Employ a Clay@TMSPDETA hybrid material as an adsorbent to remove textile dyes from wastewater effluents.

A grafting of N1-(3-trimethoxysilylpropyl)diethylenetriamine (TMSPDETA) on natural clay was carried out to obtain an organic-inorganic hybrid clay material that was applied as an adsorbent to the uptake of Reactive Blue 19 (RB-19) and Reactive Green 19 (RG-19) dyes from aqueous wastewaters. This research demonstrates the effect of TMSPDETA contents on amino-functionalized clay materials' hydrophobic/hydrophilic behavior. The resultant material was utilized to uptake reactive dyes in aqueous solutions. The clay@TMSPDETA hybrid material was characterized by isotherm of adsorption and desorption of nitrogen, FTIR, elemental analysis, TGA, pHpzc, total acidity, total basicity groups, and hydrophilic balance. The hybrid samples were more hydrophilic than the pristine clay for ratios from 0.1 up to 0.5 due to adding amino groups to the pristine clay. FTIR spectra suggest that TMSPDETA was grafted onto the clay. The hybrid material presents a surface area 2.17-fold (42.7 m2/g) lower than pristine clay (92.7 m2/g). The total volume of pores of hybrid material was 0.0822 cm3/g, and the pristine clay material was 0.127 cm3/g, corresponding to a diminution of the total pore volume (Vtot) of 1.54 times. The kinetic data followed the pseudo-second-order (PSO) model for RB-19 and RG-19 reactive dyes. The equilibrium data were better fitted to the Liu isotherm model, displaying a Qmax as 178.8 and 361.1 mg g-1 for RB-19 and RG-19, respectively, at 20.0 °C. The main mechanism of interactions of the reactive dyes with the hybrid clay is electrostatic interaction. The clay@TMSPDETA has a very good effect on treating synthetic dye-textile wastewater. The removal percentage of simulated wastewater was up to 97.67% and 88.34% using distilled water and plastic industry wastewater as the solvents, respectively. The clay@TMSPDETA-0.1 could be recycled up to 5 cycles of adsorption and desorption of both dyes, attaining recoveries of 98.42% (RB-19) and 98.32% (RG-19) using 0.1 M HCl + 10% ethanol.

Adsorption of Omeprazole on Biobased Adsorbents Doped with Si/Mg: Kinetic, Equilibrium, and Thermodynamic Studies.

This paper proposes an easy and sustainable method to prepare high-sorption capacity biobased adsorbents from wood waste. A biomass wood waste (spruce bark) was employed to fabricate a composite doped with Si and Mg and applied to adsorb an emerging contaminant (Omeprezole) from aqueous solutions, as well as synthetic effluents loaded with several emerging contaminants. The effects of Si and Mg doping on the biobased material's physicochemical properties and adsorptive performance were evaluated. Si and Mg did not influence the specific surface area values but impacted the presence of the higher number of mesopores. The kinetic and equilibrium data presented the best fitness by the Avrami Fractional order (AFO) and Liu isotherm models, respectively. The values of Qmax ranged from 72.70 to 110.2 mg g-1 (BP) and from 107.6 to 249.0 mg g-1 (BTM). The kinetic was faster for Si/Mg-doped carbon adsorbent, possibly due to different chemical features provoked by the doping process. The thermodynamic data showed that the adsorption of OME on biobased adsorbents was spontaneous and favorable at four studied temperatures (283, 293, 298, 303, 308, 313, and 318 K), with the magnitude of the adsorption correspondent to a physical adsorption process (ΔH° < 2 kJ mol-1). The adsorbents were applied to treat synthetic hospital effluents and exhibited a high percentage of removal (up to 62%). The results of this work show that the composite between spruce bark biomass and Si/Mg was an efficient adsorbent for OME removal. Therefore, this study can help open new strategies for developing sustainable and effective adsorbents to tackle water pollution.

Wood waste-based functionalized natural hydrochar for the effective removal of Ce(III) ions from aqueous solution.

In this study, a sustainable and easily prepared hydrochar from wood waste was studied to adsorb and recover the rare earth element cerium (Ce(III)) from an aqueous solution. The results revealed that the hydrochar contains several surface functional groups (e.g., C-O, C = O, OH, COOH), which largely influenced its adsorption capacity. The effect of pH strongly influenced the Ce(III) removal, achieving its maximum removal efficiency at pH 6.0 and very low adsorption capacity under an acidic solution. The hydrochar proved to be highly efficient in Ce(III) adsorption reaching a maximum adsorption capacity of 327.9 mg g-1 at 298 K. The kinetic and equilibrium process were better fitted by the general order and Liu isotherm model, respectively. Possible mechanisms of Ce(III) adsorption on the hydrochar structure could be explained by electrostatic interactions and chelation between surface functional groups and the Ce(III). Furthermore, the hydrochar exhibited an excellent regeneration capacity upon using 1 mol L-1 of sulfuric acid (H2SO4) as eluent, and it was reused for three cycles without losing its adsorption performance. This research proposes a sustainable approach for developing an efficient adsorbent with excellent physicochemical and adsorption properties for Ce(III) removal.

Use of Biochar Prepared from the Açaí Seed as Adsorbent for the Uptake of Catechol from Synthetic Effluents.

This work proposes a facile methodology for producing porous biochar material (ABC) from açaí kernel residue, produced by chemical impregnation with ZnCl2 (1:1) and pyrolysis at 650.0 °C. The characterization was achieved using several techniques, and the biochar material was employed as an adsorbent to remove catechol. The results show that ABC carbon has hydrophilic properties. The specific surface area and total pore volume are 1315 m2·g−1 and 0.7038 cm3·g−1, respectively. FTIR revealed the presence of oxygenated groups, which can influence catechol adsorption. The TGA/DTG indicated that the sample is thermally stable even at 580 °C. Adsorption studies showed that equilibrium was achieved in <50 min and the Avrami kinetic model best fits the experimental data, while Freundlich was observed to be the best-fitted isotherm model. Catechol adsorption on ABC biochar is governed by van der Waals forces and microporous and mesoporous filling mechanisms. The Qmax is 339.5 mg·g−1 (40 °C) with 98.36% removal of simulated effluent, showing that açaí kernel is excellent biomass to prepare good biochar that can be efficiently used to treat real industrial effluents.

Biosorption of Neodymium (Nd) from Aqueous Solutions Using Spirulina platensis sp. Strains.

Rare earth elements such as neodymium (Nd) are important elements used mainly in developing new technologies. Although they are found in low concentrations in nature, they can be obtained by extracting solid samples such as phosphogypsum. Among the techniques, adsorption has been used successfully with several adsorbent materials. In this work, two strains of Spirulina platensis (LEB-18 and LEB-52) were employed as biosorbents for efficiently removing the Nd element from the aqueous media. Biosorption tests were carried out in a batch system, and the results of the biosorption kinetics showed that for both materials, the biosorption of Nd was better described by the Avrami model. Moreover, it could be considered that 80 min would be necessary to attain the equilibrium of Nd(III) using both biosorbents. The result of the biosorption isotherms showed that for both strains, the best-fitted model was the Liu model, having a maximum biosorption capacity of 72.5 mg g−1 for LEB-18 and 48.2 mg g−1 for LEB-52 at a temperature of 298 K. Thermodynamics of adsorption showed that for both LEB-18 and LEB-52 the process was favorable (∆G° < 0) and exothermic (∆H° −23.2 for LEB-18 and ∆H° −19.9 for LEB-52). Finally, both strains were suitable to uptake Nd, and the better result of LEB-18 could be attributed to the high amount of P and S groups in this biomass. Based on the results, a mechanism of electrostatic attraction of Nd3+ and phosphate and sulfate groups of both strains of Spirulina platensis was proposed.

Composite of methyl polysiloxane and avocado biochar as adsorbent for removal of ciprofloxacin from waters.

Two carbon composite materials were prepared by mixing avocado biochar and methyl polysiloxane (MK). Firstly, MK was dissolved in ethanol, and then the biochar was added at different times. In sample 1 (R1), the time of adding biochar was immediately after dissolving MK in ethanol, and in sample 2 (R2), after 48 h of MK dissolved in ethanol. The samples were characterized by nitrogen adsorption/desorption measurements obtaining specific surface areas (SBET) of 115 m2 g-1 (R1) and 580 m2 g-1 (R2). The adsorbents were further characterized using scanning electron microscopy, FTIR and Raman spectroscopy, adsorption of vapors of n-heptane and water, thermal analysis, Bohem titration, pHpzc, and C H N elemental analysis. R1 and R2 adsorbents were employed as adsorbents to remove the antibiotic ciprofloxacin from the waters. The t1/2 and t0.95 based on the interpolation of Avrami fractional-order were 20.52 and 246.4 min (R1) and 14.00 and 157.6 min (R2), respectively. Maximum adsorption capacities (Qmax) based on the Liu isotherm were 10.77 (R1) and 63.80 mg g-1 (R2) for ciprofloxacin. The thermodynamic studies showed a spontaneous and exothermic process for both samples, and the value of ΔH° is compatible with physical adsorption.

Application of biowaste generated by the production chain of pitaya fruit (Hylocereus undatus) as an efficient adsorbent for removal of naproxen in water.

Pharmaceutical compounds are a serious problem in the environment. They cause damage to the aquatic, animal, and human organisms and soon became considered emerging pollutants where their removal is extremely urgent. Among the techniques used, adsorption has been used with success, where several adsorbent materials, including those from residual biomass, have been used to remove these pollutants. In this study, the skins of the pitaya fruit (Hylocereus undatus) productive chain were carbonized with ZnCl2 to obtain activated carbon and later used in the adsorption of the drug naproxen (NPX) in a batch system. The Freundlich model demonstrated a better adjustment for the equilibrium isotherms. A high adsorption capacity for NPX (158.81 mg g-1) was obtained at 328 K, which can be attributed to the remarkable textural properties of the adsorbent, besides certain functional groups present on its surface. Thermodynamic studies confirmed the endothermic nature of the adsorption process (∆H0 = 0.2898 kJ mol-1). The linear driving force model (LDF) presented a good statistical adjustment to the experimental kinetic data. The application of the material in the treatment of simulated wastewater composed of various pharmaceutical drugs and salts was very promising, reaching 75.7% removal. Therefore, it can be inferred that the application of activated carbon derived from pitaya bark is highly promising in removing the NPX drug and treating synthetic mixtures containing other pharmaceutical substances.

Process Parameters Optimization, Characterization, and Application of KOH-Activated Norway Spruce Bark Graphitic Biochars for Efficient Azo Dye Adsorption.

In this work, Norway spruce bark was used as a precursor to prepare activated biochars (BCs) via chemical activation with potassium hydroxide (KOH) as a chemical activator. A Box-Behnken design (BBD) was conducted to evaluate and identify the optimal conditions to reach high specific surface area and high mass yield of BC samples. The studied BC preparation parameters and their levels were as follows: pyrolysis temperature (700, 800, and 900 °C), holding time (1, 2, and 3 h), and ratio of the biomass: chemical activator of 1: 1, 1.5, and 2. The planned BBD yielded BC with extremely high SSA values, up to 2209 m2·g-1. In addition, the BCs were physiochemically characterized, and the results indicated that the BCs exhibited disordered carbon structures and presented a high quantity of O-bearing functional groups on their surfaces, which might improve their adsorption performance towards organic pollutant removal. The BC with the highest SSA value was then employed as an adsorbent to remove Evans blue dye (EB) and colorful effluents. The kinetic study followed a general-order (GO) model, as the most suitable model to describe the experimental data, while the Redlich-Peterson model fitted the equilibrium data better. The EB adsorption capacity was 396.1 mg·g-1. The employment of the BC in the treatment of synthetic effluents, with several dyes and other organic and inorganic compounds, returned a high percentage of removal degree up to 87.7%. Desorption and cyclability tests showed that the biochar can be efficiently regenerated, maintaining an adsorption capacity of 75% after 4 adsorption-desorption cycles. The results of this work pointed out that Norway spruce bark indeed is a promising precursor for producing biochars with very promising properties.

Facile fabrication of hybrid titanium(IV) isopropoxide/pozzolan nanosheets (TnS-Pz) of high photocatalytic activity: characterization and application for Cr(VI) reduction in an aqueous solution.

This paper presents the synthesis of a hybrid material through the use of natural pozzolan and titanium(IV) isopropoxide using the sol-gel method and its application in the photocatalytic hexavalent chromium reduction. The characterization data indicated a mesoporous material possessing a surface area of 271.7 m2 g-1. The morphology studies (SEM and TEM) showed nanosheet hybrid structures. The analysis of DRUV, FTIR, XRD, and Mössbauer spectroscopy provides a different electronic structure of the synthetized material when compared with the originals, proving the hybridization process between pozzolan and titanium(IV) isopropoxide. The photocatalytic reduction of Cr(VI) to Cr(III) using the hybrid material showed a better performance than conventional photocatalysts (precursor and TiO2-P25). Operational conditions such as chromium initial concentration (0.02-0.20 mM), solution pH (3-6), and type of scavenger (citric or tartaric acid) were evaluated in order to determine the best experimental conditions for the Cr(VI) photoreduction. At their optimum (catalyst load of 15 mg L-1, tartaric acid as scavenger, [scavenger]0/[Cr(VI)]0 M ratio = 3:1, pH 3, and 25 °C), the total photoreduction of 0.20 mM Cr(VI) was achieved in 180 min. The novel hybrid materials synthesized from pozzolan and titanium(IV) isopropoxide showed to be a potential catalyst for the Cr(VI) reduction in aqueous solution. Graphical abstract.

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.

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.

Activated carbons from avocado seed: optimisation and application for removal of several emerging organic compounds.

In this study, avocado seed was successfully used as raw material for producing activated carbons by conventional pyrolysis. In order to determine the best condition to produce the activated carbons, a 22 full-factorial design of experiment (DOE) with three central points was employed by varying the temperature and time of pyrolysis. The two evaluated factors (temperature and time of pyrolysis) strongly influenced the SBET, pore volumes, hydrophobicity-hydrophilicity ratio (HI) and functional groups values; both factors had a negative effect over SBET, pore volumes and functional groups which means that increasing the values of factors leads to decrease of these responses; on the other hand, with regards to HI, both factors caused a positive effect which means that increasing their values, the HI has an enhancement over its values. The produced activated carbon exhibited high specific surface areas in the range of 1122-1584 m2 g-1. Surface characterisation revealed that avocado seed activated carbons (ASACs) have hydrophilic surfaces and have predominantly acidic groups on their surfaces. The prepared ASACs were employed in the adsorption of 25 emerging organic compounds such as 10 pharmaceuticals and 15 phenolic compounds which presented high uptake values for all emerging pollutants. It was observed that the activated carbon prepared at higher temperature of pyrolysis (700 °C), which generated less total functional groups and presented higher HI, was the activated carbon with higher sorption capacity for uptaking emerging organic contaminants. Based on results of this work, it is possible to conclude that avocado seed can be employed as a raw material to produce high surface area and very efficient activated carbons in relation to treatment of polluted waters with emerging organic pollutants.

Synthesis of grafted natural pozzolan with 3-aminopropyltriethoxysilane: preparation, characterization, and application for removal of Brilliant Green 1 and Reactive Black 5 from aqueous solutions.

Natural pozzolan is an amorphous silicate-based material of volcanic origin. In this work, the natural pozzolan was modified by using 3-aminopropyltriethoxysilane (APTES) as a grafting agent. This material was characterized by pHpzc, N2 adsorption/desorption curves, FTIR, TGA/DTG, DRUV, SEM, and elementary analysis. The functionalized materials were used for the removal of Reactive Black 5 (RB-5) and Brilliant Green 1 (BG-1) dyes from aqueous solutions using batch-contact adsorption. The characterization of modified pozzolan by FTIR, TGA/DTG, BET, and DRUV-vis revealed the effectiveness of grafting of amine functional group on pozzolan structure. The kinetic adsorption data were better fitted with general order for both dyes while for equilibrium models were better fitted by the Liu isotherm model. The maximum sorption capacities Q max (at 50 °C) obtained with the modified pozzolan were 350.6 and 300.9 mg g-1 for BG-1 and RB-5, at pH 9.0 and 2.0, respectively. The thermodynamic parameters show that the removal of dyes was spontaneous and endothermic. The modified material was also tested for the treatment of simulated dye house effluents showing very high efficiency.

Alternative treatments to improve the potential of rice husk as adsorbent for methylene blue.

Alternative treatments, such as, NaOH, ultrasound assisted (UA) and supercritical CO2 (SCO2), were performed to improve the potential of rice husk as adsorbent to remove methylene blue (MB) from aqueous media. All the treatments improved the surface characteristics of rice husk, exposing its organic fraction and/or providing more adsorption sites. The Langmuir and Hill models were able to explain the MB adsorption for all adsorbents in all studied temperatures. The experimental and modeled parameters demonstrated that the MB adsorption was favored by the temperature increase and by the use of NaOH-rice husk. The maximum adsorption capacities for the MB solutions (ranging from 10 to 100 mg L-1), estimated from the Langmuir model at 328 K, were in the following order: NaOH rice-husk (65.0 mg g-1) > UA-rice husk (58.7 mg g-1) > SCO2-rice husk (56.4 mg g-1) > raw rice husk (52.2 mg g-1). The adsorption was a spontaneous, favorable and endothermic process. In general, this work demonstrated that NaOH, UA and SCO2 treatments are alternatives to improve the potential of rice husk as adsorbent.

Efficient removal of amoxicillin and paracetamol from aqueous solutions using magnetic activated carbon.

Activated carbon (AC)/CoFe2O4 nanocomposites, MAC-1 and MAC-2, were prepared by a simple pyrolytic method using a mixture of iron(III)/cobalt(II) benzoates and iron(III)/cobalt(II) oxalates, respectively, and were used as efficient adsorbents for the removal of amoxicillin (AMX) and paracetamol (PCT) of aqueous effluents. The synthesized nanocomposites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). The sizes of cobalt ferrite nanoparticles formed from benzoates of iron(III)/cobalt(II) and oxalates of iron(III)/cobalt(II) precursors were in the ranges of 5-80 and 6-27 nm, respectively. The saturation magnetization (M s), remanence (M r) and coercivity (H c) of the MAC-2 nanocomposites were found to be 3.07 emu g-1, 1.36 emu g-1 and 762.49 Oe; for MAC-1, they were 0.2989 emu g-1, 0.0466 emu g-1 and 456.82 Oe. The adsorption kinetics and isotherm studies were investigated, and the results showed that the as-prepared nanocomposites MAC-1 and MAC-2 could be utilized as an efficient, magnetically separable adsorbent for environmental cleanup. The maximum sorption capacities obtained were 280.9 and 444.2 mg g-1 of AMX for MAC-1 and MAC-2, respectively, and 215.1 and 399.9 mg g-1 of PCT using MAC-1 and MAC-2, respectively. Both adsorbents were successfully used for simulated hospital effluents, removing at least 93.00 and 96.77% for MAC-1 and MAC-2, respectively, of a mixture of nine pharmaceuticals with high concentrations of sugars, organic components and saline concentrations.

Mesoporous Nb2O5/SiO2 material obtained by sol-gel method and applied as adsorbent of crystal violet dye.

In this work, SiO2/Nb2O5 (SiNb) material was prepared using sol-gel method and employed as adsorbent for removal of crystal violet dye (CV). The material was characterized using nitrogen adsorption-desorption isotherms, FTIR spectroscopy, pHpzc, and SEM-EDS. The analysis of N2 isotherms revealed the presence of micro- and mesopores in the SiNb sample with specific surface area as high as 747 m2 g-1. For the CV adsorption process, variations of several parameters such as of pH, temperature, contact time, and concentration of dye of the process were evaluated. The optimum initial pH of the CV dye solution was 7.0. The adsorption kinetic and equilibrium data for CV adsorption were suitably represented by the general-order and Liu models, respectively. The maximum adsorption capacity of the CV dye by SiNb was achieved at 303 K, which attained 116 mg g-1 at this temperaure. Dye effluents were simulated and used to check the applicability of the SiNb material for treatment of effluents - the material showed very good efficiency for decolorization of dye effluents.