Rare Met.

(2022) 41(5):1677–1687
[Link] RARE METALS
ORIGINAL ARTICLE

Synthesis of novel hydrated ferric oxide biochar nanohybrids

for efficient arsenic removal from wastewater
Tong Zhu, Yun Zhang, Yu Chen, Jun-Liang Liu* , Xiao-Li Song*

Received: 18 April 2021 / Revised: 9 October 2021 / Accepted: 18 October 2021 / Published online: 21 February 2022
Ó Youke Publishing Co., Ltd. 2022

Abstract Hydrated ferric oxide (HFO) has high adsorp- toxicity and mobility, and is more difficult to be removed.
tion efficiency for As(III). However, its high self-aggre- Ingestion of water containing arsenic can cause chronic
gation usually reduces the efficiency and limits the scaled- poisoning and even carcinogenesis because arsenic can
up application. Herein, biochar (BC), with large surface bind to active components in the human body to form the
area and amounts of surface functional groups was used to complex. Arsenic can directly affect human physiological
tune the loading and distribution of HFO to prepare an function if it is enriched to a certain extent in human body,
efficient adsorbent (HFO/BC) via in-situ synthesis method. so arsenic pollution in water has a huge threat to human
The influence of the mass ratio of iron salt to BC on HFO/ health and the ecological environment. Both the United
BC morphology was investigated, and the mechanism was States Environmental Protection Agency and World Health
discussed. The results showed that novel HFO was formed Organization profess that the highest arsenic concentration
and distributed uniformly on the surface of BC when the in water ingested by the human should not surpass
mass ratio of iron salt to BC was 5:1. The adsorption 10 lgL-1 [1]. China stipulates that the upper limit of
kinetics and isotherms studies show that the novel HFO/BC As(III) discharge in sewage is 500 lgL-1 [2]. Therefore,
(5:1) composite can fast treat As(III) with a high adsorption the treatment of arsenic wastewater has attracted great
capacity of 104.55 mgg-1, indicating that it is a potential attention from many researchers.
material for removing arsenic from polluted water. Several methods dealing with arsenic wastewater have
now been proposed, among which adsorption gets wide
Keywords Hydrated ferric oxide; Arsenic removal; acceptatance and application due to its large capacity,
Biochar; Water treatment simplicity, and promising economic benefits [3]. Industrial
byproducts and waste materials, surfactants, iron-contain-
ing materials, synthetic activated carbon, mineral products,
1 Introduction and many other materials were used as adsorbents for
arsenic removal [4–6]. Because iron has a strong affinity
Arsenic mainly exists in the form of arsenate (As(V)) and for inorganic arsenic [7–9], the As(III) removal efficiency
arsenite (As(III)) in natural water, which is highly toxic to of iron-based adsorbents is outstanding [10]. In previous
the human body. Especially, As(III) possesses higher studies, hydrous ferric oxide (HFO) has been confirmed to
be an economical scavenger with high efficiency for arse-
nate/arsenite-contaminated wastewater [11]. These disor-
Tong Zhu and Yun Zhang contributed equally to this work. dered nano-iron oxyhydroxides have high specific surface
areas and reactivity, which can provide amphoteric func-
T. Zhu, Y. Zhang, Y. Chen, J.-L. Liu*, X.-L. Song*
College of Chemistry and Chemical Engineering, Yangzhou tional groups [12, 13]. Although HFO has great potential in
University, Yangzhou 225002, China water purification, the widespread application of HFO still
e-mail: liujunliang@[Link] has many problems, such as the tendency to self-aggregate
X.-L. Song and the potential harm to human life due to the possibility
e-mail: xlsong@[Link]

1
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1678 T. Zhu et al.

of releasing nanoparticles into the environment [14–16]. scallion sheathings were dried and ground to powder,
Biochar (BC) is a solid product achieved by the pyrolysis which were then pyrolyzed in a muffle furnace under N2 at
of biomass in the environment with limited oxygen and 700 °C for 2 h. Finally, biochar based on the scallion
relatively high temperatures. The advantages of the high sheathings was obtained.
specific surface area, porosity, and the reactive surface of HFO/BC was prepared by in-situ synthesis using
BC are making it to be a potential candidate material for FeCl36H2O, NaOH and BC [21]. 0.1 g biochar was dis-
the treatment of heavy metal wastewater [17–19]. Regret- persed in a certain concentration of FeCl36H2O aqueous
tably, the arsenic removal efficiency of pure BC is unsat- solution without pH adjustment under magnetic stirring for
isfactory. Therefore, the focus of this research is to 24 h. Then the supernatant was removed, and the solid part
introduce BC to induce the surface formation of HFO to was vacuum dried at 60 °C for 3 h after being washed three
improve its distribution and limit its release into the times. NaOH solution (5 molL-1, 20 ml) was added into
environment, hoping to get a new As(III) adsorbent with the above-dried mixture under magnetic stirring for 24 h.
wide application and high adsorption efficiency. The solid mixture was then washed three times with ddH2O
The most-reported biochar is three-dimensional (3D) and dried in the oven at 60 °C for 5 h. Finally, a biochar
biochar, which has a large surface area but the surface is composite named HFO/BC was obtained. Pure iron-hy-
uneven and is considered not to be conducive for the dis- drated ferric oxide (HFO) was also prepared for compar-
persion of other materials [20–23]. Compared to 3D bio- ison by the same method for the synthesis of HFO/BC, but
char, two-dimensional (2D) biochar is probably beneficial without adding BC. In addition, a NaOH-pretreated BC
for the loading and distribution because of the flat surface under the same conditions was prepared.
[20, 21]. Scallion sheathings are natural cortical materials
with flat surfaces. Therefore, in this research, scallion 2.3 Determination of As(III) concentration [24]
sheathings were used to prepare a 2D biochar with a flat
surface and Fe3? was used as HFO precursors to prepare a 2.3.1 Preparation of As(III) standard stock solution
new composite for As(III) adsorption. Several HFO/BC
nanocomposites were prepared by the method of in-situ The As(III) standard stock solution was prepared first.
synthesis. The effect of the ratio of iron salt mass to that of Briefly, 0.25 g arsenite oxide (As2O3) were accurately
BC on the morphology and adsorption efficiency of the weighed and then dissolved in 2.5 molL-1 NaOH solution.
nanocomposites was investigated and the growth mecha- Then the volume was adjusted to 30 ml with ddH2O, and
nism was discussed. The synthesized novel HFO/BC was the pH of the solution was adjusted to 6.5 with 6 molL-1
successfully used to remove As(III) from the aqueous HCl and 2 molL-1 NaOH. Finally, 0.2 g NaHCO3 was
phase. The influence of experimental parameters like pH, added to the solution, and the As(III) standard stock solu-
original arsenic concentration, dosage, and time during the tion (5 gL-1) was obtained after being diluted to 50 ml
adsorption process were respectively explored, and the with ddH2O.
mechanism of As(III) adsorption was discussed through the
adsorption isotherm model and X-ray photoelectron spec- 2.3.2 Determination of As(III) standard curve
troscopy (XPS).
A 30 ll 7 mgL-1 As(III) solution was added into a 10 ml
volumetric flask, and then 1 ml 6 molL-1 HCl and 1 ml
2 Experimental 5% thiourea-ascorbic acid were added. Finally, the volume
was fixed with ddH2O. A series of As(III) standard stock
2.1 Materials solutions (0, 3, 6, 9, 12, 15, 18 and 21 lgL-1) were pre-
pared with the step-by-step dilution method. The As(III)
Ferric chloride hexahydrate (FeCl36H2O), NaOH, concentration was determined by an atomic fluorescence
NaHCO3 and HCl were bought from Sinopharm Chemical spectrometer (AFS) and the standard curve was drawn with
Reagent Co., Ltd., China. As2O3 was bought from J&K the concentration as the abscissa and the corresponding
China Chemical Ltd, in Shanghai, China. fluorescence value as the ordinate.

2.2 Preparation of BC, HFO and HFO/BC 2.3.3 Measurements of As(III) concentration

Considering that scallion sheathings have a 2D flat surface, For the determination of As(III) concentration in the
which is beneficial for the loading and distribution of HFO, samples, 200 ll of the samples were added into a 10 ml
scallion sheathings were chosen to prepare the biochar. volumetric flask and were pretreated as in Sect. 2.3.2. The
After being washed by deionized water (ddH2O), the samples were measured by AFS, and the arsenic

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Synthesis of novel hydrated ferric oxide biochar nanohybrids for efficient arsenic removal 1679

concentration in the supernatant was obtained according to concentrations were 0, 0.1, 1.0 and 10.0 mmolL-1,
the standard curve. respectively. The contact time was 24 h.
To assess the recovery properties of the composites, the
2.4 Batch adsorption experiments As(III)-adsorbed HFO/BC (4.0 mg HFO/BC (5:1) in 4 ml
As (III) solution (0.5 mgL-1) for 24 h at pH 7.0) was
To evaluate the removal performance for As(III) of these eluted by 20 ml NaOH solution (0.5 molL-1) for 2 h and
hydrated ferric oxide/biochar composites, we conducted the process was repeated three times. After being washed
batch experiments. The influence of pH value, incubation with ddH2O three times, the exhausted adsorbent was dried
time, As(III) concentration, adsorbent dosage, and other at 60 °C and reused in the next adsorption–desorption
coexisting ions on the equilibrium removal efficiency was cycle. The process was repeated 5 times to investigate the
investigated. The solution pH was adjusted with HCl or adsorption of HFO/BC after regeneration.
NaOH (0.1 molL-1). In a typical experiment, adsorbents
(4.0 mg) were dispersed in a centrifuge tube containing 2.5 Characterization
4 ml As(III) solution at pH 6, which were then shaken at
200 rmin-1 in the incubator after being sonicated in a Field emission scanning electron microscopy (SEM,
water bath for 10 min at room temperature. The general S-4800 II, Hitachi, Japan) was used to observe the syn-
contact time was set at 24 h. The As concentration in the thesized materials. Fourier transform infrared-spectroscopy
supernatant was measured by AFS at the required time and (FTIR, TENSOR27, Bruker optic, Germany) was applied
all the tests were repeated three times. to characterize the functional groups of BC, HFO and
The adsorption efficiency and capacity of HFO/BC at HFO/BC. AFS (3100, BJ haiguang, China) was applied to
equilibrium were achieved by using Eqs. (1, 2) as detect the concentration of the arsenic solution. X-ray
following. photoelectron spectroscopy (XPS, ESCALAB 250Xi,
ðC i  C e ÞV Thermo, USA) was used to carry the surface analysis of
qe ¼ ð1Þ materials. Thermo gravimetric analyzer (TGA, Pyris 1,
M
PerkinElmer, USA) was applied to study the thermal
ðC i  C e Þ properties. The specific surface area and pore diameter of
Removal ¼  100% ð2Þ
Ce the products were measured by N2 adsorption–desorption
where qe (mgg-1) is the equilibrium As(III) adsorption using Autosorb IQ3 (Quantachrome Instruments, USA).
capacity; Ci and Ce (mgg-1) are the original and equilib- The surface charge of the HFO/BC was measured by Nano-
rium arsenite concentrations, respectively; M (g) and ZS90 (Malvern Panalytical, British).
V (L) represent HFO/BC dosage and the solution volume,
respectively.
Adsorption kinetics were investigated to discuss the 3 Results and discussion
relationship between adsorption capacity and the incuba-
tion time. The following equations express the pseudo first- 3.1 Characteristic of HFO/BC nanocomposites
order model and the pseudo second-order model,
respectively: To better understand the preparation of the novel HFO/BC,
Pseudo first-order kinetic model linear equation: several HFO/BC composites were synthesized by changing
the mass ratio of BC to HFO (1:0, 1:1, 1:3, 1:5, 1:7, 1:9,
K1 and 1:11). SEM images of BC, HFO and HFO/BC are
lgðqe  qt Þ ¼ lgqe  t ð3Þ
2:303 presented in Fig. 1. It can be found that the surface of BC
Pseudo second-order kinetic model linear equation: was flat and smooth (Fig. 1a), while only irregular HFO
t 1 t was produced without BC and the obtained HFO piled up
¼ þ ð4Þ together with serious agglomeration (Fig. 1b). After the
qt K 2 q2e qe
introduction of HFO, the surface of BC became rough
where qe (mgg-1) and qt (mgg-1) are the adsorption (Fig. 1c–h). For HFO/BC preparation, BC was soaked with
capacity of the equilibrium and given time (t), respectively; ferric chloride solution for 24 h under stirring, and then the
K1 (min-1) and K2 (gmg-1min-1) are adsorption rate impregnated biochar was dried. In this case, iron ions were
constants of the two model equations. loaded onto the BC surface for the subsequent reaction
The effect of coexisting ions was conducted as follows: with NaOH. It is expected that the iron ions introduced by
4.0 mg HFO/BC (5:1) were added into 4 ml As(III) solu- pretreatment can serve as the nucleation center for HFO
tion (0.5 mgL-1) containing different coexisting ions deposition to promote the dispersion of HFO on BC
(Cl-, NO3-, HCO3-, SO42- and PO43-), of which [1, 25, 26]. When the mass ratio of iron salt to biochar is

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1680 T. Zhu et al.

Fig. 1 SEM images of a BC, b HFO, c HFO/BC 1:1, d HFO/BC 3:1, e HFO/BC 5:1, f HFO/BC 7:1, g HFO/BC 9:1, h HFO/BC 11:1, and
i typical sample of HFO/BC (5:1); corresponding elemental mappings of j iron and k oxygen

relatively low (Fig. 1c), only a little HFO formed since and 3699 cm-1 in HFO/BC (5:1) could be attributed to the
there was too less iron ion loaded onto the BC surface to corresponding Fe–O bond at 588 cm-1 [27] and the O–H
form enough nucleation centers to grow up. With the mass stretching vibration peak at 3743 cm-1 [28] in HFO,
ratio increasing (Fig. 1d), HFO on the BC surface gradu- respectively. Furthermore, the absorption peak at
ally increased, and the novel HFO began to appear. 1057 cm-1 in BC corresponded to the vibration of the C–C
Expectedly, a unique novel HFO fully covered the surface framework in the biochar, and the vibration of the C–C
of BC when the mass ratio of iron salt to biochar is 5:1 framework could also be found in the composite at
(Fig. 1e), which might be due to the fact that there were 1064 cm-1. In addition, HFO/BC (5:1) had a broad and
enough nucleation sites on the BC surface and the spatial strong absorption peak of O–H at 3356 cm-1, which was
effect that induced it to form the particular shape. In detail, also related to the absorption peak of BC at 3450 cm-1.
HFO nanorods twisted together and formed a dendritic Moreover, the increase in peak intensity may be due to the
structure, which was then shaped into the novel HFO from introduction of HFO. By comparing the infrared spectra of
end to end. When the mass ratio further increased, the the three materials, it can be observed that almost all the
novel HFO layer piled up and disordered since there were characteristic absorption peaks of BC and HFO could be
too many nucleation sites formed to grow up orderly within found in the HFO/BC (5:1) spectra, proving that the
the limited space (Fig. 1f–h). The higher the mass ratio is, composite material has been successfully prepared.
the more serious the agglomeration of HFO is, and the To further confirm the composition of HFO/BC (5:1),
more unordered products formed. These results prove that the TG curves of BC, HFO and HFO/BC (5:1) were studied
the skeleton of BC is very important for the formation of (Fig. 2b). The TGA curve of HFO showed that 25.18% of
novel HFO/BC as well as its distribution. The elemental the weight was lost, which might correspond to the loss of
maps of HFO/BC (5:1) (Fig. 1i–k) also showed that HFO bound water. HFO/BC (5:1) and BC showed similar two-
appeared as nanorods and distributed evenly on the surface stage weight loss curves. The first mass loss at about
of BC, which might be beneficial for As(III) adsorption. In 30–100 °C was attributed to the desorption of adsorbed
addition, Fe and O are uniform and closely related to the water on the surface of the BC and HFO/BC (5:1) mate-
shape of the sample area. rials, respectively. The second mass loss at 300–600 °C
The infrared spectra of BC, HFO and HFO/BC (5:1) are (79.9%) and 400–700 °C (73.2%) was mainly attributed to
shown in Fig. 2a. The absorption peaks appearing at 582 the decomposition of biochar and the 6.7% difference

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Synthesis of novel hydrated ferric oxide biochar nanohybrids for efficient arsenic removal 1681

Fig. 2 a FTIR spectra and b TGA plots of BC, HFO and HFO/BC (5:1)

between BC and HFO/BC (5:1) composites was mainly As(III) containing water under the same conditions. Fig-
related to the introduction of HFO. ure 3 indicated that the removal ability of pure BC and
The specific surface areas of the novel HFO/BC (5:1), NaOH-pretreated for As(III) is very poor. When HFO and
which is critical for adsorption, was studied by N2 BC were combined, the removal efficiency of HFO/BC to
adsorption–desorption analysis. The Brunauer–Emmett– As(III) was greatly improved. Especially, the uniform
Teller (BET) area of HFO/BC (5:1) is up to 260.21 m2g-1, novel HFO/BC (5:1) displayed the highest removal effi-
indicating that the obtained novel HFO/BC (5:1) is a ciency for As(III), which is consistent with the structural
competitive candidate for removing As(III). It is reported features as analyzed above. Thus, HFO/BC (5:1) is used for
that the BET area of BC is 152.18 m2g-1 [20] and that of further research.
HFO is 16.28 m2g-1 [26], respectively. Compared with
the BET areas of the sole HFO and BC and combined with 3.3 Adsorption of As(III) by novel HFO/BC
Fig. 1e, the large increase in the surface area of the com-
posite HFO/BC (5:1) might indicate that the BC improved 3.3.1 Effect of solution pH on As(III) adsorption
the loading and dispersion of HFO.
Figure 4a displays the influence of solution pH on the
3.2 As(III) adsorption properties of HFO/BC As(III) adsorption by HFO/BC (5:1). It was shown that
nanocomposites As(III) adsorption by the novel HFO/BC (5:1) was less
affected by pH of the solution. When the pH value rose
To study the As(III) removal efficiency of HFO/BC, dif- from 4 to 9, the adsorption efficiency of HFO/BC (5:1) is
ferent HFO/BC composite materials were used to treat always maintained at around 96.5%. When the pH
increased to 10, the adsorption efficiency dropped by about
10%. However, pure HFO was more likely to be affected
by pH, and the removal efficiency of pure HFO on As(III)
gradually decreased with pH increasing. As reported, the
solution pH not only exerted an influence on the existing
form of As(III) but also affected the charge on the surface
of the adsorbent [29], both of which will impact the
adsorption efficiency. Iron oxide surface usually shows
strong attraction to As(III) species, and the internal
spherical bidentate or mononuclear As(III)-Fe(III) complex
can be formed except by ion exchange between the
hydroxyl group of the iron oxide-based adsorbent and
As(III) [24, 30]. The zeta-potential was measured at dif-
ferent solutions with pH (4–10) to further study the dif-
ference in adsorption efficiency since the surface charge of
Fig. 3 As (III) removal efficiency by BC, HFO and different HFO/ the adsorbent can be reflected by the potential. As shown in
BC composites (C0 = 0.5 mgL-1; T = 303 K; pH = 7; Fig. 4b and Table 1, the isoelectric point exists between 5
dosage = 1 mgml-1; time = 24 h)

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1682 T. Zhu et al.

Fig. 4 a Solution pH effect on As (III) adsorption by BC, HFO and HFO/BC (5:1) (C0 = 0.5 mgL-1; T = 303 K; time = 24 h;
dosage = 1 mgml-1); b Zeta potential of BC, HFO and HFO/BC (5:1)

Table 1 Values of zeta potential of BC, HFO and HFO/BC (5:1) (III). Considering the practical application, pH 7 was
(mV) selected for the following tests.
pH BC HFO HFO/BC (5:1)
3.3.2 Effects of incubation time, HFO/BC (5:1) dosage
4 10.86 ± 0.23 30.50 ± 1.1 31.60 ± 0.8 and initial arsenic concentration on As(III)
5 8.93 ± 0.18 29.81 ± 0.9 31.76 ± 1.2 adsorption
6 -5.66 ± 0.15 -28.70 ± 1.2 30.36 ± 0.7
7 -50.76 ± 2.60 -40.11 ± 2.0 -41.00 ± 0.8 As shown in Fig. 5a, the adsorption proceeded fast and
8 -45.86 ± 1.80 -44.40 ± 1.9 -45.10 ± 1.5 83.33% As(III) can be removed at 60 min, as well as the
9 -50.96 ± 2.80 -48.50 ± 1.2 -45.13 ± 1.1 adsorption could reach equilibrium at 600 min. These
10 -45.23 ± 2.50 -51.80 ± 1.1 -48.10 ± 1.4 results showed that HFO/BC (5:1) can achieve a good
removal effect within a quite short time, which is of great
benefit to practical application. Compared to BC and HFO,
the novel HFO/BC (5:1) showed the fastest removal rate
and 6 for HFO/BC, HFO and BC. The zeta potentials of and the highest removal efficiency. According to Fig. 5b,
HFO are slightly lower than those of HFO/BC (5:1) at the the adsorption efficiency increases sharply with the
studied pH range. Especially, when the pH is greater than adsorbent dosage increasing and then tends to equilibrium.
8.0, the zeta potential of HFO is more negative than that of 1 mgml-1 of HFO/BC (5:1) reached the highest adsorp-
HFO/BC (5:1), leading to more repulsive interaction tion efficiency, indicating this dosage of HFO/BC (5:1) was
between As(III) and HFO than that between As(III) and enough to adsorb the As(III) under the settled conditions.
HFO/BC (5:1), resulting in lower adsorption efficiency and Thus, 1 mgml-1 HFO/BC (5:1) is chosen for the following
higher susceptibility to pH of HFO. According to previous adsorption tests. Figure 5c displays that with the increase
studies, neutral H3AsO3 is the main existing form of As(III) in As(III) concentration, the removal efficiency decreased
species in the pH range of 2–9, while the anionic form gradually. This is due to the fact that when the adsorption
(H2AsO3- and HAsO32-) only dominates when the pH is capacity of HFO/BC is saturated, a high concentration of
higher than 9 [31]. When pH B 9, the adsorption efficiency As(III) will no longer be adsorbed, resulting in the decrease
of As(III) remains high, even if the surface charge of HFO/ of the removal efficiency. Therefore, 0.5 mgL-1 As(III)
BC (5:1) is exchanged from positive to negative, which can was chosen for the other following experiments.
be explained by the fact that electrostatic attraction is
weaker than surface complexing force. As the pH is higher 3.4 Adsorption kinetics and adsorption isotherms
than 9, the decrease of As(III) adsorption efficiency may
have resulted from the electrostatic repulsion that existed Figure 6a, b shows the linear relationship of pseudo first-
between HFO/BC (5:1) and As(III). At the same time, there order dynamics and pseudo second-order dynamics,
are a lot of hydroxide ions at higher pH, which would respectively, and the parameters based on the kinetic
compete with As(III) to bind with the surface active sites equations are concluded in Table 2. It can be found that the
on HFO/BC (5:1) and further reduce the adsorption of As determination coefficient (R2) of the pseudo second-order

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Synthesis of novel hydrated ferric oxide biochar nanohybrids for efficient arsenic removal 1683

Fig. 5 Effect of a contact time (C0 = 0.5 mgL-1; pH = 7; T = 303 K; dosage = 1 mgml-1), b dosage (C0 = 0.5 mgL-1; pH = 7;
time = 24 h; T = 303 K), and c initial concentration of As(III) (C0 = 0.5–500 mgL-1; pH = 7; T = 303 K; time = 24 h;
dosage = 1 mgml-1) on removal rate of As(III)

Fig. 6 a Pseudo first-order kinetics, b pseudo second-order kinetics of As(III) adsorption (C0 = 0.5 mgL-1; pH = 7; T = 303 K;
dosage = 1 mgml-1) and c As(III) removal isotherms (Ce = 3–500 mgL-1; T = 303 K; pH = 6; time = 24 h; dosage = 1 mgml-1)

model is closer to 1 than that of the pseudo first-order 3.5 As(III) adsorption mechanism study
model, suggesting that chemical adsorption is the main
adsorption pathway for As(III) by HFO/BC (5:1) [29]. According to the previous analysis, the novel HFO/BC
The fitting isotherm of BC, HFO and HFO/BC (5:1) for (5:1) mainly adsorbs As(III) through chemical adsorption.
removing As(III) is more in line with the Langmuir model: The structure of the adsorbent before and after the uptake
qm K L C e of As(III) was analyzed by XPS to better explore the
qe ¼ ð5Þ adsorption mechanism. XPS spectra of As(III)-HFO/BC
1 þ K L Ce
contained the photoelectrons peaks of Fe 2p (711.5 eV), C
where qm (mgg-1) is the maximum adsorption capacity; 1s (284.08 eV), O 1s (530.95 eV), and As 3d (44.3 eV)
Ce (mgL-1) is the equilibrium arsenic concentration in (Fig. 7a) resulted from HFO, BC and As(III). The peaks of
solution; KL (Lmg-1) is the constant of Langmuir iso- Fe 2p3/2 are displayed in the Fe 2p spectrum of the
therm. It can be seen from Fig. 6c that qm (104.55 mgg-1) adsorbents (Fig. 7b). In addition, we can also find that after
of HFO/BC is higher than that of the other two materials, the adsorption of As(III), the binding energy of Fe 2p1/2
which is consistent with our hypothesis and its structure and Fe 2p3/2 declined from 710.49 to 710.09 eV and 724.1
feature (Table 2). to 723.6 eV, respectively.

Table 2 Kinetic parameters of pseudo first-order and pseudo second-order models for As(III) adsorption on adsorbents
Samples Pseudo first-order model Pseudo second-order model
K1 R2 qe K2 R2 qe
–3 –3
BC 2.76 9 10 0.9783 1.747 1.63 9 10 0.9829 4.756
HFO 2.72 9 10–3 0.7578 1.691 3.18 9 10–3 0.9995 13.077
HFO/BC 2.44 9 10–3 0.9834 1.721 2.93 9 10–3 0.9985 14.556

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1684 T. Zhu et al.

Fig. 7 a XPS of BC, HFO/BC (5:1) and HFO/BC-As(III), high-resolution XPS of b Fe 2p; c O 1s-BC; d O 1s-HFO/BC; e O 1s-HFO/BC-
As(III); f As 3d-HFO/BC-As(III)

To further study the chemical bonds, several fine peaks were much influence on the As(III) removal efficiency. There-
deconvoluted from the peaks of O 1s. As shown, there were four fore, the influence of the coexisting ions on the As(III)
peaks in the O 1s spectrum of the HFO/BC (5:1) before and after removal efficiency was studied. The results showed that the
As(III) absorption (Fig. 7c–e). The four fine peaks corre- existence of Cl-, NO3-, SO42-, HCO3- and PO43- (less
sponded to O=C–O (535.5 eV), O–H (533 eV), C=O (532 eV), than 0.1 mmolL-1) had little effect on the removal of
and Fe–O (530.7 eV) before the adsorption of As(III), while As(III) by HFO/BC (5:1) (Fig. 8a). On the contrary, the
O=C–O (535.2 eV), –OH (532.1 eV), C=O (530.5 eV), and adsorption efficiency of As(III) was distinctly reduced for
Fe–O/As–O (529.5 eV) corresponded to the four fine peaks the coexistence with high concentrations of PO43-
after adsorbing As(III), respectively [32–34]. The Fe–O/As–O (10 mmolL-1), which might be due to that phosphorus
peak (529.5 eV) indicated the adsorption of As(III) onto the shares the similar structures with As(V) and competes with
HFO/BC (5:1) surface. The peak at 44.4 eV in the spectrum arsenic for adsorption. Therefore, the application strategies
after the adsorption of As(III) can be ascribed to the As(III) of HFO/BC (5:1) in sewage treatment for the coexistence
photoelectron peak (Fig. 7f). The strong peak at 533 eV (O–H) of As(III) and high amount of PO43- should be further
confirmed that a lot of hydroxyl groups existed in HFO/BC investigated since high concentrations of PO43- exerted a
(5:1), which was of great significance in removing arsenic [35]. negative impact on As(III) removal efficiency.
According to previous reports, inner monodentate and double- Besides adsorption efficiency, recycling capacity is also
dentate complexes can be formed through the bonding of As important for the adsorbent application. For regeneration,
(III) with the hydroxyl groups on the surface of iron oxide 0.5 molL-1 NaOH was taken as the eluent to desorb
[30, 36, 37]. These results indicated that the adsorption mech- As(III) from HFO/BC (5:1). Figure 8b shows that the
anism was mostly associated with the replacement of the –OH As(III) adsorption efficiency of HFO/BC (5:1) is still
groups of Fe–OH and C–OH by As(III) [15]. higher than 80% after 5 cycles, suggesting that HFO/BC is
a promising adsorbent.
3.6 Effect of coexisting ions and recovery of HFO/
BC (5:1)
4 Conclusion
In the natural water environment, there are always various
anions that coexisted (such as NO3-, Cl-, HCO3-, PO43- In conclusion, the novel HFO/BC (5:1) can effectively
and SO42-), and the interaction between ions may have remove As(III) from the aqueous phase. By compounding

1 Rare Met. (2022) 41(5):1677–1687

 18677185, 2022, 5, Downloaded from [Link] Wiley Online Library on [01/02/2026]. See the Terms and Conditions ([Link] on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Synthesis of novel hydrated ferric oxide biochar nanohybrids for efficient arsenic removal 1685

Fig. 8 a Impact of coexisted ions on As(III) adsorption by HFO/BC (5:1) (C0 = 0.5 mgL-1; T = 303 K; pH = 7; dosage = 1 mgml-1;
time = 24 h); b recycling efficiency of HFO/BC (5:1) for As (III) adsorption during cyclic experiments (C0 = 0.5 mgL-1; T = 303 K;
pH = 7; dosage = 1 mgml-1; time = 24 h)

with BC, the loading and distribution of HFO are well improve the loading and dispersion of the iron-based
improved, and the As(III) adsorption capacity of the materials and the design of multifunctional composites
composites is enhanced. It was found that when the mass based on BC for heavy metal and other pollutants removal
ratio of iron salt to BC was 5:1, HFO was evenly dis- are now in progress.
tributed on the BC surface and formed the novel HFO/BC
(5:1) composites. The adsorption isotherms well fitted the Acknowledgments This study was financially supported by the
National Natural Science Foundation of China (No. 52173208), the
Langmuir model, and the qm is 104.55 mgg-1, which is Priority Academic Program Development of Jiangsu Higher Educa-
higher than that of a lot of the other reported adsorbents tion Institutions and Qing Lan Project of Yangzhou University (Dr.
(some are listed in Table 3 [38–44]). Moreover, the LJL).
regeneration performance of HFO/BC (5:1) is wonderful,
Declarations
and the arsenic removal efficiency still exceeds 80% after 5
cycles. Besides, other common coexisting ions almost had Conflict of interests The authors declare that they have no conflict
no influence on the adsorption of As(III) by HFO/BC (5:1) of interest.
except for the high concentrations of PO43-. This investi-
gation indicates that the introduction of the two-dimen-
sional BC can dramatically reduce the self-aggregation of References
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