Honeycomb structured activated carbon synthesized from Pinus roxburghii cone as effective bioadsorbent for toxic malachite green dye

Journal of Water Process Engineering 32 (2019) 100931

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Honeycomb structured activated carbon synthesized from Pinus roxburghii cone as effective bioadsorbent for toxic malachite green dye

T

Gaurav Sharmaa,b,c, Shweta Sharmac, Amit Kumara,b,c, Mu. Naushad ,d, Bing Dua, Tansir Ahamadd, Ayman A. Ghfard, Ayoub A. Alqadamid, Florian J.Stadlera ⁎

a

College of Materials Science and Engineering, Shenzhen Key Laboratory of Polymer Science and Technology, Guangdong Research Center for Interfacial Engineering of Functional Materials, Nanshan District Key Lab for Biopolymers and Safety Evaluation, Shenzhen University, Shenzhen 518060, PR China b Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, PR China c School of Chemistry, Shoolini University, Solan 173212, Himachal Pradesh, India d Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia

ARTICLE INFO

ABSTRACT

Keywords: Activated carbon Adsorption Malachite green Waste water Bioadsorbent

Herein, we have demonstrated the designing of activated carbon from Pinus roxburghii cone (PRCAC) by facile carbonization method. The synthesized PRCAC was utilized for the removal of malachite green (MG), a basic dye from aqueous medium. The surface properties of PRCAC were elucidated by N2 adsorption- desorption and point zero charge studies. Quite attractive adsorption results were obtained by PRCAC due to it’s high surface area (202 m2/g). Influence of numerous elements; concentration of MG, pH, time, adsorbent dose and temperature were studied in detail. Low acidic medium found to be preferential for the adsorption process. The adsorption isotherm studies were also carried out and results showed that the data fitted well to Langmuir isotherm. Maximum adsorption capacity of PRCAC was found to be 250 mg/g. Different kinetic model were also studied for the undertaken adsorption reaction.

1. Introduction Number of pollutant related problems has raised concern among people due to their high toxicity and bio-accumulative nature. During the last few decades there have been a marked increase in use of toxic dyes by the paper, leather and textile industries [1]. Consumption of water containing dyes can cause serious health issues such as neurological, renal, reproductive and intestinal dysfunctionality, etc [2,3]. Industrial dye such as malachite green (MG) contributes to water and soil pollution. MG is mainly used in leather, cosmetics, pharmaceutical and plastic industries [4,5]. Color of dyes act as a shield and affects the penetration of sunlight into water. Decrease in sunlight availability decreases the photosynthesis process, which ultimately affects the quality of aquatic life [6,7]. MG is dangerous to freshwater animals in acute or chronic disclosure and is extremely noxious to mammalian cells and organs like kidney, liver, spleen, lung and skin. It also forms carcinogenic degradation products which further results in secondary pollution that affects the quality and purity of water [8–10]. So, their removal from the water bodies is necessary so to make the water worth of usage.

⁎

Several technologies have been used or explored for their removal from water. These include reverse osmosis, adsorption, biosorption [11–13], photocatalytic degradation [14–17], ion exchange [18,19], electrochemical degradation [20], integrated adsorption/precipitation process [21], combined chemical/ biological degradation [22] and Fenton-biological treatment [23–25], etc. Adsorption is a well-established method used for water detoxification applications [26]. It has been quite in use in the recent years due to its potential to use renewable materials, application flexibility, designing simplicity, operation simplicity and applicability in elimination of various types of toxic pollutants [27–29]. Its major advantages is its ability of non-production of toxic end products [30–32]. Plenty of approaches have been put forward for the development and application of cheaper and active adsorbents [33–35]. Numerous researchers have suggested many nonconventional low-cost adsorbents [36–38] which include agricultural and industrial waste materials for the adsorption of persistent pollutants present in water and air [39–41]. Activated carbon (AC) is considered to be the best among current adsorbents as a universal multipurpose material because of its exceptional properties [42]. It has potential applications in nuclear, food

Corresponding author. E-mail address: [email protected] (M. Naushad).

https://doi.org/10.1016/j.jwpe.2019.100931 Received 24 June 2019; Received in revised form 20 August 2019; Accepted 26 August 2019 2214-7144/ © 2019 Elsevier Ltd. All rights reserved.

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processing, automobile, chemical, pharmaceuticals, petroleum, vacuum manufacturing and mining industries [21,43]. It derive its supreme adsorptive abilities from its internal pore structure which can be categorized into microporous, mesoporous and macroporous [44–46]. Due to its extraordinary surface area and porous structure, AC is a potential adsorbent for extensive range of persistent pollutants. For it’s activation, two different approaches; physical and chemical are widely employed. The major difference between two approaches is the temperature requirement and activating agents. Physical activation implicates the activation by oxidizing gases (air, carbon dioxide and steam, etc.) at temperature range of 650–900 °C. However, in case chemical approach, NaOH, FeCl3 and KOH are used as the activating agent with low temperature requirement in range of 300–500 °C. Temperature conditions effects its porous nature. Chief perks of chemical over physical approach includes large surface area, low temperature requirement and minimized reaction completion time. In the present paper, Pinus roxburghii cone based activated carbon (PRCAC) was synthesized by carbonization. PRCAC had high adsorption capacity due to it’s mesoporous structure and employed for the adsorption of MG dye from aqueous solution. Pictorial presentation of PRCAC synthesis and it’s use for MG adsorption has been presented in Scheme 1. The role of several adsorption parameters influencing the adsorption rate was also analyzed. Reusability studies of PRCAC upto 5 cycles were also carried out.

Emmett Teller (Quanta chrome Autosorb 1C BET Surface Area & Pore Volume Analyzer) and Muffle furnace (Instrument and Chemical Pvt. Ltd., New Delhi, India).

2. Experimental

FTIR spectra of PRCAC before and after adsorption of MG molecules were carried out using Perkin Elmer Spectrum FTIR spectrophotometer operated in the range of 4000 to 450 cm−1 with resolution of 4 cm-1. Surface and morphological identification of PRCAC before and after adsorption of MG molecules was performed by F E I Quanta FEG 200 SEM under an operating voltage of 20 kV [47]. Total surface area and pore information of synthesized PRCAC was analyzed by Quanta chrome Autosorb 1C BET Surface Area & Pore Volume Analyzer functioned at 77 K. PRCAC was degassed at 200 °C under vacuum before starting N2 adsorption. The pH zero point of charge is a characteristic technique for determining the point of neutral charge on the surface. pHpzc of PRCAC was determined by pH drift method [48]. Batch experiments were performed in which 50 mL of 0.01 M NaCl solutions were mixed with 150 mg PRCAC with solution pH 2, 4, 6, 8 and 10. All the test sets were agitated at 240 rpm for 48 h in an incubator shaker at 25 °C. The final pH was noted after 48 h after equilibrium point

2.2. Synthesis of activated carbon In the present study, cone derived from Pinus roxburghii was used as carbon precursor and activated by acetic acid. Firstly, derived cone was cleaned properly using double distilled water, dried in hot air oven at 80 °C for 12 h and then converted into small pieces. Afterwards, it was carbonized at 800 °C with ramping rate 10 °C/min for 80 min in nitrogen atmosphere. After cooling to room temperature, remained out char was properly crushed in agate mortar, washed with double distilled water and dried in hot air oven at 50 °C. Chemical activation of carbonized powder was carried out using 0.1 M acetic acid solution. Synthesized powdered char was immersed into acetic acid and then stirred rapidly for 5 h. Afterwards, the powder was dried and again activated at 600 °C for 1 h in N2 atmosphere at ramping rate of 10 °C/min. After cooling to room temperature, the powder was thoroughly washed with double distilled water several times and dried in vacuum hot air oven at 50 °C. The obtained dried PRCAC powder was used for further studies. 2.3. Characterization

2.1. Apparatus and chemicals used The cones used here were taken from local Pinus roxburghii trees in Solan, Himachal Pradesh, India. Acetic acid (CH3COOH), Sulphuric acid (H2SO4) and sodium hydroxide (NaOH) were bought from Central Drug House, Solan, India. Malachite green (MG) was obtained from Loba Chemie., Pvt Ltd, Solan, India. All chemicals and reagents were of analytical grade and used without any treatment. Double distilled water was used for the solution preparation. Instruments used in the presents study were: Fourier Transform Infrared (FTIR) spectrophotometer (Perkin Elmer Spectrum), Scanning Electron Microscope (F E I Quanta FEG 200), Electronic balance (Mxrady Lab Solutions Pvt. Ltd., New Delhi, India), double beam UV–vis spectrophotometer (Perkin Elmer LAMBDA 950), Bruaneur-

Scheme 1. Pictorial presentation of synthesis of PRCAC and its utilization for adsorption of MG. 2

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Table 1 Specifications of Malachite green dye. Name

Abbreviation

Malachite green

MG

Structure

acquired. Plot between initial and final pH gives the pHpzc of PRCAC [49].

Ce m

×V

λmax

364.911 g/mol

1.4 nm × 1.1 nm × 0.5 nm

620 nm

Co

Ce Co

× 100

(2)

Exploration of equilibrium data is important for specifying the type of adsorption and nature of bonding between the adsorbate molecules and adsorbent. It also helps in understanding the operating mechanism in the adsorption process. In this study, Langmuir, Freundlich, Temkin and Redlich- Peterson isotherms have been investigated for understanding the nature of adsorption. For kinetic studies, 20 mg PRCAC was dispersed into 60 ppm MG solution and placed in a thermostatic shaker with conditions as mentioned before. The aliquots of sample were taken at various time intervals between 10–80 min, centrifuged and analyzed by UV–vis spectrophotometer.

Batch adsorption experiments were performed for analyzing the adsorption capability of PRCAC for MG. Effect of various factors such as MG concentration (30–90 ppm), contact time (10–80 min), adsorbent dose (10–50 mg), temperature (25–45 °C) and pH (3–8) were analyzed. For adjusting the pH, 0.1 M NaOH and HNO3 solutions were employed. Table 1 shows the important specifications of MG dye. In typical process, 20 mg PRCAC was added to 30 mL of 60 ppm MG solution. All the experiments were performed in thermostatic shaker at 25 °C with 200 rpm. After equilibrium point, solution was centrifuged at 3600 rpm for 5 min and remained MG concentration was analyzed by UV–vis spectrophotometer. Percent uptake and amount of adsorption per unit mass of PRCAC at equilibrium; qe (mg/g) was evaluated by following equations [50,51]:

Co

Size

% Adsorption =

2.4. Adsorption of MG molecules onto PRCAC

qe =

Molecular weight

2.5. Desorption studies Desorption studies are important for generalizing the reusable nature of synthesized material. In typical process, MG was firstly adsorbed onto PRCAC. After adsorption, the sample was washed with double distilled water and dried in hot air oven. Afterwards, for desorption studies, the dried sample was dipped into 2 different solutions of 0.1 M HCl and 0.1 M NaOH. After reaction completion (10 h), the %

(1)

Fig. 1. FTIR spectra of PRCAC (a) before adsorption; (b) after adsorption of MG and SEM images of PRCAC (c) before adsorption (d) after adsorption of MG. 3

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Fig. 2. (a) Nitrogen adsorption- desorption isotherm of PRCAC and (b) pHpzc of PRCAC.

adsorbed dye (ppm), respectively.

Table 2 Textural properties of PRCAC. Material

Surface area (m2/g)

Pore volume (cm3/g)

Pore size (nm)

PRCAC

202

8.57

5.2

3. Result and discussion 3.1. Characterization

desorption was calculated by [52]:

% Desorption =

Cd × 100 Ca

PRCAC before and after adsorption of MG molecules has been characterized by FTIR and SEM. The changes in the absorbance of functional groups before and after the adsorption are shown in Fig. 1(a, b). Fig. 1(a) shows the adsorption peaks of PRCAC before adsorption. Peak at 2976 cm−1 is due to the C–H stretching [53]. However, C]C

(3)

Where Cd and Ca denotes the concentration of desorbed dye and

Fig. 3. Optimization of adsorption parameters for adsorption of MG onto PRCAC (a) Concentration with time; (b) Temperature; (c) pH and (d) adsorbent dose. 4

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Scheme 2. Probable interaction mechanism of PRCAC with MG.

stretching band has been ascertained by the peak at 1595 cm−1 [54]. Peaks between 700 – 470 cm−1 are assigned to the CeC stretching. Peak at 3443 cm−1 is ascribed to the presence of hydroxyl groups [55]. Fig. 1(b) shows the peaks of PRCAC after adsorption of MG. Malachite green shows characteristic finger print region in the range of 1550500 cm-1 for the monosubstituted and para-substituted benzene rings [56]. A sharp peak at 2868 cm−1 is observed for the C–H stretching of −CH3 groups [57]. The peak at 1550 cm−1 is characteristic for the C]C aromatic stretching of benzene ring [58,59]. All the characteristic peaks of the PRCAC shows the change after adsorption of MG. The morphological analysis of PRCAC before and after adsorption of MG has been determined by SEM and the results are presented in Fig. 1(c, d). SEM depicts the highly porous nature of PRCAC (Fig. 1(c)). High porosity introduced can be due to the activation treatment and temperature effect. Fig. 1(d) shows the surface of PRCAC after adsorption of MG molecules. Adsorption onto the surface and into the pores are clearly visible. N2 adsorption- desorption isotherm of PRCAC has been presented in Fig. 2(a). Graph indicate the mesoporous nature with type- IV isotherm. Table 2 revealed the surface area of PRCAC to be 202 m2/g and total pore volume of 8.57 cm3/g. The average pore size has been found to be 5.2 nm. Chemical activation and high synthesizing temperature can be considered as the factor for the obtained surface area and pore size. The size of MG molecules as reported is (1.4 nm × 1.1 nm × 0.5 nm) [60], which shows that it can be easily adsorbed onto PRCAC surface and into the pores and is thus considered as the model pollutant. Electrostatic interactions or repulsions play crucial role in adsorption process. pHpzc of PRCAC has been found to be 8.4 which implies the positively charge

surface of PRCAC below this value and negatively charge surface above it (Fig. 2(b)). 3.2. Adsorption of MG onto PRCAC The mesoporous nature of PRCAC allowed the adsorption of dye onto its surface through electrostatic interactions. The adsorbed PRCAC can easily be removed from the water by filtration, thus reducing the secondary pollution. The effects of various factors has been studied and reported in Fig. 3(a–d). 3.2.1. Effect of time and MG concentration Adsorption of MG by PRCAC was highly affected by its initial concentration. Variation in % adsorption of MG w.r.t contact time at different MG concentrations (30, 60 and 90 ppm) has been presented in Fig. 3(a). Results have generalized that the uptake of MG was constantly increasing upto equilibrium, viz. 60 min, and thereafter became steady. Variation of MG uptake with changes in initial concentrations has been observed to be very fast in the initial stages due to high ratio of PRCAC active site to MG molecules and after equilibrium point attainment; no significant change has occurred. This can probably be due to the saturation of the maximum adsorption limit onto PRCAC. Maximum uptake has been observed at 60 ppm initial MG concentration after 60 min. 3.2.2. Effect of temperature and pH It can be generally found that rise in temperature strengthens the rate of adsorption [61,62]. However, in the present study, temperature 5

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Fig. 4. Adsorption isotherms for MG adsorption onto PRCAC (a) Langmuir; (b) Freundlich; (c) Temkin and (d) Redlich-Peterson models.

studied at various pH values in the range of 3-8. Results of pH effect on percent adsorption are shown in Fig. 3(c) and it has been found that maximum adsorption occurred at pH 6. The pH effect can be explained in relation to the pHpzc value. The pHpzc value of PRCAC as calculated was 8.4 denoting that at pH 6 the surface to be positively charged. At this pH, MG molecules are either neutral or slightly negatively charged thus showing their maximum interactions with PRCAC ultimately resulting in high adsorption rate.

Table 3 Adsorption isotherm constant and parameter values. Langmuir

MG

Freundlich

MG

Temkin

MG

RedlichPeterson

MG

qm KL R2

250 0.004 0.995

KF 1/n R2

1.463 0.715 0.986

Bt KT R2

25.16 0.311 0.976

β A R2

0.280 −0.683 0.915

has different effects on the adsorption of MG onto PRCAC. Fig. 3(b) signifies the maximum adsorption at 25 °C and further temperature increase decreased the % uptake signifying the exothermic adsorption process. Solution pH influences the rate of adsorption to a greater influence as it governs the electrostatic interactions between the adsorbent and adsorbate [63]. Effect of pH on MG adsorption onto PRCAC has been

3.2.3. Effect of adsorbent dose The effect of varying adsorbent dosage has been analyzed for adsorption of MG in range of 10–50 mg. Adsorption of MG molecules increased upto 20 mg (Fig. 3(d)) and then decreased. Increase in concentration of PRCAC above 20 mg decreased the adsorption rate which may be due to the agglomeration of the PRCAC particles. Decrease may also be due the reduction in the accessibility to active adsorption sites.

Fig. 5. Adsorption kinetic studies for adsorption of MG onto PRCAC (a) Pseudo-first order and (b) Pseudo-second order models. 6

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Redlich-Peterson isotherm is a three parameter model. It is basically a combined version of two models; Langmuir and Freundlich and it’s linear form is given as [70]:

Table 4 Adsorption kinetics constant and parameter values. Pseudo- First order MG Pseudo- second order MG

k1 0.048 k2 0.003

qe 15.55 qe 34.48

R2 0.826 R2 0.980

ln

3.3. Adsorption isotherms In the present study, in order to derive the exact mechanism of adsorption followed by MG molecules onto PRCAC, below presented isotherms models were employed. According to Langmuir isotherm, monolayer adsorption of adsorbate molecules onto the adsorbent of homogeneous energy sites takes place. Linearized form of Langmuir isotherm is [65,66]:

1 logCe n

Adsorption kinetic studies helps in determining the rate and physical or chemical nature of adsorption process. Pseudo-first order kinetics is based on the hypothesis that the mechanism following the adsorption is more inclined towards the physisorption nature [71]. It can be explained by the following equation:

(4)

ln(qe

qt ) = lnqe

k1 ×t 2.303

(8)

Where k1 is the pseudo-first order rate constant and its value was calculated from the slope of linear plot between time (t) versus log (qe - qt). Pseudo-second order kinetics signifies the inclination of the adsorption process towards chemisorption [72]. Equation given by Ho and McKay for pseudo second order kinetics is given as:

(5)

The value of 1/n determines the type of adsorption process which can be evaluated from the linear plot of log qe and log Ce. Temkin isotherm model assumes that heat of adsorption in the layer would reduce linearly instead of logarithmic. Linear form of this model is plotted between qe and lnCe and is given by the following equation [69]:

qe = Bt ln(KT ) + Bt ln(Ce )

(7)

3.4. Adsorption kinetics

Here, the values of qm and KL were calculated from the slope and intercept of the isotherm which was plotted between Ce/qe versus Ce [67]. Freundlich isotherm denotes the multilayer adsorption on the energetically heterogeneous adsorbent surface [68]. Its linear equation is given as:

log qe = logkf +

lnA

Linear plot of ln Ce/qe versus ln Ce helps in evaluating the RedlichPeterson constants, where β and A are determined from the slope and intercept, respectively. Fig. 4 shows the isotherm studies and values of various constants derived from them were presented in Table 3. Assessment of R2 values of all models have generalized the maximum ability of Langmuir isotherm model in better explaining the adsorption process. Maximum adsorption capacity of PRCAC for MG as calculated from Langmuir model is 250 mg/g. All isotherm studies have been analyzed at room temperature. Langmuir isotherm constant, KL specifies the extent of interactions between adsorbent and adsorbate molecules which ultimately concludes the extent of adsorption. In Freundlich isotherm, the value of 1/n specifies the ability of an adsorbent for a specific adsorbate and also the favorability of the undertaking adsorption process [53]. In our case, the value of 1/n is 0.715, less than 1 which indicates that the adsorption process was favorable at low as well as at high adsorbate concentrations.

3.2.4. Adsorption mechanism MG is a green colored dye having positively charged surface. Synthesized PRCAC’s surface was enriched with functional groups such as −COOH and −OH. Electrostatic and π-π interactions could be considered to be the major ones favoring the MG adsorption onto PRCAC [64]. The pH of the dye solution also influenced the interaction extent since the surface properties of PRCAC varied extensively under different pH solutions. Scheme 2 presents the probable interaction mechanism between MG molecules and PRCAC.

Ce C 1 = e + qe qm KL qm

Ce = lnCe qe

t 1 t = + qt k2 qe 2 qe

(9)

Where k2 specifies the rate constant for pseudo-second-order kinetics (g/mg/min); qt is the measure of MG adsorbed at time t (mg/g) and qe is the amount of MG adsorbed at equilibrium (mg/g). Applicability of kinetic model has been ascertained by the comparison of correlation coefficient value. Results indicated the suitability

(6)

where Temkin isotherm equilibrium binding constant; KT is determined from the intercept and heat of sorption constant; Bt from the slope.

Fig. 6. Reusability studies of PRCAC for consecutive 5 cycles. 7

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Scheme 3. Schematic presentation of adsorption of MG onto PRCAC followed by desorption for reusability studies. Table 5 Comparison of MG adsorption ability of PRCAC with already reported AC having different precursors. Precursor

Activator

Reaction conditions

Maximum adsorption capacity (mg/g)

Reference

Oil Palm Fruit Fibre

KOH

353.43

[73]

Borassus aethiopum flower

H2SO4

48.23

[74]

Cocoa (Theobroma Cacao) Shell

H2SO4

37.03

[75]

Rice husk

Oxalic acid

71.49

[76]

Pinus roxburghii cone

Acetic acid

Concentration = 150 mg/L pH = 6 Temperature=60 °C Concentration = 100 mg/L pH = 6.87 Temperature=40 °C Concentration=80 mg/L pH = 7 Temperature = 35C Concentration = 100 mg/L pH = 7 Temperature = 40 Concentration=60 ppm; pH = 6; Temperature=25 °C

250

Present study

of pseudo- second order in describing the absorption process and various obtained has been presented in Fig. 5(a, b) and Table 4. In addition, intraparticle diffusion model was also employed for the presented adsorption process. It helps in specifying the exact mechanism. It is explained by the following equation:

qt = kid t

1

2

+C

model for explaining the current adsorption process. 3.5. Reusability Desorption studies were performed in two different solutions; 0.1 M HCl and NaOH. Results presented in Fig. 6(a) have generalized that maximum desorption rate of 77% was perceived in case of 0.1 M HCl in comparison to 58% in case of 0.1 M NaOH solution after 10 h. High rate in case of HCl solution can probably be due to the H+ ions that interacted strongly with the surface functional groups of PRCAC and helped in the desorption of adsorbed dye. The reusability of PRCAC was evaluated for MG adsorption and results have been presented in Fig. 6(b). In typical process, MG

(10)

Where kid represents the intraparticle diffusion rate. Graph for intraparticle model shows the two step adsorption mechanism (Fig. 5(c)). In the step, bulk diffusion across the surface and second step for the surface adsorption. However, extension of the graph doesn’t make it pass thorough the origin indicating this model wasn’t the probable 8

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adsorption experiments were firstly carried out for 6 h and then filtered and washed with double distilled water. Afterwards, the adsorbed MG onto PRCAC was desorbed using 0.1 M HCl solution. Desorbed PRCAC was again filtered and utilized for the adsorption again. Same procedure was followed and percent adsorption activity was determined after each cycle. Adsorption followed by desorption experiments were performed for consecutive 5 times. Results presented have shown that adsorption capacity decreased to 83% from 93% after 5 cycles indicating appreciable reusable ability of PRCAC for adsorption of MG molecules. Schematic presentation of adsorption of MG onto PRCAC followed by desorption for reusability studies has been presented in Scheme 3. Table 5 presents the comparison of MG adsorption ability of PRCAC with already reported AC having different precursors.

[16]

[17] [18] [19]

[20]

4. Conclusion

[21]

Current paper presents the synthesis of Pinus roxburghii cone based activated carbon by carbonization and it’s use for the adsorptional exclusion of MG from the aqueous medium. Existence of −COOH and −OH groups on the PRCAC surface enhanced the adsorption process. The structure of PRCAC before and after adsorption was characterized to explore it’s structure and bonding. BET analysis showed surface area of PRCAC to be 202 m2/g and pore size 5.2 nm. Adsorption of MG followed pseudo-second order kinetics. Monolayer adsorption followed by MG was elucidated by the high R2 value of Langmuir isotherm. Presented data aid for the designing of bioadsorbents for the removal of lethal contaminants from the water bodies.

[22] [23] [24] [25] [26] [27] [28]

Acknowledgements

[29]

The authors extend their appreciation to the Deanship of Scientific Research at King Saud University for funding this work through research group no. RG-1436-034.

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