Chemosphere 264 (2021) 128378

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Great enhancement in phosphate uptake onto lanthanum carbonate

grafted microfibrous composite under a low-voltage electrostatic field
Yi Yang a, b, c, Kok Yuen Koh a, Haoxin Huang b, Huiping Zhang b, Ying Yan b, J. Paul Chen a, *
a
Department of Civil and Environmental Engineering, National University of Singapore, Kent Ridge Crescent, Singapore, 119260, Singapore
b
School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of
Technology, Guangzhou, 510640, PR China
c
College of Education for the Future, Beijing Normal University, Zhuhai, 519087, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

LC-MC composite is applied in

electro-assisted adsorption.

Electric-assisted adsorption of phos-
phorous exhibits higher efficiency
and faster rate.

Uptake kinetics is well described by
an intraparticle surface diffusion
model.

a r t i c l e i n f o a b s t r a c t

Article history: Removal of phosphorus from water via cost-effective measures becomes important for water industry
Received 20 May 2020 mainly due to eutrophication in waterbody. In our lab, a novel lanthanum carbonate-microfibrous
Received in revised form composite (LC-MC) with good performance was previously synthesized for the removal of phos-
4 September 2020
phorus. In this study, we further improved our technology by applying the electrostatic field (direct
Accepted 15 September 2020
Available online 18 September 2020
current, DC) to the adsorption system. It was showed that the applied DC can greatly improve the
adsorption of phosphate in particular the adsorption capacity. Better removal was seen in the pH range of
1
Handling Editor: Dr. E. Brillas 5e9 at a higher temperature. The maximum adsorption capacity of 47.57 mg-PO3 4 g was achieved,
which was 1.4 times of that operated in the absence of applied DC. The adsorption equilibrium was
Keywords: established at the contact time of 240 min; the adsorption history was well described by the intraparticle
Electro-assisted adsorption surface diffusion model. The negative effect from oxygen-containing anions on the phosphate uptake
Phosphate
followed the decreasing sequence of: humic acid > carbonate > nitrate > sulfate; on the other hand, the
Lanthanum carbonate
halogen anions had almost no influence on it. Finally, the mechanism study by XPS, XRD, and IR
Microfibrous composite
Adsorption kinetics modeling demonstrated that the ligand exchange played an important role in the electro-assisted phosphate up-
take process.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction

In our modern society, phosphate-containing wastewater dis-

charged from industries and households is increasingly becoming
* Corresponding author. an issue to one of the most critical environmental problems that
E-mail addresses: [email protected], [email protected] (J.P. Chen). need to be solved (Lee et al., 2009). Phosphate is an essential

https://doi.org/10.1016/j.chemosphere.2020.128378
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
Y. Yang, K.Y. Koh, H. Huang et al. Chemosphere 264 (2021) 128378

nutrient for algae, and the excessive phosphate content in the water or as an adsorbent in a batch reactor. The LC-MC was tested for its
can cause water eutrophication and lead to human diseases (Tezuka stability and performance in the phosphorus uptake. The results
et al., 2004; Chitrakar et al., 2005; Yu et al., 2015a; Koh et al., 2020a; showed that the LC-MC well performed in the decontamination of
b). In the occurrence of eutrophication, large amounts of plants and phosphorus (Yang et al., 2020).
algae rapidly reproduce themselves, resulting in hypoxia, fish- In this study, we further extended our study into the electro-
death and destruction of aquatic ecosystem (Rydin et al., 2017). assisted adsorption for phosphorus uptake by our developed LC-
Therefore, it is important to treat phosphate in wastewater by cost- MC. Several key parameters were studied, namely, applied
effective technologies. voltage, electrode distance, temperature, ionic strength, pH and
Available technologies for the phosphate removal include presence of co-existing anions. The uptake kinetics, absorption
chemical precipitation/coagulation, biological treatment, crystalli- isotherm and the mechanism of phosphate adsorption were stud-
zation, ion exchange, adsorption and membrane technology (Morse ied. The objectives of this study were to optimize the operating
et al., 1998; De-Bashan et al., 2004; Lee et al., 2006; Huang et al., conditions of the electro-assisted adsorption and better understand
2011; Koh et al., 2020b). Among them, adsorption is one of the the mechanisms of the removal of phosphorus by the LC-MC in the
most promising technologies, due to several advantages such as applied electrostatic field.
ease in operation, relatively lower cost and wide industrial accep-
tance (Wang et al., 2015; Yu et al., 2015a; Ghasemi et al., 2018). 2. Experimental
However, it has a few drawbacks such as low adsorption capacity
and slow kinetics. It is therefore of importance to search highly 2.1. Materials
efficient adsorptive materials and systems for the treatment. In
addition, the improvement of operational conditions can further All materials were used as received without further purification
enhance the treatment efficiency as well as reduce the operating unless specified and all chemicals are of analytical grade. The MC
expenditure. has a round shape with a diameter of 2 cm and a thickness of 2 mm.
Electro-assisted adsorption by applying an electrostatic field to It owns a network structure (95% porosity) made by numerous
an adsorption system appears to be a promising method for the stainless-steel fibers (diameter of 6.5 mm and length of 2e3 mm for
removal of ionic substances, due to its high efficiency, time-saving each fiber) purchased from the Huitong Advanced Material Com-
and facile adsorbent regeneration (Huang et al., 2013; Porada et al., pany, Guangzhou, China. NaF, NaCl, Na2CO3 and HNO3 (69%) were
2013; Macías et al., 2014; Hu et al., 2015; Suss et al., 2015; Garcia- purchased from Fisher Scientific, while La(NO3)3$6H2O, CH4N2O
Quismondo et al., 2016; Wang et al., 2018; Koh et al., 2019). The (>98%), KH2PO4, NaOH, NaNO3, NaHCO3, Na2SO4, KBr, KI and humic
change in surface charges of the adsorptive materials can influence acid sodium salt were purchased from the Sigma Aldrich
the interactions (electrostatic attraction) between an ionizable (Singapore). The deionized water was obtained from a Milli-Q
adsorbate and an adsorbent, leading to an enhancement in the (Millipore) water purification system in our lab and used for the
affinity between the adsorbate and the adsorbent. Thus, a higher preparation of all solutions in the experiment.
removal efficiency is expected from the electro-assisted adsorption
system as compared to that without electro-assistance (Bai et al., 2.2. Electrode synthesis
2019). The existence of the external electric field can drive the
ionic components to move toward the oppositely charged electrode The MC as an anode was pre-treated through a wet lay-up paper
rapidly. This additional driving force can greatly increase the making process and a sintering process (Yang et al., 2019a, b). The
adsorption kinetics (Hu et al., 2018). LC-MC was synthesized according to our approach given in the
However, there is limited work on the electro-assisted adsorp- literature (Yang et al., 2020). In short, the MC was first soaked in a
tion in the last several years. One of the reasons is that there is no NaOH solution so that the hydroxyl groups were formed on the
suitable adsorptive materials as the electrodes (Huang et al., 2014). surface, which can link the lanthanum ions. The NaOH-treated MC
Such materials should have these two properties, such as being was washed and soaked in a lanthanum nitrate solution, by which
highly efficient in the adsorption and highly conductive. the lanthanum ions were attached onto the MC surface. Finally,
Lanthanum species have been proved to be highly effective in urea was added into the solution to react with the lanthanum ions
removing such anionic contaminants as arsenic, fluoride, and that were on the MC surface, resulting to the formation of the LC-
phosphate, due to the strong interactions between the lanthanum MC.
compounds and the contaminants (Xie et al., 2014a, 2014b; Yu
et al., 2018). However, the lanthanum compounds are mainly in 2.3. Characterization of LC-MC
powder form and non-conductive, making them unsuitable for the
electro-assisted adsorption. Therefore, lanthanum species need to The morphology of LC-MC was characterized by the scanning
be incorporated into a conductive support for a better adsorption. electron microscopy (SEM, Zeiss Merlin FE-SEM) with an acceler-
Microfibrous composite (MC) is a kind of novel supports with an ating voltage of 200 kV. The phase structure of LC-MC was verified
unique spatial structure and such advantages as good stability, through the X-ray diffraction (XRD, D/Max-3A) with a voltage of
adjustable shape, ease in preparation and modification, and good 40 kV and a current of 30 mA using the Cu Ka radiation.
mechanical strength. Hence, MC is suitable as a support medium for The specific surface area and porosity of LC-MC were deter-
adsorbents and catalysts (Chang et al., 2006; Yang et al., 2019a). mined by the surface area analyzer (Micromeritics Tristar II 3020).
In one of our previous studies (Koh et al., 2020a), a lanthanum The samples were degassed at 150  C in a vacuum for 6 h before the
carbonate (LC) nanorod was synthesized for the phosphorus up- measurement. The N2 adsorptiondesorption isotherms were ob-
take. We found that it had an excellent adsorption performance. For tained under 77 K. The specific surface area was calculated from the
example, the phosphate uptake can be as high as 303 mg g1 with adsorption branches in the relative pressure range of 0.06e0.3 by
an equilibrium time of 5 h; most importantly, it worked well in the the BrunauereEmmetteTeller (BET) method.
pH ranging from 3 to 8. The chemical composition and chemical state of LC-MC were
In a recent study, we developed a lanthanum carbonate grafted studied by the X-ray photoelectron spectroscopy (XPS, Kratos Axis
microfibrous composite (LC-MC) for the removal of phosphorus Ultra (DLD)) with the aluminum Ka radiation source operated at a
(Yang et al., 2020). The objective was to use it as a mesh-typed filter voltage of 15 kV and a current of 10 mA. The XPS result was
2
Y. Yang, K.Y. Koh, H. Huang et al. Chemosphere 264 (2021) 128378

collected in the binding energy form, and then fitted by a non-

linear least-square curve fitting software (XPSPEAK41 Software)
(Yu et al., 2015a; b).

2.4. Electro-assisted adsorption study

The schematic diagram of electro-assisted adsorption system is

shown in Fig. SI-1. Two parallel electrodes were connected to the
power supply/rectifier (direct current (DC)), with the LC-MC as the
anode and the undecorated MC as the cathode. During the exper-
iments, two electrodes were immersed in the phosphate solution,
where the DC was provided. The error analysis was included in all
experiments. The experimental errors were within 3% throughout
the study.
The important effects of several key parameters were studied as
follows. The detailed experimental conditions were all given
together with the results in the figures in this paper. No stirring was
applied during the experiments.
To investigate the effect of voltage on the uptake of phosphate, a Fig. 1. Effect of voltage on LC-MC and MC performance. Experimental condition:
voltage (U) of 0e16 V was applied to a solution containing 1.5-g L1 m ¼ 1.5 g L1, C0 ¼ 150 mg L1, electrode gap: 8 cm; the initial pH was 6.9 and it was
not controlled during the experiment. Noted that no stirring was applied during the
LC-MC (m) with 150-mg L1 phosphate (C0), where the electrode experiments.
gap was set at 8 cm. The pH was 6.9 initially and was not controlled
during the experiment. The samples were taken from the phos-
phate solution at a fixed time interval for the measurement of increased with an increase in voltage. At the voltage of 16 V, the
phosphate concentration using an inductively coupled plasma op- 1
adsorption achieved 77.1 mg-PO3
4 g , which was nearly eight
tical emission spectrometer (ICP-OES, Optima 3000DV, Perkin times higher than the case without applied voltage (8.9 mg-
Elmer). Through this experiment, the optimal voltage was obtained 1
PO3
4 g ) (Yang et al., 2020).
together with the uptake kinetics data.
The increase in the adsorption capacity can be attributed to the
In the effect of pH experiment, the pH of a 100-mg L1 phos-
strengthened interactions between the LC-MC and the phosphate
phate solution was varied from 3 to 12 using NaOH and HNO3 so-
ions. The stronger surface complex formation (SCF) and greater
lutions; it was run at the conditions: the voltage of 5 V, the LC-MC
effect from the compression of the electric double layer (EDL)
of 1.5 g L1 and the electrode gap of 8 cm. At the end of the
would be the important factors for the enhancement (Chen, 2012).
experiment, the samples were taken and tested for the phosphate
According to the theories of SCF model and colloid science, the
concentration by the ICP-OES.
affinity between an adsorbent and an adsorbate is dependent upon
The electro-assisted adsorption isotherm experiment was per-
several factors, being, the surface complex formation (namely
formed with the initial phosphate concentration of 20e200 mg L1
adsorption reactions) and the effect of compression of EDL. These
at pH 6.9. The other conditions and procedures were the same as
factors coexist and lead to the phosphate uptake by such adsor-
the aforementioned pH effect study.
bents as the LC-MC in the batch reactor reported in our previous
The effect of ionic strength was studied with the ionic strength
paper (Yang et al., 2020; Koh et al., 2020a). In this study, the second
varying from 0 to 1 M (NaNO3). The other conditions were the same
factor is greatly enhanced due to the presence and effect of the
as the pH effect study.
applied DC.
The competitive adsorption was studied by adding 100-mg L1
According to the SCF and the theory for the EDL, an adsorption
common co-existing anions such as humic acid (HA), fluoride (F ),
between the functional group on the surface of an adsorbent (e.g.,
chloride (Cl ), bromide (Br ), iodide (I ), carbonate (CO2
3 ), sulfate SOH) and the anionic substance (e.g. mono-anionic Y) follows the
 1
(SO2
4 ) and nitrate salts (NO3 ) separately to the 100-mg L reaction below (Yiacoumi et al., 1995; Chen, 2012):
phosphate solutions. In addition, a phosphate solution with all
these anions (100 mg L1 each) was used to study the overall
SOH þ Hþ þ Y ¼ SOHþ
2Y

(1a)
competitive effect of these anions on the phosphate uptake
(marked as “mixed” solution). The experiments were conducted
   eðj  j Þ
with the same procedure as that of the pH effect study. SOHþ
2Y

0 b
The effect of electrode gap and that of temperature on the up- þ ¼ KY exp 
 (1b)
½SOHfH gfY g kT
take were studied. In the electrode gap study, the gap was varied
from 5 to 15 cm. In the effect of temperature study, the solution where, jo and jb are electrostatic potentials at the surface plane
temperature was set at 20, 30, 40 and 50  C respectively. Other and the inner helmholtz plane of solid (adsorbent), respectively; KY
experimental conditions were similar to those in the pH effect is the reaction constant; e, k and T are electron charge, Boltzmann
study. constant, and absolute temperature, respectively (Chen et al.,
2001a,b).
3. Results and discussion Due to the presence of positive charge from the applied current
at the anode (LC-MC) and negative charge of anionic phosphate
3.1. Effect of voltage and uptake kinetics ions, the EDL becomes greatly compressed, leading to a smaller
value of (jo and jb), and thus the reaction listed in Eq. (1a) becomes
The voltage is the most important parameter in the electro- enhanced. As a result, we can see a much higher uptake of phos-
assisted adsorption system. Thus, the effect of voltage was first phate when a DC is applied.
studied. As shown in Fig. 1, the adsorption capacity (qt) was A higher voltage is beneficial to the uptake. However, if the
3
Y. Yang, K.Y. Koh, H. Huang et al. Chemosphere 264 (2021) 128378

applied voltage becomes too high, the large anode potential can  
cause many side reactions and result in the dissolution of the 1 vq 1 v 2 vq
¼ 2 r 0  r  ap ; t > 0 (4)
adsorbent material. Numerous fine bubbles were observed during Ds vt r vr vr
the experiment, due to the electrolysis of water (Equation (2a) and The equations for initial and boundary conditions are specified
(2b)). Hence, the applied voltage of 5 V was chosen for the as:
following experiments in this study to investigate the performance
of the electro-assisted phosphate adsorption. vq
¼0 at r¼0 (5)
vr
 þ
2H2 O  4e ¼ 4H þ O2 Anode (2a)
vq
Ds rp ¼ kf ðC  C * Þ at r ¼ ap (6)
2Hþ þ 2e ¼ H2 Cathode (2b) vr

In addition, it can be seen that the applied DC enhanced the q¼0 at t¼0 (7)
uptake kinetics. Fig. 1 shows that the adsorption curve became
steeper at a higher voltage, indicating an increase in the adsorption where C and q are the concentrations of phosphate in the bulk and
rate. At the voltage of 5 V, the adsorption equilibrium time was solid phases, respectively; C* is the aqueous phase concentration at
240 min. the surfaces of LC-MC, in equilibrium with the corresponding
In our previous studies, the adsorption took 300 min to achieve concentration in the solid phase q*; Ds is the surface diffusivity
equilibrium for the phosphate uptake by the lanthanum carbonate within the LC-MC; rp is the density of LC-MC; r is the distance from
nanorod (Koh et al., 2020a) and nearly 325 min for that by LC-MC in the internal surface of LC-MC; ap is the characteristic length of LC-
a batch reactor (without electro-assistance) (Yang et al., 2020). On MC; kf is the external mass transfer coefficient, and t is the time.
the other hand, the LC-MC exhibited a higher adsorption rate in the The above equations can be solved by a finite difference method
presence of electrostatic field in this study (equilibrium time of available in the literature (Tien, 1994). The benefit of using the
240 min), as shown in Fig. 1. intraparticle surface diffusion model is that the model can well
Under the applied electrostatic field, the positively charged LC- predict the kinetics of uptake as the functions of concentration of
MC surface and the electric field between the electrodes offer an adsorbate and dosage of adsorbent (Chen et al., 2007). The
external driving force, leading to a rapid penetration of phosphate commonly used pseudo-1st and -2nd order reaction kinetics equa-
ions through the liquid film to the internal surface of LC-MC for the tions fail to do so.
uptake. Similar results have been reported in the literatures (Du The parameters used for the modeling are: solution
et al., 2017; Hong et al., 2019). volume ¼ 1.00  104 m3; LC-MC mass ¼ 1.50  104 kg; surface
The Nernst-Planck equation given below can be used to illus- diffusivity ¼ 1.00  109 m2 s1; external mass transfer
trate the reason causing the faster kinetics (Galama et al., 2014; coefficient ¼ 1.50  104 m s1; density of LC-MC ¼ 5.00 
Tang et al., 2015, 2016; Tedesco et al., 2016). 103 kg m3; porosity of LC-MC ¼ 0.69; and characteristic length of
  LC-MC ¼ 1.50  104 m. The equilibrium relationship used was
vCi vf from the Langmuir isotherm study.
Ji ¼  Di þ z i Ci (3)
vX vX As shown in Fig. 1, the intraparticle surface diffusion model well
describes the phosphate uptake history. This indicates that the ki-
where Ji is the ion flux (mol s1 m2), Di is the diffusion coefficient netics of uptake process is controlled by the surface diffusion.
of ion i (m2 s1), Ci is the concentration of ion i (M), zi is the ion Comparison of the kinetics parameters (kf and Ds) with the reported
charge number, f is the electric potential (V) and X is the electric studies (e.g., Wei et al., 2011) shows that, the external mass transfer
field distance (m). coefficient in this study (1.5  104 m s1) is in the same range of
The effect of electric flux gradient would become greater than the published values (2  104 and 2.1  104 m s1, respectively)
the effect of concentration gradient (Tang et al., 2015, 2016). As a (Wei et al., 2011; Ma et al., 2011), while the surface diffusivity
result, the ion transfer in the diffusion boundary layer near the (1.00  109 m2 s1) is larger than that published (e.g., 1.6 
electrode’s surface becomes faster. The enhancement of the ion 1012 m2 s1) (Wei et al., 2011). It is noted that the diffusion co-
transport in the diffusion boundary layer together with that in the efficients for liquids are in the range of 1010 to 109 m2 s1 ac-
liquid film also helps to reduce the resistance in the mass transfer. cording to the literatures (e.g., Coker, 1995). This indicates that the
Hence, it increases the uptake kinetics. applied electrostatic field greatly reduces the resistance in the solid
The simulation of phosphorus uptake kinetics was carried out phase and leads to the diffusivity coefficient at the same range of
with the intraparticle diffusion model that assumes the so-called that in the water.
“two-step mass transport mechanism” (Tien, 1994; Wei et al., It is noted that no stirring was applied in our study, while a
2011; Chen, 2012). The phosphorus ions first transfer through the stirring was applied in the previous studies (Ma et al., 2011; Wei
external liquid film from the bulk solution and subsequently diffuse et al., 2011; Yang et al., 2020; Koh et al., 2020a). This indicates the
into the LC-MC before being exchanged with carbonate ions. improvement of the uptake kinetics by the applied electrical field.
Finally, the phosphorus ions are attached onto the functional The application of an electrical field can well replace the stirring
groups. In the modeling, it was assumed that the physical proper- from the uptake kinetics standpoint.
ties are the same during the uptake process. In addition, it was observed that the current measured during
It is noted that the specific surface area of the LC-MC was very the experiments was below 0.001 A (negligible level). The voltage
small (0.84 and 3.44 m2 g1 for the virgin and the phosphorus- of 5 V was selected in this study (Fig. 1). This indicates that the
loaded LC-MC, based on the BET study demonstrated later in this energy consumption is low if it is used for industrial operations.
paper). Therefore, it was reasonable to assume that the internal
mass transfer (diffusion) of the ions of interest occurs along the
internal surface of the LC-MC. Therefore, the intraparticle surface 3.2. Effect of solution pH
diffusion model was used to simulate the uptake history with the
control equation expressed as follows. The pH effect on the electro-assisted phosphate adsorption is
4
Y. Yang, K.Y. Koh, H. Huang et al. Chemosphere 264 (2021) 128378

crucial. As shown in Fig. 2a, the adsorption decreases gradually as higher than that in the absence of electrostatic field, which may
1 limit the performance in the uptake of phosphorous (in presence of
pH was increased. It decreases from 55 to 40 mg-PO3 4 g when
the pH was increased from 3 to 5 and then remained almost un- electrostatic field).
changed between pH 5 and 9. It started to decrease from pH 9 and The uptake of phosphate is due to the ion exchange between the
1 carbonate ions on the LC-MC and the phosphate ions in the bulk
reached 30 mg-PO3 4 g at pH 12. The finding on the pH effect is
solution, where the following reaction may play a key role (Yang
quite consistent with that on the LC nanorod (Koh et al., 2020a) and
et al., 2020).
the LC-MC (without electric field, data shown in Fig. 2) (Yang et al.,
2020).
La2 ðCO3 Þ3 þ 2H2 PO
4 /2ðLaH2 PO4 Þ
2þ
þ 3CO2
3 (8a)
Compared with the phosphate adsorption onto the LC-MC (only
being stirred and not electro-assisted) (Yang et al., 2020), we find As shown in Fig. 2b, the phosphorus species exist mainly as
that the adsorption in this study is higher than the previously re- H2 PO 2
4 and HPO4 ions. As pH was increased from 2 to 9, the uptake
ported. An increase as high as over 30% can be observed in the slightly reduced, which is consistent with the decrease in the per-
Fig. 2a. centage of H2 PO4 ions. As the pH was further increased from 9 to
It is noted that the enhancement observed here is not as great as
12, a good uptake of phosphate was still maintained, which is likely
that in Fig. 1. This may be due to several reasons: 1. a stirring was
due to another reaction with the presence of HPO2 4 ions as the
applied in our previous study while no stirring was applied in the
case of U ¼ 0 in Fig. 1; the stirring enhanced the uptake; 2. the initial major species.
concentration in our previous study and that in the study given in  
Fig. 2 were 100 mg L1, while that in Fig. 1 was 150 mg L1; the La2 ðCO3 Þ3 þ 3HPO2
4 /La2 HPO2
4 þ 3 CO2
3 (8b)
3
loading of phosphorus may cause small difference in the uptake
(presence of electrostatic field vs. absence of electrostatic field); 3. The reason for the less uptake at a high pH may be due to the
presence of more carbonate ions in the water. As the experiment
the final solution pH in the presence of electrostatic field was
was conducted in the atmosphere (so called open system in water
chemistry), more carbonate ions are present at a higher pH (e.g. pH
11 to 12), which can retard the uptake of phosphorus species ac-
cording to the above reactions.
It can be seen that a high uptake occurred when the DC was
applied. The uptake can occur with the mechanisms as follows.
After the exchange, the phosphate ions are attached/adsorbed onto
the surface of the electrode. When the surface of the electrode is
positively charged, more uptake occurs as explained.

3.3. Adsorption isotherm

An adsorption isotherm experiment was conducted. Both

Langmuir and Freundlich isotherms were used to fit the experi-
mental data with the data given in Fig. 3. The Langmuir isotherm
(regression coefficient (r2) ¼ 0.999) worked better than the
Freundlich isotherm (r2 ¼ 0.934). The maximum adsorption

Fig. 2. Effect of pH on LC-MC performance. Experimental condition: U ¼ 5 V,

m ¼ 1.5 g L1, C0 ¼ 100 mg L1, electrode gap ¼ 8 cm, pH was initially adjusted and not
controlled during the experiment. Noted that the empty points in Fig. 2a are from our Fig. 3. Adsorption isotherm in uptake of phosphorus. Experimental condition: U ¼ 5 V,
previously reported study (Yang et al., 2020), in which a continuous stirring was m ¼ 1.5 g L1, C0 ¼ 20e200 mg L1, electrode gap ¼ 8 cm, initial pH 6.9 (not controlled
applied during the experiment. after the initial adjustment of pH).

5
Y. Yang, K.Y. Koh, H. Huang et al. Chemosphere 264 (2021) 128378

capacity (qmax) and the adsorption reaction constant (b) were presence of ionic strength retards the uptake of anions such as the
0.5 mmol g1 (47.6 mg g1) and 12.05 mM1 (0.127 L mg1), uptake of fluoride onto a lanthanum-modified carbon, because of
respectively. the outer-sphere complexation (namely lower affinity) (Yu et al.,
The better fitting with the Langmuir isotherm indicates that the 2015b).
uptake process occurs homogeneously through chemical in- However, the result obtained in this study indicates the negative
teractions. The phosphorus adsorption onto the LC-MC (without influence of ionic strength on the uptake of phosphorus during the
electric field) in our previously reported study follows the electro-assisted adsorption. This is an interesting finding, which
Freundlich Isotherm (Yang et al., 2020). However, the Langmuir has yet to be reported in the literature. The negative effect of ionic
isotherm better describes the adsorption data in this study. The strength is likely due to the overcrowding anionic substances on
applied electric field seems to change the adsorption mechanism the surface of LC-MC, which reduces the availability of active sites
from the multi-layer adsorption (Freundlich typed) to the mono- for the uptake of phosphorus.
layer adsorption (Langmuir typed). The change due to the appli-
cation of electric field in the adsorption, leading to the re- 3.5. Effect of co-existing anions
arrangement of the adsorbed species from a less uniform distri-
bution to a more uniform distribution. In both domestic and industrial wastewater, several common
The best-fit maximum adsorption capacity calculated according anions coexist and may affect the phosphate removal efficiency. As
1
to the Langmuir isotherm was 47.57 mg-PO3 4 g , which was
a result, it is of importance to study their effects on the uptake.
nearly 1.4 times of the adsorption capacity of LC-MC (without As shown in Fig. 4, halogen anions (Cl , F , I and Br ) had
electric field) in our previously reported study (Yang et al., 2020). almost no influence on the uptake, which is consistent with the
This further demonstrates that the existence of an electric field can finding when the LC-MC was used in the absence of electric field
gently improve the performance of LC-MC in the phosphate (Yang et al., 2020). The uptake of these halogen anions is illustrated
adsorption. Additionally, the adsorption capacity of LC-MC in the in Fig. SI-3. Interestingly, the LC-MC can adsorb halogens with a
electro-assisted phosphate adsorption is higher than that of re- capacity of 12e16 mg g1. As the presence of halogens does not
ported lanthanum-incorporated support adsorbents (based on
fitting by Langmuir isotherm), as shown in Table 1, demonstrating
the high effectiveness of the electro-assisted adsorption.

3.4. Effect of ionic strength

The effect of ionic strength on the phosphate adsorption was

studied with the results given in Fig. SI-2. As the ionic strength
(NaNO3) was increased from 0 to 1 M (TDS of 0e85 g L1), the
1
adsorption decreased from 40 to 28 mg-PO3 4 g . As fresh water
(e.g., reservoir and river water where algae bloom may easily occur)
has a low ionic strength/TDS, our technology would be suitable for
the phosphate removal. For an industrial phosphorus-containing
wastewater that has a higher TDS, this technology may still be
applied. However, a higher dosage should be used.
The presence of ionic strength has different effects on the up-
take of anions, which is dependent upon the affinity between the
anions and the functional groups on the surface of an adsorbent.
Zheng et al. (2012) and Koh et al. (2019) reported that the presence
of ionic strength had no influence on the adsorption of arsenite and
phosphorus onto the zirconia nanoparticle and gadolinium-1,4- Fig. 4. Effect of co-existing anions on LC-MC performance. Experimental condition:
benzenedicarboxylate composite, respectively, which is due to the U ¼ 5 V, m ¼ 1.5 g L1, electrode gap ¼ 8 cm, C0 ¼ 100 mg L1, co-existing anion
concentration: 100 mg L1 each, “Mixed”: all the anions included with each of
inner-sphere complexation (namely higher affinity). Similarly, the 100 mg L1; pH not controlled. Noted that the data labeled as “Data with electric field”
LC-MC demonstrated the same phenomenon in our reported study are those in this study, while those as “Data without electric field” are from our pre-
(Yang et al., 2020). However, some studies have shown that the viously reported study (Yang et al., 2020).

Table 1
Comparison of performance of adsorbents in the literatures.

Adsorbent Langmuir constant (L mg1) Solution pH qmax (mg g1) Reference

Lanthanum oxide/zeolite 0.26 6 15.8 He et al. (2017)

Lanthanum/MCM-41 0.561 4e8 26.7 Jianda et al. (2010)
Lanthanum/Flower-like mesoporous silica 0.35 3e6 42.8 Huang et al. (2015)
Lanthanum hydroxide/Activated carbon fiber 1.426 natural 15.3 Zhang et al. (2012)
Lanthanum oxide/Activated carbon fiber 0.78 4 6.34 Liu et al. (2011)
Ferric(III) and Lanthanum/Activated carbon fiber 8.6 4 29.44 Liu et al. (2013)
Lanthanum oxide/Expended graphite 0.072 4 12.6 Ling et al. (2015)
Lanthanum oxide/Fe3O4@SiO2 0.22 5e9 27.8 Lai et al. (2016)
Lanthanum/Bentonite NT-25 0.1 natural 14.0 Kuroki et al. (2014)
Lanthanum/aluminum@ montmorillonite 0.078 3.0e4.2 13.0 Tian et al. (2009)
Lanthanum/Ferrihydrite loaded magnetite 0.42 6.28 44.8 Fu et al. (2018)
Lanthanum carbonate/microfibrous composite 0.99 6.9 34.2 Yang et al. (2020)
Lanthanum carbonate/microfibrous composite (electro-assisted) 0.127 6.9 47.6 This study

6
Y. Yang, K.Y. Koh, H. Huang et al. Chemosphere 264 (2021) 128378

greatly retard the uptake of phosphorus, it is hypothesized that the When the electrode gap is small, the effective area between the
uptake of halogens is due to the adsorption onto the functional electrodes is small. As a result, the mass transfer of the phosphate
group(s) other than those for the phosphorus. Another possible ions towards the surface of the anode is negatively affected, leading
reason might be that the concentration of halogen anions is rather to a decrease in the adsorption. When the distance is large, the
low (e.g., [Cl ] ¼ 100 mg L1 or 1.71 mM), and they do not compete electric field between the electrodes becomes weak, thus reducing
with the phosphorus ions for the adsorption sites. the uptake capacity. Hence, a gap of 8 cm between the anode and
However, a less uptake was observed in the presence of car- the cathode was used in the experimental study reported in this
bonate and sulfate ions with a concentration of 100 mg L1 each, paper.
which is similar to that reported on the LC-MC (Yang et al., 2020). In The effect of temperature on the phosphorus uptake was stud-
term of percentage removal, the decrease may be due to the higher ied. As demonstrated in Fig. SI-5, the uptake increases as the
concentration of co-existing carbonate or sulfate ions than that in temperature is increased from 20 to 50  C. According to the Van’t
the reported study. Hoff equation (Hong et al., 2019):
Phosphate, carbonate and sulfate are all oxyanion (An Om l ),
DH DS
where A and O represent a chemical element and oxygen, respec- lnK ¼  þ (9)
tively). Due to the aforementioned ion exchange reaction, it is un- RT R
derstandable that the presence of carbonate ions would reverse the where K is the equilibrium constant, DH is the change of enthalpy (J
uptake, which was also reported in the literature (Fu et al., 2018). mol1) and DS is the change of entropy (J$mol1 K1), R is the ideal
When the anode (LC-MC) is positively charged, some of anionic gas constant (J mol1K1), T is the temperature (K).
carbonate ions in the bulk solution can be attracted towards the The reaction equilibrium is influenced by temperature. As dis-
anode. Some carbonate ions were adsorbed onto the LC-MC
cussed, the electro-assisted phosphate adsorption onto the LC-MC
1
(15.2 mg-CO23 g ), as shown in Fig. SI-3. This leads to an in- is chemisorption, which is temperature dependent. According to
crease in the carbonate concentration near the surface of LC-MC, the result in Fig. SI-5, the increase in the adsorption with temper-
leading to the higher decrease in the uptake than the previously ature suggests that the phosphate uptake by the LC-MC is
reported LC-MC. endothermic.
As sulfate ion has a similar structure as phosphate ion, they The temperature effect on the electro-assisted phosphate
would compete with each other for the exchangeable carbonate on adsorption can be further explained by the fact that temperature
the LC-MC (Gu et al., 2018). As a result, the uptake of phosphorus can influence the diffusion boundary layer by two mechanisms
becomes retarded. The presence of electrical potential can enhance (Sosa-Fernandez et al., 2019): 1. the diffusion of the ions is affected
the uptake of phosphorus. It can also cause a better removal of (Benson et al., 1945; Yuan-Hui et al., 1974); 2. the viscosity of the
1
sulfate; the adsorption capacity was 35 mg-SO2 4 g (Fig. SI-3). fluid is changed (Sosa-Fernandez et al., 2018). Specifically, in this
One can see that the presence of nitrate and humic acid reduced study, the higher temperature results in higher diffusion of phos-
the uptake. On the other hand, our previous study showed that phate ions and lower viscosity in phosphate solution, leading to a
both of them almost did not change the uptake (Yang et al., 2020). thinner boundary layer and a higher ion mobility. These two factors
During the experiment, some nitrate ions may be reduced on the make the ion mobility less susceptible to diffusion limitation. As a
cathode to nitrite, nitrogen gas or ammonia (with removal of result, the concentration of phosphate near the electrode surface is
37 mg-NO 3 g
1
shown in Fig. SI-3), leading to a less nitrate content increased, which causes an increase in the adsorption capacity.
in the solution and a higher pH (more OH ions in the solution).
Due to its strong coordination ability, the excessive OH ions may 3.7. Characterization and mechanism
compete with phosphorus ions for the exchangeable carbonate,
resulting in the low uptake. (Wasay et al., 1996; Yaguchi et al., Fig. SI-6 shows the SEM images of virgin and phosphorus-
2016). loaded LC-MC after the electro-assisted adsorption. The LC parti-
Being a large organic molecule with molecular weight above cles were dispersed evenly on the fibers of the virgin LC-MC. After
1000, humic acid (sodium salt used) may attach onto the anode the uptake process, the fibers were covered by the large film-typed
during the operation. This would reduce the availability of car- solid substances, similar to those seen in our previous study where
bonate ions for exchanging with the phosphate ions, leading to the no electrical power was applied. Due to the previously reported
lower uptake similar to the findings from the literatures (Lürling ligand exchange mechanism, some of the carbonate ions on LC are
et al., 2014). replaced by the phosphate ions. This would lead to the formation of
In the mixed solution, the effect of competitive substances lanthanum phosphate complex that is easier agglomerated due to
became more obvious, as shown in Fig. 4. As carbonate, sulfate and its higher insolubility (Firsching et al., 1991). The faster kinetics in
nitrate ions all negatively affect the uptake of phosphorus, the co- the complex formation would be beneficial in forming the film-
existence of these ions greatly retards the uptake. As the afore- typed solids instead of other type of solids.
mentioned discussion, the competition and the increase in pH are Fig. 5a depicts the N2 adsorption-desorption isotherms of the
the reasons for the decrease. virgin and phosphorus-loaded LC-MC. Both isotherms showed a
typical shape of Type III adsorption, indicating a weak interaction
between N2 and LC-MC, which is typically seen from the micro-
3.6. Effect of electrode gap and temperature
fibrous composites (Yang et al., 2018a, b). After the uptake of
phosphorus, a higher adsorption was seen, and a hysteresis loop
The gap (distance) between the anode and the cathode can
occurred at a higher relative pressure, indicating the formation of
affect the electric field and hence the adsorption performance. As
some mesopores along with the formation of the surface complexes
shown in Fig. SI-4, the adsorption capacity of LC-MC increased from
(Sing, 1985; Chen et al., 2015). This is consistent with the obser-
1
30 to 40 mg-PO3
4 g as the electrode gap was increased from 5 to vation that the BET surface area of the phosphorus-loaded LC-MC
15 cm. A further increase in the gap however did not help to in- (3.44 m2 g1) is higher than that of the virgin LC-MC (0.84 m2 g1)
crease the uptake. The adsorption capacity decreased to less than and the findings in the SEM study.
1
20 mg-PO3
4 g when the gap was 15 cm. The XRD patterns of the virgin and phosphorus-loaded LC-MC as
7
Y. Yang, K.Y. Koh, H. Huang et al. Chemosphere 264 (2021) 128378

Fig. 5. Surface analysis of LC-MC: (a) N2 adsorption-desorption isotherm; (b) XRD

Fig. 6. High-resolution XPS spectra of phosphorus-loaded LC-MC: (a) La 3d; (b) P 2p.
pattern.

depicted in Fig. 5b show several characteristic peaks of

and 852.3 eV, respectively. These shifts can be attributed to the
La2(CO3)3,8H2O at 2q ¼ 21, 24 , 25 and 28 (He et al., 2013). The
surface complexation of lanthanum phosphate (Hong et al., 2019),
peaks due to the presence of the stainless steel fiber are significant
indicating the change in chemical surrounding of La due to the
(Ji et al., 2015); a few peaks due to the LaCO3OH are seen between
ligand exchange between phosphate and carbonate.
35 and 45 (Mao et al., 2012).
Fig. 6b shows the high-resolution scan spectrum of P2p, proving
After the uptake, the intensities of the characteristic peaks of
the successful loading of phosphate on the LC-MC. The spectrum
lanthanum carbonate obviously decrease, and some peaks even
can be deconvoluted into three peaks: 130.6, 132.8 and 134.0 eV,
disappear. According to the previous study, the ligand exchange

between carbonate group and phosphate ions is an important which are corresponded to PO3 2
4 , HPO4 and H2 PO4 , respectively
mechanism of the uptake (Acelas et al., 2015; Hu et al., 2017), (Yin et al., 2014). The composition percentages of these three spe-
causing the decrease in the carbonate content on the LC-MC and cies were 23.5, 41.2 and 35.3%, respectively; this indicates that
the decline in the peak intensity. Additionally, two new peaks can HPO24 and H2 PO4 ions are more favored during the adsorption
be observed at 77 and 83 , ascribing to Cr2O3 and MoO2, respec- process, which are hypothesized in the aforementioned Equations
tively. Cr and Mo are two elements existing in the stainless steel (8a) and (8b).
with relatively high contents (Cr: 10e15% and Mo: 16e18%). During
the electro-assisted adsorption, the MC can be oxidized due to the 3.8. Perspectives
voltage of 5 V, leading to the formation of metal oxides.
The XPS was applied to determine the mechanism of the Algae bloom may easily occur at the water stagnation in the
phosphate uptake by the LC-MC. As shown in Fig. 6a, characteristic presence of sufficient nutrients (nitrogen and phosphorous) and
peaks of La corresponded to La 3d3/2 and La 3d5/2 can be observed in sunlight. As such an area is typically large and the problem occurs
the high resolution scan spectrum (Yu and Chen, 2015; He et al., in shallow water, the low-voltage electrostatic technology with the
2017; Koh et al., 2020a; b). After the adsorption, slight shifts can lanthanum carbonate grafted microfibrous composite in this study
be observed in the binding energy. The peaks of La 3d3/2 are shifted may provide a good solution to the problem. The microfibrous
from 832.6 and 835.7 eV to 832.4 and 835.6 eV, respectively, while composite electrode can be packed in series and placed in the
the peaks of La 3d5/2 are shifted from 849.3 and 852.5 eV to 849.1 shallow water to adsorb the phosphorus, by which the nutrient S (N
8
Y. Yang, K.Y. Koh, H. Huang et al. Chemosphere 264 (2021) 128378

and P) can be removed. The algae bloom problem may thus be Acknowledgement
minimized and even solved.
This technology can also be used to treat the phosphorus- K.Y.K. appreciates the NUS for providing him with the presti-
containing industrial wastewater. Due to the faster kinetics and gious NUS Presidential Scholarship for his PhD study. This research
higher phosphorus uptake capacity, the traditional rapid mixing is partially supported by the Singapore National Research Foun-
(for higher kinetics) and higher dosage of adsorbent would become dation (NRF) under the Campus for Research Excellence and
less necessary. One would anticipate that a smaller adsorption Technological Enterprise (CREATE) program.
system would be needed for treating the wastewater efficiently at
lower operating and capital expenses. Appendix A. Supplementary data
It was observed that both voltage and current were rather low.
In addition, the water temperature slightly increased during the Supplementary data to this article can be found online at
experiment. This indicates low energy consumption for the oper- https://doi.org/10.1016/j.chemosphere.2020.128378.
ation. This technology would be suitable for industrial scale oper-
ations due to less energy requirement.
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