Sage Journals: Discover world-class research

Abstract

Due to the widespread production of maize, the waste created by this crop has become a serious concern. This study applied the concept of waste circulation to the production of magnetic biochar from corn husk waste to remediate paraquat-contaminated water. Magnetic biochar (MB) was produced by impregnating maize husks with iron and carbonizing the residue in a nitrogen environment. Carbonized MB at the temperature of 850°C (MB-01-850) exhibited a combination of microporous and mesoporous structures ( $V_{meso} = 0.30 c m^{3} / g$ , $V_{micro} = 0.12 c m^{3} / g$ ), while biochar created only a microporous structure ( $V_{micro} = 0.11 c m^{3} / g$ ). According to the findings, Fe(NO₃)₃ significantly affected the increase in mesopore formation after carbonization. In addition, biochar exhibits excellent magnetic responsiveness. MB-01-850 reached equilibrium within approximately 20 min in synthetic water. Batch adsorption studies showed that MB-01-850 had maximum adsorption capacities ( $Q_{0}$ ) of 34.97 mg/g and 31.63 mg/g for synthetic and natural water, respectively. The unmodified biochar (without mesopores) had a $Q_{0}$ of 4.08 mg/g. This indicates that the presence of mesopores improves the effectiveness of paraquat adsorption. Additionally, the adsorption performance of magnetic biochar exhibited no statistically significant variance when tested under natural water conditions. Furthermore, magnetic biochar demonstrates impressive regeneration capacity, allowing it to be regenerated almost entirely for a minimum of four cycles using a sodium hydroxide (NaOH) solution with a concentration equal to or greater than 0.5 M.

1. Introduction

The increase in agricultural waste has been a serious concern over the last few decades, with maize being one of the most produced crops in the world. Significant by-products of maize production, including cobs, stems, leaves, and husks, are produced during harvest. Unfortunately, the combustion of these agricultural wastes releases several air pollutants, such as solid greenhouse gases, and suspended particulate matter, such as PM2.5 and PM10. These poisons have been shown to be harmful to human health and the environment [1]. Therefore, the development and implementation of sustainable disposal options for agricultural waste are essential to reduce this problem. The cellulose, hemicellulose, and lignin of maize husk may be utilized to produce biochar, a porous carbon substance. Biochar is widely utilized in environmental applications due to its distinct characteristics, ecological compatibility, cost-effectiveness, and robustness in both mechanical and thermal aspects [2, 3]. In particular, it effectively removes pollutants from wastewater by acting as an adsorbent. It is important to note that biochar serves as an adsorbent for removing pollutants from wastewater. However, unmodified biochar has limitations in water treatment applications because of its low adsorption capacity, inadequate selectivity, limited reusability, and challenges in regeneration [4]. Consequently, modification of biochar is imperative to enhance its adsorption capacity and practical efficacy. Several methods have been used to modify the properties of biochar, with physical and chemical modifications being the most common ones.

Physical modification involves subjecting biochar to high-temperature steam and gas, which effectively increases its surface area by modifying its pore structure, whereas chemical modification [5] represents the predominant technique. These include acid modification [6, 7], alkalinity modification [8], modification using metal salts or oxidizing agents [9], and modification with carbonaceous materials such as graphene and carbon nanotubes [10].

Moreover, unmodified biochar with a fine particle size poses challenges in terms of separation from aqueous solutions after the adsorption process. This difficulty hampers its reusability and transforms it into a secondary pollutant. Therefore, modifying the magnetic properties of biochar is highly desirable because it enables efficient separation from aqueous solutions in the presence of an external magnetic field. This characteristic significantly facilitates the separation and regeneration processes. Magnetic biochar can be produced through various techniques, including impregnation-pyrolysis, coprecipitation, reductive codeposition, and hydrothermal carbonization [11, 12]. Typically, magnetic biochar is synthesized using impregnation-pyrolysis processes with activators, such as iron chloride (FeCl₃) [13] or iron sulfate heptahydrate (FeSO₄·7H₂O) [14]. Several studies have shown that impregnating Fe(NO₃)₃ onto biomass not only enhances its magnetic properties but also induces a mesoporous structure in the adsorbent material [15, 16], making it particularly suitable for water treatment applications.

Intensive seasonal farming, especially maize cultivation, generates a substantial amount of wastewater that becomes contaminated with pesticides or herbicides. Unfortunately, these contaminants can potentially infiltrate groundwater and surface water sources, thereby posing a significant environmental risk. In line with the principles of waste cycling and pollutant elimination, the use of biochar derived from corn waste has emerged as an ideal solution to address the problem of pesticide or herbicide removal from contaminated wastewater. This sustainable approach not only effectively addresses the issue of pollutant removal but also maximizes the utilization of agricultural waste materials. When corn waste is utilized in biochar as an adsorbent, harmful pesticides or herbicides can be efficiently captured and removed from wastewater, thereby reducing the risk of further water pollution. This approach not only offers a solution to the environmental challenges posed by intensive farming practices but also promotes the circular economy by transforming agricultural waste into a valuable resource for water treatment.

Paraquat is a highly toxic herbicide used worldwide to control weeds in agricultural and nonagricultural settings. Paraquat (PQ; 1,1-dimethyl-4,4-bipyridyl dichloride) or methyl viologen is a nonselective contact herbicide used to control broadleaf weeds and grasses by inhibiting photosynthesis and destroying plant organelles [17]. It is now known to be harmful to both humans and animals. Furthermore, it may be an environmental factor in neurodegenerative diseases such as Parkinson’s disease [18, 19]. In particular, PQ exhibits considerable water solubility (620 g/L at 25°C) in the environment [20], thereby raising the potential risk of contamination from water sources. Consequently, these contaminants significantly affect aquatic ecosystems and human health. Additionally, it forms strong bonds with the soil particles, resulting in long-lasting bonds. [21]. In Thailand, PQ concentrations are 1.5 to 18.9 μg/L for groundwater and 9.3 to 87.0 μg/L for surface water [22]. European standards require that the concentration of PQ in water sources be no more than 0.1 μg/L for drinking water and 1-3 μg/L for surface water [23]. These values suggest that PQ residues in water threaten human health and the environment, especially during the rainy season. Given the health and environmental risks associated with PQ use, many countries have restricted or banned its use. However, paraquat is still widely used in some parts of the world due to its effectiveness and low cost [24]. Thus, removal of PQ from contaminated water sources is a challenging and attractive task.

Several techniques, such as ozonation [25], photocatalytic processes, Fenton reactions [25, 26], and adsorption, have been applied to remove contaminated PQ from water sources. Among the many techniques, adsorption is one of the best methods for treating wastewater, with high efficiency, low cost, ease of operation, and absence of hazardous by-product formation [27, 28]. Various adsorbents have been used for wastewater treatment, including natural adsorbents [29, 30], activated carbon [31], carbon-based materials (carbon nanotubes), and biochar. The prevalence of biochar derived from agricultural residues has significantly increased in recent years. This increased recognition is primarily attributed to its effectiveness in addressing environmental problems and suitability as an adsorbent to remove pollution.

This study is aimed at developing an affordable adsorbent material derived from agricultural waste to treat water sources contaminated with PQ. To achieve this objective, we used corn husks as the carbon precursor and synthesized magnetic biochar materials by impregnating corn husks with Fe(NO₃)₃ followed by carbonization under a nitrogen atmosphere. The resulting biochars were used as adsorbents to remove PQ from aqueous solutions. Our research focused on investigating the influence of Fe(NO₃)₃ on the properties of the adsorbent and understanding the underlying mechanism of paraquat (PQ) adsorption using magnetic biochar under both synthetic water (DI water) and natural water conditions. In addition, a study on the regeneration of magnetic biochar was conducted.

2. Materials and Methods

2.1. Materials and Chemicals

Corn husks were collected from an agricultural area in Lamphun Province. After cutting into small pieces, they were washed with DI water and dried at 80°C for 24 h. Analytical standard paraquat (C₁₂H₁₄Cl₂N₂, PESTANAL) was purchased from Sigma-Aldrich. Gramoxone (C₁₂H₁₄Cl₂N₂, 37% paraquat) and iron(III) nitrate nonahydrate (Fe(NO₃)₃·9H₂O, >99%) were purchased from Syngenta Thailand and AnalaR BDH, respectively.

2.2. Preparation of Magnetic Biochars and Biochar

To prepare the magnetic biochars, the corn husks were immersed in Fe(NO₃)₃ solution at 80°C for 2 h, dried at 80°C for 24 h, and carbonized in a nitrogen atmosphere at a heating rate of 10°C/min for 2 h. The preparation conditions of the samples are listed in Table 1.

Table 1

Synthesis conditions of magnetic biochars and biochar derived from corn husk.

Samples	Concentration of Fe(NO₃)₃ (M)	Carbonization temperature (°C)
B-00-850	0.00	850
MB-001-850	0.01	850
MB-005-850	0.05	850
MB-01-850	0.10	850
MB-01-750	0.10	750
MB-01-650	0.10	650
MB-01-550	0.10	550

2.3. Paraquat Adsorption Experiments

The experiments were performed using a batch process. It was carried out by contacting adsorbent dosages (0.25-3.00 g/L) with 100 mL of PQ solution with varied initial concentrations (5-200 mg/L) and shaken at 200 rpm at 30 to 50°C until the equilibrium time was reached. The pH range of 4 to 10 was examined at an initial PQ concentration of 40 mg/L, and the pH levels were controlled using buffer solutions containing acetic acid/sodium acetate and ammonium hydroxide/ammonium chloride. PQ concentration was analyzed using an ultraviolet-visible spectrophotometer (SPECORD® 50 PLUS, Analytik Jena) at a maximum absorbance wavelength of 258 nm. The amount of PQ at equilibrium ( $q_{e}$ ) and the removal percentage ( $% Removal$ ) were calculated using $\begin{matrix} (1) & q_{e} = \frac{(C_{0} - C_{e}) V}{W}, \\ (2) & % Removal = \frac{(C_{0} - C_{e})}{C_{0}} \times 100, \end{matrix}$ where $C_{0}$ and $C_{e}$ are the initial and equilibrium concentrations of PQ (mg/L), respectively, $V$ is the volume of the solution (L), and $W$ is the weight of the adsorbent (g).

The reusability of spent magnetic biochar was investigated by comparing the adsorbent with and without regeneration. The experiments were carried out at an initial concentration, adsorbent dosage, temperature, pH, and contact time of 20 mg/L, 2.0 g/L, 30°C, 7, and 24 h, respectively. The regenerated sorbent was immersed in NaOH solutions with concentrations of 0.1, 0.5, and 1.0 M for 24 h [32]. The mixture was dried and subjected to subsequent adsorption under the same conditions. This cycle was repeated multiple times, until four trial cycles were completed.

2.3.1. Adsorption Isotherm Models

The Langmuir and Freundlich models were used to describe the adsorption mechanism of PQ.

The Langmuir isotherm model [33, 34] is expressed by $\begin{matrix} (3) & q_{e} = \frac{Q_{0} {b C}_{e}}{1 + {b C}_{e}}, \end{matrix}$ where $q_{e}$ is the amount of PQ at equilibrium (mg/g), $Q_{0}$ is the maximum adsorption capacity (mg/g), and $b$ is the Langmuir constant (L/mg).

The Freundlich isotherm model [34, 35] is determined by $\begin{matrix} (4) & q_{e} = K_{F} C_{e}^{1 / n}, \end{matrix}$ where $K_{F}$ is the Freundlich constant ((mg/g)(L/mg)^1/ $^{n}$ ) and $n$ is the intensity of adsorption.

2.3.2. Thermodynamic Adsorption Models

The thermodynamic parameters, including the change of standard enthalpy ( $Δ H^{0}$ ), change of standard entropy ( $Δ S^{0}$ ), and change of standard Gibbs free energy ( $Δ G^{0}$ ), were calculated using the linearized van’t Hoff equation as given in $\begin{matrix} (5) & \ln K_{EQ}^{0} = - (\frac{Δ H^{0}}{R}) \frac{1}{T} + \frac{Δ S^{0}}{R}, \end{matrix}$ where $K_{EQ}^{0}$ , $R$ , and $T$ are the equilibrium constant, universal gas constant (8.314 J/mol·K), and temperature (K), respectively.

The $K_{EQ}^{0}$ is calculated from [36] $\begin{matrix} (6) & K_{EQ}^{0} = b \times {MW}_{a} \times 1000 \times \frac{C_{a}^{0}}{γ_{a}}, \end{matrix}$ where $b$ (L/mg) is the Langmuir constant, ${MW}_{a}$ (g/mol) is the molecular weight of paraquat, $C_{a}^{0}$ (mol/L) is the standard concentration of paraquat (assumed to be 1 mol/L), and $γ_{a}$ is the activity coefficient (assumed as unity).

$Δ H^{0}$ and $Δ S^{0}$ were determined from the slope and $y$ -intercept point of the linear plot of $\ln K_{EQ}^{0}$ vs. $1 / T$ , respectively, and the $Δ G^{0}$ was calculated as follows: $\begin{matrix} (7) & Δ G^{0} = Δ H^{0} - T Δ S^{0} . \end{matrix}$

2.3.3. Kinetic Adsorption Models

Both pseudo-first-order (PFO) and pseudo-second-order (PSO) models were used to determine the kinetic and rate constants.

The original equation of the PFO model proposed by Lagergren [37] is represented by $\begin{matrix} (8) & \frac{{d q}_{t}}{d_{t}} = k_{1} (q_{t} - q_{e}) . \end{matrix}$

Integrating Equation (9) for $q_{0} = 0$ yields [38] $\begin{matrix} (9) & q_{t} = q_{e} (1 - e^{- k_{1} t}), \end{matrix}$ where $k_{1}$ is the rate constant (1/min) and $t$ is the time (min).

The PSO model is widely used for adsorption on solid surface [39]. The original form of the kinetic model is determined by $\begin{matrix} (10) & \frac{{d q}_{t}}{d_{t}} = k_{2} {(q_{e} - q_{t})}^{2}, \end{matrix}$

The integrated PSO model is described as follows [38]. $\begin{matrix} (11) & q_{t} = \frac{k_{2} q_{e 2}^{2} t}{1 + k_{2} q_{e 2} t}, \\ (12) & h_{2} = k_{2} q_{e 2}^{2}, \end{matrix}$ where $k_{2}$ is the constant PSO constant (g/mg·min), $q_{e 2}$ is the equilibrium concentration of PQ calculated using the PSO model (mg/g), and $h_{2}$ is the initial rate constant (mg/g·min).

The intraparticle diffusion model [40] is calculated by $\begin{matrix} (13) & q_{t} = k_{p} t^{1 / 2} + C, \end{matrix}$ where $k_{p}$ is the rate constant of the intraparticle diffusion model (mg/g·min^1/2) and $C$ is the thickness of the boundary layer (mg/g).

2.4. Characterization

The specific surface area, micropore volume, and mesopore volume were determined using an N₂ adsorption-desorption apparatus (Autosorb MP, Quantachrome). The surface morphology was examined using a field emission scanning electron microscope (FE-SEM, JSM-6335F, JEOL) equipped with an energy-dispersive X-ray spectroscopy (EDS) detector (Inca, Oxford). The crystalline phase and iron composition were analyzed using a powder X-ray diffractometer (PXRD; D8 Advanced, Bruker diffractometer with Cu Kα radiation, $λ = 1.545 Å$ ). Raman spectroscopy (Jobin Yvon T64000, HORIBA) was used to study the graphitic features. Magnetic properties were investigated using a vibrating sample magnetometer (VSM, model 73098, Lake Shore). The thermal properties were assessed using a simultaneous thermal analyzer (STA, model 449 F3, Netzsch Jupiter).

3. Results and Discussion

3.1. Preparation of Magnetic Biochar

3.1.1. Effect of Fe(NO₃)₃ Concentration and Carbonization Temperature on Porosity

Figure 1(a) shows the N₂ adsorption-desorption isotherm of biochar without magnetic properties (B-00-850). It exhibited a type I isotherm according to the IUPAC classification, indicating the presence of a microporous structure (pore $diameter < 2 nm$ ) [41]. However, magnetic biochars (MB-001-850, MB-005-850, and MB-01-850) presented a combination of type I and type IV isotherms with an H₃ hysteresis loop, indicating microporous and mesoporous structure [42]. Specific surface area and micro-mesoporous properties were calculated by the BET, DR, and BJH model (Table 2). The results indicated that B-00-850 was only a microporous structure ( $V_{micro} = 0.11 c m^{3} / g$ ) and the surface area was 278 m²/g. The micro-mesoporous structures of the samples (MB-001-850, MB-005-850, and MB-01-850) improved with increasing Fe(NO₃)₃ concentrations. The micropore volume of the samples was almost 0.10 cm³/g, and the mesoporous volume was 0.10 cm³/g, 0.28 cm³/g, and 0.30 cm³/g for MB-001-850, MB-005-850, and MB-01-850, respectively. The N₂ adsorption-desorption isotherms of MB-01-550, MB-01-650, MB-01-750, and MB-01-850 are illustrated in Figure 1(b). MB-01-550 displayed a type I isotherm, indicating a microporous structure. On the other hand, MB-01-650, MB-01-750, and MB-01-850 exhibited type I and type IV isotherms with H₃ hysteresis loop characteristics, indicating the existence of microporous and mesoporous structures with plate-like particles. MB-01-550 only shows a microporous structure ( $V_{micro} = 0.13 c m^{3} / g$ , $S_{BET} = 325 m^{2} / g$ ). A mesoporous structure was created when the temperature exceeded 650°C. The mesoporous volume of MB-01-650, MB-01-750, and MB-01-850 was 0.35 cm³/g, 0.35 cm³/g, and 0.30 cm³/g, respectively. The presence of Fe(NO₃)₃ at carbonization temperatures lower than 550°C did not generate a mesoporous structure. In conclusion, Fe(NO₃)₃ concentration and carbonization temperature play an important role in developing microporous and mesoporous structures [15, 16, 43]. The mesopore size distributions are shown in Figure S3.

Figure 1

N₂ adsorption-desorption isotherm at -196°C of (a) B-00-850, MB-001-850, MB-005-850, and MB-01-850 and (b) MB-01-550, MB-01-650, MB-01-750, and MB-01-850.

(b)

Table 2

N₂ adsorption-desorption isotherm at -196°C and porosity of adsorbents derived from corn husk.

Sample	Type of isotherm	$S_{BET}$ (m²/g)	$V_{mic}$ (cm³/g)	$V_{meso}$ (cm³/g)
B-00-850	I	278.00	0.11	N/D
MB-001-850	I+IV	258.00	0.10	0.10
MB-005-850	I+IV	261.00	0.11	0.28
MB-01-850	I+IV	275.00	0.12	0.30
MB-01-550	I	325.00	0.13	N/D
MB-01-650	I+IV	254.00	0.10	0.35
MB-01-750	I+IV	252.00	0.10	0.35

Remark: N/D = not determined.

3.1.2. Effect of Fe(NO₃)₃ Concentration on the Thermal Properties of Corn Husk

Thermogravimetric analysis (TGA) (Figure S2 (a)) revealed that the addition of Fe(NO₃)₃ to the corn husk increased its thermal stability compared to that of the untreated corn husk [44]. The residual mass and %burn-off data in Table S1 reinforce this conclusion. The data indicate that the samples with more Fe(NO₃)₃ had a lower %burn-off and a higher residual mass. This suggests that increasing the iron content enhances thermal stability. Figure S2 (b) shows a differential thermogravimetric (DTG) curve, which demonstrates three distinct stages of weight loss. In the first stage, within the temperature range of 32–120°C, an 8.20% weight loss was observed owing to water evaporation. Subsequently, between 180 and 280°C, the thermal decomposition of glycosides, hemicellulose, and pectin units resulted in a weight loss of 32.80%. Finally, at approximately 300°C, a weight loss of approximately 40% indicated cellulose decomposition [45, 46]. A comparative analysis between activated Fe(NO₃)₃-treated corn husk and untreated corn husks demonstrated that the former exhibited a distinctive peak in the temperature range of 500–600°C, indicative of the presence of iron compounds. This peak confirmed the formation of iron within the samples, with varying iron concentrations resulting in the formation of iron compounds at slightly different temperatures within the 500–600°C range. Iron compounds can be described as follows: Fe³⁺ ions require hydrolysis to generate amorphous Fe species, including Fe(OH)₃ and FeO(OH), below 350°C. Subsequently, the conversion of these amorphous Fe species to Fe₂O₃ was observed at temperatures below 400°C. At higher temperatures (500–700°C), further reduction of hematite (Fe₂O₃) to magnetite (Fe₃O₄) is facilitated by reducing components such as amorphous carbon and CO gas. The formation of metallic Fe was achieved by the reduction of Fe₂O₃ and Fe₃O₄ using amorphous carbon [47–49].

3.1.3. Effect of Carbonization Temperature on Crystallinity

The XRD spectra of B-00-850, MB-01-550, MB-01-650, MB-01-750, and MB-01-850 are shown in Figure 2(a). XRD spectra of MB-01-650, MB-01-750, and MB-01-850 show a sharp peak at 26.20° referring to the graphite phase (JCPDS 01-089-8487). Furthermore, B-00-850 and MB-01-550 exhibited broad peaks at 23.16°, indicating the characteristic peak of amorphous carbon. Clearly, Fe(NO₃)₃ carbonized at temperatures above 650°C can improve the formation of graphitic structures and other iron compounds. There were six peaks at 2θ around 37.76°, 42.94°, 43.74°, 44.59°, 48.69°, and 49.14°, including the characteristic peak of iron carbide (Fe₃C) (JCPDS 00-076-1877). Additionally, the peak appears at 35.35° and 43.74°, showing the characteristic peak (Fe₃O₄) (JCPDS 00-019-0629). Finally, the iron metal is (Fe⁰) phase displayed at 45.00° (JCPDS 00-076-1877).

Figure 2

(a) XRD spectra and (b) Raman spectra of B-00-850, MB-01-550, MB-01-650, MB-01-750, and MB-01-850. Magnetization curve of (c) B-00-850, MB-001-850, MB-005-850, and MB-01-850 and (d) MB-01-550, MB-01-650, MB-01-750, and MB-01-850.

(b)

(c)

(d)

3.1.4. Effect of Carbonization Temperature on Graphitic Characteristic

The Raman spectra of B-00-850, MB-01-550, MB-01-650, MB-01-750, and MB-01-850 are shown in Figure 2(b). All samples show the D band and the G band at 1340 cm^-1 and 1580 cm^-1, respectively, which represent a characteristic feature of graphitic materials. The D band represents local defects and disorders at the edges, which correspond to the out-of-plane vibration of sp³ defects [50]. The G band is related to the vibration of sp² hybridization in the hexagonal graphene structure. Furthermore, the 2D and D+D $'$ bands at around 2700 cm^-1 and 2920 cm^-1 were clearly observed for MB-01-850, indicating that the sample underwent more transformation to the graphitic phase than the other samples [51].

The intensity ratio of the D and G bands ( $I_{D} / I_{G}$ ) serves as a measure of the degree of graphitization and abundance of functional groups present on the surface of the materials. If the ratio is less than 1, the biochar has a high degree of graphitization; if the ratio is greater than 1, a significant number of functional groups are present on the surface of the biochar [52]. As can be seen in Figure 2(b), the $I_{D} / I_{G}$ ratio initially increases from 0.80 for MB-01-550 to 1.10 for MB-01-650, after which it decreases to 1.08 for MB-01-750, before finally decreasing to 0.94 for MB-01-850. Increasing the carbonization temperature from 550°C to 750°C increased the $I_{D} / I_{G}$ ratio from 0.80 to 1.08, indicating the presence of surface defects resulting from iron oxide formation in the biochars, which is in agreement with the XRD results discussed earlier. However, at 850°C, the $I_{D} / I_{G}$ ratio decreased to 0.94, indicating an increasing degree of graphitization when the temperature increased, supporting the presence of a graphitic phase, as indicated by the XRD results.

3.1.5. Magnetic Properties of Adsorbents

Figure 2(c) displays the effect of Fe(NO₃)₃ concentration on the magnetization curve. An increase in Fe(NO₃)₃ concentration resulted in a higher saturation magnetization ( $M_{s}$ ); these were 1.64 emu/g, 11.93 emu/g, and 14.84 emu/g for MB-001-850, MB-005-850, and MB-01-850, respectively (Table 3). The coercive forces ( $H_{c}$ ) are 290.80 O_e, 313.60 O_e, and 270.52 O_e for MB-001-850, MB-005-850, and MB-01-850, respectively (Table 3). A hysteresis loop indicates ferromagnetism. The effect of carbonization temperature on the saturation magnetization and coercive force is shown in Figure 2(d). A hysteresis loop appears at temperatures higher than 650°C, indicating ferromagnetism [53]. In contrast, the hysteresis loop did not appear at a carbonization temperature of 550°C because this temperature was insufficient to form Fe₃C, Fe₃O₄, or Fe⁰ [54].

Table 3

Magnetic properties of adsorbents.

Sample	Magnetic properties
Sample	$M_{s}$ (emu/g)	$H_{c}$ (O_e)
B-00-850	0.00	0.00
MB-001-850	1.64	290.80
MB-005-850	11.93	313.60
MB-01-850	14.84	270.52
MB-01-750	20.30	371.20
MB-01-650	21.60	421.90
MB-01-550	4.70	67.31

3.1.6. Effect of Fe(NO₃)₃ on Morphologies and Textures

The morphologies and textures of B-00-850 and MB-01-850 are shown in Figure 3. The morphologies of B-00-850 and MB-01-850 were flakes. The textures exhibited surface roughness and spherical-like particles for B-00-850 and MB-01-850, respectively. Figure 4 shows the distribution of the chemical compositions on the surfaces of B-00-850 and MB-01-850, characterized by SEM-EDS mapping. The distributions of carbon and oxygen were uniform for B-00-850. Carbon, oxygen, and iron were uniformly distributed in MB-01-850. The atomic weight of the sample is listed in Table S2.

Figure 3

Morphology and surface properties of B-00-850 and MB-01-850.

Figure 4

SEM-EDS mapping of (a) B-00-850 and (b) MB-01-850.

(b)

3.2. Paraquat Adsorption Test

Microporous adsorbents (B-00-850) and micro-mesoporous adsorbents (MB-01-850) were investigated experimentally.

3.2.1. Effect of Adsorbent Dosage

The effect of adsorbent dosage on the removal of PQ is shown in Figure 5(a). An increase in adsorbent dosage resulted in an increase in the removal percentage (2.42% to 73.33% for B-00-850 and 13.78 to 99.99% for MB-01-850). The removal percentage of MB-01-850 was higher than that of B-00-850 for all adsorbent dosages. The experimental data confirm that mesopores are more efficient at removing PQ than micropores are. The highest removal percentage achieved at an adsorbent dosage of 2.0 g/L was found to be optimal.

Figure 5

(a) Effect of adsorbent dosages of B-00-850 and MB-01-850 and (b) effect of initial concentrations of B-00-850 and MB-01-850.

(b)

3.2.2. Effects of Initial Concentrations and pH

The effect of the initial concentration of PQ in the synthetic water (concentration 5–200 mg/L, pH 7, and 20 h) was studied. Figure 5(b) shows that the PQ removal percentage of MB-01-850 was greater than that of B-00-850, peaking at 99.99% and 55.42% at an initial concentration of 5 mg/L. Moreover, the removal percentage of PQ decreased when the initial concentration of PQ was insufficient due to insufficient adsorption sites.

The effect of pH on PQ adsorption of PQ was examined over a pH range of 4 to 10, as shown in Figure 6. Furthermore, examination of the effects of the initial pH on the adsorption capacity of the sorbent provides insight into the influence of various electrostatic attractions, including ion-dipole or hydrogen bonds. If electrostatic attraction is the predominant factor driving the adsorption mechanism, the adsorption capacity of biochar would be significantly influenced by the pH of PQ adsorption [55, 56]. The PQ adsorption experiments were conducted at an initial concentration, adsorbent dosage, temperature, and contact time of 40 mg/L, 2.0 g/L, 30°C, and 24 h, respectively. An increase in paraquat removal was observed when the pH was increased from 4 to 5, resulting in an increase in PQ removal from 0.33% to 16.02% and an increase in adsorption capacity ( $q_{e}$ ) from 0.07 mg/g to 3.34 mg/g. Subsequently, a significant improvement in the removal efficiency was observed with a further increase in the pH from 5 to 7. Within this range, PQ removal increased substantially from 16.02% to 93.48%, and $q_{e}$ also showed a notable increase, ranging from 3.34 mg/g to 22.50 mg/g.

Figure 6

Performance of PQ removal in an initial pH range of 4 to 10.

Additionally, a slight improvement in paraquat removal was observed as pH increased. The investigation yielded PQ removal percentages ranging from 96.34% to 99.99% and $q_{e}$ ranging from 20.59 mg/g to 20.10 mg/g. These findings demonstrate the influence of pH on the adsorption of PQ, as increasing the pH led to progressively higher removal percentages and enhanced the adsorption capacities.

The observed effect of pH on the adsorption of MB-01-850 can be explained by considering its point of zero charge ( $p H_{PZC}$ ), as depicted in Figure S4. The $p H_{PZC}$ value for MB-01-850 is 7. When the pH of the solution falls below $p H_{PZC}$ , the surface of the carbon material becomes positively charged, resulting in repulsion of PQ from the carbon surface [57, 58]. Referring to Figure S1, PQ is an organic cation composed of 4,4 $'$ -bipyridine with two N-methyl substituents at the 1- and 1 $'$ positions. When the pH of the solution exceeded that of $p H_{PZC}$ , the carbon surface became negatively charged, facilitating attractive interactions between the bipyridinium (N+-benzene ring) in the PQ structure of PQ and the carbon surface [59]. Therefore, based on the results of this experimental investigation, it can be concluded that electrostatic attraction plays a significant role as the primary mechanism governing the adsorption process between the bipyridinium in the PQ structure and MB-01-850.

3.2.3. Equilibrium Isotherms, Thermodynamics, and Kinetic Models

The maximum adsorption capacity ( $Q_{0}$ ) was analyzed using the Langmuir model, based on the assumption of monolayer adsorption. At a temperature of 30°C, $Q_{0}$ was 4.08 mg/g and 34.97 mg/g for B-00-850 and MB-01-850, respectively. The efficiency of PQ removal can be explained by the theory of adsorption; an appropriate adsorption efficiency occurs when the pore diameter of the adsorbent is larger than 1.7 to 3.0 times of the adsorbate [60]. The dimension of the PQ was $1.34 nm \times 0.36 nm$ [61, 62]. Although MB-01-850 has a pore width of 2.60 nm (Figure S3), approximately 2 times larger than PQ, therefore, this absorbent was more effective for PQ adsorption than B-00-850 because it had only a microporous structure, roughly the same size as PQ. Therefore, the presence of a microporous structure did not increase the PQ adsorption efficiency. The mesopore volume is key for PQ adsorption because of its suitable pore size with the PQ structure. Owing to the low PQ adsorption efficiency of B-00-850, the equilibrium isotherm, kinetics, and thermodynamics of PQ adsorption were only examined for MB-01-850.

The adsorption mechanism of PQ onto MB-01-850 was studied using equilibrium isotherm models. The correlation coefficient ( $R^{2}$ ) was used to determine the consistency between experimental and theoretical values (Table 4). Figures 7(b) and 7(c) show that the equilibrium isotherms of MB-01-850 at 30-40°C fitted better with the Langmuir isotherm model ( $R^{2} = 0.99$ ), suggesting that the adsorption was monolayer. MB-01-850 at 50°C (Figure 7(d)) fit better with the Freundlich isotherm model ( $R^{2} = 0.99$ ), explaining the multilayer adsorption mechanism [63]. The parameters obtained from the models are listed in Table 4.

Table 4

Isotherm parameters of the Langmuir and Freundlich models and kinetic parameters of PFO and PSO for PQ adsorption on adsorbents.

Models	Parameters	Synthetic water				Natural water
Models	Parameters	B-00-850 (at 30°C)	MB-01-850 (at 30°C)	MB-01-850 (at 40°C)	MB-01-850 (at 50°C)	MB-01-850 (at 30°C)
Langmuir	$Q_{0}$ (mg/g)	4.08	34.97	12.69	9.03	31.63
	$b$ (L/g)	0.13	1.82	1.08	0.58	0.90
	$R^{2}$ (-)	0.97	0.99	0.99	0.98	0.99

Freundlich	$K_{F}$ ((mg/g)(L/mg)^1/ $^{n}$ )	0.95	12.76	5.62	4.67	13.40
	$n$ (-)	2.96	3.85	4.63	5.79	4.00
	$R^{2}$ (-)	0.99	0.99	0.98	0.99	0.97

PFO	$k_{1}$ (1/min)		1.09
	$q_{e 1}$ (mg/g)		8.40
	$R^{2}$ (-)		0.40

PSO	$k_{2}$ (g/mg·min)		0.06
	$q_{e 2}$ (mg/g)		9.59
	$h$ (mg/g·min)		5.66
	$R^{2}$ (-)		0.99

Figure 7

The equilibrium adsorption isotherms of (a) B-00-850 at a temperature of 30°C, (b) MB-01-850 at a temperature of 30°C, (c) MB-01-850 at a temperature of 40°C, and (d) MB-01-850 at a temperature of 50°C.

(b)

(c)

(d)

In addition, the $K_{EQ}^{0}$ value derived from the van’t Hoff equation was used to calculate the thermodynamic parameters (Table 5). The negative value of $Δ H^{0}$ for MB-01-850 (-46.47 kJ/mol) indicated an exothermic adsorption process. The evaluation of the adsorption mechanisms depends on the magnitude of the standard enthalpy change ( $Δ H^{0}$ ). Research has shown that if the magnitude of the standard enthalpy change ( $Δ H^{0}$ ) is less than 80 kJ/mol, it corresponds to physical adsorption; if it exceeds 200 kJ/mol, it corresponds to chemical adsorption [64]. The adsorption mechanism between PQ and MB-01-850 is physical adsorption, which involves electrostatic attraction, ion-dipole, or hydrogen bonding [64–66]. The adsorption forces may arise from ion-dipole interactions associated with bipyridinium (N+-benzene ring) in the PQ structure, as mentioned in Section 3.2.2, or stem from interactions between the π-electrons in the carbonaceous adsorbent and the π-electrons in the aromatic ring of the adsorbate [56, 67]. The negative $Δ S^{0}$ (-44.62 J/mol·K) and $Δ G^{0}$ (-32.95, -32.50, and -32.05 kJ/mol for 30, 40, and 50°C, respectively) for MB-01-850 indicate a decrease in randomness at the adsorbent-adsorbate interface and spontaneous adsorption, respectively [68].

Table 5

Thermodynamic parameter for PQ adsorption on MB-01-850.

Sample	$Δ H^{0}$ (kJ/mol)	$Δ S^{0}$ (J/mol·K)	$Δ G^{0}$ (kJ/mol)			$R^{2}$ (-)
Sample	$Δ H^{0}$ (kJ/mol)	$Δ S^{0}$ (J/mol·K)	30°C	40°C	50°C	$R^{2}$ (-)
MB-01-850	-46.47	-44.62	-32.95	-32.50	-32.05	0.99

Kinetic experiments were performed at an initial concentration of 20 mg/L and 30°C. MB-01-850 reached equilibrium within approximately 20 minutes. These results indicate that the presence of a mesoporous structure enhanced the PQ adsorption rate. The experimental data of MB-01-850 were fitted with $R^{2}$ values of PSO models of 0.99, as shown in Figure 8(a). Furthermore, the kinetic parameters for PFO ( $k_{1}$ ) and PSO ( $k_{2}$ , $h_{2}$ ) are shown in Table 4, and the initial rate constant ( $h$ ) is 5.66 mg/g·min that correlated with the reaction rate of the adsorption process. If the regression of $q_{t}$ versus $t^{1 / 2}$ is linear and passes through the origin, then intraparticle diffusion is the rate-limiting step [69, 70]. It was found that none of the straight lines passed through the origin; therefore, intraparticle diffusion was not the rate-limiting step. The corresponding correlation coefficients and parameters were calculated and are listed in Table S3.

Figure 8

(a) Adsorption kinetics of MB-01-850 at temperature of 30°C and (b) the intraparticle diffusion curve of MB-01-850.

(b)

3.2.4. Application to Natural Water

The investigation of the equilibrium adsorption of PQ in various sources, namely, synthetic water and natural water, is illustrated in Figure 9, under PQ concentrations of 5–200 mg/L, temperature of 30°C, and pH of 7. As the concentration of the PQ solution increased, a decrease in the percentage of PQ removed was observed, with values decreasing from 99.99% to 26.68% in synthetic water and from 97.74% to 22.41% in natural water. The adsorption capacities were found to be 34.97 mg/g and 31.63 mg/g for the synthetic water and natural water, respectively, as presented in Table 4. Notably, the adsorption capacity tends to decrease under natural water conditions. This decline can be attributed to the presence of organic substances, metal ions, and other contaminants in natural water, which interfered with the PQ adsorption process on MB-01-850. To support this observation, a reduction in the chemical oxygen demand (COD) value was confirmed after PQ adsorption, decreasing from 17 mg/L to 5.1 mg/L (Table S4).

Figure 9

(a) Removal percentage and (b) equilibrium adsorption of PQ in synthetic water and natural water on MB-01-850.

(b)

3.2.5. Reusability of MB-01-850

The reusability of MB-01-850 after several adsorption-desorption cycles is presented in Figure 10. In the absence of the regeneration process, the PQ adsorption efficiency of MB-01-850 significantly decreased. After the first cycle, the PQ of the adsorption and removal percentages decreased to 21.69% and dropped to 4.33% after four cycles. However, the regeneration process involved varying the concentrations of NaOH from 0.1 to 1.0 M. It was observed that a NaOH concentration of 0.1 M resulted in PQ removal percentages ranging from 75.13% to 51.70% after four cycles. Importantly, as the NaOH concentration increased to 0.5 and 1.0 M, a gradual improvement in desorption efficiency was observed. Throughout all four cycles, the PQ removal percentage exceeded 95.00% for NaOH concentrations in the range 0.5 to 1.0 M. The NaOH concentration increased, and the hydroxyl ions interfered with the adsorption between paraquat and the carbon surface charge. As a result, higher NaOH concentrations result in effective regeneration efficiency [71, 72].

Figure 10

Adsorption and regeneration performance of MB-01-850 (initial concentration, 20 mg/L; adsorbent dosage, 2.0 g/L; time, 24 h; temperature, 30°C; and pH, 7).

For MB-01-850 with and without regeneration, it was evident that the regenerated adsorbent demonstrated excellent adsorption efficiency and could be reused for up to four cycles. These observations highlight the enhanced adsorption performance and increased longevity of the regenerated adsorbent compared to those of the nonregenerated adsorbent.

3.2.6. Comparison of the Current Results with Other Adsorbents

Table 6 comprehensively compares the maximum adsorption capacities of carbon-based and nonporous carbon materials from various related studies [22, 23, 29–31, 59, 73–83]. When evaluating the adsorption efficiency of MB-01-850 compared with carbon-based adsorbents, it was observed to reach a moderate level ( $Q_{0} = 34.97 mg / g$ ). Significantly, this value exceeded the adsorption efficiencies of activated carbon synthesized from spent rubber and nanoporous activated carbon, which recorded values of 16.61 mg/g [74] and 75.80 mg/g [31], respectively. However, $Q_{0}$ of MB-01-850 remains lower than that of commercial activated carbon, with a value of 33.70 mg/g [31].

Table 6

Comparison of various adsorbents for removal of PQ.

Adsorbents	Magnetic responsibility	$Q_{0}$ (mg/g)	pH	Adsorbent dosage (g/L)	Time (h)	T (°C)	Ref.
Biochar from corn husk	No	4.07	7.0	2.0	20	30	This work
Magnetic biochar from corn husk	Yes	34.97	7.0	2.0	20	30	This work
Activated carbon derived from used tired	No	33.70	7.0	4.0	48	25	[31]
Commercial activated carbon	No	75.80	7.0	4.0	48	25	[31]
Carbon tubes from biomass	No	218.61	NR	0.4	20 min	20	[73]
Nanoporous activated carbon	No	16.61	NR	1.0	5	$T_{R}$	[74]
Modified carbon sphere	No	134.63	NR	1.0	30 min	20	[75]
Algerian bentonite	No	100.00	NR	2.0	24	25	[23]
Activated clay	No	58.48	11	2.0	24	25	[29]
Activated bleaching earth	No	34.96	NR	2.0	120 min	25	[30]
Ayous sawdust	No	9.47	NR	6.0	1	25	[76]
Bentonite/mesoporous silica composite	No	11.75	NR	NR	NR	$T_{R}$	[77]
Humic acid-coated goethite	No	4.40	4.0	0.6	24	$T_{R}$	[59]
Kaolin	No	5.45	NR	2.0	24	23	[78]
Mesoporous silica modified with titania	No	13.68	9.5	6.3	4	25	[79]
Montmorillonite-alginate beads	No	71.49	5.5	NR	6	25	[80]
TEMPO-oxidized cellulose nanofibers	No	108.00	NR	0.1	2	30	[81]
Zeolite LTL	No	166.71	NR	2.5	24	30	[22]
Zeolite Y	No	26.38	6.0	1.0	24	$T_{R}$	[82]
Fe₃O₄@SiO₂/SiCRG and Fe₃O₄@SiO₂/SiStarch	Yes	257.00	7.3	0.5	1	25	[83]

Remark: NR = no report; $T_{R}$ = room temperature.

Additionally, compared to noncarbon materials, MB-01-850 exhibited higher adsorption efficiency than several inorganic materials. For example, the bentonite/mesoporous silica compound [77], humic acid-coated goethite [59], kaolin [78], and zeolite Y [82] showed $Q_{0}$ values of 11.75 mg/g, 4.40 mg/g, 5.45 mg/g, and 26.38 mg/g, respectively. In summary, the adsorbents used for paraquat removal demonstrated removal efficiencies ranging from 4.40 mg/g to 257 mg/g.

One distinguishing characteristic of MB-01-850 is its ability to be easily separated from the aqueous solution using an external magnet after adsorption, facilitating convenient reuse. Another noteworthy aspect of this research is the practical operating conditions, that is, a pH value of 7, eliminating the need for additional chemicals to adjust the pH. Furthermore, this study used agricultural waste, specifically corn husk, as a precursor material, highlighting its sustainability and ecofriendliness.

4. Conclusions

This study revealed that corn husk carbon can remove paraquat from synthetic and natural wastewater. These results suggest that the presence of Fe(NO₃)₃ and carbonization temperatures above 650°C caused the formation of microporous and mesoporous structures, graphitic characteristics, and iron phases. Furthermore, the experimental results demonstrated that the structure of the carbon adsorbent synthesized without Fe(NO₃)₃ was microporous. Furthermore, this study provided strong evidence that the mesoporous structure promoted PQ adsorption; the maximum adsorption capacity for MB-01-850 was 34.97 mg/g. In contrast, the microporous structure showed modest adsorption capacities; the highest adsorption capacity for B-00-850 was 4.08 mg/g. Based on the analysis of enthalpy change through thermodynamics and investigation of the effect of the initial pH on the adsorption capacity, the findings consistently indicate that electrostatic attraction primarily governs the adsorption process. Furthermore, this adsorbent material exhibits remarkable regenerative capability, which can be regenerated almost completely for at least four cycles using a sodium hydroxide (NaOH) solution with a concentration of 0.5 M or greater.

Footnotes

Data Availability

The data used to support the findings of this study are available from the corresponding authors upon request.

Conflicts of Interest

The authors declare that there is no conflict of interest with respect to the research, authorship, and/or publication of this article.

Authors’ Contributions

Sakonsupa Damdib was responsible for methodology, investigation, original draft preparations, and writing—review and editing. Phamornsiri Phamornpiboon and Bhawaranchat Vanichsetakul were assigned for investigation. Chanchana Thanachayanont and Patiparn Punyapalakul were responsible for supervision. Adisak Siyasukh was responsible for conceptualization, methodology, investigation, supervision, original draft preparations, and writing—review and editing. Nattaporn Tonanon was responsible for conceptualization, methodology, supervision, writing—review and editing, and funding acquisition. All authors have read and approved the final manuscript.

Acknowledgments

The authors would like to acknowledge Assistant Professor Dr. Yothin Chimupala from the Department of Industrial Chemistry, Faculty of Science, Chiang Mai University, for consulting the XRD analysis. The authors also sincerely thank the Faculty of Science, Chiang Mai University, and the Bio-Circular-Green Economy Technology and Engineering Center (BCGeTEC), Chulalongkorn University, for supporting and providing the research facilities to carry out this research work. This research project was financially supported by Ratchadapiseksompotch Fund Chulalongkorn University and Thai Graduate Institute of Science and Technology (TGIST), National Science and Technology Development Agency (SCA-CO-2561-6940-TH). This work was also partially supported by Chiang Mai University.

Supplementary Materials

References

Lehmann

Gaunt

Rondon

Bio-char sequestration in terrestrial ecosystems – a review

Mitigation and Adaptation Strategies for Global Change 2006 11

5512881

2 403 427

10.1007/s11027-005-9006-5

2-s2.0-33745727778

Son

E.-B.

Poo

K.-M.

Chang

J.-S.

Chae

K.-J.

Heavy metal removal from aqueous solutions using engineered magnetic biochars derived from waste marine macro-algal biomass

Science of The Total Environment 2018 615

5512881

161 168

10.1016/j.scitotenv.2017.09.171

2-s2.0-85030169101

28964991

Tan

Liu

Zeng

Wang

Yang

Application of biochar for the removal of pollutants from aqueous solutions

Chemosphere 2015 125

5512881

70 85

10.1016/j.chemosphere.2014.12.058

2-s2.0-84923604349

Praveen

Jegan

Bhagavathi Pushpa

Gokulan

Bulgariu

Biochar for removal of dyes in contaminated water: an overview

Biochar 2022 4

5512881

1 10

10.1007/s42773-022-00131-8

Wang

Preparation, modification and environmental application of biochar: a review

Journal of Cleaner Production 2019 227

5512881

1002 1022

10.1016/j.jclepro.2019.04.282

2-s2.0-85065096142

Murtaza

Ahmed

Usman

Feedstock type, pyrolysis temperature and acid modification effects on physiochemical attributes of biochar and soil quality

Arabian Journal of Geosciences 2022 15

5512881

3 305

10.1007/s12517-022-09539-9

Zeng

X.-Y.

Wang

R.-X.

Cao

H.-L.

Y.-F.

Lü

Impacts of temperatures and phosphoric-acid modification to the physicochemical properties of biochar for excellent sulfadiazine adsorption

Biochar 2022 4

5512881

1 14

10.1007/s42773-022-00143-4

Tang

Song

Chen

Yue

Yang

Effect of biochar on immobilization remediation of Cd⁃contaminated soil and environmental quality

Environmental Research 2022 204

5512881

Part A, article 111840

10.1016/j.envres.2021.111840

34403669

Tan

Liu

Zeng

Liu

Wang

Liu

Biochar-based nano-composites for the decontamination of wastewater: a review

Bioresource Technology 2016 212

5512881

318 333

10.1016/j.biortech.2016.04.093

2-s2.0-84991733072

27131871

10.

Amusat

S. O.

Kebede

T. G.

Dube

Nindi

M. M.

Ball-milling synthesis of biochar and biochar–based nanocomposites and prospects for removal of emerging contaminants: a review

Journal of Water Process Engineering 2021 41, article 101993

5512881

10.1016/j.jwpe.2021.101993

11.

Huang

Xian

Tsang

E. P.

Cheng

Fang

Magnetic biochar for environmental remediation: a review

Bioresource Technology 2020 298, article 122468

5512881

10.1016/j.biortech.2019.122468

31839494

12.

Wei

Dong

Wang

Zhang

Cyclodextrin-functionalized magnetic alginate microspheres for synchronous removal of lead and bisphenol a from contaminated soil

Chemical Engineering Journal 2023 461, article 142079

5512881

10.1016/j.cej.2023.142079

13.

Zhang

Huang

Zhang

Shen

Wang

Development of iron-based biochar for enhancing nitrate adsorption: effects of specific surface area, electrostatic force, and functional groups

Science of The Total Environment 2023 856, Part 1, article 159037

5512881

10.1016/j.scitotenv.2022.159037

36179839

14.

Isaac

Siddiqui

Sequestration of Ni(II) and Cu(II) using FeSO4 modified Zea mays husk magnetic biochar: isotherm, kinetics, thermodynamic studies and RSM

Journal of Hazardous Materials Advances 2022 8, article 100162

5512881

10.1016/j.hazadv.2022.100162

15.

Siyasukh

Chimupala

Tonanon

Preparation of magnetic hierarchical porous carbon spheres with graphitic features for high methyl orange adsorption capacity

Carbon 2018 134

5512881

207 221

10.1016/j.carbon.2018.03.093

2-s2.0-85047436590

16.

Damdib

Vanichsetakul

Pimpapoat

Mikhalovsky

Busquets

Siyasukh

Tonanon

Removal of reactive black dye in water by magnetic mesoporous carbon from macadamia nutshell

Adsorption Science & Technology 2022 2022

5512881

9884474

10.1155/2022/9884474

17.

Oehme

F. W.

Mannala

Paraquat

Small Animal Toxicology 2006

Elsevier

964 977

18.

Berry

La Vecchia

Nicotera

Paraquat and Parkinson’s disease

Cell Death and Differentiation 2010 17

5512881

7 1115 1125

10.1038/cdd.2009.217

2-s2.0-77953611763

19.

Franco

Rodriguez-Rocha

Burns

Panayiotidis

M. I.

Molecular mechanisms of pesticide-induced neurotoxicity: relevance to Parkinson’s disease

Chemico-Biological Interactions 2010 188

5512881

2 289 300

10.1016/j.cbi.2010.06.003

2-s2.0-77956650279

20542017

20.

Halfon

Galassi

Brüggemann

Provini

Selection of priority properties to assess environmental hazard of pesticides

Chemosphere 1996 33

5512881

8 1543 1562

10.1016/0045-6535(96)00274-3

2-s2.0-0030271345

21.

Veríssimo

Moreira

J. C.

Meyer

Paraquat contamination in surface waters of a rural stream in the mountain region in the state of Rio De Janeiro Southeastern Brazil

Journal of Environmental and Toxicological Studies 2018 2

5512881

10.16966/2576-6430.111

22.

Insuwan

Rangsriwatananon

Removal of paraquat from aqueous solutions onto zeolite LTL

Engineering Journal 2017 21

5512881

2 15 23

10.4186/ej.2017.21.2.15

2-s2.0-85022328431

23.

Ait Sidhoum

Socías-Viciana

M. M.

Ureña-Amate

M. D.

Derdour

González-Pradas

Debbagh-Boutarbouch

Removal of paraquat from water by an Algerian bentonite

Applied Clay Science 2013 83-84

5512881

441 448

10.1016/j.clay.2013.07.007

2-s2.0-84885052490

24.

Rajaram

Neelakantan

Recent advances in estimation of paraquat using various analytical techniques: a review

Results in Chemistry 2023 5, article 100703

5512881

10.1016/j.rechem.2022.100703

25.

Lee

J.-C.

Kim

M.-S.

Kim

B.-W.

Removal of paraquat dissolved in a photoreactor with TiO₂ immobilized on the glass-tubes of UV lamps

Water Research 2002 36

5512881

7 1776 1782

10.1016/S0043-1354(01)00378-5

2-s2.0-0036219865

26.

Desipio

M. M.

Thorpe

Saha

Photocatalytic decomposition of paraquat under visible light by carbon nitride and hydrogen peroxide

Optik 2018 172

5512881

1047 1056

10.1016/j.ijleo.2018.07.124

2-s2.0-85050888098

27.

Cartaxo

M. A. M.

Borges

C. M.

Pereira

M. I. S.

Mendonça

M. H.

Electrochemical oxidation of paraquat in neutral medium

Electrochimica Acta 2015 176

5512881

1010 1018

10.1016/j.electacta.2015.07.099

2-s2.0-84938486900

28.

Dhaouadi

Adhoum

Degradation of paraquat herbicide by electrochemical advanced oxidation methods

Journal of Electroanalytical Chemistry 2009 637

5512881

1-2 33 42

10.1016/j.jelechem.2009.09.027

2-s2.0-77949287726

29.

Tsai

W. T.

Lai

C. W.

Hsien

K. J.

Effect of particle size of activated clay on the adsorption of paraquat from aqueous solution

Journal of Colloid and Interface Science 2003 263

5512881

1 29 34

10.1016/S0021-9797(03)00213-3

2-s2.0-0037834613

12804881

30.

Tsai

W. T.

Lai

C. W.

Hsien

K. J.

Adsorption kinetics of herbicide paraquat from aqueous solution onto activated bleaching earth

Chemosphere 2004 55

5512881

6 829 837

10.1016/j.chemosphere.2003.11.043

2-s2.0-1642355821

15041287

31.

Hamadi

N. K.

Swaminathan

Chen

X. D.

Adsorption of paraquat dichloride from aqueous solution by activated carbon derived from used tires

Journal of Hazardous Materials 2004 112

5512881

1-2 133 141

10.1016/j.jhazmat.2004.04.011

2-s2.0-3042632968

15225939

32.

Ding

Tao

Qian

Zhang

A novel PEI-grafted N-doping magnetic hydrochar for enhanced scavenging of BPA and Cr(VI) from aqueous phase

Environmental Pollution 2023 321, article 121142

5512881

10.1016/j.envpol.2023.121142

36702430

33.

Langmuir

The constitution and fundamental properties of solids and liquids. Part I. SOLIDS

Journal of the American Chemical Society 1916 38

5512881

11 2221 2295

10.1021/ja02268a002

2-s2.0-4043158815

34.

Wang

Guo

Adsorption isotherm models: classification, physical meaning, application and solving method

Chemosphere 2020 258, article 127279

5512881

10.1016/j.chemosphere.2020.127279

32947678

35.

Freundlich

Über die adsorption in Lösungen

Zeitschrift für Physikalische Chemie 1907 57U

5512881

1 385 470

10.1515/zpch-1907-5723

36.

Tran

H. N.

Lima

E. C.

Juang

R.-S.

Bollinger

J.-C.

Chao

H.-P.

Thermodynamic parameters of liquid–phase adsorption process calculated from different equilibrium constants related to adsorption isotherms: a comparison study

Journal of Environmental Chemical Engineering 2021 9

5512881

6, article 106674

10.1016/j.jece.2021.106674

37.

Y. S.

Porter

J. F.

McKay

Equilibrium isotherm studies for the sorption of divalent metal ions onto peat: copper, nickel and lead single component systems

Water, Air, and Soil Pollution 2002 141

5512881

1 33

10.1023/A:1021304828010

2-s2.0-0036874989

38.

Wang

Guo

Adsorption kinetic models: physical meanings, applications, and solving methods

Journal of Hazardous Materials 2020 390, article 122156

5512881

10.1016/j.jhazmat.2020.122156

32006847

39.

Y.-S.

Review of second-order models for adsorption systems

Journal of Hazardous Materials 2006 136

5512881

3 681 689

10.1016/j.jhazmat.2005.12.043

2-s2.0-33746672575

16460877

40.

McKay

Otterburn

M. S.

Sweeney

A. G.

The removal of colour from effluent using various adsorbents—III. Silica: rate processes

Water Research 1980 14

5512881

1 15 20

10.1016/0043-1354(80)90037-8

2-s2.0-0018865478

41.

Sing

K. S. W.

Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984)

Pure and Applied Chemistry 1985 57

5512881

4 603 619

10.1351/pac198557040603

2-s2.0-84939775172

42.

Thommes

Kaneko

Neimark

A. V.

Olivier

J. P.

Rodriguez-Reinoso

Rouquerol

Sing

K. S. W.

Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC technical report)

Pure and Applied Chemistry 2015 87

5512881

9-10 1051 1069

10.1515/pac-2014-1117

2-s2.0-84944241280

43.

Cho

D.-W.

Yoon

Kwon

E. E.

Biswas

J. K.

Song

Fabrication of magnetic biochar as a treatment medium for As(V) via pyrolysis of FeCl3-pretreated spent coffee ground

Environmental Pollution 2017 229

5512881

942 949

10.1016/j.envpol.2017.07.079

2-s2.0-85026501133

28778792

44.

Dai

Sun

Wang

Liu

Yang

Sun

Zhang

Zheng

Yang

Gao

Chen

Zhang

Gao

Zhang

Utilizations of agricultural waste as adsorbent for the removal of contaminants: a review

Chemosphere 2018 211

5512881

235 253

10.1016/j.chemosphere.2018.06.179

2-s2.0-85050958184

30077103

45.

Morán

J. I.

Alvarez

V. A.

Cyras

V. P.

Vázquez

Extraction of cellulose and preparation of nanocellulose from sisal fibers

Cellulose 2008 15

5512881

1 149 159

10.1007/s10570-007-9145-9

2-s2.0-38049000340

46.

Paul Guin

Bhardwaj

Y. K.

Varshney

Radiation grafting: a voyage from bio-waste corn husk to an efficient thermostable adsorbent

Carbohydrate Polymers 2018 183

5512881

151 164

10.1016/j.carbpol.2017.11.101

2-s2.0-85037685340

29352870

47.

Neeli

S. T.

Ramsurn

Synthesis and formation mechanism of iron nanoparticles in graphitized carbon matrices using biochar from biomass model compounds as a support

Carbon 2018 134

5512881

480 490

10.1016/j.carbon.2018.03.079

2-s2.0-85045550854

48.

Zhu

Qian

Liu

Matera

Zhang

Chen

Controllable synthesis of magnetic carbon composites with high porosity and strong acid resistance from hydrochar for efficient removal of organic pollutants: an overlooked influence

Carbon 2016 99

5512881

338 347

10.1016/j.carbon.2015.12.044

2-s2.0-84959373813

49.

González-García

Activated carbon from lignocellulosics precursors: a review of the synthesis methods, characterization techniques and applications

Renewable and Sustainable Energy Reviews 2018 82

5512881

1393 1414

10.1016/j.rser.2017.04.117

2-s2.0-85027253172

50.

Zong

Tan

Sun

Lan

Ren

Zheng

Solvothermal synthesis of nitrogen-doped graphene decorated by superparamagnetic Fe₃O₄ nanoparticles and their applications as enhanced synergistic microwave absorbers

Carbon 2017 115

5512881

493 502

10.1016/j.carbon.2017.01.036

2-s2.0-85009919946

51.

Mohandoss

Gupta

S. S.

Nelleri

Pradeep

Maliyekkal

S. M.

Solar mediated reduction of graphene oxide

RSC Advances 2017 7

5512881

2 957 963

10.1039/C6RA24696F

2-s2.0-85008685949

52.

Ahmed

M. B.

Zhou

J. L.

Ngo

H. H.

Guo

Johir

M. A. H.

Sornalingam

Single and competitive sorption properties and mechanism of functionalized biochar for removing sulfonamide antibiotics from water

Chemical Engineering Journal 2017 311

5512881

348 358

10.1016/j.cej.2016.11.106

2-s2.0-85027954049

53.

Wan

Chen

Wang

Yang

Qian

A soft-template-assisted hydrothermal approach to single-crystal Fe₃O₄ nanorods

Journal of Crystal Growth 2005 276

5512881

3-4 571 576

10.1016/j.jcrysgro.2004.11.423

2-s2.0-15344342254

54.

Lei

Wang

Zhao

Yang

High saturation magnetization of Fe₃C nanoparticles synthesized by a simple route

Dyes and Pigments 2017 139

5512881

448 452

10.1016/j.dyepig.2016.12.046

2-s2.0-85007125146

55.

Ncibi

M. C.

Hamissa

A. M. B.

Fathallah

Kortas

M. H.

Baklouti

Mahjoub

Seffen

Biosorptive uptake of methylene blue using Mediterranean green alga Enteromorpha spp.

Journal of Hazardous Materials 2009 170

5512881

2-3 1050 1055

10.1016/j.jhazmat.2009.05.075

2-s2.0-69049097026

19520507

56.

Tran

H. N.

Wang

Y.-F.

You

S.-J.

Chao

H.-P.

Insights into the mechanism of cationic dye adsorption on activated charcoal: the importance of π–π interactions

Process Safety and Environmental Protection 2017 107

5512881

168 180

10.1016/j.psep.2017.02.010

2-s2.0-85013763134

57.

Nasiruddin Khan

Sarwar

Determination of points of zero charge of natural and treated adsorbents

Surface Review and Letters 2007 14

5512881

3 461 469

10.1142/S0218625X07009517

2-s2.0-34547456976

58.

Dey

A. K.

Dey

Goswami

Adsorption characteristics of methyl red dye by Na₂CO₃-treated jute fibre using multi-criteria decision making approach

Applied Water Science 2022 12

5512881

8 179

10.1007/s13201-022-01700-9

59.

Iglesias

López

Gondar

Antelo

Fiol

Arce

Adsorption of paraquat on goethite and humic acid-coated goethite

Journal of Hazardous Materials 2010 183

5512881

1-3 664 668

10.1016/j.jhazmat.2010.07.077

2-s2.0-77956449504

20708336

60.

Tang

Pang

Zeng

Deng

Wang

Ren

Peng

Feng

Sustainable efficient adsorbent: alkali-acid modified magnetic biochar derived from sewage sludge for aqueous organic contaminant removal

Chemical Engineering Journal 2018 336

5512881

160 169

10.1016/j.cej.2017.11.048

2-s2.0-85034112289

61.

Draoui

Denoyel

Chgoura

Rouquerol

Adsorption of paraquat on minerals: a thermodynamic study

Journal of Thermal Analysis and Calorimetry 1999 58

5512881

597 606

10.1023/A:1010152411288

62.

Raupach

Emerson

W. W.

Slade

P. G.

The arrangement of paraquat bound by vermiculite and montmorillonite

Journal of Colloid and Interface Science 1979 69

5512881

3 398 408

10.1016/0021-9797(79)90129-2

2-s2.0-0000378787

63.

Boparai

H. K.

Joseph

O’Carroll

D. M.

Kinetics and thermodynamics of cadmium ion removal by adsorption onto nano zerovalent iron particles

Journal of Hazardous Materials 2011 186

5512881

1 458 465

10.1016/j.jhazmat.2010.11.029

2-s2.0-79551556859

21130566

64.

Lima

É. C.

Dehghani

M. H.

Guleria

Sher

Karri

R. R.

Dotto

G. L.

Tran

H. N.

Adsorption: fundamental aspects and applications of adsorption for effluent treatment

Green Technologies for the Defluoridation of Water 2021

Elsevier

41 88

10.1016/b978-0-323-85768-0.00004-x

65.

Baev

A. K.

Specific intermolecular interactions of organic compounds 2012

Springer Science & Business Media

10.1007/978-3-642-21622-0

2-s2.0-84929895601

66.

Chang

Thoman

J. W.

Jr.

Intermolecular Forces. Physical Chemistry for the Chemical Sciences 2014 792

5512881

University Science Books

67.

Coughlin

R. W.

Ezra

F. S.

Role of surface acidity in the adsorption of organic pollutants on the surface of carbon

Environmental Science & Technology 1968 2

5512881

4 291 297

10.1021/es60016a002

2-s2.0-33947301450

68.

Tan

I. A. W.

Ahmad

A. L.

Hameed

B. H.

Adsorption of basic dye on high-surface-area activated carbon prepared from coconut husk: equilibrium, kinetic and thermodynamic studies

Journal of Hazardous Materials 2008 154

5512881

1-3 337 346

10.1016/j.jhazmat.2007.10.031

2-s2.0-43049133280

18035483

69.

Zheng

Liu

Zheng

Liang

Liu

Sorption isotherm and kinetic modeling of aniline on Cr-bentonite

Journal of Hazardous Materials 2009 167

5512881

1-3 141 147

10.1016/j.jhazmat.2008.12.093

2-s2.0-67649255960

19171429

70.

F.-C.

Tseng

R.-L.

Juang

R.-S.

Initial behavior of intraparticle diffusion model used in the description of adsorption kinetics

Chemical Engineering Journal 2009 153

5512881

1-3 1 8

10.1016/j.cej.2009.04.042

2-s2.0-67749085881

71.

Larasati

Fowler

G. D.

Graham

N. J. D.

Insights into chemical regeneration of activated carbon for water treatment

Journal of Environmental Chemical Engineering 2021 9

5512881

4, article 105555

10.1016/j.jece.2021.105555

72.

Martin

R. J.

W. J.

Chemical regeneration of exhausted activated carbon—II

Water Research 1985 19

5512881

12 1527 1535

10.1016/0043-1354(85)90398-7

2-s2.0-0022336867

73.

Yin

Chen

Deng

Wang

Carbon tubes from biomass with prominent adsorption performance for paraquat

Chemosphere 2021 262, article 127797

5512881

10.1016/j.chemosphere.2020.127797

32799143

74.

Mueanpun

Srisuk

Chaiammart

Panomsuwan

Nanoporous activated carbons derived from water ferns as an adsorbent for removal of paraquat from contaminated water

Materialia 2021 15, article 100986

5512881

10.1016/j.mtla.2020.100986

75.

Miao

Chen

Yin

Yang

Deng

Wang

Modified carbon spheres as universal materials for adsorption of cationic harmful substances (paraquat and dyes) in water

Microporous and Mesoporous Materials 2020 297, article 110040

5512881

10.1016/j.micromeso.2020.110040

76.

Nanseu-Njiki

C. P.

Dedzo

G. K.

Ngameni

Study of the removal of paraquat from aqueous solution by biosorption onto Ayous (Triplochiton schleroxylon) sawdust

Journal of Hazardous Materials 2010 179

5512881

1-3 63 71

10.1016/j.jhazmat.2010.02.058

2-s2.0-77952890020

20334968

77.

Dehgani

Sedghi asl

Ghaedi

Sabzehmeidani

M. M.

Adhami

Removal of paraquat from aqueous solutions by a bentonite modified zero-valent iron adsorbent

New Journal of Chemistry 2020 44

5512881

13368 13376

10.1039/D0NJ02259D

78.

Martins

D. A.

Simões

Melo

Adsorption of paraquat dichloride to kaolin particles and to mixtures of kaolin and hematite particles in aqueous suspensions

Journal of Water Security 2015 1

5512881

1 25 36

10.15544/jws.2015.003

79.

Brigante

Schulz

P. C.

Adsorption of paraquat on mesoporous silica modified with titania: effects of pH, ionic strength and temperature

Journal of Colloid and Interface Science 2011 363

5512881

1 355 361

10.1016/j.jcis.2011.07.061

2-s2.0-80052078229

21843892

80.

Etcheverry

Cappa

Trelles

Zanini

Montmorillonite-alginate beads: natural mineral and biopolymers based sorbent of paraquat herbicides

Journal of Environmental Chemical Engineering 2017 5

5512881

6 5868 5875

10.1016/j.jece.2017.11.018

2-s2.0-85033372759

81.

Huang

C.-F.

C.-W.

Lee

R.-H.

Yang

C.-H.

Hung

W.-C.

Andrew Lin

K.-Y.

Study of various diameter and functionality of TEMPO-oxidized cellulose nanofibers on paraquat adsorptions

Polymer Degradation and Stability 2019 161

5512881

206 212

10.1016/j.polymdegradstab.2019.01.023

2-s2.0-85060860177

82.

Sirival

Patdhanagul

Preecharram

Photharin

Removal of paraquat solution onto zeolite material

AIP Conference Proceedings 2018 1954, article 030006

5512881

10.1063/1.5033386

2-s2.0-85046099047

83.

Fernandes

Soares

S. F.

Trindade

Daniel-da-Silva

A. L.

Magnetic hybrid nanosorbents for the uptake of paraquat from water

Nanomaterials 2017 7

5512881

10.3390/nano7030068

2-s2.0-85015886058

28336902

Efficient Removal of Paraquat Pollutants Using Magnetic Biochar Derived from Corn Husk Waste: A Sustainable Approach for Water Remediation

Abstract

1. Introduction

2. Materials and Methods

2.1. Materials and Chemicals

2.2. Preparation of Magnetic Biochars and Biochar

2.3. Paraquat Adsorption Experiments

2.3.1. Adsorption Isotherm Models

2.3.2. Thermodynamic Adsorption Models

2.3.3. Kinetic Adsorption Models

2.4. Characterization

3. Results and Discussion

3.1. Preparation of Magnetic Biochar

3.1.1. Effect of Fe(NO3)3 Concentration and Carbonization Temperature on Porosity

3.1.2. Effect of Fe(NO3)3 Concentration on the Thermal Properties of Corn Husk

3.1.3. Effect of Carbonization Temperature on Crystallinity

3.1.4. Effect of Carbonization Temperature on Graphitic Characteristic

3.1.5. Magnetic Properties of Adsorbents

3.1.6. Effect of Fe(NO3)3 on Morphologies and Textures

3.2. Paraquat Adsorption Test

3.2.1. Effect of Adsorbent Dosage

3.2.2. Effects of Initial Concentrations and pH

3.2.3. Equilibrium Isotherms, Thermodynamics, and Kinetic Models

3.2.4. Application to Natural Water

3.2.5. Reusability of MB-01-850

3.2.6. Comparison of the Current Results with Other Adsorbents

4. Conclusions

Footnotes

Data Availability

Conflicts of Interest

Authors’ Contributions

Acknowledgments

Supplementary Materials

References

3.1.1. Effect of Fe(NO₃)₃ Concentration and Carbonization Temperature on Porosity

3.1.2. Effect of Fe(NO₃)₃ Concentration on the Thermal Properties of Corn Husk

3.1.6. Effect of Fe(NO₃)₃ on Morphologies and Textures