Separation and Purification Technology 329 (2024) 125184

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Separation and Purification Technology

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

Waste Camellia oleifera shell-derived hierarchically porous carbon modified

by Fe3O4 nanoparticles for capacitive removal of heavy metal ions
Ning Wang a, 1, Mingyue Wang a, 1, Hongying Quan a, b, *, Shoujun Wang a, c, Dezhi Chen a, *
a
Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, School of Environmental and Chemical Engineering, Nanchang Hangkong
University, Nanchang 330063, China
b
School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang 330063, China
c
Jiangxi Ganfeng LiEnergy Technology Co., Ltd., Xinyu 338004, China

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

Keywords: Capacitive deionization is an efficient technology for water purification and treatment. The electrode material is
Waste biomass-derived hierarchically porous crucial to improving the performance of capacitive deionization. Herein, Fe3O4 nanoparticles-modified hierar­
carbon chically porous carbon (Fe3O4 NPs/HPC) was successfully synthesized by the pyrolysis of waste Camellia oleifera
Fe3O4 nanoparticles modification
shell coupling with the post-modification. Owing to its unique structure and composition, the as-prepared Fe3O4
Rational pore structure
Capacitive deionization
NPs/HPC delivered great potential in capacitive deionization and heavy metal removal. Under the current
Heavy metal ions density of 0.5 A g-1, the Fe3O4 NPs/HPC electrode showed a high specific capacitance of 134.5 F g− 1 in 1 M NaCl
solution, much more than the bare HPC electrode of 99.9 F g− 1. In addition, the Fe3O4 NPs/HPC electrode
exhibited excellent cycle stability with negligible loss of capacitance after 1000 cycles at 2 A g-1. At an operating
voltage of 1.2 V, the Fe3O4 NPs/HPC electrode released high uptake capacity of 34.22 and 39.52 mg g− 1 for Cd
(II) and Pb(II) ions, respectively. XPS spectra and competitive adsorption demonstrated that Cd(II) was mainly
removed by the oxygen-containing groups of HPC through an electrosorption coupling with an electrodeposition
multilayer process, but Pb(II) was uniformly adsorbed on the active sites including the oxygen-containing groups
of HPC and the modified Fe3O4 NPs by a monolayer electrosorption process. The impressive results indicate that
the as-prepared Fe3O4 NPs/HPC composites possess potential for the selective removal of heavy metal ions from
saline wastewater.

1. Introduction electrode of opposite charge by applying an electrostatic field, and then

adsorb charged species in a double electric layer (EDL) formed by the
Heavy metal ions, the main components of water pollutants, cause polarization of a pair of electrodes under an applied electric field [8,9].
serious harm to living organisms and ecological imbalance when their Currently, the main feature of CDI is to design high-performance elec­
content exceeds the allowed value due to their toxicity, permeability, trode materials with high specific surface area and reasonable pore size
persistence, and easy accumulation through the food chain [1,2]. distribution as well as excellent electrical conductivity, wettability, and
Therefore, effective removal of heavy metals from wastewater has electrochemical stability. Various carbon materials have been developed
become a critical issue [3,4]. To date, several methods have been as candidates for CDI electrode materials, including activated carbon
developed to remove heavy metal ions from water, including chemical [10,11], graphene [12,13], carbon nanotubes [14,15], carbon aerogels
precipitation, solvent extraction, membrane filtration, electrodialysis, [16], biomass-derived porous carbon [17,18], etc.
and capacitive deionization (CDI) [5,6]. Among these methods, the CDI Among them, biomass-derived carbon materials are inexpensive and
technique has been attracting widespread attention due to its high easily available and have a wide range of application prospects. Some
adsorption capacity, easy regeneration, and simple operation [7]. natural products such as eggplant, sucrose, and coconut shells had been
The basic principle of CDI is to force ions to move toward the used as carbon sources to prepare porous carbon as electrode materials

* Corresponding authors at: Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, School of Environmental and Chemical
Engineering, Nanchang Hangkong University, Nanchang 330063, China (H. Quan).
E-mail addresses: [email protected] (H. Quan), [email protected] (D. Chen).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.seppur.2023.125184
Received 17 July 2023; Received in revised form 20 September 2023; Accepted 22 September 2023
Available online 28 September 2023
1383-5866/© 2023 Elsevier B.V. All rights reserved.
N. Wang et al. Separation and Purification Technology 329 (2024) 125184

for CDI [19–23]. However, the low uptake severely limited the appli­ 2.3. Electrochemical analysis
cation of biomass-derived porous carbons in CDI for the removal of
heavy metal ions. To further enhance the capacity of biomass-derived To prepare the work electrode, 80 mg of active material, 10 mg of
porous carbons in the uptake of heavy metal ions, the modification of conductive carbon black, and 10 mg of PVDF were dispersed in N-
metal oxide/sulfide nanomaterials, including ZnO [24], MnO2 [25], methyl pyrrolidone to form a uniform slurry, and the slurry was coated
Fe3O4 [26], and MoS2 [27], is usually considered an effective approach, evenly on carbon cloth. The fabricated electrode was dried at 60 ℃ for
which can not only tune the physicochemical properties of the biomass- 12 h. The active material on the work electrode was about 3 ~ 4 mg
derived porous carbon materials, such as wettability, surface area, and cm− 2. The electrochemical properties of the as-prepared work electrode
zeta potential, but also increase active sites, resulting in the improve­ were measured on an electrochemical workstation (CHI 760E) using a
ment of the CDI performance. In addition, the high ratio of mesopores is three-electrode system, in which the counter electrode was Pt flake, the
conducive to the double-layer capacitance, because mesopores stabilize reference electrode was Ag/AgCl electrode, and the electrolyte was 1 M
the structure and conductivity of the electrode material and also facili­ NaCl solution. The gravimetric specific capacitance (C, F g− 1) of the
tate the rapid transfer of electrolyte ions in the electrode material [28]. electrode material was calculated using the discharge curve as the
Recently, our group found that mesopores dominate the CDI perfor­ following Eq. (2).
mance of N-doped carbon with hierarchical porous structure for water
I × Δt
purification [29]. N-doped mesoporous carbon derived from pomelo C= (2)
m × ΔV
peel exhibited enhanced electrosorption and selectivity of Pb2+ and
Cu2+ ions [30]. Hierarchical porous carbon delivered improved capac­ Where I (A) is the operational current, Δt (s) is the discharge time,
itive removal of hardness ions because of its abundant mesopores and ΔV (V) is the working potential range, m (g) is the mass loading of active
negative surface charges [31]. material.
Considering the advantages of nanomaterial modification and high
mesoporosity, herein, Fe3O4 nanoparticles-modified hierarchically 2.4. CDI measurement
porous carbon (Fe3O4 NPs/HPC) was successfully synthesized by the
pyrolysis of waste Camellia oleifera shell coupling with the post- Fig. 1 shows the entire CDI measurement system including the CDI
modification. The electrochemical properties of as-prepared Fe3O4 cell, peristaltic pump, conductivity meter, and battery cycler. The CDI
NPs/HPC composites were evaluated in 1 M NaCl solution. The asym­ unit cell consists of plexiglass plates, rubber gaskets, and CDI electrodes.
metric device, using Fe3O4 NPs/HPC as cathode material and commer­ The CDI electrode was prepared by coating the previous slurry prepared
cial activated carbon (AC) as anode material, was assembled and its in Section 2.3 on 60 mm × 60 mm × 0.5 mm graphite paper and drying
capacitive deionization performance for removal of heavy metal was at 60 ℃. The mass of active material was about 120 mg, and the active
studied. area was 50 mm × 50 mm. CDI experiments were carried out using 50
mL of Cd2+ and Pb2+ solutions with an initial concentration of 100 mg/L
2. Experiment section at operating voltages of 0.8, 1, 1.2, and 1.4 V. The flow rate was 20 mL
min− 1.
2.1. Preparation of materials The electrosorption capacity (SAC, mg g− 1) and the electrosorption
rate (v, mg g− 1 min− 1) of metal ions can be calculated using Eq. (3) and
Firstly, the Camellia oleifera shell powder, which originated from (4), respectively.
Jiangxi province of China, was pre-carbonized by pyrolysis at 500 ℃ for (C0 − Ct ) × Vfs
1 h under N2 atmosphere. The produced biochar (BC) was mixed evenly SAC = (3)
m
with 4 times the mass of ZnCl2 and activated at 800 ℃ for 1 h under N2
atmosphere. Then, the obtained hierarchically porous carbon (HPC) was SAC
v= (4)
immersed into 10 % HCl solution to remove impurities and washed t
using deionized water until pH = 7.0 and dried at 80 ℃ for 24 h. Fe3O4 Where C0 and Ct are the initial and final concentrations of the heavy
NPs/HPC composites were prepared using the following process. 1 g of metal solution (mg L-1), respectively, Vfs is the total volume of the feed
HPC was dispersed in 70 mL of deionized water under continuous solution (L), m is the total mass of active material on both electrodes (g),
magnetic stirring. Then, 0.35 g FeSO4⋅7H2O and 0.68 g FeCl3⋅6H2O were t is the working time (min).
dosed into the above dispersion, and the pH was adjusted to between 10 The removal efficiency (RE, %) of metal ions is calculated theoreti­
and 11 using NH3⋅H2O (~25 wt%). The reaction (Eq.1) was performed cally by Eq. (5).
at 180 ℃ for 12 h. Finally, the obtained Fe3O4 NPs/HPC was separated
by permanent magnets and washed using deionized water and dried in a RE =
C0 − Ct
(5)
vacuum oven at 40 ℃ for 24 h. C0

Fe2+ + 2Fe3+ + 8NH3 • H2 O = Fe3 O4 ↓ + 8NH+

4 + 4H2 O (1) 3. Results and discussion

3.1. Characterization
2.2. Characterization
As shown in Fig. 2a, the two diffraction peaks near 26◦ and 44◦ for
The as-prepared materials were characterized using a scanning the BC and HPC correspond to the (0 0 2) and (1 0 0) crystallographic
electron microscope (SEM, FEI Quanta 450), transmission electron mi­ planes of carbon, respectively. The broad diffraction peaks indicate the
croscope (TEM, FEI Talos F200X), X-ray powder diffractometer (XRD, poor crystallinity and the high disorder of BC and HPC. After modifi­
Bruker, D8 Advance) equipped with Cu Ka radiation (λ = 1.5406 Å), cation of Fe3O4 nanoparticles, the emerging peaks at 2θ = 30.10◦ ,
Raman spectrometer (HORIBA JobinYvon, LabRAM HR800) with an 35.45◦ , 43.09◦ , 53.46◦ , 56.94◦ , and 62.57◦ match well with (2 2 0),
excitation wavelength of 633 nm, Fourier transform infrared spec­ (3 1 1), (4 0 0), (4 2 2), (5 1 1), (4 4 0), and (5 3 3) crystal planes of Fe3O4
trometer (FTIR, Thermo Nicolet, 5700), surface area & pore distribution (JPCDS No. 65–3107). The weak diffraction intensity indicates the nano-
analyzer (BELSORP max), X-ray photoelectron spectrometer (XPS, Kra­ size of Fe3O4 NPs. The disorder characteristic was further investigated
tos, Axis Ultra), and simultaneous thermal analyzer (TGA/DSC, NSK, by Raman spectroscopy. As shown in Fig. 2b, two broad peaks in all
Dimond). samples near 1327 and 1584 cm− 1 correspond to the D and G bands of

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

Fig. 1. CDI measurement system.

Fig. 2. (a) XRD patterns, (b) Raman spectra, (c) Fe 2p and (d) C 1s XPS spectra, (e) N2 adsorption/desorption isotherms, and (f) pore size distribution curves of BC,
HPC, Fe3O4 NPs/HPC.

carbon materials, respectively, where the D band is attributed to the respectively. It indicates that there are abundant defects in BC and HPC,
local defects and disorder carbon with sp3 bonding and the G band and the modification of Fe3O4 NPs could improve the graphitization
represents the in-plane stretching vibration of the sp2 carbon atoms degree of HPC, which is conducive to the mass transfer on the surface of
[32]. The intensity ratio of the D band to the G band (ID/IG) is usually Fe3O4 NPs/HPC composites.
used to compare the defect degree of the carbon material, and the higher The surface groups and chemical environment of as-prepared mate­
ID/IG value suggests more defects in porous carbon. The ID/IG of BC, rials were analyzed by XPS. Fig. S1 shows the XPS scan spectra of BC,
HPC, and Fe3O4 NPs/HPC materials were 1.36, 1.41, and 1.16, HPC, and Fe3O4 NPs/HPC. Apart from C and O signals, Fe 2p

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

photoelectron peaks can be observed in Fe3O4 NPs/HPC. Fe 2p spectrum loading mass of Fe3O4 NPs on HPC, thermogravimetric analysis (TGA)
in Fig. 2c shows two main peaks of Fe 2p3/2 at 710.8 eV and Fe 2p1/2 at was carried out in air with a heating rate of 5 ℃ min− 1. As presented in
724.7 eV and their satellite peaks at 718.2 and 732.5 eV. The main peaks Fig. S4, the weight loss below 400 ℃ is mainly because of the removal of
can be further fitted to four peaks at 710.5, 712.2, 724.1, and 726.7 eV, oxygen-containing functional groups on the surface of HPC. The sharp
corresponding to Fe2+ and Fe3+. The presence of Fe2+ and Fe3+ further drop from 400 to 500 ℃ in the TGA curve is attributed to the oxidation
confirms the phase of Fe3O4. The redox reaction between Fe3+ and Fe2+ removal of carbon in the air. The mass percent of Fe3O4 NPs in the
could improve the charge storage capacity of the electrode material, composites is about 18.6 %.
thereby enhancing the capacitive deionization performance [33].
Fig. 2d presents the C 1s XPS spectra, which can be fitted to three peaks 3.2. Evaluation of electrochemical property
of C–C (284.6 eV), C-O (285.4 eV), and C=O (288.5 eV), respectively. As
displayed in Fig. S2, XPS spectra of O 1s for BC and HPC can be The evaluation of the electrochemical properties of electrode mate­
deconvoluted into three species of C=O (531.5 eV), C-O (532.6 eV) and rial is critical for their capacitive deionization performance. Fig. 4a ~ c
adsorbed H2O/O2 (533.7 eV). In addition, the peak at 530.2 eV in Fe3O4 display cyclic voltammetry (CV) curves of BC, HPC, and Fe3O4 NPs/HPC
NPs/HPC is assigned to the Fe-O in Fe3O4. Moreover, the above oxygen- electrodes at scan rates of 10 ~ 200 mV s− 1 and the voltage window of
containing groups are analyzed by FTIR spectra (Fig. S3). The band at − 1 ~ 0 V (vs. Ag/AgCl) in 1 M NaCl solution. All CV curves exhibit good
584 cm− 1 for Fe3O4 NPs/HPC is attributed to Fe-O vibration, and the symmetry, indicating the effective diffusion of ions in these as-prepared
characteristic bands of C=O, C-O-C, and C-OH can be observed in materials. In addition, no obvious redox peaks appear in all CV curves,
agreement with the XPS results. The presence of oxygen-containing suggesting that the charge/ion storage in all three electrodes is domi­
groups on the surface of BC and HPC is beneficial for the adsorption nated by double electric layer capacitance (EDLC) [37]. To gain insight
of metal ions. into the charge storage process of BC, HPC, and Fe3O4 NPs/HPC elec­
To study the porous structure of BC, HPC, and Fe3O4 NPs/HPC, N2 trodes, Fig. S5a-c show the linearly fitted results between the peak
adsorption/desorption isotherm measurements were performed. As current and the scan rate (v1/2) through the CV curve. The value of b is
displayed in Fig. 2e, a vertical rise for N2 adsorption at low relative obtained from the slope of the linear fit line to the log (scan rate) and log
pressures P/P0 < 0.05 indicates the presence of micropores in all sam­ (current density) of the CV curve via Eq. (6) and (7) [38].
ples. The obvious hysteresis loops at P/P0 > 0.4 for HPC, Fe3O4 NPs/
i = avb (6)
HPC demonstrate the presence of abundant mesopores. The calculated
specific surface area (SBET) of BC, HPC, and Fe3O4 NPs/HPC is 506.8,
log(i) = blog(v) + log(a) (7)
1688.8, and 1330.0 cm2 g− 1, respectively, as shown in Table 1. Because
of the activation of ZnCl2 in the molten state, the SBET of HPC is signif­ Where a and b are the parameters obtained by linear fitting. The
icantly larger than that of BC. After the modification of Fe3O4 NPs, some calculated b-values range from 0.5 to 1, which implies that the charge
of the pore channels are blocked, resulting in a decrease in the SBET of storage process at all three electrodes is controlled by both capacitive
the Fe3O4 NPs/HPC. Fig. 2f shows the pore size distribution curves and diffusion-controlled behaviors. The contribution ratio of capacitive
calculated using the BJH method. Micropores are main in BC and the and diffusion control was further estimated according to the modified
ratio of mesopore/micropore is 0.39. The peaks between 2 and 10 nm for Power-law method presented in Eq. (8) and (9).
HPC and Fe3O4 NPs/HPC samples further indicate the dominant role of
i(V) = k1 v + k2 v0.5 (8)
mesopores, and the corresponding ratio of mesopore/micropore is 2.01
and 1.88, respectively. The reduced mesoporousity in Fe3O4 NPs/HPC
i(v)
may be attributed to that some mesopores in HPC are occupied by the = k1 v0.5 + k2 (9)
v0.5
modified Fe3O4 NPs. The high mesoporosity in HPC and Fe3O4 NPs/HPC
can shorten the diffusion path of ions and accelerate the ion transfer Where k1v and k2v0.5 represent the capacitance contribution and
rate, thus enhancing the capacitive deionization performance of the diffusion contribution, respectively.
material [34–36]. As presented in Fig. S5d-f, the percent of capacitance contribution is
The morphology and structure of Fe3O4 NPs/HPC composites were 77 %, 79 % and 71 % for BC, HPC and Fe3O4 NPs/HPC, respectively. The
further observed by SEM and TEM. SEM image (Fig. 3a) of Fe3O4 NPs/ charge/ion storage of BC, HPC, and Fe3O4 NPs/HPC mainly originated
HPC composites shows the typical morphology of biomass-derived car­ from the capacitance contribution. The capacitance contribution of HPC
bon materials. No obvious mineral agglomeration can be observed, is higher than BC, which is mainly attributed to its higher SBET and
suggesting that Fe3O4 NPs are uniformly distributed on the surface of mesoporosity [39,40]. After modification of Fe3O4 NPs, the capacitance
HPC. Fig. 3b displays the TEM image of Fe3O4 NPs/HPC composites. contribution in the charge storage for Fe3O4 NPs/HPC electrode reduces,
Many Fe3O4 NPs are anchoring on the surface of HPC nanosheets. The implying that the modified Fe3O4 NPs may provide the active sites for
HRTEM image presented in Fig. 3c demonstrates the average size of the charge/ion storage [41].
Fe3O4 NPs is about 10 nm. The clear lattice stripes shown in the HRTEM Fig. 4d-f present the galvanostatic charge/discharge (GCD) curves of
image of Fig. 3d are attributed to the Fe3O4 NPs. The calculated inter­ BC, HPC, and Fe3O4 NPs/HPC electrodes at 0.5 ~ 5 A g− 1. All GCD
layer spacing is 2.97 Å, matching well with the (2 2 0) plane of Fe3O4 curves of three electrodes show a symmetric isosceles triangle shape,
(JCPDS No. 65–3107). In addition, the disorder stripes presented in further suggesting their fast reversibility for charge/ion storage. The
Fig. 3e show the amorphous characteristics of HPC. To determine the area of the CV curve can reflect the specific capacitance of the material.
Fig. 4g shows the CV plots of BC, HPC, and Fe3O4 NPs/HPC electrodes at
10 mV s− 1. The CV curve of Fe3O4 NPs/HPC electrode has the largest
Table 1 area in comparison to BC and HPC electrodes, indicating that the Fe3O4
Specific surface area, pore volume of BC, HPC, Fe3O4 NPs/HPC. NPs/HPC electrode has the highest specific capacitance. It is mainly
attributed to the hydroxylation of Fe3O4 NPs on the surface of HPC,
Sample SBET Smeso Smicro Meso/ Vtotal Vmeso Vmicro
(m2 (m2 (m2 Micro (cm3 (cm3 (cm3 which could improve the charge/ion storage in Fe3O4 NPs/HPC elec­
g− 1) g− 1) g− 1) g− 1) g− 1) g− 1) trode shown in Eqs. (10) and (11).
BC 506.8 141.9 364.3 0.39 0.29 0.17 0.11 Fe3 O4 (H2 O)n = Fe3 O4 (OH)−n + nH+ (10)
HPC 1688.8 1127.9 560.2 2.01 1.43 1.22 0.19
Fe3O4/ 1330.0 867.4 461.8 1.88 1.13 0.95 0.16
HPC
Fe3 O4 (OH)−n + nNa+ = Fe3 O4 (OH)n Nan (11)

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

Fig. 3. (A) SEM, (b) TEM, (c, d, and e) high resolution TEM (HRTEM) images of Fe3O4 NPs/HPC.

Meanwhile, the GCD curves displayed in Fig. 4h also illustrate the further confirming the excellent charge/ion storage ability of the Fe3O4
specific capacitance of Fe3O4 NPs/HPC electrode is higher than HPC and NPs/HPC. Finally, compared with BC and HPC, the Fe3O4 NPs/HPC
BC. According to Eq. (2), the calculated specific capacitance of Fe3O4 electrode exhibits a larger slope in the low-frequency region, proving its
NPs/HPC, HPC, and BC is 134.5, 99.9, and 64.5 F g− 1 at the current good ion mass transfer ability. Fig. S7 displays the GCD cycle stability of
density of 0.5 A g− 1, respectively. The specific capacitance at the current the Fe3O4 NPs/HPC electrode at a current density of 2 A g− 1. After 1000
densities from 0.5 to 5 A g− 1 is shown in Fig. 4i. Owing to the high cycles, the Fe3O4 NPs/HPC electrode still maintains a high capacitance
mesoporosity and modification of Fe3O4 NPs, the Fe3O4 NPs/HPC retention of 98.1 %, demonstrating its excellent cycle stability. The
electrode exhibits an enhanced capacitive performance. above evaluation of the electrochemical properties indicates that Fe3O4
To better clarify the improvement of the charge/ion storage for NPs/HPC composites should possess the best CDI performance among all
Fe3O4 NPs/HPC, the electrochemical impedance spectra (EIS) of BC, the prepared samples.
HPC, and Fe3O4 NPs/HPC electrodes were achieved in the frequency
from 0.01 to 105 Hz at an AC voltage of 5 mV amplitude. The obtained
3.3. CDI performance for removal of Cd2+ and Pb2+
Nyquist plots and the used equivalent circuit model are shown in Fig. S6.
A semi-circle in high-frequency region and a bias in low-frequency re­
The CDI performance of the Fe3O4 NPs/HPC electrode was deter­
gion can be observed in all electrodes, indicating a typical capacitance
mined by the electrosorption removal of Cd2+ and Pb2+ from water.
behavior. The cutoff point of the plot at real part Z’ corresponds to the
Fig. 5a and b show the electrosorption curves of Cd2+ and Pb2+ on the
bulk resistance of the electrode electrochemical system, marked as
Fe3O4 NPs/HPC electrode at different work voltages from 0.8 to 1.4 V.
equivalent series resistance (Rs) [42]. The diameter of the semicircle
The electrosorption uptake of heavy metal ions increases continuously
demonstrates the internal resistance of mass transfer (Rct) between the
with the increase of the reaction time until adsorption equilibrium at
electrode and the electrolyte [29]. The fitted values of Rs and Rct are
120 min. In addition, the higher work voltage results in the high uptake
listed in Table S1. After the activation of ZnCl2, the obtained HPC ex­
of metal ions because the ion diffusion driving force and ion diffusion
hibits lower Rs (2.31 Ω) and Rct (0.33 Ω) than BC (2.76 and 0.48 Ω). The
rate are accelerated by increasing the voltage. Fig. 5c and d displays the
high SBET and mesoporosity are conducive to improving the conductivity
correlation between the electrosorption capacity and the electrosorption
and the charge transfer of electrode materials [43]. Furthermore, the
rate (v) for ion uptake, known as Kim-Yoon plot. The electrosorption
Fe3O4 NPs/HPC electrode presents the slightly increased Rs (2.35 Ω) and
capacity and the electrosorption rate of Cd2+ and Pb2+ on the Fe3O4
significantly reduced Rct (0.15 Ω), indicating that the Fe3O4 NPs/HPC
NPs/HPC electrode increase obviously with the increase of operating
electrode possesses the improved charge transfer in all electrodes,
voltage. Fig. 5e and f exhibit the electrosorption capacity and the

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

Fig. 4. (a-c) CV and (d-f) GCD curves for BC, HPC, Fe3O4 NPs/HPC electrodes, (g) CV curves for a sweep rate of 10 mV s− 1, (h) GCD curves for a current density of 0.5
A g-1, (i) specific capacitance values for different current densities.

corresponding removal efficiency of Cd2+ and Pb2+ by the Fe3O4 NPs/ deionization capacities of Fe3O4 NPs/HPC electrodes are 4.32, 8.13,
HPC electrode. The experimental adsorption capacity of Fe3O4 NPs/HPC 18.22 and 34.22 mg g− 1 for Cd2+ and 4.21, 8.18, 20.67, and 39.52 mg
electrode is 11.08, 22.31, 34.22, and 40.33 mg g− 1 for Cd2+, and 15.78, g− 1 for Pb2+ at initial concentrations of 10, 20, 50 and 100 mg/L. Fig. 6c
26.67, 39.52, and 42.56 mg g− 1 for Pb2+ at 0.8, 1, 1.2, and 1.4 V. The and 6d display the corresponding Kim-Yoon plots. It implies that the
removal efficiency of heavy metal ions increases with the increase of Fe3O4 NPs/HPC electrode has a faster deionization rate in the solution
voltage, and 92.72 % of Cd2+ and 97.85 % of Pb2+ could be removed at with a high initial ion concentration. Fig. 6e and f show the removal
1.4 V. It indicates that the high operating voltage is conducive to the CDI efficiency and electrosorption capacity in Cd2+ and Pb2+ solutions by
performance for the removal of heavy metal ions. It is mainly attributed the Fe3O4 NPs/HPC electrode. With the increase of initial ion concen­
to that the higher the voltage, the more charge generated on the elec­ tration, the electrosorption capacity increases but the removal efficiency
trode surface, the greater the electric field force between the electrodes, decreases. It is mainly attributed to the adsorption limit of the electrode
and the stronger the electrostatic force on the heavy metal ions, which being reached as the concentration increases. In addition, the low
improves the electrosorption capacity and removal efficiency [44]. In electrical conductivity of the deposits generated on the surface of the
addition, the electrosorption capacity of the Fe3O4 NPs/HPC electrode electrode is not conducive to electrosorption [47,48].
for Pb2+ is larger than that of Cd2+ ions at the same voltage, which may To analyze the adsorption mechanism of Cd2+ and Pb2+ on the Fe3O4
be caused by the smaller hydrated ionic radius of Pb2+ [45,46]. NPs/HPC electrode. Pseudo-first-order (PFO) kinetic and pseudo-
The CDI performance of the Fe3O4 NPs/HPC electrode was further second-order (PSO) kinetic models were used to fit the experimental
studied for the removal of Cd2+ and Pb2+ with various initial concen­ data of Cd2+ and Pb2+ on Fe3O4 NPs/HPC electrodes at different
trations. Fig. 6a and b show the electrosorption curves of the Fe3O4 NPs/ external voltages and different metal solution concentrations. The
HPC electrode at 1.2 V (preventing water decomposition) in Cd2+ and nonlinear fitting plots (Fig. S8) and the corresponding parameters
Pb2+ solutions with different initial concentrations. The electrosorption (Table S2 and S3) indicate that the electrosorption of Cd2+ and Pb2+ on
uptake of heavy metal ions increased with the increase of ion concen­ the Fe3O4 NPs/HPC electrode could be fitted better with PFO kinetic
tration. According to fitting results presented in Table S2, the model than PSO kinetic model, which suggests that the PFO kinetic

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

Fig. 5. Electrosorption curves of (a) Cd2+ and (b) Pb2+ on the Fe3O4 NPs/HPC electrode at different applied voltages; KimYoon plots of Fe3O4 NPs/HPC electrodes for
(c) Cd2+ and (d) Pb2+ electrosorption at different applied voltages; removal rate and electrosorption capacity of (e) Cd2+ and (f) Pb2+ on the Fe3O4 NPs/HPC
electrode at different applied voltages.

model could better explain the electrosorption process of Cd2+ and Pb2+, In addition, Langmuir and Freundlich isotherms were used to fit the
indicating that the electrosorption of Cd2+ and Pb2+ is mainly due to the electrosorption process of Cd2+ and Pb2+. Langmuir isotherm assumes
electrostatic interactions between the ions at the electrode and the ions that monolayer adsorption forms on homogeneous surfaces, and the
in the solution [49]. Moreover, the kinetic rate constant of Pb2+ is higher surface adsorption energy is homogeneous. Freundlich model assumes
than those of Cd2+, indicating that the Fe3O4 NPs/HPC has a higher that multilayer adsorption occurs at active binding sites with a hetero­
selectivity for Pb2+ [50]. Similarly, as shown in Table S2 and S3, the geneous energy distribution and that there are interactions between the
calculated maximum adsorption capacities are very close to the exper­ adsorbed species [51]. The nonlinear fitted plots shown in Fig. S9
imental values, and the Fe3O4 NPs/HPC electrode has higher electro­ indicate that the electrosorption of Pb2+ on the Fe3O4 NPs/HPC elec­
sorption capacities for Pb2+ than those of Cd2+. trode increases rapidly with the increase of the equilibrium ion

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

Fig. 6. Electrosorption curves of (a) Cd2+ and (b) Pb2+ on the Fe3O4 NPs/HPC electrode at different ion concentrations; Kim-Yoon plots of the Fe3O4 NPs/HPC
electrode at different concentrations of (c) Cd2+and (d) Pb2+; removal rate and electrosorption capacity of (e) Cd2+ and (f) Pb2+ on the Fe3O4 NPs/HPC electrode at
different ion concentrations.

concentration, which can be attributed to the compression of the double the Fe3O4 NPs/HPC is uniform and independent of the surface coverage
electric layer at higher metal ion concentrations [52]. [53]. The maximum electrosorption capacity of Pb2+ ions calculated
As shown in Table S4, the correlation coefficient (R2) of Langmuir from Langmuir model is up to 66.86 mg g− 1. However, Freundlich (R2 =
isotherm (0.987) for Pb2+ is higher than Freundlich isotherm (0.976), 0.977) model is more consistent with the adsorption isotherm of Cd2+
indicating that the electrosorption isotherm of Pb2+ matches better with ions than Langmuir model (R2 = 0.938). This implies that the Fe3O4
Langmuir isotherm. Therefore, monolayer adsorption and uniform sur­ NPs/HPC electrode includes a heterogenous and energetically inhomo­
face adsorption are the main mechanisms of Pb2+ electrosorption on the geneous surface for the electrosorption of Cd2+ ions and the adsorption
Fe3O4 NPs/HPC electrodes in this study. Based on the assumptions of proceeds through a multilayer adsorption process. In addition, the
Langmuir isotherm model, the electrosorption sites of Fe3O4 NPs/HPC electrosorption rate and uptake of Pb2+ ions are significantly larger than
are uniformly distributed, and the surface of the electrode is completely that of Cd2+ ions, suggesting that the adsorption of Pb2+ on the Fe3O4
covered by Pb2+ ions. In addition, the adsorption energy of Pb2+ ions on NPs/HPC electrode is an actively promoted process.

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

3.4. Deionization mechanism of Cd2+ and Pb2+ the modified Fe3O4 NPs for the Pb2+ electrosorption.

To investigate the deionization mechanism, XPS analysis of the 3.5. Selectivity and reusability of Fe3O4 NPs/HPC
Fe3O4 NPs/HPC electrode was carried out after the electrosorption of
Cd2+ and Pb2+. Fig. S10 displays the survey XPS spectra. The obvious The selectivity of CDI electrodes is critical for the removal of heavy
signals for Cd and Pb indicate the deposition of Cd2+ and Pb2+ ions on metal ions from water. The selectivity of the Fe3O4 NPs/HPC electrode
the Fe3O4 NPs/HPC electrode. As shown in Fig. 7a, XPS scan spectra of for the removal of Cd2+ and Pb2+ was explored in the NaCl solution.
Cd 3d display two peaks centered at 405.8 eV of Cd 3d5/2 and 412.6 eV Generally, the hydration radius and the charge of metal ions may jointly
(Cd 3d3/2). The two peaks can be further deconvoluted into four peaks, affect the selectivity of electrosorption [56]. First, the electrosorption of
of which 405.7 and 412.4 eV are attributed to metal Cd0 monomer, and ions is highly dependent on the charge rather than the hydration radius
the peaks at 406.7 and 412.4 eV are assigned to Cd2+ ions adsorbed on while the adsorption capacity of the ions with the same valence state
the surface of the electrode. It indicates that the contribution for Cd2+ decreases with increasing ionic hydration radius [57]. The charge of
uptake includes electrosorption and electrodeposition. Fig. 7b shows the Pb2+ and Cd2+ is higher than that of Na+, indicating that Pb2+ and Cd2+
XPS spectra of Pb 4f. Two peaks at 138.8 and 143.7 eV correspond to the are more preferentially adsorbed on the surface of the electrode under
Pb 4f7/2 and Pb 4f5/2 of Pb2+, respectively [54], which suggests that the the applied potential and have the energy advantage of shielding the
removal of Pb2+ is mainly attributed to electrosorption. Furthermore, charged surface [58,59]. In addition, the oxygen-containing functional
both Pb 4f7/2 and Pb 4f5/2 peaks can be fitted into two species, including groups and the modified Fe3O4 nanoparticles on the surface of HPC can
Pb native oxide (PbO) and Pb(OH)2/PbCO3. improve the selectivity toward the electrosorption of heavy metal ions in
To further determine the active sites on the surface of the Fe3O4 NPs/ NaCl solution. According to the Hard and Soft Acid and Base (HSAB)
HPC electrode, O 1s and Fe 2p XPS spectra after heavy metal ions theory, these C = O and C-O groups are soft bases, which prefer to bind
adsorption were obtained. Generally, the oxygen-containing groups on with soft acids of Pb2+ and Cd2+.
the surface of carbon materials and the modified metal oxides NPs play Fig. 8 shows the electrosorption results from the Fe3O4 NPs/HPC
the important role for the adsorption of heavy metal ions [55]. Fig. 7c electrode at 1.2 V in the solution containing nitrate (10 mg L-1) and NaCl
shows that four species, including metal oxide, C=O, C-O, and H2O/O2, (100 mg L-1). From Fig. 8a, the concentration of both Cd2+ and Na+
still can be observed in the O 1s XPS spectra after electrosorption of Cd2+ rapidly decreases in the initial 30 min. After 180 min of reaction time,
and Pb2+. The increased intensity for the metal oxide signal in Fig. 7c the removal efficiency of Cd2+ and Na+ is 100 % and 84.44 %, respec­
after Cd2+ adsorption may be attributed to the generation of CdO. In tively. The Fe3O4 NPs/HPC electrode indicates highly efficient for the
addition, the obvious increase in the intensity of the C=O signal after removal of both Cd2+ and Na+ ions. No clear selectivity can be observed
Pb2+ adsorption is mainly due to the presence of PbCO3, which has been between Cd2+ and Na+ ion on the Fe3O4 NPs/HPC electrode, which
confirmed in the Pb 4f XPS spectra (Fig. 7b). Fig. 7d presents the Fe 2p further confirms that the adsorption sites on the Fe3O4 NPs/HPC for
XPS spectra of the Fe3O4 NPs/HPC electrode after electrosorption of Cd2+ and Na+ ions are different. The above XPS results (Fig. 7) indicate
metal ions. An almost identical signal for the Fe 2p after Cd2+ adsorption that the main active sites for Cd2+ removal are the oxygen-containing
implies that the Fe3O4 NPs in the adsorption are not the active sites for functional groups on HPC. Therefore, Fe3O4 NPs can be used as the
Cd2+ electrosorption. However, the signal of Fe 2p after Pb2+ adsorption active site to remove Na+ ions based on the reaction Eq. (11).
became very weak (Fig. 7d) because of the perfect cover of Pb(OH)2 and Fig. 8b displays the electrosorption removal of Pd2+ and Na+ by the
PbCO3 on the surface of the electrode, suggesting the important role of Fe3O4 NPs/HPC electrode. In the initial 60 min, the Pb2+ concentration

Fig. 7. XPS spectra of the Fe3O4 NPs/HPC electrode after electrosorption. (a) Cd 3d, (b) Pb 4f, (c) O 1s, (d) Fe 2p.

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

Fig. 8. Removal curve and removal efficiency of (a) Cd2+ and (b) Pb2+ by the Fe3O4 NPs/HPC electrode at 1.2 V in the solution containing nitrate (10 mg L-1) and
NaCl (100 mg L-1) with the flow rate of 20 mL min− 1.

gradually decreases and 100 % of Pb2+ ions can be removed after 180
min. However, the removal efficiency of Na+ ions is only 9.02 %. The Fe − O− + Pb2+ →Fe − O − ⋯Pb2+ (13)
Fe3O4 NPs/HPC electrode possesses a high selectivity for the removal of Furthermore, the leaching of Fe ions from the Fe3O4 NPs/HPC
Pb2+ ions in NaCl solution. It indicates that the Pb2+ ions almost electrode after Pb2+ electrosorption was determined by ICP-MS. As
completely occupy the active sites on the Fe3O4 NPs/HPC electrode, shown in Table S5, the extremely low concentration (0.036 mg L-1) in­
including the oxygen-containing groups and the modified Fe3O4 NPs on dicates that the electrode is stable. Therefore, the cyclic stability of the
the surface of HPC, which is consistent with the XPS analysis (Fig. 7). Fe3O4 NPs/HPC electrode for the removal of Pb2+ from NaCl solution
The previous work reported that the Fe3O4 nanoparticles exhibited a was carried out repeatedly. Fig. S11 shows the repeated removal of Pb2+
high affinity with Pb ions [60], and can adsorb Pb ions according to the (10 mg L-1) using the Fe3O4 NPs/HPC electrodes from the NaCl solution
following Eq. (12) and (13). The possible mechanism for the selective (100 mg L-1). After 5 cycles, the Pb2+ uptake maintained 10.17 mg g− 1,
adsorption of Cd2+ and Pb2+ ions from NaCl solution is presented in and almost 100 % of Pb2+ could be removed from the NaCl solution. It
Fig. 9. indicates that the Fe3O4 NPs/HPC electrode possesses high cycle sta­
bility. Based on the high selectivity and reusability, the Fe3O4 NPs/HPC
Fe − OH + Pb2+ →Fe − O − Pb+ + H+ (12)
exhibits the potential for the selective removal of Pb2+ from saline
wastewater. Finally, the removal of Cd2+ and Pb2+ by Fe3O4 NPs/HPC

Fig. 9. Possible electrosorption mechanism of Pb2+ and Cd2+ on the Fe3O4 NPs/HPC electrode from NaCl solution.

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N. Wang et al. Separation and Purification Technology 329 (2024) 125184

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Declaration of Competing Interest Biomass Convers. Biorefin. 10 (2019) 1327–1356, https://doi.org/10.1007/
s13399-019-00463-9.
[19] C. Zhao, S. Zhang, N. Sun, H. Zhou, G. Wang, Y. Zhang, H. Zhang, H. Zhao,
The authors declare that they have no known competing financial Converting eggplant biomass into multifunctional porous carbon electrodes for
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