Environmental Technology & Innovation 35 (2024) 103701

Contents lists available at ScienceDirect

Environmental Technology & Innovation

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

Biodegradable chelator GLDA intercalated magnesium/aluminum

layered double hydroxides for efficient phosphate capture and
removal from wastewater
Guiyin Wang a, b, *, 1, Yilin Liao a, 1, Shirong Zhang a, b, *, Xiaoxun Xu a, b, Guochun Lv a,
Changlian Xu a, Junzhuo Cai a, Zhanbiao Yang a, Zhang Cheng a
a
College of Environmental Science, Sichuan Agricultural University, Wenjiang 611130, China
b
Sichuan Provincial Key Laboratory of Soil Environmental Protection, Chengdu 611130, China

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

Keywords: Phosphate removal and recovery from wastewater play a vital role in controlling water eutro­
Layered double hydroxides phication and facilitating resource recycling. Adsorbents of layered double hydroxides (LDHs)
Intercalation exhibit promising potential in the removal of phosphate; however, the removal efficiency often
Adsorption
suffers insufficient as easy aggregation and inevitable loss of LDHs. Herein, a novel N, N–bis
Phosphate recovery
(carboxymethyl)–L–glutamic acid intercalated magnesium–aluminum LDH (GLDA@MgAl–LDH)
Wastewater treatment
were successfully synthesized. Intercalating with GLDA spawned dual functionality, i.e., the layer
spacing expansion elevated the loading of phosphate, while GLDA also acted as additional
binding sites toward phosphate. A higher phosphate capture (＞90%) was obtained in pH 5.0–8.0.
Phosphate uptake was predominantly observed within the first1h, reaching equilibrium in
approximately 4 h. The maximum adsorption capacity of 44.17 mg g–1 was attained for
GLDA@MgAl–LDH at pH 6.70, which are far higher than that of pristine MgAl–LDH.
GLDA@MgAl–LDH also had the excellent stability and reusability in five adsorption/desorption
experiments. The GLDA@MgAl–LDH demonstrated significant efficacy in treating actual
phosphate-containing wastewater in the fixed–bed adsorption column. Spectroscopic analysis, in
conjunction with density functional theory, elucidated that GLDA intercalation enhanced the
adsorption efficiency of MgAl–LDH. The key mechanisms facilitating phosphate removal included
electrostatic attraction, anion and ligand exchange, and surface complexation. The above results
highlight that GLDA@MgAl–LDH could serve as a promising and environmentally friendly
candidate for phosphate treatment from the real wastewater.

1. Introduction

Phosphorus is an essential nutrient for biological growth and reproduction on earth, playing a crucial role in ecosystem functioning
(Alewell et al., 2020; Lu et al., 2023). Nevertheless, the extensive utilization of chemical fertilizers, livestock manures, and pesticides in
agricultural activities could result in phosphate surplus and accumulation in soils, which in turn dissolve into rainwaters and

* Corresponding authors at: College of Environmental Science, Sichuan Agricultural University, Wenjiang 611130, China.
E-mail addresses: [email protected] (G. Wang), [email protected] (S. Zhang).
1
These two authors contributed equally to this work.

https://doi.org/10.1016/j.eti.2024.103701

Available online 28 May 2024

2352-1864/© 2024 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

subsequently discharge into streams and rivers through the land run–off. Moreover, significant quantities of industrial wastewater and
domestic sewage lavish in phosphate has also been released into the aquatic environment. Superfluous phosphate discharge into the
aquatic environment will inevitably trigger serious eutrophication and deterioration problems (Cakmak et al., 2022), including the
production of harmful algal blooms, massive death of aquatic life, and loss of biodiversity in aquatic ecosystems. Therefore, imple­
menting effective measures for phosphate treatment from wastewater from the waste stream is important for protecting public health
and maintaining environmental sustainability. Adsorption has evolved as an effective and promising strategy for this purpose recently
owing to its easy operation, strong adaptability, and high eliminated ability (Bolbol et al., 2019; Keyikoglu et al., 2022; Li et al., 2022).
Developing a highly efficient adsorbent integrated with a suitable structure and more restricting sites is extremely urgent for real–­
world applications.
Layered double hydroxides (LDHs) are emerging bidimensional nanostructured materials with electropositive host layers and
electronegative intercalated anions that are extensively applied in multiple fields such as drug carriers, energy storage, and envi­
ronmental control (Fang et al., 2021; Keyikoglu et al., 2022). Their structure can be expressed as [M2+ 3+ x+ m−
1− xMx (OH)2] [A ]x/m•nH2O
2+ 3+ m−
(Nie et al., 2022), where M , M , and A are the divalent metal cation (i.e., Ca , Ni , Mg , Zn , Mn , Fe2+, Co2+, etc.),
2+ 2+ 2+ 2+ 2+

trivalent metal cation (i.e., Al3+, Fe3+, Ga3+, Eu3+, V3+, Co3+, Mn3+, etc.), and interlayer exchangeable anion (i.e., CO2– 3 , NO3, Cl ,
– –
2–
OH , SO4 , etc.), respectively. Such an adjustable composition structure of LDHs with large quantities of exchangeable anions and
–

sizable interlayer spaces has the advantage of high surface–to–volume ratios, abundant surface–active sites, and strong ion–exchange
abilities (Rybka et al., 2022). The exchangeable anions in LDHs and –OH groups on their metal hydroxide surfaces create the possibility
of electrostatic interaction and ion exchange with contaminant (Nie et al., 2022; Wang et al., 2022a). Given their attractive features, an
intensive effort has been devoted to synthetic different types of LDHs like MgAl–LDH (Han et al., 2011; Koilraj and Sasaki, 2016; He
et al., 2019; Jung et al., 2021; Nie et al., 2022), FeMg–LDH (Nuryadin et al., 2021; Rahman et al., 2021; Zhang et al., 2021), ZnFe–LDH
(Gupta et al., 2020), and CaAl–LDH (Qiu et al., 2022) for efficient capture of phosphate. However, the pristine LDHs suffer from
drawbacks like self–aggregation (Fang et al., 2021) and metal ion leaching y (Nie et al., 2022) during adsorption, limiting their
practical application. To address these limitations, an intercalation modification approach has been extensively proposed to enhance
their performances by ameliorating the specific surface area and proliferating the considerable interlayer distance. The intercalation of
phosphonic acid (Zhu et al., 2020), L–cysteine (Zhang et al., 2020; Wang et al., 2022a), sulfides (Zhou et al., 2020; Guan et al., 2022),
3–amino–1 H–1,2,4–triazole (Amer et al., 2021), biochar (Rahman, et al., 2021), and polystyrene anion exchanger D201 (Nie et al.,
2022), which rich in active functional groups as guests were introduced to intercalate into the LDHs interlayer for the enhancement of
their adsorption performance in previous works. The intercalated LDHs showed gorgeous chemical stability with a trifling metal
release because of the shielding effect compared with the bare LDHs (Buates and Imai, 2020; Nie et al., 2022). Organic anions, with
larger sizes, are preferred intercalation agents by comparison because of their ability to increase interlayer distances effectively (Amer
et al., 2021).
In recent years, biodegradable chelator, is particularly an attractive option because of its environmental compatibility and excellent
complexation affinity to contaminants, as well as its adequate surface functional groups. Among these, N, N–bis (carboxymethyl)–
L–glutamic acid (GLDA) stands out as a widely used aminopolycarboxylate biodegradable chelating agent, boasting over 60%
degradation within 28 d (VanThinh et al., 2021). Moreover, it exhibits remarkable chelating capacity with five coordinating sites
(Fig. S1) and has shown no toxic effects on biotic systems or human health, making it environmentally safe (Gluhar et al., 2020).
Thanks to these advantages, GLDA (guest) might be served as a promising intercalating agent for LDHs (host) to meliorate their
structure and adsorption capacities. For instance, Zhang et al. (2020) and Wang et al. (2022a) synthesized L–cysteine functionalized
LDHs, demonstrating effective removal of heavy metals from wastewater due to the –NH2, –COOH, and –SH groups on the LDHs
surface could enhance the elimination capacity. However, for all we know, the controllable construction of novel GLDA@LDH
composites pinpointing efficient capture and removal of phosphate has scarcely been investigated. Furthermore, the phosphate
removal performance and mechanism from practical wastewater via GLDA@LDH adsorbents have also not been reported.
To bridge the identified research gaps and achieve the objectives of this study, we aimed to: (1) synthesize GLDA@MgAl–LDH
composites via a facile coprecipitation method; (2) explore the overall phosphate adsorption performance of as–prepared
GLDA@MgAl–LDH composites towards stimulated and real wastewater; and (3) unravel the potential adsorption mechanisms of
phosphate by GLDA@MgAl–LDH composites via spectroscopic analysis and density functional theory. This work will also provide
useful references to the development of intercalated LDHs materials for phosphate treatment.

2. Materials and methods

2.1. Materials

The MgCl2⋅6 H2O (≥99.5%) and AlCl3⋅6 H2O (≥99.5%) were adopted to prepare the Mg2+ and Al3+ solutions, respectively.
Phosphate stock solutions were obtained by dissolving dried KH₂PO₄ (≥99.9%) in distilled deionized water and diluting them to
suitable concentrations. GLDA (47% and 1.40 g cm–3) was acquired from Akzo Nobel Chemicals Co., Ltd., Shanghai, China.

2.2. Preparation and characterization of MgAl–LDH and GLDA@MgAl–LDH composites

The MgAl–LDH composites were synthesized through an improved typical co–precipitation method described in previous works
(Zhang et al., 2020; Zhu et al., 2020). Initially, solutions containing AlCl3 (0.10 mol L–1) and MgCl2 (0.20 mol L–1) were dissolved in
CO2–free distilled water. To make hydroxylation and LDH structure formation, alkaline solutions were also prepared by dissolving

2
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

0.64 mol of NaOH and 0.20 mol of Na2CO3 in 100.00 mL of distilled water. The pH of the reaction system was maintained at 10.00 by
gradually adding the above solution using a liquid feeding pump (Longer Pump YZ1515x, Longer Precision Pump Co., Ltd, Hebei,
China) to avoid agglomeration of the produced hydroxides. The resulting slurry was vigorously stirred at 25 ◦ C for 1 h and then aged at
65 ◦ C for 24 h to enhance crystallinity. The entire process was conducted under N2 protection. The solid product was then centrifuged,
washed several times with ethanol, and DI water to eradicate all unreacted salts and any impurities. The finally attained precipitates
were lyophilized for 48 h using a vacuum freeze–dryer (FDU–1100, Shanghai, China) and subsequently milled to pass through a
100–mesh sieve.
The GLDA@MgAl–LDH composites were synthesized through an ultrasonic–assisted ion exchange process, wherein the GLDA
anion replaced Cl-/CO2- 3 in the interlayer of MgAl–LDH (Wang et al., 2022a). Initially, the previously obtained MgAl–LDH was dis­
solved in 0.10 mol L–1 GLDA solution, followed by steps consistent with the synthesis process of MgAl–LDH. A schematic illustration of
the synthetic strategy for GLDA@MgAl–LDH composites is depicted in Fig. S2.
Characterization of MgAl–LDH and GLDA@MgAl–LDH before and after phosphate adsorption was conducted. This involved
comprehensive analyses including Fourier transform infrared (FTIR), scanning electron microscopy (SEM) and Energy Dispersive
Spectrometer analysis, X–ray diffraction (XRD), and X–ray photoelectron spectroscopy (XPS). Additional details were available in the
Supplementary Information (SI).

2.3. Phosphate removal experiment

Batch experiments were implemented in 100 mL blue cap bottle to determine the adsorption capacities of MgAl–LDH and
GLDA@MgAl–LDH composites for phosphate. The reaction mixtures were stirred at 180 rpm in an oscillator (ZQPL–200, Laboratory,
China) until the attainment of equilibrium. After centrifugation at 5000 rpm for 10 min (DL–8 M, Luxiangyi Co. Ltd., Shanghai, China),
the supernatants were filtered through 0.45–μm filters, and the remaining phosphate was measured at 700 nm by a UV–V spec­
trometer. The effect of adsorbent dosage was investigated by adding 1.00–4.00 mg L–1 of MgAl–LDH or GLDA@MgAl–LDH composites
into 100 mg L–1 phosphate solution (pH 6.70). The initial pH value of phosphate solution was adjusted to 4.00–10.00 using NaOH and
HCl solution (0.10 mol L–1). For adsorption kinetics, samples (5.00 mL) were collected at pre–determined intervals (0–240 min) from
an initial 100.00 mg L–1 phosphate solution. Adsorption isotherms were studied with initial phosphate concentrations ranging from
25.00 mg L–1 to 250.00 mg L–1 at 298 K. Each experiment was replicated three times. Phosphate adsorption performance was evaluated
by removal efficiency (R, %) via Eq. 1 and the equilibrium adsorption capacity (Qe, mg g–1) by Eq. 2. Kinetic and isotherm models were
fitted to the experimental data, with equations detailed in Eqs. S1–S8.
C0 –Ct
R(%) = × 100% (1)
C0

(C0 –Ce )V
Qe = (2)
m
where C0, Ct, and Ce (mg L–1) are the initial, at time t (min), and equilibrium phosphate concentrations, respectively. V (L) is the
volume of phosphate solution, and m (g) stands for the weight of MgAl–LDH or GLDA@MgAl–LDH composites.

2.4. Reusability and regeneration study

Adsorption–desorption experiments were carried out to assess the possibility of recovering phosphate from the loaded
GLDA@MgAl–LDH surfaces, as well as their reusability for subsequent use. After the equilibrium adsorption study with the initial
phosphate concentration of 100 mg L–1 (dosage of 3.0 g L–1, pH of 6.70, and contact time of 240 min), the spent adsorbents were
collected by centrifugation, followed by mixing 0.5 mol L–1 NaOH solution for 240 min to desorb the adsorbed phosphate. The
recycled GLDA@MgAl–LDH were repeatedly washed with deionized water, lyophilized for 48 h, and reused for further phosphate
adsorption cycles. The adsorption–desorption cycle tests were repeated five times to assess the reusability and stability of the
adsorbents.

2.5. Applications to actual wastewater

Fixed–bed column tests (Fig. S3) were conducted to examine the applicability of GLDA@MgAl–LDH composites in removing
phosphate from real wastewater. The specific experimental details were summarized in Text S4.

2.6. Density functional theory calculation

We employed the first–principles density functional theory calculations (DFT) (Kresse and Furthmiiller, 1996), following the
generalized gradient approximation with the Perdew–Burke–Ernzerhof formulation (Perdew et al., 1996). The calculations utilized
projected augmented wave potentials (Kresse, 1999) to describe ionic cores and account for valence electrons. The parameters
involved in the calculation are available in previous work (Bai et al., 2003). Electrostatic potential and charge density difference
analyses were conducted, and adsorption energies (Eads) were calculated.

3
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

2.7. Statistical analysis

Statistical analyses were processed using IBM SPSS software. Origin 2019 software (Origin Lab Co., Ltd; USA) was used to plot the
experimental data graphs. Differences in experimental results among treatments were assessed via one–way analysis of variance, with
Duncan’s test at P < 0.05. The R2 and RMSE were calculated to verify the satisfaction and accuracy of the adsorption models.

3. Results and discussion

3.1. Characterizations

The FTIR spectroscopy bands (Fig. 1 A) at approximately 3460 and 1590–1627 cm–1 corresponded to the –OH stretching vibration
of water molecules (Wang et al., 2022b), indicating the presence of a gap between water molecules or hydrotalcite layer board M–OH
(M=Mg or Al) (Nie et al., 2022). In MgAl–LDH, the 1362 cm− 1 peak was ascribed to the vibration of CO2– 3 groups (Jung et al., 2021)
that was introduced as a pH regulating reagent during LDHs synthesis. However, this peak was apparently weakened in GLDA@M­
gAl–LDH, demonstrating that the intercalated CO2– 3 was partially replaced by GLDA. The bands at 677, 554, and 448 cm
− 1
were
ascribed to M− O, and M− O− M, and O− M− O (M=Mg or/and Al) stretching vibration of the layered framework (Jung et al., 2021;
Wang et al., 2022b). Notably, compared with the pristine LDHs, a new peak at 1407 cm− 1 was observed in GLDA@MgAl–LDH, which
belonged to stretching vibration of C− H of GLDA (Fig. S1). Moreover, the XPS of GLDA@MgAl–LDH (Fig. S4) revealed an obvious peak
of N 1 s with a N content of 5.26% (Table S1), further confirming the introduction of GLDA. These findings collectively validated that
GLDA had successfully entered the MgAl–LDH interlayer.
The characteristic diffraction peaks observed for MgAl–LDH at approximately 11.4◦ , 23.1◦ , 34.6◦ , 38.8◦ , 46.2◦ , 60.7◦ , and 62.1◦
(Fig. 1B) correspond to the (003), (006), (009), (015), (018), (110) and (113) crystal plane, indicative of the typical hydrotalcite
layered structure of Mg2Al(OH)7 (JCPDS No. 48–0601) (Li et al., 2020). Upon intercalating GLDA into MgAl–LDH, the characteristic
diffraction peaks retained their positions, suggesting preservation of the original crystal structure of MgAl–LDH in GLDA@MgAl–LDH
(Wang et al., 2022a). The prepared MgAl–LDH and GLDA@MgAl–LDH displayed quintessential nature s of LDHs, as well as sufficient
structural sites. Notably, the d–spacing (d003) of GLDA@MgAl–LDH increased from 0.756 nm for MgAl–LDH to 0.780 nm (Table S2), as
calculated by the Bragg’s law, consistent with prior studies (Zhang et al., 2020; Bi et al., 2022a). This increase confirmed the successful

Fig. 1. FTIR spectra (A) and XRD pattern (B) of the MgAl–LDH and GLDA@MgAl–LDH before and after adsorption of phosphate. N2 adsorp­
tion–desorption isotherms (C) and BJH pore size distributions of MgAl–LDH and GLDA@MgAl–LDH (D).

4
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

intercalation of GLDA into the MgAl–LDH interlayer gallery. The successful insertion of GLDA expands the size of interlayer anions and
enhances the binding strength between anions and interlayer hydroxyls (Zhang et al., 2020; Amer, et al., 2021), resulting in an increase
in the interlayer spacing of MgAl–LDH from 0.276 nm to 0.300 nm (Table S2), which would promote adsorption capacities of
phosphate (Bolbol et al., 2019; Li et al., 2022).
As described in Fig. S5, both composites displayed noticeably layered structures, which was representative of the LDHs morphology
(Jung et al., 2021; Bi et al., 2022b; Wang, et al., 2022a). Pristine MgAl–LDH displayed a relatively dense layered structure with a
blurred laminate boundary. In contrast, the GLDA@MgAl–LDH showed a roughened morphology with a more porous lamellar
structure, clear edges, and a well-defined orientation, suggesting broader interlayer spacing and larger surface areas conducive to
enhanced phosphate adsorption. This structural transformation was attributed to GLDA intercalation into the MgAl–LDH interlayer,
leading to partial laminate stripping. Moreover, homogeneous distribution of Mg, Al, C, O, and N elements in the interlayer of
GLDA@MgAl–LDH. The Mg/Al atomic ratios of MgAl–LDH and GLDA@MgAl–LDH were 2.16 and 2.11 (Table S1), respectively, closely
aligning with defined values. Simultaneously, the N2 adsorption–desorption isotherms of both materials exhibited comprehensible
type–IV isotherms (IUPAC classification) with a H3–type hysteresis loop appeared in P/P0 of 0.20–1.0 (Fig. 1 C), indicating mesoporous
characteristics (Lu et al., 2022), as further supported by the average pore size distributions shown in Fig. 1D. Besides, the BET surface
areas of MgAl–LDH and GLDA@MgAl–LDH were no obvious change (Table S3). Different from other intercalation materials (Rahman
et al., 2021; Bi et al., 2022a; Bi et al., 2022b), GLDA molecules did not adhere to the surface of MgAl–LDH and block interlayer
channels. Furthermore, their isoelectric points (pHPZC) were at pH ~ 8.3 and 9.4 (Fig. S6), respectively. Below pHPZC, their surfaces
were positively charged (Elkhlifi et al., 2022; Feng et al., 2022), facilitating phosphate removal over a wide pH range.

3.2. Phosphate adsorption performance of MgAl–LDH and GLDA@MgAl–LDH

3.2.1. Effect of dosage

The phosphate adsorption capacity dramatically decreased as MgAl–LDH dosages increased (P < 0.05), while the removal effi­
ciency notably increased, particularly for GLDA@MgAl–LDHH (Fig. S7A). The increase of phosphate removal rates was probable

Fig. 2. Effect of initial solution pH on the adsorption capacities of phosphate by MgAl–LDH and GLDA@MgAl–LDH (A). Distribution diagram of
phosphate species as a function of solution pH (B). Effect of solution pH on the Mg2+ and Al3+ leaching from MgAl–LDH and GLDA@MgAl–LDH (C)
(Initial phosphate concentration: 100 mg L− 1; Volume: 50 mL; pH: 4.0–10.0; Temperature: 298 K; Adsorbent dosage: 3.0 g L− 1; Agitation speed:
180 rpm; Contact time: 240 min). Solution pH changes (δpH=pHe–pHini) during the adsorption (D).

5
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

ascribed to the growing of effective functional groups and adsorbed active sites (Qiu et al., 2022; Wang et al., 2022c) as adsorbent
dosages increase. However, this led to the overlapping of adsorption sites and a reduction in effective contact surface area, resulting in
lower adsorption capacity in turn (Zhang et al., 2021; Lee et al., 2022). Meanwhile, the higher removal efficiencies and adsorption
capacities of GLDA@MgAl–LDH compared with MgAl–LDH were due to the increase of interlayer space of LDHs after adding GLDA
(Yan et al., 2015; Bernardo et al., 2017), which had strong chemical adsorption and surface complexation that is conducive to
improving the removal of PO3– 4 . When adsorbent dosages were grown from 1.00 to 3.00 g L , the phosphate removal ratios increased
–1

from 38.51% to 80.83% and 48.90–87.03%, respectively (Fig. S7A). However, further increasing the dosages to 4.00 g L–1 did not
achieve satisfactory lifting rate, on the contrary, excessive amount of adsorbent may aggregate in the solution system, resulting in the
disappearance or masking of some active adsorption sites (Zhang et al., 2021; Feng et al., 2022). Considering the removal rate,
adsorption capacity, and economic benefit, subsequent experiments were carried out with 3.00 g L− 1 of LDHs. Similar reports were
made in previous findings, where phosphate adsorption capacity onto Ce–doped MIL–100(Fe) decreased from 5.54 to 4.34 mg g–1 on
the increasing dosages from 0.25 to 1.00 g L–1 (Jiao et al., 2022a).

3.2.2. Influence of initial pH

As presented in Fig. 2 A, both MgAl–LDH (66.11 mg g–1) and GLDA@MgAl–LDH (87.22 mg g–1) exhibited the highest capacity at
pH=4.00 and showed a sharply decrease when pH increased to 9.00 (P < 0.05), and subsequently maintained almost constants (P >
0.05). The variations in phosphate adsorption capacity with pH primarily result from ligand exchange and electrostatic attraction
interactions between MgAl–LDH and GLDA@MgAl–LDH and phosphate influenced by phosphate species (Chitrakar et al., 2007; Lu
et al., 2022), zeta potential (Buates and Imai, 2020), metal release (Akram et al., 2021), and protonation of LDHs (Rybka et al., 2022;
Wang et al., 2022b). In this work, the pH effect test was carried out between 4.0 and 10.0. As shown in Fig. 2B, the phosphate mainly
exists as H2PO−4 and H3PO4 when that the pH of solution is between 2.2 and 4.0, while neutral H3PO4 is the main species when the pH
below 2.2 (pKa1=2.2). Because of the lack of electrostatic force between H3PO4 and adsorbent, H3PO4 was weakly attached to the

Fig. 3. Phosphate adsorption kinetics of MgAl–LDH and GLDA@MgAl–LDH (A; Initial concentration of phosphate: 100 mg L–1; Volume: 50 mL; pH:
6.70; Temperature: 298 K; Adsorbent dosage: 3.0 g L− 1; Agitation speed: 180 rpm; Contact time: 1–240 min). The fitting of phosphate isotherm
adsorption by MgAl–LDH and GLDA@MgAl–LDH (B; Initial concentration of phosphate: 5–250 mg L− 1; Volume: 50 mL; pH: 6.70; Temperature:
298 K; Adsorbent dosage: 3.0 g L− 1; Agitation speed: 180 rpm; Contact time: 240 min). Treatment of actual farming wastewater (C) and phosphate
fertilizer plant polluted wastewater (D) at different doses by MgAl–LDH and GLDA@MgAl–LDH. The data are represented as average ± stan­
dard error.

6
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

adsorbent (Lin and Chen, 2021). They were protonated at 4.00 < pH < 7.00 which enhanced electrostatic attraction against phosphate
anions. Moreover, the phosphate existed as H2PO−4 (pKa2=7.20, Fig. 2B) at pH < 7.00 (Lee et al., 2022), and the positive values of zeta
potential were observed (Fig. S6), demonstrating that the electrostatic attraction between LDHs and H2PO−4 was strong (Elkhlifi et al.,
2022; Wang et al., 2022a). Furthermore, the release of Mg2+ and Al3+ decreased with the increase in pH (Fig. 2 C), which suggested
that ligand exchange obviously occurred at pH < 7.00 (Feng et al., 2022). Moreover, the final pH rose post–phosphate adsorption
increased (Fig. 2D) due to partial OH– release neutralization by H+ deprotonation at pH < 7.00. As pH escalated from 7.00 to 10.00,
HPO2− 4 became the dominant phosphate form, theoretically strengthening the electrostatic attraction with LDHs. However, the
negative zeta potential of MgAl–LDH and GLDA@MgAl–LDH when pH > 8.30 generated deprotonated of LDHs thoroughly, therefor
the phosphate adsorption capacities began to decline. Although the dominant phosphate species was still anion HPO2− 4 , the Lewis
acid–base interaction between M–O (M=Mg or Al) and HPO2− 4 would enhance under alkaline conditions (Gupta et al., 2020; Rahman
et al., 2021). Nevertheless, a surplus of OH− competed with HPO2− 4 in solution, limiting ligand exchange (Akram et al., 2021) (Akram
et al., 2021). Furthermore, the substantial decline in zeta potential hindered electrostatic attraction, resulting in decreased phosphate
adsorption capacities due to the combined effects of these two factors.

3.2.3. Adsorption kinetics

The GLDA@MgAl–LDH elucidated analogous removal kinetics as the MgAl–LDH sample (Fig. 3 A and Figs. S8–S12). The phosphate
removal ratios and capacities of both samples increased sharply in the first 30 min (P < 0.05), with up to 85 and 90% of phosphate
being removed, respectively. In this period, GLDA@MgAl–LDH demonstrated a superior adsorption velocity compared to the
MgAl–LDH. The larger interlayer spacing (Table S2) and abundant functional groups (Fig. 1 A) can explain this phenomenon, which
enhanced the adhesion of phosphate to the LDHs (Jung et al., 2021). After 60 min, although continued phosphate capture persisted,
the rates slowed significantly (P > 0.05) due to the saturation of active sites by phosphate, leading to subsequent adsorption primarily
within the LDH interlayer (Lu, et al., 2022). Subsequently, equilibrium phosphate adsorption was reached at 240 min due to the
limited availability of active adsorption sites on the LDHs (Yan et al., 2018). These results manifested that, the intercalation of GLDA
into MgAl–LDH mightily promoted the phosphate removal capacity, but these intercalations did not introduce pronounced changes in
the reaction kinetics.
To further investigate the relation between phosphate adsorption by MgAl–LDH and GLDA@MgAl–LDH, four commonly used
equations (Eqs. S1–S4) were used to fit the experimental kinetics data. The fitted parameters of these models are presented in Table 1
and Fig. S9. The Elovich equation (R2=0.0.943 and 0.964, respectively) can better reflect the phosphate adsorption kinetics of
MgAl–LDH and GLDA@MgAl–LDH than the Pseudo–second–order model (R2 = 0.821 and 0.759, respectively). Furthermore, the
Pseudo–second–order model fits to the phosphate adsorption kinetics of MgAl–LDH and GLDA@MgAl–LDH better than the Pseu­
do–first–order model (R2 =0.671 and 0.523, respectively). The Elovich equation has been widely used to describe chemisorptions data
(Ji et al., 2022). The good fitting of the Elovich equation to the kinetic data in this work (Table 1) indicating the adsorption of
phosphate on MgAl–LDH and GLDA@MgAl–LDH is chemisorption process. This conclusion was further supported by the relatively
good fitting of the Pseudo–second–order model to the kinetic data of phosphate on MgAl–LDH and GLDA@MgAl–LDH (Bolbol et al.,
2019; Nuryadin et al., 2021; Li et al., 2021; Qing et al., 2024).
Additionally, the intra–particle diffusion model was further employed to determine the rate–controlling step of the phosphate
adsorption (Fig. S9C). It revealed two distinct stages of adsorption (Stage I and Stage II), indicating a multi–stage adsorption process
involving rapid transfer of phosphate adsorbate followed by adsorption equilibrium (Feng et al., 2022). The Stage I with the largest

Table 1
Estimated kinetic model parameters for phosphate adsorption onto MgAl–LDHs and GLDA@MgAl–LDHs.
Models Parameters Unit MgAl–LDHs GLDA@MgAl–LDHs

/ qe, exp mg g− 1 32.29 32.96

Pseudo–first–order qe, cal mg g− 1 29.41 29.97
K1 min− 1 0.368 1.315
R 0.819 0.724
R2 0.671 0.523
RMSE 4.082 2.640
Pseudo–second–order qe, cal mg g− 1 30.76 30.99
K2 g mg-1 min-1 0.021 0.063
R 0.906 0.871
R2 0.821 0.759
RMSE 2.680 1.886
Elovich a 15.82 22.07
b 3.348 2.139
R 0.971 0.982
R2 0.943 0.964
RMSE 1.439 0.728
1 1/2
Intra–particle diffusion Kt mg g− min− 1.086 0.698
1
c mg g− 19.12 24.15
R 0.854 0.868
R2 0.730 0.754
RMSE 3.145 1.898

7
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

diffusion rate was representative of the rapid transfer of phosphate adsorbate from the bulk solution to MgAl–LDH or GLDA@M­
gAl–LDH surface (Fig. S S9C). The Stage II was considered the adsorption equilibrium stage, signifying a further slowdown in intra­
–particle diffusion (Fig. S S9C). Neither the lines fitted in Stage I nor Stage II have passed through the origin, highlighting other
speed–limiting steps, for instance, film diffusion, and surface adsorption, were involved in the phosphate adsorption process (Lan et al.,
2022), which could be also proved by the fact that the C2 values were not equal to 0 (Mahapatra et al., 2022). Furthermore, the higher
slope of Stage I (Kd1) compared to Stage II (Kd2) indicated increased diffusion resistance due to phosphate diffusion from the outer
surface into the pores of MgAl–LDH or GLDA@MgAl–LDH (Dragan et al., 2019; Wang et al., 2022b). Therefore, the phosphate removal
mechanisms were predominantly controlled by chemisorption, and these processes were determined by multiple stages
simultaneously.

3.2.4. Adsorption isotherms

The phosphate adsorption capacities of both MgAl–LDH and GLDA@MgAl–LDH composites showed a significant enhance from
8.57 and 8.40 mg g–1 to 43.94 and 47.06 mg g–1 (Fig. S7B), respectively, as the initial phosphate concentration increased. This in­
dicates that higher initial phosphate concentrations result in greater adsorption capacities, likely due to the increased driving force for
phosphate to overcome mass transfer resistance between liquid and solid phases (Jung et al., 2021; Lan et al., 2022), thereby
enhancing adsorption. Conversely, the corresponding removal efficiencies reduced from 99.92 and 97.94% to 50.70 and 54.13%,
respectively. The reason for this phenomenon was for that the constant number of active sites in the solution, but these adsorptive sites
were sufficiently occupied as the phosphate concentration increase, hence declining the phosphate removal efficiencies (Ahmed et al.,
2021).
The Langmuir model presumes specific homogeneous sites and monolayer sorption on the adsorbents without any steric hindrance
(Jung et al., 2021), while the Freundlich model suggests multilayer adsorption on heterogeneous surfaces (Wang et al., 2022a). The
Sips and Redlich–Peterson models are the combination of the above two models which represent the three–parameter models for
monolayer adsorption (Keyikoglu et al., 2022). The experimental phosphate adsorption data were well fitted to the four chosen models
with an extremely high squared multiple regression coefficient for the Redlich–Peterson model (R2 =0.991 and 0.924) and with a
relatively lower R2 with the Langmuir model (R2 = 0.940 and 0.906). Based on the R2 values (Table 2), it can be suggested that
Redlich–Peterson model is more suitable to describe the phosphate adsorption by MgAl–LDH and GLDA@MgAl–LDH than the other
models. The model assumes that the adsorption process of phosphate follows a combined Freundlich and Langmuir model; a multilayer
physical and chemical adsorption with a saturation value at high phosphate concentrations. Furthermore, the maximum phosphate
removal capacities calculated via the Langmuir model were 37.82 and 44.17 mg g–1 for MgAl–LDH and GLDA@MgAl–LDH, respec­
tively (Fig. 3B and Table 2). The GLDA@MgAl–LDH exhibited higher phosphate removal capacities than MgAl–LDH, confirming that
the intercalation with GLDA into LDHs greatly contributed to the adsorption ability, which makes it as a promising candidate for
capturing phosphate from wastewater.

3.3. Regeneration ability of GLDA@MgAl–LDH

As presented in Fig. S10, the first desorption cycle recovered 97.6% of the adsorption capacity, with GLDA@MgAl–LDH retaining
approximately 77.4% of its original adsorption capacity after five subsequent recycles, equivalent to 25.74 mg g− 1. The retention

Table 2
Estimated adsorption isotherm model parameters for phosphate adsorption onto MgAl–LDHs and GLDA@MgAl–LDHs.
Isothermal model Parameters Unit MgAl–LDHs GLDA@MgAl–LDHs

Freundlich Kf (mg g-1) (L mg-l)1/n 21.431 20.205

n 6.805 5.491
R 0.989 0.960
R2 0.979 0.921
RMSE 2.247 4.684
Langmuir qm mg g-1 37.821 44.173
KL L mg-1 10.833 0.715
R 0.970 0.952
R2 0.940 0.906
RMSE 3.816 5.943
Redlich–Peterson KR L g-1 1.066 5.583
αR L g-1 0.422 0.301
g 0.893 0.798
R 0.995 0.961
R2 0.991 0.924
RMSE 1.545 4.585
1
Sips qm mg g− 63.164 92.327
1
Ks L mg− 0.571 0.283
r 0.260 0.274
R 0.992 0.961
R2 0.984 0.924
RMSE 1.987 4.623

8
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

adsorption capacity was still higher than that of various LDHs–based adsorbents such as alginate/MgAl LDH (Han et al., 2011),
biochar/MgAl–LDH (Li et al., 2021), attapulgite/MgAl–LDH (Gan et al., 2011), FeMgZr–LDH (Zhang et al., 2021), and bio­
char/MgFe–LDH (Bolbol et al., 2019) in the previous studies. The desorption efficiencies reduced to 82.5% in the fifth cycle. This
reduction might be likely due to some active sites on GLDA@MgAl–LDH becoming tightly filled in subsequent adsorption–desorption
cycles (Zhou et al., 2022), thus diminishing recyclability. Additionally, the slight decline in adsorption capacity may also result from
the inevitable leaching of Mg2+ and Al3+ (Fig. 2 C and Fig. S11). Accordingly, these results proved that GLDA@MgAl–LDH is a
pleasurable candidate for highly efficient phosphate removal with satisfactory reusability.

3.4. Comparison of adsorption capacities with other materials

Up to now, many LDHs had been reported for phosphate capture such as Fe3O4@ZnAl–LDH (Yan et al., 2015), FeMgZr–LDH (Zhang
et al., 2021), MgAl–LDH (Jung et al., 2021), Fe3O4@MgAl–LDH (Yan et al., 2015; Koilraj and Sasaki, 2016), etc. The Qmax of
GLDA@MgAl–LDH in this work revealed highly encouraging results up to 44.17 mg g–1 (Table 3), which was found greater compared
to majority of previously reported LDHs–based adsorbents (Bolbol et al., 2019; Han et al., 2011; Chitrakar et al., 2007; Lee and Kim,
2013; Nuryadin et al., 2021; Gan et al., 2011; Li et al., 2021; Qing et al., 2024; Li et al., 2021). Simultaneously, the phosphate
adsorption process of GLDA@MgAl–LDH showed a lesser equilibrium time compare well with other intercalated or modified LDHs
(Fig. 3 A), which is pleasurable for industrial implementation. In addition, GLDA is a biodegradable aminopolycarboxylate chelator
with more than 60% degradation rate within 28 days (VanThinh et al., 2021), and exhibits no toxicity threat to organisms (Gluhar
et al., 2020). Above all, GLDA@MgAl–LDH was expected to be a feasible candidate with extensive application prospect for the
phosphate capture from wastewater. It could be also subsequently recovered as a slow–release fertilizer after being loaded with
phosphate considering the scarcity and future availability of phosphate (Bernardo et al., 2018; Yan et al., 2018; Lee et al., 2022).

Table 3
Comparison of adsorption capacities for phosphate with the known high-performing LDHs–based adsorbents.
Adsorbents Temperature Dosage (g pH Time Isotherm Kineticsa qm (bmg References
(K) L-1) (h) g-1)

Mg–Al LDH–alginate beads 298.15 66.67 4.90 12.0 Langmuir Pseudo- 1.04 Han et al. (2011)
second- order
Biochar–MgAl–LDHs 303.15 / 6.5 / Freundlich Pseudo-first- 6.10 Li et al. (2021)
order
MgAl–LDHs–coated attapulgite 298.15 4.0 / 24.0 Freundlich / 6.90 Gan et al. (2011)
Biochar–Mg–Fe LDH / 5.0 4.0 1.0 Langmuir Pseudo- 17.46 Bolbol et al.
second- order (2019)
Fe–Mg–Zr–LDHs 298.15 7.67 6.71 / Langmuir Pseudo- 21.16 Zhang et al.
second- order (2021)
Magnetic core–shell Fe3O4@Ni–Al–LDH 298.15 2.0 / / Langmuir Pseudo- 26.50 Yan et al. (2015)
second- order
4+
Zr –MgAl–LDHs / / 8.7 / Freundlich / 30.00 Chitrakar et al.
(2007)
Magnetic core–shell Fe3O4@Mg–Al–LDH 298.15 2.0 / / Langmuir Pseudo- 31.70 Yan et al. (2015)
second- order
Mg–Al LDHs–FHC composite 298.15 1.25 7.0 / Freundlich / 33.21 Jung et al. (2021)
Magnetic Fe3O4/Mg2Al–NO3–LDH / 1.0 8.2 6.0 Langmuir Pseudo- 33.40 Koilraj and Sasaki
second- order (2016)
Amorphous–ZrO2/MgFe–LDH composite 290 0.1 7.0 36.0 Freundlich Pseudo- 35.40 Nuryadin et al.
second- order (2021)
Magnetic core–shell Fe3O4@zn–Al–LDH 298.15 2.0 / / Langmuir Pseudo- 36.90 Yan et al. (2015)
second- order
MgAl–LDHs 298.15 3.0 6.70 6.0 Freundlich Pseudo- 37.82 This work
second- order
Magnetic alginate–MgAl–LDH composites 298.15 1.67 / 24.0 Freundlich Pseudo- 39.10 Lee and Kim
second- order (2013)
Carbonization of tobacco 318.15 5.0 / 24.0 Freundlich Pseudo- 41.16 He et al. (2019)
stalk–MgAl–LDHs second- order
GLDA@MgAl–LDHs 298.15 3.0 6.70 6.0 Freundlich Pseudo- 44.17 This work
second- order
2:1 Mg/Al-LDHs biochar 298.15 2.5 3.0 / Langmuir Pseudo- 53.39 Li et al. (2016)
second- order
La-doped layered double hydroxide/ 288.15 0.4 6.0 1.0 Langmuir Pseudo- 212.1 Qing et al. (2024)
biochar (La–MgAl–LDH/BC) second- order
a
Only the Pseudo-first-order and Pseudo-second-order kinetic fitting results were compared.
b
The maximum phosphate removal capacities (qm, mg g-1) was calculated via the Langmuir model.

9
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

Fig. 4. Surface chemistry of MgAl–LDH and GLDA@MgAl–LDH before and after adsorption of phosphate: C 1 s (A–B), O 1 s (C–D), N 1 s (E–F), and
P 2p (G–H) high–resolution spectra (Initial concentration of phosphate: 100 mg L− 1; pH: 6.70; Temperature: 298 K; Adsorbent dosage: 3.0 g L− 1;
Agitation speed: 180 rpm; Contact time: 240 min).

10
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

3.5. Potential adsorption mechanisms

3.5.1. FTIR, XRD, and XPS analysis

A new typical peak at 1100 cm–1 appeared post–phosphate adsorption (Fig. 1 A), ascribable to the bending vibration of O–P–O or/
and P–O bonds (Lu et al., 2022), proving GLDA@MgAl–LDH capture phosphate successfully by the M–O–P coordination bonds to form
complexes (Jung et al., 2021). When phosphate was adsorbed, in comparison with FTIR spectra before the adsorption on
GLDA@MgAl–LDH, the band at 1590 and 3460 cm− 1 (in relationship with–OH bond stretching of the hydroxyl group) slightly shifted
in wavenumber to 1640 and 3471 cm− 1, respectively, indicating phosphate interaction with –OH groups in GLDA@MgAl–LDH
through ion–exchange mechanism (Buates and Imai, 2020). In addition, the intensity of the peaks at 677, 554, and 448 cm− 1 increased
post-adsorption, suggesting involvement of metallic oxide bonds in the formation of monodentate and bidentate inner− sphere surface
complexations of M–O–P, M− O− P− M, and O− M− O− P (Li et al., 2022). Besides, no shift was observed in the peak at 1362 cm− 1
corresponding to CO2– 2–
3 stretching vibration, implying that CO3 in the layers of LDHs exists not in free but in hydrogen bonding form. It
occurs as an interlayer anion together with abundant of Cl . Phosphate could enter the interlayer of GLDA@MgAl–LDH as HPO2−
−
4 or
H2PO−4 to substitute Cl− via ion exchange (Yan et al., 2018; Elkhlifi et al., 2022).
The LDHs’ characteristic peaks persisted in GLDA@MgAl–LDH, indicating LDHs’ structural integrity post-phosphate immobili­
zation (Fig. 1B). While phosphate-bearing mineral composition wasn’t evident in the XRD spectrum, a slight shift towards lower 2θ
values in the peak position of the (003) crystal plane, coupled with increased interlayer d-spacing d003 values (Table S2) post-
phosphate adsorption, was observed. Beyond that, Cl– resides in LDHs’ interlayer, and phosphate likely replaces Cl− within this re­
gion, significantly altering the interlayer spacing (Jung et al., 2021). This underscores anion exchange, specifically intercalation, as a
prominent feature during the adsorption processes.
XPS analysis was further conducted to examine the surface element chemical state of MgAl–LDH and GLDA@MgAl–LDs composites
before and after phosphate adsorption. Overall, the XPS of MgAl–LDH, GLDA@MgAl–LDH, and their phosphate-loaded counterparts
displayed peaks corresponding to Mg 1 s, O 1 s, N 1 s, C 1 s, P 2p, and Al 2p (Fig. S4), indicating structural integrity post-adsorption. In
the C1s spectra (Fig. 4A–B), three peaks were observed for MgAl–LDH, representing O–C– –O (~288.3 eV), C–O (286.4 eV), and C–C
(284.8 eV) bonds (Li et al., 2022), while GLDA@MgAl–LDH exhibited an additional peak at ~285.4 eV attributed to C–N from the
intercalated substance GLDA (Fig. S4 and Fig. 4D). The peak areas of C–O and C–C increased, while that of O–C– –O reduced from
19.88% to 15.70% in MgAl–LDH and 26.31–16.65% in GLDA@MgAl–LDH. While the peak areas of C–N showed a similar trend in
GLDA@MgAl–LDH (from 20.35% to 10.04%). These results indicated the involvement of oxygen-containing functional groups in
phosphate elimination, possibly through inner sphere complexation (Feng et al., 2022; Li et al., 2022).
The N 1 s high–resolution spectra only existed in GLDA@MgAl–LDH composites (Fig. 4C–D), which proved that GLDA was suc­
cessfully intercalated on MgAl–LDH. Deconvolution of the N 1 s spectra of GLDA@MgAl–LDH revealed peaks at 399.4 eV for C–N and
401.1 eV for –NH– (amino group) (Wang et al., 2022b). Following phosphate adsorption, the peak of –NH– presented a slight shift,
suggesting that it could be protonated into positive charges to participate in the capture of phosphate via electrostatic interaction
(Zhou et al., 2022). Moreover, the peaks of O 1 s of two LDHs (Fig. 4E–F) were asymmetrical and deconvoluted into two different
oxidation forms, C– –O and metal oxide (M–O, where M = Mg and Al) (Feng et al., 2022). The integral area ratios of the M–O peak
reduced from 44.94% to 28.86% of MgAl–LDH and 39.30–19.59% of GLDA@MgAl–LDH, consistent with observations in Al 2p
(Fig. S12) and Mg 1 s orbitals (Fig. S14). Besides, the percentage of M–OH from the XPS spectra of Al 2p (Fig. S12) and Mg 1 s (Fig. S14)
increased in two materials, indicating phosphate exchange with –OH groups and subsequent formation of surface complexes via the
M–O–P (M=Mg or Al) coordination bonds (Yan et al., 2018; Jung et al., 2021; Li et al., 2022). These findings corroborated previous
works that the formation of monodentate and bidentate inner-sphere surface complexes with LDHs, or outer spherical surface com­
2+
plexes with protonated OH+ 2 of LDHs through electrostatic adsorption (Wang et al., 2022b). Additionally, low levels of dissolved Mg
and Al3+ on GLDA@MgAl–LDH affirmed its high stability, further supporting the effectiveness of phosphate removal mechanisms
mediated by LDHs. (Fig. 2 C and Fig. S11).
Compared with the pristine MgAl–LDH and GLDA@MgAl–LDH before adsorption (Fig. S4 and Fig. 4G–H), a new signal peak
relevant to P 2p at ~133.0 eV appeared in the wide–scan survey spectra, revealing successful phosphate loading onto these LDHs (Feng
et al., 2022; Li et al., 2022). These results were supported via fine–scan XPS spectrum, where the spectra intriguingly confirm the
presence of a P 2p peak after phosphate adsorption (Fig. 4G–H). The high–resolution P 2p spectra of the reacted adsorbent could be
divided into two characteristic peaks of ~132.8–132.9 eV (P–Mg) and ~133.7–133.8 eV (P–Al), corresponding to Mg– or Al– phos­
phate complex (such as AlPO4, Mg3(PO4)2), indicating that surface complexation predominantly occurred between phosphate and
active sites of MgAl–LDH and GLDA@MgAl–LDH (Nie et al., 2022), which corroborated the FTIR analysis results (Fig. 1 A) and
previously reported results (He et al., 2019; Elkhlifi et al., 2022).

3.5.2. Theoretical DFT calculation

Based on the aforesaid FTIR, XRD, and XPS results, the presence of oxygen functional groups on the adsorbent surfaces was
confirmed (Fig. 1 and Fig. 4), along with the noticeable increase in interlayer space of MgAl–LDH upon GLDA introduction (Table S2),
indicative of enhanced van der Waals forces via electrostatic interaction. In this work, the most stable geometric structures of the two
LDHs were first optimized (Fig. S14) and then their ESP were visualized. ESP distribution map usually is considered on vdW surface
and it was a valuable tool for predicting active sites of adsorbent surface through electrophilic attraction based on electron density
(Han et al., 2023). Notably, the ESP maximum points were observed in proximity to –OH groups, with GLDA@MgAl–LDH
(27.137 kcal mol− 1) exhibiting a significantly higher ESP value compared to MgAl–LDH (22.195 kcal mol− 1) (Fig. 5 A and B). This
suggests that GLDA@MgAl–LDH was more favorable for the capture of negatively charged of H2PO−4 , HPO2− 3−
4 , and PO4 . Deprotonated

11
 G. Wang et al.
12

Environmental Technology & Innovation 35 (2024) 103701

Fig. 5. The electrostatic potential mapped molecular of MgAl–LDH (A) and GLDA@MgAl–LDH (B). The charge density difference between the adsorption configurations: MgAl–LDH/phosphate (C) and
GLDA@MgAl–LDH/phosphate (D). The Eads and optimized structures of phosphate absorbed on the surfaces of MgAl–LDH (E) and GLDA@MgAl–LDH (F).
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

molecules were found to favorably localize near hydroxyl oxygen atoms (Lee et al., 2022), offering an explanation for the superior
adsorption performance of GLDA@MgAl–LDH at pH<7.00, as observed experimentally (Fig. 2 A).
To elucidate the intrinsic enhancement mechanism during the phosphate adsorption process, the Eads of phosphate adsorbed on
MgAl–LDH and GLDA@MgAl–LDH was calculated. The phosphate fractions in the aqueous medium mainly include H3PO4, H2PO−4 ,
HPO2− 3− 2−
4 , and PO4 (Fig. 2B) (Lee et al., 2022), yet our experiments primarily involved H2PO4 and HPO4 due to their prevalence in both
−

the experimental conditions (pH 4.0–10.0) and the actual polluted water body. Therefore, the following parts were mainly to discuss
the interaction mechanism of MgAl–LDH and GLDA@MgAl–LDH with H2PO−4 , since the HPO2− 4 mechanism was similar to H2PO4 (Luo
−

et al., 2022). As seen in Fig. 5E and F, the calculated Eads of MgAl–LDH (− 0.387 eV) demonstrates that the adsorption of H2PO−4
through interlayer anion exchange was energetically spontaneous (Kong et al., 2022; Lin et al., 2022). Conversely, GLDA@MgAl–LDH
exhibited a higher Eads (− 0.961 eV) for H2PO−4 , indicative of a stronger binding affinity (Kong et al., 2022). This suggests that
intercalating GLDA into MgAl–LDH enhanced its affinity for phosphate. This conclusion is supported by both theoretical calculations
and experimental data, confirming the pivotal role of GLDA in enhancing phosphate removal by MgAl–LDH.
The charge density difference (CDD) in the adsorption configurations was further calculated by simulation (Fig. 5 C and D) to gain
deeper insight into how the MgAl–LDH and GLDA@MgAl–LDH affect the phosphate adsorption. CDD elucidates electron transfer by
quantifying the disparity in charge density between the adsorbed and isolated systems (Zhang et al., 2023). Yellow color indicates
charge accumulation, while cyan color signifies a reduction in charge. As illustrated in Fig. 5 C and D, obvious electron–rich region was
existed around H2PO−4 , while electron depletions occurred on the surface of LDHs, suggesting the presence of electron donor-acceptor
interactions. In addition, the electron density between intercalation substance GLDA and H2PO−4 decreased, implying that phosphate
adsorption weakens the bonding between GLDA and MgAl–LDH. Such weakened bonding made them susceptible to attack by protons,
which in turn made intercalated MgAl–LDH and H2PO−4 tightly combined to benefit adsorption, forming monodentate or/and
bidentate inner–sphere surface complexes. Greater exchange of charge densities correlates with enhanced adsorption capability of the
adsorbent (Zhang et al., 2023). Therefore, the above results revealed the charge transfer process between LDHs adsorbent and
phosphate, underscoring the superior phosphate adsorption capability of GLDA@MgAl–LDH over MgAl–LDH, providing valuable
insight for designing novel LDHs adsorbents for capturing oxygen–containing anionic pollutants.
Based on the experimental data, spectroscopic analysis, and theoretical calculation, the mainly proposed capture phosphate
mechanism by MgAl–LDH and GLDA@MgAl–LDH may be the synergistic effect of electrostatic attraction, anion and ligand exchange,
and surface complexation, which was further presented in Fig. 6.

3.6. GLDA@MgAl–LDH potential in the capture of phosphate from actual wastewater

The actual phosphate adsorption capacity of GLDA@MgAl–LDH a local farm and fertilizer plant wastewater was also investigated
(Table S4). Batch phosphate adsorption experiments were carried out at both the initial and adjusted pH levels of 4.0. An increase of
the dosage to 3.0 g L− 1 resulted to a dramatically reduce in residual phosphate concentration from farming wastewater with the
adsorption efficiencies of 55.26 and 71.41% for MgAl–LDH and GLDA@MgAl–LDH (Fig. 3 C), respectively. The phosphate adsorption
efficiencies increased by 9.6–22.0% when the pH of the reaction solution optimized to 4.0. The phosphate fertilizer plant wastewater
also showed similar results (Fig. 3D). It should be noticed that both wastewaters contained an abundant of cations and anions
(Table S4). Nevertheless, the phosphate removal efficiencies of GLDA@MgAl–LDH were still as high as 94%, which proves that

Fig. 6. The potential removal mechanism phosphate by MgAl–LDH and GLDA@MgAl–LDH.

13
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

GLDA@MgAl–LDH can tolerant to interfering coexisting ions, and maintain a remarkable phosphate removal property in the coex­
istence of ions. These results showed that the residual phosphate concentration of the wastewater treated with GLDA@MgAl–LDH was
less than 5.00 mg L-1, which can meet the requirements of the three-level standard of Pollutant Discharge Standard for Urban Sewage
Treatment Plants (GB18918–2002) under the optimized pH and dosage.
Furthermore, the GLDA@MgAl–LDH composites were filled in a fixed–bed column to validate its applicability in the flow–through
systems. The practical phosphate–containing wastewater was pumped up–to–down through the columns at a constant flow rate
(2.0 mL min− 1). As depicted in Fig. S15, the residual phosphate concentration in the treated wastewater gradually increased with the
volume of wastewater processed, consistent with findings from prior research (Jiao et al., 2022b; Tee et al., 2022; Cao et al., 2023).
Importantly, the phosphate removal rate from farm wastewater and phosphate fertilizer plant wastewater was above 90% at the initial
approximately 410 and 320 BV, respectively. These results underscore the significant potential of the GLDA@MgAl–LDH composites
developed in this study for practical application in capturing and removing phosphate-containing wastewater. Further works are
highly encouraged to develop a new approach for resource utilization of phosphate–loaded adsorbent, for example, as a slow–release
fertilizer (Keyikoglu et al., 2022; Qiu et al., 2022; Wang et al., 2022c) and soil amendment (Guan et al., 2022).

4. Conclusion

Herein, an eco–friendly and high–performance adsorbent, GLDA@MgAl–LDH, was synthesized for phosphate capture by inter­
calating the biodegradable chelator GLDA into the interlayer space of MgAl–LDH via co–precipitation. Characterization confirmed
successful intercalation, resulting in more porous lamellar architectures with broader interlayer spacing compared to MgAl–LDH.
Notably, GLDA intercalation introduced –COOH and –NH–groups, enhancing coordinating sites and ligand exchange, thereby
significantly improving phosphate capture efficiency. Batch experiments demonstrated that satisfactory phosphate capture (＞90%)
could be attained by GLDA@MgAl–LDH within a broad pH range (5.00–8.00) and a fast contact time (< 60 min). Kinetic model
presented chemisorption of phosphate on GLDA@MgAl–LDH, while multilayer phosphate adsorption on the heterogeneous surface
was recommended by isotherm model. GLDA@MgAl–LDH exhibited superior adsorption capacities, with a maximum experimental
capacity of 44.17 mg g–1 towards phosphate, surpassing pure MgAl–LDH and most other reported LDHs-based adsorbents. More
significantly, exhausted GLDA@MgAl–LDH could efficiently regenerate with NaOH solution and still conduct with high capacity after
five adsorption–desorption recycles. The GLDA@MgAl–LDH adsorbent also demonstrated satisfactory performance in fixed–bed
experiment for the treatment of phosphate–containing farm and fertilizer plant wastewater. The recovery phosphate mechanisms for
included electrostatic attraction, anion and ligand exchange, and surface complexation. Overall, GLDA@MgAl–LDH could be served as
a promising candidate with great selectivity, efficiency and applicability for phosphate treatment. Future studies should explore the
resource utilization of phosphate-loaded adsorbents as slow-release fertilizers and soil amendments to promote environmental pro­
tection and resource sustainability.

CRediT authorship contribution statement

Changlian Xu: Writing – review & editing, Visualization. Junzhuo Cai: Writing – review & editing, Software. Xiaoxun Xu:
Writing – review & editing. Guochun Lv: Writing – review & editing. Zhanbiao Yang: Writing – review & editing. Zhang Cheng:
Writing – review & editing. Yilin Liao: Writing – original draft, Software, Investigation. Shirong Zhang: Writing – review & editing,
Writing – original draft, Conceptualization. Guiyin Wang: Writing – review & editing, Writing – original draft, Methodology,
Investigation, Conceptualization.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Data Availability

Data will be made available on request.

Acknowledgements

This work was financially supported by the Key Research and Development Projects of Sichuan Province, China (2021YFN0018)
and the Natural Science Foundation of Sichuan Province, China (2022NSFSC0237).

Appendix A. Supplementary data

Supplementary data to this article can be found online.

14
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

Appendix A. Supporting information

Supplementary data associated with this article can be found in the online version at doi:10.1016/j.eti.2024.103701.

References

Ahmed, M., Aziziha, M., Anwar, R., Johnson, M.B., Lin, L.S., 2021. Magnetic sludge byproducts for adsorptive phosphorus removal: resource recovery from iron–based
anaerobic sewage sludge. Waste Manag. 120, 269–276. https://doi.org/10.1016/j.wasman.2020.11.050.
Akram, M., Xu, X., Gao, B., Wang, S., Khan, R., Yue, Q., Duan, P., Dan, H., Pan, J., 2021. Highly efficient removal of phosphate from aqueous media by pomegranate
peel co–doping with ferric chloride and lanthanum hydroxide nanoparticles. J. Clean. Prod. 292, 125311 https://doi.org/10.1016/j.jclepro.2020.125311.
Alewell, C., Ringeval, B., Ballabio, C., Robinson, D.A., Panagos, P., Borrelli, P., 2020. Global phosphorus shortage will be aggravated by soil erosion. Nat. Commun. 11,
4546. https://doi.org/10.1038/s41467–020–18326–7.
Amer, A., Sayed, G.H., Ramadan, R.M., Rabie, A.M., Negm, N.A., Farag, A.A., Mohammed, E.A., 2021. Assessment of 3–amino–1H–1,2,4–triazole modified layered
double hydroxide in effective remediation of heavy metal ions from aqueous environment. J. Mol. Liq. 341, 116935 https://doi.org/10.1016/j.
molliq.2021.116935.
Bai, J., Su, C.R., Parra, R.D., Zeng, X.C., Tanaka, H., Koga, K., Li, J.M., 2003. Ab initio studies of quasi-one-dimensional pentagon and hexagon ice nanotubes. J. Chem.
Phys. 118, 3913–3916. https://doi.org/10.1063/1.1555091.
Bernardo, M.P., Guimarães, G.G.F., Majaron, V.F., Ribeiro, C., 2018. Controlled release of phosphate from LDH structures: dynamics in soil and application as smart
fertilizer. ACS Sustain. Chem. Eng. (4), 5152–5161. https://doi.org/10.1021/acssuschemeng.7b04806.
Bernardo, M.P., Moreira, F.K.V., Ribeiro, C., 2017. Synthesis and characterization of eco–friendly Ca–Al–LDH loaded with phosphate for agricultural applications.
Appl. Clay Sci. 137, 143–150. https://doi.org/10.1016/j.clay.2016.12.022.
Bi, R., De, Y., Lei, B., Chen, F., Zhang, R., Li, W., 2022a. Mercaptocarboxylic acid intercalated MgAl layered double hydroxide adsorbents for removal of heavy metal
ions and recycling of spent adsorbents for photocatalytic degradation of organic dyes. Sep. Purif. Technol. 289, 120741 https://doi.org/10.1016/j.
seppur.2022.120741.
Bi, R., Yin, D., Zhang, S., Zhang, R., Chen, F., 2022b. Efficient removal of Pb(II) and Hg(II) with eco–friendly polyaspartic acid/layered double hydroxide by
host–guest interaction. Appl. Clay Sci. 225, 106536 https://doi.org/10.1016/j.clay.2022.106536.
Bolbol, H., Fekri, M., Hejazi–Mehrizi, M., 2019. Layered double hydroxide–loaded biochar as a sorbent for the removal of aquatic phosphorus: behavior and
mechanism insights. Arab. J. Geosci. 12, 503. https://doi.org/10.1007/s12517–019–4694–4.
Buates, J., Imai, T., 2020. Biochar functionalization with layered double hydroxides composites: Preparation, characterization, and application for effective phosphate
removal. J. Water Process Eng. 37, 101508 https://doi.org/10.1016/j.jwpe.2020.101508.
Cakmak, E.K., Hartl, M., Kisser, J., Cetecioglu, Z., 2022. Phosphorus mining from eutrophic marine environment towards a blue economy: The role of bio–based
applications. Water Res 219, 118505. https://doi.org/10.1016/j.watres.2022.118505.
Cao, Y.H., Wu, X.W., Li, B.Q., Tang, X., Lin, X.R., Li, P.F., Chen, H., Huang, F., Wei, C.H., Wei, J., Qiu, G.L., 2023. Ca–La layered double hydroxide (LDH) for selective
and efficient removal of phosphate from wastewater. Chemosphere 325, 138378. https://doi.org/10.1016/j.chemosphere.2023.138378.
Chitrakar, R., Tezuka, S., Sonoda, A., Sakane, K., Ooi, K., Hirotsu, T., 2007. Synthesis and phosphate uptake behavior of Zr4+ incorporated MgAl–layered double
hydroxides. J. Colloid Interf. Sci. 313, 53–63. https://doi.org/10.1016/j.jcis.2007.04.004.
Dragan, E.S., Humelnicu, D., Dinu, M.V., 2019. Development of chitosan–poly(ethyleneimine) based double network cryogels and their application as
superadsorbents for phosphate. Carbohydr. Polym. 210, 17–25. https://doi.org/10.1016/j.carbpol.2019.01.054.
Elkhlifi, Z., Sellaoui, L., Zhao, M., Ifthikar, J., Jawad, A., Shahib, I.I., Sijilmassi, B., Lahori, A.H., Selvasembian, R., Meili, L., Gendy, E.A., Chen, Z., 2022. Lanthanum
hydroxide engineered sewage sludge biochar for efficient phosphate elimination: mechanism interpretation using physical modelling. Sci. Total Environ. 803,
149888 https://doi.org/10.1016/j.scitotenv.2021.149888.
Fang, Q., Ye, S., Yang, H., Yang, K., Zhou, J., Gao, Y., Lin, Q., Tan, X., Yang, Z., 2021. Application of layered double hydroxide–biochar composites in wastewater
treatment: Recent trends, modification strategies, and outlook. J. Hazard. Mater. 420, 126569 https://doi.org/10.1016/j.jhazmat.2021.126569.
Feng, L., Zhang, Q., Ji, F., Jiang, L., Liu, C., Shen, Q., Liu, Q., 2022. Phosphate removal performances of layered double hydroxides (LDH) embedded polyvinyl
alcohol/lanthanum alginate hydrogels. Chem. Eng. J. 430, 132754 https://doi.org/10.1016/j.cej.2021.132754.
Gan, F., Zhou, J., Wang, H., Zhao, H., 2011. Layered double hydroxide (LDH)–coated attapulgite for phosphate removal from aqueous solution. Water Sci. Technol. 64
(11), 2192–2198. https://doi.org/10.2166/wst.2011.721.
Gluhar, S., Kaurin, A., Lestan, D., 2020. Soil washing with biodegradable chelating agents and EDTA: technological feasibility, remediation efficiency and
environmental sustainability. Chemosphere 257, 127226. https://doi.org/10.1016/j.chemosphere.2020.127226.
Guan, X., Yuan, X., Zhao, Y., Wang, H., Wang, H., Bai, J., Li, Y., 2022. Application of functionalized layered double hydroxides for heavy metal removal: A review. Sci.
Total Environ. 838, 155693 https://doi.org/10.1016/j.scitotenv.2022.155693.
Gupta, N.K., Saifuddin, M., Kim, S., Kim, K.S., 2020. Microscopic, spectroscopic, and experimental approach towards understanding the phosphate adsorption onto
Zn–Fe layered double hydroxide. J. Mol. Liq. 297, 111935 https://doi.org/10.1016/j.molliq.2019.111935.
Han, Y., Lee, W., Lee, C., Park, S., Kim, K., Kim, S., 2011. Entrapment of Mg–Al layered double hydroxide in calcium alginate beads for phosphate removal from
aqueous solution. Desalin. Water Treat. 36, 178–186. https://doi.org/10.5004/dwt.2011.2254.
Han, S., Tao, Y., Cui, Y., Xu, J., Ju, H., Fan, L., Zhang, L., Zhang, Y., 2023. Lanthanum–modified polydopamine loaded Acinetobacter lwoffii DNS32 for phosphate and
atrazine removal: Insights into co–adsorption and biodegradation mechanisms. Bioresour. Technol. 368, 128266 https://doi.org/10.1016/j.
biortech.2022.128266.
He, H., Zhang, N., Chen, N., Lei, Z., Shimizu, K., Zhang, Z., 2019. Efficient phosphate removal from wastewater by MgAl–LDHs modified hydrochar derived from
tobacco stalk. Bioresour. Technol. R. 8, 100348 https://doi.org/10.1016/j.biteb.2019.100348.
Ji, Y., Zheng, N., An, Q., Sun, S., Wang, S., Li, X., Li, P., Hua, X., Dong, D., Zhao, C., Li, Z., Zhang, W., 2022. The effect of carbonization temperature on the capacity
and mechanisms of Cd(II)–Pb(II) mix–ions adsorption by wood ear mushroom sticks derived biochar. Ecotoxicol. Environ. Saf. 239, 113646 https://doi.org/
10.1016/j.ecoenv.2022.113646.
Jiao, G., Ma, J., Zhang, J., Zhou, J., Sun, R., 2022b. High–efficiency capture and removal of phosphate from wastewater by 3D hierarchical functional
biomass–derived carbon aerogel. Sci. Total Environ. 827, 154343 https://doi.org/10.1016/j.scitotenv.2022.154343.
Jiao, Z., Miao, Z., An, H., Li, Q., Meng, X., 2022a. Fabrication of Ce–doped MIL–100(Fe), its adsorption performance, and the mechanisms to adsorb phosphate from
water. Environ. Technol. Innov. 28, 102847 https://doi.org/10.1016/j.eti.2022.102847.
Jung, K., Lee, S.Y., Choi, J., Hwang, M., Shim, W.G., 2021. Synthesis of Mg–Al layered double hydroxides–functionalized hydrochar composite via an in situ one–pot
hydrothermal method for arsenate and phosphate removal: structural characterization and adsorption performance. Chem. Eng. J. 420, 129775 https://doi.org/
10.1016/j.cej.2021.129775.
Keyikoglu, R., Khataee, A., Yoon, Y., 2022. Layered double hydroxides for removing and recovering phosphate: recent advances and future directions. Adv. Colloid
Interfac. 300, 102598 https://doi.org/10.1016/j.cis.2021.102598.
Koilraj, P., Sasaki, K., 2016. Fe3O4/MgAl–NO3 layered double hydroxide as a magnetically separable sorbent for the remediation of aqueous phosphate. J. Environ.
Chem. Eng. 4, 984–991. https://doi.org/10.1016/j.jece.2016.01.005.

15
G. Wang et al. Environmental Technology & Innovation 35 (2024) 103701

Kong, L., Zhang, J., Wang, Y., Yan, Q., Xu, J., Quan, X., Andrews, C.B., Zhang, Z., Zheng, C., 2022. Bowknot–like Zr/La bimetallic organic frameworks for enhanced
arsenate and phosphate removal: combined experimental and DFT studies. J. Colloid Interf. Sci. 614, 47–57. https://doi.org/10.1016/j.jcis.2022.01.033.
Kresse, G., 1999. From ultrasoft pseudopotentials to the projector augmented–wave method. Phys. Rev. B 59, 1758–1775. https://doi.org/10.1103/
PhysRevB.59.1758.
Kresse, G., Furthmiiller, J., 1996. Efficiency of ab–initio total energy calculations for metals and semiconductors using a plane–wave basis set. Comp. Mater. Sci. 6,
15–50. https://doi.org/10.1016/0927-0256(96)00008-0.
Lan, Y., Gai, S., Cheng, K., Li, J., Yang, F., 2022. Lanthanum carbonate hydroxide/magnetite nanoparticles functionalized porous biochar for phosphate adsorption
and recovery: advanced capacity and mechanisms study. Environ. Res. 214, 113783 https://doi.org/10.1016/j.envres.2022.113783.
Lee, C., Kim, S., 2013. Magnetic alginate–layered double hydroxide composites for phosphate removal. Environ. Technol. 34 (19), 2749–2756. https://doi.org/
10.1080/09593330.2013.788043.
Lee, J., Oh, J., Yoo, S., Jho, E.H., Lee, C., Park, S., 2022. Removal of phosphorus from water using calcium–rich organic waste and its potential as a fertilizer for rice
growth. J. Environ. Chem. Eng. 10, 107367 https://doi.org/10.1016/j.jece.2022.107367.
Li, G., Chen, T., Zhao, Z., Ling, L., Li, Q., Chen, S., 2020. Green and high yield synthesis of CdTe@Hydrotalcite nanocrystals with enhanced photoluminescence
stability toward white light emitting diodes. J. Lumin. 228, 117625 https://doi.org/10.1016/j.jlumin.2020.117625.
Li, H., Cui, S., Tan, Y., Peng, Y., Gao, X., Yang, X., Ma, Y., He, X., Fan, B., Yang, S., Chen, Q., 2022. Synergistic effects of ball–milled biochar–supported exfoliated LDHs
on phosphate adsorption: Insights into role of fine biochar support. Environ. Pollut. 294, 118592 https://doi.org/10.1016/j.envpol.2021.118592.
Li, S., Ma, X., Ma, Z., Dong, X., Wei, Z., Liu, X., Zhu, L., 2021. Mg/Al–layered double hydroxide modified biochar for simultaneous removal phosphate and nitrate from
aqueous solution. Environ. Tech. Innov. 23, 101771 https://doi.org/10.1016/j.eti.2021.101771.
Li, R., Wang, J., Zhou, B., Awasthi, M., Ali, A., Zhang, Z., Gaston, L., Lahori, A., Mahar, A., 2016. Enhancing phosphate adsorption by Mg/Al layered double hydroxide
functionalized biochar with different Mg/Al ratios. Sci. Total Environ. 559, 121–129. https://doi.org/10.1016/j.scitotenv.2016.03.151.
Lin, Z., Chen, J., 2021. Magnetic Fe3O4@MgAl-LDH@La(OH)3 composites with a hierarchical core-shell structure for phosphate removal from wastewater and
inhibition of labile sedimentary phosphorus release. Chemosphere 264, 128551. https://doi.org/10.1016/j.chemosphere.2020.128551.
Lin, Z., Huan, Z., Zhang, J., Li, J., Li, Z., Guo, P., Zhu, Y., Zhang, T., 2022. CTAB–functionalized δ–FeOOH for the simultaneous removal of arsenate and phenylarsonic
acid in phenylarsenic chemical warfare. Chemosphere 292, 133373. https://doi.org/10.1016/j.chemosphere.2021.133373.
Lu, B., Wang, G., Zhao, L., Wang, S.Y., Pan, Z.H., Dong, S.S., 2023. Bimetallic capture sites on porous La/Bi hydroxyl double salts for efficient phosphate adsorption:
multiple active centers and excellent selective properties. Chemosphere 344, 140304. https://doi.org/10.1016/j.chemosphere.2023.140304.
Lu, Z., Zhang, K., Liu, F., Gao, X., Zhai, Z., Li, J., Du, L., 2022. Simultaneous recovery of ammonium and phosphate from aqueous solutions using Mg/Fe modified NaY
zeolite: integration between adsorption and struvite precipitation. Sep. Purif. Technol. 299, 121713 https://doi.org/10.1016/j.seppur.2022.121713.
Luo, G., Bi, Z., Liu, C., Wan, Z., Chen, Z., Chen, M., Huang, Z., 2022. Regenerable neodymium–doped zirconium–based MOF adsorbents for the effective removal of
phosphate from water. J. Environ. Chem. Eng. 10, 108610 https://doi.org/10.1016/j.jece.2022.108610.
Mahapatra, U., Manna, A.K., Chatterjee, A., 2022. A critical evaluation of conventional kinetic and isotherm modeling for adsorptive removal of hexavalent chromium
and methylene blue by natural rubber sludge–derived activated carbon and commercial activated carbon. Bioresour. Technol. 343, 126135 https://doi.org/
10.1016/j.biortech.2021.126135.
Nie, G., Wu, L., Qiu, S., Xu, Z., Wang, H., 2022. Preferable phosphate sequestration using polymer–supported Mg/Al layered double hydroxide nanosheets. J. Colloid
Interf. Sci. 614, 583–592. https://doi.org/10.1016/j.jcis.2022.01.158.
Nuryadin, A., Imai, T., Kanno, A., Yamamoto, K., Sekine, M., Higuchi, T., 2021. Phosphate adsorption and desorption on two–stage synthesized amorphous–ZrO2/
Mg–Fe layered double hydroxide composite. Mater. Chem. Phys. 266, 124559 https://doi.org/10.1016/j.matchemphys.2021.124559.
Perdew, J.P., Burke, K., Ernzerhof, M., 1996. Generalized gradient approximation made simple. Phys. Rev. Lett. 77 (18), 3865–3868. https://doi.org/10.1103/
PhysRevLett.77.3865.
Qing, Z., Qin, Q., Wang, L., Jiang, C., Yang, Z., Liu, Y., Zhang, S., Chen, J., 2024. Rapid and efficient removal of phosphate by La-doped layered double hydroxide/
biochar from aqueous solution. N. J. Chem. 48, 3208. https://doi.org/10.1039/d3nj05213c.
Qiu, S., Zhao, D., Feng, Y., Li, M., Liang, X., Zhang, L., Luo, Y., Zhang, K., Wang, F., 2022. Adsorption performance and mechanism of Ca–Al–LDHs prepared by oyster
shell and pop can for phosphate from aqueous solutions. J. Environ. Manag. 303, 114235 https://doi.org/10.1016/j.jenvman.2021.114235.
Rahman, S., Navarathna, C.M., Krishna Das, N., Alchouron, J., Reneau, P., Stokes, S., Thirumalai, V.K.G., Perez, R., Barbary Hassan, F., Mohan, E., Pittman, D., Mlsna,
T, C.U., 2021. High capacity aqueous phosphate reclamation using Fe/Mg–layered double hydroxide (LDH) dispersed on biochar. J. Colloid Interf. Sci. 597,
182–195. https://doi.org/10.1016/j.jcis.2021.03.114.
Rybka, K., Matusik, J., Marzec, M., 2022. Mg/Al and Mg/Fe layered double hydroxides derived from magnesite and chemicals: the effect of adsorbent features and
anions chemistry on their removal efficiency. J. Clean. Prod. 332, 130084 https://doi.org/10.1016/j.jclepro.2021.130084.
Tee, K.A., Badsha, M.A.H., Khan, M., Wong, K.C.J., Lo, I.M.C., 2022. Lanthanum carbonate nanoparticles confined within anion exchange resin for phosphate removal
from river water: batch and fixed–bed column study. Process Saf. Environ. 159, 640–651. https://doi.org/10.1016/j.psep.2022.01.008.
VanThinh, N., Osanai, Y., Adachi, T., SinhVuong, B.T., Kitano, I., Chung, N.T., Thaie, P.K., 2021. Removal of lead and other toxic metals in heavily contaminated soil
using biodegradable chelators: GLDA, citric acid and ascorbic acid. Chemosphere 263, 127912. https://doi.org/10.1016/j.chemosphere.2020.127912.
Wang, Z., Lu, J., Wu, C., Dan, Y., Li, G., Wu, D., Hu, S., 2022c. Efficient reclamation phosphate by alginate–g–BMOF using poly(N–isopropyl
acrylamide–co–acrylamide) as coating for temperature–responsive slow–release P–fertilizer. Int. J. Biol. Macromol. 201, 437–447. https://doi.org/10.1016/j.
ijbiomac.2022.01.061.
Wang, D., Repo, E., He, F., Zhang, X., Xiang, H., Yang, W., Min, X., Zhao, F., 2022a. Dual functional sites strategies toward enhanced heavy metal remediation:
interlayer expanded Mg–Al layered double hydroxide by intercalation with L–cysteine. J. Hazard. Mater. 439, 129693 https://doi.org/10.1016/j.
jhazmat.2022.129693.
Wang, X., Wu, L., Huang, Y., Li, J., Hua, G., Liu, C., Li, N., Lai, B., 2022b. Efficient removal and selective recovery of phosphorus by calcined La–doped layered double
hydroxides. J. Water Process Eng. 47, 102722 https://doi.org/10.1016/j.jwpe.2022.102722.
Yan, H., Chen, Q., Liu, J., Feng, Y., Shih, K., 2018. Phosphorus recovery through adsorption by layered double hydroxide nano–composites and transfer into a
struvite–like fertilizer. Water Res 145, 721–730. https://doi.org/10.1016/j.watres.2018.09.005.
Yan, L.G., Yang, K., Shan, R.R., Yan, T., Wei, J., Yu, S.J., Yu, H.Q., Du, B., 2015. Kinetic, isotherm and thermodynamic investigations of phosphate adsorption onto
core–shell Fe3O4@LDHs composites with easy magnetic separation assistance. J. Colloid Interf. Sci. 448, 508–516. https://doi.org/10.1016/j.jcis.2015.02.048.
Zhang, Y., Li, M., Zhang, G., Liu, W., Xu, J., Tian, Y., Wang, Y., Xie, X., Peng, Z., Li, A., Zhang, R., Wu, D., Xie, X., 2023. Efficient treatment of the starch wastewater by
enhanced flocculation–coagulation of environmentally benign materials. Sep. Purif. Technol. 307, 122788 https://doi.org/10.1016/j.seppur.2022.122788.
Zhang, Y., Qin, J., Wang, X., Chen, Z., Zheng, X., Chen, Y., 2021. Advanced treatment of phosphorus–containing tail water by Fe–Mg–Zr layered double hydroxide
beads: performance and mechanism. J. Environ. Manag. 296, 113203 https://doi.org/10.1016/j.jenvman.2021.113203.
Zhang, X., Yan, L., Li, J., Yu, H., 2020. Adsorption of heavy metals by L–cysteine intercalated layered double hydroxide: kinetic, isothermal and mechanistic studies.
J. Colloid Interf. Sci. 562, 149–158. https://doi.org/10.1016/j.jcis.2019.12.028.
Zhou, Y., Liu, Z., Bo, A., Tana, T., Liu, X., Zhao, F., Sarina, S., Jia, M., Yang, C., Gu, Y., Zheng, H., Zhu, H., 2020. Simultaneous removal of cationic and anionic heavy
metal contaminants from electroplating effluent by hydrotalcite adsorbent with disulfide (S2–) intercalation. J. Hazard. Mater. 382, 121111 https://doi.org/
10.1016/j.jhazmat.2019.121111.
Zhou, Y., Wang, Y., Dong, S., Hao, H., Li, J., Liu, C., Li, X., Tong, Y., 2022. Phosphate removal by a La(OH)3 loaded magnetic MAPTAC–based cationic hydrogel:
enhanced surface charge density and Donnan membrane effect. J. Environ. Sci. 113, 26–39. https://doi.org/10.1016/j.jes.2021.05.041.
Zhu, S., Asim Khan, M., Wang, F., Bano, Z., Xia, M., 2020. Rapid removal of toxic metals Cu2+ and Pb2+ by amino trimethylene phosphonic acid intercalated layered
double hydroxide: a combined experimental and DFT study. Chem. Eng. J. 392, 123711 https://doi.org/10.1016/j.cej.2019.123711.

16