Next Article in Journal
Connexin 43: An Interface Connecting Neuroinflammation to Depression
Next Article in Special Issue
Regulatory Mechanism of Opposite Charges on Chiral Self-Assembly of Cellulose Nanocrystals
Previous Article in Journal
Efflux Pump (QacA, QacB, and QacC) and β-Lactamase Inhibitors? An Evaluation of 1,8-Naphthyridines against Staphylococcus aureus Strains
Previous Article in Special Issue
Orbital Polarization-Dependent Fragment Twist-Induced Intramolecular Electric-Field-Driven Charge Transfer
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 28
Issue 4
10.3390/molecules28041821
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Adsorptive Features of Magnetic Activated Carbons Prepared by a One-Step Process towards Brilliant Blue Dye

by
Victoria X. Nascimento
1,
Carlos Schnorr
2,
Sabrina F. Lütke
1,
Maria C. F. Da Silva
1,
Fernando Machado Machado
3,
Pascal S. Thue
4,
Éder C. Lima
5,
Julien Vieillard
6,
Luis F. O. Silva
2,* and
Guilherme L. Dotto
1,6,*
1
Research Group on Adsorptive and Catalytic Process Engineering (ENGEPAC), Federal University of Santa Maria, Av. Roraima, 1000-7, Santa Maria 97105-900, RS, Brazil
2
Department of Civil and Environmental, Universidad De La Costa, Calle 58 # 55-66, Barranquilla 080002, Atlántico, Colombia
3
Technology Development Center, Federal University of Pelotas-UFPEL, Gomes Carneiro St., Pelotas 96010-610, RS, Brazil
4
Environmental Science Graduate Program, Engineering Center, Federal University of Pelotas (UFPel), 989 Benjamin Constant St., Pelotas 96010-020, RS, Brazil
5
Institute of Chemistry, Federal University of Rio Grande do Sul-UFRGS, Av. Bento Gonçalves 9500, P.O. Box 15003, Porto Alegre 91501-970, RS, Brazil
6
Laboratoire de Chimie Organique, Normandie Université, UNIROUEN, INSA Rouen, CNRS, COBRA (UMR 6014), 27000 Evreux, France
*
Authors to whom correspondence should be addressed.
Molecules 2023, 28(4), 1821; https://doi.org/10.3390/molecules28041821
Submission received: 16 January 2023 / Revised: 8 February 2023 / Accepted: 11 February 2023 / Published: 15 February 2023
(This article belongs to the Special Issue Carbon Nanomaterials: Design and Applications)
Browse Figures
Versions Notes

Abstract

:
Water pollution by dyes has been a major environmental problem to be tackled, and magnetic adsorbents appear as promising alternatives to solve it. Herein, magnetic activated carbons were prepared by the single−step method from Sapelli wood sawdust, properly characterized, and applied as adsorbents for brilliant blue dye removal. In particular, two magnetic activated carbons, MAC1105 and MAC111, were prepared using the proportion of biomass KOH of 1:1 and varying the proportion of NiCl2 of 0.5 and 1. The characterization results demonstrated that the different proportions of NiCl2 mainly influenced the textural characteristics of the adsorbents. An increase in the surface area from 260.0 to 331.5 m2 g−1 and in the total pore volume from 0.075 to 0.095 cm3 g−1 was observed with the weight ratio of NiCl2. Both adsorbents exhibit ferromagnetic properties and the presence of nanostructured Ni particles. The different properties of the materials influenced the adsorption kinetics and equilibrium of brilliant blue dye. MAC111 showed faster kinetics, reaching the equilibrium in around 10 min, while for MAC1105, it took 60 min for the equilibrium to be reached. In addition, based on the Sips isotherm, the maximum adsorption capacity was 98.12 mg g−1 for MAC111, while for MAC1105, it was 60.73 mg g−1. Furthermore, MAC111 presented the potential to be reused in more adsorption cycles than MAC1105, and the use of the adsorbents in the treatment of a simulated effluent exhibited high effectiveness, with removal efficiencies of up to 90%.

Graphical Abstract

1. Introduction

Due to its pollution and scarcity, the water crisis has generated widespread concern worldwide. Several complex contaminants from industrial and domestic activities are indirectly or directly released into water bodies [1]. In this context, dyes are the main organic contaminants [2]. These compounds are widely used in textile, leather, cosmetics, plastic, pharmaceutical, food processing, and other industrial sectors [3]. Currently, more than 100,000 commercial dyes are available, and the estimated annual production of synthetic dyes is about 30,000 tons [2]. A large part of these dyes is usually discharged into water bodies through untreated wastewater, a considerable pollution source [4]. In general, dyes have a complex chemical construction, making their degradation difficult, and consequently, they remain longer in the environment [2]. The presence of dyes in water bodies can affect the photosynthetic activity of aquatic life [5,6]. In addition, it can affect some conditions, such as biological and chemical oxygen demands, dissolved oxygen concentration, pH, and the life of aquatic animals and their predators [2]. Thus, the treatment of wastewater containing dyes is a very relevant issue.
Several technologies have been used to remove dyes from wastewater, such as advanced oxidation processes [7], flocculation/coagulation [8], biological treatments [9], ion exchange [10], and adsorption [11]. Among these methods, adsorption is a promising technique for removing colored contaminants from wastewater [12,13]. Adsorption is promising since it has advantages such as applicability in different scenarios, ease of implementation, low space requirement, design simplicity, economic feasibility, and high efficiency [13,14].
In adsorption operations, activated carbon (AC) is widely used for removing inorganic and organic contaminants from aqueous solutions [15,16]. This adsorbent presents high surface area, pore volume, and abundant surface functional groups [17]. In parallel, the utilization of lignocellulosic wastes as precursor materials for AC production is a viable alternative due to its low cost, availability, and ecological suitability [18,19,20]. In previous literature, several studies have been carried out on developing AC from different lignocellulosic wastes such as pecan nutshells [21], tangerine seed [22], banana peel [23], apple peel [24], pistachio wood wastes [25], and teak wood sawdust [26]. Specifically, sawdust, a lignocellulosic waste obtained from various woodworking operations, is an accessible, abundant, and low-cost by-product and presents disposal problems [27,28]. Thus, the conversion of sawdust into adsorbents is a good alternative for managing this waste. In addition, the development of magnetic adsorbents has also been highlighted since it facilitates the separation of the solid from the liquid phase without requiring centrifugation [29,30,31,32]. Therefore, magnetic-activated carbons (MAC) have recently been proposed to remove contaminants [33,34,35,36,37]. Generally, these magnetic-activated carbons are prepared by co-precipitation, the activated carbon’s impregnation of the precursor material, followed by pyrolysis [37]. In the last procedure, carbonization, activation, and magnetization occur in a single step—an economic and convenient advantage [38]. However, regardless of the preparation method, evaluating different experimental conditions to prepare AC is fundamental to finding a material with relevant features for adsorption [12].
Herein, MACs were produced from Sapelli wood sawdust, characterized, and applied in dye adsorption from an aqueous solution. The precursor was first impregnated with NiCl2 and KOH; then, the impregnated materials underwent pyrolysis. The effect of different weight ratios of NiCl2 was investigated regarding their characteristics and performance on dye adsorption. Characterization was performed by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR), N2 adsorption/desorption isotherms, X-ray diffraction (XRD), thermogravimetric analysis (TGA/DTG), and vibrating sample magnetometer (VSM). Adsorption studies involved kinetic and equilibrium experiments, regeneration/reuse tests, and tests with simulated industrial effluent.

2. Results and Discussion

2.1. Features of the Magnetic Activated Carbons

2.1.1. Scanning Electron Microscopy Images

The SEM images of MAC1105 and MAC111, with magnifications of 5000× and 10,000×, are shown in Figure 1a,b and Figure 1d,e, respectively. It is possible to observe that both materials had an irregular surface, the presence of roughness and some grains, and cavities along their surfaces. In addition, MAC111 seems to have a higher quantity of cavities than MAC1105, which is the main difference observed between the surface morphology of the produced MACs. These cavities are favorable for application in adsorption processes because they enable the BB molecules to penetrate the adsorbent until reaching the pores [39,40]. Such cavities can be formed by the decomposition induced by KOH [41]. In addition, since both MACs were prepared with the same weight ratio of KOH, the higher quantity of cavities observed for MAC111 can be attributed to the higher weight ratio of NiCl2, which can cause the dehydration and decomposition of the lignocellulosic material [40]. This effect will be further explained in this paper.
Figure 1c shows the EDS spectrum of MAC1105, and Figure 1f shows the EDS spectrum of MAC111. For both MACs, carbon (C), oxygen (O), and nickel (Ni) were the major elements. The appearance of Si comes from the precursor material (Sapelli wood sawdust) used in the production of the adsorbents. Ni indicates that the Ni compounds formed during the pyrolysis were not eliminated with the acid wash but remained embedded in the carbon matrix. This behavior is important since these Ni compounds generate magnetization in the samples.

2.1.2. Functional Groups on the Magnetic Activated Carbons Surface

Figure 2 shows the FTIR spectra of MAC1105 (Figure 2a) and MAC111 (Figure 2b). Bands at 3431, 1625, and 1558 cm−1 can be observed for both materials. The bands at 3431 cm−1 can be ascribed to the stretching vibrations of O–H bonds from alcohols, phenols, or carboxyls present as functional groups on the surface of the MACs and can also be ascribed to the presence of adsorbed water [42]. The bands at 1625 cm−1 can be attributed to the C=O bonds [43]. At 1558 cm−1, the bands observed can be attributed to the C=C stretching vibrations of the aromatic rings of the activated carbons’ structure [44]. Besides that, bands at 1034 e 1028 cm−1 can be observed for MAC1105 and MAC111, respectively, and are due to the C–O stretching vibrations of hydroxyl in alcohols, phenols, or carboxyls [45].

2.1.3. Textural Characteristics

Figure 3 shows the N2 adsorption/desorption isotherms and the BJH desorption pore size distributions for MAC1105 (Figure 3a) and MAC111 (Figure 3b). According to the IUPAC classification of adsorption isotherms, the adsorption isotherms of both materials were Type IV, accompanied by hysteresis [46]. Type IV isotherm is a characteristic of mesoporous materials. The adsorption hysteresis exhibited by both MACs was Type H4. This type of hysteresis loop is characteristic of micro/mesoporous carbonaceous materials [46]. From the pore size distribution, mesopores are observed for both materials.
Table 1 presents both materials’ surface area, total pore volume, and average pore size. It can be observed that MAC111 presented a higher BET surface area and higher total pore volume than MAC1105. This behavior is because the salt KOH used as the activating agent can react with the carbonaceous material. Since both MAC1105 and MAC111 were prepared with the same weight ratio of KOH, the superior features presented by MAC111 may be due to the higher weight ratio of NiCl2 used to prepare this material. Therefore, in addition to generating magnetization, NiCl2 can affect the textural characteristics of the samples. Similar behavior was observed by Thue et al. [37]. The authors prepared magnetic activated carbons from tucumã seed using ZnCl2 and NiCl2. They found out that the increase in the weight ratio of NiCl2 led to an increase in the surface area and total pore volume of the obtained material. In addition, several other authors found that increasing the proportion of transition metal chlorides, such as ZnCl2, FeCl3, CoCl2, and CuCl2, led to improved textural properties [40,46,47,48,49,50]. The transition metals impregnated in the precursor material are cross-linked to the surface functional groups of the biomass, promoting the chemical dehydration and decomposition of the lignocellulosic material during pyrolysis. After acid washes, the transition metals are removed, and the previously occupied spaces become free, forming the pores. Therefore, with higher weight rations of these salts, more transition metal ions are available, improving the formation of the pore structure [40,48,49,50]. In the present work, although the presence of Ni in the carbon matrix was shown by the EDS spectra (Figure 1), part of it may have been eliminated with the acid wash. Therefore, with a higher weight ratio of NiCl2, more pores may have been created and, subsequently, become free with the acid wash. This behavior may explain the higher surface area and total pore volume observed for MAC111.
Regarding the average pore sizes, values of 3.69 and 3.60 nm were found for MAC1105 and MAC111, respectively (Table 1). According to IUPAC, the pores of an adsorbent can be classified as micropores (inner diameter < 2 nm), mesopores (2 nm ≤ inner diameter ≤ 50 nm), and macropores (inner diameter > 50 nm) [46]. Therefore, both MACs can be classified as mesoporous materials, corroborating the isotherms in Figure 3.

2.1.4. Thermal Analysis

Figure 4 shows the thermal profile of the produced MACs. The thermal behavior was evaluated from room temperature to 800 °C under an N2 atmosphere. The curve obtained for MAC1105 can be divided into four regions, while the curve obtained for MAC111 can be divided into five regions. The first region of weight loss was 21.4–98.9 °C and 19.9–104.9 °C for MAC1105 and MAC111, respectively, and can be attributed to the evaporation of moisture [37,51]. The temperature range for the second region of weight loss was 98.9–253.9 °C and 104.9–217.4 °C for MAC1105 and MAC111, respectively. This stage corresponds to the loss of water from the channels and pores of the material [37,51]. The weight loss sum until these temperatures were 7.37% for MAC1105 and 9.60% for MAC111. The third region of weight loss varied from 253.9–463.9 °C MAC1105. For MAC111, a third stage of weight loss occurred from 217.4–367.4 °C, and a fourth stage occurred from 367.4–504.9 °C. These stages of weight loss can be assigned to the decomposition of oxygenated functional groups on the activated carbon surface [39]. The last stage for MAC1105 (fourth stage) was 763.9–798.9 °C, and the last stage for MAC111 (fifth stage) was 504.9–793.3 °C. These weight-loss stages correspond to the carbon matrix’s oxidation [51]. The total weight loss was 21.74% for MAC1105 and 24.80% for MAC111.

2.1.5. X-ray Diffraction

Figure 5 shows the XRD diffractograms of MAC1105 and MAC111. Both samples show patterns of metallic Ni (crystalline system: cubic; JCPDS Card 00-004-0850). According to Thue et al. [37], the formation of metallic Ni occurs due to the reduction of the previously impregnated Ni2+ to Ni0. During pyrolysis, this reaction occurs at high temperatures and in the presence of reducing gases, such as H2 and CH4. MAC1105 also shows patterns of nickel oxide (NiO; crystalline system: rhombohedral; JCPDS Card 00-044-4459). These results also confirm that the Ni was not completely eliminated during the acid wash. Besides that, both MACs show patterns of silicon oxide (SiO2; crystalline system: hexagonal; JCPDS Card 00-046-1045). The presence of SiO2 in the samples comes from the Sapelli wood sawdust.
Nanostructured Ni particles with average crystallite sizes of 18.96 and 25.34 nm for MAC1105 and MAC111, respectively, were obtained (calculated using Scherrer’s equation).

2.1.6. Magnetic Features

Magnetization curves of the MACs are shown in Figure 6, and the values of the hysteresis parameters are shown in Table 2. As can be seen, both exhibit ferromagnetic properties, with coercivity (HC) values of 150.2 Oe and 200.2 Oe and remanence (MR) values of 3.2 emu g−1 and 4.1 emu g−1 for MAC1105 and MAC111, respectively. These are interesting values for this kind of material [37,52,53]. On the other hand, the saturation magnetization (MS) value, 13.6 emu g−1 for both MACs, is slightly lower than that which the literature reported [37,52,53]. Despite the relatively low MS value, the MACs produced can be easily moved and controlled in aqueous media by external magnetic fields.

2.2. Adsorption Results

2.2.1. Kinetic Profiles of BB Adsorption

The kinetic behavior of BB dye adsorption was studied for both MACs with an initial adsorbate concentration of 50 mg L−1 and pH 4. The adsorption capacity curves as a time function are shown in Figure 7a,b for MAC1105 and MAC111, respectively. It is possible to observe that the curve obtained for MAC111 was characterized by a faster adsorption rate. MAC111 reached equilibrium in around 10 min. For MAC1105, the equilibrium was reached in around 60 min. This behavior can be explained due to the higher total pore volume presented by MAC111 (Table 1). A high pore volume can enhance the kinetic of adsorption by allowing a faster diffusion rate of the dye molecules inside the pores to the adsorption sites [54].
The experimental kinetic data were fitted to the pseudo-first-order (PFO) and pseudo-second-order (PSO) models. The parameters of the models are depicted in Table 3. Based on the higher values of R2 and R2adj and the lower values of ARE, it can be concluded that the PSO model was the more suitable to represent the BB dye adsorption kinetic for both MACs. Furthermore, Table 3 confirms the faster kinetic and the higher adsorption capacity of MAC111 because k2 and q2 for this adsorbent were around two times higher concerning the same parameters for MAC1105. For comparison, several authors demonstrated that the PSO model was more suitable for representing the kinetic data of anionic dye adsorption [21,55,56,57].

2.2.2. Adsorption Isotherms

The equilibrium study for BB dye adsorption was carried out at 25 °C with initial adsorbate concentrations from 0 to 200 mg L−1 and pH 4. Figure 8 shows the equilibrium curves obtained for MAC1105 (Figure 8a) and for MAC111 (Figure 8b). According to Giles classification [58], the isotherms obtained for MAC1105 and MAC111 are typical type L1 and L2 isotherms, respectively. L-type isotherms indicate a high affinity between the adsorption sites of the adsorbent and the adsorbate molecules. Besides that, it is possible to observe (Figure 8b) that MAC111 presented a higher adsorption capacity than MAC1105. This result can also be explained due to the superior textural features exhibited by MAC111 (Table 1). The higher surface area presented by MAC111 makes more surface active sites available to capture the adsorbate molecules.
Langmuir, Freundlich, and Sips models were used to interpret the equilibrium curves. Table 4 shows the equilibrium parameters. Based on the R2, R2adj, and ARE values, it is possible to observe that only the Sips model adequately represents the equilibrium data for MAC1105. On the other hand, for MAC111, all three models presented a good fit. However, the Sips model presented slightly higher R2 and R2adj values and a slightly lower ARE value. Therefore, the experimental equilibrium data for both MACs established that the Sips model was the best choice.
For comparison, Table 5 shows the maximum adsorption capacity of different adsorbents for BB dye adsorption reported in the literature. It can be seen that the values found in the present study are quite promising, and further studies on the adsorption conditions are required to increase the adsorption capacity.

2.2.3. Regeneration and Reuse Study

Different chemical agents in different concentrations were tested for regenerating the MACs. Table 6 shows the equilibrium adsorption capacity for the second cycle of adsorption. It can be seen that the best results were obtained using NH4OH in the concentration of 0.5 mol L−1 for both MACs. Therefore, additional adsorption/regeneration cycles were performed using this regeneration condition to access the potential of reusing both materials. Figure 9 shows the equilibrium adsorption capacity of BB dye for four cycles using MAC1105 (Figure 9a) and MAC111 (Figure 9b). It is possible to notice that the adsorption capacity gradually decreased over the cycles. This trend suggests that some BB dye molecules were not removed from the adsorbent surface upon regeneration. Therefore, the active sites occupied by these molecules become unavailable for adsorption in the next cycle.
It also can be observed that MAC111 showed a smaller decrease in adsorption capacity over the cycles than MAC1105 (Figure 9). In addition, the adsorption capacity observed for MAC111 at the end of the fifth cycle (around 29 mg g−1) is higher than the adsorption capacity observed for MAC1105 even in the first cycle (around 25 mg g−1). Overall, the results showed that MAC111 has a higher potential to be reused in more adsorption cycles, directly affecting the operating costs.

2.2.4. Application of MACs to Treat a Simulated Effluent

A simulated effluent was prepared from a grape drink mix to verify the applicability of the MACs for removing BB dye in a complex matrix. The MACs were evaluated regarding the removal efficiency using different adsorbent dosages (1, 5, and 10 g L−1) and contact times (5–30 min). The visible spectra (400–800 nm) of the simulated effluent before and after the adsorption tests are shown in Figure 10. It was observed that the adsorption was fast since the removal efficiencies were virtually the same for all contact times studied. However, the removal efficiency obtained using a dosage of 1 g L−1 was below 40%. The active sites are easily saturated with low adsorbent dosages since the simulated effluent contains several compounds other than the BB dye. However, using higher adsorbent dosages, high removal efficiencies were obtained. In 30 min, MAC1105 and MAC111 were capable of removing, respectively, 73% and 88% using the adsorbent dosage of 5 g L−1, and 93% and 95% using the adsorbent dosage of 10 g L−1. These results indicated that the MACs are promising adsorbents for treating effluents from the food industry containing BB dye.

3. Material and Methods

3.1. Materials

Sapelli wood sawdust (E. cylindricum), used as a precursor material for producing the magnetic activated carbons, was obtained from sawmills in Ngaoundere (Cameroon). The sawdust was milled, obtaining particle sizes lower than 250 μm. The anionic dye Brilliant Blue (BB, CI 42090, molar weight 792.8 g mol−1, λmax 630.0 nm) was supplied by Duas Rodas company (Brazil). Figure S1 (Supplementary Material) shows the chemical structure of the BB dye obtained by the Chemsketch software. All other reagents used were of analytical grade.

3.2. Preparation of the Magnetic Activated Carbons

In the MACs preparation, NiCl2 produced magnetic features, and KOH was used as an activating agent to increase pore size and specific surface area. Initially, 100.0 g of the Sapelli wood sawdust was mixed with 100.0 g of KOH and 50.0 or 100.0 g of NiCl2 (weight ratios of 1:1:0.5 and 1:1:1, respectively). Then, about 50 mL of distilled water was added to the mixtures, which were stirred with a magnetic stirrer at 90 °C for 2 h. The homogeneous pastes formed were oven-dried at 105 °C for 8 h, and after drying, each paste was introduced into a quartz reactor in a conventional furnace (Sanchis, Brazil). The heating was carried out from room temperature to 600 °C at a heating rate of 10 °C min−1 and an inert gas (N2) flow rate of 150 mL min−1. After reaching the final temperature, it was maintained for 30 min. Then, the furnace was turned off and kept under the inert gas flow until it reached a temperature below 200 °C. After cooling, the obtained materials were washed with a 0.1 mol L−1 HCl solution under a reflux system at around 80 °C for 2 h. Subsequently, the materials were exhaustively washed with distilled water until the pH of the washing waters attained the pH of distilled water (pH 6–7). Finally, the materials were oven-dried at 105 °C for 8 h. The materials obtained were MAC1105 and MAC111, according to the weight ratios of Sapelli sawdust: KOH: NiCl2 of 1:1:0.5 and 1:1:1, respectively.

3.3. MACs Characterization

The textural properties (BET surface area, total pore volume, and average pore size) were obtained from N2 adsorption/desorption isotherms at 77 K in a volumetric adsorption analyzer (Micromeritcs, ASAP 2020, USA) using BET and BJH methods.
The surface morphologies of the materials were obtained by scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS) (Tescan, MIRA 3, Czech Republic). The working voltage was 12 kV, and the magnifications were 5000× and 10,000×.
Investigations concerning the surface functional groups were realized by Fourier transform infrared spectroscopy (FTIR) (Shimadzu, Prestige 21210045, Japan). The spectra were obtained with a resolution of 4 cm−1 in the range from 4000 to 400 cm−1 by diffuse reflectance technique with KBr.
Thermogravimetric (TGA) and derivative thermogravimetric (DTG) curves of the magnetic activated carbons were obtained in a TA instrument (Netzsch, STA 449 F3 Jupiter®, Germany). The analysis was carried out in the following conditions: temperature from 20 °C to 800 °C, a heating rate of 25 °C min−1, and an N2 flow rate of 50 mL min−1.
The crystalline nature of the MACs was accessed by Powder X-Ray Diffraction (XRD) (Rigaku, Miniflex 300, Japan). The instrument was operated at 30 kV and 10 mA with Cu Kα radiation (λ = 1.541861 Å). Measurements were done over the 10° ≤ 2θ ≤ 100°, using a scanning step of 0.06° s−1. Scherrer’s equation obtained the Ni particles’ average crystallite size (D) in the magnetic activated carbons.
The magnetic properties were investigated at room temperature utilizing a vibrating-sample magnetometer (VSM) (MicroSense, EZ9, USA), performing from −20 kOe to +20 kOe.

3.4. Kinetic and Equilibrium Adsorption Experiments

Adsorption studies of BB dye from aqueous solutions were performed to evaluate the adsorption performance of the MACs. BB dye is extensively used in the food industry and can be found in various foods such as drink mixes, ice creams, candies, and gelatins.
For the adsorption assays, 20 mL of the BB dye solution at pH 4.0 (adjusted with 0.1 mol L−1 HCl solution) were added in Erlenmeyer flasks with 0.02 g of the MAC (adsorbent dosage of 1 g L−1). The flasks were stirred in a thermostatic agitator (Solab, SL222, Brazil) at 25 °C and 150 rpm. The kinetic study was performed with an initial BB dye concentration of 50 mg L−1 at set intervals (0–240 min). The equilibrium study was carried out with initial BB dye concentrations from 0 to 200 mg L−1 until it reached equilibrium. Afterward, the adsorbent was separated from the liquid phase using a magnet. The remaining BB concentration in the liquid was measured by spectrophotometry (Biospectro SP-22, Brazil) at 630 nm. The adsorption results were represented according to the standard of our group (supplementary material S1).

3.5. Kinetic and Equilibrium Models

See Supplementary Materials Sections S2 and S3.

3.6. Regeneration and Reuse Experiments

Regeneration and reuse tests were conducted to verify the possibility of reusing the MACs. First, the MACs were loaded with BB dye at the following experimental conditions: initial dye concentration of 50 mg L−1, pH 4.0, an adsorbent dosage of 1 g L−1, 25 °C, stirring rate of 150 rpm, and 2 h. Then, the adsorbent was separated from the medium by a magnet and oven-dried at 105 °C for 8 h.
In the regeneration step, four different regeneration agents—namely sodium chloride (NaCl), sodium hydroxide (NaOH), ammonium hydroxide (NH4OH), and acetone (C3H6O)—in the concentrations of 0.5 and 1.0 mol L−1 were tested to desorb the BB dye from the adsorbent. In this step, 20 mL of the regeneration agent was added to Erlenmeyer flasks with the magnetic-activated carbon previously loaded with BB dye. The flasks were stirred for 2 h at 25 °C and a stirring rate of 150 rpm. Subsequently, the regenerated adsorbent was separated from the medium using a magnet and oven-dried at 105 °C for 8 h. After that, the regenerated magnetic activated carbons were used again for BB dye adsorption. The adsorption-regeneration cycle was realized several times using the regeneration agent that showed the best results.

3.7. Application in a Simulated Effluent

The simulated effluent was prepared using a grape drink mix from the local industry and presented a BB dye concentration of 52 mg L−1 and a pH of 3.0. The matrix of the simulated effluent was composed of sugars, dehydrated grape juice, vitamin C, acidulant (citric acid), acidity regulator (trisodium citrate), flavorings, sweeteners (potassium aspartame and acesulfame), anti-humectant (tricalcium phosphate), thickeners (sodium carboxymethylcellulose and xanthan gum) and dyes (brilliant blue, titanium dioxide derivatives, red 40, and indigotin blue). The experiments were carried out with 20 mL of the simulated effluent, a temperature of 25 °C, and a stirring rate of 150 rpm. Different adsorbent dosages (1, 5, and 10 g L−1) and contact times (5–30 min) were tested. Before and after the adsorption tests, the spectra were obtained in a UV-vis spectrometer (Shimadzu, UV240, Japan). The spectra were recorded from 400 to 800 nm, and the areas under the absorption bands were used to obtain the removal efficiencies.

4. Conclusions

In this work, magnetic activated carbons from Sapelli wood sawdust were successfully prepared, characterized, and applied in the adsorption of BB dye from an aqueous solution. The different weight ratios of NiCl2 mainly influenced the textural properties of the materials. The increase in the weight ratio of NiCl2 led to an increase in the surface area from 260.0 m2 g−1 (MAC1105) to 331.5 m2 g−1 (MAC111) and in the total pore volume from 0.075 cm3 g−1 (MAC1105) to 0.095 cm3 g−1 (MAC111). The average pore size remained virtually the same, around 3.6 nm, regardless of the weight ratio of NiCl2. Both MACs exhibit ferromagnetic properties at room temperature. Nanostructured Ni particles with average crystallite sizes of 18.96 nm (MAC1105) and 25.34 nm (MAC111) were observed. According to the FTIR spectra, very similar surface chemistry was obtained for both MACs exhibiting hydroxyl and carboxyl groups. Furthermore, a very similar thermal behavior was also observed for both materials.
From the adsorption study, important differences between the MACs were observed. MAC111 exhibited faster kinetics and reached equilibrium in around 10 min. For MAC1105, on the other hand, the equilibrium was reached only in 60 min. For both adsorbents, the pseudo-second-order model represented the kinetic data well. Regarding the adsorption isotherms, the Sips model satisfactorily represented the data. In addition, MAC111 showed a higher maximum adsorption capacity (qs = 98.12 mg g−1) than MAC1105 (qs = 60.73 mg g−1). The regeneration and reuse study showed that MAC111 had a higher potential to be reused in more adsorption cycles. Finally, MAC1105 and MAC111 were promising for treating a simulated effluent containing the BB dye, achieving removal efficiencies of 93% and 95%, respectively. These results demonstrated that the MACs were promising adsorbents for BB dye removal from an aqueous solution with good efficiency and easy magnetic separation. Besides that, it is noteworthy that MAC111 showed the best results due to its best features arising from the higher weight ratio of NiCl2 in its production. Nevertheless, further and more complete studies are required for application purposes, such as the effect of the adsorbent dosage, pH and temperature, and the adsorption thermodynamics.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules28041821/s1, Figure S1: Chemical structure of the brilliant blue dye; Section S1: Adsorption quantification; Section S2: Kinetic models; Section S3: Isotherm models [64,65,66,67].

Author Contributions

Conceptualization, V.X.N. and G.L.D.; methodology, M.C.F.D.S. and S.F.L.; software, P.S.T.; validation, L.F.O.S., É.C.L. and J.V.; formal analysis, É.C.L. and F.M.M.; investigation, V.X.N.; resources, S.F.L.; data curation, V.X.N. and S.F.L.; writing—original draft preparation, G.L.D.; writing—review and editing, L.F.O.S.; visualization, C.S.; supervision, G.L.D.; project administration, G.L.D.; funding acquisition, G.L.D. and J.V. All authors have read and agreed to the published version of the manuscript.

Funding

This work was founded by UNIVERSITY of ROUEN NORMANDY, INSA Rouen Normandy, the Centre National de la Recherche Scientifique (CNRS), European Regional Development Fund (ERDF), Labex SynOrg (ANR-11-LABX-0029), Carnot Institut I2C, the graduate school for research Xl-Chem (ANR-18-EURE-0020 XL CHEM), and by Region Normandie. This work was funded by Brazilian National Council for Scientific and Technological Development/CNPq (Grant 405982/2022-4 and Grant 303992/2021-2), and Coordination for the Improvement of Higher Education Personnel/CAPES (CAPES-PRINT program).

Informed Consent Statement

Not applicable.

Data Availability Statement

The data will be available on request.

Conflicts of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

References

  1. Patra, B.R.; Mukherjee, A.; Nanda, S.; Dalai, A.K. Biochar production, activation and adsorptive applications: A review. Environ. Chem. Lett. 2021, 19, 2237–2259. [Google Scholar] [CrossRef]
  2. Haleem, A.; Shafiq, A.; Chen, S.-Q.; Nazar, M. A Comprehensive Review on Adsorption, Photocatalytic and Chemical Degradation of Dyes and Nitro-Compounds over Different Kinds of Porous and Composite Materials. Molecules 2023, 28, 1081. [Google Scholar] [CrossRef]
  3. Alias, S.S.; Harun, Z.; Azhar, F.H.; Ibrahim, S.A.; Johar, B. Comparison between commercial and synthesised nano flower-like rutile TiO2 immobilised on green super adsorbent towards dye wastewater treatment. J. Clean. Prod. 2019, 251, 119448. [Google Scholar] [CrossRef]
  4. Shah, L.A.; Malik, T.; Siddiq, M.; Haleem, A.; Sayed, M.; Naeem, A. TiO2 nanotubes doped poly(vinylidene fluoride) polymer membranes (PVDF/TNT) for efficient photocatalytic degradation of brilliant green dye. J. Environ. Chem. Eng. 2019, 7, 103291. [Google Scholar] [CrossRef]
  5. Bhatti, H.N.; Safa, Y.; Yakout, S.M.; Shair, O.H.; Iqbal, M.; Nazir, A. Efficient removal of dyes using carboxymethyl cellulose/alginate/polyvinyl alcohol/rice husk composite: Adsorption/desorption, kinetics and recycling studies. Int. J. Biol. Macromol. 2020, 150, 861–870. [Google Scholar] [CrossRef]
  6. Wekoye, J.N.; Wanyonyi, W.C.; Wangila, P.T.; Tonui, M.K. Kinetic and equilibrium studies of Congo red dye adsorption on cabbage waste powder. Environ. Chem. Ecotoxicol. 2020, 2, 24–31. [Google Scholar] [CrossRef]
  7. Ortiz-Martínez, A.; Godínez, L.A.; Martínez-Sánchez, C.; García-Espinoza, J.; Robles, I. Preparation of modified carbon paste electrodes from orange peel and used coffee ground. New materials for the treatment of dye-contaminated solutions using electro-Fenton processes. Electrochim. Acta 2021, 390, 138861. [Google Scholar] [CrossRef]
  8. Dotto, J.; Fagundes-Klen, M.R.; Veit, M.T.; Palácio, S.M.; Bergamasco, R. Performance of different coagulants in the coagulation/flocculation process of textile wastewater. J. Clean. Prod. 2018, 208, 656–665. [Google Scholar] [CrossRef]
  9. Arunprasath, T.; Sudalai, S.; Meenatchi, R.; Jeyavishnu, K.; Arumugam, A. Biodegradation of triphenylmethane dye malachite green by a newly isolated fungus strain. Biocatal. Agric. Biotechnol. 2019, 17, 672–679. [Google Scholar] [CrossRef]
  10. Hassan, M.M.; Carr, C.M. A critical review on recent advancements of the removal of reactive dyes from dyehouse effluent by ion-exchange adsorbents. Chemosphere 2018, 209, 201–219. [Google Scholar] [CrossRef]
  11. de Salomón, Y.L.O.; Georgin, J.; Franco, D.S.P.; Netto, M.S.; Foletto, E.L.; Allasia, D.; Dotto, G.L. Application of seed residues from Anadenanthera macrocarpa and Cedrela fissilis as alternative adsorbents for remarkable removal of methylene blue dye in aqueous solutions. Environ. Sci. Pollut. Res. 2020, 28, 2342–2354. [Google Scholar] [CrossRef]
  12. Dotto, G.L.; McKay, G. Current scenario and challenges in adsorption for water treatment. J. Environ. Chem. Eng. 2020, 8, 103988. [Google Scholar] [CrossRef]
  13. Tahir, M.A.; Bhatti, H.N.; Iqbal, M. Solar Red and Brittle Blue direct dyes adsorption onto Eucalyptus angophoroides bark: Equilibrium, kinetics and thermodynamic studies. J. Environ. Chem. Eng. 2016, 4, 2431–2439. [Google Scholar] [CrossRef]
  14. Jawad, A.H.; Abdulhameed, A.S.; Reghioua, A.; Yaseen, Z.M. Zwitterion composite chitosan-epichlorohydrin/zeolite for adsorption of methylene blue and reactive red 120 dyes. Int. J. Biol. Macromol. 2020, 163, 756–765. [Google Scholar] [CrossRef]
  15. Puchana-Rosero, M.; Adebayo, M.A.; Lima, E.C.; Machado, F.M.; Thue, P.S.; Vaghetti, J.C.; Umpierres, C.S.; Gutterres, M. Microwave-assisted activated carbon obtained from the sludge of tannery-treatment effluent plant for removal of leather dyes. Colloids Surf. A Physicochem. Eng. Asp. 2016, 504, 105–115. [Google Scholar] [CrossRef]
  16. Yunus, Z.M.; Al-Gheethi, A.; Othman, N.; Hamdan, R.; Ruslan, N.N. Removal of heavy metals from mining effluents in tile and electroplating industries using honeydew peel activated carbon: A microstructure and techno-economic analysis. J. Clean. Prod. 2019, 251, 119738. [Google Scholar] [CrossRef]
  17. Rashid, J.; Tehreem, F.; Rehman, A.; Kumar, R. Synthesis using natural functionalization of activated carbon from pumpkin peels for decolourization of aqueous methylene blue. Sci. Total. Environ. 2019, 671, 369–376. [Google Scholar] [CrossRef]
  18. Kang, K.; Nanda, S.; Lam, S.S.; Zhang, T.; Huo, L.; Zhao, L. Enhanced fuel characteristics and physical chemistry of microwave hydrochar for sustainable fuel pellet production via co-densification. Environ. Res. 2020, 186, 109480. [Google Scholar] [CrossRef]
  19. Sarker, T.R.; Pattnaik, F.; Nanda, S.; Dalai, A.K.; Meda, V.; Naik, S. Hydrothermal pretreatment technologies for lignocellulosic biomass: A review of steam explosion and subcritical water hydrolysis. Chemosphere 2021, 284, 131372. [Google Scholar] [CrossRef]
  20. Supong, A.; Bhomick, P.C.; Baruah, M.; Pongener, C.; Sinha, U.B.; Sinha, D. Adsorptive removal of Bisphenol A by biomass activated carbon and insights into the adsorption mechanism through density functional theory calculations. Sustain. Chem. Pharm. 2019, 13, 100159. [Google Scholar] [CrossRef]
  21. Zazycki, M.A.; Godinho, M.; Perondi, D.; Foletto, E.L.; Collazzo, G.C.; Dotto, G.L. New biochar from pecan nutshells as an alternative adsorbent for removing reactive red 141 from aqueous solutions. J. Clean. Prod. 2018, 171, 57–65. [Google Scholar] [CrossRef]
  22. Wang, Y.; Wang, S.-L.; Xie, T.; Cao, J. Activated carbon derived from waste tangerine seed for the high-performance adsorption of carbamate pesticides from water and plant. Bioresour. Technol. 2020, 316, 123929. [Google Scholar] [CrossRef] [PubMed]
  23. Van Thuan, T.; Quynh, B.T.P.; Nguyen, T.D.; Ho, V.T.T.; Bach, L.G. Response surface methodology approach for optimization of Cu2+, Ni2+ and Pb2+ adsorption using KOH-activated carbon from banana peel. Surf. Interfaces 2017, 6, 209–217. [Google Scholar] [CrossRef]
  24. Enniya, I.; Rghioui, L.; Jourani, A. Adsorption of hexavalent chromium in aqueous solution on activated carbon prepared from apple peels. Sustain. Chem. Pharm. 2018, 7, 9–16. [Google Scholar] [CrossRef]
  25. Sajjadi, S.-A.; Meknati, A.; Lima, E.C.; Dotto, G.L.; Mendoza-Castillo, D.I.; Anastopoulos, I.; Alakhras, F.; Unuabonah, E.I.; Singh, P.; Hosseini-Bandegharaei, A. A novel route for preparation of chemically activated carbon from pistachio wood for highly efficient Pb(II) sorption. J. Environ. Manag. 2019, 236, 34–44. [Google Scholar] [CrossRef] [PubMed]
  26. Kumar, A.; Gupta, H. Activated carbon from sawdust for naphthalene removal from contaminated water. Environ. Technol. Innov. 2020, 20, 101080. [Google Scholar] [CrossRef]
  27. Chikri, R.; Elhadiri, N.; Benchanaa, M.; El Maguana, Y. Efficiency of Sawdust as Low-Cost Adsorbent for Dyes Removal. J. Chem. 2020, 2020, 8813420. [Google Scholar] [CrossRef]
  28. Mallakpour, S.; Sirous, F.; Hussain, C.M. Sawdust, a versatile, inexpensive, readily available bio-waste: From mother earth to valuable materials for sustainable remediation technologies. Adv. Colloid Interface Sci. 2021, 295, 102492. [Google Scholar] [CrossRef]
  29. Vieira, L.H.S.; Sabino, C.M.S.; Júnior, F.H.S.; Rocha, J.S.; Castro, M.O.; Alencar, R.S.; da Costa, L.S.; Viana, B.C.; de Paula, A.J.; Soares, J.M.; et al. Strategic design of magnetic carbonaceous nanocomposites and its application as multifunctional adsorbent. Carbon 2020, 161, 758–771. [Google Scholar] [CrossRef]
  30. Liu, X.; Wang, Y.; Zhang, T.C.; Xiang, G.; Wang, X.; Yuan, S. One-Pot Synthesis of a Magnetic TiO2/PTh/γ-Fe2O3 Heterojunction Nanocomposite for Removing Trace Arsenite via Simultaneous Photocatalytic Oxidation and Adsorption. Ind. Eng. Chem. Res. 2020, 60, 528–540. [Google Scholar] [CrossRef]
  31. Moosavi, S.; Lai, C.W.; Gan, S.; Zamiri, G.; Pivehzhani, O.A.; Johan, M.R. Application of Efficient Magnetic Particles and Activated Carbon for Dye Removal from Wastewater. ACS Omega 2020, 5, 20684–20697. [Google Scholar] [CrossRef]
  32. Wang, Y.; Zhang, Y.; Zhang, T.C.; Xiang, G.; Wang, X.; Yuan, S. Removal of Trace Arsenite through Simultaneous Photocatalytic Oxidation and Adsorption by Magnetic Fe3O4@PpPDA@TiO2 Core–Shell Nanoparticles. ACS Appl. Nano Mater. 2020, 3, 8495–8504. [Google Scholar] [CrossRef]
  33. Du, Q.; Zhang, S.; Song, J.; Zhao, Y.; Yang, F. Activation of porous magnetized biochar by artificial humic acid for effective removal of lead ions. J. Hazard. Mater. 2020, 389, 122115. [Google Scholar] [CrossRef]
  34. Feng, Z.; Chen, H.; Li, H.; Yuan, R.; Wang, F.; Chen, Z.; Zhou, B. Preparation, characterization, and application of magnetic activated carbon for treatment of biologically treated papermaking wastewater. Sci. Total. Environ. 2020, 713, 136423. [Google Scholar] [CrossRef]
  35. Pereira, D.; Rocha, L.S.; Gil, M.V.; Otero, M.; Silva, N.J.O.; Esteves, V.I.; Calisto, V. In situ functionalization of a cellulosic-based activated carbon with magnetic iron oxides for the removal of carbamazepine from wastewater. Environ. Sci. Pollut. Res. 2020, 28, 18314–18327. [Google Scholar] [CrossRef]
  36. Salem, S.; Teimouri, Z.; Salem, A. Fabrication of magnetic activated carbon by carbothermal functionalization of agriculture waste via microwave-assisted technique for cationic dye adsorption. Adv. Powder Technol. 2020, 31, 4301–4309. [Google Scholar] [CrossRef]
  37. Thue, P.S.; Umpierres, C.S.; Lima, E.C.; Lima, D.R.; Machado, F.M.; dos Reis, G.S.; da Silva, R.S.; Pavan, F.A.; Tran, H.N. 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. J. Hazard. Mater. 2020, 398, 122903. [Google Scholar] [CrossRef]
  38. Bai, X.; Yu, L.; Hua, Z.; Tang, Z.; Zhang, J. Synthesis and characterization of superparamagnetic activated carbon adsorbents based on cyanobacteria. Mater. Chem. Phys. 2015, 163, 407–415. [Google Scholar] [CrossRef]
  39. Lütke, S.F.; Igansi, A.V.; Pegoraro, L.; Dotto, G.L.; Pinto, L.A.; Cadaval, T.R. Preparation of activated carbon from black wattle bark waste and its application for phenol adsorption. J. Environ. Chem. Eng. 2019, 7, 103396. [Google Scholar] [CrossRef]
  40. Thue, P.S.; Lima, E.C.; Sieliechi, J.M.; Saucier, C.; Dias, S.L.; Vaghetti, J.C.; Rodembusch, F.S.; Pavan, F.A. Effects of first-row transition metals and impregnation ratios on the physicochemical properties of microwave-assisted activated carbons from wood biomass. J. Colloid Interface Sci. 2017, 486, 163–175. [Google Scholar] [CrossRef]
  41. Muniandy, L.; Adam, F.; Mohamed, A.R.; Ng, E.-P. The synthesis and characterization of high purity mixed microporous/mesoporous activated carbon from rice husk using chemical activation with NaOH and KOH. Microporous Mesoporous Mater. 2014, 197, 316–323. [Google Scholar] [CrossRef]
  42. Ogungbenro, A.E.; Quang, D.V.; Al-Ali, K.A.; Vega, L.F.; Abu-Zahra, M.R. Synthesis and characterization of activated carbon from biomass date seeds for carbon dioxide adsorption. J. Environ. Chem. Eng. 2020, 8, 104257. [Google Scholar] [CrossRef]
  43. Ferreira, S.D.; Altafini, C.R.; Perondi, D.; Godinho, M. Pyrolysis of Medium Density Fiberboard (MDF) wastes in a screw reactor. Energy Convers. Manag. 2015, 92, 223–233. [Google Scholar] [CrossRef]
  44. Duan, S.; Ma, W.; Pan, Y.; Meng, F.; Yu, S.; Wu, L. Synthesis of magnetic biochar from iron sludge for the enhancement of Cr (VI) removal from solution. J. Taiwan Inst. Chem. Eng. 2017, 80, 835–841. [Google Scholar] [CrossRef]
  45. Fontana, K.B.; Chaves, E.S.; Sanchez, J.D.; Watanabe, E.R.; Pietrobelli, J.M.; Lenzi, G.G. Textile dye removal from aqueous solutions by malt bagasse: Isotherm, kinetic and thermodynamic studies. Ecotoxicol. Environ. Saf. 2016, 124, 329–336. [Google Scholar] [CrossRef] [PubMed]
  46. Thommes, M.; Kaneko, K.; Neimark, A.V.; Olivier, J.P.; Rodriguez-Reinoso, F.; Rouquerol, J.; Sing, K.S.W. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 2015, 87, 1051–1069. [Google Scholar] [CrossRef] [Green Version]
  47. da Silva, M.C.; Schnorr, C.; Lütke, S.F.; Knani, S.; Nascimento, V.X.; Lima, C.; Thue, P.S.; Vieillard, J.; Silva, L.F.; Dotto, G.L. KOH activated carbons from Brazil nut shell: Preparation, characterization, and their application in phenol adsorption. Chem. Eng. Res. Des. 2022, 187, 387–396. [Google Scholar] [CrossRef]
  48. Li, Y.; Li, Y.; Li, L.; Shi, X.; Wang, Z. Preparation and analysis of activated carbon from sewage sludge and corn stalk. Adv. Powder Technol. 2016, 27, 684–691. [Google Scholar] [CrossRef]
  49. Yu, F.; Zhu, X.; Jin, W.; Fan, J.; Clark, J.H.; Zhang, S. Optimized synthesis of granular fuel and granular activated carbon from sawdust hydrochar without binder. J. Clean. Prod. 2020, 276, 122711. [Google Scholar] [CrossRef]
  50. Yuan, Y.; Huang, L.; Zhang, T.C.; Ouyang, L.; Yuan, S. One-step synthesis of ZnFe2O4-loaded biochar derived from leftover rice for high-performance H2S removal. Sep. Purif. Technol. 2021, 279, 119686. [Google Scholar] [CrossRef]
  51. Cunha, M.R.; Lima, E.C.; Lima, D.R.; da Silva, R.S.; Thue, P.S.; Seliem, M.K.; Sher, F.; dos Reis, G.S.; Larsson, S.H. Removal of captopril pharmaceutical from synthetic pharmaceutical-industry wastewaters: Use of activated carbon derived from Butia catarinensis. J. Environ. Chem. Eng. 2020, 8, 104506. [Google Scholar] [CrossRef]
  52. Cazetta, A.L.; Pezoti, O.; Bedin, K.C.; Silva, T.L.; Junior, A.P.; Asefa, T.; Almeida, V.C. Magnetic Activated Carbon Derived from Biomass Waste by Concurrent Synthesis: Efficient Adsorbent for Toxic Dyes. ACS Sustain. Chem. Eng. 2015, 4, 1058–1068. [Google Scholar] [CrossRef]
  53. Zhou, L.; Shao, Y.; Liu, J.; Ye, Z.; Zhang, H.; Ma, J.; Jia, Y.; Gao, W.; Li, Y. Preparation and Characterization of Magnetic Porous Carbon Microspheres for Removal of Methylene Blue by a Heterogeneous Fenton Reaction. ACS Appl. Mater. Interfaces 2014, 6, 7275–7285. [Google Scholar] [CrossRef] [PubMed]
  54. Lawtae, P.; Tangsathitkulchai, C. The Use of High Surface Area Mesoporous-Activated Carbon from Longan Seed Biomass for Increasing Capacity and Kinetics of Methylene Blue Adsorption from Aqueous Solution. Molecules 2021, 26, 6521. [Google Scholar] [CrossRef]
  55. Lyu, W.; Yu, M.; Li, J.; Feng, J.; Yan, W. Adsorption of anionic acid red G dye on polyaniline nanofibers synthesized by FeCl3 oxidant: Unravelling the role of synthetic conditions. Colloids Surfaces A Physicochem. Eng. Asp. 2022, 647, 129203. [Google Scholar] [CrossRef]
  56. Patra, C.; Gupta, R.; Bedadeep, D.; Narayanasamy, S. Surface treated acid-activated carbon for adsorption of anionic azo dyes from single and binary adsorptive systems: A detail insight. Environ. Pollut. 2020, 266, 115102. [Google Scholar] [CrossRef]
  57. Wang, Q.; Luo, C.; Lai, Z.; Chen, S.; He, D.; Mu, J. Honeycomb-like cork activated carbon with ultra-high adsorption capacity for anionic, cationic and mixed dye: Preparation, performance and mechanism. Bioresour. Technol. 2022, 357, 127363. [Google Scholar] [CrossRef]
  58. Giles, C.H.; Smith, D.; Huitson, A. A general treatment and classification of the solute adsorption isotherm. I. Theoretical. J. Colloid Interface Sci. 1974, 47, 755–765. [Google Scholar] [CrossRef]
  59. Şenol, Z.M.; Gürsoy, N.; Şimşek, S.; Özer, A.; Karakuş, N. Removal of food dyes from aqueous solution by chitosan-vermiculite beads. Int. J. Biol. Macromol. 2020, 148, 635–646. [Google Scholar] [CrossRef]
  60. Mittal, A. Use of hen feathers as potential adsorbent for the removal of a hazardous dye, Brilliant Blue FCF, from wastewater. J. Hazard. Mater. 2006, 128, 233–239. [Google Scholar] [CrossRef]
  61. Arabkhani, P.; Javadian, H.; Asfaram, A.; Sadeghfar, F.; Sadegh, F. Synthesis of magnetic tungsten disulfide/carbon nanotubes nanocomposite (WS2/Fe3O4/CNTs-NC) for highly efficient ultrasound-assisted rapid removal of amaranth and brilliant blue FCF hazardous dyes. J. Hazard. Mater. 2021, 420, 126644. [Google Scholar] [CrossRef] [PubMed]
  62. Gupta, V.; Mittal, A.; Krishnan, L.; Mittal, J. Adsorption treatment and recovery of the hazardous dye, Brilliant Blue FCF, over bottom ash and de-oiled soya. J. Colloid Interface Sci. 2006, 293, 16–26. [Google Scholar] [CrossRef] [PubMed]
  63. Hernández-Hernández, K.A.; Solache-Ríos, M.; Díaz-Nava, M.C. Removal of Brilliant Blue FCF from Aqueous Solutions Using an Unmodified and Iron-Modified Bentonite and the Thermodynamic Parameters of the Process. Water Air Soil Pollut. 2013, 224, 1562. [Google Scholar] [CrossRef]
  64. Ho, Y.S.; McKay, G. A Comparison of Chemisorption Kinetic Models Applied to Pollutant Removal on Various Sorbents. Process Saf. Environ. Prot. 1998, 76, 332–340. [Google Scholar] [CrossRef] [Green Version]
  65. Langmuir, I. The adsorption of gases on plane surfaces of glass, mica and platinum. J. Am. Chem. Soc. 1918, 40, 1361–1403. [Google Scholar] [CrossRef] [Green Version]
  66. Freundlich, H.M.F. Über die Adsorption in Lösungen. Z. Phys. Chem. 1907, 57U, 385–470. [Google Scholar] [CrossRef]
  67. Sips, R. On the Structure of a Catalyst Surface. J. Chem. Phys. 1948, 16, 490–495. [Google Scholar] [CrossRef]
Molecules 28 01821 g001 550
Figure 1. (a,b) SEM images and (c) EDS spectrum of MAC1105 and (d,e) SEM images and (f) EDS spectrum MAC111.
Figure 1. (a,b) SEM images and (c) EDS spectrum of MAC1105 and (d,e) SEM images and (f) EDS spectrum MAC111.
Molecules 28 01821 g001
Molecules 28 01821 g002 550
Figure 2. FTIR vibrational spectra of (a) MAC1105 and (b) MAC111.
Figure 2. FTIR vibrational spectra of (a) MAC1105 and (b) MAC111.
Molecules 28 01821 g002
Molecules 28 01821 g003 550
Figure 3. Nitrogen adsorption/desorption isotherms and the BJH pore size distribution of (a) MAC1105 and (b) MAC111.
Figure 3. Nitrogen adsorption/desorption isotherms and the BJH pore size distribution of (a) MAC1105 and (b) MAC111.
Molecules 28 01821 g003
Molecules 28 01821 g004 550
Figure 4. TGA and DTG curves of (a) MAC1105 and (b) MAC111.
Figure 4. TGA and DTG curves of (a) MAC1105 and (b) MAC111.
Molecules 28 01821 g004
Molecules 28 01821 g005 550
Figure 5. XRD patterns of MAC1105 and MAC111.
Figure 5. XRD patterns of MAC1105 and MAC111.
Molecules 28 01821 g005
Molecules 28 01821 g006 550
Figure 6. M-H hysteresis loops of MAC1105 and MAC111 at room temperature. The inset is a magnified view of the M-H curves.
Figure 6. M-H hysteresis loops of MAC1105 and MAC111 at room temperature. The inset is a magnified view of the M-H curves.
Molecules 28 01821 g006
Molecules 28 01821 g007 550
Figure 7. The kinetic curve of BB dye adsorption onto (a) MAC1105 and (b) MAC111.
Figure 7. The kinetic curve of BB dye adsorption onto (a) MAC1105 and (b) MAC111.
Molecules 28 01821 g007
Molecules 28 01821 g008 550
Figure 8. Equilibrium isotherms of BB blue dye adsorption onto (a) MAC1105 and (b) MAC111.
Figure 8. Equilibrium isotherms of BB blue dye adsorption onto (a) MAC1105 and (b) MAC111.
Molecules 28 01821 g008
Molecules 28 01821 g009 550
Figure 9. Reuse cycles of (a) MAC1105 and (b) MAC111.
Figure 9. Reuse cycles of (a) MAC1105 and (b) MAC111.
Molecules 28 01821 g009
Molecules 28 01821 g010 550
Figure 10. Absorption spectra of simulated effluent before and after adsorption with 1 g L−1: (a) MAC1105 and (b) MAC111; 5 g L−1: (c) MAC1105 and (d) MAC111; 10 g L−1: (e) MAC1105 and (f) MAC111.
Figure 10. Absorption spectra of simulated effluent before and after adsorption with 1 g L−1: (a) MAC1105 and (b) MAC111; 5 g L−1: (c) MAC1105 and (d) MAC111; 10 g L−1: (e) MAC1105 and (f) MAC111.
Molecules 28 01821 g010
Table
Table 1. Textural characteristics of the magnetic activated carbons.
Table 1. Textural characteristics of the magnetic activated carbons.
Activated CarbonBET Surface Area (m2 g−1)Total Pore Volume (cm3 g−1)Average Pore Size (nm)
MAC1105260.00.0753.69
MAC111331.50.0953.60
Table
Table 2. Magnetic properties of the magnetic activated carbons.
Table 2. Magnetic properties of the magnetic activated carbons.
SampleCoercivity (HC, Oe)Saturation Magnetization (MS, emu g−1)Remanence (MR, emu g−1)
MAC1105150.213.63.2
MAC111200.213.64.1
Table
Table 3. Kinetic parameters for the adsorption of BB dye.
Table 3. Kinetic parameters for the adsorption of BB dye.
ModelActivated Carbon
MAC1105MAC111
PFO
q1 (mg g−1)25.7947.93
k1 (min−1)0.3960.612
R20.97850.9983
R2adj0.94800.9959
ARE (%)3.831.00
PSO
q2 (mg g−1)26.6248.36
k2 (g mg−1 min−1)0.0350.072
R20.99310.9991
R2adj0.98320.9977
ARE (%)2.120.70
Table
Table 4. Equilibrium parameters for the adsorption of BB dye.
Table 4. Equilibrium parameters for the adsorption of BB dye.
ModelActivated Carbon
MAC1105MAC111
Langmuir
qm (mg g−1)37.3291.80
KL (L mg−1)0.3141.655
R20.95420.9946
R2adj0.93590.9910
ARE (%)7.582.28
Freundlich
KF ((mg g−1)(mg L−1)−1/nF)21.4667.52
1/nF0.1140.077
R20.97850.9927
R2adj0.96990.9878
ARE (%)5.792.44
Sips
qS (mg g−1)60.7398.12
KS (L mg−1)0.3461.938
mS0.3350.483
R20.99370.9957
R2adj0.98900.9894
ARE (%)2.942.24
Table
Table 5. Adsorption capacities of different adsorbents for BB dye adsorption.
Table 5. Adsorption capacities of different adsorbents for BB dye adsorption.
AdsorbentDosage
(g L−1)		pHT (°C)Adsorption capacity
(mg g−1)		Reference
MAC11051.04.02560.7This study
MAC1111.04.02598.1This study
Chitosan vermiculite beads5.0 a10.225181.6[59]
Hen feather0.4 a2.030317.0 b[60]
Magnetic tungsten disulfide/carbon nanotubes nanocomposite0.3 a3.025166.7[61]
Bottom ash4.0 a3.0506.9 b[62]
De-oiled soya2.0 a3.05018.2 b[62]
Unmodified clay10.0 a5.4306.2[63]
Iron-modified clay10.0 a5.43014.2[63]
a Calculated; b Original values converted to a mass base using the BB molar weight of 792.8 g mol−1.
Table
Table 6. Regeneration test using different regeneration agents in different concentrations.
Table 6. Regeneration test using different regeneration agents in different concentrations.
Activated CarbonRegenerating AgentConcentration of the Regenerating Agent (mol L−1)qe in the Second Cycle
(mg g−1) a
MAC1105NaCl0.56.05 ± 0.65
1.05.80 ± 0.58
NaOH10.57.09 ± 0.74
1.05.89 ± 0.63
NH4OH0.510.78 ± 1.01
1.05.72 ± 0.69
C3H6O0.58.58 ± 0.95
1.07.35 ± 0.71
MAC111NaCl0.534.96 ± 0.87
1.030.59 ± 1.23
NaOH10.529.21 ± 0.91
1.022.52 ± 1.13
NH4OH0.536.64 ± 0.87
1.031.04 ± 0.92
C3H6O0.536.31 ± 1.04
1.030.91 ± 0.98
NaCl0.534.96 ± 0.87
a Mean ± standard deviation (n = 3).
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Nascimento, V.X.; Schnorr, C.; Lütke, S.F.; Da Silva, M.C.F.; Machado Machado, F.; Thue, P.S.; Lima, É.C.; Vieillard, J.; Silva, L.F.O.; Dotto, G.L. Adsorptive Features of Magnetic Activated Carbons Prepared by a One-Step Process towards Brilliant Blue Dye. Molecules 2023, 28, 1821. https://doi.org/10.3390/molecules28041821

AMA Style

Nascimento VX, Schnorr C, Lütke SF, Da Silva MCF, Machado Machado F, Thue PS, Lima ÉC, Vieillard J, Silva LFO, Dotto GL. Adsorptive Features of Magnetic Activated Carbons Prepared by a One-Step Process towards Brilliant Blue Dye. Molecules. 2023; 28(4):1821. https://doi.org/10.3390/molecules28041821

Chicago/Turabian Style

Nascimento, Victoria X., Carlos Schnorr, Sabrina F. Lütke, Maria C. F. Da Silva, Fernando Machado Machado, Pascal S. Thue, Éder C. Lima, Julien Vieillard, Luis F. O. Silva, and Guilherme L. Dotto. 2023. "Adsorptive Features of Magnetic Activated Carbons Prepared by a One-Step Process towards Brilliant Blue Dye" Molecules 28, no. 4: 1821. https://doi.org/10.3390/molecules28041821

APA Style

Nascimento, V. X., Schnorr, C., Lütke, S. F., Da Silva, M. C. F., Machado Machado, F., Thue, P. S., Lima, É. C., Vieillard, J., Silva, L. F. O., & Dotto, G. L. (2023). Adsorptive Features of Magnetic Activated Carbons Prepared by a One-Step Process towards Brilliant Blue Dye. Molecules, 28(4), 1821. https://doi.org/10.3390/molecules28041821

Article Metrics

Back to TopTop