed. These isotherms fitted to the linear Langmuir and Freundlich models.

Use of Ponkan mandarin peels as biosorbent for toxic metals uptake from aqueous solutions.

Waste Ponkan mandarin (Citrus reticulata) peel was used as biosorbent to extract Ni(II), Co(II) and Cu(II) from aqueous solutions at room temperature. To achieve the best adsorption conditions the influence of pH and contact time were investigated. The isotherms of adsorption were fitted to the Langmuir equation. Based on the capacity of adsorption of the natural biosorbent to interact with the metallic ions, the following results were obtained 1.92, 1.37 and 1.31 mmol g(-1) for Ni(II), Co(II) and Cu(II), respectively, reflecting a maximum adsorption order of Ni(II)>Co(II)>Cu(II). The quick adsorption process reached the equilibrium before 5, 10 and 15 min for Ni(II), Co(II) and Cu(II), respectively, with maximum adsorptions at pH 4.8. In order to evaluate the Ponkan mandarin peel a biosorbent in dynamic system, a glass column was fulfilled with 1.00 g of this natural adsorbent, and it was fed with 5.00 x 10(-4)mol l(-1) of Ni(II) or Co(II) or Cu(II) at pH 4.8 and 3.5 ml min(-1). The lower breakpoints (BP(1)) were attained at concentrations of effluent of the column attained the maximum limit allowed of these elements in waters (>0.1 mg l(-1)) which were: 110, 100 and 130 bed volumes (V(effluent)/V(adsorbent)), for Ni(II), Co(II) and Cu(II), respectively. The higher breakpoints (BP(2)) were attained when the complete saturation of the natural adsorbent occurred, and the values obtained were: 740, 540 and 520 bed volumes for Ni(II), Co(II) and Cu(II), respectively.

Statistical design of experiments as a tool for optimizing the batch conditions to Cr(VI) biosorption on Araucaria angustifolia wastes.

In order to reduce the total number of experiments for achieving the best conditions for Cr(VI) uptake using Araucaria angustifolia (named pinhão) wastes as a biosorbent, three statistical design of experiments were carried out. A full 2(4) factorial design with two blocks and two central points (20 experiments) was experimented (pH, initial metallic ion concentration-C(o), biosorbent concentration-X and time of contact-t), showing that all the factors were significant; besides, several interactions among the factors were also significant. These results led to the performance of a Box-Behnken surface analysis design with three factors (X, C(o) and t) and three central points and just one block (15 experiments). The performance of these two statistical designs of experiments led to the best conditions for Cr(VI) biosorption on the pinhão wastes using a batch system, where: pH 2.0; C(o) = 1200 mg l(-1) Cr(VI); X = 1.5 g l(-1) of biosorbent; t = 8 h. The maximum Cr(VI) uptake in these conditions was 125 mg g(-1). After evaluating the best Cr(VI) biosorption conditions on pinhão wastes, a new Box-Behnken surface analysis design was employed in order to verify the effects of three concomitant ions (Cl(-), NO(3)(-) and PO(4)(3-)) on the biosorption of Cr(VI) as a dichromate on the biosorbent (15 experiments). These results showed that the tested anions did not show any significant effect on the Cr(VI) uptake by pinhão wastes. In order to evaluate the pinhão wastes as a biosorbent in dynamic system, a glass column was fulfilled with pinhão wastes (4.00 g) as biosorbent, and it was fed with 25.0 mg l(-1) Cr(VI) at pH 2.0 and 2.5 ml min(-1). The breakpoint was attained when concentrations of effluent of the column attained the value of 0.05 mg l(-1) Cr(VI) using 5550 ml of the metallic ion solution. In these conditions, the biosorbent was able to remove completely Cr(VI) from aqueous solution with a ratio of Cr(VI) effluent volume/biosorbent volume of 252.3.

A mathematical simulation of H+ ion chemisorption by anilinepropylsilica xerogels.

A study of the basic characteristics of the hybrid anilinesilica xerogel, which shows promising metal sorption properties, was carried out. A simplified approach to describe the protonization affinity of the immobilized aniline was developed, and it was compared with the known values for free aniline. The proton chemisorption process may be described properly by a model based on the Langmuir equation, and the immobilized groups have less affinity to the H(+) than to the free aniline.

Anilinepropylsilica xerogel used as a selective Cu (II) adsorbent in aqueous solution.

The metal ion adsorption properties of the microporous hybrid anilinepropylsilica xerogel were studied using divalent copper, zinc, and cadmium ions in aqueous solutions in concentrations ranging from 10(-4) up to 5x10(-3) moll(-1). At low concentrations the surface of the solid phase presents selectivity for Cu (II), even in competitive conditions. This preferential sorption ability for copper in relation to zinc and cadmium ions was interpreted by considering the xerogel morphology.