Applied Clay Science 173 (2019) 29–34

Contents lists available at ScienceDirect

Applied Clay Science

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

Research paper

Calcium chloride addition to overcome the barriers for synthesizing new Ca- T
Ti layered double hydroxide by mechanochemistry
⁎ ⁎
Jun Qua, Lin Shaa, Zhigao Xua, , Zhengyan Hea, Ming Wua, Chenjie Wua, Qiwu Zhangb,
a
Key Laboratory of Resources Green Conversion and Utilization of the State Ethnic Affairs Commission, Ministry of Education, College of Resources and Environmental
Science, South-Central University for Nationalities, Wuhan 430074, PR China
b
School of Resources and Environment Engineering, Wuhan University of Technology, Wuhan 430070, China

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, a new binary Ca-Ti layered double hydroxide (LDH) has been synthesized for the first time by a
Layered crystal structures two-step (dry and wet) milling of calcium hydroxide, hydrated titanium dioxide and a third phase of calcium
Calcium hydroxide chloride. No reactions were observed while milling calcium hydroxide and hydrated titanium dioxide unless the
Titanium dioxide further addition of a third phase of calcium chloride which triggered the solid state reaction to form LDH phase.
Mechanochemical synthesis
The traditional co-precipitation process failed to synthesize Ca-Ti LDH due to the barriers of the precipitation pH
Ca-Ti layered double hydroxide
and ion radius differences between Ca2+ and Ti4+. The X-ray diffraction (XRD), Thermogravimetric Analysis
(TGA), X-ray photoelectron spectroscopy(XPS) and Scanning electron microscopy (SEM) techniques were ap-
plied to characterize the prepared samples. The characterization results demonstrated the successful production
of high crystalline Ca-Ti LDH phase. This work proved the feasibility of mechanochemistry to produce novel
binary LDH which may be of help for the synthesis of other new layered materials in general.

1. Introduction
Layered double hydroxide (LDH with the chemical formula of
[M1‐x2+Mx3+(OH)2]x+(An‐)x/n− • mH2O in which M2+ and M3+ were
the bivalent and trivalent metal ions respectively) can be manufactured
by either liquid-phase or solid-state processes. Liquid-phase methods
such as co-precipitation by sodium hydroxide, ammonia solution or
urea dominated the routing for the synthesis of LDH because of its good
adaptability for component adjustment, controllability of grain mor-
phology (Kuramoto et al., 2017; Intasa-ard et al., 2018). To form the
structure of LDH, the M2+ and M3+ must have comparable ion radius to
allow isomorphous substitution, which was the widely accepted em-
pirical rule for the synthesis of LDH (Basu et al., 2014). Our previous
work (Qu et al., 2016c) has summarized the existing binary LDH (by
solvent methods) reported in patents and literature. More combination
of different metals could be further explored to synthesize new species
of LDH.
The solvent-free ball milling process (also known as mechan-
ochemical approach) was first reported in the year of 2007 for the
synthesis of MgeAl LDH (Tongamp et al., 2007). Since then, research
work on the LDH mechanochemical preparation and application had
developed rapidly (Qu et al., 2016b; Wang et al., 2016). LieAl, CaeAl,
ZneAl, CueAl, CaeSn LDH have been successfully manufactured
(Ferencz et al., 2014; Qu et al., 2017a,b; Qu et al., 2016a,d) and various
inorganic and organic anions have been intercalated into LDH (Ferencz
et al., 2014; Milanesio et al., 2010), proving that mechanochemistry
could controllably synthesize LDH with different layer constituents and
intercalated anions. Moreover, the mechanochemically prepared LDH
showed better performance for anionic pollutants adsorption and an-
ionic dye photo degradation (Li et al., 2018; Qu et al., 2017c). It was
anticipated that the application of mechanochemically prepared LDH
could be further developed in different areas. However, the existing
work only demonstrate that LDH synthesized by solvent methods can
also be produced through mechanochemistry. Is it possible to synthe-
size fresh species of LDH through mechanochemistry under different
mechanism?
Co-precipitation of different metal ions in water (also can be in-
terpreted as an isomorphous substitution) must be achieved while using
the traditional wet process to form the structure of LDH. Small gaps of
precipitation pH value and ion radius between the metal ions were
essential for the LDH synthesis (Cavani et al., 1991). It would turn out
to be the negative consequences when the metal ions of raw materials
failed to meet these two conditions. To overcome the big precipitation
difference between metals, extremely concentrated base solutions
(≥10 M) was needed (Srankó et al., 2010). Although Ca-Al (Zhang
et al., 2012), Ca-Fe (Pinnavaia et al., 1992) LDH were successfully

⁎
Corresponding authors.
E-mail addresses: xuzhigaotc@126.com (Z. Xu), zhangqw@whut.edu.cn (Q. Zhang).

https://doi.org/10.1016/j.clay.2019.02.017
Received 29 October 2018; Received in revised form 8 February 2019; Accepted 19 February 2019
Available online 12 March 2019
0169-1317/ © 2019 Elsevier B.V. All rights reserved.
J. Qu, et al. Applied Clay Science 173 (2019) 29–34

synthesized using solvent method, no data has been reported for the
synthesis of Ca-Ti LDH as the precipitation pH value of Ti4+ (< 2) was TiO2 Anatase
even lower than that of Fe3+ and Al3+(Haynes, 2014). Eliminating the
negative effects of the precipitation pH value and ions radius differ-

Intensity (a.u.)
ences between the metal ions was the key to manufacturing new binary
LDH. As the solvent-free mechanochemistry operation could enforce
isomorphous substitution and involves no precipitation reaction, it may
theoretically overcome that physical obstacle to prepare brand new
species of LDH.
Milling the hydroxides (Ca(OH)2 and Al(OH)3) produced katoite
phase (Ca3Al2(OH)12) rather than LDH unless a third phase of chloride
or carbonate as the pillared anion was added and ground together. The 10 20 30 40 50 60 70
addition of the third phase induced the occurrence of mechan- 2-theta (°)
ochemically synthetic reaction of LDH. In this work, the Al3+ was Fig. 1. the XRD pattern of the sample prepared by co-precipitation of
substituted by Ti4+ to prepare the new binary Ca-Ti LDH using calcium CaCl2·2H2O and TiCl4 with urea.
hydroxide, hydrated titanium dioxide, and hydrated calcium chloride
as raw materials. Characterization results of the product confirmed a
3. Results and discussion
structure of high crystalline Ca-Ti LDH phase, which was reported for
the first time to the best of our knowledge, demonstrating the feasibility
3.1. Ca-Ti LDH synthesis by co-precipitation
of mechanochemistry to produce new binary LDH.

The traditional solvent process was applied to synthesize the Ca-Ti

LDH by co-precipitation of CaCl2·2H2O and TiCl4 using urea as alkali
2. Experimental procedures
source at 130 °C for 15 h. The obtained dispersion was filtered to collect
the solid for characterization. Fig. 1 shows the XRD pattern of the
2.1. Materials and methods
sample.
The XRD pattern confirmed the phase of anatase TiO2 which came
Ca(OH)2, TiO2·H2O, and calcium chloride dihydrate (CaCl2·2H2O)
from the hydrolysis of TiCl4 (Zhang et al., 2000) with no other identi-
(Sinopharm Group Co Ltd., Shanghai, Analytical reagent) were used as
fied substance. The final pH of the solution after hydrothermal treat-
raw materials without further purification. Mechanochemical operation
ment was about 11 which was not high enough for the precipitation of
was conducted on a planetary ball mill (Pulverisette-7, Fritsch,
Ca2+. Therefore, 1 mol/L NaOH solution was used as precipitant for the
Germany), which has two mill pots (45 cm3 inner volumes each) made
co-precipitation of Ca2+ and Ti4+ according to the reference (Srankó
of zirconia with 7 zirconia balls of 15 mm in diameter. The rotational
et al., 2010). The XRD pattern of the obtained solid was shown in Fig.S7
speed of the planetary ball mill was kept constantly at 600 r/min.
with the main phase of CaCO3 which was caused by the CO2 adsorption
A two-step dry and wet milling operation was applied for the
during the drying operation. This result proved the impossibility of
synthesis of Ca-Ti LDH. In the first dry grinding step, two grams of Ca
Ca2+ and Ti4+ co-precipitation to form the structure of LDH which can
(OH)2, CaCl2·2H2O and TiO2·H2O mixture were ground for 2 h. In the
be explained by the following three reasons:
second wet grinding step, a small amount of water was added into the
milled sample and ground for another 1 h. The obtained samples were
(1) The big precipitation pH value gap between Ca2+ and Ti4+. Fig. 2
gathered and dried in a desiccator (silica-gel drier) for 12 h, then cru-
shows the precipitation value (start and finish pH value) of different
shed into powder in a mortar for the next step of characterization.
metal ions. Ti4+ would be completely precipitated when the pH
The optimization experiments: Ca(OH)2/CaCl2·2H2O molar ratio
value of the solution reached 2. However, Ca2+ would maintain its
optimization experiments, varied the Ca(OH)2/CaCl2·2H2O molar ratio
ionic state until the pH value was 12. The big precipitation pH value
at 3/0, 3/0.5 and 3/1 (Ca/Ti molar ratio was fixed at 2/1 with Ca
gap between Ca2+ and Ti4+ gave no chance for them to co-pre-
(OH)2/CaCl2·2H2O/TiO2·H2O molar ratio at 3/0/1.5, 3/0.5/1.75 and 3/
cipitate, even using urea as alkali source which could create a
1/2 respectively) in the first dry step and then wet milled with 0.3 mL
uniform precipitation environment (Arai and Ogawa, 2009).
water; TiO2·H2O dosage optimization experiments, varied the Ca(OH)2/
CaCl2·2H2O/TiO2·H2O molar ratio at 3/1/3, 3/1/2.5, 3/1/2, 3/1/1.5
(2) Dehydration of Ti hydroxide. LDH could also be synthesized by an
and 3/1/1 and then wet milled with 0.3 mL water. A co-precipitation
“imbibition” process such as LieAl LDH, which Li+ entered the
process using urea as alkali source (according to the urea co-pre-
structure of aluminum hydroxides to form the LDH phase by
cipitation process to prepare ZneTi LDH (Shao et al., 2011)) was also
conducted to synthesize Ca-Ti LDH using CaCl2·2H2O and TiCl4 as raw
0
materials for comparison.

-1
2.2. Characterizations
lg({Mn+}/mol L-1)

-2 Ni2+
Co2+
A Rigaku MAX-RB RU-200B diffractometer (MAX-RB RU-200B,
Rigaku, Japan) using CuKα radiation (λ = 1.5403 Å) was utilized to -3
test the XRD patterns of the samples. Microstructure image of the Fe3+
Cu2+
prepared sample was observed by SEM (JSM-5610LV, JEOL, Japan) -4
Al3+ 3+
Mg2+ Ca2+
spectroscopy. A simultaneous thermal analyzer (STA449F3, NETZSCH, Bi Zn2+
Ti4+
Germany) in nitrogen gas from 30 °C to 1000 °C at a heating rate of -5
20 °C/min was implemented to give the TGA curve of the sample. 0 2 4 6 8 10 12 14
pH

Fig. 2. S-pH curves of different metal ions (log({Mn+}/mol < −5 means

completely precipitation)(Dyer et al., 1998; Haynes, 2014).

30
J. Qu, et al. Applied Clay Science 173 (2019) 29–34

phase (Ca3Al2(OH)12) rather than LDH unless a third phase of chloride

0.12
or carbonate as the pillared anion was added and ground together. Dry
Existed binary LDH
Shannon ions radius of M3+ (nm)
milling of the raw materials to produce the amorphous precursor,
0.11
which was believed to be a displacement solid solution, was essential
for the mechanochemical preparation of LDH. The precursor could be
0.10
quickly transformed into the high crystalline LDH phase. In the case of
MgeAl LDH, the displacement solid solution could be easily achieved
0.09
because of the small difference of ion radius, ion valence and electro-
negativity between Mg2+ and Al3+ (Tan et al., 2012). Ca2+ and Al3+
0.08
failed to meet the conditions (similar ion radius, ion valence and
Ca-Ti electronegativity) for the synthesis of a displacement solid solution and
0.07
Ca-Al tended to form Ca-O-Al chemical bond as tricalcium aluminate hydrate
(Ca3Al2(OH)12). However, the third phase of CaCl2∙2H2O addition helps
0.06
0.06 0.07 0.08 0.09 0.10 0.11 0.12
overcome the big difference between Ca2+ and Al3+ to form an
amorphous precursor in the dry milling process which then formed the
Shannon ions radius of M2+ (nm)
CaeAl LDH in the wet milling process as shown in Fig. S1. The me-
Fig. 3. Shannon ions radius of bivalent M2+ and trivalent M3+ of LDH. chanochemical synthesis of CaeAl LDH proved that milling the hy-
droxides did not result in the formation of LDH phase unless a third
phase substance was added (Qu et al., 2016d). This work replaced Al
thermal motion (Fogg et al., 2002). However, dehydration of Ti
(OH)3 with TiO2·H2O for the purpose of synthesizing Ca-Ti LDH. It was
hydroxide forming stable TiO2 as shown in Fig. 1 made it im-
found that the third phase addition of CaCl2·2H2O was the key to pro-
possible for the formation of LDH phase. The Gibbs free energy of
ducing LDH which was similar to that of the CaeAl LDH mechan-
the Ti hydroxide dehydration reaction was negative, meaning that
ochemical synthesis. Fig. 4 displays the XRD patterns of the samples
dehydration reaction took place spontaneously (Dalun, 2002).
prepared by the dry-wet milling under different Ca(OH)2/CaCl2·2H2O
(3) The big ion radius gap between Ca2+ and Ti4+. The ion radius of
molar ratio, in which the Ca(OH)2/CaCl2·2H2O/TiO2·H2O molar ratio
Ca2+ (0.114 nm) was significantly bigger than that of Ti4+
varied at 3/0/1.5, 3/0.5/1.75 and 3/1/2 (Ca/Ti was fixed at 2/1) re-
(0.075 nm) (Haynes, 2014). Even if co-precipitation of Ca2+ and
spectively in the first dry step and then wet milled with 0.3 mL water.
Ti4+ occurred, the layers would quickly break down because of its
No new phase was observed while milling Ca(OH)2 with TiO2·H2O
metastable state aroused by the big ion radius gap between them.
(sample 3/0/1.5) and the XRD pattern result showed exact high crys-
According to the data in Fig. 2, the easy preparation of CoeTi
talline Ca(OH)2. The ion radius, ion valence and electronegativity gaps
(Saber et al., 2005), ZneTi (Shao et al., 2011), and MgeTi (Sharma
between Ca2+ and Ti4+ were too big to formed a solid solution by the
and Jeevanandam, 2018) LDH by co-precipitation could be ex-
dry milling. When CaCl2·2H2O was involved (sample 3/0.5/1.75), new
plained by their similar precipitation pH value and ion radius. Fig. 3
peaks around 10° (a new phase) in the XRD pattern of the sample
displays the bivalent M2+ and trivalent M3+ Shannon ions radius of
showed up indicating the occurrence of the solid reaction between raw
LDH (Shannon, 1976) and the dashed diagonal represents bivalent
materials. The sample 3/1/2 displayed an entirely new substance pro-
M2+ and trivalent M3+ have an equal value of the Shannon ions
duced by the mechanochemical operation. The d value of the three
radius. The spots in the dotted box represent the existed binary LDH
major XRD diffraction peaks of the new phase were 0.82 nm, 0.41 nm,
such as MgeAl LDH, ZneAl LDH, CueAl LDH, et al. (Qu et al.,
and 0.27 nm respectively which showed clear multiple relationships.
2016c). The spots in the box closely distributed on both sides of the
That multiple relationship was a typical diffraction characteristics of a
dashed diagonal which meant the M2+ and M3+ possessed similar
layered structure proving that the material could be classified as LDH
Shannon ions radius. That was consistent with the so-called “prin-
and also the successful synthesis of novel binary Ca-Ti LDH. The ad-
ciple of similar ionic radius” for the successful preparation of LDH.
dition of third phase of CaCl2·2H2O induced the occurrence of me-
However, two discrete points attributed to CaeAl and Ca-Ti LDH
chanochemically synthetic reaction of LDH.
were observed which was caused by the significantly bigger ion
In Fig. 4, the 3/1/2 sample still observed considerable unreacted
radius of Ca2+ than that of the other metal ions. The third phase
raw materials (the peaks around 18°). More optimization experiments
addition was essential to manufacture CaeAl LDH (Qu et al.,
were needed to be done to achieve the pure phase of Ca-Ti LDH. Fig. 5
2016d), which illustrated that the third phase addition overcame
displays the XRD patterns of the samples prepared by the dry-wet
the drawback of the ion radius difference between Ca2+ and Al3+
milling with different TiO2·H2O dosages in which the Ca/Ti molar ratio
and successfully synthesized CaeAl LDH. Therefore, the mechan-
was fixed at 3/1 and the Ca(OH)2/CaCl2·2H2O/TiO2·H2O molar ratio
ochemical approach with the specific phase addition might elim-
inate the barrier of ion radius gap to synthesize new LDH.
0.82 nm Ca-Ti LDH Ca(OH)2
To sum up, the extensive pH value gap of precipitation blocked the Ca(OH)2/CaCl2 2H2O/TiO2 H2O
co-precipitation reaction; the big ion radius gap resulted in an unstable 0.41 nm
Intensity (a.u.)

layered structure; the dehydration of Ti hydroxide formed stale TiO2 0.27 nm

preventing ion diffusion. It was unlikely to synthesize Ca-Ti LDH by 3/1/2
solvent methods. The mechanochemical process involved no solvent
indicating no precipitation pH value difference interference on the LDH 3/0.5/1.75
synthesis. With the specific phase addition, it could overcome the
drawback arisen by the ion radius difference of different metal ions.
3:0:1.5
Therefore, manufacturing new LDH by the mechanochemical methods
possessed great possibility.
0 10 20 30 40 50 60 70 80 90
2-theta (°)
3.2. Ca-Ti LDH synthesis by mechanochemistry
Fig. 4. XRD patterns of the samples prepared by the dry-wet milling with dif-
Milling the hydroxides (Ca(OH)2 and Al(OH)3) produced katoite ferent CaCl2·2H2O dosage.

31
J. Qu, et al.
Ca-Ti LDH [CaCl2 Ca(OH)2 H2O]
Ca(OH)2
Intensity (a.u.) Ca(OH)2/CaCl2 2H2O/TiO2 H2O
0 10 20 30 40 50 60
2-theta (°)
Fig. 5. XRD patterns of the samples prepared by the dry-wet milling with dif-
ferent TiO2·H2O dosage.
varied at 3/1/3, 3/1/2.5, 3/1/2, 3/1/1.5, and 3/1/1. The XRD pattern
of sample 3/1/1 confirmed the formation of three phases: Ca-Ti LDH,
unreacted Ca(OH)2 and [CaCl2·Ca(OH)2·H2O] mixed salt which in-
dicated insufficient addition of TiO2·H2O. An Amorphous substance and
a pure phase of [CaCl2·Ca(OH)2·H2O] mixed salt were obtained when Ca
(OH)2/CaCl2·2H2O/TiO2·H2O molar ratio was 3/1/2.5 and 3/1/3 re-
spectively. The XRD data clarified the easy occurrence of the [CaCl2·Ca
(OH)2·H2O] mixed salt when TiO2·H2O was insufficiently or over added.
The XRD pattern of the 3/1/1.5 sample showed high crystalline Ca-Ti
LDH phase but with small amount of unreacted raw Ca(OH)2 and
TiO2·H2O as shown in Fig.S4. More work was conducted to synthesize
pure Ca-Ti LDH by increasing the amount of used water in the second
wet-milling process and the XRD patterns were shown in Fig. S5. The
peaks attributed to the Ca(OH)2 (peak in the box in Fig. S5) gradually
disappeared with the increasing of water addition. Fig. S6 displayed the
XRD patterns of raw materials and Ca-Ti LDH with 1 mL water. The d
values of the peaks in the sample (3/1/1.5 with 1 mL H2O) were 8.32,
4.15, 3.52, 3.88, 3.02, 2.92, 2.87, 2.77, 2.66, 2.5, 2.42, 2.35, 2.29, 2.21,
2.19, 1.99, 1.95, 1.89, 1.85, 1.79, 1.75, 1.68, 1.65. The tree major peaks
of Ca(OH)2, [CaCl2·Ca(OH)2·H2O] and TiO2∙H2O were (2.63, 4.94,
1.92), (2.34, 3.17, 1.92) and (3.52, 1.89, 2.37) respectively. Results
showed that more or less of TiO2·H2O could be found in the sample with
1 mL water which could be explained by the high stable property of
TiO2·H2O with low chemical activity.
Fig. 6 exhibits the SEM images of the prepared sample with Ca
(OH)2/CaCl2·2H2O/TiO2·H2O at 3/1/1.5 to show the microstructure of
Ca-Ti LDH. The sample presented a layered morphology and aggregated
together forming micron-grade particles because of the existence of
water which was similar to that of other LDH manufactured by me-
chanochemistry (Tongamp et al., 2008).
The X-ray electron spectra of raw TiO2·H2O and Ca-Ti LDH were
tested and the Ti2p level were given in Fig. 7. The Ti2p level of Ca-Ti
LDH was 0.93 eV lower than that of TiO2·H2O. This was due to the
formation of Ca-O-Ti chemical bonds (Avvakumov et al., 2001) which
Applied Clay Science 173 (2019) 29–34
Ti2p
3/1/3 Ca-Ti LDH
Counts (a.u.)
3/1/2.5 TiO2
3/1/2
3/1/1.5
Ti2p
3/1/1
70 80
466 464 462 460 458 456
Binding Energy (eV)
Fig. 7. X-ray photoelectron spectra of the Ti2p level in raw TiO2·H2O and Ca-Ti
LDH.
was the basic chemical bonds in LDH sheets. The data of XPS proved the
reaction between calcium compounds and hydrated titanium dioxide
forming a layered double hydroxide hydrate which could be defined as
LDH.
The above data proved that the solvent-free ball milling process
indeed avoided the drawback of precipitation pH value and ion radius
differences of Ca2+ and Ti4+ on the synthesis of LDH and successfully
produced new binary Ca-Ti LDH.
3.3. Solid-state reaction pathways
The XRD and TGA characterization techniques were applied to il-
lustrate the solid state reaction pathway in the ball mill process. Fig. 8
depicts the XRD patterns of the intermediate prepared by dry milling
and the Ca-Ti LDH prepared by the dry-wet milling process. The dry
milling sample showed a low crystalline phase of LDH illustrating the
formation of the basic structure of LDH. After the addition of water, the
crystallinity of LDH increased and finally formed LDH layered structure.
Fig. 9 exhibits the TGA curves of the raw materials, the precursor
prepared by dry milling and the Ca-Ti LDH. Raw materials showed a
three-stage mass loss characteristic according to the temperature: de-
hydration of CaCl2•2H2O and TiO2·H2O with 10.2% mass loss at
30–350 °C, completely dehydration of TiO2·H2O forming anatase with
3.63% mass loss at 350–500 °C, Ca(OH)2 to CaO with 4.35% mass loss
at 500–600 °C and the dechlorination of CaCl2 with 1.39% mass loss at
600–1000 °C. After the milling operation, both the precursor and LDH
exhibited a continuous mass loss characteristic which was the typical
TGA feature of LDH. The total mass loss of precursor was higher than
that of the raw materials which may be caused by moisture absorption
during the test because the dry milling operation transformed the raw
material into activated state possessing extraordinary adsorption ac-
tivity. The mass loss of LDH was 23.64% which was higher than that of
Fig. 6. The SEM images of the Ca-Ti LDH.
32
J. Qu, et al.
Ca-Ti LDH
Intensity (a.u.)
Dry-wet milling
0 10 20 30 40 50
2-theta (°)
Fig. 8. XRD patterns of the intermediate prepared by dry milling and the Ca-Ti
LDH prepared by the dry-wet milling process.
Mass loss /%
5% mass loss
0 200 400 600
Temperature /
Fig. 9. the TG patterns of the raw materials, the precursor prepared by dry
milling and the Ca-Ti LDH.
the precursor (22.44%) indicating the precursor reacted with water to
form LDH phase. TGA data in Fig. 8 is consistent with XRD data in Fig. 7
which the dry milling induced solid reaction of raw material to con-
struct the basic structure of LDH and the wet milling realized the re-
action between water and the precursor to form high crystalline Ca-Ti
LDH.
Combing the XRD,TGA and XPS data, it could be concluded that the
dry milling process realized the formation of LDH elementary structure
as in Eq. (1):
dry
3Ca(OH)2 + 1.5TiO2 ·H2O + CaCl2•2H2 O → Ca 4 Ti1.5 (OH)12 Cl2·0.5H2 O
The wet milling induced the reaction between the precursor and
water to produce high crystalline Ca-Ti LDH as in Eq. (2):
wet
Ca 4 Ti1.5 (OH)12 Cl2·0.5H2 O + xH2 O → Ca 4 Ti1.5 (OH)12 Cl2·(0.5 + x)H2 O
The whole solid-state reaction, Ca(OH)2, CaCl2·2H2O, TiO2·H2O, and
water reacted with each other during balling milling process to con-
struct Ca-Ti LDH as in Eq. (3)
3Ca(OH)2 + 1.5TiO2 ·H2O + CaCl2•2H2 O + xH2 O
dry − wet
→ Ca 4 Ti1.5 (OH)12 Cl2·(0.5 + x)H2 O
The co-precipitation process failed to synthesize Ca-Ti LDH because
of the big precipitation pH value and ion radius differences between
Ca2+ and Ti4+. The mechanochemistry process overcame those barriers
to produce new binary Ca-Ti LDH. This work clearly demonstrated the
feasibility of mechanochemistry to produce novel LDH.
Applied Clay Science 173 (2019) 29–34
4. Conclusions
The results in this paper clearly confirmed that Ca-Ti LDH cannot be
manufactured by the solvent methods due to the negative effects of the
precipitation pH value and ion radius differences between Ca2+ and
Ti4+. A two-step solvent-free mechanochemical process was introduced
to overcome those barriers to produce Ca-Ti LDH. It was noted that the
addition of the third phase of CaCl2·2H2O induced the occurrence of
Dry milling mechanochemically synthetic reaction of LDH and was essential for the
successful preparation of Ca-Ti LDH. The data reported in this work
clearly demonstrated that the mechanochemical approaches possessed
60 70 80 the ability to increase the diversity of LDH for its wider application
area.
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.clay.2019.02.017.
Acknowledgements
This work was supported by the Fundamental Research Funds for
the Central Universities, South-Central University for Nationalities
[grant No. YZZ18012, CZQ19015, CZP19002], the Scientific Research
Foundation of South-Central University for Nationalities [grant No.
YZZ16002], The National Natural Science Foundation of China [grant
NO. 51734001].
Raw materials
References
Precursor
Arai, Y., Ogawa, M., 2009. Preparation of Co–Al layered double hydroxides by the hy-
LDH drothermal urea method for controlled particle size. Appl. Clay Sci. 42, 601–604.
Avvakumov, E.G., Avvakumov, G.V., Senna, M., Kosova, N.V., 2001. Soft
Mechanochemical Synthesis: A Basis for New Chemical Technologies. Springer
800 1000 Science and Business Media, Germany, pp. 176–178 (chapter 8).
Basu, D., Das, A., Stöckelhuber, K.W., Wagenknecht, U., Heinrich, G., 2014. Advances in
layered double hydroxide (LDH)-based elastomer composites. Prog. Polym. Sci. 39,
594–626.
Cavani, F., Trifiro, F., Vaccari, A., 1991. Hydrotalcite-type anionic clays: preparation,
properties and applications. Catal. Today 11, 173–301.
Dalun, Y., 2002. Thermodynamic Data Directory of Inorganic Matter Beijing.
Metallurgical Industry Press.
Dyer, J.A., Scrivner, N.C., Dentel, S.K., 1998. A practical guide for determining the so-
lubility of metal hydroxides and oxides in water. Environ. Prog. 17 (1), 1–8.
Ferencz, Z., Szabados, M., Ádok-Sipiczki, M., Kukovecz, Á., Kónya, Z., Sipos, P., Pálinkó,
I., 2014. Mechanochemically assisted synthesis of pristine Ca(II)Sn(IV)-layered
double hydroxides and their amino acid intercalated nanocomposites. J. Mater. Sci.
49, 8478–8486.
Fogg, A.M., Freij, A.J., Parkinson, G.M., 2002. Synthesis and anion exchange chemistry of
rhombohedral Li/Al layered double hydroxides. Chem. Mater. 14, 232–234.
Haynes, W.M., 2014. CRC Handbook of Chemistry and Physics. CRC press.
Intasa-ard, S.G., Imwiset, K.J., Bureekaew, S., Ogawa, M., 2018. Mechanochemical
methods for the preparation of intercalation compounds, from intercalation to the
formation of layered double hydroxides. Dalton Trans. 47 (9), 2896–2916.
Kuramoto, K., Intasa-Ard, S.G., Bureekaew, S., Ogawa, M., 2017. Mechanochemical
synthesis of finite particle of layered double hydroxide-acetate intercalation com-
(1) pound: swelling, thin film and ion exchange. J. Solid State Chem. 253, 147–153.
Li, Z., Zhang, Q., Liu, X., Wu, L., Hu, H., Zhao, Y., 2018. One-step mechanochemical
synthesis of plasmonic Ag/Zn–Al LDH with excellent photocatalytic activity. J. Mater.
Sci. 53, 12795–12806.
Milanesio, M., Conterosito, E., Viterbo, D., Perioli, L., Croce, G., 2010. New efficient in-
tercalation of bioactive molecules into layered double hydroxide materials by solid-
state exchange: an in situ XRPD study. Cryst. Growth Des. 10, 4710–4712.
(2) Pinnavaia, T.J., Amarasekera, J., Polansky, C.A., 1992. Layered Double Hydroxide
Sorbents for the Removal of SOx from Flue Gas and Other Gas Streams. Google
Patents.
Qu, J., He, X., Wang, B., Zhong, L., Wan, L., Li, X., Song, S., Zhang, Q., 2016a. Synthesis of
Li–Al layered double hydroxides via a mechanochemical route. Appl. Clay Sci. 120,
24–27.
Qu, J., Li, X., Lei, Z., Li, Z., Chen, M., Zhang, Q., 2016b. Mechano-hydrothermal synthesis
of tetraborate pillared Li-Al layered double hydroxides. J. Am. Ceram. Soc. 99,
1151–1154.
(3) Qu, J., Zhang, Q., Li, X., He, X., Song, S., 2016c. Mechanochemical approaches to syn-
thesize layered double hydroxides: a review. Appl. Clay Sci. 119, 185–192.
Qu, J., Zhong, L., Li, Z., Chen, M., Zhang, Q., Liu, X., 2016d. Effect of anion addition on
the syntheses of Ca–Al layered double hydroxide via a two-step mechanochemical
process. Appl. Clay Sci. 124–125, 267–270.
Qu, J., He, X., Chen, M., Hu, H., Zhang, Q., Liu, X., 2017a. Mechanochemical synthesis of
Cu-Al and methyl orange intercalated Cu-Al layered double hydroxides. Mater. Chem.
Phys. 191, 173–180.
33
J. Qu, et al.
Qu, J., He, X., Chen, M., Huang, P., Zhang, Q., Liu, X., 2017b. A facile mechanochemical
approach to synthesize Zn-Al layered double hydroxide. J. Solid State Chem.
250, 1–5.
Qu, J., He, X., Li, X., Ai, Z., Li, Y., Zhang, Q., Liu, X., 2017c. Precursor preparation of Zn-
Al layered double hydroxide by ball milling for enhancing adsorption and photo-
catalytic decoloration of methyl orange. RSC Adv. 7, 31466–31474.
Saber, O., Hatano, B., Tagaya, H., 2005. Preparation of new layered double hydroxide,
Co-TiLDH. J. Incl. Phenom. Macrocycl. Chem. 51, 17–25.
Shannon, R., 1976. Revised effective ionic radii and systematic studies of interatomic
distances in halides and chalcogenides. Acta Crystallogr. A 32, 751–767.
Shao, M., Han, J., Wei, M., Evans, D.G., Duan, X., 2011. The synthesis of hierarchical
Zn–Ti layered double hydroxide for efficient visible-light photocatalysis. Chem. Eng.
J. 168, 519–524.
Sharma, U., Jeevanandam, P., 2018. Layered double hydroxides as precursors to Ti4+
doped MgO nanoparticles with tunable band gap. J. Nanosci. Nanotechnol. 18,
264–278.
Srankó, D., Pallagi, A., Kuzmann, E., Canton, S.E., Walczak, M., Sápi, A., Kukovecz, Á.,
34
Applied Clay Science 173 (2019) 29–34
Kónya, Z., Sipos, P., Pálinkó, I., 2010. Synthesis and properties of novel Ba (II) Fe (III)
layered double hydroxides. Appl. Clay Sci. 48 (1–2), 214–217.
Tan, Q., Yin, W., Liu, L., Li, X., 2012. Synthesis of nano-hydrotalcite by mechan-
ochemistry/crystallization. J. Northeast. Univ. 33 (4), 576–579.
Tongamp, W., Zhang, Q., Saito, F., 2007. Preparation of meixnerite (Mg–Al–OH) type
layered double hydroxide by a mechanochemical route. J. Mater. Sci. 42, 9210–9215.
Tongamp, W., Zhang, Q., Saito, F., 2008. Mechanochemical route for synthesizing nitrate
form of layered double hydroxide. Powder Technol. 185, 43–48.
Wang, B., Qu, J., Li, X., He, X., Zhang, Q., 2016. Precursor preparation to promote the
adsorption of Mg-Al layered double hydroxide. J. Am. Ceram. Soc. 99, 2882–2885.
Zhang, Q., Gao, L., Guo, J., 2000. Effects of calcination on the photocatalytic properties of
nanosized TiO2 powders prepared by TiCl4 hydrolysis. Appl. Catal. B Environ. 26,
207–215.
Zhang, P., Qian, G., Shi, H., Ruan, X., Yang, J., Frost, R.L., 2012. Mechanism of inter-
action of hydrocalumites (Ca/Al-LDH) with methyl orange and acidic scarlet GR. J.
Colloid Interface Sci. 365, 110–116.