Environmental Research 214 (2022) 114044

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Polyethylene glycol functionalized reduced graphene oxide coupled with

zinc oxide composite adsorbent for removal of phenolic wastewater
Dibya Ranjan Rout, Hara Mohan Jena *
Department of Chemical Engineering, National Institute of Technology, Rourkela, 769008, Orissa, India

A R T I C L E I N F O A B S T R A C T

Keywords: The development of agricultural activities and industrialization recently has various adverse impacts on living
Organic pollution organisms. The ever-increasing problem of organic pollution has been an environmental concern to the com­
Phenol munity. Among these, phenolic pollutants like 2,4–dichlorophenol (2,4–DCP), phenol, 2–chlorophenol (2–CP),
Zinc oxide
and bisphenol–A (BPA) are priority toxic pollutants that are continuously released into environment from many
Polyethylene glycol
Reduced graphene oxide
industries. In this work, a biocompatible zinc oxide incorporated polyethylene glycol functionalized reduced
Endothermic graphene oxide composite (RGO-PEG-ZnO) was synthesized and explored for the adsorptive removal of toxic
phenolic pollutants from water. The optimized adsorption parameters were solution pH 7, adsorption time 60
min, temperature 25 ◦ C, and dosage 0.25 g/L. The isotherms were well fitted by the Langmuir model for BPA and
phenol, whereas for 2–CP, and 2,4–DCP, Freundlich was the best-fitted model, and the maximum uptake of BPA,
phenol, 2–CP, and 2,4–DCP were 485.756, 511.248, 531.804, 570.641 mg/g, respectively. The kinetic data for
all the phenolic pollutants follow the pseudo-second-order model. The thermodynamic analysis shows that
Gibb’s free energy (ΔGo) values for all the pollutants were negative, confirming that the process was sponta­
neous. The positive values of change in enthalpy (ΔHo) 28.261, 37.205, 46.182, and 61.682 kJ/mol for BPA,
phenol, 2–CP, and 2,4–DCP, respectively, confirm that the above adsorption process was endothermic. The
composite can be used for up to five cycles with a small reduction in the removal percentage. Adsorption per­
formance of the synthesized composite for synthetic industrial effluents shows that up to 86.54% removal
occurred in 45 min adsorption time. Based on the remarkably rapid adsorption and high adsorption capacity,
RGO-PEG-ZnO composite can be considered an efficient adsorbent for treating phenolic pollutants from
wastewater.

1. Introduction long period (Li et al., 2013).

The wastewater from some chemical industries contains substantial
The release of toxic hazardous pollutants and effluents from amounts of phenolic pollutants, among the notorious chemicals formed
anthropogenic activities and industrial operations into water has naturally and generated anthropogenically in the environment. Pollut­
become a severe environmental issue and public concern (Rasheed et al., ants like bisphenol-A (BPA), phenol, 2,4–dichlorophenol (2,4–DCP), and
2019). In recent times, there has been increased apprehension among 2–chlorophenol (2–CP) are considered the most toxic pollutants (Pani­
scientists and researchers around the world concerning the effects of grahy et al., 2022). The physicochemical properties of these four toxic
hazardous pollutants in the water system on wildlife, aquatic, and pollutants are listed in Table S1. Chlorophenols like 2,4–DCP and 2–CP
human beings. Phenolic pollutants in surface water and groundwater are formed by the reaction of phenols with disinfecting chlorine
have been considered highly toxic due to their high toxicity, poor nat­ (Núñez-Gaytán et al., 2010). These chemicals are used in paper, dyes,
ural biodegradation, long-term ecological damages, and high oxygen petrochemicals, antioxidants, plastics, wood preservatives, waste
demand (Zhu et al., 2007). The US Environmental Protection Agency incineration, and pesticide industries (Jing et al., 2021). In addition,
(USEPA) has listed phenolic pollutants as a priority ones due to their these are produced as byproducts during the chlorination disinfection of
bio-recalcitrant and acute toxic nature, toxic effects on animals and drinking water as well as bleaching of pulp with chlorine (Ram et al.,
human beings, and stickiness in the aquatic environment over a very 2020). Due to the presence of chlorine functional groups in 2–CP and 2,

* Corresponding author.
E-mail addresses: [email protected] (D.R. Rout), [email protected], [email protected] (H.M. Jena).

https://doi.org/10.1016/j.envres.2022.114044
Received 3 March 2022; Received in revised form 31 July 2022; Accepted 2 August 2022
Available online 17 August 2022
0013-9351/© 2022 Elsevier Inc. All rights reserved.
D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

4–DCP, even at low concentrations, these are very hazardous (Badu properties than RGO. Polyethylene glycol is a synthetic polymer derived
Latip et al., 2021). Chlorophenols and phenols are poisoning and dam­ from petroleum with many applications. PEG is low-cost and environ­
age human skin, lungs, kidneys, liver, and digestive tract (Anku et al., mentally friendly, and the results of the biological evaluation showed
2017). Whereas BPA is an endocrine disruptive chemical (EDC) and is that PEG is non-toxic, eco-friendly, and biocompatible, making it a su­
extensively used in producing a wide variety of consumer products, perior additive in the water purification industry (Keihan et al., 2017; Li
polycarbonate plastics, and epoxy resins (Encarnação et al., 2019; et al., 2019; Tian et al., 2018; Zavastin et al., 2010). On the other hand,
Monneret, 2017). Continuous exposure to BPA can potentially result in nano-sized zinc oxide (ZnO) has very remarkable properties such as
harmful health effects, including developmental and neurological dis­ chemical and physical stability, non-toxic, eco-friendly, high specific
orders, metabolic syndrome disorders, cardiovascular diseases (CVD), surface area, mild operational conditions, biodegradability, low cost,
male infertility, adverse immune effects, congenital disabilities, and efficient decomposition of organic compounds, and natural abundance
cancerous tumors (Chouhan et al., 2014). Therefore, cost-effective, (Zbair et al., 2018). The ZnO is extra specific for eliminating anionic
efficient, and quick treatment methods are required to remove the organic compounds because of its high point of zero charges (pHPZC =
phenolic contaminants from the wastewater before that released into the 9.3–10.5) and its favourable electrostatic attraction to various anionic
natural water body. particles (Fatehah et al., 2014). These remarkable properties make ZnO
Various conventional techniques have been used for the treatment of particles a better adsorbent material for the removal of phenolic
phenolic pollutants from wastewater, like solvent extraction (Poonguz­ pollutants.
hali et al., 2021), chemical oxidation (Hadi et al., 2021), photocatalytic In order to reduce the environmental hazards brought by the
degradation (Dong et al., 2017; Margaret et al., 2021), electrochemical phenolic pollutants into the wastewater as much as possible, polymers
coagulation (Olya and Pirkarami, 2013), biological degradation (Hed­ with low toxicity and good biocompatibility are the ideal modification
bavna et al., 2016), ion exchange (Camacho et al., 2021), and adsorption choice for synthesizing adsorbents. Thus considering all the advantages
(Abd Razak et al., 2021; Al Bsoul et al., 2021; de Lima et al., 2021; and disadvantages of the RGO, PEG, and ZnO an effort has been made to
Hamad, 2021; Rout and Jena, 2022a). However, most of these methods synthesize novel PEG functionalized RGO coupled with ZnO (RGO-PEG-
have limited application due to their high cost, the longer time required ZnO) composite through calcination at low temperature. It has been
to attain higher efficiency, and the production of unnecessary secondary estimated that modification of the RGO-PEG solution with ZnO could
pollutants. A thorough review of the literature suggests that adsorption enhance the adsorptive performance of BPA, phenol, 2,4–DCP, and 2–CP
is a promising method for wastewater treatment. It has many advantages from the aqueous solution in a batch study. The physicochemical
over other methods like high removal efficiency, cost-effectiveness, properties of the prepared RGO-PEG-ZnO composite have been charac­
operational simplicity, design simplicity, insensitivity to toxic pollut­ terized using EDAX, FESEM, BET surface area analyzer, XRD, BJH pore
ants, and application flexibility (Xiang et al., 2021). Herein, selecting an size distribution, Zeta potential, FTIR, and RAMAN spectra. In addition,
efficient adsorbent for treating phenolic wastewater is of great impor­ the effect of pH, time, phenolic pollutant concentration, dosage, and
tance. An efficient adsorbent should accumulate large quantities of temperature on the extent of adsorption of phenolic pollutants from
pollutants on its surface and possess a high surface area. In an enormous wastewater has been investigated. The kinetic models, isotherm models,
number of studies, various adsorbents like metal oxides (Wang et al., thermodynamic parameters, and plausible mechanisms for phenolic
2018), agricultural byproducts (Khenniche and Benissad-Aissani, 2010), pollutants adsorption have also been studied. Finally, the adsorbent
carbon nanotubes (Lee et al., 2018), activated carbon (Kumar and Jena, regeneration has been done to access the adsorbent’s reusability and
2016a), graphene (Sahoo et al., 2020), and graphitic carbon nitride minimise the adsorption process’s cost.
(Chegeni et al., 2019) have been explored for the effective removal of
toxic environmental pollutants. Recently, researchers have given much 2. Materials and methods
attention to synthesize graphene-based composite adsorbents, for taking
the benefits of various precursor materials into one adsorbent (Gadipelli 2.1. Materials
and Guo, 2015). In recent years, bio/conducting polymeric composite
adsorbents have gained much emphasis because of their low cost, Natural graphite powder (<20 μm), Hydrogen peroxide (H2O2, 30%
presence of many functional groups, wide availability, and outstanding aqueous solution), hydrazine monohydrate (50–60% solution) were
adsorption performance (De Gisi et al., 2016). purchased from Molychem, India. Polyethylene glycol (PEG), Zinc ace­
From the last decade, graphene has been showing remarkable per­ tate extra pure, Sodium hydroxide pellet (NaOH), phosphoric acid
formance in wastewater treatment. It has extraordinary properties such (H3PO4), hydrochloric acid (HCL, 36%), acetone (C3H6O), potassium
as a fast adsorption rate, abundant functional groups, high surface area permanganate (KMnO4, 99%), sulfuric acid (H2SO4, 98%), BPA, phenol,
(2630 m2/g), good chemical stability, and high adsorption capacity 2–CP, and 2,4–DCP were purchased from Sigma Aldrich. All solutions
(Rout et al., 2019). However, instead of graphene, researchers nowadays were prepared by deionized water (DIW) throughout this work.
are more interested in derivatives of graphene-like reduced graphene
oxide (RGO) and graphene oxide (GO) as adsorbents for the removal of 2.2. Synthesis of GO and RGO
organic and inorganic pollutants (Joshi and Gururani, 2022; Majumder
and Gangopadhyay, 2022). The GO and RGO molecules are strongly For synthesis of GO from graphite powder, the Improved Hummers’
bonded to water molecules through hydrogen and ionic bonds because method was used. For this method, the oxidant NaNO3 was replaced by
of the functional groups (carboxyl, epoxy, and hydroxyl) present on H3PO4. The GO synthesis procedure follows both oxidation and exfoli­
their surface (Magne et al., 2021; Rout and Jena, 2021). The presence of ation. The detailed procedure followed was; in a 1 L beaker, H3PO4 (30
π-electron domains, lots of defect sites, residual oxygen functionalities, mL) and H2SO4 (270 mL) was poured in the ratio (1:9) and stirred for 15
wrinkles in the planar structure of RGO, and accessible synthesis ap­ min (Rout and Jena, 2022a). 5 g of graphite powder was added to the
proaches promise the potential of RGO as an adsorbent for the removal above-prepared acidic solution and stirred for 45 min. The oxidizing
of organic pollutants from contaminated water (Rout et al., 2019; Gupta agent KMnO4 (15 g) was added slowly to the above mixture, and as the
and Khatri, 2017). However, RGO has specific problems like aggregation above reaction was exothermic in nature, an ice bath was used to
susceptibility, surface area reduction, easy loss, and difficulty in sepa­ maintain the temperature below 5 ◦ C. After 6 h of vigorous stirring, a
ration from treated wastewater (Nekouei and Nekouei, 2017). Due to dark green solution appeared, and then 250 mL of DIW was added to the
these specific problems, it has recently become a research hotspot to solution dropwise. The above solution was put in an ice bath to control
overcome this drawback by functionalizing RGO with polyethylene the exothermic reaction temperature below 10 ◦ C. After 15 min ice bath,
glycol (PEG) and zinc oxide (ZnO) to form composites with better 150 mL of DIW was added to the solution to exfoliate the graphene

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Scheme 1. Schematic diagram for the synthesis of RGO-PEG-ZnO composite.

sheets and the colour of the solution changed to dark brown. 9 mL of continually bathed with DIW to make the pH of the solution 7. Finally,
H2O2 was added into the solution to stop the reaction, and 15 min the suspensions were put in an oven at 70 ◦ C for 24 h to obtain the
stirring was done to mix the H2O2 properly. After that, the colour of the graphene oxide (GO) powder.
solution changed to yellowish-brown after 24 h of cooling. The solution The reduced graphene oxide (RGO) synthesis procedure follows;
was centrifuged at 8000 rpm to remove the unwanted extracts and first, the GO suspension was prepared by adding GO powder (1.25 g)

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Fig. 1. FESEM images of (a) GO, (b) RGO, (c) RGO-PEG-ZnO composite, and EDAX spectra of (d) RGO-PEG-ZnO composite.

with DIW (250 mL) and stirred for 15 min. The pH of the suspension was room temperature to form a black suspension. After that, the black
adjusted to 10 by adding 0.1 N HCl or 0.1 M NaOH solution as and when suspension was washed in DIW and filtered with Whatman filter paper
required. After that, into the solution, Hydrazine monohydrate (5 mL) (pore dia. 12.5 cm) to remove the unwanted Zn2+ ions from the solution.
was added as a reducing agent at 65 ◦ C and stirred for another 4 h for the The filtered sample was put in a hot air oven at a temperature of 80 ◦ C
reduction of GO to RGO. The product was centrifuged at 10,000 rpm for for 12 h to obtain the precursor of RGO-PEG-ZnO. Finally, the dried
5 min to separate DIW from the solution. The black suspension was then precursor was calcined at 300 ◦ C in a muffle furnace for 20 min to obtain
put in an oven for drying at 60 ◦ C to obtain RGO powder. the RGO-PEG-ZnO composite. The schematic diagram for the synthesis
of RGO-PEG-ZnO is shown in Scheme 1.
2.3. Synthesis of RGO-PEG-ZnO composite
2.4. Characterization technique
For the synthesis of the RGO-PEG-ZnO composite, 0.5 g of as-
prepared RGO and 100 mL of PEG were dispersed in 100 mL of DIW Field emission scanning electron microscope (FESEM) on JSM-
in a beaker. The above-dispersed solution was ultra-sonicated for 60 min 6480LV, Japan, was used to characterize the surface texture and
at room temperature. In another beaker, 0.1 M zinc acetate (1.097 g) morphological characteristics of the RGO-PEG-ZnO composite and its
was added to 50 mL DIW to prepare a water-soluble zinc acetate solu­ starting materials. Fourier-transform infrared spectroscopy (FTIR) was
tion. After that, the above two solutions were mixed properly in a used to study the surface chemistry properties of the samples by KBr
magnetic stirrer for 1 h at 500 rpm and 25 ◦ C and then ultra-sonicated pellets in a PerkinElmer spectrum (Nicolet 6700, Thermo Fisher, USA) in
for 1 h. The resulting solution was named solution A. In another the 4000 to 400 cm− 1 frequency range. The crystal structure was
beaker, solution B was prepared by adding 0.1 M NaOH in 100 mL DIW. analyzed using X‒ray diffraction (XRD) pattern in the range of 5◦ ≤2θ ≤
Then, solutions A and B were mixed and stirred for 4 h at 500 rpm and 80◦ at a scan rate of 10◦ /min with Cu Kα radiation. The operating

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Fig. 2. (a) XRD spectra, (b) RAMAN spectra, and (c) FTIR spectra of RGO, GO, and RGO-PEG-ZnO composite, (d) BET isotherm, and (e) BJH pore size distribution of
RGO-PEG-ZnO composite.

current and voltage were 30 mA and 40 kV, with a wavelength of 0.174 = 0–150 min. HCl or NaOH solution (0.05 mol/L) was used to adjust the
nm. Malvern Nano ZS instrument was used to determine the prepared phenolic pollutants pH as and when required. The remaining concen­
material’s zeta (ζ) potential by dispersing it in water media at different trations of phenol, BPA, 2–CP, and 2,4–DCP were determined using a
pH (2–10). By Brunauer-Emmett-Teller (BET) method, the pore infor­ UV-VIS spectrometer (Shimadzu UV-3150 Japan) at the wavelengths of
mation and surface area were measured at − 196 ◦ C using ASAP 2000 278, 270, 275, and 284 nm, respectively. The reusability of the RGO-
surface area analyzer with liquid nitrogen as the adsorbate. A UV-VIS PEG-ZnO composite was explored via consecutive adsorption/desorp­
spectrophotometer (Shimadzu UV-3150 Japan) was used to determine tion cycles. The uptake capacity at equilibrium (qe) was evaluated ac­
the concentrations of BPA, phenol, 2–CP, and 2,4–DCP in the superna­ cording to the formula:
tant solutions at the wavelengths of 278, 270, 275, and 284 nm,
(Co − Ce ) × V
respectively. qe = (1)
ms

where Ce and Co (mg/L) are the equilibrium and initial phenolic

2.5. Batch experiments
pollutant concentration, and ms (mg) is the amount of adsorbent. The
removal rate was evaluated according to the formula:
Batch experiments were performed in a thermostatic shaker with
180-RPM shaking speed. A total of 15 mg of RGO-PEG-ZnO composite (Co − Ct )
%R = × 100 (2)
was added to 50 mL of phenol solution (100, 150, 200, 250, and 300 mg/ Co
L) under the optimized parameter conditions. The various adsorption
parameters were varied to find out the optimal condition for higher
adsorption, like pH = 2–10, temperature = 15–40 ◦ C, initial concen­
tration = (100–300 mg/L), dosage = 0.1–0.6 g/L, and adsorption time

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Fig. 3. Effect of (a) solution pH, (b) Zeta potential, (c) RGO-PEG-ZnO composite dosage, (d) Initial phenolic pollutant concentration, (e) Contact time, and (f)
Temperature on phenolic pollutants removal efficiency.

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

2.6. Experiment with simulated effluent 3.1.3. Raman spectra

To classify the crystallographic structures of the synthesized mate­
As the real wastewater contains various organic and inorganic pol­ rials and to investigate the relative change of structural defects/layer by
lutants, a simulated effluent was used to study the effectiveness of the layer exfoliation, Raman spectroscopy (Fig. 2(b)) was used. Fig. 2(b)
RGO-PEG-ZnO composite for the adsorptive removal of phenols. The evidenced that two broad peaks are observed in each sample at 1591 and
composition of the simulated effluent used is as follows: phenol (25 mg/ 1341 cm− 1, which belong to the G and D bands. The G-band occurs
L), BPA (25 mg/L), 2–CP (25 mg/L), 2,4–DCP (25 mg/L), 2-Naphthol because of the first-order dispersion of the E2g mode, whereas the D-
(20 mg/L), 2-Nitro phenol (15 mg/L), hydroquinone (15 mg/L), so­ band is due to the defects on the basal plane of graphene (Yang et al.,
dium chloride (40 mg/L), potassium phosphate (25 mg/L), and sodium 2009). In the Raman spectra of RGO, the intensity of the D-band in­
carbonate (40 mg/L). The pH of the simulated effluent was recorded as creases compared to GO, which indicates more defects are present on the
pH = 8.2. Next, 12.5 mg of RGO-PEG-ZnO composite was added to the RGO surface. The Raman spectra of the RGO-PEG-ZnO composite shows
simulated effluent, and the solution was put in a thermostatic shaker for similar peaks of ZnO (Zhang et al., 2009) and G and D bands of RGO. The
60 min at 298 K. The removal percentage was calculated using the area ID/IG ratio for GO, RGO, and RGO-PEG-ZnO are 1.08, 1.33, and 0.885,
under the absorption band. respectively. It shows that the defects are less in the RGO-PEG-ZnO
composite compared to GO and RGO.
3. Results and discussions
3.1.4. FTIR analysis
3.1. Characterization of RGO-PEG-ZnO composite In order to identify the existence of functional groups and chemical
structural information on the RGO-PEG-ZnO composite surface, FTIR
3.1.1. FESEM analysis analysis was conducted in the wavelength range of 4000–400 cm− 1.
The surface properties and morphology of the synthesized GO, RGO, Fig. 2(c) shows the FTIR spectra of synthesized GO, RGO, and RGO-PEG-
and RGO-PEG-ZnO composite were studied using FESEM microscopy. It ZnO composite. The FTIR peaks appeared at 3448, 1643, 1390, 1217,
is observed from Fig. 1(a) that in GO, the sheets are stuck together and 1030 cm− 1 in GO, assigned to –OH stretching of absorbed water
because of the oxygen-containing functional groups, wrinkles are pre­ molecules, –COOH stretching vibrations in carboxylic acids, C–OH
sent, randomly aggregated, rough surface, sheets are thin, and hetero­ stretching, C–O–C vibration, and C–O vibration, respectively (Faniyi
geneous surface structure (Rout and Jena, 2022a). In the FESEM image et al., 2019). In the FTIR spectra of RGO, the peaks at 1560, 1217, and
of RGO (Fig. 1(b)), it is observed that the RGO surface is wrinkled 2342 cm− 1 are for O– – C–O from carboxylate, C–O–C vibration, and C––C
paper-like structure, corrugated surface, less aggregate, and irregular vibration. There is no hydroxyl peak around 3300–3400 cm− 1 suggests
structure (Ranjan Rout and Mohan Jena, 2022). This change in surface the successful synthesis of RGO. The spectrum of RGO-PEG-ZnO shows a
properties of RGO is because of the elimination of oxygenated functional peak at 1448 cm− 1 assigned to C–OH vibration of PEG (Ma et al., 2012)
groups from the GO surface. In the FESEM image of the RGO-PEG-ZnO and the peak at 940 cm− 1 is assigned to Zn–O stretching vibration. The
composite (Fig. 1(c)), it can be observed that the ZnO particles are peaks at 2375, 1587, and 1225 cm− 1 are assigned to C– – C vibration of
anchored on the RGO surface, and most of the ZnO particles are un-oxidized graphitic domains, O– – C–O from carboxylate, and C–O–C
spherical. The ZnO particles act as a stabilizer to prevent the aggregation vibration, respectively, which are observed because of the presence of
of RGO sheets and separate them from each other. Also, the loading of RGO in the composite. The above results confirm that the RGO-PEG-ZnO
PEG on the RGO surface reduced the aggregation and separated them composite is successfully synthesized and ZnO particles are dispersed on
from each other. The elemental composition of the composite is the surface of RGO.
confirmed by EDAX analysis (Fig. 1(d)). In the composite, mainly Zn, O,
and C elements are present, and the presence of Si is due to the coating of 3.1.5. N2 adsorption/desorption isotherm
the material. This indicates that in the synthesized composite, no im­ The textural characteristics of the RGO-PEG-ZnO composite were
purities are present and only ZnO particles are dispersed on the RGO measured by using N2 adsorption/desorption technique. The adsorption
surface. performance is closely related to the pore structure and specific surface
area of adsorbents. The result (Fig. 2(d)) displays a type-IV isotherm
3.1.2. XRD patterns with type H4 hysteresis loop at about P/P0 ≈ 0.51, associated with the
The XRD pattern of the RGO-PEG-ZnO composite is shown in Fig. 2 co-existence of both mesoporous and microporous networks. It is
(a). In the XRD spectra of graphite powder, a sharp peak is obtained at a believed that the synthesized RGO-PEG-ZnO composite is porous in
2θ value of 26.62◦ with a d-spacing of 0.33 nm (Hidayah et al., 2017). In nature, which provides more active sites. The Barrett-Joyner-Halendra
the GO XRD pattern, a strong diffraction peak is observed at 12.12◦ with (BJH) plot (Fig. 2(e)) shows sharp peaks are formed between 2.91 and
(001) plane and d-spacing of 0.83 nm, which confirms the successful 13.15 nm, indicating that the synthesized RGO-PEG-ZnO composite is
oxidation of graphite powder (Rout and Jena, 2022b). In GO, some weak mesoporous in nature. The total pore volume and BET surface area of the
intensity peaks are also observed at 25.12◦ having (002) plane these may composite are 0.15 cm3/g and 70.5 m2/g, respectively. The enlarged
be due to the presence of some un-oxidized graphite powder, and the pore size and pore volume of the RGO-PEG-ZnO composite are favour­
peak at 42.25◦ having (100) plane is due to the presence of Mn residue. able feature for supporting the transfer of solvent and adsorbate mole­
For RGO, a sharp peak is observed around 2θ value 28.68◦ , having cules inside the mesopore during the adsorption process.
d-spacing of 0.35 nm, corresponding to (002) plane confirms the suc­
cessful reduction of GO. The narrow and sharp diffraction peak of the 3.2. Adsorption study
RGO-PEG-ZnO composite indicates that the particles are highly crys­
tallized. The XRD peaks at 2θ = 70.035◦ , 62.177◦ , 51.115◦ , 37.714◦ , 3.2.1. Influence of solution pH
35.521◦ , and 32.393◦ correspond to the (112), (110), (102), (101), In the adsorption process, solution pH is an essential parameter to
(002), and (011) crystal planes and hexagonal crystal geometry of ZnO maintain the overall acidity or alkalinity of the solution. This work ex­
particles. The crystal planes of RGO-PEG-ZnO composite are found using plores the adsorption performance of RGO-PEG-ZnO composite to
JCPSD card no. 98-001-1316. It can also be seen that the peak at 2θ phenolic pollutants (BPA, phenol, 2–CP, and 2,4–DCP) using in the pH
value 28.68◦ of RGO is disappeared in the XRD pattern of RGO-PEG-ZnO range of 2.0–10.0, at 60 min of contact time, 0.3 g/L of adsorbent
composite, which clearly reveals that the ZnO particles are completely dosage, 100 mg/L initial phenolic pollutant concentration, and at 25 ◦ C
distributed on the surface (Clarina and Rama, 2018). temperature. The resulting adsorption performance is shown in Fig. 3
(a). It has been observed that for all the phenolic pollutants, the removal

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Fig. 4. (a) Non-linear Langmuir, Freundlich, and Temkin isotherm model (solution pH = 7.0, dosage = 0.3 g/L, contact time = 60 min, phenolic pollutant con­
centration = 100–300 mg/L, and temperature = 30 ◦ C), (b) Non-linear pseudo-first-order, pseudo-second-order, and Elovich kinetic model (solution pH = 7.0,
dosage = 0.3 g/L, contact time = 60 min, phenolic pollutant concentration = 100 mg/L, and temperature = 30 ◦ C), (c) Intra-particle diffusion model, (d) Boyd kinetic
plot for the adsorption of phenolic pollutants adsorption onto RGO-PEG-ZnO composite, (e) Van’t Hoff plot, and (b) Regeneration studies of phenolic pollutants
adsorption onto RGO-PEG-ZnO composite.

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Table 1
Langmuir, Freundlich, and Temkin isotherm parameters for the adsorption of phenolic pollutants onto RGO-PEG-ZnO composite.
Adsorbate Langmuir Freundlich Temkin
2 1/n 2
Parameters qm (mg/g) kL (L/mg) R R2adj kF (mg/g)(L/mg) 1/n R R2adj bT (J/mol) AT (L/mg) R2 R2adj

BPA 485.756 0.057 0.992 0.989 143.701 0.235 0.958 0.942 28.344 1.547 0.981 0.974
Phenol 511.248 0.093 0.991 0.979 195.523 0.216 0.968 0.951 29.966 2.338 0.984 0.971
2–CP 531.804 0.185 0.971 0.962 204.022 0.173 0.991 0.986 31.532 3.812 0.948 0.935
2,4–DCP 570.641 0.311 0.921 0.894 262.251 0.151 0.987 0.974 37.831 20.128 0.985 0.981

percentage (%R) decreases at pH < 6 and pH > 7. The maximum sites of the adsorbent decrease because of the agglomeration of pollut­
adsorption performance for BPA, phenol, 2–CP, and 2,4–DCP are 81.65, ants on the adsorbent surface, so the decline rate of adsorption occurs.
86.52, 91.74, and 94.52%, respectively, observed in pH = 6–7. Further, Fig. 3(e) shows that the adsorption removal percentage decreases with
an increase in pH results decrease in removal percentage and the surface an increase in the initial concentration of phenolic pollutants. This may
charge could elucidate this by analyzing the Zeta potential of the RGO- be because an increase in the initial concentration of pollutant increases
PEG-ZnO composite. The point of zero charge (pHPZC) of the composite the mass transfer driving force as a result, it overcomes the mass transfer
is observed at pH 7.2 and displayed in Fig. 3(b). From the zeta potential resistance between the adsorbent surface and adsorbate present in the
analysis, it is observed that for pH < 7.2, the surface of the composite is aqueous solution. Therefore, more adsorbate molecules starts diffusing
positive in charge, whereas above pH 7.2, the surface is negatively from the adsorbent surface to the bulk solution, causing a reduction in
charged. As the phenolic pollutant starts to deprotonate and forms a percentage removal.
phenolate anion for pH values greater than 7, the hydrogen bond be­
tween adsorbate and adsorbent decreases, causing a reduction in 3.2.4. Effect of temperature
adsorption performance. Also, the phenolate anion is negatively Batch adsorption experiments using RGO-PEG-ZnO composite were
charged, and the RGO-PEG-ZnO composite surface is negative (pHZPC = performed in the temperature range of 15–40 ◦ C under optimized
7.12) in charge, so both repels each other resulting in a decrease in parameter conditions such as solution pH 7, contact time 45 min, 100
adsorption performance. At pH values lower than 7, the protonation of mg/L initial phenolic pollutant concentration, and adsorbent dosage 0.3
phenolic pollutant starts and the H+ ions increases in the solution. As a g/L. Fig. 3(f) presents the temperature effect on the removal of phenolic
result, the electrostatic repulsion between protonated phenolic com­ pollutants. The plot shows that as the temperature increases, the
pounds and the H+ ions increases and causes the depletion of the removal percentage increases, suggesting that the adsorption process is
adsorption process (Zhao et al., 2021). Therefore, pH is set at 7 for endothermic. It is observed that up to 30 ◦ C the removal rate increases
further experiments to obtain high adsorption efficiency. highly, and then the removal rate gradually slows down. As a result,
30 ◦ C is chosen as the optimal temperature for further experiments. This
3.2.2. Effect of RGO-PEG-ZnO dosage increase in removal percentage with temperature occurs because of the
Another key parameter is the amount of adsorbent, which de­ acceleration of phenolic pollutants present in the solution, enhancing
termines the uptake capacity for a given adsorbate concentration. The the pollutants’ kinetic energy (Jiang et al., 2018). As a result, the
influence of RGO-PEG-ZnO composite dosage on adsorption perfor­ transfer of phenolate ions accelerated to the surface of the
mance was investigated from 0.1 to 0.6 g/L at solution pH 7, 60 min of RGO-PEG-ZnO composite, which enhances the adsorption performance.
contact time, 100 mg/L initial phenolic pollutant concentration, and at However, with increasing temperature, beyond 30 ◦ C the attractive
25 ◦ C temperature. Based on the results depicted in Fig. 3(c), it is forces between the adsorbent surface and phenolic pollutants weaken,
observed that from 0.1 to 0.3 g/L, the removal of phenolic pollutants that reduce the adsorption performance.
sharply increases and then attains equilibrium on the further increase.
As the adsorbent dosage increases, the available active sites increase, 3.3. Isotherm study
which results in the adsorption of more phenolic pollutants on the RGO-
PEG-ZnO composite surface. However, the increment of adsorbent The isotherm study could analyse the adsorption equilibrium be­
dosage above 0.3 g/L does not allow any additional improvement in the tween the solute and solvent at a constant temperature (Desta, 2013). It
adsorption performance. This is due to the agglomeration of phenolic is also crucial to the optimal utilization of the adsorbent. The equilib­
pollutants to the RGO-PEG-ZnO composite (Srivastava et al., 2016). rium data of phenolic pollutants were examined using Temkin, Lang­
Also, with an increase in adsorbent dosage, equilibrium starts between muir, and Freundlich isotherm models. In the Langmuir model, the
unadsorbed molecules in the solution with the molecules bonded to the adsorbent surface is energetically homogeneous, and the adsorption
adsorbent surface. As a result, adsorption of new molecules does not process is driven in a ratio of 1:1, where one molecule of adsorbate binds
occur, so the adsorption attains equilibrium. Therefore, 0.3 g/L is the to one binding site only (Langmuir, 1918). Freundlich isotherm assumes
optimum adsorbent dosage considered for further experiments to obtain that heterogeneous adsorption occurs in the process, where the
high adsorption efficiency with the conditions described above. adsorption sites are diverse and the binding sites are not saturated
(Prabhakar et al., 2011). The assumption for the Temkin model is for all
3.2.3. Effect of initial phenolic pollutant concentration and adsorption time the molecules, adsorption heat decreases linearly rather than exponen­
The initial concentration of the adsorbate is one of the most impor­ tially with an increase in the amount of adsorbent. The non-linear form
tant parameters of an adsorption process as it gives an essential driving of the above isotherm models could be expressed as:
force, which is required in all mass transfer operations to overcome the
qm KL Ce
resistances between solid and liquid phases (Gholizadeh et al., 2013). qe = (4)
1 + KL Ce
Batch experiments were performed in the concentration range of
100–300 mg/L of phenol, 2–CP, BPA, and 2,4–DCP keeping other pa­
qe = kF Ce1/n (5)
rameters constant such as pH of solution 7, 0–150 min of contact time,
0.3 g/L of adsorbent dosage, and 25 ◦ C of temperature. The results are RT
illustrated in Fig. 3(d), it is observed that rapid adsorption occurs qe = ln(AT Ce ) (6)
bT
initially because of the presence of more active sites on the adsorbent
surface. However, with the progress of adsorption operation, the active where qm (mg/g) is the theoretical maximum uptake of phenolic

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Table 2 Table 3
Comparison of the uptake capacities for phenolic pollutant adsorption with Pseudo-first order, pseudo-second-order, and Elovich kinetic model parameters
previously reported adsorbents in literature. for the adsorption of phenolic pollutants onto RGO-PEG-ZnO composite.
Adsorbent Adsorption Conditions pH Conc. Ref. Parameters Phenol 2–CP 2,4–DCP BPA
Pollutants Capacity (mg/L) Temp.(K)
qexp (mg/g) 293.852 309.018 316.951 270.985
(mg/g)
PFO
BPA MIL-101 252.5 7 40 303 Qin et al. qcal (mg/g) 269.748 289.278 300.112 262.214
(Cr) (2015) k1 (min− 1) 0.095 0.112 0.126 0.096
β-CDP 164.4 6.7 100 298 Zhou et al. R2 0.978 0.984 0.981 0.979
(2019) ARE (%) 7.908 6.245 5.258 3.236
CD/CA-g- 79 6.5 50 298 Zhou et al. RMSE 13.854 11.015 9.722 5.064
PDMAEMA (2018) PSO
RGO-PEG- 485.756 6.15 300 308 This work k2 × 103 (g/mg.min) 0.453 0.506 0.587 0.069
ZnO qcal (mg/g) 294.545 314.478 321.095 273.425
composite R2 0.994 0.991 0.994 0.992
Phenol PVAm-GO- 224.21 6 300 298 Zhou et al. ARE (%) 0.239 1.545 1.307 0.901
(o- (2020) RMSE 0.412 3.152 2.392 1.408
MWCNTs)- Elovich model
Fe3O4 α 77.055 112.245 120.165 60.686
CNT-PEG 21.23 7 100 303 Bin-Dahman β 0.021 0.019 0.023 0.018
and Saleh R2 0.948 0.936 0.954 0.951
(2020)
GO-FE3O4/ 226.2 7 250 303 Parvin et al.
PRd (2020) then attachment to the active sites of adsorbent (Rudzinski and Pla­
RGO-PEG- 511.248 6.2 300 308 This work
zinski, 2009). In this context, kinetic models such as Intraparticle
ZnO
composite
diffusion (IPD), Elovich, pseudo-second-order (PSO), and
2–CP TNTs/ACF 122.1 5 300 295 Duan et al. pseudo-first-order (PFO) are widely used to interpret the experimental
(2021) adsorption data obtained from the contact time study to know the
Activated 150 6 300 328 Machado adsorption mechanism. The non-liner form of these kinetic models are
biochars et al. (2020)
given as follows:
CCM 117.5 5 600 323 Teoh et al.
(2015)
qt = kid t1/2 + Ci (7)
RGO-PEG- 531.804 6.2 300 308 This work
ZnO
composite 1
qt = ln(αβt) (8)
2,4–DCP Pristine 155.3 7.03 1000 318 Fan et al. β
graphene (2017)
Fe3O4@AC 188.7 6 100 298 Badu Latip k2 q2e t
et al. (2021) qt = (9)
1 + k2 qe t
GN/HCPC 348.43 6 500 298 Liu et al.
(2020) ( )
RGO-PEG- 570.641 7 300 308 This work qt = qe 1 − exp− k1 t
(10)
ZnO
composite where k2 (g/mg.min) and k1 (min− 1) are the rate constants of PSO and
PFO models, kid (mg/g.t1/2) is the diffusion rate constant, α (mg/g.min)
pollutant, AT is the binding energy (L/mg), qe (mg/g) is the uptake ca­ is the initial adsorption rate, and β (g/mg) is the desorption constant.
pacity at equilibrium, KL (L/mg) is the affinity constant, bT (J/mol) is the The non-linear plot for the adsorption of BPA, phenol, 2–CP, and
Temkin constant, 1/n is the heterogeneity factor, and T (K) is the tem­ 2,4–DCP onto the RGO-PEG-ZnO composite is shown in Fig. 4(b). The
perature. The non-linear plot of the above-described isotherm models is kinetic parameters were estimated from the non-linear plots using
shown in Fig. 4(a). Based on non-linear regression (Fig. 4(a)), the Origin Pro 2021 Software and presented in Table 3. As can be seen in
isotherm model parameters were estimated using Origin Pro 2021 Table 3, the correlation coefficient (R2), root mean square error (RMSE),
software and documented in Table 1. For the Langmuir isotherm model, and average relative error (ARE) of PSO model for all the pollutants are
the regression coefficient (R2) and adjusted regression coefficient (R2adj) more significant than that of PFO and Elovich model. These findings
both are maximum for phenol and BPA, whereas for 2–CP, and 2,4–DCP suggest that the PSO is the best-fitted kinetic model for this adsorption
the R2 and R2adj of Freundlich isotherm model are maximum. This process, implying that chemisorption occurs in adsorption (Zhou et al.,
observation indicates that the adsorption of BPA and phenol on the 2020). It is also observed from Table 3 that the calculated equilibrium
surface of the RGO-PEG-ZnO composite is monolayer adsorption and the adsorption capacity (qcal) from the PSO model are 273.425, 294.545,
adsorption of 2–CP and 2,4–DCP is heterogeneous type of adsorption. 314.478, and 321.045 mg/g for BPA, phenol, 2–CP, and 2,4–DCP, which
Accordingly, the qm values calculated from the Langmuir model are is closer to the experimental data (qexp) 270.985, 293.852, 309.018, and
485.756, 511.248, 531.804, and 570.641 mg/g for the BPA, phenol, 316.951. The order of fitness of the kinetic models for the adsorption of
2–CP, and 2,4–DCP, respectively, which are higher than other adsor­ BPA, phenol, 2–CP, and 2,4–DCP by RGO-PEG-ZnO composite are: PSO
bents reported in the literature (Table 2) as compared to the amount of > PFO > Elovich model (see Table 4).
RGO-PEG-ZnO composite.
3.4.1. Intra-particle diffusion (IPD) model
The IPD model was used to identify the exact rate-limiting steps.
3.4. Kinetic study Fig. 4(c) illustrates the IPD plots of BPA, phenol, 2–CP, 2,4–DCP, and the
values of Ci and kid are calculated from the plot and tabulated in
For any adsorption process, the mechanism involves three diffusion Table S2. Accordingly, IPD is the rate-controlling step if the plot is good
steps such as: (i) from the bulk of the solution transport of the adsorbate linear and passes the origin (Kumar and Jena, 2016b). The result in­
occurs towards the film covering the adsorbent, (ii) diffusion of adsor­ dicates that none of the straight-line passes through the origin and a
bate into the adsorbent surface from the adsorbent film, and (iii) significant intercept and three stages of linearity are observed in the IPD
adsorbate molecules entering into the internal sites of the adsorbent and

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D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Table 4
Thermodynamic parameters for the adsorption of phenolic pollutants onto RGO-PEG-ZnO composite at different temperatures.
Parameters Temperature (K)
Adsorbate
288 293 298 303 308 313

BPA ΔHo (kJ/mol) 28.261

ΔSo (J/mol.K) 189.509
ΔGo (kJ/mol) − 26.317 − 27.265 − 28.212 − 29.163 − 30.107 − 31.055
ΔHo (kJ/mol) 37.205
Phenol ΔSo (J/mol.K) 219.356
ΔGo (kJ/mol) − 25.969 − 27.066 − 28.163 − 29.259 − 30.356 − 31.453
ΔHo (kJ/mol) 46.182
2 – CP ΔSo (J/mol.K) 256.644
ΔGo (kJ/mol) − 27.731 − 29.014 − 30.298 − 31.581 − 32.864 − 34.147
ΔHo (kJ/mol) 61.682
2,4 – DCP ΔSo (J/mol.K) 317.711
ΔGo (kJ/mol) − 29.818 − 31.407 − 32.996 − 34.584 − 36.173 − 37.761

plot. The above findings imply that IPD and other diffusion mechanisms
also affect the adsorption rate. Among the three linear sections pre­
sented in the IPD plot (Fig. 4(c)), the first section is for film diffusion,
where adsorbate molecules diffuse rapidly into the adsorption sites of
the RGO-PEG-ZnO composite. In the second linear section, the adsorbate
molecules start diffusing into the macrospore, mesopore, and micro­
spores of the RGO-PEG-ZnO composite from the adsorbent surface,
called intra-particle diffusion (IPD) stage. In the final section, equilib­
rium starts between adsorbate and adsorbent surface, and IPD decreases.
This study confirms that the adsorption of phenolic pollutants onto the
RGO-PEG-ZnO composite is controlled by IPD (pore diffusion) and film
diffusion (Ohemeng-Boahen et al., 2021).

3.4.2. Boyd-kinetic model

The Boyd kinetic plot defines the exact rate-limiting steps of the
process and the equation used is given as [Eq. (11)] (Liu et al., 2014).
Bt = − 0.4977 − ln(1 − F) (11)
F = qt/qo represents the fraction of phenolic pollutant and Bt is a
function of F. Fig. 4(d) shows the Bt vs. t plot for different phenolic
pollutant concentrations. All the plots have y-intercept and linear, sug­
gesting film diffusion as the rate-determining step for the adsorption
BPA, phenol, 2–CP, and 2,4–DCP onto the RGO-PEG-ZnO composite. Fig. 5. UV–Vis spectra of treated simulated industrial effluent using RGO-PEG-
ZnO composite as an adsorbent (solution pH = 7.0, dosage = 0.3 g/L, tem­
3.5. Thermodynamics study perature = 30 ◦ C, and contact time = 60 min).

The experimental data obtained from the adsorption of phenolic endothermic process occurs in the adsorption, which is already dis­
pollutants for the thermodynamic analysis of the RGO-PEG-ZnO com­ cussed in the effect of temperature section.
posite at different temperatures (288, 293, 298, 303, 308, and 313 K)
were investigated. The thermodynamics parameters, for instance, the
change in enthalpy (ΔHo), Gibbs free energy (ΔGo), and entropy (ΔSo) 3.6. Regeneration study
were evaluated by using Eqs. 12 and 13 (Rout and Jena, 2022a):
The two most important factors to be considered during adsorption
qe
Kd = ρ (12) are adsorption capacity and regeneration studies. The adsorbent mate­
Ce rial must possess a higher desorption rate and high adsorption capacity
to achieve a higher adsorption rate. The above two factors reduce ma­
ΔSo ΔH o
ln(Kd ) = − (13) terial costs significantly. The reusability and stability of adsorbents are
R RT
the most important parameters in evaluating their performance as it
ΔGo = ΔH o − TΔSo (14) directly relates to the cost of the adsorbent. The adsorption-desorption
experiments were performed at optimal parameter conditions such as
where ρ is the solution density (g/L) and Kd is the adsorption coefficient. pH of solution 7, contact time 60 min, 0.3 g/L of RGO-PEG-ZnO com­
By plotting Eq. (13) it is possible to calculate the values of ΔHo and ΔSo posite dosage, and 30 ◦ C temperature for five consecutive cycles. After
from the Van’t Hoff plot (Fig. 4(e)), and the obtained results are given in adsorption, exhausted RGO-PEG-ZnO composites were subject to
Table4. For all the temperatures, the ΔG◦ values are negative for BPA, regeneration by using 0.05 M HNO3 and 0.05 M NaOH solutions as the
phenol, 2–CP, and 2,4–DCP illustrating the process is spontaneous. combined eluting agents. It is observed that the removal of phenolic
Furthermore, the ΔGo decreases with temperature increase, implys that pollutants declines as the cycle progresses (Fig. 4(f)) due to the reduc­
the higher temperature is more favourable to the adsorption. As the ΔSo tion of accessible active sites of the RGO-PEG-ZnO composite. Further­
is positive, it indicates the randomness increase at the solid/liquid more, many chemical reactions might have occurred on the adsorbent
interface because of the displacement of water molecules from the surface after the adsorption of phenolic pollutants, resulting in the
binding sites of the adsorbate ions. The positive ΔHo value confirms collapse of the composite’s pore structure. The removal percentage of

11
D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

Scheme 2. Schematic diagram for proposed phenolic pollutants removal mechanism.

phenolic pollutants remained at 69.38, 74.52, 79.57, and 83.25%, phenolic pollutants and inorganic salts the adsorption performance of
respectively, for BPA, phenol, 2–CP, and 2,4–DCP after five cycles of the RGO-PEG-ZnO composite was evaluated. Fig. 5 shows the absorption
regeneration. These results indicate that the synthesized RGO-PEG-ZnO spectra of simulated wastewater before and after treatment using a UV-
composite is cost-effective and can be repeatedly used for water VIS spectrophotometer. It is observed that after treatment with RGO-
purification. PEG-ZnO composite, the spectra of simulated effluent decrease and
86.54% removal percentage is achieved after 45 min of contact time as
3.7. Adsorption of simulated effluent compared to the removal of single components; BPA (81.21%), phenol
(87.15%), 2–CP (92.73%), and 2,4–DCP (95.08%). This average
Using the simulated industrial effluent prepared using various decrease in removal percentage compared to many single components

12
D.R. Rout and H.M. Jena Environmental Research 214 (2022) 114044

may be because of the presence of various types of pollutants in the positive values of change in enthalpy (ΔHo) 28.261, 37.205, 46.182, and
simulated water. All the pollutants may be trying to adsorb on the 61.682 kJ/mol for BPA, phenol, 2–CP, and 2,4–DCP confirms that the
adsorbent surface during adsorption, as a result, competitions among above adsorption process is endothermic in nature. The positive values
pollut ants occur, resulting in decreased adsorption performance. of change in entropy (ΔSo) are 189.509, 219.356, 256.644, and 317.711
J/mol.K for BPA, phenol, 2–CP, and 2,4–DCP confirms that the above
3.8. Adsorption mechanism adsorption process is favourable. In the adsorption study of simulated
effluent, the novel RGO-PEG-ZnO composite removes up to 86.54% of
Several literatures reported various mechanisms for the removal of phenolic pollutants. Moreover, after five regeneration cycles, the
phenolic pollutants by adsorption. Out of these, the most widely removal percentage of BPA, phenol, 2–CP, and 2,4–DCP are 69.38,
accepted mechanisms are; the interaction of π–π electron pairing, 74.52, 79.57, and 83.25%, respectively. These remarkable results
hydrogen bond interactions, electrostatic interaction, dispersion, hy­ conclude that the synthesized RGO-PEG-ZnO composite is an economi­
drophobic effect, and physical adsorption. The presence of oxygen cally feasible candidate with great application prospects for treating
functional groups in the RGO-PEG-ZnO composite at π-electron-rich phenolic contaminated wastewater for several cycles. Barring all these
regions provides complexes with aromatic rings of phenolic pollutants advantages of this approach, one drawback is dealing with toxic pol­
(Zhang et al., 2013). During the adsorption, the π-electron-rich regions lutants, as in the adsorption process, the pollutants are only transferred
of the composite act as a donor, and the phenol rings act as an acceptor. from the aqueous phase to the adsorbent phase.
As a result, the adsorption of phenolic pollutants onto the composite is
controlled by the dispersive interaction of π–π electrons (Mojoudi et al., Author’s contributions
2019). In the RGO-PEG-ZnO composite, the RGO molecules react with
PEG molecules through covalent bonding, which strongly binds both Dibya Ranjan Rout: Conceptualization; Methodology; Formal anal­
these molecules and due to this, the composite did not break in the ysis; Writing – original draft preparation. Hara Mohan Jena: Supervi­
adsorption process (Díez-Pascual and Díez-Vicente, 2016). Adsorption sion; Conceptualization; Investigation; Writing Reviewing and editing.
on the RGO-PEG-ZnO composite surface is due to the hydrogen bond
formation between the oxygen functional groups of the adsorbent and
hydroxyl groups of phenolic molecules which makes the RGO-PEG-ZnO Declaration of competing interest
composite more hydrophilic (Dąbrowski et al., 2005). As a result, more
and more phenolic molecules are attracted towards the adsorbent sur­ The authors declare that they have no known competing financial
face, enhancing the adsorption process. As the reaction between interests or personal relationships that could have appeared to influence
phenolic molecules and RGO-PEG-ZnO composite occurs on the entire the work reported in this paper.
surface of the composite, so the adsorbed phenolic molecules are uni­
formly distributed on the composite. In the adsorption of phenolic pol­ Data availability
lutants, two different electron donor-acceptor interaction occurs. The
first one involves the interaction of carbonyl and hydroxyl groups Data will be made available on request.
(electron donor) of composite with the aromatic ring of phenolic com­
pound (electron acceptor). The second one involves the interaction be­
Appendix A. Supplementary data
tween zinc oxide (electron donor) of composite with the aromatic ring of
phenolic compound (electron acceptor). The interaction between
Supplementary data to this article can be found online at https://doi.
donor-acceptor of the adsorbent and phenolic compounds during the
org/10.1016/j.envres.2022.114044.
adsorption depends on the dipole moment of the functional groups
present on the basal plane. The schematic presentation of the adsorption
mechanism of phenolic pollutants is shown in Scheme 2. References

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