This paper presents a mineralogical and physicochemical characterization of a Colombian clay found in an area with the greatest exploitation potential of smectites and possible use as an adsorbent for the removal of chromium. The clay was characterized by using X-ray diffraction (XRD), cation exchange capacity (CEC), X-ray fluorescence (XRF), Fourier transform infrared spectroscopy (FT-IR), thermal analysis (TGA/DSC), and nitrogen adsorption at 77 K. The homoionized clay was used as an adsorbent for the removal of Cr(III) in an aqueous solution. The homoionized clay was modified with hexadecyltrimethylammonium bromide (HDTMA-Br), and the organoclay obtained was evaluated for the adsorption of Cr(VI) in aqueous solution. The XRD analysis showed that the clay from Armero-Guayabal is primarily constituted by smectite (48 wt%) followed by quartz mineral (21 wt%). The chemical analysis of bulk clay showed that the predominant oxides are SiO2 (55.81 wt%), Al2O3 (16.25 wt%), and Fe2O3 (7.51 wt%), and the nitrogen adsorption indicated that the bulk clay has a specific surface area of 45.1 m2/g. Homoionized clay and organoclay achieved Cr(III) and Cr(VI) removals greater than 85.05 ± 2.04% (pH between 3 and 4) and 82.93 ± 1.03% (pH between 3 and 5), respectively, proving the potential of these materials for the removal of heavy metals in an aqueous solution.

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Clay minerals can be modified organically by a cationic surfactant resulting in materials known as organoclays. The organoclays have been used as adsorbents of most of the organic contaminants in the aqueous solution and oxyanions of the heavy metal. In this study, a Colombian bentonite was modified with hexadecyltrimethylammonium bromide to obtain an organobentonite, and its capacity to adsorb Cr(VI) oxyanions in the aqueous solution was evaluated. The effect of pH, stirring speed, adsorbent amount, contact time, and ionic strength were investigated at 25°C. Stirring speeds above 200 rpm, contact times greater than 120 min, and the addition of NaCl (0.1 to 2.0 mM) did not have a significant effect on Cr(VI) removal. The influence of the adsorbent amount and pH on Cr(VI) adsorption was studied by the response surface methodology (RSM) approach based on a complete factorial design 32. Results proved that the Cr(VI) adsorption follows a quadratic model with high values of coefficient of determination (R2 = 95.1% and adjusted R2 = 93.9%). The optimal conditions for removal of Cr(VI) from an aqueous solution of 50 mg/L were pH of 3.4 and 0.44 g amount of the adsorbent. The adsorption isotherm data were fitted to the Langmuir and Freundlich adsorption isotherm models, and the model parameters were evaluated. The maximum adsorption capacity of Cr(VI) onto organobentonite calculated from the Langmuir model equation was 10.04 ± 0.34 mg/g at 25°C. The results suggest that organobentonite is an effective adsorbent for Cr(VI) removal, with the advantage of being a low-cost material.

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Catalytic degradation of textile dyes in diluted aqueous solutions with minimal consumption of energy is a great challenge for wastewater treatment and environmental protection. Efficient heterogeneous catalysts are needed to completely oxidize azo-dyes under soft conditions. In this work, catalysts of Cu-Co oxide (1:2 molar ratio) supported on halloysite (Ha) nanotubes (CuCo(5%)/Ha and CuCo(10%)/Ha) were synthesized and used in the catalytic wet peroxide oxidation of reactive yellow 145 (RY-145) and basic red 46 (BR-46). The catalysts were characterized by chemical analysis, X-ray diffraction, Raman spectroscopy, N 2 adsorption isotherms, scanning electron microscopy and transmission electron microscopy. The results showed that the synthesized catalysts possess nanotubular structure with good mesoporosity, and the spinel structure CuCo 2 O 4 was identified as the active phase deposited on Ha. The catalysts degraded these azo-dyes in diluted solutions (22 mg l −1 of RY-145 and 35 mg l −1 of BR-46) under mild reaction conditions (25 • C, atmospheric pressure, pH 4 and minimum amounts of both catalyst and H 2 O 2). Significant levels of dye conversion (93.1 ± 2.2% for RY-145 and 54.4 ± 2.0% for BR-46) were achieved in a relatively short time. In addition, significant values of total organic carbon removal (59.5 ± 1.8% for RY-145 and 33.9 ± 1.4% for BR-46) were obtained, indicating the total oxidation of a significant fraction of these dyes to CO 2 and H 2 O.

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The effect of pH, ionic strength (NaCl added), agitation speed, adsorbent mass, and contact time on the removal of tartrazine from an aqueous solution, using an organobentonite, has been studied. A complete factorial design 32 with two replicates was used to evaluate the influence of the dye concentration (30, 40, and 50 mg/L) and amount of adsorbent (25, 35, and 45 mg) on decolorization of the solution. Experimental data were evaluated with Design Expert® software using a response surface methodology (RSM) in order to obtain the interaction between the processed variables and the response. pH values between 2 and 9, stirring speed above 200 rpm, and contact time of 60 min did not have a significant effect on decolorization. The optimum conditions for maximum removal of tartrazine from an aqueous solution of 30 mg/L were follows: pH = 6.0, NaCl concentration = 0.1 M, stirring speed = 230 rpm, temperature = 20°C, contact time = 60 min, and the organobentonite amount = 38.04 mg. The equilibrium isotherm at 20°C was analyzed by means of the Langmuir and Freundlich models, and the maximum adsorption capacity obtained was 40.79 ± 0.71 mg/g. This adsorption process was applied in a sample of industrial wastewater containing tartrazine and sunset yellow, having obtained a decolorization rate higher than 98% for both dyes. These results suggest that organobentonite is an effective adsorbent for the removal of anionic dyes from an aqueous solution.

A systematic literature review of publications from 2000 to 2020 was carried out to identify research trends on adsorbent materials for the removal of caffeine from aqueous solutions. Publications were retrieved from three databases (Scopus, Web of Science, and Google Scholar). Words “adsorption AND caffeine” were examined into titles, abstracts, and keywords. A brief bibliometric analysis was performed with emphasis on the type of publication and of most cited articles. Materials for the removal of caffeine were classified according to the type of material into three main groups: organic, inorganic, and composites, each of them subdivided into different subgroups consistent with their origin or production. Tables resume for each subgroup of adsorbents the key information: specific surface area, dose, pH, maximum adsorption capacity, and isotherm models for the removal of caffeine. The highest adsorption capacities were achieved by organic adsorbents, specifically those with granular activated carbon (1961.3 mg/g) and grape stalk activated carbon (916.7 mg/g). Phenyl-phosphate-based porous organic polymer (301 mg/g), natural sandy loam sediment (221.2 mg/g), composites of MCM-48 encapsulated graphene oxide (153.8 mg/g), and organically modified clay (143.7 mg/g) showed adsorption capacities lower than those of activated carbons. In some activated carbons, a relation between the specific surface area (SSA) and the maximum adsorption capacity (Qmax) was found.