Materials Research Bulletin 70 (2015) 336–342

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Materials Research Bulletin

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Rare earth and zinc layered hydroxide salts intercalated with the
2-aminobenzoate anion as organic luminescent sensitizer
Ana Cristina Trindade Cursino a , Vicente Rives b , Gregorio Guadalupe Carbajal Arizaga c,
Raquel Trujillano b , Fernando Wypych a, *
a
CEPESQ – Research Centre of Applied Chemistry, Department of Chemistry, Universidade Federal do Paraná – P.O. Box 19081, 81531-980 Curitiba, PR, Brazil
b
GIR-QUESCAT – Department of Inorganic Chemistry, Universidad de Salamanca, Plaza de la Merced S/N, 37998 Salamanca, Spain
c
Universidad de Guadalajara, Department of Chemistry, Boulevard Marcelino García Barragán 1421, C.P. 44430 Guadalajara, Jalisco, Mexico

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

Article history: Rare earth (RE = Eu, Y and Tb) and zinc layered hydroxide salts intercalated with nitrate anions were
Received 28 October 2014 synthesized, followed by exchange with 2-aminobenzoate. The obtained compounds were characterized
Received in revised form 11 April 2015 by powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR) and ultraviolet visible (UV–vis)
Accepted 27 April 2015
spectroscopies, fluorescence measurements and thermal analysis (TGA/DTA). The results from FTIR
Available online 29 April 2015
spectroscopy suggest a direct coordination of 2-aminobenzoate to the metal cations of the inorganic
layered structure. The organic derivative products from the intercalation reactions absorb a broader
Keywords:
range of UV-light in relation to that shown by the parent material; the photoluminescence
Layered compounds
Intercalation reactions
measurements present a strong violet, blue and green luminescence under UV-light excitation for
X-ray diffraction layered compounds with, Zn, Y and Tb, respectively. Rare earth hydroxide salts (RE-LHS) are potential
Luminescence alternative matrices for the immobilization of organic species to produce luminescent materials.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Layered compounds such as layered double hydroxides (LDH)
and some layered hydroxide salts (LHS) have been found to
exchange anions and attract intense interest due to their structural
anisotropy, variable chemical composition and the ease to produce
intercalated/grafted compounds. LHS have the general formula M2
+
(OH)2
x(An
)x/nyH2O, where M2+ is a metal cation (e.g., Mg2+,
Ni2+, Zn2+, Ca2+, Cd2+, Co2+ and Cu2+) and An
is the intercalated
exchangeable anion (e.g., Cl
, NO3
, SO42
, CH3COO
among
others) [1–4].
In 1960s, the first layered lanthanide hydroxide salts were
reported, with generic composition represented by
(Ln)2(OH)6
m(Ax
)m/xnH2O (Ln = lanthanide trivalent ion = Ln+3,
and Ax
= anion). These compounds belongs to a new type of
layered crystalline materials closely related to LDH, in which the
positive charge of the layer is generated by varying the number of
hydroxyl groups or water molecules coordinated to the Ln3+ cation.
These compounds can be divided in two classes (m = 1 and m = 2 in
* Corresponding author. Tel.: +55 41 3361 3473; fax : +55 41 33613186.
E-mail addresses: anacursino@ufpr.br (A.C.T. Cursino), vrives@usal.es (V. Rives),
gregoriocarbajal@yahoo.com.mx (G.G.C. Arizaga), rakel@usal.es (R. Trujillano),
wypych@ufpr.br, wypych.ufpr@gmail.com (F. Wypych).
the generic formula above), which are based in the chemical
composition and structural aspects. In the first class where m = 1
(Ln2(OH)5(Ax
)1/xnH2O), the intercalated anions are free to move
between the layers and in the second class, where m = 2
(Ln2(OH)4(Ax
)2/xnH2O or Ln(OH)2(Ax
)1/xnH2O), the anions
are covalently bonded to the layers.
Thereafter some other publications appeared where these
layered lanthanide salts were the basis of multifunctional
materials for diverse applications, such as luminescent materials
and biomedical devices [5,6]. Most of the lanthanide cations (Ln3+)
display intense luminescence and are good activators in lumines-
cent compounds. These excitations can be improved by using
organic sensitizers to capture energy from external light sources
followed by internal transfers to excite electrons in Ln3+ [7–9].
In a recent paper, Cursino et al. described the intercalation of
2-aminobenzoate, an organic anion with ultraviolet absorption
ability, by replacing nitrate anions from layered zinc hydroxide
nitrate [10]. Since the intercalated 2-aminobenzoate in the zinc
hydroxide nitrate-like compound absorbed a broader range of
ultraviolet radiation than its sodium salt, it is expected that the
organic anion presents different UV absorption if it is intercalated
into a layered inorganic matrix containing rare earth cations.
On this basis, the aim of this work was to use different layered
rare-earth (Eu3+, Tb3+ and Y3+) hydroxides salts intercalated/
grafted with 2-aminobenzoate to explore the properties of the

http://dx.doi.org/10.1016/j.materresbull.2015.04.055
0025-5408/ ã 2015 Elsevier Ltd. All rights reserved.
 A.C.T. Cursino et al. / Materials Research Bulletin 70 (2015) 336–342
resulting material, specially to examine the sensitization or any
antenna effect of the rare earth fluorescent matrix by 2-amino-
benzoate. The possible future application is to explore these
materials as functional luminescent fillers in polymer nano-
composites to produce technologically important flexible sheets
devices with a broad range of applications.
2. Materials and methods
2-Aminobenzoic acid (Aldrich, 98%), zinc nitrate hexahydrate
(Panreac, 98%), europium chloride hexahydrate (Aldrich, 99.9%),
terbium chloride hexahydrate (Aldrich, 99.9%), yttrium chloride
hexahydrate (Aldrich, 99%) and sodium hydroxide (Vetec, 99%)
were used without any further purification. All the reactions were
conducted in distilled water.
2.1. Syntheses of zinc, europium and terbium hydroxide salts
Zinc, europium and terbium layered hydroxides salts interca-
lated with nitrate anions were synthesized by the slow addition of
a NaOH aqueous solution (1 mol L
1) to 70 mL of a solution
containing 8 mmol of Zn(NO3)26H2O, EuCl36H2O or TbCl36H2O,
respectively, under magnetic stirring; the final pH was adjusted to
neutrality. The solids were separated by centrifugation at
3000 rpm for 5 min, followed by extensive washing with distilled
water (5 times), dispersion and centrifugation. The resulting
layered hydroxide salts (named respectively as LHS-Zn/NO3, LHS-
Eu/NO3, and LHS-Tb/NO3) were dried under vacuum at room
temperature until constant mass.
The synthesis of yttrium hydroxide nitrate (LHS-Y/NO3) was
performed by a hydrothermal route [11]. A mixture of 7.5 mL of an
aqueous solution (0.44 mol L
1) of yttrium nitrate, 2.5 mL of NaNO3
(1.44 mol L
1) and 2.5 mL of NaOH (2.1 mol L
1) was placed in a
sealed teflon vessel. The mixture was stirred and hydrothermally
treated at 125  C for 48 h. The resulting white solid was extensively
washed with distilled water (5 times), recovered by centrifugation
and dried under vacuum at room temperature for 24 h.
2.2. Intercalation of 2-aminobenzoate by anion exchange and
coprecipitation
A solution of sodium 2-aminobenzoate (2AB-Na) was prepared
by the slow addition of 20 mL of NaOH (1 mol L
1) to 50 mL of a
suspension containing 22 mmol of 2-aminobenzoic acid in
decarbonated water, then 0.6 g of the solid hydroxide salt (LHS-
Zn/NO3, LHS-Y/NO3, or LHS-Tb/NO3) was added to this solution,
and the suspension was magnetically stirred at room temperature
for 40 min, centrifuged and extensively washed with distilled
water (5 times). The final white solids LHS-M/2AB (where M = Zn, Y
and Tb) were dried under vacuum at room temperature for 24 h.
Europium matrix intercalated with 2-aminobenzoate was
prepared by coprecipitation reaction by dissolving 15 mmol of
2-aminobenzoic acid (2AB-H) in 20 mL of an aqueous solution of
NaOH (0.4 mol/L). To this solution, 20 mL of a solution containing
2.5 mmol of EuCl36H2O was slowly added and the final pH was
adjusted to around 7 by the addition of a NaOH (1 mol/L) solution.
The suspension was magnetically stirred at room temperature for
6 h. Later, this suspension was centrifuged and washed with
distilled water four times. The final white solid (LHS-Eu/2AB) was
dried under vacuum at 45  C for 24 h.
2.3. Characterization
Powder X-ray diffraction (PXRD) patterns were recorded with a
Siemens D-500 instrument using CuKa radiation (l = 1.54050 Å)
controlled by the Diffrac AT software. The current and tension were
337
set respectively to 30 mA and 40 kV and the patterns were
collected with dwell time of 2  min
1.
Specific surface area assessment was carried out in a Gemini
instrument from Micromeritics. The sample (ca. 50–100 mg) was
previously degassed in flowing nitrogen at 110  C for 2 h in a
FlowPrep 060 apparatus (Micromeritics) in order to remove
physisorbed water, and the data were analyzed using published
software [12].
The FTIR spectra were recorded in a PerkinElmer Spectrum-One
using approximately 1% of the sample in 100 mg of spectroscopic
grade KBr, the pellets being pressed at 10 tons. The measurements
were performed in the transmission mode with accumulation of
32 scans and recorded with a nominal resolution of 4 cm
1.
Thermal analyses (TGA/DTA) were performed on SDT Q600
equipment. All measurements were carried out at a heating rate of
10  C min
1 under an oxygen flow of 20 mL min
1 (Air Liquide,
Spain, 99.999%). The TGA/DSC curves were recorded in an
equipment of simultaneous thermal analysis STA, NETZSCH, STA
449 F3 Jupiter.
The UV–vis reflectance spectra (DRU-Vis) were recorded at
room temperature in the 200–800 nm range, at intervals of 0.5 nm,
in a VARIAN Cary 100 spectrophotometer equipped with an
integration sphere.
The photoluminescence spectra of powders were collected at
room temperature in a PerkinElmer LS55 spectrofluorometer.
3. Results and discusion
3.1. X-ray diffraction
The powder X-ray diffraction pattern of LHS-Zn/NO3 shown in
Fig. 1 matches with the profile reported in the ICDD card
corresponding to Zn5(OH)8(NO3)22H2O, which is characterized
by a major basal reflection at 9.7 Å caused by the 2 0 0 plane of the
monoclinic structure [13,14]. The rare earth (RE) layered hydroxide
salts (LHS), presented typical profiles of layered compounds whose
signals at the lowest angle indicate basal reflections of 8.6 Å, 9.3 Å
and 8.2 Å for LHS-Eu/NO3, LHS-Y/NO3 and LHS-Tb/NO3, respective-
ly (Fig. 1). These results suggest the formation of LHS with
composition RE2(OH)5NO3xH2O, where RE = Eu, Y and Tb [11,15].
From these nitrate LHS, the noisy pattern of LHS-Eu/NO3 indicates
that the synthesis conditions are not suitable to achieve a high
degree of crystallinity, i.e., a different level of energy is required
to improve the atoms packing in this particular structure,
* *
h
g
f
* *
e
Intensity (a.u.)
d
c
b
a
10 20 30 40 50 60
2 θ (Degree)
Fig. 1. PXRD patterns of LHS-Zn/NO3 (a), LHS-Zn/2AB (b), LHS-Eu/NO3 (c), LHS-Eu/
2AB (d), LHS-Y/NO3 (e), LHS-Y/2AB (f), LHS-Tb/NO3 (g), LHS-Tb/2AB (h). * = Alumi-
num sample holder.
338 A.C.T. Cursino et al. / Materials Research Bulletin 70 (2015) 336–342

Table 1
Basal distance (d100), nCOO
(asym), nCOO
(sym.), lexc and lemi of the LHS-M/NO3 and LHS-M/2AB compounds, where M = Zn, Eu, Y and Tb.

Sample d100 Interlayer spacing (Å) nCOO
(asym) nCOO
(sym) (cm
1) COO
lmaxexc lmaxemi
(Å) (cm
1) Dn (cm
1) (nm) (nm)
LHS-Zn/NO3 9.7 4.9 – – – – –
LHS-Zn/2AB 13.5 8.7 1591 1407 185 275 386
LHS-Eu/NO3 8.6 3.8 – – – 394 614
LHS-Eu/2AB 16.5 11.7 1577 1396 180 282 404
LHS-Y/NO3 9.3 4.5 – – – – –
LHS-Y/2AB 17.6 12.8 1580 1400 180 366 424
LHS-Tb/NO3 8.2 3.4 – – – 352 542
LHS-Tb/2AB 18.3 13.5 1582 1395 187 382 543
2AB-Na – – 1580 1394 186 – –

asym = antisymmetric; sym = symmetric. Interlayer spacing = estimated from the basal space minus the approximate layer thickness (4.8 Å) [19].

nonetheless, the X-ray diffraction pattern is clear enough to
identify the layered structure.
Intercalation of 2AB in LHS increased the basal distances to
13.5 Å in LHS-Zn/2AB; 16.5 Å in LHS-Eu/2AB; 17.6 Å in LHS-Y/2AB;
and 18.3 Å in LHS-Tb/2AB. These values comprise the thickness of
one inorganic layer plus the interlayer distance, then the space
available to allocate the 2AB anions can be determined by
subtracting the layer thickness. In the case of inorganic layers
formed by M2+ cations with radii close to that of Mg2+ (like layered
double hydroxides), the thickness is 4.8 Å [16]. For the set of rare
earth LHS, although they contain slightly larger cations [17], the
thickness can be assumed similarly once the basal space of rare
earth LHS are equal to the space of layered double hydroxides with
the same interlayer anion [10,18,19].
Therefore it is reasonable to accept the subtraction of 4.8 Å from
the basal space to determine the space between layers. Such values
are included in Table 1. The 2AB-intercalated zinc hydroxide salt
presented an interlayer space of 8.7 Å while for the RE salts the
interlayer spacing ranges from 11.7 to 13.5 Å. Since the length of the
2AB anion is around 6.2 Å (estimated from the anion larger axis
with software Hyperchem) [20], there is room enough to form a
monolayer in LHS-Zn/2AB and two layers in the RE salts (LHS-Eu/
2AB, LHS-Y/2AB, LHS-Tb/2AB).
It is possible to observe a low degree of crystallinity in the PXRD
patterns of the LHS-Eu/2AB, which is probably due to the
amorphization of the layered compound and the excess of organic
material as verified by thermal analysis.
3.2. Infrared spectroscopy
FTIR spectra of all LHS were compared with those of 2-
aminobenzoate sodium salt (2AB-Na) and the protonated 2-
aminobenzoic acid (2AB-H) (Fig. 2). The nitrate-containing Zn, Eu,
Y and Tb LHS show a broad band around 3500 cm
1, which can be
carboxylate group is evidenced by the antisymmetric and
symmetric stretching modes whose precise positions are included
in Table 1.
According to the literature [24], the difference between the
wavenumbers of the antisymmetric and symmetric carboxylate
bands (Dn = nasym
nsym) gives information related to the carbox-
ylate coordination with the layered matrix [24,25]. From the Dn
values listed in Table 1, those of LHS are between 180 and 187 cm
1,
which are very close to that of the sodium salt. According to these
values, the most probable arrangement is a carboxylate bridge
between two different metal cations [24,25]. As in 2AB the
carboxylate group is perpendicularly oriented in relation to the
benzene ring, this bridge formation between two different metals
forces the 2AB anion to be perpendicularly oriented to the
inorganic layers. This information also corroborated with the
interlayer spacing measurements of LHS-M/2AB compounds,
where M = Zn, Eu, Y and Tb, as described in the X-ray diffraction
section (Table 1).
3.3. Texture analyses
The nitrogen adsorption/desorption isotherms were recorded
for nitrate- and 2AB-intercalated LHS (data included as Supple-
mentary material 1—S1). The isotherms correspond to type IV
according to IUPAC classification, which is related to non-porous or
mesoporous materials exhibiting monolayer/multilayer adsorp-
tion, similar to those found for other hydrotalcite-like structures
[26–28]. Except for LHS-Zn/NO3, the isotherms for all compounds
showed a hysteresis loop in the pressure range from 0.45 to
0.9 corresponding to a narrow type H3 profile, according to the
COO
-

attributed to the stretching mode of multiple hydroxyl groups j

with hydrogen bonds to water molecules. Typical bands of nitrate i
were also observed at 1352, 1050 and 1767 cm
1, the latter being h
Transmittance (a.u.)

characteristic of the combination of nitrate n1 and n3 modes,

g
while the second band, which should be absent for a D3h
symmetry, is activated by a symmetry decrease when the anion is f
e
grafted to the layers [21]. The intense band at 1384 cm
1 is due to
the n3 mode of nitrate [14]. The spectrum of 2AB-H shows a single d
band around 1677 cm
1, attributed to carbonyl stretching of
c
carboxylic groups. The absence of this signal in the LHS, as
b
expected, indicates that the protonated form is not intercalated.
a
Bands from amino groups of this acid molecule appeared at
3321 and 3233 cm
1 [22,23]. In the spectrum of 2AB-Na two bands
of special interest are recorded at 1580 and 1394 cm
1, which are 4000 3500 3000 1500 1000 500
-1
characteristic of the antisymmetric and symmetric stretching Wavenumber (cm )
modes of the ionized carboxylate group, respectively [10]; this
Fig. 2. FTIR spectra of 2AB-Na (a), 2AB-H (b), and the samples LHS-Zn/NO3 (c) LHS-
ionized group neutralizes the positive charge of the layers. In Zn/2AB (d), LHS-Eu/NO3(e), LHS-Eu/2AB (f), LHS-Y/NO3 (g), LHS-Y/2AB (h), LHS-Tb/
the LHS intercalated with 2AB, the presence of the ionized NO3 (i) and LHS-Tb/2AB (j).
 A.C.T. Cursino et al. / Materials Research Bulletin 70 (2015) 336–342 339

Table 2 3.4. UV–vis spectroscopy

Specific surface area (BET, m2 g
1), external surface area (St, m2 g
1) and pore
volume (Vp, 10
3 cm3 g
1) of the samples prepared.
To study the ultraviolet-visible behavior of the compounds, the
Sample SBET St Vp DRUV-VIS spectra were recorded (Fig. 3).
LHS-Zn/2AB 5 5 8.05 It is possible to confirm the intercalation of 2AB anion based on
LHS-Eu/NO3 25 25 81.44 the fact that the nitrate LHS absorption occurs in the range of 210–
LHS-Eu/2ab 34 39 76.57
220 nm and weakly at 300 nm (Fig. 3A, and for LHS-Zn/NO3 see
LHS-Y/NO3 46 40 161.74
LHS-Y/2ab 43 49
reference [10]), while that of 2AB presents a broad peak in the
LHS-Tb/2ab 26 26 77.75 range of 300–400 nm, which clearly appears in the spectra of
samples LHS-Zn/2AB, LHS-Eu/2AB, LHS-Y/2AB and LHS-Tb/2AB
(Fig. 3B).
IUPAC classification. The specific surface area values (Table 2) do
not follow any clear trend after the exchange of nitrate by 2- 3.5. Photoluminescence
aminobenzoate. In all cases a good correlation coefficient was
determined for the corresponding plots. Despite the high Photoluminescence spectra were collected to analyze the
crystallinity of yttrium compounds, this compound shows the emission response of RE LHS (Fig. 4). The excitation (Fig. 4A)
largest specific surface area. Probably these measured areas are and emission (Fig. 4B) spectra were collected fixing the emission at
more related to the specific drying conditions of the samples than 543 nm and the excitation at 352 nm, respectively, for LHS-Tb/NO3
to the specific nature of the cations in the layers. The specific and LHS-Tb/2AB. The emission spectrum of the Tb3+ ion displays
surface area and the external surface area provide similar or bands at 488, 544, 584, and 620 nm, assigned to transitions from
coincident values, indicating the lack of microporosity in the the 5D4 to the 7FJ level (J = 6, 5, 4, and 3), respectively [29]. After
samples. incorporation of 2-aminobenzoate the narrow band due to f–f
transition of Tb3+ ion is observed, characterizing the antenna effect.
Briefly, this broad band excitation at 408 nm is attributed to the
5
c
A
A
4
b

LHS-Eu/NO3 (a)
3
Intensity (a.u.)

LHS-Y/NO3(b)
F(R)

LHS-Tb/NO3 (c)
2
b
a

a
0
200 300 400 500 600
300 350 400 450 500
Wavelength (nm)
Wavelength (nm)
341
B
c B
LHS-Zn/2AB (a)
3 LHS-Eu/2AB (b)
LHS-Y/2AB (c)
LHS-Tb/2AB (d)
Intensity (a.u.)

2AB-Na (e)
237
2
F(R)

332
b

1
305 332 b
a d
a
358
e
0 400 450 500 550 600 650
200 300 400 500 600 Wavelength (nm)
Wavelength (nm)
Fig. 4. Excitation spectra monitored at 543 nm (A) and emission spectra excited at
Fig. 3. DRUV-VIS spectra of nitrate (A) and 2AB-intercalated LHS (B). 352 nm (B) of LHS-Tb/NO3 (a) and LHS-Tb/2AB (b) compounds.
340 A.C.T. Cursino et al. / Materials Research Bulletin 70 (2015) 336–342

absorption by the 2-aminobenzoate anion followed by energy
transfer to the levels of the excited state of terbium, which
subsequently decays via a non-radiative process and populate the
emitting 5D4 level.
Fig. 5 shows the excitation and emission spectra of LHS-Eu/NO3
and LHS-Eu/2AB. The excitation spectra of europium LHS were
obtained by fixing the emission at 612 nm. Emission spectra were
obtained by fixing the excitation wavelength in the higher
intensity in the excitation spectrum (394 nm). The emission
spectrum displays bands at 589, 612, and 695 nm, assigned to
transitions from the 5D0 to the 7FJ level (J = 1, 2 and 4) [30].
After intercalation of 2AB anion the spectra of LHS-Eu/2AB
showed three bands related to transitions 5D0 ! 7F1,2,4 at 586,
610 and 704 nm. It is possible to observe that these bands have
lower intensity and are shifted compared to the emission in LHS-
Eu/NO3. The narrow excitation bands of LHS-Eu/NO3 (Fig. 5A-a)
give rise to a broad band excitation (Fig. 5A-c). The benzene ring
and carboxylate groups may enhance the luminescence of Eu3+, but
the
NH2 may quench the luminescence, possibly as a result of
significant nonradioactive relaxation channels as observed by Gu
A
et al. [31]. However, although the 2-aminobenzoate anion
enhances the luminescence of Tb3+, this anion decreased the
emission intensity of Eu3+.
On the other hand, the sodium salt, 2AB-Na, was also submitted
to photoluminescence analysis. The excitation spectrum presented
a maximum signal at 348 nm with a shoulder at 294 nm [32].
Regarding the emission, a maximum absorption was detected at
383 nm. The compounds LHS-Y/2AB and LHS-Tb/2AB present a
similar excitation spectrum (Fig. 6). However, there was a large
shift in the position of the maximum absorption of the excitation/
emission band due to stronger p delocalization of the carboxyl
group and the electron pair of the amino group with the aromatic
ring [32]. The changes in fluorescence of these samples are
additionally demonstrated by their photographs irradiated with
UV light (365 nm) (Supplementary material 2—S2).
A
366
382
c
348
d
e
302

b 380 394 Intensity (a.u.) a

a 360
282
Intensity (a.u.)

282

404
b

464

c 200 250 300 350 400 450

Wavelength (nm)

300 400 500

B
Wavelength (nm) 386

a
B

424
404
Intensity (a.u.)

c 404)
383
Intensity (a.u.)

e e

586 610 b
704
f
408 d
d
589 612 695
300 350 400 450 500 550 600 650 700
300 400 500 600 700 Wavelength (nm)
Wavelength (nm)
Fig. 6. Excitation spectra monitored at 386, 404, 424, 488 and 383 nm (A) and
Fig. 5. Excitation (A) spectra monitored at 612 nm (a) of LHS-Eu/NO3 and at 404 nm Emission spectra excited at 275, 282, 366, 353 and 294 nm (B) of LHS-Zn/2AB (a),
(b) and 586 nm (c) of LHS-Eu/2AB. Emission (B) spectra excited at 394 nm (d) of LHS- LHS-Eu/2AB (b), LHS-Y/2AB (c), LHS-Tb/2AB (d) and 2AB-Na (e) compounds,
Eu/NO3 and excited at 282 nm (e) and 404 nm (f) of LHS-Eu/2AB. respectively.
 A.C.T. Cursino et al. / Materials Research Bulletin 70 (2015) 336–342 341

3.6. Thermal analyses The thermal analysis curves of LHS-Y/2AB (Fig. 7-b) show three
main thermal events at 73, 359 and 588  C. The first correspond to
TGA/DTA measurements were performed to estimate the the removal of physisorbed/intercalated water molecules. The
composition of the rare earth hydroxide nitrate and the intercala- other mass losses are attributed to the oxidation of organic matter
tion compounds (Fig. 7). and dehydroxylation of the layered matrix, producing Y2O3 [33].
Thermal analysis (TGA/DTA) curves from LHS-Y/NO3 (Fig. 7-a) With this information, it was possible to estimate the composition
reveal a decomposition profile with three endothermic events at of the compound Y2(OH)5(NO3)0.17(C6H4NH2COO)0.832.4H2O close
90, 285 and 498  C. The first mass loss is attributed to the removal to the stoichiometric value.
of adsorbed/structural water molecules, which comprises 6% of the The thermal decomposition profile of LHS-Tb/2AB (Supplemen-
total mass. The second mass loss is attributed to the matrix tary material 3—S3) showed two main events, the first one
dehydroxylation, with a mass loss of 11%, associated to an corresponding to the removal of water up to 200  C and the second
endothermic peak at 285  C. A mass loss of 19.2% occurs in the one to the burning of organic matter and dehydroxylation of the
last mass loss step with the complete decomposition to Y2O3 matrix. The residue at 900  C was 69% of the original mass. From
[11,15]. The mass losses are consistent with the formula the data, the formula could be estimated as being Tb2(OH)5
Y2(OH)5(NO3)1.52H2O where the total mass loss observed during (NO3)0.3(C6H4NH2COO)0.71.4H2O.
the decomposition until the formation of yttrium oxide was The thermal analysis curves (TGA/DSC) (Supplementary
36.38%, which agrees with the calculated value of 35.90%. material 3—S3) show that the decomposition of LHS-Eu/2AB
The same process was used to estimate the compositions to the occurs in two main steps, the first between 40 and 275  C (mass
lanthanide hydroxide nitrate salts. The calculated formula loss of 5.9%) and the second step begins in 275  C (mass loss of
Tb2(OH)5(NO3)11.2H2O and Eu2(OH)5(NO3)11.6H2O agreed well 10.1%). The first event is attributed to release of water and the main
with the expected values (theoretical = 76% and experimental = 74% mass loss event is associated to the burning of organic matter.
for LHS-Tb/NO3; theoretical = 73% and experimental = 70% for LHS- The final residue observed was 43%. Considering that all nitrate
Eu/NO3). anion was replaced by 2-aminobenzoate (Eu2(OH)5(C6H4NH2-
COO)1xH2O), the calculated value of the total residue is 63%. This
difference may be due to the excess of organic compound or even
the formation of a complex with europium ion, although it is not
100 a 0,6 possible to observe the characteristic peaks in the X-ray diffraction
patterns of the complexes and precursors (2-aminobenzoic acid
and sodium 2-aminobenzoate). One possible complexes formed in
the exchange reaction can be Eu(C7H6O2N)3H2O (identified by the
Temperature Difference (°C)

Endo 0,3
90 JCPDS 36-1826).
Mass (%)

0,0 4. Conclusions

80 Zinc, europium, yttrium and terbium hydroxide nitrate were

DTA
-0,3 successfully synthesized, subsequently they were used to ex-
change nitrate by 2-aminobenzoate anion. All products after ion
exchange showed significant increases in their basal distance,
70
-0,6 confirming the intercalation of the 2-aminobenzoate anion. These
TGA anions are grafted to the layers establishing a carboxylate bridge
between two metal centers of the layer.
-0,9 The UV absorption ability was improved in relation to the use of
60
0 200 400 600 800 1000 the parent organic material and the photoluminescence measure-
ments present a strong violet, blue and green luminescence under
Temperature (°C)
UV-light excitation for intercalated/grafted layered compounds
with Zn, Y and Tb, respectively showing that layered hydroxide
100 salts (LHS) can be good alternative matrixes for the immobilization
b 4
TGA of organic species to develop new luminescent materials.
It would also be expected that this rare earth hydroxide salts are
90 good candidates to be used as luminescent fillers after delamina-
Temperature Difference (°C)

3
Endo tion/exfoliation to produce functional luminescent polymer nano-
composites.
80
Mass (%)

2
Acknowledgements
70
We gratefully acknowledge the Brazilian funding agencies
1
CNPq, CAPES, FINEP and the project Nennan (Fundação Araucária/
60 DTA CNPq) for their financial support of this work. ACTC thanks CAPES
0 and CNPq/Ciência sem Fronteiras for the doctorate grant. VR
acknowledges a grant from MICINN (MAT2009-08526) and ERDF.
50
-1 Appendix A. Supplementary data
0 200 400 600 800 1000
Supplementary data associated with this article can be
Temperature (°C)
found, in the online version, at http://dx.doi.org/10.1016/j.
Fig. 7. TGA/DTA curves for the LHS-Y/NO3 (a) and LHS-Y/2AB (b) compounds. materresbull.2015.04.055.
342 A.C.T. Cursino et al. / Materials Research Bulletin 70 (2015) 336–342
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