Carbonaceous material obtained from bark biomass as adsorbent of phenolic compounds from aqueous solutions

Journal Pre-proof Carbonaceous material obtained from bark biomass as adsorbent of phenolic compounds from aqueous solutions Mohamed Abatal, Ioannis Anastopoulos, Dimitrios A. Giannakoudakis, M.T. Olguin

PII:

S2213-3437(20)30132-9

DOI:

https://doi.org/10.1016/j.jece.2020.103784

Reference:

JECE 103784

To appear in:

Journal of Environmental Chemical Engineering

Received Date:

22 October 2019

Revised Date:

7 February 2020

Accepted Date:

14 February 2020

Please cite this article as: { doi: https://doi.org/ This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier.

Carbonaceous material obtained from bark biomass as adsorbent of phenolic compounds from aqueous solutions Mohamed Abatal1*, Ioannis Anastopoulos2, Dimitrios A. Giannakoudakis3, M. T. Olguin4 1

Facultad de Ingeniería, Avenida Central SN, Col. Mundo Maya, C.P. 24156, Ciudad del Carmen, Campeche, México (*e-mail: [email protected]). 2 Radioanalytical and Environmental Chemistry Group, Department of Chemistry, University of Cyprus, P.O. Box 20537, Nicosia CY-1678, Cyprus. 3 Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland 4 Departamento de Química, Instituto Nacional de Investigaciones Nucleares, A.P. 18–1027, C.P. 11801, Ciudad de México, México.

of

Abstract: In this work, a novel carbonaceous material from Haematoxylum campechianum (C-HC) was obtained as an alternative adsorbent for eliminating phenol (Phen), 4-chlorophenol (4-ClPhen)

ro

and 4-nitrophenol (4-NPhen) from aqueous solutions. The carbonaceous material was prepared from bark biomass after phosphoric acid impregnation followed by thermal treatment at 500 °C for 60 min.

-p

The material was characterized by X-ray diffraction (XRD) and Scanning Electron Microscopy/Energy dispersive X-ray Spectroscopy (SEM/EDS). The textural parameters and the point of zero charge of the C-HC adsorbent were determined as well. The results show that the

re

carbonaceous material was obtained as a mixed graphitized/amorphous phase. The major components of this material were carbon, oxygen, and in a minor amount, the phosphorous and sodium. The

lP

surface area, pore-volume, and mean pore diameter of this material were 181.49 m2/g, 0.09396 cm3/g, and 2.07 nm, respectively, with a pHpzc of 7.02. To determine the optimal conditions and the maximum adsorptive capability of the obtained C-HC material against phenolic compounds, various conditions

ur na

such as the contact time (15-180 min), initial adsorbate concentration (10-1000 mg L-1), C-HC dose (5-25 mg L-1) and solution pH (2-10) were investigated using batch experiments. The time to reach the equilibrium for 4-NPhen and 4-ClPhen was approximately 60 min, comparted to 120 min for Phen. The experimental data fit well to the pseudo-second-order kinetic model (R 2 ≥0.99) in all cases, and the kinetic constant of pseudo-second-order was highest for 4-NPhen (k2=0.075 g/(mg min). The experimental data of the isotherms were well fitted to Langmuir and Lui model. The maximum

Jo

adsorption capacity (Qm) based on the Langmuir model was obtained for Phen (94.09 mg/g). The dose of the C-HC and the pH of the phenolic aqueous solutions influence the sorption capacity of the carbonaceous material. The best conditions to reach the maximum adsorption of the phenolic compounds were with a dose of 20 mg/L and at pH 2. The solubility, pKa and the dipolar moment of the phenolics affect notably the kinetic and the maximum adsorption capacity of the C-HC, considering that 4-Phen has the lowest solubility and pKa constant, and the highest dipolar moment. Keywords: Phenolic compounds, Carbonaceous material, Haematoxylum campechianum.

1

1. Introduction Phenolic compounds are classified by the United States Environmental Protection Agency (USEPA) and the European Union (EU) as one of the high priority hazardous chemicals due to the high toxicity for humans and animals, even at low concentration [1]. Phenol and nitrophenols (NPs) are the principal phenolic compounds responsible for water pollution [2]. Industrial activities such as coal conversion, pesticides, insecticides, dyes, and pharmaceuticals synthesis, as well as metal casting and paper manufacturing, are the main sources for these compounds disposal in the environment [3]. Recently, the presence of phenolic compounds was confirmed in the rivers of many countries as the

of

result of the effluent from various industrial activities [4]. Therefore, there is the need to develop several techniques to sufficiently eliminate these organic pollutants from wastewater.

ro

In the literature, photocatalytic degradation, chemical oxidation, electrochemical and biological methods, as well as solvent extraction are the conventional water treatment technologies used for removing of phenolic compounds from wastewaters [5]–[10]. Although, these technologies are

-p

widely used for removing phenols, some of them have shown disadvantages such as generation of toxic products and undesired by-products, high cost of operate, and in many cases not so elevated

re

efficiency [9].

Adsorption is an attractive method for wastewater remediation against organic and inorganic pollutants. This process is considered to be one of the most promising green oriented techniques for

lP

wastewater treatment as its low cost, facile of operated, simplicity of design, and it does not result in the formation of harmful chemical products [11]–[13]. The most crucial aspect for water adsorptive remediation processes is the adsorbent. Carbonaceous materials and especially porous carbons are

ur na

considered as the best candidates, especially since they can be obtained from abundant and renewable resources like biomass.

Despite the high adsorption ability of commercial activated carbon (AC) for the removal of phenolics, ACs remain an expensive material for big scale real-life applications [13]. In the last decades, there is has been an increase in the exploration for alternative adsorbents to replace costly ACs. Some of

Jo

these low-cost materials were natural and modified clays and zeolites, specially bentonite, kaolinite, montmorillonite, and clinoptilolite [11], [12], [14], [15]. Many representatives from the abovementioned classes of the materials were tested as sorbents in previous researches, and revealed to be effective for the removal of phenolic pollutants from aqueous solutions. However, the adsorption capacity of ACs was found most of the times as the superior compared for instance with clays and zeolites [16].

2

Recently, there is has been a growing interest to produce ACs from less expensive abundant and renewable raw materials such as biomass and more specifically, from plants and agricultural residues [17]–[19]. This allows unwanted wastes to be transformed into a useful and desired value-added adsorbent for removing organic and inorganic contaminants. It was reported that activated carbon and/or carbonaceous materials were successfully obtained with an economic feasible manner from various waste materials as orange peels [20], coffee husks [21], waste wood [22], pine cones [23], coir pith [24], pine-fruit shells [25], oil palm shells [26], cashews nut shells [27], or coconut husks [28], that

of

revealed superior adsorptive capabilities against various wastewater pollutants. Various features of the adsorbent play a key role towards a sufficient removal of the targeted pollutant, such as porosity, surface chemistry heterogeneity, or graphitization level of the

ro

carbonaceous material, with the process of synthesis to be of an uppermost importance in order to tune these features [27], [29]. Barin et. al.[30] presented in 2014 the curved graphite carbon-based

-p

structures prepared from crude biomass/lignocellulosic precursor (from coconut coir dust), opening the path for the utilization of agricultural bio-wastes in view of synthesizing valuable adsorbents.

re

Mexico is considered one of the world's largest producers of coconut, with an annual production of over one million tons; approximately 80-85 % of the total mass of this fruit is discarded as solid waste [31]. Another natural resource that extends throughout the southeast Mexico is the tree

lP

Haematoxylum campechianum. This species is native to the tropical region of the Center America continent, which is naturally distributed throughout Guatemala, Belize and the Yucatan Peninsula, Mexico [32]. According to the Official Mexican Norm NOM-059-SEMARNAT-2010,

ur na

Haematoxylum campechianum is not listed as a threatened species although it has been subject to commercial exploitation for more than 10 centuries [32]. To the best of our knowledge, not researches exist on the utilization of Haematoxylum campechianum bark as a biosource for the preparation of carbonaceous based adsorbent. Therefore, the objective of the present investigation was to obtain a carbonaceous material from Haematoxylum campechianum bark and to evaluate its application in

Jo

removing three phenolic compounds, phenol, 4-chlorophenol, and 4-nitrophenol, from aqueous solution taking account that these phenolic compounds are pollutants of aquatic systems. The effects of contact time, initial concentration of phenolic compounds, solution pH, and adsorbent dose on the adsorption capacity were also considered in this work. Finally, to elucidate the interaction mechanism between adsorbate-adsorbent, the correlation between the physicochemical characteristics of the phenolic compounds (solubility, pKa, and dipolar moment) and adsorption parameters (kinetic and maximum adsorption capacity of the carbonaceous material) was essential.

3

2. Materials and methods 2.1.Reagents Phenol (Phen), 4-nitrophenol (4-NPhen), as well as 4-chlorophenol (4-ClPhen) were acquired from Sigma-Aldrich (purity of ≥99%) and stock solutions of these phenolic compounds (1000 mg L-1) were obtain when the compounds were dissolved in deionized water (18.218.2 M cm-1, resistivity) which were then stored in amber bottles. The desired solutions were prepared, taking different aliquots of the stock solutions and diluting in water. Phosphoric acid (Merker, 85%) was used for

ro

2.2.Carbonaceous material from Haematoxylum campechianum

of

impregnation process.

Residue from the bark of Haematoxylum campechianum (HC) was collected from the Technological Institute of Centla located in state of Tabasco, Mexico. The barks were cut, ground, and sieved to

-p

fractions between 0.2 and 0.5 mm. Later, the solids were washed using distilled water at 50 °C to eliminate any dirt from the surface and finally oven-dried at 70 °C overnight. The method used to

re

obtain this carbon (C) consisted of two main steps: 1) impregnation/chemical modification and 2) thermal treatment.

lP

For the impregnation, 50 g of HC was mixed with 250 mL of H3PO4 solutions with a gH3PO4/gHC ratio of 0.5. The liquid/solid mixture was stirred for 3 h at 50 °C, and then the solids were dried in an oven at 70 ° C for 12 h. Thermal treatment was carried on by introducing 50 g of impregnated sample into a muffle at 500 °C for 60 min with considering 10°C min-1. Then, the obtained product was cooled at

ur na

around 20oC.

The obtained carbonaceous material was washed with NaHCO3 (ACS reagent, ≥ 99.7%) to remove any residual compound. Then, the solids were washed with deionized water by filtration until the pH of filtrate reached 6-7 values. Finally, the Haematoxylum campechianum derived carbonaceous material was dried at 110 °C for 12 h and kept in a hermetically closed glass bottle for future use.

Jo

This sample is referred to as C-HC and the yield of this process was found to be 45 %

2.3.Adsorbent characterization

The morphology of sample was examined with a HITACHI S-3400N scanning electron microscope (SEM). The elemental chemical composition of C-HC was determined in several zones of the surfaces of each sample by energy-dispersive X-ray spectroscopy (EDS). The X-ray diffractogram of the CHC sample was recorded on an APD 2000 PRO diffractometer using CuKα radiation (λ = 1.5405 Å). 4

The diffraction patterns were taken at 35 kV and 25 mA in the range of 2θ angle values between 20° and 70° by a scanning speed of 0.025 degrees s-1 and step time of 10 s. The textural characteristics was determined from the isotherm based on the Brunauer–Emmett–Teller (BET) method using nitrogen as the adsorbate gas. The measurements were taken using a BELSORP MAX (BEL. Japan. Inc) surface analyzer.

2.4.Point of Zero Charge (pHPZC)

of

The following experimentation was considered to determine the pH of the point of zero charges (pHPZC) for C-HC. Samples of 0.10 g of the adsorbent were in contact with 50 mL of 0.01 M NaCl

ro

solution at different pH values (2, 4, 5, 6, 8, 10, and 12). The mixtures were shaken for 24 h at 25.0 ± 0.1°C, and then the phases were separated by decantation. The pH of each remaining solution were measured with a Thermo Scientific (ORNION 3 star pH Benchtop) pH-meter. The experiments were

-p

repeated under the same experimental conditions for reproducibility purposes. The point of intersection between the curve obtained plotting pHfinal vs. pHinitial with the diagonal curve (pHfinal vs.

re

pHinitial) corresponds to the pHPZC of the biosorbent [33].

lP

2.5.Sorption experiments

Batch experiments were carried out for the evaluation of the sorption capabilities of C-HC against the three phenolic compounds; Phenol (Phen), 4-nitrophenol (4-NPhen), and 4-chlorophenol (4-ClPhen).

ur na

The kinetic experiments were performed for constant initial concentration of the Phen, 4-NPhen and 4-ClPhen aqueous solutions (100 mg L-1), C-HC dosage mass (10 g L-1) and pH=5.65. The C-HC samples were in contact with in 10 mL of the aqueous solution at 150 rpm in an orbital shaker at 25 °C for different periods from 15 to 180 min. After that, the mixtures were centrifuged at 4500 rpm for 2 min, and the adsorbents were separated by filtration. The amounts of Phen, 4-Nphen, and 4-

Jo

Clphen in the remaining solutions were determined using a Thermo-Scientific UV-visible spectrophotometer by absorbance at a wavelength of 268, 239, and 235 nm, respectively. The experiments were repeated twice for reproducibility purposes. The quantities of the phenolic compounds adsorbed by C-HC (qt, mg/g) was obtained applying the mass balance relationship equation (Eq. 1):

𝑞𝑡 =

(𝐶0 − 𝐶𝑡 )𝑉 𝑊

(𝐸𝑞. 1)

5

In this equation, V corresponds to the phenolic solution volume (mL), W is the amount of C-HC (g), Co and Ct are the initial and final concentrations of the phenolic compounds (mg L -1), at time t (min), which was calculated based on calibration curves. The influence of solution pH, adsorbate dosage mass and initial concentrations of Phen, 4-NPhen, and 4-ClPhen on the sorption capacity were also investigated. Table 1 show the experimental conditions used in this study.

Table 1. Parameters considered in the sorption processes of Phen, 4-NPhen, and 4-ClPhen using C-

of

HC samples. Time (min)

Ci (mg L-1)

pHi

Sorbent dose (g L-1)

Contact time

15-180

100

5-6

10

Initial solution pH

180

100

2-10

10

Sorbent dose

180

100

5-6

5-25

Initial concentration

180

10-1000

5-6

10

-p

ro

Studied parameters

re

The experimental of the kinetic were fitted to the pseudo-first-order and pseudo-second-order models

𝑞𝑡 = 𝑞𝑒 (1 − 𝑒 −𝑘1 𝑡 )

Eq. 2

lP

[34]. These models are described by the equations (Eq.2) and (Eq.3), as follows:

𝑘2 𝑞𝑒 2 𝑡 1 + 𝑘2 𝑞𝑒 𝑡

Eq. 3

ur na

𝑞𝑡 =

Where qt (mg g-1) and qe (mg g-1) represent the quantities of the phenolic compounds adsorbed at time t and equilibrium; k1 (min-1) and k2 (g mg-1 min-1) are the pseudo-first order and pseudo-secondorder reaction rate constants.

The data of the adsorption isotherms for Phen, 4-NPhen, and 4-ClPhen by C-HC samples were fitted

Jo

to Langmuir, Freundlich, and Liu models on order to describe the adsorption behavior [35], [36]. Equations 4, 5, and 6 describe these models, respectively:

𝑞𝑒 = 1

𝑞𝑒 = 𝐾𝐹 𝐶𝑒 𝑛

𝑞𝑚 𝐾𝐿 𝐶𝑒 1 + 𝐾𝐿 𝐶𝑒

(Eq. 4)

(Eq. 5) 𝑄𝑚𝑎𝑥 (𝐾𝑔 . 𝐶𝑒 )𝑛𝐿 𝑞𝑒 = 1 + (𝐾𝑔 . 𝐶𝑒 )𝑛𝐿

(Eq. 6) 6

Where qm (mg g-1) is the monolayer adsorption capacity of the C-HC, qe is the amount of phenolic compound adsorbed at equilibrium (mg/g), Ce (mg/L) is the equilibrium phenols concentration, KL (L mg-1) is the adsorption constant related to the sorption energy. KF (mg g-1)(L mg-1)1/n is related primarily to the capacity of the C-HC for the phenolic compound, and 1/n is a function of the adsorption strength. Kg (L mg−1) is the Liu equilibrium constants; nF and nL are the exponents of Freundlich and Liu models, respectively, (nF and nL are dimensionless) [36]. In this work, reduced chi-square, Standard Deviation (SD) and Adjusted Coefficient of Determination

of

(R²adj) are calculated in order to testing the equilibrium model. The good model is the one, which their value of with R² adj is near to unity, and the value reduced chi-square and SD is lowest. The

equations 7-10, respectively. 𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑐ℎ𝑖 − 𝑠𝑞𝑢𝑎𝑟𝑒 = ∑ 𝑖

(𝑞𝑖,𝑒𝑥𝑝 − 𝑞𝑖,𝑚𝑜𝑑𝑒𝑙 )2 𝑛𝑝 − 𝑝

-p

𝑛

ro

expressions of reduced chi-square, SD, Coefficient of Determination (R²) and R²adj are presented in

𝑛

re

1 𝑆𝐷 = √( ) . ∑(𝑞𝑖,𝑒𝑥𝑝 − 𝑞𝑖,𝑚𝑜𝑑𝑒𝑙 )2 𝑛𝑝 − 𝑝 𝑖=0

𝑅 =

2 ∑𝑛𝑝 ̅ 𝑖,𝑒𝑥𝑝 )2 − ∑𝑛𝑝 𝑖 (𝑞𝑖,𝑒𝑥𝑝 − 𝑞 𝑖 (𝑞𝑖,𝑒𝑥𝑝 − 𝑞𝑖,𝑚𝑜𝑑𝑒𝑙 )

lP

2

∑𝑛𝑖(𝑞𝑖,𝑒𝑥𝑝− 𝑞̅𝑖,𝑒𝑥𝑝 )2

𝑛𝑝 − 1 ) 𝑛𝑝 − 𝑝 − 1

(Eq. 8)

(Eq. 9) (Eq. 10)

ur na

𝑅2 𝑎𝑑𝑗 = 1 − (1 − 𝑅2 ). (

(Eq. 7)

where 𝑞𝑖,𝑚𝑜𝑑𝑒𝑙 is the value of q calculated by the fitted model, 𝑞𝑖,𝑒𝑥𝑝 and 𝑞̅𝑖,𝑒𝑥𝑝 are the experimental and average values of q, respectively. np is the number of experiments performed and p is the number of parameters of the fitted model.

Jo

3. Results and discussions

3.1.Characterization

The morphology of the obtained material was analyzed by Scanning Electron Microscopy (SEM). Micrographs of the C-HC sample is presented in Figure 1. It can be observed that the texture and morphology of the material displayed a randomly and heterogeously in shape C-HC particles, with a high level of roughness and with a variety of arbitrarily distributed cages/voids, resulted from the thermal treatment. The presence of these cages can be beneficial providing easy access/mass transport

7

towards the adsorption sites [37]–[40]. The various bright spots could be due to the presence of rare

lP

Figure 1. SEM image of C-HC.

re

-p

ro

of

earth or transition metal moities.

In order to determine if the bark biomass and the final obtained C-HC possess metalic moities, element analysis of the C-HC sample was perfromed by EDS. The results collected in Table 1 show

ur na

that the material consists predominately from carbon and oxygen, with the summary of these two elements to be 97.12 % per weight. The presence of an imortant amount of heteroatoms like P, Na and Ca was found in the range of 1 %, while limited amounts of Fe, Ca, Mg, Si, and Al, are also present in less than 0.08 wt. % (Table 2).

Jo

Table 2: EDS analysis of the C-HC.

Element

Wt%

Atomic %

C

76.97±0.10

82.5±0.10

O

20.15±0.10

16.21±0.10

P

1.07±0.01

0.45±0.01

Na

1.05±0.01

0.59±0.01

Fe

0.07±0.01

0.02±0.01

Ca

0.60±0.01

0.19±0.01 8

Mg

0.03±0.01

0.02±0.01

Si

0.03±0.01

0.01±0.01

Al

0.02±0.01

0.01±0.01

Total:

100.00

100.00

In order to determine if the functionalization/impregnation with acid prior the thermal treatment in addition with the presence of metal impurites led to an purely amorphous carbanaceous phase or graphitization also occured, C-HC was analyzed by XRD and the diffractogram is presented in Figure

of

2. It can be observed that the pattern of the sample exhibit two broad peaks of low intensity at 2θ ranges from 17° to 30° and 38° to 46°. These peaks corresponce to the characteristic reflexions of the (002) and (100) planes in the case of graphitized carbanaceous materials [30], [40]–[44]. Although,

different

graphitic phases

ro

these reflections have a broad and asymmetrik shape of a low intensity, suggesting a mixture of and amophous/no-ordered carbon phase,

creating a mixed

-p

matrix/framework [41]. These results reveal that a graphitic carbanaceous phase can be produced from renewable carbon sources, like biomass, even at a relatively low temperature of

re

carbonization/pyrolysis (500 oC) without the use of templates, addition of transition metals (like Fe, Co, Ni, Al, Zr etc) or mettalic compounds (like MnO2, Fe3O4, Cr2O3), known acting as catalyst for

Jo

ur na

lP

the graphitization process in order to obtaine graphitized carbon materials [42], [43].

Figure 2. XRD pattern of C-HC. The surface area of C-HC, determined by nitrogen sorption test, was found to be 181 m2 g-1, a value analogs with other graphitized carbon reported in the literature [41]. Complementary, the mean pore diameter was 2.07 nm and a total pore volume 0.094 cm3/g. The porosity could influence the 9

adsorption of Phen, 4-NPhen, and 4-ClPhen. The effective molecule diameters for Phen and Cl-Phen were 0.75 nm and 0.783 nm [45], [46], respectively. Therefore, it is feasible that the molecules to be diffused throughout the pores of C-HC in order to reach the adsorption sites. Figure 3 shows the pHfinal (pH of the remaining solutions after contact with C-HC as a function of pHinitial of the solution. It can be seen that the pHPZC of C-HC is 7.02. If the pH
ur na

lP

re

-p

ro

of

from solution.

Figure 3. pHfinal vs. pHinitial to determine the pHpzc for C-HC.

3.2.Kinetic studies

The amount of Phen, 4-NPhen and 4-ClPhen sorbed (qt, mg g-1) by C-HC vs. time (t, min) is presented

Jo

in Figure 4a. As seen in this Figure, the adsorption process for 4-NPhen and 4-ClPhen consist of two main stages; in the first stage (30-60 min) occur a strong fast removal of the phenols, while afterwards, a negligible removal is observed. For Phen, the removal process is closer and occurs either at the second stage, but with a significant lower rate. These adsorption evolutions can be explained by the large number of vacant surface sites that were available for adsorption at the first stage. The rest of the vacant surface sites were difficult to occupy close to equilibrium, possibly due to the slow pore diffusion of the solute 4-NPhen and 4-ClPhen on the C-HC and the bulk phase [49]. Due to the smaller in size nature of Phen compared to the other two compounds, it can be assumed that it is possible the 10

penetration of Phen molecules to occur to smaller in size pores, and for that reason removal was observed even up to 180 min. From Figure 4a, it can be observed that the equilibrium time for 4-NPhen and 4-ClPhen was approximately 60 min, whereas for the Phen solution, a larger equilibrium time was required (180 min). The short equilibrium time found in this work is an important result because equilibrium time is considered an essential parameters for economical wastewater treatment [50]. In other works, it was reported that the equilibrium time for removal of phenolic compounds was reached within a range from 3 to 20 h using other sorbents like modified zeolite or activated carbon prepared from different

lP

re

-p

ro

of

biomass materials [51]–[57].

Figure 4. a) Adsorption of Phen, 4-ClPhen and 4-NPhen by C-HC (qt) vs. time, b) Linear plots of the

ur na

pseudo-second-order equation t/qt vs. t.

The experimental data of Phen, 4-NPhen, and 4-ClPhen sorption by the C-HC samples were fitted to the equations of pseudo-first and pseudo-second order models. From the plotting t/qt against t (Figure 4b) and Table 3, the kinetic parameters corresponding to the sorption of phenolic compounds by CHC fit absolutely to the pseudo-second order model; since the qe value (which corresponds to the

Jo

quantity of the phenolic compounds adsorbed at equilibrium) obtained from the pseudo second-order (qe,cal) was very close to the experimental value (qe,exp). In addition, the coefficient of determination (R2) showed that the pseudo-second-order reaction model fits the experimental data better (ranging from 0.998-0.999) than that of the pseudo-first-order model. This result agrees with the kinetic behavior for the adsorption of phenolic compounds on other AC samples [51], [58], [59]. This result show that the adsorption process of phenolic compounds is carried out via surface exchange interactions [60]. Juang et al., reported that the adsorption mechanism can be attributed to the formation of hydrogen bonding between the phenolic compounds and the functional groups (e.g., 11

carboxylic) from the C-AC [58]. According to the results presented in Table 3, it can be observed that the k2 depends on the substituted group in the phenolic compound and it is the highest for 4nitrophenol. The physicochemical properties of the phenolic compounds could be the reason for this behavior [61].

Table 3. Sorption kinetic constants of Phen, 4-ClPhen and 4-NPhen from aqueous solutions on CHC. Kinetic models

compounds

Pseudo-second order

Pseudo-first order

qe,cal

k2

R2

qe,cal

k1

R2

Phen

9.79

10.14

0.012

0.99

3.184

0.012

0.98

4-ClPhen

10.04

10.20

0.057

0.99

0.669

0.013

0.42

4-NPhen

10.32

10.40

0.075

0.99

0.515

0.013

0.54

re

3.3. Isotherms

-p

Note: qe (mg/g), k2 (g mg−1 min−1) and k1 (min−1)

ro

qe,exp

of

Phenolic

The adsorption isotherms of Phen, 4-NPhen, and 4-CPphen onto C-HC at 25 °C are shown in Figure

lP

5. It can be observed that when increase equilibrium concentration, the amount of phenolic compounds increase also on C-HC. According to the result, the phenolic compounds exhibited a high affinity toward the C-HC surface. This result is attributed to the formation of the electron donor-

ur na

acceptor complexes formed between the aromatic ring of the phenols and the basic site of the C-HC [61]. Furthermore, it can observed that the maximum adsorption capacity of C-HC depends on the physico-chemical characteristics of each phenolic compound among other pK a, solubility and dipole

Jo

moment [48].

12

of ro -p re lP

ur na

Figure 5. Sorption isotherms of a) Phen, b) 4-ClPhen and c) 4-NPhen for C-HC.

The experimental data was fitted to the isotherms of Langmuir, Freundlich and Liu models (Table 4). Based on reduced chi-square, SD and R²adj values, the best fit isotherm for Phen and 4-CLPhen was Langmuir whereas for 4-NPhen was fitted by Liu model.

Jo

Table 4. Parameters obtained from adsorption isotherms models for phenolic derivatives using C-HC Isotherm models

Langmuir

Parameters Qm (mg.g-1) KL (L.mg-1) Reduced 2 R2adj R2 SD (mg.g-1) KF (mg.g-1(mg.L-1)-1/nF NF

Phenolic compounds Phenol 4-CLPhen 94.09 92.58 0.0022 0.0040 3.0387 1.9701 0.992 0.996 0.997 0.998 1.7432 1.4036 1.2371 2.4171 1.7019 1.9357

4-NPhen 84.80 0.0118 5.4839 0.990 0.992 2.3418 6.1027 2.4337 13

Freundlich

Liu

Reduced 2 R2adj R2 SD (mg.g-1) Qm (mg.g-1) Kg (L.mg-1) nL Reduced 2 R2adj R2 SD (mg.g-1)

6.1665 0.9840 0.9931 2.4832 106.077 0.00172 0.91635 3.45246 0.99106 0.99361 1.85808

12.465 0.9767 0.9800 3.5305 96.1810 0.00365 0.95961 2.28201 0.99574 0.99695 1.51063

10.3406 0.9821 0.9847 3.2157 107.592 0.00602 0.73436 1.76731 0.99694 0.99781 1.32940

of

Table 5 present a comparison between the maximum uptake capacities (Qm) of various adsorbents reported in the literature and the values obtained in the present work. It can be seen that the differences

ro

in sorption capacities can be related to different surface characteristics that depended with the presence of the different functional groups and specific area of the sorbents as well as the

-p

physicochemical characteristics of the phenolic compounds (pKa, solubility and dipole moment, among others) (Table 6). An important outcome can be derived by calculating the maximum uptakes per surface area (Qm/SBET), presented also in Table 5. The herein studied material showed the highest

re

removal capability per surface area compared to all the others tested activated porous and graphitic carbons, revealing the importance of the surface heterogeneity and the nature of the precursor and

lP

synthetic process. Additionally, the Q m/SBET value for C-HC was the highest in the case of 4-NPhen by ~ 10% compared to Phen and 4Cl-Phen, a strong evidence of the adsorption favorability upon the

ur na

presence of nitro group.

Table 5. Adsorption capacities of different sorbents and their comparison with C-HC sample Phenolic

Sorbent

Qm

SBET

Qm/SBET

(mg g-1)

(m2g-1)

(μg m-2)

AC from biomass

149

1083

138

[55]

AC from bacterial residue

199

1593

125

[60]

A Wood based AC

243

1618

150

[49]

94

197

477

In

Jo

compounds

Phen

C

from

Haematoxylum

campechianum bark

4-ClPhen

Ref

this

study

AC from rattan sawdust

189

1083

175

[52]

AC from bituminous coal

300

825

364

[63]

Functional Chitosan (CS-SA)

45

-

-

[64]

Granular Activated Carbon

310

929

334

[65]

14

C

from

Haematoxylum

93

197

472

campechianum bark

4-NPhen

In study

AC peach stones

234

1521

154

[53]

N-doped graphitic carbon

53

208

255

[2]

Clinoptilolite-HDTMA

18

-------

C

108*

197

from

this

Haematoxylum

[66] 548

campechianum bark

In

this

study

3.4 Effect of adsorbent dose

of

The uptake percentage of Phen, 4-NPhen, and 4-ClPhen with respect to the C-HC dose (mg L-1) is presented in Figure 6. As can be seen, the sorption (in percentage) of the phenolic compounds

ro

increased from 41.6, 66.8 and 73.9 % to 86.2, 96.0, and 98.4 % when the C-HC dose is 15 mg L-1. The high sorption capacity of carbonaceous material against phenolic compounds is attributed to the

-p

increment of available adsorption sites resulting from the addition of the adsorbent in solution (adsorbent dose) [50]. Similar results were also reported in previous works which used AC and other

re

type of adsorbents [55]. Noticeable, after 15 mg L-1, no significant removal capacity was observed

Jo

ur na

lP

for 4-NPhen and 4-ClPhen, as discussed above at the kinetic evaluation part.

Figure 6. Phenolic compounds removed by C-HC as a function of the dosage. (Solution pH = 5-6, and contact time = 180 min).

15

3.5 Effect of pH The effect of the pH on the removal of phenolic compounds (Phen, 4-ClPhen and 4-Nphen) is presented in Figure 7. The adsorption of phenolic compounds decreases when the pH of the solution increases. At pH = 2, the percentage of removal of Phen, 4-ClPhen and 4-Nphen was found to be 73.6, 89.2 and 93.2 %, respectively, and decreased to 36.4, 47.1 and 53.1 % when initial solution had

ur na

lP

re

-p

ro

of

a pH value of 10.

Figure 7. Phenolic compounds removed by C-HC as a function of the initial pH. . (Sorbent dose = 10 g/L, concentration = 100 mg/L and contact time = 180 min)

Jo

As it was shown in Table 6, Phen, 4-ClPhen and 4-Nphen are considered weak acids. The lower removal percentage of phenol derivatives under basic medium can be explained with the base on the similitude in the surfaces charges of both the C-HC and the sorbates. This is because in the basic region, the phenolic compounds are dissociated to anions, and in this region, the C-HC surface has negative charges because the pH is up to the pHPZC. In an acidic region, the magnitude of negative charge on the C-HC is reduced and there is maximum uptake because the phenols are undissociated and Phen, 4-ClPhen and 4-Nphen molecules predominates [47].

16

3.6 Interaction between C-HC and phenolic compounds The phenol is soluble in water due to the formation of hydrogen bonds. However, the 4-ClPhen and 4-NPhen present less solubility than phenol [48]. It is explained based on the addition of substituent groups (Cl- and NO2-) in the benzene ring of the phenol molecule in the para-position, which confer a hydrophobic nature and consequently the solubility decreases (Table 6). Therefore, the solubility and the hydrophobic character of the phenolic compounds determine the interaction with the C-HC [45]. However, another important characteristic of phenol and derivatives, which influence the

of

interactions with the carbonaceous material, is the acidity (pKa), which is derived by the negative unlocalized charge in the benzene ring. It is essential to mention that these changes also influence the

ro

dipole moment () (Table 6).

In previously reported articles [3], [62], it is mentioned that for graphitized carbons, the interactions with these phenolic compounds are of the hydrophobic type due to the Van der Waals and π–π

-p

electrons interactions from the benzene rings.

Water

Partitional

Solubility

coefficient

at (g/L) 83

4-ClPhen

24

4-NPhen

15.6

Dipole

at 25 oC

moment (Debyes)

1.46

9.99

1.61

2.39

9.41

2.15

1.91

7.15

5.05

ur na

Phen

25°C

pKa

lP

Compound

re

Table 6. Physicochemical properties of phenolic compounds

Figures 8 and 9 represent the correlation of the kinetic constant of the pseudo-second-order (k2) and the maximum adsorption capacity (Qm) of the C-HC for Phen, 4-ClPhen, and 4-NPhen obtained from

Jo

Langmuir isotherm, with the solubility, pKa, and dipole moment of Phen, 4-ClPhen and 4-NPhen. When the solubility and the pKa of the phenolic compounds increase, the kinetic constant k2 decreases, however, when the dipole moment increases, the kinetic constant of pseudo-second-order increases as well. These results evidence that these parameters (solubility, pKa and the dipolar moment) affect notably the kinetic of the adsorption process, considering that 4-Phen has the lowest solubility and pKa constant and the highest dipolar moment (Table 6).

17

Figure 8. Pseudo-second- order kinetic constant as a function of the a) solubility, b) pKa and c) dipolar

of

moment of the phenolic compounds (Phen, 4-ClPhen and 4-NPhen).

In the case of the maximum adsorption capacities (Qm), the trends of the correlations are in contrary

ro

to that of the kinetic when the solubility and the pKa of the phenolic compounds increase the maximum adsorption capacity (Q m) of the C-HC increases. Although, when the dipole moment

-p

increases, the maximum adsorption capacity of the carbonaceous material decreases. The pKa of the Phen and 4-ClPhen (around 9) indicates that the carbonaceous material adsorbs neutral molecules of these compounds. On the contrary, the 4-NPhen (pKa=7.15) could be present in the aqueous solution

re

as phenolic anions decreasing the affinity by the adsorbent, which shows a pH pzc of 7. The almost perfect linearity of the correlation between Q m on pKa and dipole moment reveals the key role of these

ur na

lP

factors on the maximum adsorptive capability.

Figure 9. Maximum adsorption capacity as a function of the a) solubility, b) pK a and c) dipolar

Jo

moment of the phenolic compounds (Phen, 4-ClPhen and 4-NPhen).

Conclusions

The herein treatment of Haematoxylum campechianum bark biomass, impregnation with phosphoric acid followed by thermal treatment at 500 °C, led to a mixed matrix material, a graphitized carbanaceous material (C-HC). The major components of the C-HC are C and O, while a minor amount P and Na also exist (around 1% of each) among with traces of various other elements like Ca, Fe, Mg, Si, and Al. The textural characteristics of this carbonaceous material showed a surface area 18

of 181 m2 g-1, a total pore volume of 0.094 cm3g-1, and a mean pore diameter of 2.07 nm, while the pHpzc was found 7.02. The study of C-HC as adsorbent against three different phenolic compounds, phenol (Phen), 4nitrophenol (4-NPhen), as well as 4-chlorophenol (4-ClPhen), revealed that the time to reach the adsorption equilibrium is more than twice higher for Phen than for 4-ClPhen and 4-NPhen. The experimental data fit well to the pseudo-second-order kinetic model. The k2 follows the order 4-NPhen > 4-ClPhen > Phen. The pseudo-second-order kinetic constant (k2) and the maximum adsorption capacity of C-HC depend of the solubility, pKa and dipolar moment of the phenolic compounds

of

(Phen, 4-ClPhen and 4-NPhen). The Langmuir model fit well the adsorption isotherms for Phen and 4-CLPhen and the Liu model in the case of 4-NPhen. The maximum adsorption capacities (Q m from Langmuir isotherm) of the carbonaceous material from Haematoxylum campechianum bark were

ro

similar for Phen and 4-CLPhen (94.09, mg/g, 92.58 mg/g, respectively) and 9.8 % lower for 4-NPhen (84.8 mg/g). The adsorption capacities per surface area for each compound were found as superior

-p

compared to all the other reported in the literature materials, like activated porous or graphitic carbons. The pKa and dipole moment played the key role on the maximum adsorptive capability. The

re

parameters KL is the highest for 4-NPhen. The dose of C-HC as well as the initial pH of the aqueous solutions had a strong influence on the uptake of the phenolic compounds by the carbonaceous

lP

material.

ur na

CRediT author statement Mohamed Abatal: Preparation of the samples, characterization, experiments methodology and Writing- Original draft preparation Ioannis Anastopoulos The application of different models to the sorption process, as well as the discussion of them. Dimitrios A. Giannakoudakis. Discussion of the results and the analysis of characterization. M. T. Olguín: Discussion of the results and contribution to the final manuscript.

Jo

Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgement The Author is grateful to National Council of Science and Technology of Mexico for grant (No. 169133). M. T. Olguin thanks National Council of Science and Technology of Mexico for grant No. 254665. The authors also acknowledge the help of Prof. Eder Claudio Lima to estimate the nonlinear isotherms’ parameters and for designing the graphs (Figure 5a-c).

19

References [1] J. Michałowicz, W. Duda, Phenols-Sources and Toxicity, Pol. J. Environ. Stud. 16 (2007) 347-362. [2] A.B. RanguMagar, B.P. Chhetri, C.M. Parnell, A. Parameswaran-Thankam, F. Watanabe, T. Mustafa, A.S. Biris, A. Ghosh, Removal of nitrophenols from water using cellulose derived nitrogen doped graphitic carbon material containing titanium dioxide, Particul. Sci. Technol. 37 (2019) 444452. https://doi.org/10.1080/02726351.2017.1391906.

ro

of

[3] A. Da̧browski, P. Podkościelny, Z. Hubicki, M. Barczak, Adsorption of phenolic compounds by activated carbon- A critical review, Chemosphere 58 (2004) 1049-1070. https://doi.10.1016/j.chemosphere.2004.09.067.

-p

[4] W. Zhong, D. Wang, Z. Wang, Distribution and potential ecological risk of 50 phenolic compounds in three rivers in Tianjin, China, Environ. Pollut. 235 (2018) 121–128. https://doi.org/10.1016/j.envpol.2017.12.037.

re

[5] J. Araña, J.M. Doña-Rodríguez, D. Portillo-Carrizo, C. Fernández-Rodríguez, J. Pérez-Peña, O. González Díaz, J.A. Navío, M. Macías, Photocatalytic degradation of phenolic compounds with new TiO2 catalysts, Appl. Catal. B-Environ. 100 (2010) 346-354. https://doi.org/10.1016/j.apcatb.2010.08.011.

lP

[6] R. Thankappan, S.V. Srinivasan, R. Suthanthararajan, M. Sillanpää, Studies on removal of phenol sulfonic acid-syntan in aqueous medium using ozonation, Environ. Technol. 39 (2018) 2434– 2446. https://doi.org/10.1080/09593330.2017.1355936.

ur na

[7] G. Annadurai, R. Juang, D. Lee, Microbiological degradation of phenol using mixed liquors of Pseudomonas putida and activated sludge, Waste Manage. 22 (2002) 703–710. https://doi.org/10.1016/S0956-053X(02)00050-8.

Jo

[8] M.S.A. Palma, J.L. Paiva, M. Zilli, A. Converti, Batch phenol removal from methyl isobutyl ketone by liquid – liquid extraction with chemical reaction, Chem. Eng. Process. Process Intensification 46 (2007) 764-768. https://doi.org/10.1016/j.cep.2006.10.003. [9] O. Abdelwahab, N.K. Amin, E.Z. El-ashtoukhy, Electrochemical removal of phenol from oil refinery wastewater, J. Hazard. Mater. 163 (2009) 711-716. https://doi.org/10.1016/j.jhazmat.2008.07.016. [10] S. Ansaloni, M. Castellino, A. Massa, S. Hern, N. Russo, D. Fino, Enhanced electrochemical oxidation of phenol over manganese oxides under mild wet air oxidation conditions, Electrochim. Acta 273 (2018) 53-62. https://doi.org/10.1016/j.electacta.2018.03.178.

20

[11] Y. Park, G.A. Ayoko, R. Kurdi, E. Horváth, J. Kristóf, R.L. Frost, Adsorption of phenolic compounds by organoclays : Implications for the removal of organic pollutants from aqueous media, J. Colloid. Interf. Sci. 406 (2013) 196-208. https://doi.org/10.1016/j.jcis.2013.05.027. [12] Y. Li, X. Hu, X. Liu, Y. Zhang, Q. Zhao, P. Ning, S. Tian, Adsorption behavior of phenol by reversible surfactant-modi fi ed montmorillonite : Mechanism, thermodynamics, and regeneration, Chem. Eng. J. 334 (2018) 1214-1221. https://doi.org/10.1016/j.cej.2017.09.140. [13] Md. Ahmaruzzaman, Adsorption of phenolic compounds on low-cost adsorbents : A review, Adv. Colloid. Interfac. 143 (2008) 48-67. https://doi.org/10.1016/j.cis.2008.07.002.

ro

of

[14] U.F. Alkaram, A.A. Mukhlis, A.H. Al-dujaili, The removal of phenol from aqueous solutions by adsorption using surfactant-modified bentonite and kaolinite, J. Hazard. Mater. 169 (2009) 324332. https://doi.org/10.1016/j.jhazmat.2009.03.153.

-p

[15] M. Abatal, M. T. Olguin, Evaluating of effectiveness of a natural and modified surface mexican clinoptilolite-rich tuff in removing phenol and p-Nitrophenol from aqueous solutions, Environ. Prot. Eng. 38 (2012) 53-65. https://doi: 10.5277/EPE120405.

lP

re

[16] N. Blommaerts, F. Dingenen, V. Middelkoop, J. Savelkouls, M. Goemans, T. Tytgat, S.W. Verbruggen, S. Lenaerts, Ultrafast screening of commercial sorbent materials for VOC adsorption using real-time FTIR spectroscopy, Sep. Purif. Technol. 207 (2018) 284-290. https://doi.org/10.1016/j.seppur.2018.06.062.

ur na

[17] I. Anastopoulos, I. Pashalidis, A. Hosseini-Bandegharaei, D.A. Giannakoudakis, A. Robalds, M. Usman, L.B. Escudero, Y. Zhou, J.C. Colmenares, A. Núñez- Delgado, E.C. Lima, Agricultural biomass/waste as adsorbents for toxic metal decontamination of aqueous solutions, J. Mol. Liq. 295 (2019) 111684 (1-17). https://doi.org/10.1016/j. molliq.2019.111684. [18] I. Anastopoulos, A. Robalds, H.N. Tran, D. Mitrogiannis, D.A. Giannakoudakis, , A. Hosseini Bandegharaei, G.L. Dotto, Removal of heavy metals by leaves-derived biosorbents. Environ. Chem. Lett. 17 (2019) 755-766. https://doi.org/10.1007/s10311-018-00829-x.

Jo

[19] D. A. Giannakoudakis, A. Hosseini-bandegharaei, P. Tsafrakidou, K.S. Triantafyllidis, M. Kornaros, I. Anastopoulos, Aloe vera waste biomass-based adsorbents for the removal of aquatic pollutants : A review, J. Environ. Manage. 227 (2018) 354–364. https://doi.org/10.1016/j.jenvman.2018.08.064. [20] A. Khaled, A. El Nemr, A. El-sikaily, O. Abdelwahab, Treatment of artificial textile dye effluent containing Direct Yellow 12 by orange peel carbon, Desalination 238 (2009) 210–232. https://doi.org/10.1016/j.desal.2008.02.014. [21] M.A. Ahmad, N.K. Rahman, Equilibrium , kinetics and thermodynamic of Remazol Brilliant Orange 3R dye adsorption on coffee husk-based activated carbon, Chem. Eng. J. 170 (2011) 154– 161. https://doi.org/10.1016/j.cej.2011.03.045. 21

[22] J. Acharya, J.N. Sahu, B. K. Sahoo, C.R. Mohanty, B.C. Meikap, Removal of chromium (VI) from wastewater by activated carbon developed from Tamarind wood activated with zinc chloride, Chem. Eng. J. 150 (2009) 25–39. https://doi.org/10.1016/j.cej.2008.11.035. [23] Ü. Geçgel, H. Kolancılar, Adsorption of Remazol Brilliant Blue R on activated carbon prepared from a pine cone, Nat. Prod. Res. https://doi.org/10.1080/14786419.2010.541878.

of

[24] C. Namasivayam, D. Kavitha, Removal of Congo Red from water by adsorption onto activated carbon prepared from coir pith , an agricultural solid waste, Dyes pigm. 54 (2002) 47–58. https://doi.org/10.1016/S0143-7208(02)00025-6.

ro

[25] B. Royer, N.F. Cardoso, E.C. Lima, J.C. Vaghetti, N.M. Simon, T. Calvete, R.C. Veses, Applications of Brazilian pine-fruit shell in natural and carbonized forms as adsorbents to removal of methylene blue from aqueous solutions — Kinetic and equilibrium study, J. Hazard. Mater. 164 (2009) 1213–1222. https://doi.org/10.1016/j.jhazmat.2008.09.028

re

-p

[26] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Adsorption of basic dye using activated carbon prepared from oil palm shell : batch and fixed bed studies, Desalination 225 (2008) 13-28. https://doi:10.1016/j.desal.2007.07.005.

lP

[27] A.A. Spagnoli, D.A. Giannakoudakis, S. Bashkova, Adsorption of methylene blue on cashew nut shell based carbons activated with zinc chloride : The role of surface and structural parameters, J. Mol. Liq. 229 (2017) 465–471. https://doi.org/10.1016/j.molliq.2016.12.106.

ur na

[28] A.M. Aljeboree, A.N. Alshirifi, A.F. Alkaim, Kinetics and equilibrium study for the adsorption of textile dyes on coconut shell activated carbon, Arab. J. Chem. 10 (2017) S3381–S3393. https://doi.org/10.1016/j.arabjc.2014.01.020.

Jo

[29] A. Geczo, D.A. Giannakoudakis, K. Triantafyllidis, M.R. Elshaer, E. Rodríguez-aguado, S. Bashkova, Mechanistic insights into acetaminophen removal on cashew nut shell biomass-derived activated carbons, Environ. Sci. Pollut. Res. (2020) 1-14. https://doi.org/10.1007/s11356-019-075620. [30] G.B. Barin, I. de Fátima Gimenez, L.P. da Costa, A.G. Souza Filho, L.S. Barreto, Influence of hydrothermal carbonization on formation of curved graphite structures obtained from a lignocellulosic precursor, Carbon 78 (2014) 609-612. https://doi.org/10.1016/j.carbon.2014.07.017 [31] K. Gunasekaran, P.S. Kumar, M. Lakshmipathy, Mechanical and bond properties of coconut shell concrete, Constr. Build. Mater. 25 (2011) 92-98. https://doi.org/10.1016/j.conbuildmat.2010.06.053. [32] A.H.P. Vázquez, P. Villegas, Y.F. Sánchez, P.Z. Crescencio, Distribución histórica de las especies del género Haematoxylum (Leguminosae) en la Península de Yucatán, México, basada en ejemplares de herbario, Acta Bot. Mex. 119 (2017) 51-68. http://dx.doi.org/10.21829/abm119.2017.1231. 22

[33] P.C.C. Faria, J.J.M. Orf, M.F.R. Pereira, Adsorption of anionic and cationic dyes on activated carbons with different surface chemistries. Water Res. 38 (2004) 2043-2052. https://doi.org/10.1016/j.watres.2004.01.034. [34] W. Ma, F. Ya, M. Han, R. Wang, Characteristics of equilibrium, kinetics studies for adsorption of fluoride on magnetic-chitosan particle, J. Hazard. Mater. 143 (2007) 296-302. https://doi.org/10.1016/j.jhazmat.2006.09.032.

of

[35] Y.S. Ho, W.T. Chiu, C.C Wang, Regression analysis for the sorption isotherms of basic dyes on sugarcane dust, Bioresour. Technol. 96 (2005) 1285-1291. https://doi.org/10.1016/j.biortech.2004.10.021.

-p

ro

[36] M.J. Puchana-Rosero, E.C. Lima, B. Mella, D. Da Costa, E. Poll, M. Gutterres, A coagulation-flocculation process combined with adsorption using activated carbon obtained from sludge for dye removal from tannery wastewater, J. Chil. Chem. Soc. 63 (2018) 3867-3874. http://dx.doi.org/10.4067/s0717-97072018000103867.

re

[37] T. J. Bandosz, C.O. Ania, Origin and Perspectives of the Photochemical Activity of Nanoporous Carbons, Adv. Sci. 5 (2018) 180029. doi.org/10.1002/advs.201800293.

lP

[38] G.Z. Kyzas, E.A. Deliyanni, K.A. Matis, Graphene oxide and its application as an adsorbent for wastewater treatment, J. Chem. Technol. Biotechnol. 89 (2014) 196-205. https://doi.org/10.1002/jctb.4220.

ur na

[39] D.A. Giannakoudakis, M. Barczak, M. Florent, T.J. Bandosz, Analysis of interactions of mustard gas surrogate vapors with porous carbon textiles, Chem. Eng. J. 362 (2019) 758–766. https://doi.org/10.1016/j.cej.2019.01.064. [40] Z. C. Kampouraki, D. A. Giannakoudakis, E. A. Deliyanni, K. S. Triantafyllidis, Catalytic oxidative desulfurization of a 4,6-DMDBT containing model fuel by metal-free activated carbons: the key role of surface chemistry, Green Chem. 21 (2019) 6685–6698 https://doi.org/10.1039/c9gc03234g.

Jo

[41] W. Kiciński, M. Norek, M. Bystrzejewski, Monolithic porous graphitic carbons obtained through catalytic graphitization of carbon xerogels, J. Phys. Chem. Solids 74 (2012 )101–109. https://doi.org/10.1016/j.jpcs.2012.08.007. [42] M. Sevilla, A. B. Fuertes, Catalytic graphitization of templated mesoporous carbons, Carbon 44 (2006) 468-474 468–474. https://doi.org/10.1016/j.carbon.2005.08.019. [43] M. Sevilla, A. B. Fuertes, Graphitic carbon nanostructures from cellulose, Chem. Phys. Lett. 490 (2010) 63–68. https://doi.org/10.1016/j.cplett.2010.03.011.

23

A. Gutiérrez-Pardo, J. Ramírez-Rico, R. Cabezas-Rodríguez, J. Martínez-Fernández, Effect of catalytic graphitization on the electrochemical behavior of wood derived carbons for use in supercapacitors, J. Power Sources 278 (2015) 18-26. https://doi.org/10.1016/j.jpowsour.2014.12.030. [44]

[45] A. Derylo-marczewska, B. Buczek, and A. Swiatkowski, Applied Surface Science Effect of oxygen surface groups on adsorption of benzene derivatives from aqueous solutions onto active carbon samples, Appl. Surf. Sci. 257 (2011) 9466–9472. https://doi.org/10.1016/j.apsusc.2011.06.036.

of

[46] E. Lorenc-Grabowska, Effect of micropore size distribution on phenol adsorption on steam activated carbons Adsorption 22 (2016) 599–607. https://doi.org/10.1007/s10450-015-9737-x.

ro

[47] P.T. Dhorabe, D.H. Lataye, R.S. Ingole, Removal of 4-nitrophenol from aqueous solution by adsorption onto activated carbon prepared from Acacia glauca sawdust, Water Sci. Technol. 73 (2016) 955-966. https://doi.org/10.2166/wst.2015.575.

-p

[48] X. Kong, H. Gao, X. Song, Y. Deng, Y. Zhang, Adsorption of phenol on porous carbon from Toona sinensis leaves and its mechanism The adsorption performances of phenol onto porous carbon Toona

sinensis,

P06) 70P

https://doi.org/10.1016/j.cplett.2019.137046.

)020P

( 337P

m.tP

LsesehP

.mehC

re

from

lP

[49] A.A. Adeyemo, I.O. Adeoye, O.S. Bello, Adsorption of dyes using different types of clay: a review, Appl. Water Sci. 7 (2017) 543-568. https://doi.org/10.1007/s13201-015-0322-y.

ur na

[50] H. Zaghouane-boudiaf, M. Boutahala, Adsorption of 2,4,5-trichlorophenol by organomontmorillonites from aqueous solutions : Kinetics and equilibrium studies, Chem. Eng. J. 170 (2011) 120–126. https://doi.org/10.1016/j.cej.2011.03.039.

[51] K. Mohanty, D. Das, M. N. Biswas, Adsorption of phenol from aqueous solutions using activated

Jo

carbons prepared from Tectona grandis sawdust by ZnCl2 activation, Chem. Eng. J. 115 (2005) 121– 131. https://doi.org/10.1016/j.cej.2005.09.016.

[52] B.H. Hameed, L.H. Chin, S. Rengaraj, Adsorption of 4-chlorophenol onto activated carbon prepared

from

rattan

sawdust,

Desalination

225

(2008)

185–198.

https://doi:10.1016/j.desal.2007.04.095.

[53] S. Álvarez-torrellas, M. Martin-martinez, H.T. Gomes, G. Ovejero, J. García, Enhancement of 24

p-nitrophenol adsorption capacity through N2-thermal-based treatment of activated carbons, Appl. Surf. Sci. 414 (2017) 424–434. https://doi.org/10.1016/j.apsusc.2017.04.054.

[54] V.C. Srivastava, M.M. Swamy, I.D. Mall, B. Prasad, I.M. Mishra, Adsorptive removal of phenol by bagasse fly ash and activated carbon : Equilibrium, kinetics and thermodynamics, Colloid Surface A 272 (2006) 89-104. https://doi.org/10.1016/j.colsurfa.2005.07.016.

[55] B.H. Hameed, A.A. Rahman, Removal of phenol from aqueous solutions by adsorption onto

of

activated carbon prepared from biomass material, J. Hazard. Mater. 160 (2008) 576–581. https://doi.org/10.1016/j.jhazmat.2008.03.028.

ro

[56] S. Al-asheh, F. Banat, L. Abu-aitah, Adsorption of phenol using different types of activated bentonites, Sep. Purif. Technol. 33 (2003) 1–10. https://doi.org/10.1016/S1383-5866(02)00180-6.

modified

zeolite,

Appl.

Surf.

Sci.

283

(2013)

764–774.

re

https://doi.org/10.1016/j.apsusc.2013.07.016.

-p

[57] A. Dakovi, G.D. Gatta, N. Rotiroti, Characterization of lead sorption by the natural and Fe (III)-

[58] R. Juang, F. Wu, R. Tseng, Mechanism of Adsorption of Dyes and Phenols from Water Using

lP

Activated Carbons Prepared from Plum Kernels, J. Colloid Interface Sci. 227 (2000) 437-444. https://doi.org/10.1006/jcis.2000.6912.

ur na

[59] B.F. Banat, S. Al-asheh, L. Al-makhadmeh, Utilization of Raw and Activated Date Pits for the Removal of Phenol from Aqueous Solutions, Chem. Eng. Technol.: Industrial Chemistry‐ Plant Equipment‐ Process Engineering‐ Biotechnology 27 (2004) 80-86.

[60] B. Zhou, Q. Gao, H. Wang, E. Duan, B. Guo, Preparation, characterization, and phenol

Jo

adsorption of activated carbons from oxytetracycline bacterial residue, J. Air Waste Manage. Assoc. 62 (2012) 1394-1402. https://doi.org/10.1080/10962247.2012.716013.

[61] C. Moreno-Castilla, J. Rivera-Utrilla, M. V. López-Ramón, F. Carrasco-Marín, Adsorption of some substituted phenols on activated carbons from a bituminous coal, Carbon 33 (1995) 845-851.

[62] G. Yang, H. Chen, H. Qin, Y. Feng, Applied Surface Science Amination of activated carbon for enhancing phenol adsorption : Effect of nitrogen-containing functional groups, Appl. Surf. Sci. 293 25

(2014) 299–305. https://doi.org/10.1016/j.apsusc.2013.12.155.

[63] M.F.F. Sze, G. Mckay, An adsorption diffusion model for removal of para-chlorophenol by activated carbon derived from bituminous coal, Environ. Pollut. 158 (2010) 1669-1674. https://doi.org/10.1016/j.envpol.2009.12.003.

[64] J.M. Li, X.G. Meng, C.W. Hu, J. Du, Adsorption of phenol, p-chlorophenol and p-nitrophenol onto

functional

chitosan,

Bioresour.

Technol.

100

(2009)

1168-1173.

of

https://doi.org/10.1016/j.biortech.2008.09.015.

[65] O. Hamdaoui, E. Naffrechoux, Modeling of adsorption isotherms of phenol and chlorophenols

thermodynamic

parameters,

J.

Hazard.

https://doi.org/10.1016/j.jhazmat.2007.01.021.

Mater.

147

(2007)

381-394.

-p

of

ro

onto granular activated carbon. Part I. Two-parameter models and equations allowing determination

re

[66] M. Abatal, M. T. Olguin, Comparative adsorption behavior between phenol and p-nitrophenol by Na- and HDTMA-clinoptilolite-rich tuff, Environ. Earth Sci. 69 (2013) 2691-2698.

Jo

ur na

lP

https://doi.org/10.1007/s12665-012-2091-3.

26