DOI: 10.1002/ejic.
201701067 Full Paper
Layered Double Hydroxides
Anion Selectivity of Layered Double Hydroxides: Effects of
Crystallinity and Charge Density
Toshiyuki Hibino*[a]
Abstract: Layered double hydroxides (LDHs) have long been
thought to have low selectivity for NO3–. In contrast, it has re-
cently been reported that LDHs with certain compositions show
high selectivity for NO3–. The reason for the high selectivity has
been unclear, although the ion sieve effect has been proposed
as a possible mechanism. Moreover, small LDHs have been re-
ported to show good anion exchanging ability. Given this back-
ground, a systematic study was conducted using Mg-Al LDHs
with two different crystallinities. High-crystallinity LDHs with
lager particle sizes clearly showed selectivity changes that de-
Introduction
Layered double hydroxides (LDHs) have been studied for a long
time as anion adsorbents.[1–5] LDHs are a class of lamellar mate-
rials in which metal hydroxide layers lie on top of each other,
and anions and water molecules are located in the interlayer
space. Although a wide variety of LDHs have been reported in
terms of the constituent metals, the general formula of the
LDHs that have most commonly been studied can be written
as [M2+1–xM3+x(OH)2][An–x/n·mH2O], where M2+, and M3+ are di-
and trivalent metal cations, and An– refers to charge-balancing
anions, which can often be a group of different anions.[6–8] The
fact that interlayer anions are exchangeable enables LDHs to
be used as anion adsorbents.
Nitrate contamination of water has been recognized for
many years as a problem from the standpoint of both human
health and environmental pollution. Associated problems in-
clude methemoglobinemia in the former case and eutrophica-
tion in the latter.[9,10] Infants are especially vulnerable to
methemoglobinemia caused by nitrate pollution of drinking
water. Eutrophication arises from an oversupply of nutrients,
especially phosphorus and nitrogen. Excessive use of fertilizer
and inappropriate disposal of livestock excrement are potential
[a] Environmental Management Research Institute,
National Institute of Advanced Industrial Science and Technology,
16-1 Onogawa, Tsukuba 305-8569, Japan
E-mail: tsyk-hibino@aist.go.jp
http://www.aist.go.jp
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.201701067.
© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. ·
This is an open access article under the terms of the Creative Commons
Attribution-NonCommercial-NoDerivs License, which permits use and distri-
bution in any medium, provided the original work is properly cited, the use
is non-commercial and no modifications or adaptations are made.
Eur. J. Inorg. Chem. 2018, 722–730 722
pended on the Mg/Al molar ratio, compared with low-crystalli-
nity LDHs with smaller particle sizes. When the Mg/Al ratio
increased, selectivity of high-crystallinity LDHs for SO42– and F–
decreased, whereas that for NO3– increased. In the case of F–,
the diameter of which is smaller than the height of the flat
orientation of NO3–, this result indicates that an ion sieve effect
is not the only factor that determines selectivity. Other factors,
such as the interactions of NO3– with the interlayer surface and
with interlayer water, may also be involved.
causes of contamination, as well as discharges of industrial and
municipal wastes.[9–12] Biological treatment, including biological
nitrification and denitrification, is one of the principal methods
for removing nitrogen compounds, but physicochemical treat-
ment, including ion exchange, can sometimes be more effica-
cious in the case of industrial water or potable water.[12]
LDHs, which are anion exchangers, can be used to remove
nitrate from water. Actually, some studies have reported the
potential use of LDHs as adsorbents or reservoirs of
nitrate.[9,10,13–18] However, the selectivity of LDHs for nitrate is
generally considered not to be high, and a large number of
studies have reported that anions with a higher charge density
tend to be more preferentially intercalated into LDHs.[6–8,19,20]
According to a report by Miyata,[19] the order of exchange se-
lectivity for monovalent anions in the case of Mg-Al LDHs (Mg/
Al = 2.3) is OH– > F– > Cl– > Br– > NO3– > I–, and according to
a report by Costa et al.,[20] the order of exchange selectivity
based on a computational simulation with Zn-Al LDHs (Zn/Al =
2) is CO32– > OH– > F– > Cl– > Br– > NO3–. It is therefore very
questionable whether LDHs could be used as nitrate adsorb-
ents. However, several recent studies have reported that certain
LDHs with specific compositions[21–28] show high selectivity for
nitrate ions. Those reports, however, did not address the ques-
tion of whether only the nitrate anion among monovalent
anions and anions of low charge densities has a high affinity
for LDHs under certain conditions. Moreover, the mechanism
responsible for the high selectivity for nitrate ions is still unclear,
although an ion sieve effect related to the constituent cations
and charge density on host layers has been suggested in some
previous studies.[21–26] In those previous studies, only a limited
range of the M2+/M3+ molar ratios was investigated, the effect
of crystallinity or LDH size was only insufficiently examined, and
the behavior of monovalent anions other than NO3– was not
© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Full Paper

clarified. In addition, small LDHs, with crystallite dimensions of
ca. 10 nm, have been reported to exhibit a high anion exchange
ability.[29] It is therefore important to use a systematic approach
that takes account of the size or crystallinity of LDHs to deter-
mine whether some LDHs have a high affinity for nitrate, and if
so, to explore the mechanism.
By comparing the behavior of LDHs that have different crys-
tallinities in adsorption tests using various sets of anions differ-
ent in size and charge density, the present study has revealed
that even LDHs with Mg2+ and Al3+ as the constituent cations,
a combination that is among the most frequently studied,
clearly show high selectivity for nitrate when the charge density
of the host layers is low enough. This study included a system-
atic investigation of the mechanism in terms of the Mg/Al ratio
(the value of which is related to the layer charge density), crys-
tallinity (this is closely related to crystallite size or particle size
in this study), and simultaneous anion adsorption vs. individual
anion adsorption.
ranged from 2.5 to 6.5 (Table 1). These LDHs were Cl-containing
LDHs, and at each Mg/Al molar ratio, two types of LDHs were
prepared: a low-crystallinity LDH and a high-crystallinity LDH.
The low-crystallinity LDHs were obtained by a coprecipitation
method (COP-LDHs), and the high-crystallinity LDHs were ob-
tained by the coprecipitation method followed by a hydrother-
mal treatment (HYD-LDHs). Samples were named according to
the Mg/Al ratio at the preparation stage and the method used
for preparation (Table 1). For example, the sample prepared by
coprecipitation (COP-LDH) with a Mg/Al ratio at the preparation
stage of 2.5:1, was denoted as 251COP-LDH. The X-ray diffrac-
tion (XRD) patterns of the LDHs (Figure 1) revealed that the
basal spacing, d003, for each sample was about 0.8 nm (each
d003 value here was determined from the peak top position[30]).
This value is similar to the spacing of 0.79 nm reported in a
previous study for Cl-containing LDHs with a Mg/Al ratio of
2.3.[19] Scanning electron micrograph (SEM) images (Figure 2
and Figures S1 and S2 in the Supporting Information) show

Table 1. Results of chemical analyses of LDH samples.

Results
Sample Mg/Al at Mg/Al Content (mmol/g)
In this study, the term “adsorption” is used to mean that the in prod-
name preparation Mg2+ Al3+ Cl– CO32–
uct
material holds ions or molecules on the outside surface or on
internal surfaces within the material. LDHs can capture anions 251COP-LDH 2.5 2.29 8.81 3.85 2.64 0.51
through intercalation, but adsorption of anions on the external 31COP-LDH 3.0 2.74 9.37 3.42 2.73 0.53
41COP-LDH 4.0 3.55 10.25 2.89 2.40 0.51
surface of LDHs to some extent cannot be ruled out. When 51COP-LDH 5.0 4.04 10.02 2.48 2.00 0.68
necessary, adsorption on the surface in the interlayer space will 61COP-LDH 6.0 4.28 10.41 2.43 1.95 0.70
be distinguished from that on the external surface. 651COP-LDH 6.5 5.24 10.85 2.07 1.74 0.80
251HYD-LDH 2.5 2.53 9.24 3.65 2.95 0.31
31HYD-LDH 3.0 2.92 9.67 3.32 2.89 0.22
Characterization of the Starting LDHs 41HYD-LDH 4.0 3.59 10.31 2.87 2.55 0.18
51HYD-LDH 5.0 4.22 10.46 2.48 2.27 0.38
LDHs whose constituent cation combination was Mg2+ and Al3+ 61HYD-LDH 6.0 4.90 10.95 2.24 2.03 0.43
651HYD-LDH 6.5 5.77 12.43 2.15 1.85 0.45
were synthesized. Molar Mg/Al ratios at the preparation stage

Figure 1. XRD patterns of the COP-LDH and HYD-LDH series: (a) 251COP-LDH, (b) 31COP-LDH, (c) 41COP-LDH, (d) 51COP-LDH, (e) 61COP-LDH, (f) 651COP-
LDH, (A) 251HYD-LDH, (B) 31HYD-LDH, (C) 41HYD-LDH, (D) 51HYD-LDH, (E) 61HYD-LDH, and (F) 651HYD-LDH. The solid circles indicate peaks associated with
Mg(OH)2, and the arrows indicate (110) peaks. Basal spacing values (d003) are indicated in each case. Intensities of the XRD patterns in the 2θ range from 55
to 70° are enlarged. For each series, the enlargement ratio of the intensity relative to the standard scale of the panel with 2θ range from 2 to 55° is indicated
on the upper-right corner.

Eur. J. Inorg. Chem. 2018, 722–730 www.eurjic.org 723 © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

that the HYD-LDHs consist of separate individual platy particles,
whereas COP-LDHs consist of small platy particles that cohere
tightly together to form masses. The small particles in the COP-
LDHs are difficult to distinguish individually, but their lateral
sizes appear to be roughly 30–100 nm for all Mg/Al ratios. The
fact that the XRD reflection peaks of the HYD-LDHs are sharper
than those of the COP-LDHs indicates that the HYD-LDHs are
more highly crystalline than the COP-LDHs (Figure 1). Crystallite
sizes, D003, (a measure closely linked to platelet thickness) of
the HYD-LDHs are almost twice those of COP-LDHs (Supporting
Information Table S1). As for crystallite sizes D110, which are
closely linked to lateral size, they are difficult to evaluate for
some of the LDHs due to overlapping of (110) and (113) peaks,
but the sharpness of the (110) peaks of HYD-LDHs compared
with those of COP-LDHs clearly suggests that D110 values of
HYD-LDHs are much larger than those of COP-LDHs (Figure 1).
SEM images of HYD-LDHs show that the lateral size of the platy
particles increases with increasing Mg/Al molar ratio at the
preparation stage up to Mg/Al = 4, but at higher ratios the
lateral sizes decrease and reach a minimum for the 61HYD-LDH.
The lateral sizes of most of the particles are about 100–200 nm
for 251HYD-LDH, about 200–300 nm for 41HYD-LDH, and about
100–175 nm for 61HYD-LDH. The lateral sizes seem to be
slightly larger for the 651HYD-LDH than for the 61HYD-LDH
(Figure S2). These above-mentioned results clearly show that
particle sizes of HYD-LDHs are much larger than those of COP-
LDHs, and HYD-LDHs have higher crystallinity than COP-LDHs.
The results of the chemical analyses (Table 1) indicate that the
Cl content is somewhat less than the Al content of each sample.
Figure 2. SEM images of (A) 41COP-LDH and (B) 41HYD-LDH. N.B.: The view
of (A) is magnified more than that of (B).
Eur. J. Inorg. Chem. 2018, 722–730 www.eurjic.org 724
Full Paper
In principle, the sum of the charges of the anions should equal
one unit of charge times the molar Al content, as indicated by
Equation (1).
Σ(charge number) × (quantity of anion) = 1 × (quantity of Al) (1)
The discrepancy is most likely due to carbonate contamina-
tion caused by CO2 in the air during preparation, as reported
previously.[31] In fact, carbonate was detected as listed in
Table 1. Up to a Mg/Al ratio of 3 for COP-LDHs and 4 for HYD-
LDHs at the preparation stage, the total charges of Cl– and
CO32– are almost equal to the molar amounts of Al, but at
higher Mg/Al ratios, the total charges of Cl– and CO32– exceed
the molar amounts of Al. Formation of a kind of basic magne-
sium carbonate on the external surface may be one of the
causes. The molar Mg/Al ratios in the products are smaller than
the molar Mg/Al ratios at the preparation stage (Table 1), and
when samples were synthesized at Mg/Al ratios of 6.0 and 6.5
at the preparation stage, a Mg(OH)2 phase separate from the
LDH is observed in the XRD patterns of the products (Figure 1).
Simultaneous Adsorption of SO42– and NO3–
Changes of removal percentages of anions from the solutions
were measured at targeted times of 2, 8, 15, 24, and 48 h. How-
ever, the exact times lagged the targeted times by at most
about 15 minutes, and the points in Figure 3 were plotted at
the exact times. The removal percentages of both SO42– and
NO3– ions almost reached equilibrium at 8 h (Figure 3) for repre-
sentative LDHs, 31COP-, 31HYD-, and 61HYD-LDHs, and 24 h
was therefore considered long enough to reach equilibrium.
Removal percentages depend on the Mg/Al ratio, as will be
mentioned in this section later. Based on this result, the contact
time for adsorption was set to 24 h.
Simultaneous adsorption of SO42– and NO3– (each at 1 mM
initial concentration) was carried out for both COP-LDHs and
HYD-LDHs (Figure 4). The preparation stage molar Mg/Al ratios
of the LDHs varied from 2.5 to 6.5, and the corresponding Mg/
Al ratios in the products varied from 2.29 to 5.24 for the COP-
LDHs and from 2.53 to 5.77 for the HYD-LDHs. The last two
samples for each COP- and HYD-LDH, which were produced at
the preparation stage Mg/Al ratios of 6.0 and 6.5, contain minor
Mg(OH)2 phases in addition to the LDHs. Mg(OH)2 has been
confirmed to have no influence on this adsorption of SO42– and
NO3–, as will be mentioned in the next section. When the Mg/
Al ratio in the product increases (the charge density of the host
layers decreases), the results for both types of LDHs indicate
that SO42– removals begin to decrease at an Mg/Al ratio of
about 3, and there is an abrupt drop when the Mg/Al ratio
exceeds about 3.5. After that drop, removal percentages be-
come almost constant again at Mg/Al ratios greater than 4.3
and 4.9 for COP-LDHs and HYD-LDHs, respectively. In the case
of NO3– removal, the pattern is opposite to that for SO42– re-
moval. As the Mg/Al ratio in the product increases from about
2.5 to about 3.5, there is a sharp increase of the NO3– removal
percentage for both types of LDHs. Removal percentages be-
come almost constant at Mg/Al ratios greater than about 4. The
changes of the removal percentages are larger for the HYD-
© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Full Paper

Figure 3. Removal percentages of (A) SO42– and (B) NO3– as a function of time (liquid-to-solid ratio = 0.02 g/5 mL; initial concentration = 1 mM each of Na2SO4
and NaNO3).

LDHs than those for the COP-LDHs for both SO42– and NO3– Simultaneous Adsorption of SO42– and F–
adsorption. These differences between COP-LDHs and HYD-
LDHs are also clearly apparent in the values of the distribution Simultaneous adsorption of SO42– and F– (each at 1 mM initial
coefficient, Kd, and separation factor, α, in Table 2 (see detailed concentration) was carried out for both COP-LDHs and HYD-
description in the Supporting Information). LDHs (Figure 5). The LDH samples that were used have prepara-
tion stage Mg/Al ratios of 3–6. When the Mg/Al ratio in the
product increases, SO42– removals by adsorption begin to de-
crease for both types of LDHs when the Mg/Al ratios are about
3–3.5, and they drop abruptly when the Mg/Al ratios exceed
about 3.5. This pattern is the same as that of SO42– removal in
the case of simultaneous adsorption of SO42– and NO3–. The
pattern of F– removal is different from that of NO3– removal in
the case of simultaneous adsorption of SO42– and NO3–. The
percentage removal does not increase with increases of the
Mg/Al ratio. In the case of COP-LDHs, the percentage removal
fluctuates around 85 %. In the case of HYD-LDHs, the percent-
age removal of F– decreases as the Mg/Al ratio increases. The
possible reason why the percentage removal does not decrease
at high Mg/Al ratios for COP-LDHs is adsorption of F– on the
external surface of the COP-LDHs, because analogous fluctua-
Figure 4. Removal percentages as a function of the Mg/Al molar ratio in
tions in adsorption are not observed in the case of the HYD-
product in a study of the simultaneous adsorption of SO42– and NO3– (liquid-
to-solid ratio = 0.02 g/5 mL, initial concentration = 1 mM each of Na2SO4 and LDHs, which are highly crystalline LDHs and would have smaller
NaNO3). external surface areas. In addition, Mg(OH)2 and Al(OH)3 were
each synthesized by titration, during which the products were
Table 2. Results of simultaneous adsorption of SO42– and NO3–. precipitated from solutions. The Mg(OH)2 and Al(OH)3 were
Sample Mg/Al in Kd α[a]
each tested for simultaneous adsorption of SO42–, NO3–, and F–
name product SO42– NO3– under the conditions described in the next section. In that case,
251COP-LDH 2.29 > 105 162 –
for both Mg(OH)2 and Al(OH)3, F– adsorption was observed,
31COP-LDH 2.74 > 105 396 – whereas the amounts of adsorbed SO42– were very small and
41COP-LDH 3.55 7112 1507 0.2 NO3– adsorption was not detected. Therefore, Mg(OH)2- and
51COP-LDH 4.04 1558 1772 1.1 Al(OH)3-like sites on the external surface of COP-LDH crystallites
61COP-LDH 4.28 1058 2115 2.0
may have affected F– adsorption. When the Mg/Al ratio in the
651COP-LDH 5.24 1056 2940 2.8
product is less than 3, the Kd values for SO42– are very high
251HYD-LDH 2.53 > 105 94 – (Table 3), whereas the Kd values for F– are not as high for both
31HYD-LDH 2.92 > 105 413 –
41HYD-LDH 3.59 3430 2311 0.7
the COP- and HYD-LDHs. Values of Kd for the HYD-LDHs de-
51HYD-LDH 4.22 322 5465 17.0 crease for both SO42– and F– with increases of the Mg/Al ratio.
61HYD-LDH 4.90 173 5442 31.5 In the case of COP-LDHs, the Kd for SO42– decreases, as does
651HYD-LDH 5.77 163 4756 29.2 the removal percentage, with increases of the Mg/Al ratio, and
[a] Separation factor = (Kd for NO3–)/(Kd for SO42–). the Kd for F– fluctuates without an obvious trend.

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 Full Paper

used are the same as those used in the previous section. The
pattern of removal for each anion is the same as in the case of
simultaneous adsorption of SO42– and NO3– or of simultaneous
adsorption of SO42– and F–. In other words, addition of F– to
the simultaneous adsorption of SO42– and NO3– did not affect
the pattern of removal of SO42– and NO3–, and addition of NO3–
to the simultaneous adsorption of SO42– and F– did not affect
the pattern of removal of SO42– and F–. The pattern of changes
of the Kd value of each anion is the same as that in the two-
anion adsorption experiments (Table 4): when the Mg/Al ratio
increases, Kd values for SO42–decrease, those for NO3– increase,
those for F– in the case of HYD-LDHs decrease, and those for F–
in the case of COP-LDHs fluctuate. When the Mg/Al ratio in the
product is less than 3, the Kd values of SO42– are very high,
Figure 5. Removal percentages as a function of the Mg/Al molar ratio in the
product in a study of the simultaneous adsorption of SO42– and F– (liquid- whereas the Kd values of F– are not as high, and those of NO3–
to-solid ratio = 0.04 g/10 mL, initial concentration = 1 mM each of Na2SO4 are low. When the Mg/Al ratio is greater than 4, the selectivity
and NaF). for NO3– becomes relatively high compared with the selectivity
for SO42– and F–, especially for the HYD-LDHs. The selectivity
Table 3. Results of simultaneous adsorption of SO42– and F–. for F– is not comparatively high at any Mg/Al ratio.
Sample Mg/Al in Kd α[a] Table 4. Results of simultaneous adsorption of SO42–, NO3–, and F–.
name product SO42– F–
Sample Mg/Al in Kd
31COP-LDH 2.74 > 105 1877 – name product SO42– NO3– F–
41COP-LDH 3.55 7308 916 0.1
51COP-LDH 4.04 1624 1467 0.9 31COP-LDH 2.74 > 105 293 1702
61COP-LDH 4.28 794 1104 1.4 41COP-LDH 3.55 4649 1204 708
51COP-LDH 4.04 1211 1540 1437
31HYD-LDH 2.92 > 105 3831 – 61COP-LDH 4.28 584 1745 1019
41HYD-LDH 3.59 4592 1042 0.2
51HYD-LDH 4.22 467 487 1.0 31HYD-LDH 2.92 > 105 311 2762
61HYD-LDH 4.90 236 399 1.7 41HYD-LDH 3.59 1524 2341 822
51HYD-LDH 4.22 236 4809 375
[a] Separation factor = (Kd for F–)/(Kd for SO42–). 61HYD-LDH 4.90 149 4662 294

Simultaneous Adsorption of SO42–, NO3–, and F–

In the previous two sections, results were reported for the si-
multaneous adsorption of two different anions, either SO42–
and NO3– or SO42– and F–. In this section, simultaneous adsorp-
tion of SO42–, NO3–, and F– (each at 1 mM initial concentration),
which was carried out for both COP-LDHs (Figure 6A) and HYD-
LDHs (Figure 6B), will be presented. The LDH samples that were
Individual Adsorption of SO42–, NO3–, and F–
This section describes the results of experiments in which HYD-
LDHs were contacted with solutions that contained amounts of
anions expected to exceed the anion exchange capacities
(AECs) of the LDHs, in contrast to the experiments described in

Figure 6. Removal percentages as a function of the Mg/Al molar ratio in the product in a study of the simultaneous adsorption of SO42–, NO3–, and F– (liquid-
to-solid ratio = 0.04 g/10 mL, initial concentration = 1 mM each of Na2SO4, NaNO3, and NaF). Results for (A) COP-LDHs and for (B) HYD-LDHs.

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 Full Paper

the previous sections, where the amounts of anions were less
than the calculated AECs.
The patterns of removal of individual anions from solution
are the same as the patterns observed in the cases of the simul-
taneous adsorption experiments. When the Mg/Al ratio in the
product increases, the Kd values of SO42– and F– decrease,
whereas that of NO3– increases (Table 5). However, in the case
of individual anion adsorption, SO42– and F– are adsorbed rela-
tively well in terms of the amount of charge, even when the
Mg/Al ratios are high (Table 5). The ion exchange ratio in
Table 5 is defined as the ratio of the quantities of anions on a
charge basis to the AEC [Equation (2)].
ion exchange ratio = [Σ(charge number) × (quantity of anion)]/
[1 × (quantity of Al)] (2)
Table 5. Results of individual adsorption[a] of SO42–, NO3–, or F–.
the NO3– anions may have been in a flat orientation due to
insufficient amount of NO3– ions. In the cases of the 41 and
51HYD-LDHs, NO3– would have also been in a flat orientation
in the interlayer space. Actually the basal spacing in the case of
41and 51HYD-LDHs remains almost the same as in the case of
31HYD-LDH. In the case of F– adsorption (Figure 7C), the d003
value of the 31HYD-LDH after adsorption is almost the same as
that reported by Miyata (d003 = 0.77 nm, Mg/Al = 2.3).[19] The
31, 41, and 51HYD-LDHs show no obvious differences in basal
spacing, d003, before and after F– adsorption, probably because
the heights of the basal spacing of Cl-containing LDHs and F-
containing LDHs may be determined by the size of the oxygen
atom of the interlayer water molecules. However, in the case of
a Cl-containing LDH, the Cl– ions are reported to be nested into
trigonal pockets of the host layers, which are generated by
close-packed OH– ions.[32]

Sample Mg/Al Ion exchange ratio[b] Kd

in prod- 2– – –
name SO4 NO3 F SO42– NO3– F–
uct
31HYD-LDH 2.92 0.86 0.30 0.84 73 46 195
41HYD-LDH 3.59 0.80 0.51 0.66 72 101 149
51HYD-LDH 4.22 0.62 0.66 0.53 55 151 113
[a] Liquid-to-solid ratio = 0.02 g/5 mL. [b] Ion exchange ratio is the ratio of
the quantity of the adsorbed anion multiplied by its charge number to AEC.
The value of the AEC for each LDH is calculated with the following equation:
AEC = (1 unit of charge) × (quantity of Al).

In the case of Mg-Al LDH, layer charge arises by the substitu-

tion of Al for Mg. In Equation (2), AEC is calculated as the prod-
uct of the charge number difference between Mg2+ and Al3+,
which is one, and the quantity of Al. In the case of individual
adsorption, the ion exchange ratio of SO42– is almost as high as
that of NO3–, even when the Mg/Al ratio in the product is 4.22,
a Mg/Al ratio at which the selectivity for SO42– is far below that
for NO3– in the cases of simultaneous adsorptions. In addition,
the ion exchange ratio of F– at that Mg/Al ratio is not low.
Therefore, the result in Table 5 shows that, in the case of indi-
vidual adsorption, SO42– and F– are adsorbed relatively well,
even when the Mg/Al ratio is high.
The XRD pattern of 31HYD-LDH after individual adsorption
of SO42– shows broad (003) and (006) reflection peaks (Fig-
ure 7A). The basal spacing, d003, calculated from the position of
the top of the (003) peak, is 0.87 nm. This spacing corresponds
to that of the SO42–-exchanged LDH (Mg/Al = 2.3) reported by
Miyata.[19] In addition, after SO42– adsorption, splitting of the
(006) peak towards a lower angle in the case of the 41HYD-LDH
(d006 = 0.42 and 0.40 nm) and a shoulder found at the lower
angle side of the (006) peak in the case of the 51HYD-LDH
indicate that after SO42– adsorption, a portion of those LDHs
has a widened interlayer space. This result implies that SO42–
Figure 7. XRD patterns of HYD-LDHs after individual anion adsorption of (A)
ions can partly pry open the interlayer space at parts where
SO42–, (B) NO3–, and (C) F–. Basal spacing values (d003) are indicated in each
SO42– ions are concentrated, even at Mg/Al ratios of 3.59 and case.
4.22. In the case of NO3– adsorption (Figure 7B), the d003 value
of the 31HYD-LDH after adsorption of NO3– is smaller than that Concerning morphology of LDHs after adsorption of individ-
of a NO3–-exchanged LDH reported previously (d003 = 0.88 nm, ual anions, results of SEM observation showed that the
Mg/Al = 2.3);[19] this difference probably reflects the fact that morphology was not changed as compared with that before
the ion exchange ratio is not high in this study (Table 5), and adsorption (Figure S3).

Eur. J. Inorg. Chem. 2018, 722–730 www.eurjic.org 727 © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Discussion
No obvious change of interlayer space was observed for NO3–
adsorption in the individual adsorption experiment. However,
as mentioned in the Results section, NO3– adsorption by
Mg(OH)2 and Al(OH)3 were not detected under the conditions
of simultaneous adsorption of SO42–, NO3–, and F– (each at
1 mM initial concentration). Therefore, this result implies that
Mg(OH)2- and Al(OH)3-like sites on the external surface of LDHs
do not adsorb NO3–, and that NO3– adsorption proceeds almost
only through intercalation, at least under those conditions.
Moreover, the selectivity change pattern that depended on the
Mg/Al ratio was not changed even in the case of the individual
adsorption experiment. This fact suggests that adsorption of
NO3– in the interlayer space was also dominant in that case.
Consequently, it is most likely that the selectivity of LDHs for
NO3– is determined by reaction in the interlayer space.
In this study, the selectivity of LDHs for NO3– changes when
the Mg/Al ratio changes. This is the reason why different select-
ivities for NO3– were reported previously.[19–28] In the literature,
the interlayer space of LDHs containing NO3– decreases when
the Mg/Al ratio exceeds 3 (d003 changes from about 0.90 nm to
about 0.80 nm),[33–36] and a computational calculation shows
that NO3– ions change their orientation from tilted to flat when
the Mg/Al ratio exceeds 3.[36] When the Mg/Al ratio is greater
than 3, electrostatic interactions may not be strong enough to
intercalate bulky ions such as the SO42– ion preferentially. There-
fore, it is probable that NO3– ions are preferentially adsorbed
when the Mg/Al ratio is greater than 3, because they can take
on a flat orientation. In the case of high-crystallinity LDHs (HYD-
LDHs), due to the larger dimensions of crystallites of HYD-LDHs
compared to those of COP-LDHs, it is likely to be more difficult
to widen the interlayer space to intercalate bulky ions like
SO42– favorably. The Kd values, indeed, indicated a higher pref-
erence for NO3– in the case of HYD-LDHs than in the case of
COP-LDHs when the Mg/Al ratio in product exceeded 4. With
respect to these points, the ion sieve effect seems to explain
the difference between SO42– and NO3– adsorption. However,
the ion sieve effect cannot explain F– adsorption. The diameter
of the F– anion is slightly smaller than the thickness of a flat-
oriented NO3– anion when the dimensions are estimated from
the ionic radii in crystals.[37] Despite the fact that the diameter
of the F– ion is smaller than the thickness of the NO3– ion, the
selectivity for F– in the case of HYD-LDHs decreases as the
Mg/Al ratio increases, as opposed to the pattern observed for
NO3–. Therefore, the ion sieve effect, which was proposed in
previous studies,[21–26] is probably not the only factor that de-
termines selectivity. This is the new finding in this study. Other
factors that determine selectivity may include the interaction
of anions with the OH surface of host layers in interlayer space
and interlayer water molecules.[38,39] NO3– ions in the interlayer
space in a flat orientation at a high Mg/Al ratio would be in a
highly stabilized state due to their preferable size and the
strong interaction among NO3– ions, the LDH host layers, and
interlayer water. That interaction would be similar to hydrogen
bonds, as suggested in simulation studies,[20] and the shape
and size of the NO3– anion would significantly affect such an
interaction.
Eur. J. Inorg. Chem. 2018, 722–730 www.eurjic.org
Full Paper
The above discussion on selectivity for anions concerns inter-
action within the interlayer space, but if the particle size de-
creases to as small as 10 nm, as in the LDHs reported by Kuroda
et al.,[29] the effect on the external surface might be one of the
factors that determines anion selectivity. However, within the
range of LDH sizes in this study, the effect on the external sur-
face did not seem to influence anion selectivity significantly.
Finally, as for the results of individual anion adsorption ex-
periments, the amounts of adsorbed SO42– ions in terms of
charge are close to those of NO3–, even when the Mg/Al ratio
is high, that is, even in the case of the 51HYD-LDH. This result
implies that the effect of the volume of the anion (ion sieve
effect) on intercalation is not so strong in the case of the ad-
sorption of individual anions.
Conclusions
Mg-Al-Cl LDHs were synthesized with two different types of
crystallinity. In this study, high-crystallinity LDHs have larger
particle sizes as compared with low-crystallinity LDHs. First, si-
multaneous adsorption of anions was tested by using three sets
of anions: SO42– and NO3–; SO42– and F–; and SO42–, NO3–, and
F–. The results confirm that the most influential factor for anion
selectivity is the Mg/Al ratio in spite of crystallinity, and changes
in selectivity are more clearly apparent for high-crystallinity
LDHs than for low-crystallinity LDHs. High-crystallinity LDHs
show the following selectivity trends: when the Mg/Al molar
ratio increases, the selectivity for SO42– and F– decreases, while
that for NO3– increases. Next, in the study of the adsorption of
individual anions, which was carried out using high-crystallinity
LDHs and higher concentrations of anions, the patterns of ad-
sorption are also the same as those in the simultaneous adsorp-
tion experiments. In these results, unlike NO3–, F– does not
show high selectivity for highly crystalline LDHs at high Mg/Al
ratios, despite the fact that the diameter of the F– ion is slightly
smaller than the thickness of a flat-oriented NO3– anion. There-
fore, the ion sieve effect, which has been proposed to explain
selectivity in previous reports, is not the only factor that affects
selectivity. There may be involvement of other factors, such as
the interaction with the interlayer surface of host layers and
interlayer water in the case of NO3– selectivity.
Experimental Section
Materials: All chemicals used in this study were of reagent or ana-
lytical grade and were used as received. Ultrapure water, produced
with an ELGA Lab Water Pure lab Flex-3, was used for all procedures.
Synthesis of LDHs: Two types of LDHs, which differed in size and
crystallinity, were used in this study. One type of LDH was synthe-
sized by a coprecipitation method (COP-LDHs), and the other type
was synthesized by coprecipitation method followed by a hydro-
thermal treatment (HYD-LDHs). For both types of LDHs, the follow-
ing aqueous solutions were prepared: Solution A, which consisted
of MgCl2·6H2O, AlCl3·6H2O, and NaCl (Mg2+ + Al3+ = 0.5 M, NaCl =
1 M); and Solution B, which consisted of 2 M NaOH. Molar ratios of
Mg/Al varied from 2.5 to 6.5. An aliquot of 50 mL of Solution A was
added dropwise to 350 mL of water at a rate of 50 mL/h with
stirring; Solution B was added simultaneously to keep the pH at 10.
728 © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The pH was monitored with a pH meter (Eutech, Cyberscan pH110).
The LDH formed during the addition and mixing process. After ad-
dition of Solution A was finished, the mixture continued to be
stirred for 10 min and then was allowed to stand overnight with
container capped. To obtain COP-LDHs, the resulting precipitates
were vacuum filtered and washed with water several times on a
membrane filter (pore size: 0.2 μm). The washed samples were dried
at 110 °C immediately after washing. To obtain HYD-LDHs, each
precipitate obtained by coprecipitation was transferred, together
with its supernatant, to a Teflon vessel within a stainless steel jacket.
The total weight of the precipitate and supernatant was 100 g. The
vessels were tightly closed and placed in an oven at 140 °C for 24 h.
After cooling, the products were washed with water and dried at
110 °C in the same way as described for COP-LDHs. The dried COP-
and HYD-LDHs were ground to a powder with an agate pestle and
mortar.
Adsorption Experiments
Measurements of anion adsorption were carried out in a batch ex-
periment. Each measurement was done in duplicate. LDHs were
distributed into small portions in capped bottles and precisely
weighed. The liquid-to-solid ratio was fixed at 250 mL/g: 5 mL/
0.02 g or 10 mL/0.04 g. For simultaneous adsorption of SO42– and
NO3–, the concentrations of both Na2SO4 and NaNO3 were 1 mM;
for simultaneous adsorption of SO42– and F–, the concentrations of
both Na2SO4 and NaF were 1 mM; and for simultaneous adsorption
of SO42–, NO3–, and F–, the concentrations of Na2SO4, NaNO3, and
NaF were all 1 mM. In the case of individual adsorption, the concen-
tration of Na2SO4, NaNO3, or NaF was 25 mM for the 31HYD-LDH,
20 mM for the 41HYD-LDH, and 16.67 mM for the 51HYD-LDH.
Hence, compared with anion exchange capacities (AECs), the
amounts of anions in the case of simultaneous adsorption were less
than the calculated AECs (about 20–50 % of AECs), whereas those
in the case of individual adsorption exceeded the calculated AECs
(about 160–380 % of AECs). The value of the AEC here for each LDH
was calculated with the following equation: AEC = (1 unit of
charge) × (quantity of Al).
Capped bottles that each contained LDH powder and solution were
immersed in a water bath kept at 25 °C, with occasional shaking by
hand. After a specific time, the mixtures were filtered through syr-
inge filters (pore size: 0.2 μm). Concentrations of SO42– and NO3–
were measured with a Dionex ICS-1500 ion chromatography (IC)
system (IonPac AS22 analytical column, IonPac AG22 guard column,
and a hydrogen carbonate/carbonate eluent). In the case of individ-
ual anion adsorption, filtered solutions were diluted with water be-
fore IC measurements. Concentrations of F– were measured with a
F– ion selective electrode (TOA, F-2021 electrode and TOA, pH/Ion
EC/DO meter) after the filtered solutions had been conditioned ac-
cording to the method reported by Yamada et al.:[40] 25 μL of
1000 mg/L F– standard solution (NaF solution) and 5 mL of total
ionic strength adjustment buffer (TISAB) were each added to 5 mL
of filtered solution, and diluted to 50 mL with water. TISAB was
prepared as follows: 14.3 mL of acetic acid, 14.5 g of NaCl and 1 g
of CyDTA (trans-1,2-Diamino cyclohexane-N,N,N′,N′-tetraacetic acid,
monohydrate) were dissolved and diluted with water to 250 mL,
together with concurrent addition of 2 M NaOH to adjust the pH to
5.2. Measurement errors in removal percentage were within 1 % for
IC and 1.5 % for F– ion selective electrode measurement. In the case
of individual anion adsorption, concentrations of F– were measured
with an IC for the following reason. In IC measurement for F–, inter-
ference of Al3+ must be taken into account, but previous work has
indicated that Al3+ is not detected in the supernatant when a Mg-
Al-Cl LDH is soaked in water.[41] Moreover, it was confirmed in the
Eur. J. Inorg. Chem. 2018, 722–730 www.eurjic.org 729
Full Paper
case of the 41HYD-LDH that there was no difference in the F– con-
centrations measured with the IC and with an ion electrode. Anion
uptake was each calculated from the decrease in the anion concen-
tration relative to that in its corresponding control test. The distribu-
tion coefficient, Kd, is the ratio of the amount of adsorbed anion
per unit weight of adsorbent to the concentration of the anion
remaining in solution, and the Kd values in this study were calcu-
lated from Equation (3):
Kd = (C0 – C)/C × V/m (3)
where C0 was the initial concentration in the solution, C was the
concentration after adsorption, V was the amount of added solution
(mL), and m was the amount of the LDH sample (g).
Characterization: About 0.01 g of each LDH powder was precisely
weighed, and then 5 mL of 0.1 M HNO3 was added to dissolve the
sample. After dissolution, the solutions were each diluted to
100 mL. The concentrations of Mg and Al were determined by
ICP-AES using a Horiba ULTIMA2. For the Cl content, a chloride ion-
selective electrode was used (TOA, CL-2021 electrode and TOA, pH/
Ion EC/DO meter) to measure the Cl– via a modification of the pro-
cedure described in the Japanese Industrial Standards (JIS) K-0102.
Before the measurement, 5 mL of buffer solution (25 g of KNO3 and
12.5 mL of acetic acid were dissolved and diluted with water to
250 mL together with concurrent addition of 2 M NaOH to adjust
the pH to 5.0) was added to 50 mL of each of the above-mentioned
solutions in which LDHs were dissolved. Carbonate contents were
calculated from carbon contents obtained by CHN analysis which
was performed with a Perkin–Elmer 2400II. XRD profiles were re-
corded with a Rigaku Multiflex X-ray diffractometer using Cu-Kα ra-
diation. Crystallite sizes D003 were calculated with the Scherrer
equation: D003 = Kλ/(βcosθ), where λ is the X-ray wavelength, β is
integral breadth, θ is the Bragg angle and 1.0 is used for shape
factor, K, here. In that calculation, stacking disorder was not taken
into account.[30] In the case of samples after adsorption of individ-
ual anions, LDH slurries (sediments) after the adsorption tests were
placed on glass plates without washing and dried at 110 °C for XRD
measurement. The morphologies of the LDH powder samples with
no coating were observed by using a field-emission SEM (Hitachi S-
4700) with a low accelerating voltage of 1.0 kV. In the case of sam-
ples after adsorption of individual anions, the samples for SEM ob-
servation were vacuum filtered and washed with water several
times on a membrane filter (pore size: 0.2 μm), following drying at
110 °C.
Acknowledgments
This work was supported by a grant from the Japan Society for
the Promotion of Science (KAKENHI Grant Number
JP15K00611).
Keywords: Layered compounds · Ion exchange · Layered
double hydroxides · Nitrates · Selectivity · Crystallinity
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Received: September 6, 2017
© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim