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Adsorption process and mechanism of acetaminophen onto commercial

activated carbon

Dong Thanh Nguyen, Hai Nguyen Tran, Ruey-Shin Juang, Nguyen

Duy Dat, Fatma Tomul, Andrei Ivanets, Seung Han Woo, Ahmad
Hosseini-Bandegharaei, Van Phuong Nguyen, Huan-Ping Chao

PII: S2213-3437(20)30757-0
DOI: https://doi.org/10.1016/j.jece.2020.104408
Reference: JECE 104408

To appear in: Journal of Environmental Chemical Engineering

Received Date: 13 June 2020

Revised Date: 17 August 2020
Accepted Date: 18 August 2020

Please cite this article as: Nguyen DT, Tran HN, Juang R-Shin, Dat ND, Tomul F, Ivanets A,
Woo SH, Hosseini-Bandegharaei A, Nguyen VP, Chao H-Ping, Adsorption process and
mechanism of acetaminophen onto commercial activated carbon, Journal of Environmental
Chemical Engineering (2020), doi: https://doi.org/10.1016/j.jece.2020.104408

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 Adsorption process and mechanism of acetaminophen onto commercial

activated carbon

Dong Thanh Nguyen1, Hai Nguyen Tran2,3*, Ruey-Shin Juang4,5, Nguyen Duy Dat6, Fatma Tomul7,

Andrei Ivanets8, Seung Han Woo9, Ahmad Hosseini-Bandegharaei10, Van Phuong Nguyen3,11*,

Huan-Ping Chao12*

1
Institute of Environmental Technology, Vietnam Academy of Science and Technology, Hanoi, Vietnam
2
Institute of Fundamental and Applied Sciences, Duy Tan University, Ho Chi Minh City, 700000, Vietnam

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3
Faculty of Environmental and Chemical Engineering, Duy Tan University, Da Nang, 550000, Vietnam
4
Department of Chemical and Materials Engineering, Chang Gung University, Guishan, Taoyuan, 33302, Taiwan

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5
Division of Nephrology, Department of Internal Medicine, Chang Gung Memorial Hospital, Linkou, Taiwan
6
Faculty of Chemical & Food Technology, Ho Chi Minh City University of Technology and Education, Thu Duc,
Ho Chi Minh, 700000, Vietnam

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7
Burdur Mehmet Akif Ersoy University, Faculty of Arts and Science, Chemistry Department, 15100 Burdur,
Turkey
8
Institute of General and Inorganic Chemistry of National Academy of Sciences of Belarus, st. Surganova 9/1,
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220072, Minsk, Belarus
9
Department of Chemical and Biological Engineering, Hanbat National University, 125 Dongseodaero, Yuseong-
Gu, Daejeon 305-719, Republic of Korea
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10
Department of Engineering, Kashmar Branch, Islamic Azad University, PO Box 161, Kashmar, Iran
11
Institute of Research and Development, Duy Tan University, Da Nang 550000, Vietnam
12
Department of Environmental Engineering & Center for Environmental Risk Management, Chung Yuan
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Christian University, Taoyuan 32023, Taiwan

*Corresponding authors:
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Hai Nguyen Tran; Institute of Fundamental and Applied Sciences, Duy Tan University, Ho Chi Minh
City, Vietnam; Faculty of Environmental and Chemical Engineering, Duy Tan University, Da
Nang City, Vietnam; [email protected].
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Van Phuong Nguyen; Institute of Research and Development, Duy Tan University, Da Nang, Vietnam;
Faculty of Environmental and Chemical Engineering, Duy Tan University, Da Nang, Vietnam;
[email protected].
Huan-Ping Chao; Department of Environmental Engineering & Center for Environmental Risk
Management, Chung Yuan Christian University, Taoyuan, Taiwan; [email protected].

1
Abstract

The presence of acetaminophen (also known as paracetamol; PRC) micropollutant in water caused
some potential health risks for human. In this study, commercial activated carbon (CAC), which had
been oxidized with HNO3 by supplier to increase the oxygen-functional groups, was applied to
remove PRC from water. Results demonstrated that CAC is a dominantly mesoporous (accounting
for 76.3%) with high surface area (SBET = 1284 m2/g) and total pore volume (VTotal = 0.680 cm3/g).
CAC possessed abundantly oxygen-containing functionalities and low pHPZC (4.95). Raman

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spectrum of CAC indicated that CAC possessed a more disordered structure with a high intensity
ratio of D band and G band (ID/IG = 2.011). Adsorption study showed that the adsorption capacity of
CAC towards PRC was less affected by solution pH value (2.0–10), and ionic strength (0–1.0 M

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NaCl), and different water matrixes (distilled water, tap water, seawater, water treatment plant,
groundwater, and beauty salon). The adsorption process occurred rapidly, with around 52% of PRC
in solution (~517 mg/L) being removed within 5 min of contact. The Langmuir maximum

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adsorption capacity of CAC was 221 mg/g under 1.0 g/L of CAC, pH 7.0, 25 °C, and initial
concentration of paracetamol (~100–1200 mg/L). The pore-filling was the most important
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mechanism. The SBET and VTotal of CAC after adsorption decreased (by approximately 96% for both)
to 45.6 m2/g and 0.039 cm3/g, respectively. The second important mechanism involved in n-π
interaction was established by a remarkably decrease in the band intensity (the FTIR spectrum after
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adsorption) at 1630 cm-1 (the C=O group). Weak π-π interaction was confirmed a significant
decrease in the ID/IG ratio from 2.011 to 1.947 after adsorption. Hydrogen bonding formations were
recommended by decreasing band intensity in FTIR spectrum at 3448 cm -1 (–OH) and 1045 cm-1
(C–O). Weak van der Waals force was identified through the study of effect of solution temperature
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and desorption. Consequently, oxidized CAC can serve as a promising and potential material for
efficiently eliminating PRC from water environments.
Keywords: Acetaminophen; Activated carbon; adsorption mechanism; emerging contaminant;
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paracetamol; oxidation.
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2
1. Introduction

Nowadays, an increase in variety and concentration of emerging organic contaminants (i.e.,

pharmaceuticals, personal care products, endocrine disruptors, etc.) present in water environment

has caused an enormous concern among general public. Among them, pharmaceuticals have been

ubiquitously detected in different water matrixes, especially in surface and wastewaters [1]. This is

because they were extensively used not only for human but also veterinary medicine [2].

Paracetamol (PRC)—known as acetaminophen, N-acetyl-p-aminophenol, or 4-acetamidophenol—is

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one of the most common antipyretic and analgesic drug frequently used in many countries around

the world for the effective pain relief of several diseases such as headaches, fever, and minor aches

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[3, 4]. Paracetamol drug is frequently detected in ground water, surface water, drinking water,

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municipal wastewater, and especially in wastewater treatment plant [5]. Therefore, it is essential to

eliminate PRC drug from water environments.

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According to the literature, PRC can be removed from water by several advantageous methods
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(alone or combined methods). They comprise adsorption [6], biodegradation [7], membrane

filtration [8], and advanced oxidation processes (AOPs). Several common AOPs, which was applied
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to effectively remove PRC from water, includes Fenton and photo-Fenton reactions [9], UV/chlorine

and UV/H2O2 AOPs [10], photocatalytic oxidation [11], electrochemical oxidation [12], catalytic
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ozonation [13], and ozonation [14]. However, during the PRC degradation under AOPs, some by-

products (lower low-molecular weight compounds) is usually generated [15]. For example, Dao et
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al. [10] found that, approximately twenty compound structures (transformation products) were

detected during the PRC degradation by the UV/chlorine AOP. The presence of such by-products

can cause the secondary pollutant. In contrast, adsorption has been acknowledged as the green and

promising method for effectively removing various emerging contaminants from water media [4,

3
16]. Therefore, the low-cost technology of adsorption using activated carbon as adsorbent is

expected to excellently remove paracetamol from water pollution in developing countries.

In this study, commercial activated carbon (CAC) was used as a potential adsorbent to

remove PRC emerging pollutant from water media. CAC was characterized by various techniques

such as nitrogen adsorption/desorption isotherm analyzer, Scanning electron microscopy (SEM),

Fourier-transform infrared spectroscopy (FTIR), Raman technique, and their electrical state (pHPZC).

The process of PRC adsorption in solution was investigated in a common batch technique to explore

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the effects of different operational conditions (temperature, solution pH, ionic strength, initial PRC

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concentration, contact time, and desorbing agent) on the adsorption capacity of CAC towards PRC.

Three important components of the adsorption study (kinetics, isotherms, and thermodynamics)

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were also provided. The adsorption mechanism was discussed and proposed herein.

2. Materials and methods

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2.1. Material and reagent
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All chemicals were of reagent grade. Paracetamol (or acetaminophen), methanol, and ethanol

were purchased from Sigma-Aldrich. Some other chemicals (NaCl, NaOH, HCl, H2O2, acrylic acid,
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and HNO3) were obtained from Scharlau. They were directly used without any further purification.

Commercial activated carbon (CAC) was bought from a local company. According to the
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company’s information, CAC has been oxidized to enhance the density of oxygen-functional groups
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on the surface of CAC. Briefly, CAC was well mixed with HNO3 at 40 °C for 24 h. During the

mixture process, a very small amount of iron was transferred into this solution. In this study, CAC

was washed with pure water three times to remove some unexpected impurities and then dried at

105 °C for 24 h. The dried CAC was ground, sieved into the size range of 0.106–0.250 mm, dried at

4
105 °C for 24 to obtain a constant moisture percentage (~5%), and then stored in a desiccator until

further use.

2.2. Characterization of CAC

The dried particle sizes of CAC used for the study of its characterization ranged from 0.106 to

0.250 mm. The textural properties of CAC were calculated from the adsorption/desorption isotherm

of nitrogen at 77 K (PMI’s BET-Sorptometer; BET 201-A). The t-plot method was used to calculate

the surface area and volume of the micro-pores. Surface morphology of CAC was explored by

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SEM-EDS images (JSM-6510 LV). FTIR (IR Nicolet iS10) can measure the range from 400 to

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4,000 wavenumber. The CAC pelleted mixing with KBr was used to identify the main functional

groups on the surface of CAC. Raman spectrometer (Xplora Plus; HORIBA) was applied to provide

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the information on the crystal structure and molecular vibration of CAC.
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The pH value of point zero charge (pHPZC) of CAC was obtained from the common drift

method [17, 18]. Briefly, approximately 0.1 g of CAC was transferred onto an Erlenmeyer flask
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containing 50 mL of NaCl solution (0.1 M). The pH of NaCl solution (denoted as pHBefore) have

before adjusted from 2.0±0.2 to 10±0.2 using 1.0 M HCl or NaOH. After shaking at 30 °C for 6 h,
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the mixture of CAC and NaCl solution was separated by a filter paper. The pH value of the filtrate

(pHAfter) was recorded. The pHPZC value of CAC was estimated through the plot of (1) pHBefore
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versus pHAfter, (2) pHBefore versus ∆pH (pHBefore – pHAfter), or (3) pHBefore versus ∆pH (pHAfter –

pHBefore).
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2.3. Batch adsorption study

The process of PRC adsorption in solution onto CAC was conducted at different operation

conditions. The adsorption experiment was conducted in triplicate, and the result was reported as

average ± standard deviation (SD). In general, the solid/liquid (m/V) ratio of the adsorption study

5
was constant at 2.0 g/L. Approximately 0.5 g of CAC (m) was added into 0.25 L (V) of solution

containing PRC at a target concentration. The solution pH value was adjusted before and during the

adsorption using 1M HCl and 1M NaOH. The mixture of the solid/liquid was shaken at 150 rpm in a

water batch isothermal shaker at a controlled temperature. After reached equilibrium, the

solid/liquid mixture was separated using 0.45 µm filter paper. The laden solid (PRC-adsorbed CAC)

had been collected and dried at 105 °C for 48 h before it was used to characterize. Meanwhile, the

residual liquid was analyzed its concentration using HPLC (Dionex 3000 Thermo, Sunnyvale,

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California, USA) coupled with a photo-diode array. The analyzing conditions have been published

in our recently previous study [10]. Notably, the blank samples (the PRC solution) were

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simultaneously carried out without the presence of CAC. Such samples that were denoted as the

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initial PRC concentration (Co; mg/L) played an important role in correctly calculating the amount of

PRC adsorbed by CAC at equilibrium (qe; Equation 1) or any time t (qt; Equation 2). The detail on
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the adsorption conditions (i.e., pH, ionic strength, initial PRC concentration, time, temperature, etc.)

was provided along with each figure and table.

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qe 
C o Ce  V (1)
m
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qt 
Co  Ct V (2)
m
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where Co, Ct, and Ce are the concentrations of PRC in solution (mg/L) at the beginning, any time t,
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and equilibrium, respectively; V (L) is the volume of the PRC solution; and m (g) is the mass of used

CAC.

6
2.4. Feasible study of desorption and reuse of laden CAC

Desorption study was conducted after the concentration of equilibrium adsorption reached

673 mg/L, pH 7.0, 25 °C, and the solid/liquid ratio of 2.0 g/L. The laden CAC was desorbed by

different desorbing agents. They included deionized distilled water (pH 2 and pH 12), HCl (0.2 M),

NaOH (0.2 M), NaCl (0.2 M), ethanol, and methanol. The solid/liquid ratio of the desorption study

was also maintained at 2.0 g/L. After shaking with 150rpm at 25 °C for 6 h, the residual

concentration of PRC in solution was determined. The percentage of PRC desorbed (ηDes) from

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laden CAC was calculated from Equation 3.

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qe  qd (3)
Des (%)  (qe  ) 100
qe

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where qe (mg/g) is defined from Equation 1, and qd (mg/g) is the amount of PRC desorbed from the
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laden CAC.
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The common carbonization method was applied to explore the potential reuse of laden CAC.

The laden CAC was carbonized at 600 °C for 2 h. It is expected that the PRC adsorbed by CAC was

completely thermally degraded under 600 °C because the endset temperature of pure PRC
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(determined by thermogravimetric analysis) was around 380 °C [19]. The adsorption was

consecutively conducted at the solid/liquid ratio of 2 g/L, initial PRC concentration of around 500
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mg/L, 25 °C, 72 h, and pH = 7.0. The amount of PRC adsorbed by CAC after each cycle was
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calculated from Equation 1.

2.5. Error functions

The difference between the qe value obtained from experiment (qe,exp) and that predicted from

each applied model (qe,model) was reflected through error functions. To minimize error functions

during modelling, the nonlinear optimization technique was applied using the Origin software. The
7
statistics (Section S1; Supporting Information) includes adjusted coefficient of determination (adj-

R2), chi-square test (χ2), standard deviation of residues (SD), Bayesian information criterion (BIC),

and Marquardt's percent standard deviation (MPSD). The best fitting model was reflected and

selected through the highest value of adj-R2, but the lowest value of the others (SD, BIC, and

MPSD).

3. Results and discussion

3.1. Basic property of the activated carbon

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3.1.1. Textural and morphological properties

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The textural property of an adsorbent plays an essential role in estimating its maximum

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adsorption capacity and relevant mechanism (i.e., pore-filling). An adsorbent with larger specific

surface and higher total pore volume often exhibits an excellent adsorption capacity to aromatic
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pollutants (i.e., dye adsorbate) if the pore-filling is primary adsorption mechanism. The textural

parameters (i.e., the characteristics of surface area and pore volume) are calculated from the nitrogen
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gas adsorption/desorption isotherm at 77 K (Figure 1).

The gas physisorption isotherm of CAC (Figure 1a) belongs to reversible Type Ib, suggesting
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that the pore size distribution of CAC comprised both wider micropore and narrowed mesopore

[20]. In addition, a visible wide knee of the isotherm curve (also known as a H4-type hysteresis
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loop) appeared at a relative pressure (p/po) higher than 0.4, confirming that CAC was dominant
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mesoporous material with dominant pores diameter centered at 2.44 nm and 4.13 nm in mesopore

range (Figure 1c). Similarly, a porous structure of CAC was visible in a SEM image (Figure S1).

Textural parameters of CAC are provided in Table 1. As expected, CAC exhibited large SBET

(1248 m2/g) and high VTotal (0.680 cm3/g) values along with a dominant mesoporous nature (average

pore diameter ≈ 2.18 nm). Therefore, it is expected that CAC with a larger specific surface area and

8
well-developed internal pore structure can effectively remove paracetamol molecules from water

environment through pore-filling mechanism.

3.1.2. Surface chemistry

The presence of main functional groups on the surface of pristine CAC was qualitatively

detected by FTIR. Figure 2 shows some important bands within a wavenumber range of 4000–650

cm-1. Such bands were identified at proximately 3448 cm-1 (–OH groups in the carboxylic, phenols,

or absorbed water), 1630 cm-1 (C=O groups in the carboxylic and lactonic groups); 1386 cm-1 (C=C

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groups in the aromatic rings); and 1045 cm-1 (C–O groups in ethers or lactones) [21-23]. In essence,

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the oxygen-containing functionalities often play a proper role in reacting with aromatic

contaminants (i.e., phenol and dye) in solution through n-π interaction and hydrogen bonding

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formation [24-26]. CAC exited a strong band intensity at 1630 cm-1 (the C=O group) because it has
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been oxidized. This C=O group is often expected as strongly active groups to adsorbing aromatic

contaminants in solution.
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3.1.3. Aromatic structure

The presence of aromatic structures and defective natures in carbonaceous materials was
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assessed through the Raman spectroscopy. The UV-laser Raman spectrum of CAC (Figure 3)

revealed two pronounced bands of non-graphitic carbon materials at around 1290 cm-1 (D-band) and
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1590 cm-1 (G-band). The D-band corresponds to a disordered graphitic lattice or graphene layer
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edges; meanwhile, the G-band is relative to an ideal graphitic lattice [27, 28]. The defective density

present on the graphene structure or the degree of disorder in CAC is defined by an intensity ratio of

D band and G band (ID/IG). As showed in Figure 3, the indicator (ID/IG ratio) of CAC (~2.011) was

higher than unity and some other carbonaceous material in the literature, for example, porous

spheres activated carbon (ID/IG = 1.26) and spherical biochar (ID/IG = 1.14) derived from commercial

9
lignin [29], biochar from bamboo (ID/IG = 0.81) [30], biochar (ID/IG = 1.16) and AC (ID/IG = 1.10)

from tobacco waste [31], and biochar from peanut shell (ID/IG = 0.947) [32]. CAC with a high ID/IG

ratio suggested that it exhibited a more disordered structure. Similarly, Maal-Bared [30] investigated

the effect of pyrolysis temperature from 700 °C to 1000 °C on the ID/IG ratio of AC generated from

bamboo. They found that an increase in the pyrolysis temperature lead to increasing the ID/IG ratio

from 1.05 (700 °C), 1.08 (800 °C), to 1.14 (900 °C), and then to 1.16 (1000 °C). They concluded

that an increase in the ID/IG ratio demonstrated that the extent of disorder in atomic arrangement.

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Therefore, it is expected that the aromatic C=C bonds in the aromatic rings of CAC can well react

with PRC molecules in solution through π-π interaction.

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3.2. Performance of paracetamol adsorption process

3.2.1. Effect of solution pH and ionic strength

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In essence, the adsorption process of adsorbate into an adsorbent is strongly dependent on

two proper operation conditions (pH value of solution and ionic strength). This is because they
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greatly affect (1) the property of the charge surface of adsorbent and (2) the species of adsorbate in

solution.
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First, an adsorbent (i.e., activated carbon) often exhibits an amphoteric nature; it means that

the charge density on its surface often changes within the change of solution pH (pH solution). In this
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study, the pHPZC of CAC is used to identify the situation of surface charge of CAC in solution.

Figure 4a indicates three common presentations how to determine pHPZC value from the “drift
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method”. According to Figure 4a, the pHPZC of CAC was established as 4.95. This means that the

surface charge of CAC is predominantly negative when pHsolution > its pHPZC, and vice versa. In this

case, the adsorption of cationic adsorbate onto the negative surface of CAC through electrostatic

attraction is highly expected as primary adsorption mechanism.

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 Second, according to the literature [33], the dissociation constant (pKa) of paracetamol—

determined by the Raman spectroscopic technique and potentiometric method—was relatively

similar (i.e., 11.08 and 10.96, respectively). Therefore, PRC exists as an uncharged species (or

molecular form) under pHsolution from 2.0 to 10 (Figure 4b). As a result, the electrostatic attraction

was ruled out in this study. An analogous conclusion was reported in the literature [26, 34].

Because the adsorption process did not involve the electrostatic attraction, the adsorption

efficiency of PRC onto CAC was less affected by the change of pHsolution (Figure 5a) and ionic

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strength (Figure 5b). Previous studies demonstrated that the process of paracetamol removal from

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water by various porous carbonaceous materials was insignificantly dependent on the parameters of

pHsolution and ionic strength, such as activated carbons derived from spent tea leaves [35],

pomegranate woods [36], and oak acorns [34].

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As expected, CAC possessed an excellent ability of PRC adsorption under different values of

pHsolution and concentrations of NaCl. Therefore, its outstanding adsorption capacity is expectedly
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maintained under real application in removing PRC pollutant from water and wastewater streams.

3.2.2. Adsorption kinetics

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The contact time-dependent study was conducted from 2 min to 4360 min at ~517 mg/L.

Figure 6 shows that the adsorption process occurred rapidly with approximately 52% PRC in
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solution removed within 5 min of contact. The result suggested that CAC had a high affinity to PRC
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in solution. In this study, we applied three adsorption kinetic models to describe the intrinsic

adsorptive constants mathematically. They include the pseudo-first-order, pseudo-second-order,

Elovich, and Avrami models provided in Section S2 (Supporting Information).

In the literatures, some authors modelled the experimental data of time-dependent adsorption

with the selective models by two different ways: with and without the origin point (0;0). The results

11
of modelling with the contact time from 0 to 4360 min (with the origin point) and from 2 to 4360

min (without the origin point) are shown in Figure 6a and 6b, respectively. The relevant parameters

of the secretive models are listed in Table 2. Clearly, the values of the parameters obtained from

two modelling ways were the same. However, the values of adjust coefficient of determination (adj-

R2) and chi-square statistics (χ2) are remarkably different. The modelling way with the origin point

indicated a higher adj-R2 and lower χ2 values than that without the origin, suggesting that the

important role of the original point in modelling the calcinating the parameters of the adsorption

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kinetic models.

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Furthermore, the adsorption process of organic adsorbate onto porous CAC material often

takes a longer time to reach a true adsorption equilibrium. In contrast, some authors assumed that

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the adsorption reached an equilibrium at a shorter time. Therefore, the modelling trials of

experimental data from 0 to 360 min (with the origin point) and from 2 to 360 min (without the
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origin point) were explored. The results are shown in Figure 6c and 6d and Table 2. A similar
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phenomenon was repeated that (1) there was not difference on the values of the parameters of the

kinetic models from two modelling ways and (2) the origin point played an important role in

obtaining a high adj-R2 and low χ2 values. However, a shorter contact time is not enough to correctly
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modelling whole the adsorption process. Therefore, the parameters of the kinetic models obtained

from Figure 6a were selected for further discussion.

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According to the values of adj-R2, χ2, SD, BIC, and MPSD, it can be concluded that the
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experimental data of adsorption kinetics were better described by the Avrami model (0.997, 13.2,

3.51, 46.2, and 26.4) and Elovich model (0.991, 36.3, 6.17, 65.4, and 45.5) than the pseudo-second

order model (0.864, 521, 22.8, 110, and 239) and pseudo-first-order model (0.758, 929, 30.5, 120,

and 291, respectively). The initial rate constant α of the Elovich model was up to 4039 mg/(g×min).

This is well consistent with the experimental data in Figure 6a, suggesting that CAC exhibited a

12
strong affinity to PRC molecules in the solution. The half-life (t1/2; calculated based on from the

Avrami model) of the adsorption process was 17.79 min. Further experiments were conducted at 48

h to ensure that the adsorption process reached true equilibrium.

3.2.3. Adsorption isotherm

The isotherm of PRC adsorption onto CAC is provided in Figure 7. As expected, the isotherm

curve is concave downward that can be classified as an H-type shape [37]. The result suggested that

CAC exhibited high affinity of PRC adsorption even at low initial PRC concentrations. In this study,

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some adsorption isotherm models were applied to model the data of equilibrium adsorption. More

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information on such selected models are provided in Section S3 (Supporting Information).

Table 3 provides the modeling result and the calculated parameters of such models. The

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results indicated that the experimental data of adsorption equilibrium were reasonably described by
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the selective models (R2 >0.94), with the fitting model following the decreasing order: Redlich–

Peterson > Langmuir-Freundlich > Freundlich > Langmuir models. The Redlich–Peterson model
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was the best fitting model because of the highest Adj-R2 (0.993) value and the lowest others (i.e., χ2

= 43.3, SD = 7.33, BIC = 54.5, and MPSD = 59.8). However, this model does not provide the
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information on the maximum adsorption capacity of an adsorbent. Although the QLF parameter in

the Langmuir-Freundlich model indicates the maximum adsorption capacity of an adsorbent, it is

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not commonly used and reported ion the literature compared to the Qomax. Therefore, the Qomax

parameter in the Langmuir model was used for comparing the adsorption capacity of CAC and other
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materials in the literature.

Table S1 lists the Qomax value of CAC and other kinds of CAC in the literature. The

comparative result indicated that CAC (Qomax = 221 mg/g) exhibited a higher adsorption capacity to

PRC compared to some other kinds of CAC (45.4–204 mg/g), but lower than some others (255–322

13
mg/g). Moreover, there was not any relationship between SBET and Qomax (R² = 0.381; n = 17; Table

S1) as well as VTotal and Qomax (R² = 0.320; n = 15; Table S1). This means that an adsorbent with

higher SBET and VTotal value might not means that it will exhibit a higher adsorption capacity of PRC.

In this case, the pore size distribution of adsorbent (i.e., Figure 1c) often plays a determining role in

the amount of organic contaminant (i.e., PRC) adsorbed by a porous adsorbent (i.e., CAC) through

pore-filling mechanism.

3.2.4. Adsorption thermodynamics

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The effect of different solution temperatures (10 °C, 25 °C, and 50 °C) on the process of PRC

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adsorption onto CAC is presented Figure S2. The parameters of adsorption thermodynamics (∆G°,

∆H°, and ∆S°) are calculated based on the laws of thermodynamics using the van’t Hoff equation.

G  G  RT ln K Equilibriu
o
m
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When an adsorption process reaches equilibrium, the free energy change (∆G) is nearly zero.
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Equation 4 becomes Equation 5 that has been commonly applied to calculate the standard Gibbs

energy change (∆G°).

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G   RT ln K Equilibriu
o
m
(5)

The relationship between ∆G° and the others (∆H° and ∆S°) of an adsorption process is express as
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follows:
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G  H   TS  (6)

It is assumed that the change of ΔS° and ΔH° with the temperature is negligible. After

substitution Equation 5 into 6, the well-known van’t Hoff equation [32, 38, 39] is yield as follows:

14
  H  1 S  (7)
LnK Equilibrium   
R T R

K L ( L / mol)  C o (mol / L) (8)

K Equilibrium 


where KL (L/mol) is the Langmuir constant, C° is the selected standard state of adsorbate (C° = 1

mol/L); R is the universal gas constant (0.00831 kJ/mol×K); T is the absolute temperature in degrees

Kelvin (K); and γ (dimensionless) is the activity coefficient of PRC in solution. As provided in

of
Figure 4b, PRC neutral adsorbate under solution pH of 7.0, so its activity coefficient in this study is

ro
expressed as 1.0 [38, 39].

In this study, the Langmuir constant KL (L/mmol; Figure S2) was applied to calculate the

-p
thermodynamics parameters. To consist with physical meanings, the units of adsorption isotherm
re
(the plot of qe vs. Ce) needs to be presented as mol/kg for qe and mol/L for Ce. Equation 8 describes

o
the relationship between KL (with unit) and K Equilibrium (without unit) [32, 38, 40]. Table S2
lP

summaries the calculating performance of the parameters of thermodynamics for whole the

adsorption process (10 °C, 25 °C, and 50° C). The negative values of standard Gibbs free energy (–
na

∆G°) suggest that the process of PRC adsorption onto CAC occurred spontaneously without any

further requirements (i.e., energy or heating). An identical conclusion was reported by some other
ur

scholars for the adsorption of PRC onto porous carbonaceous materials [35, 36, 41]. Because the R2
Jo

value (R2 = 0.271) of the van’t Hoff equation is too low, the ∆H° and ΔS° values cannot be

adequately calculated from such equation. In addition, the adsorption capacity of PRC by CAC and

o
the equilibrium constant K Equilibrium did not followed the order of temperatures, such as 10 °C < 25

°C < 50 °C. Therefore, in this study, the thermodynamics parameters were calculated at two

processes: one at 10 °C and 25 °C (283–298 K) and another at 25 °C and 50 °C (298–323 K). The

15
∆H° value was calculated as the following equation, and the ∆S° value was obtained from Equation

9 [39]. The ∆G° and ∆S° values were calculated from Equations 5 and 6, respectively.

T T KT (9)
H   R( 2 1 ) ln( 2 )
T2  T1 KT1

where T2 and T1 are at temperature at two operation temperatures (T2 > T1); and KT1 and KT2 are the

o
equilibrium constant ( K Equilibrium ) at T2 and T1, respectively.

of
The parameters of ∆H° and ∆S° calculated at 283–298 K and 298–323 K are provided in

ro
Table 4. Clearly, an increase in solution temperature from 10 °C to 25 °C, the maximum adsorption

capacity of CAC significantly increased from 1.18 mol/kg to 1.59 mol/kg (Figure S2). This is

-p
because the phenomenon of enlargement pore network of CAC within the increasing temperature
re
simulate to increase the amount of PRC adsorbed onto CAC through common pore-filling

mechanism [42, 43]. Therefore, it can be primarily performed that the important contribution of
lP

pore-filing and van der Waals in the adsorption mechanism. The result is well consistent with the

ΔH° value. A positive value of the standard adsorption enthalpy (ΔH° = 24.1 kJ/mol) confirms that
na

the adsorption was endothermic reaction. However, a further increasing in temperature to 50 °C, the

Qomax value decreased to 1.48 mol/kg (Figure S2). A decrease in adsorption capacity at a higher
ur

temperature might be caused by two feasible reasons that (1) a continuing increase in enlarging pore

network of CAC was not favorable to adsorbed PRC molecules [17, 42] and (2) desorption
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phenomenon resulted from the weak adsorption interaction during the adsorption process (i.e., van

der Waals) [17, 32]. Because the contribution of weak van der Waals in the adsorption process, the

standard adsorption enthalpy change was negative and low magnitude (ΔH° = –6.39 kJ/mol) within

the solution temperatures of 25 °C and 50 °C.

16
 In essences, the entropy change of adsorption is generally negative because the randomness of

the adsorbates after adsorption would be decreased compared to those in the bulk liquid phase.

However, the positive value of ΔS° (Table 4) might be because of the fact that the adsorption occurs

in two consecutive steps: desorption of the adsorbed water and adsorption of the PRC adsorbate.

Similarly, Lima et al. [38] found that the positive value of ΔS° [39 and 40 J/(mol×K)] was obtained

for the PRC adsorption process onto two AC samples prepared from Brazil nutshells.

3.2.5. Feasible desorption and reuse of laden CAC

of
The result of desorption efficiency (ɳDes) by the chemical method is showed in Table 5. The

ro
best desorption efficiency was found by using ethanol (53.8%) and methanol (50.1%) a desorbing

agent. In addition, NaOH (0.2 M) can desorbed around 32.5% of PRC from laden CAC. Similarly,

-p
Lima et al. [38] found that the ɳDes value was 66.8% (using 0.1 M NaOH) and 69.9% (using 0.1 M
re
NaOH + 5% ethanol). The results the important contribution of surface interaction (i.e., hydrogen

bonding and n-π interaction) during the adsorption process. Furthermore, the PRC adsorbed by CAC
lP

can be desorbed by deionized distilled water (pH 12) and (pH 2.0), with ɳDes being 18.1% and

11.8%, respectively. The result might result from the minor contribution of weak van der Waals
na

force in the adsorption mechanism [6].

However, the chemical method was less efficient to desorb PRC from laden CAC (Table 5).
ur

According to other studies [44], PRC in the laden CAC sample can be thermally degrade when the

carbonization temperature is higher than 400 °C (determined by thermal analysis). Therefore, the
Jo

thermal method was applied. The carbonization temperature of 600 °C was used to completely

thermally degrade of PRC adsorbed on the surface and in the internal pore network of CAC. Figure

8 shows that after each adsorption/desorption cycle, the adsorption capacity of CAC significantly

increased. A similar finding was reported by Tomul [32] for the adsorption of naproxen by biochar.

The increasing adsorption capacity after each cycle might be because the proper contribution of π-π
17
interaction in the adsorption mechanism of PRC onto 600 °C-carbonized CAC. Similarly, some

authors also found that the 900 ℃-carbonized GAC (Qomax = 197 and 175 mg/g) exhibited an

excellent adsorption capacity towards the aromatic pollutants (i.e., phenol and methylene blue) than

pristine GAC did (156 and 131 mg/g), respectively [45]. A similar conclusion was reported by [46]

for the adsorption of chloramphenicol onto CAC (Qomax = 146 mg/g) and 400 ℃-treated CAC (226

mg/g), and 800 ℃-treated CAC (343 mg/g). However, the reuse of laden CAC by thermal method

has a big problem. This is because the remarkable mass loss of CAC after each cycle (data not

of
showed).

ro
3.2.6. Discussion on adsorption mechanism

In essence, the adsorption process of polar aromatic pollutants (i.e., PRC and dye) in solution

-p
onto porous carbonaceous materials (i.e., biochar and activated carbon) often combines many
re
interactions (or mechanisms) such as electrostatic attraction, van der Waals force, ion exchange,

hydrogen bonding formation, n-π interaction, π-π interaction, and pore-filling [18, 47-50]. However,
lP

the primary adsorption mechanism is often strongly dependent on the conditions of adsorption study

(i.e., solution pH, temperature, and initial adsorbate concentration), adsorbate characteristics (i.e.,
na

molecular size, solubility, pKa, and electron distribution), and adsorbent properties (i.e., surface

area, pore size distribution, and surface functional groups). Notably, Tran et al. [51] investigated the
ur

adsorption of methylene green 5 (MG5) onto porous carbonaceous biochar. They found that

although the removal efficiency of around 99% was reached at an initial low MG5 concentration (Co
Jo

≈ 50 mg/L), the mechanism of MG5 adsorption onto biochar through pore-filling was negligible

compared to the others. This is because the textural parameters (SBET and VTotal) of biochar before

(565 m2/g and 0.236 cm3/g) and after (529 m2/g and 0.264 cm3/g) adsorption were slightly different,

respectively. However, the pore-filling mechanism dominated others when an initial MG5

18
concentration was higher than ~300 mg/L because of a remarkable decease in the SBET and VTotal

values to 13.5 m2/g and 0.024 cm3/g, respectively [51].

In this study, the mechanism of PRC adsorption by CAC was discussed at solution pH 7.0, 25

°C, and 1200 mg/L. As aforementioned in Section 3.2.1, electrostatic attraction was ruled out

because PRC (pKa ≈ 11; Figure 4b) was not ionized under solution pH 7.0; a similar assumption for

ion exchange. In addition, the presence of van der Waals force in the adsorption process was certain,

but this weak force was acknowledged as a less important contributor in the adsorption mechanism

of
(see Section 3.2.4).

ro
The n-π interaction (also known as “donor-acceptor complex mechanism”) was firstly

proposed by Mattson and coworkers [48] for the adsorption of phenol and nitrophenols onto lignin-

-p
based AC. In such mechanism, the carbonyl oxygen in the surface of AC acted as an electron donor,

while the aromatic rings of phenol acted as an electron acceptor. The n-π electron interaction has
re
been reported as an integral adsorption mechanism of various aromatic pollutants onto carbonaceous
lP

materials [18, 49, 52, 53]. In this interaction, the carbonyl oxygen ions on the biochar’s surface

serve as electron donors, while the aromatic ring of PRC acts as an electron acceptor. Figure 2
na

indicated that after adsorption of CAC, the intensity of relevant band at around 1630 cm-1 (the C=O

groups) sustainably decreased. The result suggested that there was a great contribution of n-π
ur

interaction during the adsorption process.

Hydrogen bonding interaction can be categorized into two types [18]. First, dipole−dipole H-
Jo

bonding interaction often occurs between the surface hydrogens of the hydroxyl groups (H-donor)

on the surface of carbonaceous material and the appropriate atoms (i.e., oxygen and nitrogen and

oxygen; H-acceptor) of aromatic adsorbate [54]. Second, Yoshida H-bonding interaction often

occurs between the hydroxyl groups on the surface of carbonaceous material and the aromatic ring

in the adsorbate molecules [55]. Figure 2 indicates that the band intensity of the C–O and –OH
19
groups slightly decreased after adsorption, suggesting that the existence of dipole−dipole H-bonding

and Yoshida H-bonding interactions, respectively. Although the H-bonding interaction played an

integral role in the adsorption process, it did not dominant. A similar conclusion was reported

elsewhere [26].

Regarding π-π interaction (or π-π electron donor-acceptor interaction), such a mechanism that

was initially reported by Coughlin and Ezra [56] occurs between the π-electrons of carbonaceous

material (donor) and the π-electrons of the aromatic rings of adsorbate (acceptor). The π-π

of
interaction has been identified as a primary contributor for the adsorption mechanism for various

ro
aromatic pollutants onto various kinds of carbonaceous materials [18, 49, 50, 53, 57, 58]. Figure 3

shows that after adsorption of PRC, the ID/IG ratio of AC decreased from 2.011 to 1.947, suggesting

-p
the presence of π-π interaction during the adsorption process. Similarly, some other authors applied

the Raman technique to identify the molecular charge-transfer of organic adsorbates onto carbon-
re
based material [32, 59, 60]. They also found that the ID/IG ratio of CAC deceased after adsorption.
lP

Finally, Table 1 shows the change of textural properties of CAC after adsorption. Clearly,

the SBET and VTotal values of CAC dramatically decreased by approximately 96% after adsorption.
na

For example, the SBET value decreased from 1248 m2/g to 45.6 m2/g after adsorption, suggesting the

most important role of pore-filling compared to the other mechanisms in the adsorption process [18,
ur

32]. As expected, CAC exhibited a dominant mesoporous; therefore, it can effectively adsorb PRC

onto its internal porosity network. The result was supported by the un-change of porosity properties
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of CAC before adsorption (Figure 1c) and after adsorption (Figure 1d).

To sum up, the adsorption mechanisms of PRC in aqueous solution onto CAC was

combination of many interaction. According to various experiments, the order of contribution in

adsorption mechanism might be expressed as following: pore-filling > n-π interaction > π-π

interaction > hydrogen bonding.

20
3.2.7. Feasible application for real wastewater

Several kinds of water matrix samples were collected to investigate the removal process of

PRC from water environments. They include distilled water (denoted as a comparative sample), tap

water, groundwater, wastewater (from beauty salon), coastal water, and wastewater (from water

treatment plant). As expected, the applied CAC possessed an excellent capacity of PRC adsorption

in different real water samples (Figure 9). The selected water samples possessed different solution

pH, ionic strength salts, and composition (Table S3). The sweater possesses high salt content and

of
ionic strength. The groundwater could possess the lower pH and higher salt content. The little

ro
organic substance exists in the beauty salon beauty salon and wastewater. However, the qe values

ranging from 192 mg/g to 216 mg/g (average: 203 mg/g, standard deviation: 9.09, standard error:

-p
0.64). The result indicated that adsorption capacity of CAC was less-effected by the characteristic’s

parameters of water. Therefore, CAC is expected to have a great potential application for
re
eliminating PRC micropollutant from water and wastewater streams.
lP

4. Conclusions

 The oxidized carbonaceous porous material CAC with well-developed porosity (SBET = 1284
na

m2/g and VTotal = 0.680 cm3/g) and high oxygen-containing groups exhibited high adsorption

capacity towards PRC in solution. The Langmuir maximum adsorption capacity of CAC was
ur

221 milligram of PRC per gram of CAC. CAC was a dominant mesoporous material

(mesopore volume accounting for 76.3%). The pore size distribution of CAC was highly
Jo

feasible to adequately adsorb PRC in solution through pore-filling. This conclusion was

confirmed by the unchanged of pore network after adsorption. The pore-filling played

extremely important role in the adsorption mechanism of PRC, which was confirmed by a

remarkable decrease in SBET and VTotal after adsorption to 45.6 m2/g and 0.039 cm3/g,

respectively. The second important contribution in the adsorption process of PRC onto
21
 oxidized CAC (abundant oxygen-containing groups) was n-π interaction. Such interaction

was identified through the FTIR technique. A remarkably decrease in the band intensity at

1630 cm-1 (the C=O group) after adsorption supported this conclusion. The presence of π-π

interaction was established (1) a significant decrease in the ID/IG ratio from 2.011 to 1.947

after adsorption and (2) a significant increase in the adsorption capacity of CAC after each

cycle of adsorption and desorption using the thermal method. Hydrogen bonding formations

and weak van der Waals force played a less-important role in the adsorption mechanism.

of
 The Langmuir maximum adsorption capacity of CAC to PRC was 221 mg/g. The excellent

adsorption capacity of CAC was less dependent on some operation parameters (solution pH,

ro
ionic strength, and water matrix).

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 Oxidized CAC can serve as a promising adsorbent for real water treatment.

CRediT authorship contribution statement

re
The authors (Dong Thanh Nguyen, Hai Nguyen Tran, Ruey-Shin Juang, Nguyen Duy Dat, Fatma

Tomul, Andrei Ivanets, Seung Han Woo, Ahmad Hosseini-Bandegharaei, Van Phuong Nguyen,
lP

Huan-Ping Chao) have equal contributions in this work.

na

Declaration of interests

The authors declare that they have no known competing financial interests or personal
ur

relationships that could have appeared to influence the work reported in this paper.
Jo

Acknowledgement

This research is funded by Vietnam National Foundation for Science and Technology Development

(NAFOSTED) under grant number 103.02-2019.54.

22
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Figure 1. Nitrogen adsorption/desorption isotherm of CAC before and after paracetamol adsorption
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Figure 2. FTIR spectrum of CAC before and after adsorption of paracetamol

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3. Raman spectrum of CAC before and after adsorption of paracetamol
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Figure 4. (a) pH point of zero charge (pHPZC) of CAC; and (b) paracetamol distribution in
different solutions pH

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Figure 5. Effect of solution pH (a) and ionic strength (b) on the amount of PRC adsorbed onto CAC
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Figure 6. Effect of contact time on the adsorption process and some modelling ways of the
experimental data
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Figure
7. Adsorption isotherm of PRC onto CAC at 25 °C and the modelling of different adsorption
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isotherms
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 Figure 8. Feasible reuse of PRC-laden CAC through the cycle of adsorption-desorption

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Figure 9. Comparison of adsorption efficiency of CAC towards different PRC solutions. The
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abbreviation of water samples: M1 and M2 (coastal water), M3 and M4 (wastewater) from
water treatment plant), M5 and M6 (groundwater) collected nearly industrial zone, M7
(wastewater) from beauty salon, M8 (tap water from laboratory), and M9 (distilled water)
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Table 1. Textural parameters of CAC before and after adsorption

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Before After
Unit
adsorption adsorption

1. Surface area
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BET surface area SBET m2/g 1248 45.6

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t-plot micropore area SMicro m2/g 438 13.9

External surface area SExt m2/g 809 31.7

2. Pore volume

Total pore VTotal cm3/g 0.680 0.039

t-Plot micropore volume VMicro cm3/g 0.162 0.0045

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 Mesopore volume VMeso cm3/g 0.518 0.0341

Mesopore volume VMeso % 76.3 88.3

3. Pore width

Average pore diameter Lo nm 2.18 3.39

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 Table 2. Corresponding parameters of the selective kinetic models of adsorption PRC onto CAC

Contact time (≤ 4360 min) Contact time (≤ 360 min)

Without the With the

Unit With the origin Without the origin
origin origin

Value SE Value SE Value SE Value SE

1. Elovich model
α mg/(g×min) 4039 1422 4039 1472 1932 542 1932 568
β g/mg 0.053 0.002 0.053 0.002 0.048 0.002 0.048 0.002
adj-R 2
— 0.991 — 0.979 — 0.995 — 0.985 —
χ2
— 36.3 — 38.9 — 19.3 — 21.2 —

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SD — 6.17 — 6.39 — 4.46 — 21.6 —
BIC — 65.4 — 62.7 — 41.8 — 82.8 —
MPSD — 45.5 — 47.1 — 33.3 — 258 —

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2. PSO model
qe mg/g 214 7.19 214 7.44 196 6.19 196 6.49
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k2 (×10 ) g/(mg×min) 1.18 4.1E-01 1.18 4.2E-01 2.48 7.9E-04 2.48 8.3E-04

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Adj-R 2
— 0.864 — 0.691 — 0.92 — 0.766 —
χ2 — 521 — 559 — 292 — 321 —
SD — 22.8 — 23.6 — 21.6 — 22.6 —
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BIC — 110 — 105 — 82.8 — 77.7 —
MPSD — 239 — 248 — 258 — 271 —
3. PFO model
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qe mg/g 204 8.3 204 8.59 187 7.76 187 8.14

k1 1/min 0.218 0.079 0.218 0.082 0.362 0.127 0.362 0.133
adj-R2 — 0.758 — 0.45 — 0.834 — 0.517 —
χ2
— 929 — 995 — 602 — 662 —
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SD — 30.5 — 31.6 — 25.7 — 24.5 —

BIC — 120 — 114 — 80.7 — 86.2 —
MPSD — 291 — 301 — 230 — 219 —
4. Avrami model
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qe mg/g 255 4.85 255 5.03 235 11.4 235 11.9

kAV 1/min 0.039 0.006 0.039 0.006 0.071 0.025 0.071 0.027
t1/2 min 17.79 17.79 9.76 9.76 17.79
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nAV — 0.236 0.011 0.236 0.012 0.263 0.023 0.263 0.024

adj-R 2 — 0.997 — 0.992 — 0.996 — 0.988 —
χ2 — 13.2 — 14.2 — 14.4 — 16.1 —
SD — 3.51 — 3.63 — 3.62 — 3.80 —
BIC — 46.2 — 44.7 — 36.4 — 34.8 —
MPSD — 26.4 — 27.3 — 28.4 — 29.8 —

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Table 3. Corresponding parameters of the selective isotherm models of adsorption PRC onto CAC

Unit Value SE

1. Langmuir model
Qomax mg/g 221 6.31
KL L/mg 0.244 0.057
adj-R2 — 0.946 —
χ2 — 317 —
SD — 20.7 —
BIC — 81.8 —
MPSD — 238 —

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2. Freundlich model
KF (mg/g)(L/mg)n 90.1 7.15
n — 0.150 0.014

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adj-R2 — 0.963 —
χ2 — 219 —
— —

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SD 15.5
BIC — 74.1 —
MPSD — 148 —
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2. Langmuir-Freundlich model
QLF mg/g 260 12.6
KLF L/mg 0.125 0.037
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nLF — 0.461 0.052

adj-R2 — 0.992 —
χ2 — 48.9 —
SD — —
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12.6
BIC — 56.1 —
MPSD — 78.2 —
4. Redlich–Peterson model
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KRP L/g 174 35.2

aRP (L/mg)g 1.411 0.349
g — 0.902 0.010
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adj-R2 — 0.993 —
χ2 — 43.3 —
SD — 7.33 —
BIC — 54.5 —
MPSD — 59.8 —

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Table 4. Thermodynamic parameters (ΔH° and ΔS°) of the PRC adsorption by CAC at two
operation temperatures

∆H° ∆S°
Temperature
[kJ/mol] [J/(mol×K)]

283–298 K 24.11 150

298–323 K –6.36 50

Note: the values of ∆G° (–19.0, –21.3, and –22.5 kJ/mol) at different temperatures (283, 298, and
323 K, respectively) are presented in Table S2.

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Table 5. Desorption efficiency of paracetamol from the laden-CAC using different desorbing agents

Desorbing agents Desorption efficiency (%)

Deionized distilled water (pH 12) 18.1
NaOH (0.2 M) 32.5
Deionized distilled water (pH 2) 11.8
HCl (0.2 M) 11.3
NaCl (0.2 M) 4.9
Ethanol 53.8

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Note: The adsorption experimental conditions: 673 mg/L of PRC, pH 7.0, 25 °C, 2.0 g/L, and 72 h.

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