Applied Surface Science 667 (2024) 160348

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Enhancing adsorption efficiency for environmentally-friendly removal of As

(V) and Pb(II) using a biochar-iron oxide composite
Soo Hyeon Kim a, 1, Ji-In Park b, 1, Seungsoo Lee c, Ha-Rim An b, Hyeran Kim a, Byoungchul Son b,
Jiwon Seo a, ChangYeon Kim a, Yesul Jeong d, Kyuseok Choi e, Seulki Jeong f, *, Hyun Uk Lee a, *
a
Division of Material Analysis and Research, Korea Basic Science Institue Gtwahak-ro, Yuseong-gu, Daejeon 34133, Republic of Korea
b
Center for Research Equipment, Korea Basic Science Institute, Daejeon 34133, Republic of Korea
c
Seoul Center, Korea Basic Science Institute, 6-7, Inchon-ro 22-gil, Seongbuk-gu, Seoul 02855, Republic of Korea
d
Busan Center, Korea Basic Science Institute, Busan 46241, Republic of Korea
e
Iksan Joint Inter-agency Chemical Emergency Preparedness Center, Jeonbuk Regional Environmental Office, Ministry of Environment, Iksan 54526, Republic of Korea
f
Department of Environment and Energy, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul 05006, Republic of Korea

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

Keywords: In this study, we aimed to develop an absorbent for efficient removal of heavy metals. We developed a composite
Biochar (BC-IOx) using biochar (BC) obtained by carbonizing rice hull, a type of biomass, and iron(III) nitrate nonhydrate
Ultrasonication (IO). The bonding strength between BC and IO was increased through ultrasonication with high energy at 25 ℃
Iron oxide
and a 2-h heat treatment process at 350 ℃. Brunauer-Emmett-Teller analysis showed that BC-IOx had an
Absorbents
increased specific surface area, which was proportional to iron loading and provided an abundance of active
Heavy metal
heavy metal adsorption sites. This composite effectively removed Pb(II) and As(V). The addition of BC-IO3 to Pb
(II)-contaminated water for 120 min increased Pb(II) absorption capacity to 90.21 mg/g from 18.12 mg/g with
unmodified BC. The As(V) adsorption capacity increased from 8.33 mg/g for unmodified BC to 65.34 mg/g for
BC-IO10. In addition, the potential adsorption mechanism was discussed using detailed chemical and physical
analyses. The synthesis of a composite from biochar and iron oxide can inspire the cost-effective and straight­
forward production of heavy metal absorbents that can be utilized on a large scale.

1. Introduction particular, the latter two advantages play an important role in heavy
metal adsorption [10], and the higher the surface area and porosity of
Heavy metal contamination of water bodies from various water BC, the greater the number of active sites available for adsorption.
sources is potentially hazardous and is transmitted to the surrounding However, it is difficult to separate BC from aqueous solutions because of
environment through several pathways. Heavy metal pollution is its low density and hydrophilicity, which pose a problem in the treat­
emerging as an increasingly important global environmental problem in ment of contaminated water [11]. These limitations can be addressed
the agricultural sector (soil, water) [1–3]. Researchers have utilized through BC surface modification, including chemical or physical modi­
adsorption as one of the methods for removing heavy metals from soil or fication, mineral impregnation, and magnetic modification [12–14].
water because of its low cost, simple construction method, and flexible The metal oxide series have an excellent ability to adsorb heavy metals
operation [4,5]. Therefore, various adsorbents based on biostable bio­ [15].
char (BC) have been developed in recent years to remove heavy metals Iron oxide (IO) has emerged as a promising metal oxide candidate for
[6,7]. removing metals/metalloids because of its low cost, low toxicity, high
In recent decades, BC—which is usually fabricated through the py­ specific surface areas, uniform sizes, and ease of preparation [1–5]. In
rolysis process of waste biomass under oxygen-free conditions—has biochar/iron oxide (BC-IO) composites, the BC functions as a porous
drawn interest owing to advantages such as its low cost, environmen­ carbon matrix that undergoes surface modification by the metal oxide,
tally friendliness, large surface area, and high porosity [7–9]. In which increases the adsorbent surface area and enables multi-functional

* Corresponding authors.
E-mail addresses: [email protected] (S. Jeong), [email protected] (H.U. Lee).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.apsusc.2024.160348
Received 8 January 2024; Received in revised form 26 April 2024; Accepted 19 May 2024
Available online 21 May 2024
0169-4332/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-
nc/4.0/).
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

Table 1 methods required a high-temperature thermal treatment process or a

Comparison of adsorption capabilities of biochar/IO for Pb(II) and As(V) in long production time. For example, when As(V) was used, the adsorp­
previous studies. tion capacity at pyrolysis temperature was 15–168.96 mg/g [24–28],
No Type of Biochar Type of Type of Adsorption Ref but a study involving ultrasonic waves showed a high adsorption ca­
composite pollutant capacity (mg/ pacity of 65.34 mg/g. In contrast, in the case of Pb(II), most studies
g) showed an adsorption capacity of 31.21–99.82 mg/g [29–31,22,32], but
1 Rice husks BC-IOx Pb(II) 90.21 In this our results showed a very high adsorption capacity of 90.21 mg/g
As(V) 65.34 study (Table 1). In the present study, we aimed to fabricate a new BC-IOx
2 bamboo BC-ZVI As(V) 127.15 [24]
composite with high metal adsorption capacity on a large scale by ul­
3 Poplar FeBC900 As(V) 121.61 [25]
(Populus L.) trasonically treating IO and pretreated BC at 25 ℃. The BC-IOx com­
4 microspheres Iron oxide As(V) 168.96 [26] posite is a highly efficient adsorbent for the removal of heavy metals
coated from water. To the best of our knowledge, this is the first study to
Geopolymer explore the synthesis and performance of a novel iron oxide-coated
microspheres
5 red oak (RO) Fe-biochar As(V) 13.1 [27]
biochar composite (BC-IOx) and its application for remediation of As
switchgrass (V) and Pb(II) co-contamination in water systems. The objectives of this
(SG) study were to (1) synthesize BC-IOx composites and determine their
6 fruit bunch and Fe-coated Fruit As(V) 15 [28] effectiveness for As(V) and Pb(II) adsorption, (2) control the ratio of
rice husk bunch
various iron oxides (without pH control) and investigate the adsorption
7 Corn stalks Fe3O4- Pb(II) 99.82 [29]
γFe2O3@PBC capacity for As(V) and Pb(II), (3) analyze subsequent recyclability to
8 Peanut shells FeS@PSB Pb(II) 91.74 [30] determine the practical ability of the adsorbent to remove As(V) and Pb
9 − Manganoxide Pb(II) 98 [31] (II), and (4) investigate the morphological changes of IOx composites as
mineral well as elucidate the adsorption mechanisms of As(III) and Pb(II).
10 activated BC@γ-Fe2O3 Pb(II) 45.69 [22]
The crux of this study is the development and application of a BC-
sludge biomass
11 Coconut shells Fe3O4/ɤ- Pb(II) 31.21 [32] iron oxide composite (BC-IOx) aimed at efficiently removing heavy
Fe2O3/biochar metals, specifically arsenic (V) and lead (II), from contaminated water.
Leveraging the synergistic effects of the adsorptive quality of BC and
catalytic property of IO, this study showcased the enhanced perfor­
adsorption. BC is a type of biocarbon with a highly developed meso­
mance of the composite, compared with that of unmodified BC. Through
porous structure and several surface functional groups, such as C=O,
innovative synthesis, comprehensive characterization, and detailed
–OH, and –COOH. These features significantly enhance its ability to
analysis of adsorption mechanisms, this work elucidated the potential of
adsorb organic compounds [16,17]. Nevertheless, despite its relatively
the composite for sustainable and effective environmental remediation.
high efficiency in removing heavy metals, IO undergoes agglomeration
and oxidation during its preparation, making its separation from heavy
2. Experimental setup
metals difficult after use [18]. Some studies have immobilized IO on
carbon-enriched materials to overcome this problem, and these limita­
2.1. Materials and reagents
tions can also be overcome by combining IO nanoparticles with eco-
friendly BC to form a composite structure [19].
BC was obtained from Yesan-gun, Chungcheongnam-do, Republic of
However, according to a previously reported method, the particles of
Korea. The purchased BC was subjected to heat treatment for approxi­
the synthesized composite are not uniform, necessitating an extended
mately 4.5 h at 450–550 ℃. Iron (III) nitrate nonahydrate (Fe
thermal treatment time. Moreover, there are cost problems resulting
(NO3)3⋅9H2O), 1-propanol (for HPLC 99.9 %), lead nitrate (≥9 9.95 %,
from low reproducibility and high energy processing. Even under strictly
trace metals basis), and potassium nitrate (≥99.0 %, ACS reagent) were
controlled reaction conditions, it is difficult to obtain high crystalliza­
obtained from Sigma-Aldrich (St. Louis, MO, USA). CGAS (cyclic GMP-
tion and good physical properties. Other studies synthesized calcium-
AMP synthase)(5)1 (1000 ppm As(V) concentration) was purchased
rich BC with a high phosphorus adsorption capacity at a high temper­
from Inorganic Ventures (Christiansburg, VA, USA). Electrical-grade
ature through slow pyrolysis (300–900 ◦ C) [20,21], which has the dis­
nitric acid (69–71 %) and hydrochloric acid (35–40 %) were pur­
advantages of being time-consuming and requiring high temperature
chased from Chemitop (Deoksan-eup, Jincheon-gun, Chungcheongbuk-
and pressure. To overcome these disadvantages, ultrasonication, a
do, Republic of Korea). Nalgene 125-ml high-density polyethylene
physical synthesis method, has been implemented. In particular, the
(HDPE) wide-mouth bottles—cleaned with 10 % HCl solution and Milli-
ultrasonication process is a technology that facilitates the efficient and
Q distilled water—were used as batch containers. Millipore Millex-LG
rapid production of large quantities of high-performance composite
0.2 μm hydrophilic polytetrafluoroethylene (PTFE) syringe filters were
materials using a simple process conducted at low or ambient temper­
cleaned with Milli-Q water and used for filtering the mixture.
atures. Recent research has focused on improving the magnetic prop­
erties of biochar to promote effective separation from solution under
2.2. Synthesis of BC-IOx composite catalysts
external magnetic fields [22]. It has been shown that adding magnetic
Fe3O4 to biochar can significantly improve its adsorption capacity. This
First, BC was finely pulverized using a grinder and then sieved using
modification imparts self-adsorption properties to biochar, offering po­
a 30-μm sieve. Thereafter, 150 ml of 1-propanol was added to 1 g of BC
tential applications in a variety of fields. Additionally, a magnetic
and the mixture was sonicated in water for 15 min. Different amounts of
biochar-iron oxide nanocomposite (MBC-IO) was formulated for the
iron (III) nitrate nonahydrate (Fe(NO3)3⋅9H2O) (IO) powder were added
effective and swift extraction of Pb(II) heavy metals from aquatic en­
to the prepared solution and ultrasonicated for 30 min. Finally, the
vironments [23]. This study revealed that nanoparticles of Fe3O4 were
mixture was centrifuged at 4500 rpm for 30 min; the supernatant was
seamlessly integrated onto the surface of the biochar, imparting mag­
discarded and the residue was dried overnight at 60 ℃. Next, the dried
netic characteristics and a significant degree of crystalline structure
powder was heat-treated at 350 ℃ for 2 h. According to the increasing
critical for the elimination of heavy metals.
amount of Fe(NO3)3⋅9H2O (IO), the composite was named BC-IOx (BC-
Several methods, such as pyrolysis, exist for synthesizing BC-IO
IO1, BC-IO3, BC-IO7, and BC-IO10).
composites, and several studies have evaluated the adsorption capac­
ity of BC-IO-based materials. However, each of the previously reported

2
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

2.3. Adsorption experiments under the following conditions: test materials were subjected to a 4-h
degassing period at 300 ℃; dinitrogen was used as the adsorptive; the
Laboratory-scale batch adsorption experiments were carried out analysis bath temperature was maintained at − 195.85 ℃ (77.300 K);
using BC modified with Fe(NO3)3⋅9H2O. To prepare 1000 ppm of stock and the equilibration interval was set at 10 s. To ascertain the zeta po­
solution, 0.1 g of BC samples, lead (II) nitrate (Pb(NO3)2), and arsenic tential, BC-IOx was diluted with distilled water to a concentration of 0.1
oxide (As2O3) dissolved in Milli-Q water were added to 10 ppm of Pb(II) mg/mL. Zeta potential measurements were conducted utilizing a Mal­
and As(V) solution under constant ionic strength (0.05 N KNO3). The vern Zetasizer Nano ZS instrument equipped with transparent dispos­
suspensions were allowed to react at 150 rpm. Thereafter, 1 mL of ali­ able zeta cells (Model Nano ZS, Malvern Instruments, Worcestershire,
quots were collected at designated times (0, 5, 15, 30, 45, 60, 90, and UK).
120 min) and subsequently filtered through a 0.2 μm PTFE syringe filter.
All the experiments were performed in triplicates. The amounts of Pb(II) 3. Results and discussion
and As(V) removed were calculated using Eqs. (1) and (2) [33].
3.1. Ultrasonic-assisted impregnation of iron oxide
C0 − Ce
qe = ×V (1)
m
The ultrasonication method uses powerful ultrasonic energy to apply
C0 − Ce ultrasonic sound waves (19–26 KHz) to a solution. This process effec­
R= × 100(%) (2) tively dissolves, emulsifies, and crushes nanoparticles, dismantling
C0
nanoparticle clusters and facilitating their uniform dispersion
In these equations, qe represents the equilibrium adsorption capacity throughout the solution.
of the respective BC when adsorption reaches its equilibrium state (mg/ In this study, the phase transition of IO during the ultrasonication
g), R stands for the removal efficiency (%), C0 indicates the initial occurs in sequential steps, as shown below:
concentration of Pb(II) and As(V) (mg/L), Ce denotes the concentration *Activation process:
of Pb(II) and As(V) at the point of adsorption equilibrium (mg/L), V
signifies the volume of the solution involved in the adsorption reaction Fe(NO3)3⋅9H2O → Fe3+ + 3NO–3 + H2O (upon dissolution in a 1-propa­
(L), and m represents the mass of the added BC (g). Each aliquot sample nol solution) (1)
was diluted with 1 % HNO3 solution, and the concentrations of Pb(II)
Fe(OH)3 + HNO3 + H2O → FeOOH↓+ H2O + H++ NO3– (2)
and As(V) were measured using the Agilent 7700 ICP-MS (Agilent
Technologies, CA, USA). Fe concentrations were also determined to *Crystallization process:
evaluate the dissolution of Fe from modified BC during the adsorption
process. All recorded values for adsorption capacity displayed a relative 2Feo + O2 → 2FeO (3)
standard deviation (RSD %) of <5 %, signifying a high level of precision
6FeO + O2 → 2Fe3O4 (4)
and alignment with the analytical error margin. The intermediate pre­
cision was confirmed for every 10 or 15 samples using the certified 4Fe3O4 + O2 → 6Fe2O3 (5)
reference material for drinking water (CRM-TMDW), which was pur­
chased from High Purity Standards (Charleston, SC, USA). First, a precursor of IO, Fe(NO3)3⋅9H2O, formally dissociates when
dissolved in a 1-propanol solvent (Reaction (1). The 1-propanol solution
is a composite multi-component organic electrolyte solution that is
2.4. Characterization crystallized with nine water molecules and contains a large amount of
water. Another previously reported study used the spray flame method
In order to examine the surface characteristics as well as the physical to synthesize 1-propanol and Fe(NO3)3⋅9H2O [34]. The dissolved Fe3+
and chemical properties of the BC-IO composite, the samples were reacts with OH– ions to form Fe(OH)3 precipitates, which can be con­
subjected to X-ray diffraction (XRD) analysis using a Panalytical verted into FeOOH. To achieve a low-crystallinity state, the reaction
Empyrean instrument equipped with Cu Kα radiation (λ = 1.5406 Å, with H2O on BC surfaces was carefully controlled by adjusting param­
Netherlands). The XRD parameters were set as follows: voltage of 40 kV, eters such as reaction time, power, and ultrasonication frequency during
current of 30 mA, and scan rate of 5◦ min− 1. The morphological and the treatment [35]. Therefore, ‘Reaction (2)’ hydrolyzes the surface of
microstructural features of the catalysts were examined using field- the IO precursor and transforms Fe(OH)3 on the surface to hydrated
emission scanning electron microscopy (FE-SEM; Hitachi S-4800, FeOOH in an activated state. Notably, FeOOH precipitates on the surface
Japan), while high-resolution imaging was conducted using trans­ of nanozero-valent iron (nZVI) [4]. Nevertheless, under solvent-free
mission electron microscopy (TEM; FEI Tecnai F20, OR, USA) and drying conditions, air-exposed FeOOH is susceptible to oxidation,
analysis of precursors and composites at an acceleration voltage of 300 prompting its transformation into Fe2O3 through recrystallization. In
kV. TEM can be used to determine the internal structure of BC and BC- accordance with the Cabrera–Mott model, this oxidation process occurs
IOx composites, including the arrangement of carbon molecules and extremely rapidly, requiring approximately 0.2 fs to generate an initial
other minerals or elements that may be present. The chemical bonding oxide layer of 1 nm thickness on a freshly exposed iron surface at room
states of the samples were calculated using X-ray photoelectron spec­ temperature. This exposure led to the formation of oxide phases in the
troscopy (XPS; AXIS SUPRA, Kratos, UK) with a monochromatic Al Kα following sequence: FeO, Fe3O4, and Fe2O3 (Reactions 3–5) [4,36]. The
(1486.6 eV) line and a vacuum of approximately <5 × 10− 8 Torr. The 1s BC-IOx composite readily developed through the consecutive-phase
binding energy for C (284.8 eV) was used to calibrate the sample binding transition process from Eqs. (1) to (5). The proportion of the ultimate
energies. We utilized a micro-Raman spectrometer (Horiba LabRam HR- crystalline phase formed during each step was modulated by altering the
800, Kyoto, Japan) with a spectral resolution of approximately 1 cm− 1 initial IO precursor quantity.
for Raman scattering experiments. The experiments were conducted in Table S1 summarizes the XPS fitting area data for the Fe2p spectra
the frequency range of 0–4000 cm− 1, employing a 100 mW, 514 nm based on the IO precursor amount (1. 3, 7, and 10 g) in the final product.
laser. Infrared absorption spectra were obtained using the KBr method These results suggest that the probability of forming Fe2O3 as the final
(200 mg KBr, 1 mg sample) and a Bruker Vertex 80v spectrometer product increases as the content of the IO precursor rises if the ultra­
(Billerica, MA, USA), which performed 32 scans at a resolution of 2 sonication process conditions remain identical. As the content of the IO
cm− 1. The Brunauer-Emmett-Teller (BET) method was employed to precursor increased, the amount of FeO produced through Reactions (1)
assess the BET surface area using a Micromeritics ASAP 2420 instrument and (2) also proportionally increased. Subsequently, a considerable
(Micromeritics Inc., Norcross, GA, USA). The analysis was conducted

3
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

Fig. 1. SEM images of (a) IO, (b) BC, (c) BC-IO1, (d) BC-IO3, (e) BC-IO7, and (f) BC-IO10.

Fig. 2. TEM images of (a) IO, (b) BC, (c) BC-IO1, (d) BC-IO3, (e) BC-IO7, and (f) BC-IO10 IO, iron oxide; BC, biochar; BC-IO1, BC-IO3, BC-IO7, and BC-IO10, biochar/
iron oxide composites with different amounts of IO (1, 3, 7, and 10 g, respectively).

amount of FeO increased the likelihood of contact and reaction with air, distributions of IO, BC, and BC-IOx. Nanometer-sized crystals were
leading to the phase transition of Fe2O3. Therefore, two different IO agglomerated in the IO precursor owing to the aggregation effect of
phases were obtained through a simple sonication process, and the nanomaterials (Fig. 1a), whereas BC exhibited a transparent sheet with a
required composition of each phase could be controlled by adjusting the rich porous structure and a relatively smooth surface (Fig. 1b).
initial IO precursor content. Notably, IO composites with two or more Furthermore, IO particles were clearly visible on the BC surface, as
phases have several industrial applications owing to the presence of shown in Fig. 1c–f. This dispersion was directly proportional to their
numerous defects, such as cation vacancies in their cubic structures quantity and was characterized by a generally spherical shape with a
[15]. homogeneous size. The large surface area of the BC provided abundant
loading sites for IO, thereby enhancing the dispersibility of IO and the
reactivity of BC-IOx. These results indicate that well-dispersed small
3.2. Characterization of the modified biochar-iron oxide (BC-IO) particles efficiently overcome irreversible self-aggregation with strong
composite sonication and are effectively incorporated as monolayers on the BC
surface [37].
3.2.1. Surface morphology and crystallization Fig. 2 shows the TEM images and corresponding diffraction patterns
Fig. 1 depicts the SEM images of the particle shapes and size

4
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

Fig. 3. X-ray diffraction patterns of the IO, BC and BC-IO1, BC-IO3, BC-IO7, and
BC-IO10. IO, iron oxide; BC, biochar; BC-IO1, BC-IO3, BC-IO7, and BC-IO10,
biochar/iron oxide composites with different amounts of IO (1, 3, 7, and 10 g,
respectively).

Table 2
Brunauer-Emmett-Teller (BET) analyses of different compounds, including IO,
BC, BC-IO1, BC-IO3, BC-IO7, and BC-IO10. Fig. 4. (a) Nitrogen adsorption and Brunauer-Emmett-Teller desorption iso­
Sample IO BC BC-IO1 BC-IO3 BC-IO7 BC-
therms; (b) Barrett-Joyner-Halenda (BJH) pore size distribution of the IO, BC
IO10 and BC-IO1, BC-IO3, BC-IO7, and BC-IO10. IO, iron oxide; BC, biochar; BC-IO1,
BC-IO3, BC-IO7, and BC-IO10, biochar/iron oxide composites with different
Surface area (m2/g) 88.38 8.09 142.19 165.65 101.55 93.52
amounts of IO (1, 3, 7, and 10 g, respectively).
Total pore volume 0.16 0.02 0.15 0.18 0.16 0.18
(cm3/g)
Average pore 7.03 11.11 4.22 4.37 6.42 7.67 Furthermore, an increase in the Fe2O3 peak was observed with an in­
diameter (nm) crease in IO addition. This is because as the amount of iron oxide added
IO, iron oxide; BC, biochar; BC-IO1, BC-IO3, BC-IO7, and BC-IO10, biochar/iron increases, more iron oxide particles may form or more changes to Fe2O3
oxide composites with different amounts of IO (1, 3, 7, and 10 g, respectively). may occur. When ≥3 g IO was added, the resulting interaction between
BC and IO resulted in a decrease in the intensity of the BC peak and an
of IO, BC, BC-IO1, BC-IO3, BC-IO7, and BC-IO10. Moreover, the TEM increase in the intensity of the IO peak. A distinct Fe2O3 peak could be
images show that BC was conformally covered with a polycrystalline IO observed when IO content >7 g. This was likely attributable to the
structure, the amount of which increased as the amount of IO added was ultrasonication process, which enabled the creation of highly crystalline
increased. This can substantially increase the specific surface area for BC-IOx (Fe2O3) composites. The presence of characteristic peaks of BC
the catalytic reaction of the BC-IOx composites uniformly synthesized in and IO in the XRD patterns of the composites demonstrates the suc­
BC. Fig. S1 shows detailed TEM images according to the scale, and cessful growth of BC-based IOx and is consistent with the results of TEM
Fig. S2 presents the energy dispersive X-ray spectrometry (EDS) map­ analysis [41].
ping of the precursors and their respective composites. The surface properties of the IO, BC, and BC-IOx were also deter­
The XRD patterns of BC and IO are illustrated in Fig. 3. These pat­ mined using BET analysis (Table 2). Generally, the higher the specific
terns indicate the crystallization of nanoparticles because the peaks are surface area and pore volume, the higher the adsorption efficiency. The
consistent with the characteristics of BC and IO. A typical broad peak surface area of the BC-IO3 composite (165.65 m2/g) was approximately
located at approximately 2θ value of 22◦ in the BC pattern indicates the 20.47 folds that of BC (8.09 m2/g), and the composite pore volume was 9
low crystallinity of the BC [38,39]. Distinct peaks located at 24.14◦ , folds that of BC. This can be attributed to the increased bonding force
33.16◦ , 35.62◦ , 40.86◦ , 49.46◦ , 54.07◦ , 57.60◦ , 62.43◦ , and 63.99◦ in between BC and IO as a result of using an ultrasonication process that
BC-IOx correspond to the characteristic peaks of Fe2O3 crystallites emits high levels of energy, which considerably improved the surface
(0 1 2), (1 0 4), (1 1 0), (1 1 3), (0 2 4), (1 1 6), (0 1 8), (2 1 4), and (3 0 0) area and pore volume. A recent study revealed that the surface area of a
sides, respectively (JCPDS no. 33-0664) [40]. The aforementioned peaks B-FeOx composite was 122.1 m2/g [41], whereas the loading of α-Fe2O3
can also be observed in the BC-IOx (x = 7,10) pattern, while the (1 0 4) and α-FeOOH into sewage sludge biochar (SBC) showed a surface area of
and (1 1 0) peaks in BC-IO3 indicate the presence of IO in the composite. 34.99 m2/g [42]. Fig. 4 shows the N adsorption–desorption isotherms as

5
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

Table 3 distribution of the BC-IOx composite (Fig. 4b) suggests that the
Chemical compositions of IO, BC, BC-IO1, BC-IO3, BC-IO7, and BC-IO10. adsorption hysteresis loop in the isotherm can be classified as the H1
Atomic (%) Fe(NO3)3⋅9H2O Biochar B-IO1 B-IO3 B-IO7 B-IO10 hysteresis loop, which indicates the presence of mesopores. The pore
size of the BC-IOx composite is mainly concentrated at 4–10 nm, which
Fe 68.63 − 36.16 29.7 20.65 34.12
C − 89.46 15.23 25.69 56.3 33 makes it more effective in adsorbing contaminants (heavy metals) from
O 31.37 10.54 48.61 44.61 23.05 32.88 water [43]. The chemical compositions of of IO, BC, BC-IO1, BC-IO3, BC-
IO7, and BC-IO10 are shown in Table 3.
IO, iron oxide; BC, biochar; BC-IO1, BC-IO3, BC-IO7, and BC-IO10, biochar/iron
oxide composites with different amounts of IO (1, 3, 7, and 10 g, respectively).
3.2.2. Surface functional groups and chemical composition
The XPS spectrum confirmed the presence of carbon, oxygen, and
well as the Barrett-Joyner-Halenda (BJH) pore size distributions of IO,
iron elements and explored the chemical state and composition of these
BC, and BC-IOx. As shown in Fig. 4(a), the adsorption–desorption
elements by generating corresponding high-resolution spectra for C1s,
isotherm of the BC-IOx sample can be attributed to a type IV isotherm
O1s, and Fe2p (Fig. 5a). The C1s spectrum consisted of three peaks at
with a hysteresis loop. It also indicates the presence of mesoporous
284.4 eV, 286.1 eV, and 288 eV, which corresponded to C=C, C–O, and
channels beneficial for contaminant adsorption [43]. The BJH pore size
C=O bonds, respectively (Fig. 5b-e) [2]. The O1s spectrum was fitted

Fig. 5. X-ray photoelectron spectroscopy (XPS) spectra of (a) Survey, (b) BC-IO1, (c) BC-IO3, (d) BC-IO7, and (e) BC-IO10. BC-IO1, BC-IO3, BC-IO7, and BC-IO10 refer to
biochar/iron oxide composites with different amounts of IO (1, 3, 7, and 10 g, respectively).

6
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

Fig. 6. Raman spectra of the IO, BC and BC-IO1, BC-IO3, BC-IO7, and BC-IO10.
BC, biochar; BC-IO1, BC-IO3, BC-IO7, and BC-IO10, biochar/iron oxide com­
posites with different amounts of IO (1, 3, 7, and 10 g, respectively). Fig. 7. FT-IR spectra of (a) BC, (b) BC-IO1, (c) BC-IO3, (d) BC-IO7, and (e) BC-
IO10. BC, biochar; BC-IO1, BC-IO3, BC-IO7, and BC-IO10, biochar/iron oxide
into three peaks with binding energies of 529.8 eV, 531.4 eV, and 532.9 composites with different amounts of IO (1, 3, 7, and 10 g, respectively).
eV, respectively (Fig. S3a–d). The peak at 529.8 eV indicates that oxygen
is directly bonded to Fe within the IO lattice, whereas the other two and graphitization of carbon-based materials [48]. The intensity ratio of
peaks at 531.4 eV and 531.4 eV correspond to oxygen present in the the D and G bands (ID/IG ratio) facilitated the estimation of defects in the
remaining functional groups of BC and adsorbed moisture, respectively sample, with higher ratios signifying more defects in the sample. The
[37]. The Fe2p spectra of BC-IOx are depicted in Fig. 5b-e. The peak at a change in ID/IG ratio was in the order of BC (0.66) < BC-IOx (0.72),
binding energy of 710.8 eV is ascribed to Fe 2p3/2, whereas that at 724.6 suggesting that more defects occurred in the BC-IOx composite following
eV corresponds to Fe 2p1/2. Each peak was deconvoluted into two strong ultrasonication treatment. The higher ID/IG ratio of BC-IOx in­
components (Fe2O3 and FeOOH) using Gaussian fitting and a Tougaard- dicates that the modification could have resulted in the removal of non-
type baseline for phase distinction in the IO [4]. The low binding energy condensed aromatic structures in unmodified BC and increased its
peaks at 711.0 and 724.20 eV are characteristic of the Fe3+ state in reactivity with IO. The Raman spectrum of Fe2O3 displays five charac­
Fe2O3, whereas the high energy peaks at 712.95 and 726.05 eV are teristic peaks at 225, 290, 403, 607, 678, 1318 and 1596 cm− 1 [49–51].
associated with the FeOOH state [44,2,45,46]. These peaks are accom­ The peak at 225 cm− 1 corresponds to the A1g mode, which involves the
panied by a satellite peak corresponding to Fe2O3. As reported in movement of iron cations along the c-axis. In contrast, the peaks
different Fe2O3 studies, the presence of the satellite peak between Fe observed at 290, 403, and 607 cm− 1 are associated with the Eg mode,
2p3/2 and Fe 2p1/2 with 718.9 eV binding energy confirms the formation which can be observed as a symmetrical respiration mode of O atoms
of the Fe2O3 phase [47]. These findings indicate that the crystalline IO correlated with each iron cation in the plane perpendicular to the c-axis
immobilized on the BC surfaces consists of the Fe2O3 and FeOOH phases, [49]. The peak at 678 cm− 1 likely corresponds to a FeOOH vibrational
which aligns with the XRD results illustrated in Fig. 3. peak. The BC-IOx composite exhibited two typical Raman peaks at 1596
Raman spectroscopy was performed to determine the vibrational cm− 1 (G band) and 1318 cm− 1 (D band) of BC. The G band is caused by
peak modes of the materials. and additional investigations were con­ irregularities in the carbon crystal structure and lattice defects, which
ducted to verify the presence and behavior of carbon in the product. As generate in-plane vibration of the C–C bond and the D band [52]. The
(V) shown in Fig. 6, the Raman spectra of BC and BC-IOx had two peaks results were consistent with the results of XRD, XPS, and element
at 1,596 (G band) and 1318 cm− 1 (D band), which were attributed to the analyses.
graphite-like crystalline structure and disordered structure resulting The FT-IR spectra of BC and BC-IOx are shown in Fig. 7. As shown in
from carbon vibrations with broken symmetry, respectively [48]. The Fig. 7, O–H groups appear at 3445 cm− 1. The peak at 2,967 cm− 1 or the
intensity ratio of G and D bands (ID/IG) indicates the degree of disorder presence of the aliphatic C–H stretch is attributed to the presence of BC

7
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

and organic molecules [51]. This peak can also be attributed to the
similarity between the spectrum of BC and that of the BC-IO composite
used in this study. The peak at 1634 cm− 1 is the C=C and C=O stretching
vibration [53], and the vibration peak of BC-IOx at 1078 cm− 1 is the
stretching vibration of the C–O group [22]. Main peaks at 534 cm− 1 and
466 cm− 1 due to Fe–O stretching were observed in the nanocomposite
spectrum [54]. These results indicate the presence of Fe2O3 in the
composite [55].

3.3. Heavy metal adsorption on modified biochar-iron oxide (BC-IO)

composite

Fig. 8 demonstrates the adsorption capacities (mg/g) of Pb(II) and As

(V) on modified BC and BC-IOx, along with the exposure time. The
adsorption capacities for Pb(II) and As(V) were found to be closely
related to the amount of iron loading. The Pb(II) adsorption capacities of
BC-IO1, BC-IO3, BC-IO7, and BC-IO10 were significantly higher than the
absorption capacity of unmodified BC (Fig. 9a). Raw BC exhibited 20 %
Pb(II) adsorption, whereas all BC-IOx composites exhibited 88.3–95.8 %
Pb(II) adsorption, and this ratio gradually increased during the experi­
mental time (120 min). Therefore, the modified BC-IOx likely had more
pores and a greater number of active sites on the surface, compared with
raw BC. This finding is consistent with the results of BET and pore size
distribution. Furthermore, this suggests that the IO (α-Fe2O3) was uni­
formly applied to the surface of the modified BC-IOx. However, an excess
of iron concentration can result in the saturation and the aggregation of
active sites on the surface of the modified composite, which may stag­
nate the adsorption capacity [56,57]. Fig. 9(b) shows the changes in As
(V) adsorption capacity between the modified BC-IOx and Pb(II). Similar
to Pb(II) adsorption, most of the As(V) adsorption capacity increased
with BC-IOx composites, compared with that of raw BC. However, the
adsorption capacity of As(V) markedly varied with different doses of IO.
BC-IO10 showed the highest As(V) adsorption capacity with a removal
ratio of 66.98 % and an adsorption capacity of 65.34 mg/g at 120 min,
followed by BC-IO7 with a removal ratio of 59.66 % and an adsorption
capacity of 58.19 mg/g. BC-IO1 and BC-IO3 exhibited relatively low
adsorption capacities with removal ratios of 18.45 % and 26.27 % and
adsorption capacities of 17.71 and 25.64 mg/g, respectively.

3.4. Heavy metal adsorption mechanism

This discrepancy could be explained by the surface charge and zeta

Fig. 8. Adsorption capacities of (a) Pb(II), (b) As(V) by BC and BC-IOx com­ potential of the modified BC-IOx, as shown in Fig. 9. The zeta potential
posite with time. BC, biochar; BC-IOx, biochar/iron oxide composites. determines the cohesive or repulsive force between particles and has
been used to measure potential stability [58]. The unmodified BC sur­
face and IO particles (i.e., Fe(NO3)3⋅9H2O) were negatively and posi­
tively charged, respectively. BC-IO1, BC-IO3, and BC-IO7 exhibited
negative zeta potential values of − 58.8, − 56.9, and − 11.7 mV, respec­
tively, indicating that their surfaces were negatively charged. Interest­
ingly, the surface of BC-IO10 was positively charged with a zeta potential
value of 10.5 mV. Typically, a zeta potential value >30 mV or <− 30 mV
is typically indicative of a stable state with no aggregation or mutual
repulsion [59]; therefore, our observation indicates that the surface
charges of BC-IO1 and BC-IO3 were stable. In addition, the overall
negative charge on the BC surface likely reduced because of the elec­
trostatic attraction between IO (+) and the negatively charged activated
functional group of BC. In the case of an adsorbent with a negative (− )
charge on its surface, the larger the absolute value of the zeta potential,
the stronger the tendency to bind with cations; consequently, absorbents
with high zeta potentials offer advantages in the removal of heavy
Fig. 9. Profiles of zeta potential under the IO; BC; and BC-IO1, BC-IO3, BC-IO7, metals from aqueous solutions. This trend was also consistent with the
and BC-IO10. IO, iron oxide; BC, biochar; BC-IO1, BC-IO3, BC-IO7, and BC-IO10, results of Pb(II) adsorption.
biochar/iron oxide composites with different amounts of IO (1, 3, 7, and 10 g, In contrast to BC-IO1 and BC-IO3, BC-IO7 and BC-IO10 had variable
respectively). surfaces with a mix of positive and negative charges. Therefore, BC-IO7
and BC-IO10 exhibited high As(V) removal efficiencies, which exited the
water as oxyanions. Our results suggest that BC-IO10 exhibited a high Pb

8
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

(II) adsorption capacity even though it had a positive surface charge. In Data availability
the future, we plan to investigate the effects of Pb(II) concentration on
the adsorption capacities of the modified BC-IOx. This can facilitate the No data was used for the research described in the article.
practical application of the modified BC-IOx based on iron oxide dosage
and heavy metal concentration. Acknowledgments
In addition, the released iron concentration from composites was
extremely low, compared with that of unmodified BC with no IO dosage These works were supported by the Korea Basic Science Institute
(Fig. S4), implying that the chemical bonds between BC and IO within (KBSI) research [grant numbers A412310 and A439100].
the modified BC-IOx were sufficiently stable and solid. Our findings
unambiguously demonstrated that our newly synthesized and modified Appendix A. Supplementary material
BC/metal nanoparticle composites are effective at removing heavy
metals from water by improving the surface characteristics of BC, rela­ Supplementary data to this article can be found online at https://doi.
tive to those of unmodified BC. org/10.1016/j.apsusc.2024.160348.

4. Conclusions References

In this study, a simple BC-IOx composite was prepared by combining [1] Q.C. Do, S.-O. Ko, A. Jang, Y. Kim, S. Kang, Incorporation of iron (oxyhydr) oxide
nanoparticles with expanded graphite for phosphorus removal and recovery from
biomass-based BC and IO at room temperature using ultrasonication. aqueous solutions, Chemosphere 259 (2020) 127395, https://doi.org/10.1016/j.
The Raman spectra of BC and BC-IOx revealed the presence of charac­ chemosphere.2020.127395.
teristic Fe2O3 peaks. These were associated with each iron cation in the [2] S.-Y. Gu, C.-T. Hsieh, Y.A. Gandomi, Z.-F. Yang, L. Li, C.-C. Fu, R.-S. Juang,
Functionalization of activated carbons with magnetic Iron oxide nanoparticles for
plane perpendicular to the c-axis. Moreover, they were consistent with removal of copper ions from aqueous solution, J. Mol. Liq. 277 (2019) 499–505,
the outcomes of the crystallinity and elemental analyses obtained from https://doi.org/10.1016/j.molliq.2018.12.018.
XRD and XPS. Thereafter, the synthesized BC-IOx composite was used as [3] N. Khalid, M. Aqeel, A. Noman, S.M. Khan, N. Akhter, Interactions and effects of
microplastics with heavy metals in aquatic and terrestrial environments, Environ.
an adsorbent to remove heavy metals (Pb(II) and As(V)) from polluted Pollut. 290 (2021) 118104, https://doi.org/10.1016/j.envpol.2021.118104.
water. Compared with BC, the specific surface area and pore volume of [4] R. Bhateria, R. Singh, A review on nanotechnological application of magnetic iron
the BC-IO3 composite increased by approximately 17.6 folds (from 8.09 oxides for heavy metal removal, J. Water Process Eng. 31 (2019) 100845, https://
doi.org/10.1016/j.jwpe.2019.100845.
m2/g to 165.65 m2/g) and 9 folds (from 0.02 cm3/g to 0.18 cm3/g),
[5] Q.C. Do, S. Choi, H. Kim, S. Kang, Adsorption of lead and nickel on to expanded
respectively. The BC-IOx composite showed higher Pb(II) and As(V) graphite decorated with manganese oxide nanoparticles, Appl. Sci. 9 (2019) 5375,
removal efficiencies than the unmodified BC. Although the adsorption of https://doi.org/10.3390/app9245375.
Pb(II) was only 19 % when BC was used in isolation, the actual [6] J. Liu, J. Jiang, Y. Meng, A. Aihemaiti, Y. Xu, H. Xiang, Y. Gao, X. Chen,
Preparation, environmental application and prospect of biochar-supported metal
adsorption of heavy metals was 96 %, as confirmed when the composite nanoparticles: a review, J. Hazard. Mater. 388 (2020) 122026, https://doi.org/
(BC-IO3) was added and allowed to react for 120 min. The As adsorption 10.1016/j.jhazmat.2020.122026.
amount was 8.5 % when only BC was used, but it increased to 70 % at [7] H. Zou, J. Zhao, F. He, Z. Zhong, J. Huang, Y. Zheng, Y. Zhang, Y. Yang, F. Yu, M.
A. Bashir, Ball milling biochar iron oxide composites for the removal of chromium
120 min following the addition of the composite (BC-IO10). The (Cr (VI)) from water: performance and mechanisms, J. Hazard. Mater. 413 (2021)
enhanced adsorption efficiency of heavy metals is attributable to the 125252, https://doi.org/10.1016/j.jhazmat.2021.125252.
increased specific surface area and pore volume achieved through the [8] J.-Y. Kim, S. Oh, Y.-K. Park, Overview of biochar production from preservative-
treated wood with detailed analysis of biochar characteristics, heavy metals
formation of composite materials via ultrasonication. Therefore, it is behaviors, and their ecotoxicity, J. Hazard. Mater. 384 (2020) 121356, https://doi.
anticipated that the BC-IOx composite will find extensive utilization as org/10.1016/j.jhazmat.2019.121356.
an environmental remediation material capable of adsorbing heavy [9] E. Singh, A. Kumar, R. Mishra, S. You, L. Singh, S. Kumar, R. Kumar, Pyrolysis of
waste biomass and plastics for production of biochar and its use for removal of
metals, which are prevalent contaminants encountered in aqueous heavy metals from aqueous solution, Bioresour. Technol. 320 (2021) 124278,
environments. https://doi.org/10.1016/j.biortech.2020.124278.
[10] L. Leng, Q. Xiong, L. Yang, H. Li, Y. Zhou, W. Zhang, S. Jiang, H. Li, H. Huang, An
overview on engineering the surface area and porosity of biochar, Sci. Total
CRediT authorship contribution statement
Environ. 763 (2021) 144204, https://doi.org/10.1016/j.scitotenv.2020.144204.
[11] P. Zhang, D. O’Connor, Y. Wang, L. Jiang, T. Xia, L. Wang, D.C.W. Tsang, Y.S. Ok,
Soo Hyeon Kim: Writing – original draft, Methodology, Investiga­ D. Hou, A green biochar/iron oxide composite for methylene blue removal,
tion, Formal analysis, Data curation, Conceptualization. Ji-In Park: J. Hazard. Mater. 384 (2020) 121286, https://doi.org/10.1016/j.
jhazmat.2019.121286.
Writing – original draft, Methodology, Investigation, Formal analysis, [12] D.-W. Cho, K. Yoon, Y. Ahn, Y. Sun, D.C.W. Tsang, D. Hou, Y.S. Ok, H. Song,
Data curation, Conceptualization. Seungsoo Lee: Formal analysis, Data Fabrication and environmental applications of multifunctional mixed metal-
curation. Ha-Rim An: Investigation, Formal analysis. Hyeran Kim: biochar composites (MMBC) from red mud and lignin wastes, J. Hazard. Mater.
374 (2019) 412–419, https://doi.org/10.1016/j.jhazmat.2019.04.071.
Investigation, Formal analysis. Byoungchul Son: Formal analysis, [13] K.S.D. Premarathna, A.U. Rajapaksha, N. Adassoriya, B. Sarkar, N.M.S. Sirimuthu,
Investigation. Jiwon Seo: . ChangYeon Kim: Investigation, Formal A. Cooray, Y.S. Ok, M. Vithanage, Clay-biochar composites for sorptive removal of
analysis. Yesul Jeong: Investigation, Formal analysis. Kyuseok Choi: tetracycline antibiotic in aqueous media, J. Environ. Manage. 238 (2019) 315–322,
https://doi.org/10.1016/j.jenvman.2019.02.069.
Formal analysis, Investigation. Seulki Jeong: Writing – original draft, [14] Y. Sun, K.M. Iris, D.C.W. Tsang, X. Cao, D. Lin, L. Wang, N.J.D. Graham, D.S. Alessi,
Supervision, Methodology, Investigation, Formal analysis, Data cura­ M. Komárek, Y.S. Ok, Multifunctional iron-biochar composites for the removal of
tion, Conceptualization. Hyun Uk Lee: Writing – original draft, Super­ potentially toxic elements, inherent cations, and hetero-chloride from hydraulic
fracturing wastewater, Environ. Int. 124 (2019) 521–532, https://doi.org/
vision, Project administration, Methodology, Investigation, Formal 10.1016/j.envint.2019.01.047.
analysis, Data curation, Conceptualization. [15] J.-I. Park, Y. Hong, Y. Jang, M.-G. Ha, H.-R. An, B. Son, Y. Choi, H. Kim, Y. Jeong,
H.U. Lee, Efficient iron oxide/expanded graphite nanocomposites prepared by
underwater plasma discharge for removing heavy metals, J. Mater. Res. Technol.
Declaration of competing interest
14 (2021) 1884–1892, https://doi.org/10.1016/j.jmrt.2021.07.068.
[16] J.C. Colmenares, R.S. Varma, P. Lisowski, Sustainable hybrid photocatalysts:
The authors declare that they have no known competing financial titania immobilized on carbon materials derived from renewable and
interests or personal relationships that could have appeared to influence biodegradable resources, Green Chem. 18 (2016) 5736–5750, https://doi.org/
10.1039/C6GC02477G.
the work reported in this paper. [17] L. Lu, R. Shan, Y. Shi, S. Wang, H. Yuan, A novel TiO2/biochar composite catalysts
for photocatalytic degradation of methyl orange, Chemosphere 222 (2019)
391–398, https://doi.org/10.1016/j.chemosphere.2019.01.132.

9
S.H. Kim et al. Applied Surface Science 667 (2024) 160348

[18] R. Konwarh, N. Karak, S.K. Rai, A.K. Mukherjee, Polymer-assisted iron oxide [40] Z. Cai, E.S.P. Leong, Z. Wang, W. Niu, W. Zhang, S. Ravaine, N.L. Yakovlev, Y.
magnetic nanoparticle immobilized keratinase, Nanotechnology 20 (2009) J. Liu, J. Teng, X. Lu, Sandwich-structured Fe2O3@ SiO2@ Au nanoparticles with
225107, https://doi.org/10.1088/0957-4484/20/22/225107. magnetoplasmonic responses, J. Mater. Chem. C 3 (2015) 11645–11652, https://
[19] D.A. Almasri, N.B. Saleh, M.A. Atieh, G. McKay, S. Ahzi, Adsorption of phosphate doi.org/10.1039/C5TC01259G.
on iron oxide doped halloysite nanotubes, Sci. Rep. 9 (2019) 3232, https://doi. [41] J. Song, Z. Huang, M.G. El-Din, Adsorption of metals in oil sands process water by a
org/10.1038/s41598-019-39035-2. biochar/iron oxide composite: influence of the composite structure and surface
[20] L. Dai, F. Tan, H. Li, N. Zhu, M. He, Q. Zhu, G. Hu, L. Wang, J. Zhao, Calcium-rich functional groups, Chem. Eng. J. 421 (2021) 129937, https://doi.org/10.1016/j.
biochar from the pyrolysis of crab shell for phosphorus removal, J. Environ. cej.2021.129937.
Manage. 198 (2017) 70–74, https://doi.org/10.1016/j.jenvman.2017.04.057. [42] L. Yang, L. He, J. Xue, L. Wu, Y. Ma, H. Li, P. Peng, M. Li, Z. Zhang, Highly efficient
[21] J. Kim, J. Song, S.-M. Lee, J. Jung, Application of iron-modified biochar for nickel (II) removal by sewage sludge biochar supported α-Fe2O3 and α-FeOOH:
arsenite removal and toxicity reduction, J. Ind. Eng. Chem. 80 (2019) 17–22, sorption characteristics and mechanisms, PLoS One 14 (2019) e0218114.
https://doi.org/10.1016/j.jiec.2019.07.026. [43] C. Li, Z. Sun, X. Li, L. Liu, S. Zheng, Facile fabrication of g-C3N4/precipitated silica
[22] S. Deng, B. Ren, B. Hou, X. Deng, R. Deng, G. Zhu, S. Cheng, Adsorption of Sb (III) composite with enhanced visible-light photoactivity for the degradation of
and Pb (II) in wastewater by magnetic γ-Fe2O3-loaded sludge biochar: rhodamine B and Congo red, Adv. Powder Technol. 27 (2016) 2051–2060, https://
performance and mechanisms, Chemosphere 349 (2024) 140914, https://doi.org/ doi.org/10.1016/j.apt.2016.07.014.
10.1016/j.chemosphere.2023.140914. [44] Q. Gao, F. Chen, J. Zhang, G. Hong, J. Ni, X. Wei, D. Wang, The study of novel
[23] B. Latifian, T. Taghizade Firozjaee, J. Abdi, Synthesis of biochar-iron oxide Fe3O4@ γ-Fe2O3 core/shell nanomaterials with improved properties, J. Magn.
magnetic nanocomposite for efficient and rapid removal of Pb (II) heavy metal Magn. Mater. 321 (2009) 1052–1057, https://doi.org/10.1016/j.
from water, Water Pract. Technol. 19 (2024) 181–199, https://doi.org/10.2166/ jmmm.2008.10.022.
wpt.2023.223. [45] Y. Jeong, J.-I. Park, M.G. Ha, J.-S. Bae, Y. Choi, S.-A. Choi, Y.-K. Oh, H.-R. An,
[24] L. Xu, Z. Shu, L. Feng, J. Zhou, T. Li, Z. Zhao, W. Wang, Fresh biomass derived H. Kim, H.J. Kim, Effect of hydrogenated iron oxide nanoparticles with regular
biochar with high-load zero-valent iron prepared in one step for efficient arsenic spherical shape by underwater plasma discharge treatment for high-efficiency
removal, J. Clean. Prod. 352 (2022) 131616, https://doi.org/10.1016/j. water purification, Ceram. Int. 46 (2020) 23582–23591, https://doi.org/10.1016/
jclepro.2022.131616. j.ceramint.2020.06.130.
[25] Y. Xu, X. Xie, Y. Feng, M.A. Ashraf, Y. Liu, C. Su, K. Qian, P. Liu, As (III) and As (V) [46] H. Liu, E.Y. Jiang, R.K. Zheng, H.L. Bai, Structure and magnetic properties of
removal mechanisms by Fe-modified biochar characterized using synchrotron- polycrystalline Fe3O4 films deposited by reactive sputtering at room temperature,
based X-ray absorption spectroscopy and confocal micro-X-ray fluorescence Phys. Status Solidi 201 (2004) 739–744, https://doi.org/10.1002/
imaging, Bioresour. Technol. 304 (2020) 122978, https://doi.org/10.1016/j. pssa.200306762.
biortech.2020.122978. [47] A. Keller, I. Wlokas, M. Kohns, H. Hasse, Solid-liquid equilibria in mixtures of iron
[26] N. Thakur, D.W. Armstrong, Arsenic sequestration by iron oxide coated (III) nitrate nonahydrate and ethanol or 1-propanol, Fluid Phase Equilib. 536
geopolymer microspheres, J. Clean. Prod. 291 (2021) 125931, https://doi.org/ (2021) 112987, https://doi.org/10.1016/j.fluid.2021.112987.
10.1016/j.jclepro.2021.125931. [48] F. Yang, S. Zhang, Y. Sun, Q. Du, J. Song, D.C.W. Tsang, A novel electrochemical
[27] S. Bakshi, C. Banik, S.J. Rathke, D.A. Laird, Arsenic sorption on zero-valent iron- modification combined with one-step pyrolysis for preparation of sustainable
biochar complexes, Water Res. 137 (2018) 153–163, https://doi.org/10.1016/j. thorn-like iron-based biochar composites, Bioresour. Technol. 274 (2019)
watres.2018.03.021. 379–385, https://doi.org/10.1016/j.biortech.2018.10.042.
[28] F. Sadegh-Zadeh, B.J. Seh-Bardan, Adsorption of As (III) and As (V) by Fe coated [49] G. Bharath, N. Ponpandian, Hydroxyapatite nanoparticles on dendritic α-Fe2O3
biochars and biochars produced from empty fruit bunch and rice husk, J. Environ. hierarchical architectures for a heterogeneous photocatalyst and adsorption of Pb
Chem. Eng. 1 (2013) 981–988, https://doi.org/10.1016/j.jece.2013.08.009. (II) ions from industrial wastewater, RSC Adv. 5 (2015) 84685–84693, https://doi.
[29] Q. Du, S. Zhang, J. Song, Y. Zhao, F. Yang, Activation of porous magnetized org/10.1039/C5RA15703J.
biochar by artificial humic acid for effective removal of lead ions, J. Hazard. Mater. [50] J.O. Bonsu, J.I. Han, Sucrose-templated interconnected meso/macro-porous 2D
389 (2020) 122115, https://doi.org/10.1016/j.jhazmat.2020.122115. symmetric graphitic carbon networks as supports for α-Fe2O3 towards improved
[30] Z. Han, B. Sani, W. Mrozik, M. Obst, B. Beckingham, H.K. Karapanagioti, supercapacitive behavior, RSC Adv. 10 (2020) 15751–15762, https://doi.org/
D. Werner, Magnetite impregnation effects on the sorbent properties of activated 10.1039/D0RA02056G.
carbons and biochars, Water Res. 70 (2015) 394–403, https://doi.org/10.1016/j. [51] A. Taha, S. Daffalla, Biochar derived from palm waste supported greenly
watres.2014.12.016. synthesized MnO2 nanoparticles as a novel adsorbent for wastewater treatment,
[31] A. Soenmezay, M.S. Öncel, N. Bektaş, Adsorption of lead and cadmium ions from Catalysts 13 (2023) 451, https://doi.org/10.3390/catal13020451.
aqueous solutions using manganoxide minerals, Trans. Nonferrous Met. Soc. China [52] R. Siddheswaran, D. Manikandan, R.E. Avila, C.E. Jeyanthi, R.V. Mangalaraja,
22 (2012) 3131–3139, https://doi.org/10.1016/S1003-6326(12)61765-8. Formation of carbon nanotube forest over spin-coated Fe2O3 reduced thin-film by
[32] H. Wang, R. Liu, Q. Chen, Y. Mo, Y. Zhang, Biochar-supported starch/chitosan- chemical vapor deposition, Fuller. Nanotub. Carbon Nanostruct. 23 (2015)
stabilized nano-iron sulfide composites for the removal of lead ions and nitrogen 392–398, https://doi.org/10.1080/1536383X.2013.866945.
from aqueous solutions, Bioresour. Technol. 347 (2022) 126700, https://doi.org/ [53] X. Qin, R. Tao, S. Cheng, B. Xing, W. Meng, Y. Nie, C. Zhang, J. Yu, Microwave-
10.1016/j.biortech.2022.126700. assisted one-pot method preparation of ZnO decorated biochar for levofloxacin and
[33] H. Liang, C. Zhu, S. Ji, P. Kannan, F. Chen, Magnetic Fe2O3/biochar composite Cr (VI) removal from wastewater, Ind. Crop. Prod. 208 (2024) 117863, https://doi.
prepared in a molten salt medium for antibiotic removal in water, Biochar. 4 org/10.1016/j.indcrop.2023.117863.
(2022) 3, https://doi.org/10.1007/s42773-021-00130-1. [54] A. Mirzaei, K. Janghorban, B. Hashemi, S.R. Hosseini, M. Bonyani, S.G. Leonardi,
[34] K.A. Owusu, L. Qu, J. Li, Z. Wang, K. Zhao, C. Yang, K.M. Hercule, C. Lin, C. Shi, A. Bonavita, G. Neri, Synthesis and characterization of mesoporous α-Fe2O3
Q. Wei, Low-crystalline iron oxide hydroxide nanoparticle anode for high- nanoparticles and investigation of electrical properties of fabricated thick films,
performance supercapacitors, Nat. Commun. 8 (2017) 14264, https://doi.org/ Process. Appl. Ceram. 10 (2016) 209–217, https://doi.org/10.2298/
10.1038/ncomms14264. PAC1604209M.
[35] Y. Mu, F. Jia, Z. Ai, L. Zhang, Iron oxide shell mediated environmental remediation [55] S. He, L. Zhong, J. Duan, Y. Feng, B. Yang, L. Yang, Bioremediation of wastewater
properties of nano zero-valent iron, Environ. Sci. Nano. 4 (2017) 27–45, https:// by iron oxide-biochar nanocomposites loaded with photosynthetic bacteria, Front.
doi.org/10.1039/C6EN00398B. Microbiol. 8 (2017) 823, https://doi.org/10.3389/fmicb.2017.00823.
[36] M. Wu, J. Ma, Z. Cai, G. Tian, S. Yang, Y. Wang, Rational synthesis of zerovalent [56] A.A. Bhutto, J.A. Baig, T.G. Sirajuddin, R. Kazi, K. Sierra-Alvarez, S. Akhtar, H.
iron/bamboo charcoal composites with high saturation magnetization, RSC Adv. 5 I. Hussain, A. Afridi, S.S. Hol, Biosynthesis and analytical characterization of iron
(2015) 88703–88709, https://doi.org/10.1039/C5RA13236C. oxide nanobiocomposite for in-depth adsorption strategy for the removal of toxic
[37] Z. Wen, J. Xi, J. Lu, Y. Zhang, G. Cheng, Y. Zhang, R. Chen, Porous biochar- metals from drinking water, Arab. J. Sci. Eng. 48 (2023) 7411–7424, https://doi.
supported MnFe2O4 magnetic nanocomposite as an excellent adsorbent for org/10.1007/s13369-022-07477-y.
simultaneous and effective removal of organic/inorganic arsenic from water, [57] C. Xu, Y. Feng, H. Li, R. Wu, J. Ju, S. Liu, Y. Yang, B. Wang, Adsorption of heavy
J. Hazard. Mater. 411 (2021) 124909, https://doi.org/10.1016/j. metal ions by iron tailings: Behavior, mechanism, evaluation and new perspectives,
jhazmat.2020.124909. J. Clean. Prod. 344 (2022) 131065, https://doi.org/10.1016/j.
[38] C. Feng, M. Huang, C. Huang, Specific chemical adsorption of selected divalent jclepro.2022.131065.
heavy metal ions onto hydrous γ-Fe2O3-biochar from dilute aqueous solutions with [58] H. Yoo, J. Kang, N. Park, T. Kim, M.-I. Kim, Y.-S. Lee, Preparation and
pH as a master variable, Chem. Eng. J. 451 (2023) 138921, https://doi.org/ characteristics of fluorinated carbon nanotube applied capacitive desalination
10.1016/j.cej.2022.138921. electrode with low energy consumption, Appl. Chem. Eng. 27 (2016) 386–390,
[39] C. Zhao, L. Hu, C. Zhang, S. Wang, X. Wang, Z. Huo, Preparation of biochar- https://doi.org/10.14478/ace.2016.1040.
interpenetrated iron-alginate hydrogel as a pH-independent sorbent for removal of [59] E.J. Park, L.H. Bac, J.S. Kim, Y.S. Kwon, J.C. Kim, H.S. Choi, Y.H. Chung,
Cr (VI) and Pb (II), Environ. Pollut. 287 (2021) 117303, https://doi.org/10.1016/j. Production and properties of Ag metallic nanoparticle fluid by electrical explosion
envpol.2021.117303. of wire in liquid, J. Powder Mater. 16 (2009) 217–222, https://doi.org/10.4150/
KPMI.2009.16.3.217.

10