Environmental Science and Pollution Research (2022) 29:64177–64191

https://doi.org/10.1007/s11356-022-20257-3

RESEARCH ARTICLE

Efficient removal of 2,4‑D from solution using a novel antibacterial

adsorbent based on tiger nut residues: adsorption and antibacterial
study
Alexander Nti Kani1 · Evans Dovi1 · Aaron Albert Aryee1 · Runping Han1 · Lingbo Qu1

Received: 30 December 2021 / Accepted: 10 April 2022 / Published online: 26 April 2022
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
We engineered a tiger nut residue (TNR, a low-cost agricultural waste material) through a facile and simple process to take
advantage of the introduced functional groups (cetylpyridinium chloride, CPC) in the removal of 2,4-dichlorophenoxy-
acetic acid (2,4-D) in batch mode and further investigated its impingement on bacterial growth in a yeast-dextrose broth.
The surface characterizations of the adsorbent were achieved through Fourier-transform infrared spectroscopy (FTIR),
Brunauer–Emmett–Teller method (BET), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS).
The batch adsorption studies revealed that solution pH, adsorbent dose, temperature, and salt affected the adsorptive capacity
of TNR-CPC. The equilibrium data were best fitted by Langmuir isotherm model with a maximum monolayer adsorption
capacity of 90.2 mg ­g–1 at 318 K and pH 3. Pseudo-second-order model best fitted the kinetics data for the adsorption process.
Physisorption largely mediated the adsorption system with spontaneity and a shift in entropy of the aqueous solid-solute
interface reflecting decreased randomness with an exothermic character. TNR-CPC demonstrated a good reusability poten-
tial making it highly economical and compares well with other adsorbents for decontamination of 2,4-D. The adsorption of
2,4-D proceeded through a probable trio-mechanism; electrostatic attraction between the carboxylate anion of 2,4-D and the
pyridinium cation of TNR-CPC, hydrogen bonding between the hydroxyl (–OH) group inherent in the TNR and the carboxyl
groups in 2,4-D and a triggered π-π stacking between the benzene structures in the adsorbate and the adsorbent. TNR-CPC
reported about 99% inhibition rate against both gram-positive S. aureus and gram-negative E. coli. It would be appropriate
to investigate the potential of TNR-CPC as a potential replacement to the metal oxides used in wastewater treatment for
antibacterial capabilities, and its effects against airborne bacteria could also be of interest.

Keywords Tiger nut residue · Cetylpyridinium chloride · Adsorption · 2,4-dichlorophenoxyacetic · Antibacterial property

Introduction microorganisms and may be incorporated into the food chain

Farmers embraced several pests and weed management
tactics as agricultural technology improved in the bid to
increase food production. This has resulted in a global her-
bicide and pesticide usage increase of more than 1.5 times
over the last four decades. The overuse of these pesticides
poses a significant environmental and health risk. They are
known to damage fresh water, degrade soil quality, harm soil
Responsible Editor: Tito Roberto Cadaval Jr
* Runping Han
rphan67@zzu.edu.cn
1
College of Chemistry, Green Catalysis Center, Zhengzhou
University, Zhengzhou 450001, People’s Republic of China
and affect the environment (Ponnuchamy et al., 2021; Singh
et al., 2020). One major concern that the overuse of these
agrochemicals poses to our ecosystem is the contamination
of worldwide water supplies.
2,4-dichlorophenoxyacetic acid (2,4-D) is a chloro-
organic herbicide that is widely used in agriculture
(Kuśmierek et al., 2016). Its purpose is to manage weeds
while causing minimal damage to agricultural produce under
cultivation (Baharum et al., 2020). Despite the fact that
2,4-D is a weakly biodegradable contaminant in the envi-
ronment, with a maximum permitted dosage of 100 ppb in
drinking water, it is widely used because of its low cost and
high selectivity against weeds (Hameed et al., 2009). It has
been reported that 2,4-D enters the environment primarily

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by percolation, surface runoff, build-up, atmospheric deposi-
tion, and spray drift routes (Sanagi et al., 2011).
The movement of 2,4-D which is bioaccumulative
throughout the food chain, with its residue traceable in vari-
ous environmental media (Baharum et al., 2020), pose a
challenge for water utility companies, especially in relation
to drinking water sources (Cosgrove et al., 2019). Accord-
ing to the United States Environmental Protection Agency,
2,4-D is a persistent pollutant and as such sets its allowable
maximum level in drinking water at 70 µg ­L–1 while the
World Health Organization (WHO) recommends a maxi-
mum allowable level of 100 mg/L in drinking water (Ebra-
himi et al., 2020). Due to its carcinogenic effect and ability
to disrupt endocrine, it is exigent to develop protocols for
their effective removal from the environment.
Reports exist in literature on some of the processes
applied in the removal of this mutagen, 2,4-D, from drinking
water sources. The list includes photodegradation (Ebrahimi
et al., 2020), adsorption (Kuśmierek et al., 2016), Fenton
(Chen et al., 2015), and electrochemical degradation (Zhu
et al., 2012). However, adsorption is more preferred due to
its inherent characteristics of facile in design and operation,
cost effectiveness and environmental friendliness (Deokar
et al., 2016; Kuśmierek et al., 2016).
A review of studies undertaken for the adsorption of
2,4-D has shown that activated carbons have been largely
explored as adsorbents in the removal of this pollutant
(Gülen and Aslan, 2020; Bojic et al., 2019; Herrera-García
et al., 2019; Bahrami et al., 2018; Hue et al., 2018; Salman
and Hameed, 2010; Hameed et al., 2009). However, due
to the associated challenges such as high energy demand,
secondary pollution and cost, different types of adsorbent
materials such as metal–organic frameworks (MOFs) (Isaeva
et al., 2021, 2019), ultrasound-acid treated Merremia viti-
folia plant (Aswani et al., 2020), aminosilane grafted
mesoporous carbons (Goscianska and Olejnik, 2019),
multi-walled carbon nanotubes (Bahrami et al., 2018), iron
sulphide (FeS) (Chen et al., 2015), magnetic graphene (Liu
et al., 2016), single-walled carbon nanotubes (Bazrafshan
et al., 2013), layered double hydroxides (Nejati et al., 2013)
and organic polymer resin (Vergili and Barlas, 2009) have
also been explored.
Recently, agricultural waste material such as wall nut
shell (Dovi et al., 2021a,b), sugarcane bagasse (Mpatani
et al., 2021, 2020), pea nut shell (Aryee et al., 2021a,b;
Demirhan et al., 2018) and tiger nut residue (Kani et al.,
2021a, 2020) have gained attention in researchers’ quest
to develop novel but cheap and eco-friendly adsorbents.
However, the pristine agricultural waste used in pollutant
decontamination is reported to have low adsorptive capabili-
ties (Kani et al., 2021b); hence, chemical and or physical
treatments have resulted in improved adsorption capacities
as demonstrated in literature (Aryee et al., 2021b; Dovi
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Environmental Science and Pollution Research (2022) 29:64177–64191
et al., 2021b; Mpatani et al., 2020). Based on the literature
reviewed, the modified agricultural waste materials par-
ticularly from tiger nut residue have not been used for the
removal of 2,4-D pesticide, and its antibacterial property has
not been reported.
The focus of this study is to engineer a renewable, low-
cost and environment-friendly agricultural waste mate-
rial, tiger nut residue (TNR), by functionalizing it with
cetylpyridinium chloride (CPC), an eco-friendly quater-
nary ammonium compound into a novel adsorbent efficient
to decontaminate 2,4-D in aqueous solution and assess its
antibacterial activities against Staphylococcus aureus (S.
aureus) and Escherichia coli (E. coli).
After the facile synthesis of this novel but simple adsor-
bent, TNR-CPC, characterizations were done to profile its
physical and chemical properties. The adsorption tests were
carried out in a batch mode. Several parameters like temper-
ature, solution pH, contact time, adsorbent dose and effect
of salt concentration were optimized. The equilibrium and
kinetics of the adsorption process were studied as well as
the adsorption mechanism of this pesticide onto the peanut
shells. The kinetics, isotherm and thermodynamics of the
adsorption process were investigated to understand the pos-
sible adsorption mechanism. Desorption studies were also
conducted to examine the adsorbent reusability potentials
followed by antibacterial studies of TNR-CPC.
Materials and methods
Materials
Tiger nut residue (TNR), sodium hydrogen sulphate
­(NaHSO4), cetylpyridinium chloride (CPC), sodium hydrox-
ide (NaOH), sodium chloride (NaCl), sodium sulphate
­(Na2SO4), calcium chloride (­ CaCl2), 2,4-dichlorophenoxy-
acetic acid (­ C8H6Cl2O3), Escherichia coli and Staphylococ-
cus aureus (herein referred as bacteria) were used. All rea-
gents and chemicals were bought from Sinopharm Chemical
Reagent Co., Ltd, Shanghai, China, and were of analytical
grade and hence were used without further purification.
Distilled water was used to prepare reagents and working
solutions.
Preparation of cetylpyridinium modified‑tiger nut
residue adsorbent material
The TNR material was prepared according to the protocols
published by Kani et al. (2020). The adsorbent was engi-
neered as follows; 1.0 g of TNR was weighed into a 100-mL
conical flask containing 20 mL of 0.2 mol ­L–1 NaOH and
swirled continuously for 6 h at 298 K. To enhance the bind-
ing site of TNR, it was pre-treated with a solution of NaOH.
Environmental Science and Pollution Research (2022) 29:64177–64191
The TNR was then filtered and rinsed several times with
distilled water until the eluent pH was neutral, then dried for
12 h at 333 K. After being pre-treated with aqueous NaOH,
the TNR was soaked in 100 mL of CPC solution, which was
prepared by dissolving 1.0 g of CPC in 100 mL of deion-
ized water. The mixture was then shaken at 130 rpm for 24 h
at 303 K in an orbital shaker with a water bath. To elimi-
nate superficially retained CPC, the adsorbent was filtered
and rinsed with deionized water many times. Finally, the
washed adsorbent was dried for 12 h at 333 K. The facilely
engineered adsorbent (TNR-CPC) was kept in an airtight
container and labelled accordingly.
Preparation of 2,4‑dichlorophenoxyacetic acid
working solutions
The 2,4-D working solutions were prepared by diluting the
concentrated solution of 2,4-D with distilled water to the
desirable molar concentration. Few drops of 0.1 mol ­L–1 of
HCl or NaOH were used to alter the pH of 2,4-D solutions
to a pH range from 2.0 to 10.0.
Characterization of the engineered TNR‑CPC
material
The prepared adsorbent material, TNR-CPC, was char-
acterized as detailed below. The functional groups on the
engineered TNR and the pristine TNR were measured
between 4000 and 500 ­cm−1 using Fourier-transform infra-
red spectroscopy (FTIR, Nicolet iS50, American). The sur-
face region, total pore volume and average pore diameter
were calculated using the Brunauer–Emmett–Teller method
(BET, ASAP2420-4MP, American). The crystallinity of
the adsorbent materials was studied using X-ray diffraction
analysis (XRD, PANalytical, Netherlands). X-ray photo-
electron spectroscopy (XPS, Escalab 250xi, England) was
used to examine the modification and adsorption process.
The absorbance and equilibrium concentration of 2,4-D was
measured on visible spectrophotometry (UV–Vis, Persee
TU-1900, China) at 282 nm. The pH point of zero charge
(pHzpc) values of TNR-CPC was determined using the
method described by Kani et al. (2021a) with the help of
pH meter (Mettler Toledo FP30-standard).
Batch adsorption equilibrium studies
In a series of batch experiments, the same mass of adsorbent
was introduced and maintained in contact with 2,4-D solu-
tion in a 50-mL conical flask and used to study all the factors
except the effect of dosage in which case the mass of the
adsorbent was varied. The flask and its content were left in a
thermostatic shaker (Kexi Instrument KW-1000DB, China)
at a fixed shaking rate of 130 rpm at a steady temperature
64179
over a given period of time until equilibrium was achieved.
The study of the various factors which affected the adsorp-
tion processes was carried out as follows. The effects of
pH (C0 = 50 mg ­L–1, m = 0.01 g, t = 2 h, T = 293 K, pH
2–12), the effect of TNR-CPC dose (C0 = 50 mg ­L–1, t = 2 h,
T = 293 K, pH 3, m = 0.002–0.3 g), the influence of con-
tact time (C0 = 50 mg ­L–1, pH = 3.0, T = 293, 303, 313 K,
t = 1–120 min), effect of 2,4-D initial concentration at dif-
ferent temperatures (m = 0.01 g, t = 2 h, pH 3, T = 293, 303,
313 K, Co 10 to 100 mg ­L−–1), effect of salts (i.e. ­Na2SO4,
NaCl, ­C aCl 2 and ­NaHSO 4) at different concentrations
(C0 = 50 mg ­L–1, T = 293 K, t = 2 h, pH = 3.0, Co 0.02, 0.04,
0.06, 0.08, 0.1 mol L ­ –1). The samples were centrifuged at
3000 rpm for 5 min, and the concentration of the supernatant
2,4-D was measured at 282 nm on a spectrophotometer. All
experiments were performed in triplicate to ensure accuracy
and reproducibility, and the average results were used for
further data analysis using Microsoft Excel 2016 version
and Origin 8.5. The adsorption capacity (qe or qt, mg ­g–1)
and removal efficiency (P %) were derived from Eqs. 1 and
2 (Table 1).
In this study, Pseudo-first-order kinetic (Eq. 3), Pseudo-
second-order kinetic (Eq. 4), Elovich (Eq. 5) and interpar-
ticle-diffusion models (Eq. 6) were employed to investigate
the kinetics of the adsorption system. The nonlinear regres-
sion analysis was employed, and the various expressions of
the models are presented in Table 1.
To be able to investigate how the 2,4-D interacts with
TNR-CPC to help in describing the distribution of the
adsorbate on the adsorbent at equilibrium, three isotherm
models: Langmuir (Eq. 7.a), Freundlich (Eq. 8), and Koble-
Corrigan (Eq. 9) were investigated. Their expressions are
listed in Table 1. The variation of enthalpy (ΔH0), Gibbs-
free energy (ΔG0), entropy (ΔS0) (thermodynamic param-
eters) and activation energy (Ea) was examined for 2,4-D
adsorption onto TNR-CPC using Eqs. (10) to (13).
Desorption and regeneration studies
To investigate the reusability of the TNR-CPC in order to
appreciate its suitability for practical wastewater remedia-
tion processes, desorption and regeneration were carried out
using either HCl or NaOH as eluents following the protocol
described by Dovi et al. (2021a) and Mpatani et al. (2020)
as detailed below with a few modifications.
A spent TNR-CPC was obtained following the adsorp-
tion process described in “Batch adsorption equilibrium
studies.” The spent TNR-CPC was then cleaned with dis-
tilled water and dried at 60 °C to achieve a constant mass.
The obtained TNR-CPC was weighed and placed into a
flask for desorption. Next, 10 mL 0.1 mol L ­ –1 NaOH or
HCl solution was introduced into the flask and oscillated at
293 K, 130 rpm for 2 h. The desorbed TNR-CPC obtained
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64180 Environmental Science and Pollution Research (2022) 29:64177–64191

Table 1  The adsorption capacity, efficiency, non-linear expressions of kinetic and isotherm models and thermodynamic equations used for
adsorption study
Model Description Expression of equation Eq. no

Adsorption capacity (qe or qt, mg ­g–1) q is the adsorption capacity of the adsorbent (mg ­g–1), Co and C are q = V(C0 −C) 1
the initial and equilibrium concentration or concentration at any m

time t (mg/L) of 2,4-D, V is the volume (L) of 2,4-D, and m is the

mass (g) of TNR-CPC
Removal efficiency P is the removal efficiency in percentage (C −C )
P = 0C e × 100% 2
0

Pseudo-first-order kinetic model (PFO) k1 ­(min–1) is the pseudo-first order rate constant; qe or qt (mg ­g–1) qt = qe (1 − e−k1 t ) 3
are the adsorption quantities at equilibrium or any time t
Pseudo-second-order kinetic model (PSO) k2 is the pseudo-second-order rate constant (g ­mg–1 ­min–1), qt is the
adsorption quantity (mg ­g–1) at time t, qe is the equilibrium
–1
adsorption capacity (mg ­g ) q = 2 e
k q2 t 4
t 1+k2 qe t

Elovich A is a constant related to chemisorption rate (mg g ­min–1), and B is qt = A + Blnt 5

a constant which depicts the extent of surface coverage (g ­mg–1)
Interparticle-diffusion model (IPD) Kt is the intraparticle diffusion rate constant (g (mg ­min1/2)–1), and qt = Ktt1∕2 + C 6
C is a constant that gives idea about the thickness of the bound-
ary layer
Langmuir model where qe is the maximum adsorption capacity (mg ­g–1), qm is the qe =
qm KL Ce 7.a
equilibrium adsorption capacity (mg ­g–1), KL is a constant related 1+KL Ce

to the affinity of the binding sites and energy of adsorption (L

­mg–1), and Ce is equilibrium concentration (mg ­L–1)
Separation factor where RL is separation factor, C0 initial concentration of the RL = 1 7.b
adsorbate, and that the adsorption system is regarded as favour- 1+KL Co

able (0 < RL < 1) or unfavourable (RL > 1)

Freundlich model KF is the Freundlich constant related to the comparative adsorption qe = KF Ce
1∕nF 8
capacity (mg ­g–1)/(mg ­L–1) n and 1/n is the affinity of 2,4-D to
TNR-CPC
Koble-Corrigan model A and B are the Koble-Corrigan parameters qe =
ACen 9
1+BCen

Thermodynamic parameters ΔG0 is Gibbs-free energy, R is the ideal gas constant ΔG0 = RTlnKd 10
(8.314 J ­mol–1 ­K–1), K is the thermodynamic equilibrium constant
(Kd = qe/Ce), T is absolute temperature (K)
Relationship between Gibbs-free energy, enthalpy change (ΔH0), ΔG0 = ΔH0 − TΔS0 11
entropy (ΔS0) and absolute temperature (T)
How equilibrium constant is related to enthalpy change, entropy lnKd = ΔS0
− ΔH 0 12
and absolute temperature R RT

where Ea is activation energy, k2 is the pseudo-second-order rate E

lnk = − RTa + lnA 13
constant
Desorption where d is desorption efficiency (%), md is the amount of TNR- d=
md
+ 100% 14
m0
CPC desorbed (g), m0 is the amount of 2,4-D present on the
TNR-CPC before desorption (g)
Regeneration where r is regeneration efficiency (%), q0 is the initial adsorption r=
qn
× 100% 15
capacity of TNR-CPC (mg ­g–1), qn is the adsorption capacity of
q0

TNR-CPC after reuse (mg ­g–1), and n is the number of cycles

carried out (4 cycles)

was cleaned with distilled water and dried at 60 °C to Antibacterial studies

achieve a constant mass. The obtained adsorbents from this
process were the regenerated TNR-CPC (TNR-CPC-R1).
These processes were repeated five consecutive times, and
the desorption efficiency (d) and regeneration efficiency
(r) were calculated from Eqs. (14) and (15) respectively.
The method described by Shi et al. (2007) was modified
and used in the antibacterial studies. At 37 °C, E. coli and
S. aureus were cultured in 50 mL of 3.1 per cent yeast-
dextrose broth (containing 10 g ­L–1 peptone, 8 g ­L–1 beef

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Environmental Science and Pollution Research (2022) 29:64177–64191 64181

extract, 5 g ­L–1 sodium chloride, 5 g ­L–1 glucose and 3 g
­L–1 yeast extract). All glassware and adsorbent samples
(TNR and TNR-CPC) were sterilised in a 120 °C autoclave
for 20 min. The bacteria-containing broth was centrifuged
for 5 min at 3000 rpm, and the supernatant was decanted.
After washing the cells twice with sterile phosphate-buff-
ered solution (PBS), a little amount of PBS solution was
added to achieve a concentration of 107 CFU ­mL–1. The
sample was then submerged in 5 mL of this suspension in
a conical flask and agitated at 200 rpm for 4 h at 37 °C.
The bacteria’s viable cell counts were determined using
the surface spread-plate technique. Then, 1 mL of bacteria
culture was collected from the flask at the designated time,
and decimal serial dilutions with PBS were performed
with each initial sample. After that, 0.1 mL drop of the
diluted sample was placed on duplicate solid growth agar
plates. The number of viable cells (colonies) was manually
counted after 24 h of incubation at 37 °C, and the findings
after multiplication with the dilution factor were repre-
sented as mean colony-forming units (CFU) per millilitre.
Statistical analysis
All experiments were performed in triplicates, and the
means were used for the various calculations. With the
help of Origin 6.0 Professional and Microsoft excel 2010,
the parameters of adsorption isotherm and kinetic data, the
correlation coefficients (R2), sum of square of difference
(SSE) and chi-square statistics (χ2) were calculated and
the data pictorially graphed.
Table 2  Microstructure parameters of TNR and TNR-CPC
Textural Properties TNR
BET surface area ­(m2 ­g–1) 0.319
BET total pore volume ­(cm3 ­g–1) 0.000272
BET pore size (nm) 3.42
Results and discussion
Adsorbent characterization and structural analysis
Brunauer–Emmett–Teller analysis
The textural properties of TNR and TNR-CPC are presented
in Table 2. The specific surface area and pore volume of
TNR decrease significantly after grafting with CPC. The
over 91%, 86% and 85% decrease in BET surface area, pore
volume and pore size could be attributed to CPC molecules
absorbed on the surface of TNR in a possible ‘tail–tail’
interaction which occupies and blocks the structural pores
present on the surface, hence the observed decrease in the
surface textural properties. These observations are in line
with other reports (Poiana et al., 2015; Cao et al., 2021; Liu
et al., 2020; Zou et al., 2020).
Fourier‑transform infrared spectroscopy analysis
Changes in the surface structure chemistry of TNR after
modification with CPC were investigated using FTIR with
results shown in Fig. 1. The stretching and bending vibration
of –OH functional group and molecular ­H2O at 3412 ­cm–1
of TNR shifted to 3405.00 ­cm–1 in the case of TNR-CPC
(Kani et al., 2020). The vibration peaks at 2925 ­cm–1 and
2854 ­cm–1 on TNR which were slightly shifted to 2922 ­cm–1
and 2852 ­cm–1 on the TNR-CPC were assigned to the asym-
metric and symmetric stretching vibration of C–H, from
the –CH, –CH2, –CH3 methylene chains. Such a difference
could be ascribed to the intervention of the alkyl chain of
CPC, which underscores the successful grafting of CPC
onto TNR. The peaks at 3006 ­cm–1 (C–H stretching sym-
metric vibration of the double carbon bonds, –C = CH),
2154 ­cm–1 (which can be assigned in a straightforward fash-
TNR-CPC ion to CO species) and 1746 ­cm–1 (stretching vibration of
C = O) are seen to have disappeared (Poiana et al., 2015;
0.0266
Yang and Wöll, 2017). The peak at 1640 ­cm–1 which shifted
0.0000362
to 112345635 ­cm–1 could be ascribed to the C = C/C = O
0.501

Fig. 1  (a) FTIR spectra of TNR (a) TNR

100 22.57o (200)
before and after CPC modifica- 6000 (b) TNR
TNR-CPC
TNR-CPC
tion; (b) XRD patterns of TNR
80 5000
and TNR-CPC adsorbents
Intensity (a.u.)

4000 34.27o (004)

60
T (%)

3000
40

2000
20

1000
0
0
4000 3500 3000 2500 2000 1500 1000 500 10 20 30 40 50 60 70 80
Wavenumber (cm-1) 2θ (Degrees)

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64182 Environmental Science and Pollution Research (2022) 29:64177–64191

30000 Name Pos %At Name Pos %At

(a) 25000 (b) O1s
C1s 282 eV 45.6 C1s 282 eV 37.9
C1s N1s 397 eV 9.8
O1s N1s 397 eV 13.3
O1s 529 eV 42.5 C1s O1s 529 eV 45.3
20000
Cl 2p 198 eV 2.1 Cl 2p 197 eV 3.5
20000
Intensity (cps)

Intensity (cps)
15000

10000
N1s
10000
N1s 5000 Cl 2p

Cl 2p
0
0

0 200 400 600 800 1000 1200

0 200 400 600 800 1000 1200
Binding Energy (eV) Binding Energy (eV)

(C) Fitted line Fitted line

2000 2500
C-C (281.4 eV) (d) C-C (281.5 eV)
C-H (282.9 eV) C-H (283.0 eV)
C=C / C-C (284.4 eV) 2000 C=C / C-C (284.6 eV)
1500 C-N (285.6 eV) C-N (285.7 eV)
C-O-C (286.7eV)
Intensity (cps)

Intensity (cpc)
1500 C=O (287.6 eV)
1000
1000

500
500

0 0
280 282 284 286 282 284 286 288
Binding Energy (eV) Binding Energy (eV)

300
Fitted line 100 Fitted line
(e) (f)
C-N / N-H (398.2 eV) C-N (398.8 eV)
250 N-H (399.5 eV) N=C (400.3 eV)
N=C (400.9 eV) 80
C-N (401.6 eV)
200 -NH- (402.6 eV)
Intensity (cps)

Intensity (cps)

60
150

40
100

50 20

0 0
398 400 402 404 398 400 402 404
Binding Energy (eV) Binding Energy (eV)

2000
Fitted line
(g) Fitted line (h)
1500 N-O (528.6 eV)
N-O (529.2 eV) C=O (530.2 eV)
1500 C-O-C / OH (531.7 eV) C-O (532.2 eV)
C-O (532.2 eV)
Intensity (cps)
Intensity (cps)

1000
1000

500
500

0 0
528 530 532 534 528 530 532
Binding Energy (eV) Binding Energy (eV)

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 Environmental Science and Pollution Research (2022) 29:64177–64191
◂Fig. 2  Full XPS of TNR-CPC (a), TNR-CPC-2,4-D (b). Typical high
resolution XPS spectra of C1s, N1s, and O1s of TNR-CPC before (c,
e, g) and after (d, f, h) 2,4-D adsorption respectively
stretching vibrations of alkene/carboxyl groups (Njoku
and Hameed, 2011). The band at 1464 ­cm–1 of TNR which
shifted to 1466 c­ m–1 on TNR-CPC can be assigned to –CH
deformation vibration (Liu et al., 2020). The C–N stretching
at 1243 ­cm–1 in the case of TNR shifted to 1262 ­cm–1 for
TNR-CPC. The new peak at 1604 ­cm–1 indicates the pres-
ence C = N group. The intensity of the stretch at 1027 ­cm–1
associated to the C–N/C-O group was altered and appeared
at 1042 ­cm−1 after the incorporation of CPC. The various
alterations and shifting of positions of the original peaks
in TNR suggest the modifications that occurred after the
CPC incorporation. These observed changes in the surface
chemical composition could be attributed to the successful
incorporation of CPC.
X‑ray diffraction analysis
The XRD patterns of TNR and TNR-CPC are presented in
Fig. 1(b). The prominent peaks at 22.57 and 34.27° charac-
teristic of a highly organized crystalline cellulose drastically
reduced while that at 34.27° had disappeared after the modi-
fication by cetylpyridinium chloride. This confirmed that the
CPC modification had caused the crystallinity of TNR to
change into complete amorphous TNR-CPC (Mpatani et al.,
2021). The grafting of CPC onto TNR might have occurred
between the hydroxyl (–OH) groups present at the crystalline
region of the cellulose.
X‑ray photoelectron spectroscopy analysis
The XPS spectra and the deconvoluted N1s spectra of TNR
with peaks at 392.21, 396.78 and 399.59 eV have been
reported by Kani et al. (2021a). After CPC modification,
the XPS survey spectra (Fig. 2(b)) revealed that the pro-
portion of N, O and Cl and elements in TNR-CPC-2,4-D
increased from 9.8 to 13.3, from 42.5 to 45.3 and from 2.1
to 3.5 per cent, respectively. This may confirm the successful
adsorption of 2,4-D molecules on TNR-CPC. In the high-
resolution XPS spectrum (Fig. 2 (c) and (d)), TNR-CPC-
2,4-D contained C–O–C at peaks 286.7 eV and C = O at
peak 287.6 eV which were absent in TNR-CPC. The adsorp-
tion of 2,4-D, which contained carboxyl groups, was primar-
ily responsible for this. The small shift in peaks at 285.6 eV
(C–N) and 284.4 eV (C–C) to 285.7 eV and 284.6 eV after
adsorption, respectively, suggests physisorption due to the
existence of π-π stacking between TNR-CPC and 2,4-D. The
deconvoluted N 1 s spectrum (Fig. 2 (e) and (f)) shows 4
peaks for TNR-CPC; however, after 2,4-D adsorption, the
peak at 402.6 eV assigned to the presence of ­NH2 disappears
64183
probably due to their participation in the reaction. Again,
there is a slight shift in the peak positions with reduced
intensities all attributed to the adsorption of 2,4-D onto
the surface of this eco-friendly adsorbent, TNR-CPC. The
deconvoluted O1s shown in Fig. 2 (g) presents a new peak
at 530.2 eV which is assigned to C = O and was mainly due
to the adsorption of 2,4-D, which contained carboxyl groups.
Adsorption study
pH point of zero charge and effect of initial pH
The pH point of zero charge (pHzpc) determines how facile
a substrate can adsorb potentially harmful ions. TNR-CPC
presented a pHzpc of 6.5 in Fig. 3(a) whereas the unmodi-
fied TNR is reported to have pHzpc value of 5.5 (Kani et al.,
2020). The change in the surface charge can be attributed to
the presence of the pyridine which is more alkaline hence
reducing the acidity of the TNR. This increase in pHzpc
confirms the successful loading of the CPC on TNR. At
pH value below 6.5, a cationic surface is obtained, which is
highly attractive to 2,4-D ions; hence, efficient adsorption of
2,4-D was achieved in acidic medium. The decrease in the
positively charged surface of adsorbent might be responsible
for the observed decrease in the removal efficiency from pH
3 to 10.
The adsorption process on cellulose-based materials and
their engineered forms are most affected by the solution pH;
hence, optimizing the pH of the adsorption system is crucial.
Changes in pH alter the surface charge of the adsorbent and
mediate the electrostatic interactions existing between the
molecules of the adsorbate and the functional groups present
on the surface of the engineered adsorbent. The adsorption
capacity of 2,4-D on TNR-CPC is presented in Fig. 3(b). The
ability of TNR-CPC to remove 2,4-D was more efficient in
acidic medium, with the highest recorded at pH 3. With an
acid dissociation constant (pKa) of 2.7, 2,4-D will exhibit
high dissociation at pH values higher than the pKa; hence,
a sustained repulsion by the negative charges on the surface
of the negatively charged TNR-CPC and the anions of 2,4-D
will occur in alkaline medium resulting in a drastic reduction
in adsorption capacity as shown in Fig. 3(b). Based on the
above observations, pH 3 was selected as the optimal pH for
the kinetic and isotherm studies and that one of the possible
mechanisms for the efficient adsorption of 2,4-D is through
electrostatic interaction as demonstrated in Fig. 4(b). Similar
observations have existed in literature (Binh and Nguyen,
2020).
Effect of TNR‑CPC doze on adsorption performance
The consequence of varying the adsorbent mass on adsorp-
tion efficiency was investigated, and the results are presented
13
64184 Environmental Science and Pollution Research (2022) 29:64177–64191

3 (b)
(a)
60
2
50
1

qe (mg/g)
pH

40
0
2 4 6 8 10 12
30
-1 pHi
20
-2

-3 10
2 4 6 8 10
-4 pH

100
70 (c) 40 (d) Na2SO4
90 NaCl
60
CaCl2
30
50 NaHSO4
80
qe (mg/g)

qe (mg/g)
qe Blank
P%
40
P% 20
70
30

20 60
10
10
50
0 0
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.00 0.02 0.04 0.06 0.08 0.10
Mass (g) C (mol L-1)

Fig. 3  pH point of zero charge of TNR-CPC (a); effect of initial pH on 2,4-D adsorption (b); effect of adsorbent doze (c) and salts (d) on adsorp-
tion efficiency of TNR-CPC

in Fig. 3(c). The sharp increase in the pollutant removal
at higher dose could be attributed to the presence of more
active sites available for binding with the same number of
2,4-D molecules. Although 2,4-D adsorption efficiency
increased with the increasing TNR-CPC dosage, the adsorp-
tion quantity decreased as shown in Fig. 3(c). This can be
attributed to the unsaturation of the active sites on the adsor-
bent surface because of the increase in the ratio of adsorption
sites to the pollutant molecules. These excess available bind-
ing sites being generated which is under exploited results
in the decreasing adsorption quantity. This phenomenon is
consistent with reports by Dovi et al. (2021b).
Effect of ionic strength
Ionic strength has a considerable impact on the adsorp-
tion process. This is explained by the fact that the presence
of salts in an adsorption system can change the intensity
of the electrostatic interactions that occur between the
adsorbent and the adsorbate, thereby influencing the screen-
ing effect of the salt(s) (Moreno-Castilla, 2004; Kuśmierek
et al., 2016). The impact of salt concentrations of ­Na2SO4,
NaCl, ­CaCl2, and ­NaHSO4 on 2,4-D adsorption efficiency
is shown in Fig. 3(d). All of the salts tested clearly had a
substantial influence on the adsorption ability of TNR-CPC
towards 2,4-D. This could be due to the competition effect
existing between the co-existence of salts cations and the
cationic surface of the adsorbent in the solution (Mpatani
et al., 2021). Adsorption capability typically decreases with
increasing salt concentration which might be attributed to
a change in solution pH caused by the addition of salts as
well as the competitive effect between the ions of the salt
and that of the 2,4-D (Kuśmierek et al., 2016). According to
Fig. 3(d), the presence of NaCl resulted in the largest adsorp-
tion amount, whereas the presence of C ­ aCl2 resulted in the
lowest adsorption value. This pattern may be related to the
ionic radius of the generated ions in the solution. The trend
of the salt effect (­CaCl2 > ­Na2SO4 > ­NaHSO4 > NaCl) is

13
Environmental Science and Pollution Research (2022) 29:64177–64191 64185

explained by the fact that ­Ca2+ exhibits more ionic strength Table 3  Parameters of kinetic modelling for 2,4-D adsorption onto
and has a strong positive charge character than the N ­ a2+ TNR-CPC at different temperatures
+
and ­Na . 293 K 303 K 313 K

Pseudo-first-order
Contact time effects and kinetic modelling qe (mg ­g−1) 30.5 ± 0. 6 27.9 ± 0.4 24.7 ± 0.3
k1 ­(min−1) 0.268 ± 0.023 0.179 ± 0.013 0.166 ± 0.010
The evaluation of contact time is one of the most significant R2 0.947 0.949 0.973
factors when evaluating the adsorption potential of adsor- SSE 37.9 24.4 17.4
bents since it aids in modelling performance and draws χ2 5.20 3.06 1.20
appropriate conclusions. Pseudo-first-order kinetic (PSO), Pseudo-second-order
pseudo-second-order kinetic (PSO), Elovich and intra- qe (mg ­g−1) 32.8 ± 0.3 29.6 ± 0.2 26.8 ± 0.2
particle diffusion (IPD) models were fitted to the experi- k2 (g ­mg−1 ­min−1) 0.012 ± 0.000 0.010 ± 0.000 0.009 ± 0.000
mental data points shown in Fig. 3(a). To better understand R2 0.994 0.996 0.993
the nature of the adsorption system, the model depicts the SSE 3.20 2.74 4.12
influence of contact time as a function of temperature. Fol- χ2 0.683 0.233 0.319
lowing the first 10 min, the fitting offers an initial quick and Elovich
rapid adsorption, after which the rate steadily declines until A 12.3 ± 1.0 11.8 ± 1.2 7.86 ± 1.0
around 30 min, when equilibrium was virtually established. B 4.85 ± 0.32 3.95 ± 0.33 4.21 ± 0.28
This might be due to the affinity between the adsorbent and R2 0.944 0.913 0.941
the adsorbate (Tran et al., 2017). There are a high number SSE 72.4 68.0 33.9
of unoccupied active sites on the TNR-CPC that are acces- χ2 5.57 5.23 2.61
sible for adsorption in the start, and the number of vacant IPD
sites decreases over time. The system was exothermic since Kt 2.11 ± 0.35 1.41 ± 0.26 1.70 ± 0.25
higher temperatures did not favour TNR-CPC adsorption C 15.2 ± 2.0 16.0 ± 1.8 11.4 ± 1.6
capability. R2 0.713 0.673 0.759
Based on the model parameters presented in Table 3, the SSE 368 255 138
best model fit for the kinetic investigations was determined. χ 2
28.3 19.63 10.6
The pseudo-second-order kinetic model (PSO) best depicts
the kinetics of the adsorption system based on the values of
coefficient of determination (R2), squared error approxima-
increasing temperatures resulted in decreasing adsorption
tion (SSE) and chi-square statistics (χ2).
capacities. This points an exothermic reaction mechanism.
This finding is consistent with that of Liu et al. (2016)
The experimental data points were fitted using well-
and that of Mpatani et al. (2021); however, in the report
known isotherm models such as Langmuir, Freundlich
by Hameed et al. (2009), experimental data on the adsorp-
and Koble-Corrigan in order to establish and comprehend
tion of 2,4-D on activated carbon fitted best to the PFO. For
the interactions that existed between the molecules of the
temperatures of 293 K, 303 K and 313 K, PSO reported the
adsorbate and the engineered adsorbent. The characteristics
highest R2 values (0.994, 0.996 and 0.993), the lowest SSE
of the fit, such as greater coefficient of determination (R2),
(3.20, 2.74 and 4.12) and the lowest least χ2 (0.683, 0.233
lower sum of squared estimates (SSE) and smaller chi-square
and 0.319). This implies that physisorption may be influ-
statistics (χ2), were used in the nonlinear regression analysis
encing the rate-limiting phase (Dovi et al., 2021b). These
to find the best model fit for the experimental data acquired.
findings are in good agreement with other reports (Binh and
The R2 values obtained for Langmuir, Freundlich and Koble-
Nguyen, 2020; Herrera-García et al., 2019). The existence
Corrigan models from the data reported in Table 4 were
of hydrogen bonding and π-π interactions might explain the
all greater than 0.96, showing that all three models could
suggested adsorption mechanism of 2,4-D onto TNR-CPC.
represent the adsorption process. Because Koble-Corrigan
fitting is a three-parameter isotherm which incorporates
Effects of equilibrium concentration and isotherm fitting both the Langmuir and Freundlich isotherms, it expresses
some advantage over both the Langmuir and the Freundlich
The adsorption of 2,4-D at various concentrations and models, as it will descend to either the Langmuir or the Fre-
temperatures is investigated, and the findings are shown undlich isotherm depending on the experimental conditions
in Fig. 3(b). As the equilibrium concentration increased, (Nnaji et al., 2021; Ayawei et al., 2017).
the adsorption capacity increased steadily whereas the low SSE = ∑ (q – qc)2, q and qc are the experimental value
temperatures were beneficial to the adsorption system since and calculated value according to the model, respectively.

13
64186 Environmental Science and Pollution Research (2022) 29:64177–64191

Table 4  Parameters of adsorption isotherms for 2,4-D adsorption satisfactory Langmuir isotherm fitting indicates a homog-
onto TNR-CPC at different temperatures enous distribution of active sites on the TNR-CPC surface.
298 K 308 K 318 K This means that the TNR-CPC adsorbed layer is one mol-
ecule thick, with Langmuir monolayer adsorption capacities
Langmuir
of 79.3, 77.1 and 90.2 mg ­g–1 at 293 K, 303 K and 313 K,
qm (mg ­g–1) 79.330 ± 0.345 77.134 ± 0.427 90.230 ± 2.896
respectively. Furthermore, the adsorption of 2,4-D by TNR-
KL (L ­mg–1) 0.100 ± 0.001 0.064 ± 0.001 0.024 ± 0.002
CPC was investigated by calculating a dimensionless equi-
R2 0.999 0.999 0.995
librium parameter known as the separation factor (RL) using
SSE 0.907 0.731 7.087
Eq. 7.b. The computed values of RL were 0.167, 0.238 and
χ2 0.101 0.081 0.787
0.455 for temperatures of 293 K, 303 K and 313 K, respec-
Freundlich
tively, indicating that the system was favourable (Aswani
KF 18.7 ± 1.5 12.4 ± 1.4 5.76 ± 0.94
et al., 2020). Furthermore, all of the 1/n values from the
1/n 0.327 ± 0.023 0.394 ± 0.030 0.539 ± 0.040
Freundlich fitting (0.327, 0.394 and 0.539) indicate a good
R2 0.960 0.963 0.967
and favourable adsorption system because 1/n is smaller than
SSE 63.8 50.0 43.0
unity. The Freundlich model adsorption index (KF) corrobo-
χ2 7.09 5.56 4.78
rated the system’s exothermic character, since the values
Koble-Corrigan
dropped with increasing temperature (Herrera-García et al.,
A 8.86 ± 0.28 4.40 ± 0.22 0.885 ± 0.069
2019).
B 0.109 ± 0.003 0.059 ± 0.002 0.012 ± 0.000
As demonstrated in Table 5, the TNR-CPC outperforms
n 0.941 ± 0.017 1.054 ± 0.024 1.33 ± 0.03
some other adsorbents in the removal of 2,4-D. This result
R2 0.999 0.999 0.999
indicates that TNR-CPC has a high capacity for adsorption
SSE 0.358 0.441 0.353
of 2,4-D from solution, and there is some advantage in the
χ2 0.045 0.055 0.044
application of this material.

However, a rigorous review of the data suggests the
incapability of Koble-Corrigan model in defining all the
experimental data since it recorded an n value of 0.941 at
298 K which is less than unity (Aryee et al., 2021b). Lang-
muir model therefore describes best the experimental data
because its model parameters have the highest R2 and least
SSE and χ2 compared with that of the Freundlich model. A
Thermodynamic studies
Thermodynamic parameters are calculated, and the results
are listed in Table 6. The negative values (− 1.53, − 0.95
and − 0.38 kJ ­mol−1) obtained for the change in Gibbs-free
energy (∆G0) at all temperatures investigated showed the
spontaneity of the adsorption process. Increasing temper-
atures resulted in a drop in the absolute values of (∆G0),

Table 5  Langmuir adsorption capacities of adsorbents used to remove 2,4-D in aqueous medium
Adsorbent qm (mg ­g−1) T (K) pH Enthalpy Ref

Yam peels activated carbon 99.01 298.0 2.0 Exothermic Herrera-García et al. (2019)
Aminosilane-grafted mesoporous car 192.0 333.0 3.0 Endothermic Goscianska and Olejnik (2019)
Carbonaceous material (C-C6Cl6) 89.50 2.0 Kuśmierek et al. (2016)
Carbonized chest nut shell 0.93 308.0 Exothermic Gülen and Aslan (2020)
Cetylpyridinium chloride modified Bagasse 66.50 4.0 Mpatani et al. (2021)
Cetylpyridinium chloride modified Pine sawdust 90.90 308.0 2.0 Endothermic Wang et al. (2021a)
Chitosan 11.16 El Harmoudi et al. (2014)
Co-Al-Cl Layered double hydroxides 30.12 298.0 Exothermic Calisto et al. (2019)
Commercial Activated carbon 178.57 283.0 Exothermic Hue et al. (2018)
Corn cob biochar 37.40 298.0 2.0 Binh and Nguyen (2020)
Ethylenediamine modified poly (glycidyl methacrylate) resin 99.45 298.0 3.5 Endothermic Şahin and Emik (2018)
Granular activated carbon 1.431 298.2 3.5 Cho et al. (2003)
Magnetic graphene 32.31 303.2 3.0 Exothermic Liu et al. (2016)
Magnetized yam peels Activated carbon 86.21 298.0 2.0 Exothermic Herrera-García et al. (2019)
Merremia vitifolia biomass 66.93 308.0 6.0 Exothermic Aswani et al. (2020)
Cetylpyridinium chloride modified tiger nut residue 90.2 318.0 3.0 Exothermic This study

13
Environmental Science and Pollution Research (2022) 29:64177–64191 64187

Table 6  Parameters of thermodynamic studies for 2,4-D adsorption (− 18.3 kJ ­mol−1) which is less than 40 kJ ­mol−1, we propose
onto TNR-CPC at different temperatures that physisorption rather than chemisorption is the primary
ΔH0 (kJ ΔS0 ΔG0 (kJ ­mol−1) Ea (kJ process of adsorption (Kani et al., 2020).
­mol−1) (kJ·mol−1 ­K−1) ­mol−1) As described in the isotherm and kinetic studies, increas-
293 K 303 K 313 K
ing the temperature slows the adsorption system, which is
− 18.3 − 0.060 − 1.53 − 0.95 − 0.38 – 11.0 related with negative activation energy (E a) (Revell and
Williamson, 2013; Vyazovkin, 2016). This observed acti-
vation energy of − 11.0 kJ ­mol−1 also suggests physisorp-
indicating that high temperatures were detrimental to the tion (Zhang et al., 2014). Finally, the small negative value
adsorption system. The negative values of enthalpy change of ΔS0 in Table 6 indicates a shift in entropy of the aqueous
(ΔH0) in Table 6 confirm the exothermic character of the solid-solute interface reflecting decreased randomness (Dovi
adsorption system once more. Based on the value of (ΔH0) et al., 2021b; Kani et al., 2020). The results presented here

70 (b)
(a)
35
60
30
50
25
qe (mg/g)
qe (mg/g)

40
20 293 K 293 K
303 K 30 303 K
15 313 K
313 K
PFO
20 Langmuir
10 PSO
Freundlich
ELOVICH
10 Koble-Corrigan
5 IPD

0 20 40 60 80 100 120 0 10 20 30 40 50 60 70 80

t (min) Ce (mg/L)

Fig. 4  Effect of time and kinetic modelling (a), equilibrium concentration and adsorption isotherm modelling of 2,4-D adsorption onto TNR-
CPC (b)

(a) Regeneration
Desorption
100
Percentage %

80

60

40

20

0
1st 2nd 3rd 4th
Cycle

Fig. 5  Desorption and regeneration performance of TNR-CPC (a), and the possible adsorption mechanism of 2,4-D onto TNR-CPC (b)

13
64188
are consistent to those reported elsewhere (Şahin and Emik,
2018; Liu et al., 2016; Nejati et al., 2013).
Regeneration and reusability studies
A well-studied regeneration process might aid in understand-
ing the chemical interactions that drive pollutant absorption,
such as 2,4-D pesticide. In addition, reusability profiles will
aid in determining the adsorbent’s economic feasibility, as
opposed to secondary contamination (Kani et al., 2021a;
Wang et al., 2021b). Several regeneration systems including
acids, alcohols, bases, steam and heat have all been exam-
ined as eluent solutions for various adsorbents. The physico-
chemical properties of both the adsorbate and the adsorbent,
however, influence the selection of a regeneration system
(Cho et al., 2003). The optimal eluent system was discovered
to be 0.1 mol ­L–1 NaOH, and after four cycles, the adsorbent
has desorption and regeneration efficiency of 81.3 and 90%,
respectively (Fig. 4(a)), making it highly economical. We
found these results to be in line with an established data
(Wang et al., 2021a).
Adsorption mechanism
Based on the results discussed above, the plausible adsorp-
tion mechanism for 2,4-D onto TNR-CPC is explained and
depicted in Fig. 4(b). In an acidic medium, the surfaces of
the adsorbent and adsorbate are charged. The carboxylate
anion of 2,4-D is attracted to the pyridinium cation of TNR-
CPC in solution by electrostatic forces. This was evident as,
at low pH, adsorption was at its peak. Furthermore, the C–N
(398.2 eV), N − H (399.5 eV) and N = C (400.9 eV) peaks
in the N 1 s spectrum (Fig. 2(e) and (f)) shifted to 398.8 eV,
400.3 eV and 401.6 eV, respectively, due to increased elec-
tron cloud density after 2,4-D adsorption via electrostatic
attraction and hydrogen bonding between 2,4-D and TNR-
CPC (Wu et al., 2021). Hydrogen bonding might be present
between the hydroxyl (− OH) group inherent in the TNR and
the carboxyl (COOH) group present in the 2,4-D molecules.
Also, the presence of C–O–C and C = O peaks at 286.7 eV
and 287.6 eV, which are associated with the carboxyl groups
of 2,4-D, which were found on the adsorbent after adsorp-
tion, is likely to exist through hydrogen bonding. Further-
more, the benzene structures in lignin found in the TNR
plant material may have triggered a π-π stacking between
the benzene structures in the adsorbate, hence influencing
the adsorption system.
The presence of π-π stacking between TNR-CPC and
2,4-D was observed in the deconvoluted XPS profiles as
the C − N and C − C peaks, which were at 285.6 eV and
284.40 eV prior to the adsorption process but had shifted
to 285.7 eV and 284.6 eV after the adsorption process (Wu
et al., 2021). The increase in the relative amounts of Cl, N
13
Environmental Science and Pollution Research (2022) 29:64177–64191
and O elements from 2.1 to 3.5%, 9.8 to 13.3% and from
42.5 to 45.3%, respectively, affirmed the adsorption of 2,4-D
molecules on TNR-CPC. In addition, the decrease in carbon
content from 45.6 to 37.9 per cent (Fig. 2(a, b)) confirmed
the adsorption process’s success.
Antibacterial efficiency of adsorbent
The impact of the adsorbent on the growth of S. aureus
(gram-positive bacteria) and E. coli (gram-negative bacte-
ria) is shown in Fig. 5. TNR-CPC inhibited S. aureus and
E. coli growth in a yeast-dextrose broth with a 99% success
rate. In a comparable investigation, the adsorbent described
by Aryee et al. (2021a) demonstrated 96.8% inhibition effec-
tiveness against S. aureus and 82.3% inhibition efficiency
against E. coli, respectively. Aryee and Han (2022) recently
reported on another adsorbent (betaine-modified peanut
husk) that was only effective in inhibiting 50% of S. aureus
growth but had no effect on E. coli growth Fig. 6.
Because our adsorbent can inhibit the development of
both gram-positive and gram-negative bacteria, it is fair to
posit that it will be effective against a wide range of bac-
terial species. The bacteria killing potential of TNR-CPC
could be attributed to the quaternary ammonium compound
(cetylpyridinium chloride) used to modify the pristine TNR,
which likely resulted in the disruption of the cytoplasmic
membrane, causing cell death, similar to the mechanism
proposed by Shi et al. (2007). TNR-CPC might be explored
further as a potential replacement to the present metal oxides
used in wastewater treatment for antibacterial capabilities,
and its effects against airborne bacteria could also be of
interest.
Conclusion
In the present study, we have engineered tiger nut residue
with cetylpyridinium chloride to take advantage of the
introduced functional groups to remove 2,4-D from aque-
ous solution in a batch mode. The surface characteriza-
tions by FTIR, BET, XRD and XPS confirmed the success-
ful modification of the surface of TNR. Through a batch
adsorption study, we confirmed that solution pH, adsorbent
dose, temperature and salt had a significant bearing on the
adsorptive capacity of TNR-CPC. The equilibrium data
were best described by Langmuir isotherm model. Pseudo-
second-order model best described the kinetics. Physisorp-
tion largely mediated the adsorption system with spontaneity
and a shift in entropy of the aqueous solid-solute interface
reflecting decreased randomness with an exothermic char-
acter. TNR-CPC demonstrated a good reusability potential
making it highly economical and compares well with other
adsorbents for decontamination of 2,4-D. The adsorption
Environmental Science and Pollution Research (2022) 29:64177–64191 64189

Fig. 6  Inhibition effect of TNR-

CPC towards the growth of E.
coli and S. aureus (1A E. coli;
1B E. coli + TNR-CPC; 2A S.
aureus; 2B S. aureus + TNR-
CPC)

of 2,4-D proceeded through a probable trio-mechanism:
(1) electrostatic attraction between the carboxylate anion of
2,4-D and the pyridinium cation of TNR-CPC, (2) hydrogen
bonding between the hydroxyl (–OH) group inherent in the
TNR and the carboxyl groups in 2,4-D and (3) a triggered
π-π stacking between the benzene structures in the adsorbate
and the adsorbent. TNR-CPC reported about 99% inhibi-
tion rate against both gram-positive S. aureus and gram-
negative E. coli. The bacteria-killing potential of TNR-CPC
could be attributed to the quaternary ammonium compound
(cetylpyridinium chloride) used to modify the pristine TNR.
It would be appropriate to investigate the potential of TNR-
CPC as a potential replacement to the metal oxides used in
wastewater treatment for antibacterial capabilities, and its
effects against airborne bacteria could also be of interest.
5. Lingbo Qu (qulingbo@zzu.edu.cn): contributed to resources and
funding acquisition
Funding The research was supported by the National Key Research
and Development Program of China (2018YFD0401402–04) and
Zhongyuan Scholars Foundation (202101510005).
Data availability All data generated or analysed during this study are
included in this article.
Declarations
Ethics approval Not applicable.
Consent to participate Not applicable.
Consent for publication Not applicable.

Competing interests The authors declare no competing interests.

Author contribution 1. Alexander Nti Kani (mykani@yahoo.com):

contributed to conceptualization, methodology, investigation, writing-
original draft, review and editing.
2. Evans Dovi (evansdovy@gmail.com): contributed to formal
analysis, investigation, writing-review and editing.
3. Aaron Albert Aryee (a.niiayi@yahoo.com): contributed to writ-
ing-review and editing.
4. Runping Han(rphan67@zzu.edu.cn): contributed to conceptual-
ization, resources, project administration, writing-review and editing,
supervision and funding acquisition.
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