RPM2

nanomaterials
Article
Performance of Pristine versus Magnetized Orange Peels
Biochar Adapted to Adsorptive Removal of Daunorubicin:
Eco-Structuring, Kinetics and Equilibrium Studies
Ahmed S. El-Shafie * , Farahnaz G. Barah, Maha Abouseada and Marwa El-Azazy *
Department of Chemistry and Earth Sciences, College of Arts and Sciences, Qatar University, Doha 2713, Qatar
* Correspondence: aelshafie@qu.edu.qa (A.S.E.-S.); marwasaid@qu.edu.qa (M.E.-A.);
Tel.: +974-4403-4675 (M.E.-A.); Fax: +974-4403-4651 (A.S.E.-S. & M.E.-A.)
Abstract: Drugs and pharmaceuticals are an emergent class of aquatic contaminants. The existence
of these pollutants in aquatic bodies is currently raising escalating concerns because of their neg-
ative impact on the ecosystem. This study investigated the efficacy of two sorbents derived from
orange peels (OP) biochar (OPBC) for the removal of the antineoplastic drug daunorubicin (DNB)
from pharmaceutical wastewater. The adsorbents included pristine (OPBC) and magnetite (Fe3 O4 )-
impregnated (MAG-OPBC) biochars. Waste-derived materials offer a sustainable and cost-effective
solution to wastewater bioremediation. The results showed that impregnation with Fe3 O4 altered
the crystallization degree and increased the surface area from 6.99 m2 /g in OPBC to 60.76 m2 /g in
the case of MAG-OPBC. Placket–Burman Design (PBD) was employed to conduct batch adsorption
experiments. The removal efficiency of MAG-OPBC (98.51%) was higher compared to OPBC (86.46%).
DNB adsorption onto OPBC followed the D–R isotherm, compared to the Langmuir isotherm in the
case of MAG-OPBC. The maximum adsorption capacity (qmax ) was 172.43 mg/g for MAG-OPBC
and 83.75 mg/g for OPBC. The adsorption kinetics for both sorbents fitted well with the pseudo-
second-order (PSO) model. The results indicate that MAG-OPBC is a promising adsorbent for treating
pharmaceutical wastewater.
Citation: El-Shafie, A.S.; Barah, F.G.;
Abouseada, M.; El-Azazy, M.
Keywords: orange peels biochar; magnetic biochar; daunorubicin; Plackett–Burman design;
Performance of Pristine versus
Magnetized Orange Peels Biochar
desirability function
Adapted to Adsorptive Removal of
Daunorubicin: Eco-Structuring,
Kinetics and Equilibrium Studies.
Nanomaterials 2023, 13, 1444. 1. Introduction
https://doi.org/10.3390/ The past few decades have seen a growing use of antineoplastics for chemotherapy.
nano13091444 Many of the cytostatic drugs, though being used for abatement of cancer, have been
Academic Editor: Mingyi Zhang classified as CMR chemicals, i.e., carcinogenic, mutagenic, and reprotoxic. The escalating
consumption and the associated risks are prompting inevitable concerns related to their
Received: 31 March 2023 occupational exposure and the consequent ecotoxicological threats [1,2]. By and large,
Revised: 19 April 2023
the rates of consumption of cytostatic drugs are relatively low compared to the other
Accepted: 21 April 2023
pharmaceutically active compounds. Their existence in the water cycle, hence, seems
Published: 23 April 2023
questionable. Parallel to that, the environmental risk assessment process is usually executed
for newly permitted pharmaceuticals, therefore, the majority of cytostatic drugs might not
be exposed to such an assessment. With these considerations, the investigations targeting
Copyright: © 2023 by the authors.
the presence and the removal of cytostatic drugs are limited [2,3].
Licensee MDPI, Basel, Switzerland. Daunorubicin (DNB), also known as daunomycin, Scheme 1, is a cytostatic antibiotic
This article is an open access article that belongs to the family of anthracyclines. DNB is commonly used in the treatment
distributed under the terms and of different types of acute leukemia and as a combination therapy in the treatment of
conditions of the Creative Commons lymphoma, breast, and bladder cancers [4]. Being widely used, DNB is on the World
Attribution (CC BY) license (https:// Health Organization’s List of Essential Medicines [5]. As per the International Agency on
creativecommons.org/licenses/by/ the Research of Cancer (IARC), DNB is classified as category 2B carcinogenic (possibly
4.0/). carcinogenic) [6]. Compared to the other family members, higher percentage, around
Nanomaterials 2023, 13, 1444. https://doi.org/10.3390/nano13091444 https://www.mdpi.com/journal/nanomaterials

Organization’s List of Essential Medicines [5]. As per the International Agency
Nanomaterials 2023, 13, 1444 search of Cancer (IARC), DNB is classified as category 2B carcinogenic 2 of 23(possib
genic) [6]. Compared to the other family members, higher percentage, around
DNB, is excreted unmetabolized in urine within 24 h. DNB was detected in th
13–15% of DNB,
260–1350 ng/Lisin
excreted unmetabolized
oncological wardsinwastewaters
urine within 24 h. DNB
[1]. Thewas detected inof
detection theDNB in
range of 260–1350 ng/L in oncological wards wastewaters [1]. The detection of DNB in
concentrations raises concerns about the efficiency of the wastewater trea
such high concentrations raises concerns about the efficiency of the wastewater treatment
proaches
approachescurrently pursued.
currently pursued.
Scheme 1. Chemical structure of daunorubicin (DNB), molar mass (DNB hydrochloride) = 527.52 g/mol,
Scheme 1. Chemical structure of daunorubicin (DNB), molar mass (DNB hydrochlorid
pKa1 = 7.48, pKa2 = 9.68 [7].
g/mol, pKa1 = 7.48, pKa2 = 9.68 [7].
Literature surveying shows that not much attention has been paid to the removal
of antineoplastics
Literature from contaminated
surveying showswaters,
that notespecially
muchDNB. Therefore,
attention hasthe beenecological
paid to the r
impact of DNB and its fate remain poorly comprehended. Table 1 shows a glance at
antineoplastics from contaminated waters, especially DNB. Therefore, the eco
literature efforts made to remove antineoplastics from different water matrices. Removal
pact of DNB
strategies andadsorption,
included its fate remain poorlyphotocatalysis,
nanofiltration, comprehended. membraneTable 1 shows and
bioreactors, a glance a
efforts madeoxidation
Fenton/ozone to remove antineoplastics
processes [7–14]. from different water matrices. Remova
Adsorption of pharmaceuticals onto
included adsorption, nanofiltration, photocatalysis, biochars, especially those generated via
membrane the
bioreactors,
pyrolysis of agro-waste biomasses, has been the subject of several investigations [15–21].
ton/ozone oxidation processes [7–14].
However, much fewer attempts have been made to remove the cytostatic drugs via sorption
Adsorption
onto biochars. Within ofthe
pharmaceuticals
continuous rivalries onto biochars, green
for developing especially
solutions those generated
for water
rolysis
remediation of agro-waste
and under the biomasses, has been
umbrella of circular economy,therecycling
subjectagro-waste
of several investigation
materials
into value-added products is a widely used approach. On the one hand, agro-waste
However, much fewer attempts have been made to remove the cytostatic drug
materials are available at almost no cost and could represent a burden on the environment
tion
if notonto biochars.
properly recycledWithin
[22–24].the On continuous
the other hand, rivalries
biochars for developing
obtained green
via pyrolysis of solutio
ter
the remediation and under
lignocellulosic materials the umbrella
are greatly privilegedof circular
with their higheconomy,
surface area, recycling
pore sizeagro-w
and volume,
rials existence of various
into value-added products functionalities,
is a widely andused
liability for functionalization
approach. On the one andhand, a
regeneration, making them excellent candidates for scavenging of contaminants [25–30].
materials are available at almost no cost and could represent a burden on the en
Within these premises, orange peels (Citrus sinensis) are ubiquitously and copiously
ifavailable
not properly recycled
as a byproduct of the[22–24]. On theindustry.
juice processing other hand,
The world biochars
production obtained
of orangesvia pyro
6
lignocellulosic
amounted to almost materials
half of the are
global greatly privileged
production with124
of citrus fruits, their
× 10high tons,surface area, po
in 2016, as
per the UN Food and Agriculture
volume, existence of various functionalities, Organization report [31]. According to this report,
and liability for functionalization the
total imports of Qatar from citrus totaled 46.4 × 103 tons in 2016, with oranges representing
eration,
almost half. making
Recyclingthem excellent
waste candidates
peels is, therefore, for scavenging
a sustainable solution, of contaminants
especially in the [25–
majorWithin
producing these premises, orange peels (Citrus sinensis) are ubiquitously and
countries.
Parallel
available aswith the sustainability
a byproduct of theoffered
juice by the valorization
processing of agro-wastes,
industry. The world functional-
production
ization of the biochar with magnetite (Fe3 O4 ) nanoparticles is a plus. Magnetic nanosor- 6
amounted to almost half of the global production of citrus fruits, 124 × 10 ton
bents possess high surface area and could be used on a large scale to treat large volumes
as per the
of water thanksUNtoFood and Agriculture
the feasibility Organization
of their separation report [31].
using a low-strength According
external mag- to t
the total imports of Qatar from citrus totaled 46.4 × 10 tons in 2016, with oran
netic field [32–36]. In the current investigation, biochar of orange 3
peels (OPBC) and the
magnetite-loaded
senting almost biochar (MAG-OPBC)
half. Recycling will bepeels
waste synthesized and exploited
is, therefore, for the removal
a sustainable solution,
of DNB from synthetic wastewater.
in the major producing countries.
Parallel with the sustainability offered by the valorization of agro-wastes, f
ization of the biochar with magnetite (Fe3O4) nanoparticles is a plus. Magn
sorbents possess high surface area and could be used on a large scale to treat
umes of water thanks to the feasibility of their separation using a low-strengt
magnetic field [32–36]. In the current investigation, biochar of orange peels (O
the magnetite-loaded biochar (MAG-OPBC) will be synthesized and exploited
Nanomaterials 2023, 13, 1444 3 of 23
Table 1. Removal of antineoplastics from contaminated waters using different strategies.
Antineoplastic Drug Strategy Source of Drug Process Optimization Removal Efficiency Ref.
Adsorption using two sorbents:
Orange peels’ biochar (OPBC) OPBC: 86.46%
Daunorubicin Synthetic wastewater Plackett–Burman Design, PBD This Study
and the magnetic counterpart MAG-OPBC: 98.51%
(MAG-OPBC)
Under the given working conditions of 60
ppm [drug], a contact time of 60 min, 0.15 g of
adsorbent, a wastewater volume of 25 mL,
Adsorption on synthesized Synthetic pharmaceutical
Daunorubicin, doxorubicin Univariate analysis and at ambient temperature, the %R of [7]
hydrophilic silica aerogels wastewater
doxorubicin was 97.11%, which was only
slightly higher compared to daunorubicin at
96.89%.
Dead biomass showed a maximum removal
of 38% ± 5% in the case of bleomycin,
Bleomycin and vincristine Biosorption on fungal biomass Aqueous solution Central composite design (CCD) [8]
compared to 20% ± 6% using the active
biomass in the case of vincristine
Adsorption removed doxorubicin, epirubicin,
and tamoxifen, while biodegradation and
Cyclophosphamide, azathioprine, forward osmosis rejection removed
methotrexate, doxorubicin, Anaerobic osmotic membrane methotrexate and cyclophosphamide,
Synthetic domestic wastewater Univariate analysis [9]
epirubicin, flutamide, mitotane, bioreactor respectively. Mitotane, azathioprine, and
and tamoxifen flutamide were eradicated through a
combination of biodegradation and
adsorption.
The living microalga exhibited a higher
maximum sorption capacity of
Biosorption using living and 26.8 mg g−1 compared to the dead biomass at
Flutamide Synthetic wastewater RSM [10]
dead biomass of Chlorella vulgaris 12.5 mg g−1 . By utilizing the living biomass, a
%R of 98.5%
was attained.
CoFe2 O4 nanoparticles in The drug removal efficiency reached 67.7%
Flutamide Synthetic wastewater RSM [11]
Fenton/ozone oxidation process under optimal conditions.
A pair of membrane bioreactors
Cyclophosphamide (CP) and its were operated in parallel, where The operational conditions studied resulted in
metabolite: one was fed with the drug and its Municipal wastewater Univariate analysis an 80% removal of both CP and its metabolite, [12]
4-ketocyclophosphamide primary metabolites, while the 4-ketocyclophosphamide.
other received no drug.
Table 1. Cont.
Antineoplastic Drug Strategy Source of Drug Process Optimization Removal Efficiency Ref.
The drug %R of the individual algae
treatment and individual photocatalysis
A treatment process that were 67.2% and 66.6%, respectively,
Response surface
Flutamide combines photocatalysis and Synthetic wastewater under the optimum conditions. [13]
methodology (RSM)
algae in a single stage. However, the combined process
achieved a significantly higher removal
efficiency of 85.1%.
Compared to the NF270 membrane, the
Desal 5DK membrane demonstrated
Paclitaxel, etoposide, laboratory degree water, greater effectiveness. The Desal 5DK
Nanofiltration using Desal No investigation of variables
cyclophosphamide, synthetic urine, actual membrane exhibited an average rejection [14]
5DK and NF270 membranes was made
ifosfamide secondary effluent rate of more than 89% for the four drugs
that were introduced into both synthetic
urine and real secondary effluent.
Application of both sorbents in treating contaminated samples will be controlled by

implementing a multivariate-based stratagem. In this itinerary, and in alignment with the
greenness preservation, Plackett–Burman design (PBD) will be executed as the screening
design, followed by an optimization phase using the desirability function [18,37–39]. The
target is to get the utmost response with the lowest possible usage of resources and hence
generation of waste. Four variables that are expected to impact the removal efficiency (%R)
of the two sorbents will be assessed. The objective will be set to have the maximum %R
as a function of the independent variables: pH, biochar dose (AD), [DNB] and contact
time (CT). The novelty of this approach, therefore, stems from being, to the best of authors’
knowledge, the first sustainable and green approach that deals with using the biochar
of orange peels as pristine and loaded with magnetite in removing DNB executing a
multivariate-based scheme.
2. Materials and Methods

2.1. Chemicals
In this study, deionized water was taken from a Millipore-Q water system (Burlington,
MA, USA), while all reagents used were of analytical grade and used as purchased with no
additional purification. Daunorubicin (DNB) was purchased from Biosynth® Carbosynth
Ltd. (Compton, Berkshire, UK). Hydrochloric acid, sodium hydroxide, ammonium iron (III)
sulfate dodecahydrate (NH4 Fe(SO4 )2 ·12H2 O), and ferrous ammonium sulfate hexahydrate
(Fe(NH4 )2 (SO4 )2 ·6H2 O) were procured from Sigma–Aldrich (St. Louis, MO, USA). Navel
orange peels were obtained from a juice store in Doha, Qatar.
2.2. Preparation of OPBC

The orange peels underwent a thorough cleaning process, which involved washing
five times with distilled water and another five times with deionized water. The peels were
then sliced into smaller cuts, roughly 2 × 2 cm, and were allowed to dry out in open air
(in the shade) for three days. In the next stage, the peels were further dried in an oven
at 80 ◦ C for three successive days until they became brittle. Once entirely dry, the peels
were crushed into a fine powder. A clean and dry crucible was used to hold 10 g of the
powdered peels, which were then covered up with a cap and disposed of in a furnace. The
crucible was sealed and heated at 500 ◦ C for 1 h. Afterwards, the crucible was let to cool to
room temperature, and the peels were divided into two portions, labeled as OPBC, and
kept in the desiccator for future use.
2.3. Preparation of MAG-OPBC

The magnetic biochar known as MAG-OPBC was produced utilizing a co-precipitation
technique [40,41]. The process involved mixing a 200 mL aqueous solution of 0.50 M Fe(II)
with a 400 mL equimolar solution of Fe(III) and agitating the resulting mixture at 600 rpm
and 60 ◦ C for 1 h. Subsequently, 10 g of OPBC was added to the mixture and stirred at 60 ◦ C
for 3 h. A 4 M aqueous solution of sodium hydroxide was then introduced to the suspension
slowly until the pH was ~12. After 30 min. of gentle stirring at room temperature, the
suspension underwent 10 washes with distilled water followed by 5 additional washes
with methanol. The MAG-OPBC that was obtained was filtered under vacuum and dried
up overnight at 70 ◦ C before being stored in uncontaminated vials for future applications.
2.4. Measurment of the Point-of-Zero-Charge (pHPZC )

To determine the pHPZC of OPBC and MAG-OPBC, 1.0000 ± 0.0005 g of each ad-
sorbent was placed into seven separate beakers with 50 mL of aqueous sodium chloride
solution (0.01 M). The pH of the solution was then adjusted within the studied range of
2.5–10.0 ± 0.2, using diluted solutions of either hydrochloric acid or sodium hydroxide.
The samples were mixed for 24 h at 200 rpm using a mechanical shaker before detecting
the final pH. pHPZC for both OPBC and MAG-OPBC was then calculated by intersecting
the pHfinal and pHinitial curves [42].
2.5. Characterization of OPBC and MAG-OPBC

Thermal gravimetric analysis (TGA, PerkinElmer-TGA400, Waltham, MA, USA) was
carried out at a temperature range of 30–900 ◦ C at a rate of 10.00 ◦ C/min and in the presence
of air. TGA was used to investigate the thermal stability of the prepared adsorbents. Fourier
transform infrared spectroscopy (FT-IR, Bruker Alpha, MA, USA) was employed to verify
the presence of functional groups on the adsorbent surface. Raman spectroscopy (Thermo
Scientific, Waltham, MA, USA) was used to confirm the conversion of peels into carbona-
ceous material and the formation of magnetite nanoparticles on the surface of the adsorbent.
The sample was first ground with potassium bromide to form a thin and homogeneous
mixture. The mixture was then compressed into a pellet using a hydraulic press to produce
a thin, transparent film, which was used for FT-IR and Raman analyses. To examine the
morphology and textural properties of both adsorbents, a scanning electron microscope
(SEM, FEI, Quanta 200, Thermo Scientific, Waltham, MA, USA) was utilized. Moreover, the
elemental composition of both samples was determined using an energy-dispersive X-ray
spectrometer (EDX). A transmission electron microscope (TEM, FEI, TECNAI G2 TEM,
TF20) was used to characterize the microstructure of both sorbents. The preparation of the
TEM sample for both magnetic and non-magnetic sorbents was done by dispersing the
sample in warm distilled water followed by ultrasonic mixing for 30 min. The samples were
subsequently mounted on a carbon-coated grid. Porosity and surface area were measured
using a Micromeritics ASAPTM 2020 accelerated surface area and porosimetry system.
Before N2 adsorption-desorption, the samples were degassed, and isotherms collected
at 77 K were used to calculate the surface area using the Brunauer–Emmett–Teller (BET)
equation. The t-plots and the Barrett–Joyner–Halenda (BJH) equations were utilized to find
the pore volume.
2.6. Batch Adsorption Experiments

For the batch experimental runs, a stock solution of DNB in water with a concentration
of 100 ppm was used. The pH of the water used to suspend OPBC and MAG-OPBC
was adjusted to the desired levels by adding 0.1 M solutions of hydrochloric acid or
sodium hydroxide, as specified in Table 2. A pH meter from Jenway (Cole-Parmer, Stone,
Staffordshire, UK) was utilized to measure the pH, while a UV-Vis spectrophotometer
from Agilent (Santa Clara, CA, USA) with matched quartz cells of 10 mm was used to
determine the concentrations of DNB before and after it was adsorbed onto the sorbent.
The supernatant solution was filtered using a non-sterile nylon Millex syringe filter with a
pore size of 0.45 µm.
2.7. Plackett–Burman Design Execution

To spot the statistically significant variables for better removal of DNB, a saturated
orthogonal statistical screening design, PBD was executed [43,44]. Herein, the design
involved 26 experimental runs (encompassing 6 central points, Ct Pt) for 4 independent
variables coded as A, B, C, and D, as shown in Table 2. All variables were of the numerical
type. All 26 experimental runs were performed in triplicate, and an average value was
recorded as the dependent response, %R. Obtained results were further validated versus the
predicted values provided by Minitab® . Precise optimization of the statistically significant
variables was performed in a subsequent phase using the desirability function tool (d).
The coefficient of determination (R2 ), adjusted-R2 (R2 -adj), and predicted R2 (R2 -pred), as
well as the analysis of variance (ANOVA) and the impact of the standardized effects of all
variables on DNB removal, were determined using Minitab® 19 software.
2.8. Equilibrium and Kinetics Investigation

Deionized water was used to prepare a range of dilutions for DNB, with concentrations
varying from 5–300 ppm. The pH of the solutions was attuned to 9.0 ± 0.2. A mass of
0.1000 ± 0.0005 g of both OPBC and MAG-OPBC was added to each drug solution, and the
mixture was shaken for 48 h at 200 rpm using an automatic shaker. The resulting solutions
were filtered, and the absorbance was measured at 496 nm.
Table 2. Studied variables, matrix, as well as the observed (Obs.) and the predicted (Pred.) for the
PBD executed to investigate the statistical significance of each variable. Values of Obs. and Pred.
responses are contrasted using the value of the relative error (RE).
Variable Low (−) Central (0) High (+)

pH (A, pH unit) 3.0 6.0 9.0
Contact Time (CT, B, min) 10.0 50.0 90.0
Initial DNB Concentration ([DNB], C, ppm) 10.0 55.0 100.0
Sorbent Dosage (AD, D, mg/13 mL) 20.0 70.0 120.0
Trial Variable–Coded Levels * %ROPBC * %RMAG-OPBC

Number A B C D Obs. Pred. RE Obs. Pred. RE
01 − + + − 56.87 60.19 0.06 57.44 57.43 0.00
02 + + + − 62.80 65.99 0.05 62.88 60.22 0.04
03 − − + + 76.02 78.86 0.04 96.30 85.51 0.13
04 + − + − 70.62 73.53 0.04 76.15 75.26 0.01
05 + + + + 75.46 77.59 0.03 78.84 71.62 0.10
06 0 0 0 0 83.37 83.73 0.00 86.61 84.82 0.02
07 0 0 0 0 82.62 83.73 0.01 85.58 84.82 0.09
08 + − + + 84.04 86.46 0.03 86.25 89.51 0.04
09 − − − + 71.22 74.22 0.04 63.51 65.26 0.03
10 + + − + 69.68 73.04 0.05 57.95 54.66 0.06
11 + − − + 75.02 81.38 0.08 65.45 68.32 0.04
12 − + + + 67.74 70.77 0.04 68.80 68.42 0.01
13 0 0 0 0 83.39 83.73 0.00 87.49 84.82 0.03
14 − + − + 70.04 66.62 0.05 54.31 52.21 0.04
15 + + − − 64.91 62.11 0.05 43.06 45.96 0.06
16 − − − − 65.45 63.12 0.04 55.03 54.86 0.00
17 − − + − 70.05 67.06 0.04 70.06 71.89 0.03
18 + − + + 91.76 86.46 0.06 85.57 89.51 0.04
19 + + − − 65.03 62.11 0.05 45.03 45.96 0.02
20 0 0 0 0 86.04 83.73 0.03 82.41 84.82 0.03
21 − + + − 62.27 60.19 0.03 53.21 57.52 0.07
22 0 0 0 0 81.02 83.73 0.03 81.18 84.82 0.04
23 − + − + 70.08 66.61 0.05 48.30 52.21 0.07
24 0 0 0 0 86.05 83.73 0.03 85.80 84.82 0.01
25 − − − − 65.47 63.12 0.04 54.83 54.83 0.00
26 + − − − 72.93 69.21 0.05 60.08 57.47 0.05
C0 −Ce
* The response, %R, was computed using the equation: (%R) = C0 × 100%, where C0 and Ce denote the
initial and equilibrium concentrations of DNB.
To evaluate the adsorption kinetics of DNB onto OPBC and MAG-OPC, 200 mL
of DNB solution (at a concentration of 100 ppm and a pH of 9.0 ± 0.2) was added to
0.5000 ± 0.0005 g of the adsorbent and stirred continuously at 500 rpm. Aliquots of 10 mL
Nanomaterials 2023,
Nanomaterials 13,13,
2023, x FOR
1444 PEER REVIEW 8 of 238 of 24
3.were taken from the reaction mixture at various time intervals over 150 min and filtered.
Results
The absorbance of the resulting filtrate was then recorded at 496 nm.
3.1. Characterization and Surface Chemistry
3. Results
3.1.1. Thermogravimetric Analysis (TGA)
3.1. Characterization and Surface Chemistry
Figure 1 displays the TGA/dTA analysis findings. The results obtained indicate that
3.1.1. Thermogravimetric Analysis (TGA)
the OPBC and MAG-OPBC samples exhibited a weight loss of 8.29 and 7.39%, respec-
tively,Figure
in the1 displays the TGA/dTA
temperature range ofanalysis
50–200 findings. The results to
°C corresponding obtained indicate that
the evaporation of free
the OPBC and MAG-OPBC samples exhibited a weight loss of 8.29 and 7.39%, respectively,
water. Additionally, in the range of◦ 350–600 °C, there was a weight loss for both OPBC
in the temperature range of 50–200 C corresponding to the evaporation of free water.
and MAG-OPBC samples, 73.04% and 64.29%, respectively. This weight loss could be as-
Additionally, in the range of 350–600 ◦ C, there was a weight loss for both OPBC and MAG-
cribed
OPBCto the loss73.04%
samples, of the organic matter
and 64.29%, and the carbonization
respectively. This weight of the
loss polymeric
could components
be ascribed to
inthe
both
losssamples. The total
of the organic weight
matter and theloss for OPBC of
carbonization wasthe82.68%, compared
polymeric to 77.61%
components in bothin the
case of MAG-OPBC.
samples. The difference
The total weight in the
loss for OPBC wasweight
82.68%,loss betweentothe
compared two in
77.61% samples
the casecould
of be
attributed to the presence of magnetic nanoparticles on the surface of MAG-OPBC,
MAG-OPBC. The difference in the weight loss between the two samples could be attributed which
to the presence
increased of magnetic
the thermal nanoparticles
stability on the surface of MAG-OPBC, which increased
of the nanosorbent.
the thermal stability of the nanosorbent.
100
Delta Y= 7.39%
0.0
Derivative Weight (mg/min)

80 -0.1
Delta Y= 8.29%
Delta Y= 6.68%
-0.2
Weight %
60
Delta Y= 17.61%
-0.3
40
-0.4
Delta Y= 57.61%
20 OPBC, wt%
MAG-OPBC, wt% -0.5
OPBC, derivative wt
MAG-OPBC, derivative wt Delta Y= 55.43%
0 -0.6
100 200 300 400 500 600 700 800
Temperature (°C)
Figure 1. TGA/dTA analysis of OPBC and MAG-OPBC.
Figure 1. TGA/dTA analysis of OPBC and MAG-OPBC.
3.1.2. FT-IR Analysis and Point-of-Zero-Charge (pHPZC )
3.1.2. FT-IR
FT-IRanalysis
Analysiswas
andcarried
Point-of-Zero-Charge
out to identify the(pH PZC)
functional groups present on the sur-
faceFT-IR
of OPBC and MAG-OPBC
analysis was carried adsorbents and hence
out to identify the explore
functionalthe adsorption mechanism
groups present on the sur-
(Figure 2a). The results showed similarities in the spectra
face of OPBC and MAG-OPBC adsorbents and hence explore the adsorption of both adsorbents, withmechanism
some
peak shifts observed following the impregnation with Fe3 O4 . An absorption band at
(Figure 2a). The results showed similarities in the spectra of both adsorbents, with some
1558 cm−1 appeared in both samples, corresponding to carboxylic C=O or aromatic C=C
peak shifts observed following the impregnation with Fe3O4. An absorption band at 1558
stretching vibrations. The peak at 1372 cm−1 and 1347 cm−1 observed in OPBC, and
cm −1 appeared in both samples, corresponding to carboxylic C=O or aromatic C=C stretch-
MAG-OPBC, respectively, was assigned to C-O stretching, and the shift indicates bond
ing vibrations.
formation between TheFepeak at 1372 cm−1 and 1347 cm−1 observed in OPBC, and MAG-OPBC,
3 O4 and the surface of the biochar [45]. The presence of an absorption
respectively,
band at 558 cm was
−1 assigned to C-O stretching,
could be attributed to the Fe-Oand the and
bond, shiftit indicates bond
confirms the formation
existence of be-
tween Fe3Oon
magnetite 4 and
the the surface
surface of the
[46–50]. biochar
Figure [45]. The the
2b illustrates presence of an absorption
point-of-zero-charge for band
OPBCat 558
cm −1 could
and be attributed
MAG-OPBC, which was to the
foundFe-O bond,
to be and7.35,
9.28 and it confirms the This
respectively. existence ofthat
implies magnetite
if the on
pHsurface
the of the solution
[46–50].is Figure
higher than pHPZC , the
2b illustrates surface
the of OPBC or MAG-OPBC
point-of-zero-charge for OPBC would
andbeMAG-
negatively
OPBC, whichcharged. This property,
was found together
to be 9.28 with respectively.
and 7.35, the pKa value This of DNB, is fundamental
implies that if theinpH of
deciding
the upon
solution the adsorption
is higher than pHmechanism and hence the efficiency of the studied adsorbent
PZC, the surface of OPBC or MAG-OPBC would be negatively
towards the target pollutant.
charged. This property, together with the pKa value of DNB, is fundamental in deciding
upon the adsorption mechanism and hence the efficiency of the studied adsorbent to-
wards the target pollutant.
Nanomaterials 2023, 13, x FOR PEER REVIEW 9 of 24
-1
100 1558 cm OPBC
-1
1372 cm 10 MAG-OPBC
Transmittance (%)
8
80
-1
1347 cm
-1
Final pH
1558 cm
6
60
4
-1
558 cm
40 2
OPBC
MAG-OPBC 7.35 9.28
0
4000 3500 3000 2500 2000 1500 1000 500
0 2 4 6 8 10
Wavenumber (cm-1) Initial pH
(a) (b)
Figure
Figure2.2.FT−IR
FT−IRspectra
spectraof
of(a)
(a) OPBC
OPBC and MAG-OPBCand
and MAG-OPBC and(b)
(b)pH
pHPZC of both adsorbents.
PZC of both adsorbents.
3.1.3.CHN
3.1.3. CHNAnalysis
Analysis
Thedata
The data of
of the
the CHN
CHN analysis
analysisfor
forboth
bothOPBC
OPBCand andMAG-OPBC
MAG-OPBC indicate that
indicate thethe
that N%N%
increasedfrom
increased from1.83%
1.83%ininthe
thecase
caseof
ofOPBC
OPBCto to2.21%
2.21%ininthe
thecase
caseofofMAG-OPBC.
MAG-OPBC.Besides,
Besides,the
the C% decreased from 64.33% in OPBC to 64.21% in MAG-OPBC due
C% decreased from 64.33% in OPBC to 64.21% in MAG-OPBC due to the existence to the existence of of
magnetic nanoparticles on the surface. Similarly, the H% decreased from 2.34%
magnetic nanoparticles on the surface. Similarly, the H% decreased from 2.34% in OPBCin OPBC to
2.29% in MAG-OPBC due to the loss of hydrogen during the formation of Fe3 O4 on the
to 2.29% in MAG-OPBC due to the loss of hydrogen during the formation of Fe3O4 on the
surface of the nanosorbent.
surface of the nanosorbent.
3.1.4. Raman Analysis
3.1.4. Raman Analysis
Figure 3 portrays the Raman spectra of the pristine adsorbent, OPBC and their as-
Figuresample
prepared 3 portrays the Raman spectra
after impregnation of the nanoparticles
by magnetic pristine adsorbent, OPBC and
(MAG-OPBC). Thetheir
data as-
prepared
obtained sample after
in the case of impregnation
OPBC show two bydistinct
magnetic bandsnanoparticles
linked with(MAG-OPBC). The data
carbonous materials
−1 (D-band) and 1584 cm−1 (G-band), which are typically
obtained
and couldinbethe case ofatOPBC
observed 1362 cm show two distinct bands linked with carbonous materials
related
and to be
could carbonaceous
observed at materials
1362 cm−1derived
(D-band) from
andthermally
1584 cm−1 treated
(G-band),peels.
whichTheare
D-band
typically
indicates the carbon lattice attributes, including defects and sizes, while
related to carbonaceous materials derived from thermally treated peels. The D-band indi-the G-band detects
C-C stretching 2 structure. Additionally, the I :I intensity ratio for OPBC is 0.72,
the spattributes,
cates the carbonfor lattice including defects and D Gsizes, while the G-band detects C-
C stretching for the sp structure. Additionally, the ID:Inumber
whereas it is 0.66 for MAG-OPBC.
2 This suggests that the of defects on the surface
G intensity ratio for OPBC is 0.72,
whereas it is 0.66 for MAG-OPBC. This suggests that the numberofofFedefects

of OPBC decreased after impregnation with Fe 3 O 4 . The presence 3 O4 nanoparticles
on the surface
onto OPBC was confirmed by the occurrence of two weak broad peaks in the spectrum of
of OPBC decreased after impregnation with Fe 3 O 4 . The presence of Fe 3 O4 nanoparticles
MAG-OPBC located at 294 and 685 cm−1 , which could be credited to the existence of Fe–O
onto OPBC was confirmed by the occurrence of two weak broad peaks in the spectrum of
bonds of the magnetic nanoparticles [51–53].
MAG-OPBC located at 294 and 685 cm−1, which could be credited to the existence of Fe–O
bonds of the
3.1.5. BET magnetic nanoparticles [51–53].
Analysis
The BET equation was employed to calculate the surface area of OPBC and MAG-
OPBC, Table S1. Figure 4 presents the N2 adsorption-desorption isotherms for both samples.
The obtained data revealed that the Langmuir surface area has increased from 6.99 m2 /g in
OPBC to 60.76 m2 /g for MAG-OPBC, possibly due to the existence of Fe3 O4 nanoparticles
on the surface of OPBC, which enhances the surface area and improves the efficacy of
DNB removal. Mesopores (2–50 nm) and macropores (>50 nm) were also observed in both
samples. The adsorption isotherm for both sorbents was of type IV, indicating monolayer-
multilayer adsorption with subsequent capillary condensation. The H3-type hysteresis
loop was also observed, which is typical for materials with a broad range of pore diameters
and indicates the formation of slit-like pores from loose masses of plate-like particles [54].
-1 -1
Intensity (a.u.)
294 cm 685 cm

OPBC
ID/IG = 0.72
MAG-OPBC -1
1584 cm
-1
1362 cm
200 400 600 800 1000 1200 1400 1600 1800 2000
ID/IG = 0.66
Raman Shift (cm-1)
Intensity (a.u.) -1 -1
685as-prepared
294 cmspectra of the
Figure 3. Raman cm samples OPBC and MAG-OPBC.
3.1.5. BET Analysis

The OPBC
BET equation was employed to calculate the surface area of OPBC and MAG-
OPBC, Table S1. Figure 4 presents the N2 adsorption-desorption isotherms for both sam-
ples. The obtained data revealed that the Langmuir surface area has increased from 6.99
m2/g in OPBC to 60.76 m2/g for MAG-OPBC, possibly due to the existence of Fe3O4 nano-
particlesI on the surface of OPBC, which enhances the surface area and improves the effi-
D/IG = 0.72
cacy of DNB removal. Mesopores (2–50 nm) and macropores (>50 nm) were also observed
in both samples. The adsorption isotherm for both sorbents was of type IV, indicating
monolayer-multilayer
200 400
adsorption
600 800
with subsequent capillary condensation. The H3-type
1000 1200 1400 1600 1800 2000
hysteresis loop was also observed, which is typical for materials with a broad range of
pore diameters and indicates Raman the formation
Shift of
(cm -1) pores from loose masses of plate-
slit-like
like particles [54].
Ramanspectra
Figure3.3.Raman
Figure spectra of
of the
theas-prepared
as-preparedsamples OPBC
samples OPBCandand
MAG-OPBC.
MAG-OPBC.
180 0.0030
OPBC-PR
OPBC-SA
MAG-OPBC-SA
3.1.5.(a)BET Analysis (b) MAG-OPBC-PR
160
The BET equation was employed
0.0025 to calculate the surface area of OPBC and MAG-
Quantity Adsorbed (cm3/g) STP
140
OPBC, Table S1. Figure 4 presents the N2 adsorption-desorption isotherms for both sam-
Pore volume (cm3/g.nm)
120 ples. The obtained data revealed 0.0020

that the Langmuir surface area has increased from 6.99
100
m /g in OPBC to 60.76 m /g for MAG-OPBC, possibly due to the existence of Fe3O4 nano-
2 2
particles on the surface of OPBC,0.0015

which enhances the surface area and improves the effi-
80
cacy of DNB removal. Mesopores (2–50 nm) and macropores (>50 nm) were also observed
0.0010
60 in both samples. The adsorption isotherm for both sorbents was of type IV, indicating
40 monolayer-multilayer adsorption0.0005
with subsequent capillary condensation. The H3-type
20
hysteresis loop was also observed, which is typical for materials with a broad range of
pore diameters and indicates the0.0000
formation of slit-like pores from loose masses of plate-
0
0.0 0.2 like
0.4 particles
0.6 [54].
0.8 1.0 0 100 200 300 400
Relative Pressure (P/P ) Pore diameter (nm)

o
180 0.0030
OPBC-SA Figure
(a) 4.4. (a) Surface area and (b) the pore diameter for both adsorbents OPBC,
(b) and MAG-OPBC.
OPBC-PR
MAG-OPBC-SA Figure (a) Surface area and (b) the pore diameter for both adsorbents OPBC, and MAG-OPBC.
MAG-OPBC-PR
160
3.1.6. Morphological and Microstructural
0.0025 Features of OPBC and MAG-OPBC
Quantity Adsorbed (cm3/g) STP
140 SEM and TEM analyses were executed to examine the surface morphology of Fe3 O4
Pore volume (cm3/g.nm)
120 nanoparticles loaded biochar. Figure 0.0020

5 displays the topographical study and the EDX charts
of OPBC and MAG-OPBC. The SEM micrographs in Figure 5a,b depict the presence of
100 many cavities and pores on the surface
0.0015 of the OPBC because of the thermal treatment
of the peels. In contrast, the SEM micrograph for MAG-OPBC in Figure 5c,d shows the
80
coverage of the surface of the OPBC with the magnetic nanoparticles, which have been
0.0010
60 proved by FT-IR, CHN, and Raman analyses. The EDX analysis of the OPBC sample in
Figure 5e exposed a high concentration of carbon (59.84%) and oxygen (30.04%) in the
40
presence of potassium (3.45%) and calcium
0.0005 (2.34%). On the other hand, the EDX analysis of
20 MAG-OPBC, Figure 5f shows a lower concentration of carbon compared to OPBC (39.78%)
due to the presence of magnetic nanoparticles
0.0000 on the surface of OPBC, an issue that was
0
proven by the presence of a high concentration of iron (24.76%) and oxygen (30.15%).
0.0 0.2 0.4 0.6 0.8 1.0 0 100 200 300 400
Relative Pressure (P/P ) Pore diameter (nm)

o
Figure 4. (a) Surface area and (b) the pore diameter for both adsorbents OPBC, and MAG-OPBC.
proved by FT-IR, CHN, and Raman analyses. The EDX analysis of the OPBC sample in
Figure 5e exposed a high concentration of carbon (59.84%) and oxygen (30.04%) in the
presence of potassium (3.45%) and calcium (2.34%). On the other hand, the EDX analysis
of MAG-OPBC, Figure 5f shows a lower concentration of carbon compared to OPBC
(39.78%) due to the presence of magnetic nanoparticles on the surface of OPBC, an issue
that was proven by the presence of a high concentration of iron (24.76%) and oxygen
(30.15%).
Layers
Layers
Pores
(a) (b)
Fe3O4 nanoparticles
(c) (d)
3
4.0x10 4.0x103
Element Wt(%) Element Wt(%)
3.5x103 C 59.84 C 39.78
3.5x103
O 30.04 O 30.15
C K 3.45 Na 2.75
3.0x103 3.0x103
Ca 2.34 Ca 2.56
Intensity (a.u.)
Intensity (a.u.)
Total 100 Fe 24.76

2.5x103 2.5x103 Total 100
2.0x103 2.0x103 C O
1.5x103 1.5x103
1.0x103 1.0x103
O
5.0x102 5.0x102 Fe
K Ca Na Ca
0.0 0.0
0 200 400 600 800 1000 0 200 400
Energy (keV) Energy (keV)
(e) (f)
Figure 5.
Figure 5. SEM
SEM micrographs
micrographsof
of(a,b)
(a,b)OPBC,
OPBC,(c,d)
(c,d)MAG-OBPC
MAG-OBPCatat5000
5000× and10,000
× and 10,000× magnifications,
× magnifications,
(e,f) EDX analyses of OPBC and MAG-OPBC, respectively.
The microstructural
The microstructural characterization
characterization of the
the magnetic
magnetic nanoparticles
nanoparticles loaded
loaded onto
onto the
the
OPBC surface using
OPBC using TEM
TEManalysis
analysisisispresented
presentedin in
Figure 6. The
Figure findings
6. The of the
findings ofTEM anal-
the TEM
ysis align
analysis wellwell
align with thethe
with SEM
SEMmicrographs.
micrographs.InInFigure
Figure6a,b,
6a,b,the
the OPBC appears
OPBC surface appears
smooth without any particles. On the other hand, the surface of the MAG-OPBC is rough,
and Fe3O4 nanoparticles are easily visible, as shown in Figure 6c–e. Synthesized Fe3O4 na-
noparticles had an average size of 8.06 ± 1.62 nm (Figure 6f) and small particle size distri-
bution of 1.62 nm, proving the creation of uniformly sized Fe3O4 nanoparticles.
Energy (keV) Energy (keV)
(e) (f)
Figure 5. SEM micrographs of (a,b) OPBC, (c,d) MAG-OBPC at 5000× and 10,000× magnifications,
The microstructural characterization of the magnetic nanoparticles loaded onto the
OPBC surface using TEM analysis is presented in Figure 6. The findings of the TEM anal-
ysis align well with the SEM micrographs. In Figure 6a,b, the OPBC surface appears
smooth
smoothwithout
withoutany
any particles. Onthe
particles. On theother
otherhand,
hand,the
thesurface
surface of of
thethe MAG-OPBC
MAG-OPBC is rough,
is rough,
and Fe O nanoparticles are easily visible, as shown in Figure 6c–e. Synthesized
and Fe33O44 nanoparticles are easily visible, as shown in Figure 6c–e. Synthesized Fe3O4 na- Fe3 O4
nanoparticles an average size of 8.06 ±
noparticles had an average size of 8.06 ± 1.62 nm (Figure 6f) and small particle size distri-size
had 1.62 nm (Figure 6f) and small particle
distribution of nm,
bution of 1.62 1.62 proving
nm, proving the creation
the creation of uniformly
of uniformly sized Fe sized Fe3 O4 nanoparticles.
3O4 nanoparticles.
Layers
(a) (b)
Fe3O4
OPBC
(c) (d)
14 Mean = 8.06
Std. dev. = 1.62
12
N = 59
10
Frequency
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Particle size distribution (nm)
(e) (f)
Figure 6. TEM images of OPBC at (a) 200 nm, (b) 50 nm, and MAG-OPBC at (c) 500 nm, (d) 50 nm,
Figure 6. TEM images of OPBC at (a) 200 nm, (b) 50 nm, and MAG-OPBC at (c) 500 nm, (d) 50 nm,
(e) 5 nm, and (f) Fe3O4 particle size distribution (PSD) for MAG-OPBC.
(e) 5 nm, and (f) Fe3 O4 particle size distribution (PSD) for MAG-OPBC.
3.2. Adsorption Study
3.2.1. Plackett–Burman Design (PBD)
The main objective of the present investigation is to set out an economical and green
adsorbent by the reutilization of an abundantly available waste material, orange peels.
Our target was also to enhance the adsorption capacity of the biochar-derived adsorbent,
3.2. Adsorption Study

3.2.1. Plackett–Burman Design (PBD)
The main objective of the present investigation is to set out an economical and green
adsorbent by the reutilization of an abundantly available waste material, orange peels.
Our target was also to enhance the adsorption capacity of the biochar-derived adsorbent,
OPBC. This objective could be achieved by impregnation of the pristine candidate with
magnetite nanoparticles (MAG-OPBC). Controlling and boosting the performance of either
adsorbent could be achieved by controlling the process variables. Thus, an experimental
design was instigated to initially screen the statistical significance of four variables affecting
the removal of DNB. PBD was selected for this purpose. As a screening design, PBD is a
simple design in which the number of experimental runs is the smallest multiple of four
(>the number of variables) and is used when only the main effects are concerned. Therefore,
PBD is commonly used as a prelude to an optimization phase (coupled to the desirability
function tool in this investigation) to ensure that all chosen variables do certainly and
significantly contribute to the measured response, and hence further saving on the runs
to be performed [55]. Moreover, PBD permits the determination of the main effects of
all variables with the minimum variance with no concerns from the variable-variable
interactions or the non-linear effects. Therefore, PBD is always of choice for robustness,
ruggedness tests performed for the sake of method validation [43,44,55,56]. Compared to
the most popular screening design, full factorial design, where a relatively large number
of runs is needed to cover the main effects and all the possible combinations, PBD offers
an economical solution where only the main effects are considered [55,56]. The design
matrix, the obs. and pred. responses, together with the RE values, are shown in Table 2. As
could be realized from the obtained data, the values of RE were apparently small enough
to express the model’s accuracy.
3.2.2. Quality Charts and Analysis of Variance (ANOVA)

The statistical impact of each variable (main effects) was assessed using Pareto chart.
As shown in Figure 7a,b, variables surpassing the reference line are denoted as significant.
Figure 7a shows that AD (D) was the variable that mainly affects the removal of DNB
using OPBC, compared to [DNB] (C) in case of MAG-OPBC (Figure 7b). As also could
be concluded from the Pareto chart, pH (A) was statistically insignificant in case of MAG-
OPBC. In the same itinerary, similar conclusions could be derived from ANOVA testing
operated at 95.0 confidence interval. Obtained results are displayed in Table S2. Variables
with p-value > 0.05 are statistically insignificant. For both adsorbents, the lack-of-fit was
insignificant, suggesting the linearity of data.
Figure 7c–f shows the contour and surface plots portraying design data in the 2D and
3D formats, correspondingly. For contour plots, the maroon and dark green regions denote
areas with the lowest and highest %R of DNB, respectively. In the 3D plots, however,
elevated ridges are the regions with the highest %R.
3.2.3. Regression Equations

Regression models (main effects) are given by Equations (1) and (2) for OPBC and
MAG-OPBC, respectively. As reflected by the regression models, the coefficient next to
each variable signifies the magnitude of this variable, while the sign denotes the direction
of the impact of this variable.
ln(%ROPBC ) = 4.0734 + 0.01535 pH − 0.001352 CT + 0.000673 [DNB] + 0.001620 AD + 0.1793 Ct Pt,

(1)
R2 = 96.75%, R2 -adj = 95.72%, R2 -pred = 94.08%
ln(%RMAG-OPBC ) = 3.9451 + 0.00763 pH − 0.002788 CT + 0.003003 [DNB] + 0.001735 AD + 0.3023 Ct Pt,

(2)
R2 = 96.45%, R2 -adj = 95.32%, R2 -pred = 93.28%
As per model summaries given following each regression model, both R2 and R2 –adj
were high enough, indicating model linearity. The R2 -pred was used to assess the capacity
The statistical impact of each variable (main effects) was assessed using Pareto chart.
As shown in Figure 7a,b, variables surpassing the reference line are denoted as significant.
Figure 7a shows that AD (D) was the variable that mainly affects the removal of DNB
using OPBC, compared to [DNB] (C) in case of MAG-OPBC (Figure 7b). As also could be
Nanomaterials 2023, 13, 1444 concluded from the Pareto chart, pH (A) was statistically insignificant in case of MAG- 14 of 23
OPBC. In the same itinerary, similar conclusions could be derived from ANOVA testing
operated at 95.0 confidence interval. Obtained results are displayed in Table S2. Variables
with
of thep-value ˃ 0.05
proposed are statistically
model to expect theinsignificant.
response inFor both
case adsorbents,
of any the lack-of-fit
new observations, was
where
insignificant, suggesting the
2 linearity of data.
the greater the value of R –pred, the better the model’s predictive capability. Running
Figure 7c–fdesirability
the individual shows the contour
functionand surface
(d)—a plots portraying
statistical tool used todesign
attest data in the 2D and
the capability of a
3D formats, correspondingly. For contour plots, the maroon and dark green regions
certain factorial combination to maximize the response-delivered the data in Table 3. The de-
note areas with the lowest and highest %R of DNB, respectively. In the 3D plots, however,
closer the value of d to 1.0000, the more suitable the proposed factorial recipe. As shown in
elevated
Table ridges areremoval
3, maximum the regions withwas
of DNB the highest
attained%R.using MAG-OPBC where %R = 98.51%.
(a) (b)
(c) (d)
(e) (f)
Figure 7.7.PBD
Figure PBDanalysis
analysis results:
results: Pareto
Pareto charts:
charts: (a) OPBC,
(a) OPBC, (b) MAG-OPBC;
(b) MAG-OPBC; Contour
Contour 2D-plots:
2D-plots: (c)
(c) OPBC,
OPBC, (d) MAG-OPBC; and Surface 3D-plots: (e) OPBC, (f) MAG-OPBC.
(d) MAG-OPBC; and Surface 3D-plots: (e) OPBC, (f) MAG-OPBC.
3.2.3. Regression Equations

Regression models (main effects) are given by Equations (1) and (2) for OPBC and
MAG-OPBC, respectively. As reflected by the regression models, the coefficient next to
each variable signifies the magnitude of this variable, while the sign denotes the direction
of the impact of this variable.
ln(%ROPBC) = 4.0734 + 0.01535 pH − 0.001352 CT + 0.000673 [DNB] + 0.001620 AD + 0.1793 Ct Pt,
Table 3. Optimum conditions and desirability function d-values.
Adsorbent Optimum Conditions Desirability Function (d)

OPBC pH = 9.0, CT = 10 min, [DNB] = 100 ppm, AD = 120 mg/13 mL d = 0.8481, %R = 86.46%
MAG-OPBC pH = 9.0, CT = 10 min, [DNB] = 100 ppm, AD = 120 mg/13 mL d = 0.8275, %R = 98.51%
3.3. Equilibrium and Kinetic Studies for DNB Adsorption onto OPBC and MAG-OPBC
3.3.1. Adsorption Isotherms
The adsorption
Nanomaterials 2023, 13, x FOR PEER REVIEW of DNB onto OPBC and MAG-OPBC was studied using four models: 17 of 24
Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich (D–R) [57–61].
According to the Langmuir model applied in this system, the following can be sug-
gested: (I)
TheAllresults
the adsorption
obtained sites on the
for both adsorbentsuggest
adsorbents surfacethat
are equivalent with the same
the DNB adsorption energy
adsorption energy, (II) the adsorbed species occupy one location on
onto OPBC is 5.85 kJ/mol, whereas the MAG-OPBC adsorption energy is 1.97 the adsorbent surface
kJ/mol.
without
Theseany interaction
values indicatebetween
that the them, and (III)
adsorption the adsorption
of DNB mostlyand
onto both OPBC takes place on is
MAG-OPBC
the physisorption,
surface of the adsorbent. The Langmuir
with an adsorption energyisotherm is represented
of less than by Equationthe
7 kJ/mol additionally, (3) and
surface
Figure 8a,b, which illustrate the removal of DNB using OPBC and MAG-OPBC, respectively.
area of the nanosorbent appears to have a significant impact on the adsorption process.
The adsorption of DNB onto OPBC is well-fitted
qm KL Ce with the D–R isotherm, as evidenced by
an R2 value of 0.9281. qe = (3)
1 + K Ce L
Model Langmiur (User)
Equation qeq = (qmax*Kl*Ceq)/(1+Kl*Ceq)
Plot qe Model
40 Kl 0.05912 ± 0.02365 Equation
38.75106 ± 5.87927
OPBC qmax
Reduced Chi-Sqr 29.65492 MAG-OPBC
Plot
Kl
R-Square (COD) 0.82675 qmax
50
35 Adj. R-Square 0.80509 Reduced Chi-Sqr
R-Square (COD)
Adj. R-Square
30
40
25
qe (mg/g)
qe (mg/g)
30
20
15 20
10
experimental Data
experimental Data
Langmiur 10
Freundlich Langmiur
5 Freundlich
Temkin
Temkin
D-R
0 D-R
0
0 20 40 60 80 100 120 140 0 10 20 30 40 50 60 70
Ce (mg/L) Ce (mg/L)
(a) (b)
Figure 8. 8.Adsorption
Figure Adsorptionequilibrium isotherms for
equilibrium isotherms forthe
the adsorption
adsorption of DNB
of DNB ontoonto (a) OSBC
(a) OSBC and (b)and
MAG-
(b) MAG-OSBC sorbents.
OSBC sorbents.
The 4.equation
Table features
Calculated two for
parameters parameters, qm equilibrium
the adsorption and KL , which
models respectively
used for the stand for of
adsorption
the both
maximum
DNB onto adsorption
OPBC andcapacity
MAG-OPBC. and Langmuir equilibrium coefficient. Equation (4)
also presents an alternative way of expressing this relationship in a dimensionless form
Langmuir qm (mg/g)
as follows: KL (L·mole−1) R2
OPBC 38.75 0.059 1 0.8267
RL = (4)
MAG-OPBC 172.43 0.006 1 + K L C0 0.9704
Freundlich 1/n
The desirability KF (mole/g)can
of adsorption (L/mole) 1/n
be evaluated by using R the2
RL value, which is the
OPBC DNB separation
0.42 factor divided by4.721
the initial concentration (C )
0.7547
0 measured in mg/L. The
MAG-OPBC RL value 0.86
is indicative of the type of adsorption.
1.416 For both OPBC0.9639and MAG-OPBC, the RL
Temkin value bwas less than 1, indicating
T (J/mole) AT that the process was favorable.
(L/mole) R2 As the concentration of
OPBC DNB increased,
280.09 the adsorption process
0.484 became irreversible, and the maximum adsorption
0.8434
capacity (qm ) for DNB was 38.75 mg/g and 172.43 mg/g for OPBC and MAG-OPBC,
MAG-OPBC 164.25 0.247 0.9150
respectively. These results confirm the outcomes of the PBD. The data collected for2 the
D–R 𝜷 E (kJ/mole) qm (mg/g) R
adsorption of DNB onto both OPBC and MAG-OPBC (Figure 8a,b) demonstrate that DNB
OPBC 1.46 × 10−8 5.85 31.34 0.9281
MAG-OPBC 1.29 × 10−7 1.97 48.94 0.8609
3.3.2. Kinetic Models

To investigate the adsorption of DNB onto OPBC and MAG-OPBC, four kinetic mod-
adsorption onto MAG-OPBC matches well with the Langmuir isotherm, with R2 value
of 0.9704.
On the other hand, Equation (5) illustrates the Freundlich model:
1
qe = K F Cen (5)
The equation includes the Freundlich coefficients, which are denoted as KF (mole·g−1 )
(L·mole−1 ) and 1/n. These coefficients indicate the adsorbent capacity, the difference in
adsorption intensity, and the deviation from linearity. Table 4 presents the calculated values
of these parameters for the Freundlich isotherm. OPBC has a 1/n value of 0.42 and an n
value of 2.38, while MAG-OPBC has a 1/n value of 0.86 and an n value of 1.16. Therefore,
MAG-OPBC has a greater adsorption potential towards DNB drug than OPBC.
Table 4. Calculated parameters for the adsorption equilibrium models used for the adsorption of
both DNB onto OPBC and MAG-OPBC.
Langmuir qm (mg/g) KL (L·mole−1 ) R2

OPBC 38.75 0.059 0.8267
MAG-OPBC 172.43 0.006 0.9704
Freundlich 1/n KF (mole/g) (L/mole)1/n R2
OPBC 0.42 4.721 0.7547
MAG-OPBC 0.86 1.416 0.9639
Temkin bT (J/mole) AT (L/mole) R2
OPBC 280.09 0.484 0.8434
MAG-OPBC 164.25 0.247 0.9150
D–R β E (kJ/mole) qm (mg/g) R2
OPBC 1.46 × 10−8 5.85 31.34 0.9281
MAG-OPBC 1.29 × 10−7 1.97 48.94 0.8609
Equation (6) represents the Temkin isotherm, which explains the interaction between
the sorbate and the sorbent.
RT
qe = ln( A T Ce ) (6)
bT
The AT constant in this paradigm corresponds to the Temkin isotherm, while R refers
to the universal gas constant (8.314 J/mol·K), bT denotes the Temkin isotherm constant, and
T represents the temperature in Kelvin. Based on Figure 8a–d and Table 4, OPBC displays
an adsorption energy of 280.09 J/mol, while MAG-OPBC exhibits an adsorption energy of
164.25 J/mol. These findings indicate that DNB is effectively adsorbed onto the surface of
both OPBC and MAG-OPBC, which aligns with the results obtained from the Langmuir
and Freundlich models.
Equation (7) represents the Dubinin–Radushkevich (D–R) model, which was investi-
gated to estimate the adsorption mechanisms of DNB onto OPBC and MAG-OPBC.

qe = qs ·exp β· e2 (7)
Equation (8) uses β, the activity coefficient, to calculate the DNB sorption energy, E
(kJ/mol), where qs denotes the saturation capacity of both OPBC and MAG-OPBC. The
Polanyi potential is determined by e, which can be calculated using Equation (8). Similarly,
the value of E can be obtained using Equation (9).

1
e = RT 1 + (8)
Ce
1
E= p (9)
2β
The results obtained for both adsorbents suggest that the DNB adsorption energy
onto OPBC is 5.85 kJ/mol, whereas the MAG-OPBC adsorption energy is 1.97 kJ/mol.
These values indicate that the adsorption of DNB onto both OPBC and MAG-OPBC is
physisorption, with an adsorption energy of less than 7 kJ/mol additionally, the surface
area of the nanosorbent appears to have a significant impact on the adsorption process. The
adsorption of DNB onto OPBC is well-fitted with the D–R isotherm, as evidenced by an R2
value of 0.9281.
3.3.2. Kinetic Models
To investigate the adsorption of DNB onto OPBC and MAG-OPBC, four kinetic models
were employed: Pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich, and Weber–
𝑘
𝑂𝑃𝐵𝐶 &Morris
𝑀𝐴𝐺 − (WM)
𝑂𝑃𝐵𝐶 [62–65]
+ 𝐷𝑁𝐵 (Figure
(→ ) 9a,b).
{𝐷𝑁𝐵–Table
𝑂𝑃𝐵𝐶} 5 provides
𝑜𝑟 {𝐷𝑁𝐵–the estimated
𝑀𝐴𝐺 − 𝑂𝑃𝐵𝐶}parameters for each(10)
model. The results indicate that the PSO model provides a good fit for the adsorption of
DNBUsing
onto both OPBC and
the Elovich MAG-OPBC,
model, the initialwith R2 valuesrate
adsorption of 0.9353 and was
for DNB 0.8782, respectively.
determined to be
These findings suggest that the rate of the adsorption interaction between
237.04 mg·g ·min for OPBC, which is lower than the initial adsorption rate of MAG-
−1 −1 DNB and the
two nanosorbent
OPBC (513.72 mg·g is −1controlled by the drug
·min−1). However, theand adsorbent
R2 value concentrations,
of the Weber–Morris as(WM)
demonstrated
model was
by Equation (10):
too low for both adsorbents, and thus, it was unable to provide an adequate explanation
of the adsorption of DNB onto theOPBC
k
and MAG-OPBC nanosorbent in comparison to
OPBC & MAG
the other models. − OPBC + DNB → { DNB–OPBC } or { DNB–MAG − OPBC } (10)
Model
Equati
40 65 Plot
OPBC MAG-OPBC K1
qe
60 Reduc
R-Squ
35 55 Adj. R-
50
30 Model PSO (User)
Equation qtq = (qe^2*K2*tq)/ (1+qe*K2*tq)
Plot 45 qt (mg/g)
K2 0.01741 ± 0.00315
33.08795 ± 0.99885
25 qe
40
qt (mg/g)
Reduced Chi-Sqr 3.24058

qt (mg/g)
R-Square (COD) 0.93535

35
Adj. R-Square 0.92727
20
30
15 25
20
10 15
Experimental Data experimental Data
Pseudo-First Order 10 Pseud-First Order
5 Pseudo-Second Order Pseud-Second Order
Elovich 5 Elovich
Weber Morris Weber Morris
0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (min) Time (min)
(a) (b)
Figure
Figure9.9.Kinetic
Kinetic studies
studies for the sorption
for the sorptionofofDNB
DNBonto
onto(a)(a)OPBC
OPBC and
and (b)(b) MAG-OPBC
MAG-OPBC adsorbents.
adsorbents.
Table Using
5. Calculated data for
the Elovich four kinetic
model, models
the initial used forrate
adsorption the for
adsorption
DNB was of determined
DNB onto OPBC
to beand
237.04 mg·g−1 ·min−1 for OPBC, which is lower than the initial adsorption rate of MAG-
MAG-OPBC.
OPBC (513.72 mg·g−1 ·min−1 ). However, the R2 value of the Weber–Morris (WM) model
was too low for both adsorbents,
Value
Models Parameterand thus, it was unable to provide an adequate explanation
OPBC nanosorbent in
of the adsorption of DNB onto the OPBC and MAG-OPBC MAG-OPBC
comparison to
the other models. K1 (min )
−1 0.397 0.541
Pseudo-first order (PFO)
𝑑𝑞𝑡 qe (mg/g) 30.29 49.74
= k1(qe − qt) 3.4. Proposed Adsorption Mechanism
𝑑𝑡 R 2 0.78114 0.7074
Electrostatic interactions, hydrogen bonding, intra-particle interactions, and surface
K2 (g·mg ·min )
−1 −1 0.017 0.012
Pseudo-second order (PSO)diffusions might all be used to explain how DNB adheres to both OPBC and MAG-OPBC,
𝑑𝑞𝑡 qe (mg/g) 33.09 55.11
= k2(qe − qt)2 Figure 10a–d.
𝑑𝑡 R 2 0.9353 0.8782
Elovich model 𝛼 237.04 513.72
1 𝛽 0.248 0.152
qt= × 𝑙𝑛(1 + 𝛼𝛽𝑡)
𝛽 R 2 0.9130 0.8506
for MAG-OPBC. This results in a positive charge on the surface of the drug molecules
and a negative charge on the surface of MAG-OPBC, leading to a strong electrostatic
interaction between DNB and MAG-OPBC and increasing the removal efficiency. On
the other hand, the data obtained for OPBC show that the optimum pH is also 9.0,
and the pHpzc of OPBC is also 9.28. This results in a neutral surface charge, which
Nanomaterials 2023, 13, 1444 negatively affects the electrostatic interaction and thus, the removal efficiency of 18 of 23
OPBC.
2. Chemical bonding can occur between DNB and both OPBC and MAG-OPBC surfaces
through covalent or ionic bonds. This mechanism is significant for DNB, which has
Table 5. Calculated data for four kinetic models used for the adsorption of DNB onto OPBC and
functional groups that can participate in chemical reactions with the surface of the
MAG-OPBC.
nanosorbent. Different functional groups with the adsorbate’s benzene or other aro-
matic ring structures could have electron-rich or electron-deficient groups that facil-
itate Parameter
the interaction (Figure 10b,d). Additionally, there may Value
be hydrogen-bonding in-
Models
teractions between the oxygen atoms (H-acceptors)
OPBC in the nanosorbent and the hy-
MAG-OPBC
drogen of the−1hydroxyl groups (H-donors) on the DNB drug. This type of interaction
Pseudo-first order (PFO) K1 (min ) 0.397 0.541
is commonly
qe (mg/g)
referred to as hydrogen bonding
30.29
between dipoles. 49.74
dqt
dt = k1 (qe − qt ) 3. Intra-particle
R2 and surface diffusions mechanism:
0.78114 Intra-particle diffusion refers
0.7074to the
movement of adsorbate molecules within the pores of the adsorbent particle [68,69].
(g·mg −1 min−1 )
Pseudo-second order (PSO) K2 the
In case ·of OPBC and MAG-OPBC, many 0.017 pores existed on the surface, 0.012
as con-
dqt 2 firmedq (mg/g) 33.09
e by the SEM and BET analyses, and the adsorbate (DNB) diffuses into 55.11
the pores
dt = k2 (qe − qt ) R2 0.9353 of the nanosorbent. Surface 0.8782
of the adsorbent and interacts with the surface diffusion,
conversely, α refers to the movement of 237.04adsorbate molecules on the surface513.72of the
Elovich model
1
qt = β × ln(1 + αβt) OPBC andβ MAG-OPBC adsorbent. In the case
0.248 of OPBC, the DNB molecules
0.152diffuse
2
along theRsurface of the biochar and interact with either the surface functional
0.9130 0.8506groups
or the magnetic
KI nanoparticles of the MAG-OPBC.
1.50 Both mechanisms are important
2.518
Weber−Morris model (WM) for the description of adsorption of DNB19.46
onto OPBC and MAG-OPBC because
0.5 C 33.36 they
qt = K I t + C explain theR2 increased interaction between DNB and the adsorbent surface,0.7268
0.6926 which en-
hances the adsorption process.
-1
1558 cm -1
100 1372 cm
-1
1707 cm
Transmittance (%)
-1
95 1574 cm
-1
1703 cm -1
1403 cm
-1
1288 cm
-1
90 1204 cm
-1 -1
1556 cm 1369 cm
-1
984 cm
85
OPBC-DNB
DNB
OPBC
80
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
(a) (b)
100
-1
1707 cm
-1
95 1574 cm
-1
1403 cm -1
1288 cm
90 1204 cm
-1
Transmittance (%)
-1
85 984 cm
-1
1113 cm
80 1341 cm
-1
-1
1556 cm
75
70
65
60
MAG-OPBC-DNB
55 DNB
-1
MAG-OPBC 563 cm
50
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
(c) (d)
Figure 10. (a) Proposed mechanism for adsorption of DNB onto OPBC, (b) FT-IR spectrum of OPBC
Figure 10. (a) Proposed mechanism for adsorption of DNB onto OPBC, (b) FT-IR spectrum of OPBC
before and after adsorption of DNB, (c) proposed mechanism for adsorption of DNB onto MAG-
before
OPBC,and after
(b,d) adsorption
FT-IR spectrumofofDNB, (c) proposed
MAG-OPBC beforemechanism for adsorption
and after adsorption of DNB.of DNB onto MAG-OPBC,
(b,d) FT-IR spectrum of MAG-OPBC before and after adsorption of DNB.
4. Conclusions
This study aimed to remove DNB from synthetic wastewater using two adsorbents
produced from orange peels, a copiously abundant agro-waste. The performances of the
as-prepared biochars (OPBC) and magnetite-impregnated candidate (MAG-OPBC) were
compared, and MAG-OPBC was found to be more effective. Different characterization
1. Electrostatic interactions occur when the DNB-charged functional groups interact

with the charged surface of either OPBC or MAG-OPBC. The pH may impact these
interactions since it can modify the surface charge of both the DNB and the as-
prepared adsorbent [66,67]. As shown in Figure 10a,c, the optimum pH greatly affects
the surface of both the adsorbate and the adsorbent. For MAG-OPBC, the optimum
pH was found to be 9.0, which is less than the pKa2 of DNB but higher than the
pHpzc for MAG-OPBC. This results in a positive charge on the surface of the drug
molecules and a negative charge on the surface of MAG-OPBC, leading to a strong
electrostatic interaction between DNB and MAG-OPBC and increasing the removal
efficiency. On the other hand, the data obtained for OPBC show that the optimum pH
is also 9.0, and the pHpzc of OPBC is also 9.28. This results in a neutral surface charge,
which negatively affects the electrostatic interaction and thus, the removal efficiency
of OPBC.
2. Chemical bonding can occur between DNB and both OPBC and MAG-OPBC surfaces
through covalent or ionic bonds. This mechanism is significant for DNB, which
has functional groups that can participate in chemical reactions with the surface
of the nanosorbent. Different functional groups with the adsorbate’s benzene or
other aromatic ring structures could have electron-rich or electron-deficient groups
that facilitate the interaction (Figure 10b,d). Additionally, there may be hydrogen-
bonding interactions between the oxygen atoms (H-acceptors) in the nanosorbent
and the hydrogen of the hydroxyl groups (H-donors) on the DNB drug. This type of
interaction is commonly referred to as hydrogen bonding between dipoles.
3. Intra-particle and surface diffusions mechanism: Intra-particle diffusion refers to the
movement of adsorbate molecules within the pores of the adsorbent particle [68,69].
In the case of OPBC and MAG-OPBC, many pores existed on the surface, as confirmed
by the SEM and BET analyses, and the adsorbate (DNB) diffuses into the pores of
the adsorbent and interacts with the surface of the nanosorbent. Surface diffusion,
conversely, refers to the movement of adsorbate molecules on the surface of the OPBC
and MAG-OPBC adsorbent. In the case of OPBC, the DNB molecules diffuse along
the surface of the biochar and interact with either the surface functional groups or the
magnetic nanoparticles of the MAG-OPBC. Both mechanisms are important for the
description of adsorption of DNB onto OPBC and MAG-OPBC because they explain
the increased interaction between DNB and the adsorbent surface, which enhances
the adsorption process.
4. Conclusions
This study aimed to remove DNB from synthetic wastewater using two adsorbents
produced from orange peels, a copiously abundant agro-waste. The performances of the
as-prepared biochars (OPBC) and magnetite-impregnated candidate (MAG-OPBC) were
compared, and MAG-OPBC was found to be more effective. Different characterization
techniques were used to understand the adsorbent behavior, including TGA/dTA, FT-IR,
point-of-zero-charge, BET, SEM, and TEM analyses. To ensure sustainability and method
greenness, eco-structuring of the prepared adsorbent was approached by controlling the
variables impacting the adsorption process using the PBD. The Pareto chart confirmed
that the most significant variables were the adsorbent dose. In the case of pristine biochar
and the [DNB] in the case of MAG-OPBC. The desirability function was used to determine
the variables that maximize the removal of DNB. The highest removal efficiency of DNB
was 86.46% and 98.51% for OPBC and MAG-OPBC, respectively. The optimum adsorp-
tion conditions were proposed by the desirability function to be pH = 9.0, CT = 10 min,
[DNB] = 100 ppm, and AD = 120 mg/13 mL. Nonlinear equilibrium studies revealed that
DNB adsorption onto MAG-OPBC fits well with the Langmuir isotherm, compared to the
D–R isotherm model in the case of OPBC. The maximum adsorption capacity was found
to be 38.75 and 172.43 mg/g for OPBC and MAG-OPBC, respectively. The D–R isotherm
showed that the adsorption of DNB onto both adsorbents follows a physisorption mecha-
nism with an adsorption energy of <7 kJ/mol. The Elovich model showed that the initial
adsorption rate for DNB using OPBC was lower than that of MAG-OPBC. The PSO model
was able to explain the adsorption kinetics of DNB onto both adsorbents. The adsorption
of DNB onto the two adsorbents can be described using several adsorption mechanisms,
including electrostatic interactions, intra-particle interactions, and surface diffusions.
Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/nano13091444/s1, Table S1: BET analysis of the two sorbents;
OPBC and MAG-OPBC; Table S2: ANOVA findings using OPBC and MAG-OPBC.
Author Contributions: Conceptualization: M.E.-A., A.S.E.-S. and F.G.B.; methodology: M.E.-A.,
F.G.B. and A.S.E.-S.; software: M.E.-A. and A.S.E.-S.; validation: M.E.-A. and A.S.E.-S.; formal
analysis: M.E.-A. and A.S.E.-S.; investigation: A.S.E.-S., M.A. and F.G.B.; resources: M.E.-A.; data
curation: M.E.-A. and A.S.E.-S.; writing—original draft preparation: M.E.-A., F.G.B. and A.S.E.-S.;
writing—review and editing: M.E.-A., A.S.E.-S., F.G.B. and M.A.; visualization: A.S.E.-S. and M.E.-A.;
supervision: M.E.-A.; project administration: M.E.-A.; funding acquisition: M.E.-A. All authors have
read and agreed to the published version of the manuscript.
Funding: This publication was supported by Qatar University Student Grant [QUST-1-CAS-2023-854].
The findings achieved herein are solely the responsibility of the authors.
Data Availability Statement: The data presented in this study are available within this article.
Further inquiries could be directed to the authors.
Acknowledgments: The project members would like to extend their special thanks to the Central
Lab Unit (CLU) at Qatar University. The authors would also like to extend their gratitude to the lab
members of Siham Alqaradawi’s research group for accomplishing the BET analysis.
Conflicts of Interest: The authors declare no conflict of interest.
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Nanomaterials 2023, 13, 1444. https://doi.org/10.3390/nano13091444 https://www.mdpi.com/journal/nanomaterials

Table 1. Removal of antineoplastics from contaminated waters using different strategies.

Application of both sorbents in treating contaminated samples will be controlled by

2. Materials and Methods

2.2. Preparation of OPBC

2.3. Preparation of MAG-OPBC

2.4. Measurment of the Point-of-Zero-Charge (pHPZC )

2.5. Characterization of OPBC and MAG-OPBC

2.6. Batch Adsorption Experiments

2.7. Plackett–Burman Design Execution

2.8. Equilibrium and Kinetics Investigation

Variable Low (−) Central (0) High (+)

Trial Variable–Coded Levels * %ROPBC * %RMAG-OPBC

Derivative Weight (mg/min)

whereas it is 0.66 for MAG-OPBC. This suggests that the numberofofFedefects

Nanomaterials 2023, 13, x FOR PEER REVIEW 10 of 24

3.1.5. BET Analysis

120 ples. The obtained data revealed 0.0020

particles on the surface of OPBC,0.0015

Relative Pressure (P/P ) Pore diameter (nm)

120 nanoparticles loaded biochar. Figure 0.0020

Relative Pressure (P/P ) Pore diameter (nm)

Nanomaterials 2023, 13, x FOR PEER REVIEW 12 of 24

Total 100 Fe 24.76

Nanomaterials 2023, 13, x FOR PEER REVIEW 13 of 24

3.2. Adsorption Study

3.2.2. Quality Charts and Analysis of Variance (ANOVA)

3.2.3. Regression Equations

ln(%ROPBC ) = 4.0734 + 0.01535 pH − 0.001352 CT + 0.000673 [DNB] + 0.001620 AD + 0.1793 Ct Pt,

ln(%RMAG-OPBC ) = 3.9451 + 0.00763 pH − 0.002788 CT + 0.003003 [DNB] + 0.001735 AD + 0.3023 Ct Pt,

Nanomaterials 2023, 13, x FOR PEER REVIEW 15 of 24

3.2.3. Regression Equations

Table 3. Optimum conditions and desirability function d-values.

Adsorbent Optimum Conditions Desirability Function (d)

3.3.2. Kinetic Models

Langmuir qm (mg/g) KL (L·mole−1 ) R2

Reduced Chi-Sqr 3.24058

R-Square (COD) 0.93535

Time (min) Time (min)

1. Electrostatic interactions occur when the DNB-charged functional groups interact

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