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Removal of Aliphatic Amines by NiLa-Layered Double Hydroxide

Nanostructures
Zifan Liu, Zhonglong Yin, Zepeng Zhang, Chao Gao, Zhen Yang, and Weiben Yang*
Cite This: ACS Appl. Nano Mater. 2022, 5, 8120−8130 Read Online

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ABSTRACT: Dimethylamine (DMA) and diethylamine (DEA) as

precursors for the formation of potentially N-nitrosamines are
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widespread in the environment, and the removal of these

disinfection byproduct precursors from water is of great
significance to control the quality of drinking water. In this
study, a three-dimensional hierarchical NiLa-layered double
hydroxide/biochar nanocomposite (NiLa-LDH/BC) was prepared
to remove them from a synthetic solution and real surface water.
NiLa-LDH nanoplatelets endowed the biochar with an improved
porous structure, high functional groups, and more active metal
sites. NiLa-LDH/BC exhibited a high DMA and DEA adsorption
capacity of 46.45 and 40.10 mg g−1, which is 6.31 and 7.85 times
higher than that of BC, respectively. A fixed-bed column
experiment revealed that NiLa-LDH/BC could last for ∼1860 to 2400 bed volumes (BVs) before a breakthrough occurred
(approximately 9 times higher than that of BC). In addition, the leaching test and regeneration and toxicity test of Daphnia magna
demonstrate the high stability (over 88% adsorption capacity after seven adsorption−desorption cycles), extremely low metal
leaching (<0.01 mg g−1), and low toxicity (24h-EC50 and 48h-EC50 of the NiLa-LDH/BC leachates were 13.07 and 6.33%,
respectively). According to material characterization, the main removal mechanism of DMA and DEA by NiLa-LDH/BC was
electrostatic attraction, hydrogen bonding, and complexation. Density functional theory calculations were also applied to evaluate the
DMA and DEA adsorption performance of materials. Overall, this study indicated that three-dimensional hierarchical NiLa-LDH/
BC can be promising in highly efficient removal of N-nitrosamine precursors from real surface water.
KEYWORDS: layered double hydroxide, biochar, N-nitrosamine precursors, adsorption mechanism, application

1. INTRODUCTION various industrial, pharmaceutical, and chemical applications,

Disinfection is one of the methods to protect people from
waterborne diseases in drinking water treatment. However,
disinfectants can react with natural organic matter (NOM),
halides, and other compounds in source water and produce
numerous disinfection byproducts (DBPs) that are harmful to
human health.1 For example, nitrogen-containing disinfection
byproducts (N-DBPs) caused by chloramine disinfection show
higher cytotoxicity and genotoxicity to organisms than
regulated carbonaceous DBPs.2,3 The presence of N-nitros-
amines as an emerging class of N-DBPs in drinking water and
wastewater has received more and more attention because of
their high toxicity and wide distribution.4,5 However, previous
studies demonstrated that the removal of trace N-nitrosamine
was limited because of its polar character and low molecular
weight,6,7 while the removal of N-nitrosamine precursors from
water before disinfecting with chloramines can more effectively
control N-nitrosamines.8,9 N-nitrosamine precursors like
dimethylamine (DMA) and diethylamine (DEA) had been
detected in many rivers, lakes, and some raw waters of drinking
water in the range of 0.2−120 μg L−1,10,11 which can be from
the degradation of proteins and N-containing compounds,
etc.12
Different strategies have been investigated to remove
nitrosamine precursors from natural water sources, such as
flocculation, membrane filtration, and adsorption.8,9,13 Among
these technologies, adsorption was regarded as one of the
simplest to operate and cost-effective techniques to remove N-
nitrosamine precursors.6,7,14 The common adsorbents had
been used to compare their abilities to the removal of
nitrosamine precursors.15,16 However, the studies indicated
that the existing adsorbents, such as activated carbon, resin,
zeolite, etc., presented a relatively low adsorption capacity of
4.0−12.6 mg g−1 to DMA and DEA,16,17 which may come
Received: March 21, 2022
Accepted: June 1, 2022
Published: June 14, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsanm.2c01246

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ACS Applied Nano Materials
Figure 1. Schematic illustration for the synthesis of NiLa-LDH/BC.
from their few effective functional groups on the material.
Several methods have been studied to improve the removal of
N-nitrosamine precursors by adsorbents. The mordenite
zeolite and dealuminated zeolite Na-ZSM-5 have been
shown with higher sorption capacities of DMA than the
other zeolite species.16,18 A pilot-scale study showed high
removal efficiencies (>85%) of nitrosodimethylamine forma-
tion potential by biologically activated carbon.19 In addition,
Fe-modified activated carbon can improve the adsorption
capacity of DEA.20
Nowadays, one of the common modification methods is to
load metal oxides, metal hydroxides, and metal−organic
frameworks on materials, which have a good affinity for
small-molecule pollutants due to abundant functional groups
and metal active sites.21−23 Studies have applied them to
enhance the inhibition of disinfection byproduct formation.
Lately, layered double hydroxides (LDHs), a large class of
inorganic layered materials, have been widely used in the fields
of environment for water purification applications.24−26 The
high surface area, highly tunable interior architecture, and
outstanding anion-exchange ability render LDH promising
adsorbents for both inorganic and organic contaminants.27,28
However, LDH materials prepared by the conventional
methods often appear as aggregated lumps, which limits their
applications. Related research shows that the LDH grown in
situ on the template exhibits a three-dimensional (3D)
hierarchical and open structure.29 The loading of NiLa-LDH
on Fe3O4 nanoparticles could enhance phosphorus removal
and antibacterial performance in secondary wastewater.30
From this viewpoint, the LDH on the original adsorbent can
control the structure of LDH to avoid agglomeration and
improve the removal of N-nitrosamine precursors. In recent
years, using naturally biomass materials as adsorbent templates
to synthesize hierarchical porous materials is a highly desired
method because the biomorphic products usually inherit
intricate microstructures and high adjustability.20 Moreover,
waste biomass adsorbents have also attracted much attention
in the removal of nitrosamines.31 Among them, rice husk, an
agricultural waste biomass, is currently becoming highly
attractive owing to its broad usefulness and potential in
water treatment.32
Ni and La are often used as adsorbents to remove
contaminants due to their strong binding capacity.33,34 In
this study, we decorated a porous/rice straw biochar with
NiLa-layered double hydroxide to create a composite material
for drinking water treatment. We chose DMA and DEA as
experimental targeted pollutants because they are the most
direct and effective precursors of nitrosodimethylamine
(NDMA) and nitrosodiethylamine (NDEA).35 Specifically, a
NiLa-LDH/biochar nanocomposite was synthesized via the in
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situ growth of LDH nanoplatelets on the biochar. Batch
adsorption experiments, i.e., analysis of pH effects, concen-
tration effects, kinetics, isotherms, competing ions, and NOM
effects, were carried out to evaluate the adsorption perform-
ance. The characterizations and experiments were performed
to obtain insight into the DMA and DEA removal mechanisms
by the NiLa-LDH/biochar nanocomposite. Lastly, a fixed-bed
column experiment, leaching test, and regeneration and
toxicity test of Daphnia magna were carried out to evaluate
the feasibility of materials in real water treatment.
2. MATERIALS AND METHODS
2.1. Materials. In the Supporting information, we described the
details of the materials.
2.2. Preparation of Porous Biochar Derived From Rice
Straw (BC). Rice husk was used to prepare the porous biochar
material, according to the procedure reported in the literature.36 The
detailed procedure is presented in the Supporting information.
2.3. Synthesis of Ni-BC, La-BC, and NiLa-LDH. The detailed
procedure is presented in the Supporting information.
2.4. Synthesis of NiLa-LDH/BC. NiLa-layered double hydroxide-
fabricated biochar (designated as NiLa-LDH/BC) was synthesized by
an in situ growth technique.29 The synthesis processes are shown in
Figure 1. Porous biochar (0.5 g) with a size ranging from 80 to 120
mesh was immersed into 50 mL of 0.5, 1.0, 2.0, or 3.0 M LaCl3·7H2O
solution containing 20% (v/v) ethanol and then treated under
ultrasound for 0.5 h. Afterward, the mixture was stirred for 6 h at 60
°C and then 3 h at 30 °C in the flask. The La-saturated porous
biochar was then filtered out and calcined at 350 °C for 1 h using a
tube furnace under a nitrogen-flowing atmosphere. The obtained solid
was designated as La-BC-X, where X denotes the concentration of the
LaCl3·7H2O solution. Specifically, 0.24 g of NiCl2·6H2O and 0.12 g of
urea were dissolved in 30 mL of deionized water. The lanthanum-
modified biochar (0.12 g) was placed in the above solution in an
autoclave at 160 °C for 10 h. After cooling down to room
temperature, the resulting product was first washed with deionized
water until neutral pH, and then, the solid particle was filtered and
dried in air at 60 °C for 12 h. Finally, the synthesized sample was
calcined at 500 °C for 1 h and then washed with deionized water and
dried for 12 h. The obtained material was denoted as NiLa-LDH/BC-
X, where X (mM) is the concentration of LaCl3·7H2O.
2.5. Adsorption Experiments. In the Supporting information,
we described the details of the adsorption experiments.
2.6. Analytical Methods. Fourier transform infrared spectrosco-
py (FTIR, Bruker Vector-22, Germany) was used to record the
functional groups of the material surface in the 500−4000 cm−1 range.
X-ray photoelectron spectroscopy (XPS, ESCALAB Xi+) was used to
analyze the surface composition before and after adsorption. The
specific surface area (SBET), total pore volume (Vtot), and pore size
distribution of samples were measured by N2 adsorption−desorption
tests at 77 K on a physisorption instrument (ASAP 2050). The
thermal stability of materials was determined by thermogravimetric
analysis (TGA, Pyris 1) in air from room temperature to 900 °C at a
heating rate of 10 °C min−1. The elemental compositions were
measured for Ni and La content determination by inductively coupled
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Figure 2. (a) N2 adsorption isotherms and pore size distributions of the pristine BC and NiLa-LDH/BC. (b) TGA−DTG curves of the pristine BC
and NiLa-LDH/BC. (c) XRD patterns of the pristine BC and NiLa-LDH/BC-0.2. SEM images and elemental mapping of the (d) pristine BC and
(e, f) NiLa-LDH/BC-0.2 samples. TEM images of the (g) pristine BC and (h) NiLa-LDH/BC-0.2 samples and (i) HRTEM image of NiLa-LDH/
BC-0.2.
plasma-optical emission spectroscopy (ICP-OES, Varian 720). A
point of zero charge (pHpzc) of the samples was measured through the
ζ potential determination (Malvern Nano-Z, U.K.). The phase
structures of the samples were characterized by X-ray diffractometry
(XRD, D/max 2500 VL/PCX, Japan). The concentration of DMA
and DEA was measured by gas chromatography (GC, 7890B, Agilent
Technologies). Surface morphology was obtained through trans-
mission electron microscopy (TEM, JEM-2100F, Japan). Scanning
electron microscopy (SEM, JEM-7600F, Japan) equipped with
energy-dispersive spectroscopy (EDS) mapping was used to
determine the surface morphology and elemental composition of
the prepared NiLa-LDH/BC.
2.7. Models and Computational Methods. All density
functional theory (DFT) calculations in this study were performed
using a DMol3 program package in Materials Studio.37,38 The
adsorption energy of DMA and DEA molecules on the surface was
calculated by the following equation
BEads = BEsurface + DMA/DEA − (BEsurface + BE DMA/DEA ) (1)
where BEsurface and BEDMA/DEA, respectively, represent the energies of
the substrate surface and the DMA or DEA molecule, and the
BEsurface+DMA/DEA is the total energy of the adsorbate−surface complex.
The negative value of BEads indicates that the process is an exothermic
reaction. A larger BEads absolute value corresponds to a stronger
interaction. And the positive values indicate that adsorption does not
occur.
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3. RESULTS AND DISCUSSION
3.1. Characteristics of BC and NiLa-LDH/BC. The
nitrogen adsorption−desorption isotherms and nonlocalized
density functional theory (NLDFT) pore size distributions of
the BC and NiLa-LDH/BC samples are presented in Figures
2a and S1, respectively. The nitrogen adsorption−desorption
isotherm of NiLa-LDH/BC is the mixture of types I and IV,
which indicates the presence of a microporous and
mesoporous structure. Moreover, the pore size distributions
of the synthesized materials indicated that both micropore
volume and mesopore volume of NiLa-LDH/BC were
obviously increasing compared to BC in the range of 0.6−50
nm. Additionally, as shown in Table S1, the surface area and
total pore volume of BC after modification with lanthanum and
then the in situ growth of LDH presented a step-by-step
improvement. The specific surface areas of La-BC and NiLa-
LDH/BC had an obvious improvement with the reactant’s
concentration increasing from 0.05 to 0.3 mol L−1 and
decreasing with the concentration reaching 0.5 mol L−1. This
was probably because the higher La metal loading led to the
blockage of the pores and then affected the synthesis of LDH,
which caused the reduction of porosity as the concentration of
LaCl3 solution was highly increased. These observations
demonstrated that the development of specific surface areas
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and total pore volumes on NiLa-LDH/BC should be attributed
to the in situ growth of LDH on the carbon surface and pores.
The TGA differential thermogravimetry (DTG) curves of
the BC and NiLa-LDH/BC samples are shown in Figures 2b
and S2. The TGA plots exhibit three stages of weight loss
occurred in the pyrolysis process of pristine BC from 70 to 900
°C. The increase of sample’s weight loss indicated the
development of a porous structure according to the analysis
of nitrogen adsorption−desorption tests. Additionally, the
residual masses of NiLa-LDH/BC-0.05, NiLa-LDH/BC-0.1,
NiLa-LDH/BC-0.2, NiLa-LDH/BC-0.3, and NiLa-LDH/BC-
0.5 were, respectively, 26.51, 30.12, 31.98, 33.33, and 35.09%,
which were attributed to the increasing mass of nickel and
lanthanum. These results demonstrated that the different mass
ratios of metal loading on NiLa-LDH/BC were controlled by
adjusting the reactant concentration. Ni and La of NiLa-LDH/
BC samples measured by inductively coupled plasma-optical
emission spectroscopy (ICP-OES) are presented in Figure S3.
The Ni content accounting for percentage of the total mass of
the NiLa-LDH/BC-0.05, NiLa-LDH/BC-0.1, NiLa-LDH/BC-
0.2, NiLa-LDH/BC-0.3, and NiLa-LDH/BC-0.5 samples was
4.17, 4.40 4.07, 3.93, and 3.96%, respectively, and the
corresponding La content was 0.73, 1.95, 4.48, 5.13, and
6.08%. XPS survey spectra (Figure S4) confirm the presence of
Ni, La, C, O, and N on NiLa-LDH/BC.
To NiLa-LDH/BC-0.05, NiLa-LDH/BC-0.1, NiLa-LDH/
BC-0.2, NiLa-LDH/BC-0.3, and NiLa-LDH/BC-0.5 samples,
the mass ratios (Ni/La) are 13.0, 5.3, 2.1, 1.8, and 1.5,
respectively. The effect of the Ni/La ratios on the adsorption
was investigated with NiLa-LDH/BC at pH 7.5. As shown in
Figure S3b, NiLa-LDH/BC with the Ni/La ratio of about 2
has better adsorption capacities of DMA and DEA, and the
corresponding samples are NiLa-LDH/BC-0.2 and NiLa-
LDH/BC-0.3. For the 50 mg L−1 DMA or DEA solution,
the DEA and DEA adsorption capacities on NiLa-LDH/BC-
0.2 were 38.14 and 34.78 mg g−1, which were almost the same
as NiLa-LDH/BC-0.3. Therefore, NiLa-LDH/BC-0.2 was
selected to further study the adsorption characteristics of
DMA and DEA.
The crystal structure of the BC and NiLa-LDH/BC-0.2
samples was determined by XRD (Figure 2c). It was observed
that two typical diffraction peaks appeared at 2θ = 23 and 43°
in the XRD pattern of BC, corresponding to the (002) and
(110) crystal planes of graphite, respectively.39 Most notably,
the diffraction peaks at 12, 24, 34, and 60° are clearly observed,
which corresponds to the (003), (006), (012), and (110)
reflections of a typical LDH material, indicating the high
crystallinity of the product.29,40 Meanwhile, in the XRD pattern
of NiLa-LDH/BC-0.2, the peaks attributed to La(OH)3,
Ni(OH)2, and NiO appeared compared with uncalcined
NiLa-LDH/BC-0.2, indicating the formation of La(OH)3
and Ni(OH)2 and then the transformation of LDH to the
mixed metal oxides after high-temperature treatment at 500
°C.40
The SEM and TEM studies confirmed the observations from
Brunauer−Emmett−Teller (BET) and XRD. Figure 2a−f
displays the typical morphological characteristics of the BC
and NiLa-LDH/BC-0.2 samples. The surface morphology of
the BC sample is comparatively solid (Figure 2d,e), while that
of the NiLa-LDH/BC-0.2 sample presents the distinctly well-
dispersed layered nanosheets (Figure 2d,g). Notably, the
oriented LDH nanosheets evolved and grew vertically both on
the surface and pore wall of biochar, which formed a 3D
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hierarchical structure like a flower petal. The LDH nanosheets
were assembled with an edge-to-face stacking to form a highly
open structure, which avoided the formation of multilayer
stacks of LDH sheets (Figure S5) and provided more
interaction or bonding sites. These observations are corre-
sponding to the results of N2 adsorption−desorption analysis:
the increase of the specific surface area and pore volume of
NiLa-LDH/BC-0.2 was attributed to the vertical growth of
LDH nanosheets on the biochar surface. EDX mapping
analysis (Figure 2f) confirmed that Ni and La were
homogeneously distributed throughout the biochar. TEM
further demonstrates the detailed structural characteristics of
NiLa-LDH (Figure 2g,h). Meanwhile, LDH nanoplatelets
demonstrate a one-dimensional morphology with a length of
about 100−150 nm and a mean diameter of 15 nm. The high-
resolution transmission electron microscopy (HRTEM) image
shows that lattice fringes correspond to an interplanar distance
of ∼0.268 nm (Figure 2i).
3.2. Adsorption of DMA and DEA. Figure 3 presents the
adsorption capacity of DMA and DEA by the pristine BC, Ni-
Figure 3. Adsorption capacity of DMA and DEA by the pristine BC,
Ni-BC-0.2, La-BC-0.2, NiLa-LDH, and NiLa-LDH/BC-0.2 samples
(initial concentration = 50 mg L−1; pH = 7.5).
BC, La-BC, NiLa-LDH, and NiLa-LDH/BC-0.2 samples. The
DMA and DEA adsorption capacities of NiLa-LDH/BC-0.2
were 39.36 and 35.48 mg g−1, respectively, which were much
higher than those of BC with 5.44 and 3.05 mg g−1. The
improved DMA and DEA removal by NiLa-LDH/BC-0.2 was
attributed to the higher porosity and the existence of NiLa-
LDH. It was remarkable that NiLa-LDH/BC-0.2 exhibited
much more adsorption amounts than NiLa LDH. This
phenomenon illustrates that biochar as a carrier improved
the utilization efficiency of LDH by providing more active
adsorption sites. Meanwhile, the adsorption capacity of NiLa-
LDH on target pollutants before and after ultrasonic dispersion
was compared, and it was found that the adsorption capacity
increased slightly after ultrasonication (Figure S6). This
illustrated that ultrasonic treatment has no obvious improve-
ment on the dispersion of LDH. More interestingly, the
adsorption capacity of DMA and DEA on NiLa-LDH/BC-0.2
is much higher than those of Ni-BC and La-BC, which should
be attributed to the structural advantages of layered double
metal hydroxides compared to single metal hydroxides.
Meanwhile, Ni-BC has a higher adsorption capacity of DMA
and DEA compared to La-BC, which indicates that nickel
hydroxide has a stronger affinity and binding force on DMA
and DEA than lanthanum hydroxide.
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Figure 4. (a) Effect of initial pH on the adsorption capacities of DMA and DEA by the NiLa-LDH/BC-0.2 samples. (b) ζ potential of BC, NiLa-
LDH/BC-0.2, and NiLa-LDH/BC-0.2 used for DMA and DEA removal in the pH range of 3−11. Effect of various competing ions on the
adsorption to (c, e) DEA and (d, f) DMA by NiLa-LDH/BC-0.2. Initial concentration = 50 mg L−1; the concentration of competing ions was
displayed as the molar ratio to DMA or DEA; pH = 7.5.
Figure 4a presents the removal efficiency of DMA and DEA
by NiLa-LDH/BC-0.2 at pH 3, 5, 7, 9, and 11. The DMA and
DEA removal efficiency of the samples increased with the pH
increased from 3 to 11. However, an obvious change in the
removal efficiency of DMA and DEA was observed at pH 3.
More specifically, DMA and DEA exist mainly in cationic form
(over 93%) at pH between 3 and 9, while those are mainly
neutral molecules (over 50%) when the pH is higher than 11
(Figure S7). As illustrated in Figure 4b, the NiLa-LDH/BC-0.2
samples had negative ζ potentials in the pH above 3.8, and the
ζ potentials became more negative as the pH increased from 3
to 11. However, as the pH is 3, the electrostatic repulsion
between aliphatic secondary amines and the positively charged
surface of the samples would result in the reduced removal of
DMA and DEA. On the other hand, with the increase of pH in
the solution, the nonionic form of DMA or DEA accounts for a
larger proportion of the total DMA or DEA, indicating the
decrease of electrostatic attraction. However, the removal
efficiency of DMA and DEA by NiLa-LDH/BC did not
decrease at pH 9−11, reflecting the existence of other forces
besides electrostatic attraction, such as hydrogen bonding,
complexation, etc., which might contribute to the adsorption of
DMA and DEA in nonionic form by NiLa-LDH/BC-0.2.
The inorganic anions (such as SO42−, PO43−, Cl−, NO3−,
and HCO3−) and cations (such as Na+, K+, Ca2+, Mg2+, and
NH4+) ubiquitously coexist in real drinking water samples, and
it is necessary to analyze the interference of these coexisting
competing ions. The effect of ions at a molar ratio on the
adsorption of DMA and DEA by NiLa-LDH/BC-0.2 was
conducted as shown in Figure 4c−f. As observed, the
adsorption capacity of NiLa-LDH/BC-0.2 decreases with the
increasing concentration of coexisting ions. Notably, the
coexistence of Cl−, NO3−, HCO3−, SO42−, K+, and Na+ had
a slight impact on DMA or DEA adsorption onto NiLa-LDH/
BC-0.2 (capacity loss is less than 15%), while the increasing
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PO43−, Ca2+, Mg2+, and NH4+ leads to an observable capacity
loss (over 20%). The coexistence of phosphate might form
complexes with lanthanum and occupy the active sites of
biochar, which resulted in the loss of adsorption capacity.
Moreover, the effect of Ca2+, Mg2+, and NH4+ on the
adsorption should be attributed to the competitive adsorption
of cations and aliphatic secondary amines in water.
Interestingly, the effect of different cations on aliphatic
secondary amines is also different. At the same cationic
concentration, the competing effect of divalent cations Ca2+
and Mg2+ is stronger than that of monovalent cations Na+ and
K+. The presence of NH4+ seems to cause a stronger
competition compared with the other cations, which should
be due to the similarity of NH4+ with DMA and DEA.
Specifically, the −N−H bond of them can be used as a
hydrogen bond donor to form a hydrogen bond with the −OH
bond on the material.
It was reported that natural organic matter (NOM) in water
such as humic acid greatly competes with disinfection
byproduct precursors on the active sites of activated carbon.41
Figure S8 presents the effect of humic acid on the adsorption
process. Compared to coexisting inorganic ions, NOM has a
much smaller inhibitory effect on DMA and DEA adsorption
(capacity loss is less than 5%). Theoretically, NOM should
compete with DMA and DEA through complexation.
However, the mesopores of NiLa-LDH/BC with a lamellar
structure might prevent NOM with a high molecular weight
from entering the inner pore, which protects the inside
adsorption sites of materials from interaction with NOM.
3.3. Adsorption Mechanism. NiLa-LDH/BC adsorbents
before and after adsorption were characterized to reveal their
superior adsorption capacity. First, volatilization from solution
may be one reason for their reduced content because DMA
and DEA have lower boiling points. Therefore, the effects of
different DMA and DEA concentrations, temperatures, and pH
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Figure 5. High-resolution XPS spectra of (a) Ni 2p, (b) N 1s, (c) O 1s, and (d) C 1s of fresh NiLa-LDH/BC-0.2 and NiLa-LDH/BC-0.2 samples
used for the removal of DEA and DMA.
on the stability of DMA and DEA were studied in the solution
(Figure S9). These results indicated that DMA and DEA are
easier to volatilize from water at higher concentrations, and the
pH of the solution and temperature has a greater impact on
their volatilization. When DMA and DEA are trace amounts,
the effects of pH, temperature, and time on those are almost
negligible, which suggest that volatilization from water surfaces
is not expected to be important of the DMA and DEA removal.
As mentioned above, protonation of DMA and DEA
facilitated the electrostatic interactions between these species
and the negatively surface-charged adsorbent. The ζ potential
of NiLa-LDH/BC-0.2 increased after adsorption due to the
accumulation of positively charged DMA and DEA (Figure
4b). However, NiLa-LDH/BC-0.2 still has a higher removal
ratio of DMA and DEA, which indicated that the adsorption of
DMA and DEA involves other mechanisms besides electro-
static interactions. Meanwhile, an interfering ion experiment
exhibited that Mg2+ except for NH4+ is the most intense
interfering ion competing with DMA and DEA for adsorption.
To investigate the contribution of electrostatic attraction to the
adsorption of DMA and DEA onto NiLa-LDH/BC, excessive
Mg2+ (500 mg L−1) is added in the solution to compete with
DMA and DEA adsorption, as shown in Figure S10. With the
increase of Mg2+ concentration, the decreasing trend of the
adsorption capacity of DMA and DEA slowed down and finally
tended to remain unchanged, which illustrated that excessive
Mg2+ competed with DMA and DEA for most electrostatic
adsorption sites (36 and 39% of the original adsorption
capacity, respectively). Thus, the remaining DMA and DEA
adsorption capacity with excessive Mg2+ was mainly ascribed to
the contribution of other mechanisms.
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XPS analysis was conducted with the samples of NiLa-LDH/
BC-0.2 before and after adsorption to elucidate the other
adsorption mechanisms in depth (Figure 5). XPS spectra of Ni
2p indicate two spin−orbit peaks with a binding energy
difference of about 17.8 eV, namely, Ni 2p1/2 (873.8 eV) and
Ni 2p3/2 (856.0 eV), which is close to that of Ni-LDH.42 The
appearance of satellite peaks at 863.85 and 879.65 eV implies
the presence of a high-spin divalent state of Ni2+ in the NiLa-
LDH/BC sample.29,43 It is noteworthy that the XPS spectrum
of NiLa-LDH/BC-0.2 after adsorption is shifted slightly to a
lower binding energy, suggesting an interaction between Ni2+
in the LDH platelets and adsorbates.44 This is due to the
ligand−metal complexation of Ni2+ with secondary amines.45
Additionally, the XPS spectra of La do not exhibit any
significant changes (Figure S11), which indicates that only
Ni2+ has a specific interaction with DMA and DEA in NiLa-
LDH/BC. As presented in Figure 5b, the N 1s spectrum of
NiLa-LDH/BC presented three peaks at binding energies of
398.49, 400.26, and 401.82 eV, which matched to −NC−,
−NH−, and −NH3+, respectively.45,46 After adsorption, the
binding energy at 401.82 eV shifted to 402.1 eV and the peak
area increased from 13.50 to 17.00% and 16.48%, indicating
complexation of Ni2+ to the −NH− groups of aliphatic
secondary amine.45 Additionally, after adsorption of DMA and
DEA, the area percentages of −NH− increased from
approximately 44.85 to 45.97% and 45.81%, respectively.
This result was attributed to the effects of electrostatic
attraction, hydrogen bonding, etc., which pushes DMA and
DEA adsorbing onto the NiLa-LDH/BC-0.2 surface.
The high-resolution O 1s spectra (Figure 5c) deconvoluted
into three subpeaks of −O−, −OH, and H2O at 531.79,
533.04, and 534.17 eV, respectively.47 As shown, the area
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ACS Applied Nano Materials
Figure 6. (a) Contribution of complexation (Q1), hydrogen bonding (Q2), and electrostatic interactions (Q3) to DMA and DEA adsorption. (b)
Adsorption capacity of NiLa-LDH/BC after treatment on DMA and DEA compared with fresh BC and fresh NiLa-LDH/BC (initial concentration
= 50 mg L−1; pH = 7.5).
percentages of −O−, −OH, and H2O on the fresh NiLa-LDH/
BC-0.2 sample were 23.58, 52.98, and 23.44%, respectively.
Importantly, the ratio of −OH after adsorption decreased to
41.20 and 43.17%. The peak area reduction of −OH was due
to hydrogen bonds between hydroxyl groups (−OH) on NiLa-
LDH/BC-0.2 and aliphatic secondary amines.47 The wider and
weakened band of −OH from FTIR spectra (Figure S12)
indicated a decrease in −OH content, which also suggested the
formation of hydrogen bonds between hydroxyl groups and
aliphatic secondary amines. Meanwhile, one of the most
important aspects of H-bonding is determining the H-donor
and H-acceptor. It can be mentioned that −OH is a more
effective H-donor than −NH, and N is a more effective H-
acceptor than O. However, adsorbates and adsorbents can be
protonated and deprotonated under different conditions, and
the pH value of the solution strongly influences adsorption and
the direction of H-bonding. For example, the aliphatic −NH2
groups cannot be the H-acceptor under pH <∼10.5. Therefore,
in the adsorption process of DMA and DEA on NiLa-LDH/
BC, DMA and DEA should be the H-donor.48 In Figure 5d,
the area percentages of C−OH and O−CO on the fresh
NiLa-LDH/BC-0.2 sample were 20.34 and 5.27%, respectively.
After adsorption, the ratios of C−OH decreased to 16.92 and
18.46% and those of O−CO decreased to 4.75 and 4.86%,
respectively.36 This decrease could possibly be due to the
surface interaction between carboxyl groups (COOH) and
hydroxyl (OH) on NiLa-LDH/BC-0.2 and aliphatic secondary
amines. Here, it can be confirmed that NiLa-LDH/BC-0.2 is
capable of interaction with DMA and DEA by surface
functional groups on the BC substrate (i.e., COOH and OH).
Overall, the NiLa-LDH nanosheets on NiLa-LDH/BC are
believed to enhance the DMA and DEA uptake due to a
combination of electrostatic attraction, hydrogen bonding, and
complexation. The adsorption kinetics and isotherms of DMA
and DEA onto NiLa-LDH/BC-0.2 were carried out (Figure
S13). The result demonstrated that the DMA and DEA
adsorption onto NiLa-LDH/BC was better fitted with the
pseudo-second-order reaction, indicating chemical adsorption
(Table S2). In addition, the adsorption isotherm of NiLa-
LDH/BC-0.2 was better fitted with the Langmuir model (R2 =
0.98) rather than the Freundlich (R2 = 0.95) fitting (Table S3),
indicating that the complexation occurred homogeneously over
Ni2+. Moreover, the maximum DMA and DEA adsorption
capacity of 46.45 and 40.10 mg g−1 was obtained, respectively.
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The respective contributions of three forces were approx-
imately identified from adsorption capacities under the stress
of excessive Mg2+ and the analysis of N 1s XPS spectra (Figure
6a). Excessive Mg2+ dominates most electrostatic adsorption
sites, and the remaining adsorption capacity was mainly
attributed to the contribution of hydrogen bonding and
complexation. Meanwhile, the previous analysis of N 1s XPS
spectra can also estimate the contribution of complexation,
hydrogen bonding, and electrostatic attraction (Figure 5b). We
assume that the content of −CN− on the biochar was
almost unchanged during adsorption and calculate the ratio of
increase in peak area for −N− and Ni−NH− to obtain the
proportion of DMA and DEA on adsorption by complexation.
It can be estimated that 47 and 45% of DMA and DEA are
adsorbed through complexation, respectively. Moreover,
according to the peak areas, the higher ratio of Ni−NH−
after DMA adsorption indicates that the surface interaction of
NiLa-LDH/BC-0.2 with DMA is preferred over that with
DEA, which is consistent with the experimental results that the
adsorption capacity of DMA is higher than that of DEA. These
results indicated that the contribution of complexation (47 and
40%) to DMA and DEA is higher than that of hydrogen
bonding (17 and 21%) and electrostatic attraction (36 and
39%). DMA in the form of cations is more likely to be
deprotonated and complex with Ni2+ due to the fact that the
electron-donating ability of ethyl is stronger than that of
methyl. Therefore, the contribution of complexation between
NiLa-LDH/BC and DMA (47%) is higher than that of DEA
(40%).
To identify whether the synthetic process of NiLa-LDH/BC
had the effect on the adsorption of biochar on DMA and DEA,
the fresh NiLa-LDH/BC was placed in the nitric acid solution
(20 wt %) for 24 h to elute the metals on the biochar. As
presented in Figure 6b, the adsorption capacity of the treated
NiLa-LDH/BC to DMA and DEA remained almost the same
as the original BC, and the slightly higher part of adsorption
capacity may be due to the residue of metal oxide. Therefore,
the immobilization of NiLa-LDH provided a significant
contribution to the total capacity. However, the adsorption
capacity of pure NiLa-LDH only accounts for about 55% of
that of NiLa-LDH/BC-0.2, which indicated that the synergistic
effect of BC and NiLa-LDH significantly improved the
adsorption performance of the composite. It is due to the
fact that BC, as a template, can improve the dispersion of
NiLa-LDH, and the extremely strong negative charge on the
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Figure 7. Calculation models of protonated (a, c) DMA and (b, d) DEA adsorption on NiLa-LDH and BC.

Figure 8. (a) Continuous-flow fixed-bed apparatus. (b) Breakthrough curves of the DMA and DEA removal from surface water using NiLa-LDH/
BC-0.2 and BC. (c) Regeneration of NiLa-LDH/BC-0.2 in a synthetic solution (initial concentration = 50 mg L−1; pH = 7.5). (d) Effect of pH on
the leaching of Ni and La by NiLa-LDH/BC-0.2.

surface of BC can also improve the adsorption capacity of
NiLa-LDH to DMA and DEA.
3.4. DFT Calculations. To verify the interaction
mechanism between NiLa-LDH/BC and DMA and DEA
molecules, the adsorption process has been carried out by the
DFT calculations under a Material Studio (MS) computation
platform. Spin-polarized density functional calculations for the
geometry optimization and energy calculations of the
adsorbent and adsorbate were performed utilizing the GGA-
8127
PW91 functional. Figure 7 shows that LDH exhibits stronger
interaction with protonated DMA and DEA than BC.
Furthermore, LDH and BC are more inclined to select the
cationic DMA (LDH-DMA: −62.12 kcal mol−1; LDH-DEA:
−59.40 kcal mol−1; BC-DMA: −27.49 kcal mol−1; BC-DEA:
−26.11 kcal mol−1), which is consistent with the analysis of the
above experimental results. Interestingly, we also found that
the interaction force of LDH and BC on protonated DMA and
DEA is higher than that of unprotonated (Figure S14). The
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ACS Applied Nano Materials
result confirmed the role of electrostatic attraction in the
adsorption process. Overall, theoretical adsorption energies of
fabricated materials show a reasonable match with exper-
imental data and characterization. Therefore, NiLa-LDH-
modified biochar is a very attractive adsorbent in water
treatment containing DMA and DEA.
3.5. Practical Applications. The fixed-bed column is the
most widely used in the adsorption process for water
treatment. The optimized adsorbent NiLa-LDH/BC-0.2 was
tested in a lab-scale fixed-bed column apparatus. The surface
water of the Yangtze River was used to estimate the
applicability of NiLa-LDH/BC-0.2 in the actual water
treatment process. The characteristics of the raw surface
water are provided in Table S4. Pristine BC was also employed
for comparison. Figure 8a,b shows the breakthrough curves of
DMA and DEA removal from the synthetic feeding solution
onto NiLa-LDH/BC-0.2 and BC. When the breakthrough
point of DMA and DEA was set as 25 μg L−1, the effective
treatment volumes of NiLa-LDH/BC-0.2 on DMA and DEA
were ∼2400 and ∼1860 BV, whereas those of BC were only
∼240 and ∼220 BV, respectively. In addition, NiLa-LDH/BC-
0.2 could even bring down the concentration of DMA from
114.62 to 6.40 μg L−1 and that of DEA from 80.47 to 7.74 μg
L−1. The above results indicated that NiLa-LDH/BC-0.2 could
be employed as an effective and durable adsorbent in practical
applications.
An important property of adsorbents is regeneration
possibility. As shown in Figure 8c, after seven cycles of
adsorption−desorption/regeneration, NiLa-LDH/BC-0.2
maintained good adsorption capacities (88% to the initial
DMA adsorption capacity and 91% to the initial DEA
adsorption capacity). Another concern of NiLa-LDH/BC as
the adsorbent for drinking water treatment plant (DWTP) is
Ni and La leaching. The volume of our material per g is
approximately 5.24 mL, so the 2000 BV solution processed by
1 g of NiLa-LDH/BC-0.2 is around ∼10.5 L. Therefore, the
leaching test was performed in batch mode (25 °C, 160 r
min−1) with 0.05 g of adsorbent and 500 mL of surface water.
Samples were taken at 12 h. Figure 8d presents the effect of pH
on the leaching of Ni and La. Ni and La leaching decreased
with the pH increased from 3 to 11. It is remarkable that the
Ni leaching remained almost below 0.01 mg L−1 in the pH
range from 5 to 9, which is even lower than the USEPA’s
maximum contaminant level (MCL) of 100 μg L−1 in drinking
water and the limit of 0.02 mg L−1 established by standards of
China GB5749−2006. The result constituted the maximum Ni
leaching of ∼0.05 mg g−1 adsorbent at pH 7. It should be
noticed that this conservative approach of leaching testing in
batch mode is not the case at field-scale application, where the
contact time would be much lower, and the leaching
equilibrium may never be reached, resulting in even lower
Ni concentration in the effluent.30 The relationship between
the leachates of NiLa-LDH/BC and inhibition of Daphnia
magna is shown in Figure S15. The 24h-EC50 and 48h-EC50 of
the NiLa-LDH/BC leachates were 13.07 and 6.33%,
respectively, which was lower than other biomass materi-
als.49,50
4. CONCLUSIONS
To enhance the removal of N-nitrosamine precursors (DMA
and DEA) in drinking water, a three-dimensional hierarchical
porous NiLa-layered double hydroxide/rice straw biochar
nanocomposite (NiLa-LDH/BC) was synthesized by the in
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situ growth of LDH nanoplatelets on the biochar. The
improved DMA and DEA adsorption performance of NiLa-
LDH/BC compared to that of BC was attributed to a higher
specific surface area, developed micropores and mesopores,
and the existence of NiLa-LDH nanoplatelets, providing a
larger number of adsorption sites. NiLa-LDH/BC showed a
high adsorption capacity of DMA (46.45 mg g−1) and DEA
(40.10 mg g−1) in a synthetic solution and was hardly affected
by changes in pH, ionic strength, coexisting ions, and humic
acid within the common ranges of those in drinking water.
Importantly, we found that electrostatic attraction, hydrogen
bonding, and complexation made the main contribution in the
adsorption of DMA and DEA by the analysis of experiment
and characterization. A further study of the adsorption
mechanisms supported that the surface interaction of NiLa-
LDH/BC with DMA is preferred over that with DEA, which
was verified by DFT calculations. Under typical conditions, the
fixed bed of NiLa-LDH/BC-0.2 could last for ∼1860 to 2400
bed volumes before a breakthrough (25 μg L−1) occurred in
raw surface water. In addition, NiLa-LDH/BC exhibited good
regeneration capabilities during cyclic adsorption−desorption
runs, low metal leaching, and low toxicity, which demonstrated
that NiLa-LDH/BC can be a promising adsorbent for drinking
water treatment.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsanm.2c01246.
Materials; kinetic and isotherm models; TGA/DTG
spectra of NiLa-LDHs/BC-0.05, NiLa-LDHs/BC-0.1,
NiLa-LDHs/BC-0.3, and NiLa-LDHs/BC-0.5 samples;
effect of the concentration of the reaction solution on Ni
or La content and corresponding different Ni/La ratios
on the adsorption capacity; XPS analysis of the porous
NiLa-LDHs/BC-0.2, pH-dependence of DMA and DEA
species; effect of humic acid and Mg2+ on the DMA and
DEA adsorption; FTIR effects of initial pH and
temperature on on the stability of DMA and DEA;
high-resolution XPS spectra of La 3d; comparison of
adsorption kinetics and isotherms of DMA and DEA
onto NiLa-LDHs/BC-0.2, DFT; and relationship
between the leachates of NiLa-LDHs/BC and inhibition
of Daphnia magna (PDF)
LDH model (Cif)
Biochar model (Cif)
■ AUTHOR INFORMATION
Corresponding Author
Weiben Yang − Jiangsu Key Laboratory of New Power
Batteries, Jiangsu Collaborative Innovation Center of
Biomedical Functional Materials, School of Chemistry and
Materials Science, Nanjing Normal University, Nanjing
210023, China; orcid.org/0000-0002-8521-255X;
Email: yangwb007@njnu.edu.cn
Authors
Zifan Liu − Jiangsu Key Laboratory of New Power Batteries,
Jiangsu Collaborative Innovation Center of Biomedical
Functional Materials, School of Chemistry and Materials
Science, Nanjing Normal University, Nanjing 210023, China
https://doi.org/10.1021/acsanm.2c01246
ACS Appl. Nano Mater. 2022, 5, 8120−8130
ACS Applied Nano Materials
Zhonglong Yin − Jiangsu Key Laboratory of New Power
Batteries, Jiangsu Collaborative Innovation Center of
Biomedical Functional Materials, School of Chemistry and
Materials Science, Nanjing Normal University, Nanjing
210023, China
Zepeng Zhang − Jiangsu Key Laboratory of New Power
Batteries, Jiangsu Collaborative Innovation Center of
Biomedical Functional Materials, School of Chemistry and
Materials Science, Nanjing Normal University, Nanjing
210023, China
Chao Gao − Jiangsu Key Laboratory of New Power Batteries,
Jiangsu Collaborative Innovation Center of Biomedical
Functional Materials, School of Chemistry and Materials
Science, Nanjing Normal University, Nanjing 210023, China
Zhen Yang − Jiangsu Key Laboratory of New Power Batteries,
Jiangsu Collaborative Innovation Center of Biomedical
Functional Materials, School of Chemistry and Materials
Science, Nanjing Normal University, Nanjing 210023,
China; orcid.org/0000-0002-6032-3018
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsanm.2c01246
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research was financially funded by the Natural Science
Foundation of China (nos. 52070100 and 51978341).
■
REFERENCES
(1) Li, X. F.; Mitch, W. A. Drinking Water Disinfection Byproducts
(DBPs) and Human Health Effects: Multidisciplinary Challenges and
Opportunities. Environ. Sci. Technol. 2018, 52, 1681−1689.
(2) Watson, K.; Shaw, G.; Leusch, F. D.; Knight, N. L. Chlorine
disinfection by-products in wastewater effluent: Bioassay-based
assessment of toxicological impact. Water Res. 2012, 46, 6069−6083.
(3) Widger, L. R.; Combs, M.; Lohe, A. R.; Lippert, C. A.;
Thompson, J. G.; Liu, K. Selective Removal of Nitrosamines from a
Model Amine Carbon-Capture Waterwash Using Low-Cost Acti-
vated-Carbon Sorbents. Environ. Sci. Technol. 2017, 51, 10913−
10922.
(4) Chen, W.; Chen, Y.; Huang, H.; Lu, Y.; Khorram, M. S.; Zhao,
W.; Wang, D.; Qi, S.; Jin, B.; Zhang, G. Occurrence of N-
Nitrosamines in the Pearl River delta of China: Characterization
and evaluation of different sources. Water Res. 2019, 164, No. 114896.
(5) Zeng, T.; Mitch, W. A. Contribution of N-Nitrosamines and
Their Precursors to Domestic Sewage by Greywaters and Blackwaters.
Environ. Sci. Technol. 2015, 49, 13158−13167.
(6) Sgroi, M.; Vagliasindi, F. G. A.; Snyder, S. A.; Roccaro, P. N-
Nitrosodimethylamine (NDMA) and its precursors in water and
wastewater: A review on formation and removal. Chemosphere 2018,
191, 685−703.
(7) Krasner, S. W.; Mitch, W. A.; McCurry, D. L.; Hanigan, D.;
Westerhoff, P. Formation, precursors, control, and occurrence of
nitrosamines in drinking water: a review. Water Res. 2013, 47, 4433−
4450.
(8) Chuang, Y. H.; Szczuka, A.; Shabani, F.; Munoz, J.; Aflaki, R.;
Hammond, S. D.; Mitch, W. A. Pilot-scale comparison of micro-
filtration/reverse osmosis and ozone/biological activated carbon with
UV/hydrogen peroxide or UV/free chlorine AOP treatment for
controlling disinfection byproducts during wastewater reuse. Water
Res. 2019, 152, 215−225.
(9) Maqbool, T.; Zhang, J.; Li, Q.; Qin, Y.; Chen, L.; Zhang, Z.
Occurrence and fate of N-nitrosamines in three full-scale drinking
8129
www.acsanm.org Article
water treatment systems with different treatment trains. Sci. Total
Environ. 2021, 783, No. 146982.
(10) Sedlak, D. L.; Deeb, R. A.; Hawley, E. L.; Mitch, W. A.; Durbin,
T. D.; Mowbray, S.; Carr, S. Sources and Fate of Nitrosodimethyl-
amine and its Precursors in Municipal Wastewater Treatment Plants.
Water Environ. Res. 2005, 77, 32−39.
(11) Ma, F.; Wan, Y.; Yuan, G.; Meng, L.; Dong, Z.; Hu, J.
Occurrence and source of nitrosamines and secondary amines in
groundwater and its adjacent Jialu River basin, China. Environ. Sci.
Technol. 2012, 46, 3236−3243.
(12) Poste, A. E.; Grung, M.; Wright, R. F. Amines and amine-
related compounds in surface waters: A review of sources,
concentrations and aquatic toxicity. Sci. Total Environ. 2014, 481,
274−279.
(13) Beita-Sandí, W.; Ersan, M. S.; Uzun, H.; Karanfil, T. Removal
of N-nitrosodimethylamine precursors with powdered activated
carbon adsorption. Water Res. 2016, 88, 711−718.
(14) Elwakeel, K. Z. Removal of Reactive Black 5 from aqueous
solutions using magnetic chitosan resins. J. Hazard. Mater. 2009, 167,
383−392.
(15) Xue, R.; Donovan, A.; Zhang, H.; Ma, Y.; Adams, C.; Yang, J.;
Hua, B.; Inniss, E.; Eichholz, T.; Shi, H. Simultaneous removal of
ammonia and N-nitrosamine precursors from high ammonia water by
zeolite and powdered activated carbon. J. Environ. Sci. 2018, 64, 82−
91.
(16) Wu, Q.; Shi, H.; Ma, Y.; Adams, C.; Jiang, H.; Wang, J.;
Eichholz, T.; Timmons, T. Removal of N-nitrosamine precursors in
drinking water system using adsorption methods. Sep. Purif. Technol.
2015, 156, 972−979.
(17) Li, S.; Zhang, X.; Bei, E.; Yue, H.; Lin, P.; Wang, J.; Zhang, X.;
Chen, C. Capability of cation exchange technology to remove proven
N-nitrosodimethylamine precursors. J. Environ. Sci. 2017, 58, 331−
339.
(18) He, Y.; Cheng, H. Degradation of N-nitrosodimethylamine
(NDMA) and its precursor dimethylamine (DMA) in mineral
micropores induced by microwave irradiation. Water Res. 2016, 94,
305−314.
(19) Hanigan, D.; Zhang, J.; Herckes, P.; Krasner, S. W.; Chen, C.;
Westerhoff, P. Adsorption of N-nitrosodimethylamine precursors by
powdered and granular activated carbon. Environ. Sci. Technol. 2012,
46, 12630−12639.
(20) Li, H.; Cui, F.; Zhang, F.; Cui, J.; Meng, Q.; Cheng, J.
Preparation and DEA removal performance of iron-modified activated
carbon. Int. J. Environ. Sci. Technol. 2019, 16, 2927−2936.
(21) Wang, H.; Wang, S.; Chen, Z.; Zhou, X.; Wang, J.; Chen, Z.
Engineered biochar with anisotropic layered double hydroxide
nanosheets to simultaneously and efficiently capture Pb(2+) and
CrO4(2‑) from electroplating wastewater. Bioresour. Technol. 2020,
306, No. 123118.
(22) Yoo, D. K.; Bhadra, B. N.; Jhung, S. H. Adsorptive removal of
hazardous organics from water and fuel with functionalized metal-
organic frameworks: Contribution of functional groups. J. Hazard.
Mater. 2021, 403, No. 123655.
(23) Guleria, A.; Sharma, R.; Shandilya, P. Photocatalytic and
Adsorptional Removal of Heavy Metals from Contaminated Water
using Nanohybrids. Photocatal.: Adv. Mater. Reaction Eng. 2021, 100,
113−160.
(24) Zubair, M.; Ihsanullah, I.; Abdul Aziz, H.; Azmier Ahmad, M.;
Al-Harthi, M. A. Sustainable wastewater treatment by biochar/layered
double hydroxide composites: Progress, challenges, and outlook.
Bioresour. Technol. 2021, 319, No. 124128.
(25) Varadwaj, G. B. B.; Oyetade, O. A.; Rana, S.; Martincigh, B. S.;
Jonnalagadda, S. B.; Nyamori, V. O. Facile Synthesis of Three-
Dimensional Mg-Al Layered Double Hydroxide/Partially Reduced
Graphene Oxide Nanocomposites for the Effective Removal of Pb(2+)
from Aqueous Solution. ACS Appl. Mater. Interfaces 2017, 9, 17290−
17305.
(26) Shandilya, P.; Sharma, R.; Arya, R. K.; Kumar, A.; Vo, D. V. N.;
Sharma, G. Recent progress and challenges in photocatalytic water
https://doi.org/10.1021/acsanm.2c01246
ACS Appl. Nano Mater. 2022, 5, 8120−8130
ACS Applied Nano Materials
splitting using layered double hydroxides (LDH) based nano-
composites. Int. J. Hydrogen Energy 2021, DOI: 10.1016/j.ijhy-
dene.2021.08.190.
(27) Goh, K.-H.; Lim, T. T.; Dong, Z. Application of layered double
hydroxides for removal of oxyanions: a review. Water Res. 2008, 42,
1343−1368.
(28) Zubair, M.; Aziz, H. A.; Ihsanullah, I.; Ahmad, M. A.; Al-Harthi,
M. A. Enhanced removal of Eriochrome Black T from water using
biochar/layered double hydroxide/chitosan hybrid composite:
Performance evaluation and optimization using BBD-RSM approach.
Environ Res. 2022, 209, No. 112861.
(29) Shao, M.; Ning, F.; Zhao, J.; Wei, M.; Evans, D. G.; Duan, X.
Preparation of Fe3O4@SiO2@layered double hydroxide core-shell
microspheres for magnetic separation of proteins. J. Am. Chem. Soc.
2012, 134, 1071−1077.
(30) Vu, C. T.; Wu, T. Magnetic porous NiLa-Layered double
oxides (LDOs) with improved phosphate adsorption and antibacterial
activity for treatment of secondary effluent. Water Res. 2020, 175,
No. 115679.
(31) Gao, K.; Qing, W.; Du, X.; Wei, Q.; Huang, Y. Efficient
adsorption and eco-environmental oxidization of dimethylamine in
Beta zeolite. Microporous Mesoporous Mater. 2019, 282, 219−227.
(32) Moayedi, H.; Aghel, B.; Abdullahi, M. aM.; Nguyen, H.; Safuan,
A.; Rashid, A. Applications of rice husk ash as green and sustainable
biomass. J. Cleaner Prod. 2019, 237, No. 117851.
(33) Zhang, M.; Song, W.; Chen, Q.; Miao, B.; He, W. One-pot
synthesis of magnetic Ni@Mg(OH)2 core-shell nanocomposites as a
recyclable removal agent for heavy metals. ACS Appl. Mater. Interfaces
2015, 7, 1533−1540.
(34) Zhang, Y.; Pan, B.; Shan, C.; Gao, X. Enhanced Phosphate
Removal by Nanosized Hydrated La(III) Oxide Confined in Cross-
linked Polystyrene Networks. Environ. Sci. Technol. 2016, 50, 1447−
1454.
(35) Yang, L.; Chen, Z.; Shen, J.; Xu, Z.; Liang, H.; Tian, J.; Ben, Y.;
Zhai, X.; W, S.; Li, G. Reinvestigation of the Nitrosamine-Formation
Mechanism during Ozonation. Environ. Sci. Technol. 2009, 43, 5481−
5487.
(36) Koilraj, P.; Sasaki, K. Selective removal of phosphate using La-
porous carbon composites from aqueous solutions: Batch and column
studies. Chem. Eng. J. 2017, 317, 1059−1068.
(37) Zhou, K.; Ma, W.; Zeng, Z.; Ma, X.; Xu, X.; Guo, Y.; Li, H.; Li,
L. Experimental and DFT study on the adsorption of VOCs on
activated carbon/metal oxides composites. Chem. Eng. J. 2019, 372,
1122−1133.
(38) Yang, Y.; Liu, J.; Zhang, B.; Liu, F. Mechanistic studies of
mercury adsorption and oxidation by oxygen over spinel-type
MnFe2O4. J. Hazard. Mater. 2017, 321, 154−161.
(39) Cuong, D. V.; Wu, P. C.; Chen, L. I.; Hou, C. H. Active
MnO2/biochar composite for efficient As(III) removal: Insight into
the mechanisms of redox transformation and adsorption. Water Res.
2021, 188, No. 116495.
(40) Li, J.; Zhang, N.; Ng, D. H. L. Synthesis of a 3D hierarchical
structure of γ-AlO(OH)/Mg−Al-LDH/C and its performance in
organic dyes and antibiotics adsorption. J. Mater. Chem. A 2015, 3,
21106−21115.
(41) Zhang, M.; Wang, X.; Du, T.; Wang, H.; Hao, H.; Wang, Y.; Li,
Y.; Hao, T. Effects of carbon materials on the formation of
disinfection byproducts during chlorination: Pore structure and
functional groups. Water Res. 2019, 162, 1−10.
(42) Zhang, J.; Yu, L.; Chen, Y.; Lu, X. F.; Gao, S.; Lou, X. W. D.
Designed Formation of Double-Shelled Ni-Fe Layered-Double-
Hydroxide Nanocages for Efficient Oxygen Evolution Reaction. Adv.
Mater. 2020, 32, No. e1906432.
(43) Zheng, Y.; Cheng, B.; You, W.; Yu, J.; Ho, W. 3D hierarchical
graphene oxide-NiFe LDH composite with enhanced adsorption
affinity to Congo red, methyl orange and Cr(VI) ions. J. Hazard.
Mater. 2019, 369, 214−225.
(44) Liu, M.; He, Q.; Huang, S.; Zou, W.; Cong, J.; Xiao, X.; Li, P.;
Cai, J.; Hou, L. NiCo-Layered Double Hydroxide-Derived B-Doped
8130
www.acsanm.org Article
CoP/Ni2P Hollow Nanoprisms as High-Efficiency Electrocatalysts for
Hydrogen Evolution Reaction. ACS Appl. Mater. Interfaces 2021, 13,
9932−9941.
(45) Mahata, B. K.; Chung, K.-L.; Chang, S.-M. Removal of
ammonium nitrogen (NH4+-N) by Cu-loaded amino-functionalized
adsorbents. Chem. Eng. J. 2021, 411, No. 128589.
(46) Shang, H.; Li, Y.; Liu, J.; Wan, Y.; Feng, Y.; Yu, Y. Preparation
of nitrogen doped magnesium oxide modified biochar and its sorption
efficiency of lead ions in aqueous solution. Bioresour. Technol. 2020,
314, No. 123708.
(47) Zhang, Y.; Tang, Q.; Sun, Y.; Yao, C.; Yang, Z.; Yang, W.
Improved utilization of active sites for phosphorus adsorption in
FeOOH/anion exchanger nanocomposites via a glycol-solvothermal
synthesis strategy. J. Environ. Sci. 2022, 111, 313−323.
(48) Ahmed, I.; Hasan, Z.; Lee, G.; Lee, H. J.; Jhung, S. H.
Contribution of hydrogen bonding to liquid-phase adsorptive removal
of hazardous organics with metal-organic framework-based materials.
Chem. Eng. J. 2022, 430, No. 132596.
(49) Zhang, C.; Shan, B.; Jiang, S.; Tang, W. Effects of the pyrolysis
temperature on the biotoxicity of Phyllostachys pubescens biochar in
the aquatic environment. J. Hazard. Mater. 2019, 376, 48−57.
(50) Oleszczuk, P.; Josko, I.; Kusmierz, M. Biochar properties
regarding to contaminants content and ecotoxicological assessment. J.
Hazard. Mater. 2013, 260, 375−382.
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