Indigo@Silicalite: a New Organic-Inorganic

Hybrid Pigment
ARTICLE

Catherine Dejoie,† Pauline Martinetto,*,† Eric Dooryhée,†,‡ Pierre Strobel,† Sylvie Blanc,§
Patrice Bordat,§ Ross Brown,§ Florence Porcher,|,⊥ Manuel Sanchez del Rio,# and
Michel Anne†
Institut Néel, UPR 2940 CNRS, 25 avenue des Martyrs, BP 166, F-38042 Grenoble Cedex 9, France, Institut
Pluridisciplinaire de Recherche sur l’Environnement et les Matériaux (IPREM), UMR 5254 UPPA-CNRS, Hélioparc,
2 avenue Pierre Angot, F-64053 Pau Cedex 9, France, Laboratoire de Cristallographie, Résonnance Magnétique et
Modélisation (CRM2), UHP-CNRS, Faculté des Sciences BP 70239, F- 54506 Vandoeuvre-les-Nancy, France,
Laboratoire Léon Brillouin (LLB), UMR 12 CEA-CNRS, F-91191 Gif-sur-Yvette Cedex, France, European Synchrotron
Radiation Facility (ESRF), 6 rue Jules Horowitz, F-38000 Grenoble, France, and National Synchrotron Light Source-II
(NSLS-II), Brookhaven National Laboratory, Upton, New York 11973

ABSTRACT In the search for stable and enduring organic colors, we have combined indigo, a historical and industrially important
chromophore, with silicalite, the MFI zeolite. The resulting pigment presents high color durability against most external agents (e.g.,
light, temperature). This stability and its physical properties are explained by the association of indigo with an inert mineral, which
is also influenced by formation conditions such as the initial indigo concentration and the thermal treatment. The formation of the
indigo@silicalite hybrid, particularly diffusion of the organic molecule, is monitored by optical spectroscopies, thermogravimetric
measurements, and X-ray diffraction. Color stability is attested when indigo enters the pores of the zeolitic host, thus forming a new
pigment with characteristics similar to those of Maya Blue. This opens the way to the low-cost engineering of metal-free, nonhazardous
pigment powders based on indigoid and other dyes.

KEYWORDS: silicalite • zeolite • indigo • pigment • stability • UV-vis fluorescence • diffraction • color

I. INTRODUCTION studied. This new organic-inorganic pigment is inspired by

L ong-lasting resistance of pigments to acids, alkalis, the general features of the archeological pigment Maya Blue
solvents, and biodegradants is an important issue in (5, 10), created by the ancient Mayan people by the mixing
art and in the paint and pigment industries (1-4). and heating of palygorskite or sepiolite clays with indigo dye.
In the quest for stable dyes, resistant to heat and moisture Despite certain controversy on the location of the indigo
in particular, several organic-inorganic hybrids present molecule within the clays (5, 11-15), a channel structure is
good characteristics and are environmentally friendly as known to be the key point to obtain a chemically and
well: the color can be durably fixed by trapping or encap- thermally stable dye. We thus copied the tubelike arrange-
sulating an organic dye in a mineral or clay matrix (5, 6). ment of the clay by using the silicalite zeolite as the inorganic
Some of these hybrid pigments combine the properties of matrix. Indigo is a blue dye well-known to ancient civiliza-
the microporous mineral substrate (chemical resistance, tions (16). Nowadays, the massive use of indigo (17) by the
thermal and mechanical stability, harmlessness, etc.) and dye industry requires its transformation into a water-soluble
the color of the organic dye (7). The stability and appearance
(leuco) form (18). Indigo is the compound indigotin
of such hybrid pigments are affected by both the structure
C16H10N2O2 [2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-di-
of the host and the interactions between the host and dye
hydro-3H-indol-3-one], a quasi-planar molecule of approxi-
(8, 9).
mate dimensions 5 × 12 Å2. In the present work, we
A particular organomineral system is indigo/silicalite. To consider using the naturally water-insoluble (keto) form of
our knowledge, this system has never been produced or
indigo for the formation of a stable pigment. Silicalite is a
high silica zeolite belonging to the MFI family (19). Pure
* To whom correspondence should be addressed. E-mail: pauline.martinetto@ silicalite is exclusively formed by Si-O-Si bonds, which are
grenoble.cnrs.fr.
Received for review April 20, 2010 and accepted June 21, 2010
responsible for its hydrophobic properties (20). In the pres-
†
Institut Néel. ence of foreign atoms (Al, Ti, Fe, B, etc.) or structural defects,
‡
NSLS-II. internal silanol groups contribute to the catalytic activities
§
IPREM. of this type of zeolite, used in industrial applications (21).
|
CRM2.
⊥
The MFI structure may be described as a three-dimensional
LLB.
#
ESRF.
porous silicate with two interconnected tubular channel
DOI: 10.1021/am100349b systems (19, 22). Sinusoidal channels with an opening of 5.1
2010 American Chemical Society × 5.5 Å2 along the a axis (P21/n space group) are intercon-

2308 VOL. 2 • NO. 8 • 2308–2316 • 2010 www.acsami.org

Published on Web 07/20/2010
Table 1. Indigo@Silicalite Samples Studied in This Worka
initial indigo indigo content (wt %)

ARTICLE
label concn (wt %) heating temp (°C) for surface/channels obsd diffraction

SILI-1 0.5 200 mono

SILI-2 1 200 0.5/0.5 mono
SILI-3 2 200 1.1/0.9 mono + indigo
SILI-4 5 200 3.4/0.9 mono + indigo
SILI-5 10 200 mono + indigo
SILI-6 1 230 mono + ortho
SILI-7 5 230 mono + ortho
SILI-8 10 230 3.1/3.2 mono + ortho + indigo
SILI-9 1 300 mono + ortho
SILI-10 5 300 0/4.1 ortho
SILI-11 10 300 1.9/4.2 ortho + indigo
SILI-12 10 230 ortho
a
All samples, as powders or single crystal (SiLi-12), are heated 5 h at the temperature mentioned. The indigo content is deduced from analysis
of the amplitudes of features of the TGA curves at 360-380 °C (departure of surface indigo) and 500-600 °C (departure of indigo incorporated
in the zeolite channels). The last column indicates the observed diffracting phase(s): monoclinic (mono), orthorhombic (ortho), and indigo
crystals (indigo).

nected with straight channels (5.4 × 5.6 Å2) parallel to the b II. EXPERIMENTAL SECTION
axis. MFI zeolites show an orthorhombic-to-monoclinic II-1. Sample Preparation. The MFI zeolite was prepared at
phase transition, depending on the composition, structural the CRM2, Nancy, France, according to the fluoride route
elaborated by Guth et al. (40), which provides crystals of
defects, and nature/amount of sorbed molecules (23-25). aluminum-free MFI materials with fewer defects than the com-
The location of cations like tetrapropylammonium (TPA; mon hydroxide route (41, 42), using tetrapropylammonium
i.e., the template used in the MFI synthesis protocol) (26) or (TPA) cation as a templating agent. The molar composition of
the initial synthesis gel was approximately 1:0.08:0.04:20 SiO2/
aromatic molecules such as benzene (27, 28), naphthalene TPABr/NH4F/H2O. This gel was heated at 473 K for 40 days, and
(29), p-nitroaniline (30-32), dichlorobenzene (33) and py- then the reaction products were filtered, washed with water,
ridine (34), trapped in an MFI zeolite was studied by different and dried in an oven (43). The purity of the synthesized (SiO2)96
authors mainly using neutron and X-ray diffraction (XRD) silicalite was confirmed by microprobe analyses. Samples were
subsequently calcined at 600 °C in order to eliminate TPA. XRD
techniques and computer simulation. In this study, we gives evidence of good crystallization in the monoclinic form,
combine structural analyses with optical spectroscopies to while TGA reveals the low concentration of water and silanols
investigate the indigo@silicalite system. UV-vis fluores- (minor mass loss, less than 1.5 wt % between 25 and 700 °C).
cence is sensitive to the structural features of encapsulated A series of MFI samples were prepared as either powders or as
single crystals. MFI single crystals have a typical size of 300 ×
dyes, e.g., in zeolite L (35, 36) or AlPO4-5 (37) and MFI (38). 150 × 40 µm3 and exhibit a morphology similar to that
Although the fluorescence emission quantum yield of indigo described by Guth et al. with a typical hourglass pattern (44).
is low (18), fluorescence spectroscopy is a very sensitive tool Silicalite powder was mixed with synthetic indigo (from 0.5
for determining the distribution of the dye inside and at the to 10 wt %; Aldrich) and finely hand-ground in a mortar. The
powder was finally pressed into pellets to enhance contact
surface of the substrate. Roeffaers et al. (39) recently com-
between the two components. The pellets were heated for 5 h
bined electron backscattering diffraction and confocal fluo- in air at 200, 230, or 300 °C. Doping of single-crystal samples
rescence microscopy to map fluorescent reaction products follows the same procedure, omitting the cogrinding step in
in ZSM-5 crystals. order to avoid destruction of the single crystals. Table 1 lists
samples presented below. This synthesis procedure is inspired
In this work, we study a new organic-inorganic pigment by that used for modern reproduction of the Maya Blue pigment
obtained by mixing and grinding indigo powder with high- (45, 46).
silica MFI zeolite. In the absence of foreign atoms, water II-2. Techniques. The absorption and diffuse-reflectance
spectra (DRUV) were recorded with a double-beam Cary 5000
molecules, or charge-compensated cations in this type of
spectrophotometer (IPREM Pau), in steps of 0.5 nm in the range
zeolite and given its low concentration of structural defects, 400-800 nm using a 1 cm quartz optical cell (Hellma) or an
we assume that the indigo behavior is driven by a purely 11-cm-diameter integrating sphere with a custom-made powder
siliceous channel structure environment. Insertion into the holder. The diffuse-reflectance spectra were corrected versus a
white standard (Teflon, Aldrich, 55 µm) (47). The DRUV spectra
zeolite is achieved in the solid phase just by heating. The
were analyzed according to the Kubelka-Munk model (48),
influence of the synthesis parameters (indigo concentration, describing light propagation in scattering media with only two
heating procedure) on the hybrid formation is monitored parameters, an absorption coefficient, K, and an isotropic
using optical spectroscopy and XRD techniques. The chro- scattering coefficient, S (which both have units of cm-1): F(R∞)
) (1 - R∞)2/2R∞ ) K/S ) εc/S. With this model based on simple
mostability of the organic dye in its new “zeolite state” is
assumptions, the absorption coefficient K of the system is
attested by resistance to irradiation and thermogravimetric proportional to the molar absorption coefficient ε(λ) (L mol-1
analysis (TGA) experiments. cm-1) and to the concentration C (mol L-1) of the compound.

www.acsami.org VOL. 2 • NO. 8 • 2308–2316 • 2010 2309

ARTICLE

FIGURE 1. Absorption and Kubelka-Munk-scale diffuse-reflectance spectra of indigo. (a) Absorption spectra of indigo in chloroform: (4) 4.1
× 10-6 mol L-1; (s) 4.1 × 10-5 mol L-1; (O) 1.3 × 10-4 mol L-1. l ) 1 cm, room temperature. (b) Corresponding fluorescence spectra of indigo
in chloroform (λex ) 488 nm). (c) Kubelka-Munk-scale diffuse-reflectance spectrum of an indigo powder. (d) Fluorescence spectrum of an
indigo powder (λex ) 488 nm).

R∞ is the reflectance of an “infinite” layer of powder, 4 mm in III. RESULTS

the present data. III-1. Characterization of Indigo and a Nonheat-
Corrected steady-state emission and excitation spectra were ed Indigo/Silicalite Mixture. The UV-vis absorption and
measured using a photon-counting Edinburgh FLS920 fluores- fluorescence of indigo depends on the solvent used. The
cence spectrometer equipped with a xenon lamp (IPREM, Pau,
France). Fluorescence spectra of the powdered samples were optical absorption of indigo dissolved in chloroform peaks
recorded on powder adhering to sticky tape (negligible fluores- at 606 nm (Figure 1a). At concentrations above 2 × 10-5
cence), in 90° geometry. In situ fluorescence under heating was mol L-1, an additional band appears at 680 nm (Figure 1a).
carried out using a LABRAM Jobin-Yvon Raman spectrometer For indigo powder, the diffuse reflectance, shown as
(LMGP, Grenoble, France) with a LINKAM heating stage. Depth- Kubelka-Munk transforms, consists of a relatively broad
resolved fluorescence was recorded using focusing of the
absorption band (Figure 1c). The main components peak at
microscope. The laser power was modulated between 3 mW
and 300 µW at the focus. 535, 580, and 680 nm.
TGA experiments were conducted on a SETARAM TAG 24 The fluorescence of dilute indigo in chloroform appears
thermoanalyzer instrument (Institut Néel, Grenoble, France). at ca. 650 nm (Figure 1b). A second band centered at 730
Samples (∼15 mg) were heated from 25 to 700 °C at a heating nm appears at a higher indigo concentration (4.1 × 10-5 mol
rate of 10 °C min-1 under flowing nitrogen. L-1). The fluorescence of the indigo crystal powder (Figure
Powder XRD data were collected in the high-resolution 2θ 1d) shows a single band at 750 nm.
step scanning mode at the 7-circles diffractometer of Beamline The Kubelka-Munk-scale diffuse-reflectance spectra of
BM02-ESRF (49). The powders were hand-packed in 1 mm
capillary glass tubes. Data were processed using the Fullprof indigo/silicalite mixtures prior to heating are shown in Figure
software (50). In situ modifications of the indigo and zeolite 2a. The principal band peaks at 680 nm for low indigo
upon heating were followed via two-dimensional diffraction concentrations. At higher concentration, the relative ampli-
patterns recorded using a CCD detector. Samples were heated tudes of the bands change and the spectra progressively tend
in a furnace provided by the Institut Français du Pétrole, which to that of the indigo powder, shown in Figure 1c.
enabled sample oscillation and a homogeneous heating of the
At low indigo concentration (<2 wt %), fluorescence
capillary (51). The CCD camera was placed 630 mm from the
sample at an angle of 12° (2θ). This configuration was used to emission occurs at 730 nm (Figure 2b). In addition, weak
rapidly achieve sufficient resolution in a particular region of emission is detected at shorter wavelengths, around 650 nm.
interest during the heating process. Data were analyzed using When the indigo concentration is increased, the 730 nm
the Xplot2D application of the XOP software package (52). After fluorescence band shifts to 750 nm and its intensity in-
linearization, a “peak-to-peak” fitting procedure was applied to creases relative to the 650 nm contribution.
determine the position, full width at half-maximum, and inten-
sity of each diffraction peak of the ROI. A least-squares refine- Powder XRD analysis shows that the nonheated silicalite/
ment was then applied to obtain the cell parameters and volume indigo mixture has monoclinic symmetry. The 100, 1̄02, and
of the unit cell. 210 indigo reflections are clearly identified on the XRD full

2310 VOL. 2 • NO. 8 • 2308–2316 • 2010 Dejoie et al. www.acsami.org

 before heating, (ii) in an intermediate state (sample SILI-3,
5 h, 200 °C), and (iii) at the end of the heating process (SILI-
10, 5 h, 300 °C). The fluorescence spectrum corresponding

ARTICLE
to the intermediate state shows two bands at 650 and 730
nm, but only the 650 nm fluorescence band persists in the
final state. The diffuse-reflectance bands (Figure 5a) in the
420-570 nm range and at 680 nm (Kubelka-Munk scale)
are correlated to the fluorescence band at 730 nm, while the
610 nm band is linked to the 650 nm fluorescence band.
The indigo concentration dependence of the two fluores-
cence bands for two different heating temperatures (200 and
300 °C) is presented in Figure 5c. The 650 nm fluorescence
band [corresponding to a low I(730)/I(650) value] predomi-
nates at a low indigo concentration and/or a higher heating
temperature.
Evolution of the indigo@silicalite hybrid has been moni-
tored in situ by XRD (Figure 6). The heating process is shown
in Figure 6a. Upon heating, undoped silicalite shows a
monoclinic to orthorhombic phase transition around 70 °C
(Figure 6b,c), reversible when returning to room tempera-
ture. The ferroelastic behavior of the zeolite as a function of
FIGURE 2. Reflectance (a) and fluorescence (b) spectra of unheated
the temperature has been discussed previously by other
indigo/silicalite mixtures versus indigo concentrations. The fluores- authors (53, 54). At 260 °C, the unit-cell volume of the doped
cence spectra are normalized to 1000 a.u. (λex ) 488 nm). silicalite is not notably affected by the organic dye (Figure
6d). Upon a return to room temperature, the high-temper-
pattern of a 5 wt % indigo/silicalite mixture; they are ature orthorhombic phase of the zeolite is maintained
markedly broader than those of the silicalite powder (Figure (Figure 6b). The broadening of the diffracted peaks when
3). This supports the presence of small or possibly strained passing from (2) to (3) is due to the presence of an additional
indigo crystallites. The diffraction diagram was refined using room temperature monoclinic phase, in addition to the
two phases (silicalite and indigo) by a full-pattern cell- predominant indigo-induced orthorhombic one.
constrained fitting (50). The refined cell parameters and the Depending on the synthesis conditions, the diffraction
corresponding figures of merit are reported in Table 2, in pattern of the indigo@silicalite samples shows one to three
agreement with the previous structural work on MFI single contributions, which come from polycrystalline indigo and
crystals (25, 26) and powder (23) at room temperature. the zeolite in varying proportions. The zeolite pattern is
III-2. Formation of the Indigo@Silicalite Hybrid easily indexed as monoclinic or orthorhombic. This observa-
by Heating. The heat treatment applied to the indigo/ tion is summarized in Table 1. The full pattern matching of
silicalite mixture is monitored in situ by fluorescence spec- the data yields the lattice parameters, and they are found to
troscopy. An indigo/silicalite mixture is introduced in the be very close to the published data (23, 26) (Table 2). The
heating stage (see the experimental part), and the temper- unit-cell size does not change once the hybrid is formed.
ature is progressively increased from 25 to 200 °C (3 °C III-3. Stability of the Indigo@Silicalite Hybrids.
min-1). At first, only a shift from 750 to 730 nm is observed TGA and calorimetric (DSC) experiments were carried out
(Figure 4a). At 200 °C, a second 650 nm band emerges and in order to investigate the thermal stability of the hybrids.
grows in with time (temperature fixed at 200 °C; Figure 4a). The results on silicalite and a 10 wt % indigo@silicalite
The relative intensities of the two fluorescence bands sample (SILI-8) are presented in Figure 7. Silicalite is subject
(730 and 650 nm) versus depth are shown in Figure 4b, in to minor mass loss below 120 °C, attributable to the
a silicalite single crystal exposed to indigo vapor at 230 °C departure of physisorbed water (55). Pure indigo powder
for 5 h (SILI-12). The single-crystal b axis is parallel to the begins to sublime in the range 250-350 °C before total
incident excitation light (inset in Figure 4b). The 730 nm decomposition at 360 °C (56) (exothermic reaction). SILI-8
band is maximum when the whole surface of the crystal is exhibits a first mass loss at 360 °C, which corresponds to
illuminated. When the excitation light penetrates further into decomposition of the indigo powder, and a second mass loss
the crystal, the 650 nm band increases at the expense of in the 550-700 °C range, attributed to the release of indigo
the 730 nm band. Therefore, the 730 nm band is clearly due sorbed in the silicalite. An exothermic peak (550-700 °C)
to a surface contribution, while the 650 nm band is due to is correlated with the sorbed molecule decomposition. The
the bulk colored crystal. Similar results are obtained for powder indigo content and the sorbed indigo content mea-
different orientations of the single crystal. sured by TGA are reported in Table 1 for different hybrid
The diffuse-reflectance and fluorescence spectra of the 5 samples.
wt % indigo@silicalite sample are compared at three dif- The indigo@silicalite samples were also exposed to ir-
ferent times during the heat treatment (Figure 5a,b): (i) radiation tests. Fluorescence spectra were recorded for

www.acsami.org VOL. 2 • NO. 8 • 2308–2316 • 2010 2311

ARTICLE

FIGURE 3. XRD full pattern of a 5 wt % indigo/silicalite unheated mixture (red points, experimental data; black line, calculated diagram;
green, Bragg positions; blue bottom line, residuals).

Table 2. Crystallographic Results of the Full-Pattern Fitting of Sample SILI-10 (5 wt % Indigo) before and after
Heating
before heating of an indigo/
silicalite mixture after heating of SILI-10 Van Koningsveld et al. (25) Van Koningsveld et al. (26)

phase silicalite indigo silicalite ZSM-5 (single crystal) TPA@ZSM-5 (single crystal)
symetry monoclinic monoclinic orthorhombic monoclinic orthorhombic
space group P21/n P21/c Pnma P21/n Pnma
a (Å) 20.0924(3) 10.8762 (6) 20.0301(6) 20.1070(20) 20.0220(20)
b (Å) 19.8620(2) 5.8376(2) 19.8878(6) 19.879(2) 19.8990(20)
c (Å) 13.3446(2) 12.2424(7) 13.3636(4) 13.369(1) 13.383(1)
R (deg) 90.680(1) 90 90 90.67(1) 90
β (deg) 90 130.280(4) 90 90 90
γ (deg) 90 90 90 90 90
volume (Å3) 5325.1(1) 592.98(5) 5323.5(3) 5343.32 5332.03
Rp (%) 7.52 7.22
Rwp (%) 9.47 9.98

different laser powers (Figure 8) on SILI-3. The 650 nm band of the fluorescence band (65), as is observed in our spectra
is not notably affected, whereas the 730 nm band, if present, (Figure 1). Indeed, Figure 1b shows that the main band of
disappears progressively with an increase of the irradiation indigo in solution is found at 650 nm, whereas the 730 nm
power. Under similar exposure of pure indigo to the laser fluorescence band occurs when the molar concentration is
beam, the 750 nm fluorescence band of the indigo powder increased. Hence, the 650 nm band is assigned to individual
disappears even at low-power irradiation. molecules, while the 730 nm band is attributed to indigo
clusters. Our results also show the correspondence between
IV. DISCUSSION the 650 nm fluorescence and 606 nm absorbance bands,
The optical properties of pure indigo are described in the
as well as that between the 730 nm fluorescence and 680
literature (16, 57-62). The UV-vis absorption is ascribed
nm absorbance bands.
to the N-H donor to CdO acceptor transition, taking place
at the CdC bond central site (63, 64). The transition of indigo The changes observed in the two indigo fluorescence
from the aggregate state in condensed matter to the mono- bands in indigo@silicalite as a function of the indigo con-
mer state is known to be accompanied by a large blue shift centration and temperature (Figure 5c) and after irradiation

2312 VOL. 2 • NO. 8 • 2308–2316 • 2010 Dejoie et al. www.acsami.org

 bonding and the consequent disaggregation of the indigo
powder. Moreover, the origin of the 650 nm band within the
bulk of the material is clearly asserted by the depth-resolved

ARTICLE
fluorescence measurement (Figure 4b). These conclusions
are confirmed by the XRD studies (Figure 6). Indeed, the
zeolite can be locked into the orthorhombic phase at room
temperature, as a consequence of loading with organic
sorbates (26, 27, 29, 30). The stabilization at room temper-
ature of the orthorhombic phase of the indigo-doped silicalite
can thus be ascribed to the templating effect of indigo inside
the zeolite structure. We understand that, upon heating, part
of indigo transforms into monomers and enters the zeolite
channels; this doping process is responsible for locking of
the zeolite structure into its metastable orthorhombic form.
Figure 9 is a schematic representation of the room
temperature phase stability of indigo-doped silicalite in T-C
space, where T is the heat of formation temperature (5 h, in
air in all cases) and C is the initial concentration of the indigo
powder in the mixture (see Table 1 for the samples in-
volved). The solid line boundary curve separates the do-
mains in the presence of respectively the one-phase com-
pound (zeolite only) and the two-phase compound. In the
FIGURE 4. Changes of the indigo fluorescence signal versus time (a) latter case, the superimposed powder XRD patterns of both
and penetration depth (b). (a) In situ fluorescence of a 5 wt % indigo/ silicalite and indigo are observed. The presence of diffracting
silicalite mixture heated at 200 °C (λex ) 488 nm). Spectra are indigo is found to correlate with the occurrence of the above-
normalized at 730 nm. (b) Fluorescence intensity ratio I(730)/I(650)
in an indigo-doped single crystal from the surface z ) 0 to 20 µm mentioned 730-750 nm fluorescence band, as well as the
(λex ) 488 nm). Inset: crystal axes. 420-570 and 680 nm diffuse-reflectance bands. The dashed
lines show the occurrence at room temperature of either the
of the pigment formed (Figure 8) clearly suggest the pres-
monoclinicororthorhombicsymmetryoftheindigo@silicalite
ence of two states of indigo. The fluorescence bands at 650
sample after the heating process, depending again on the
and 730 nm are assigned to indigo located in the bulk and
temperature of formation and the initial indigo concentra-
at the surface of the zeolite, respectively (Figure 4b). Their
tion. T-C conditions are stringent for obtaining a single
attribution is justified by a comparison of the fluorescence
orthorhombic phase after 5 h of baking under atmospheric
and UV-vis absorption data of diluted indigo in chloroform
conditions.
and the condensed-state indigo in a crystalline powder
(Figure 1) with the data of indigo@silicalite sample (Figure The synthesis of this new hybrid is carried out directly
5d). by heating in the solid phase. The procedure to obtain the
The 730 nm fluorescence band in indigo@silicalite (Fig- stable indigo-doped silicalite seems to be easy, but several
ure 2b) is present in aggregated indigo (Figure 1b). When adjustments are required to ensure homogeneous and re-
the concentration of indigo is increased, the fluorescence producible diffusion of indigo. The heating process is a
emission shifts from 730 to 750 nm. The 750 nm band is determining factor, and the final temperature has to be
assigned to crystalline indigo (Figure 1d). The progressive carefully monitored. Effective indigo concentrations at the
shift from 750 to 730 nm is attributed to a reduction in the surface and inside the zeolite channels have been checked
size of the indigo aggregates at the silicalite surface (66). By by TGA for different hybrid samples (Table 1). Heating of
confrontation with the UV-vis absorption data (Figures 2a the mixture of ground powders of indigo and silicalite at
and 5a), the 420-570 and 680 nm Kubelka-Munk-scale moderate temperatures (below 200 °C) restricts the amount
diffuse-reflectance bands are also assigned to indigo in the of indigo admitted into the zeolite channels (samples SILI-1
condensed state, close to that of the reference indigo powder to SILI-5; see Table 1). Too high a temperature increases the
(Figure 1c). We conclude that powdered indigo lies over the mobility of indigo, but indigo is likely to sublime and to
external surface of the zeolite and the degree of aggregation diffuse out, as revealed by the significant difference between
depends on the temperature, heating time, and initial the initial and final concentrations for samples obtained at
amount of indigo. 300 °C (Table 1). The fraction of surface indigo can be
The second indigo species is assigned to the fluorescence reduced by increasing the formation temperature of the
emission at 650 nm, which predominates upon formation indigo@zeolite hybrid and by adjusting the initial amount
of the complex by heating (Figure 4a). Individual molecules of indigo in the raw mixture. A pure orthorhombic phase is
of indigo emit at 650 nm in chloroform (Figure 1b). We produced in the presence of stable internal indigo, although
interpret the blue shift of the fluorescence band from 730 this structural effect is often incomplete: a mixture of
to 650 nm by the breaking of intermolecular hydrogen monoclinic and orthorhombic zeolite is more often ob-

www.acsami.org VOL. 2 • NO. 8 • 2308–2316 • 2010 2313

ARTICLE

FIGURE 5. Diffuse-reflectance (Kubelka-Munk scale) and fluorescence spectra of the indigo@silicalite hybrids, showing the effect of the
indigo concentration and the formation temperature. (a) Kubelka-Munk-scale diffuse-reflectance spectra at three steps of the doping process
for a 5 wt % indigo/silicalite sample. (b) Fluorescence spectra at three steps of the doping process for a 5 wt % indigo/silicalite mixture
sample. (c) Fluorescence intensity I(730)/I(650) ratio (λex ) 488 nm) versus the indigo concentration for two heating temperatures (the same
heating time of 5 h). (d) Comparison between the absorption and fluorescence spectra of diluted indigo in CHCl3 and sorbed indigo in silicalite.

FIGURE 6. XRD results of in situ heating on a 10 wt % indigo/silicalite mixture: (a) temperature cycle; (b) diffraction pattern of the
silicalite (1) before heating (monoclinic form), (2) at 260 °C (orthorhombic form), and (3) after a return to room temperature (orthorhombic
form). (c) Ferroelastic behavior of the silicalite upon heating. The phase transition occurs at 68 °C. (d) Evolution of the silicalite unit-
cell volume at 260 °C.

served. Complete transition is achieved for an initial indigo Encapsulation of indigo in an inorganic matrix modifies
concentration of 5 wt % and the final temperature of 300 its color and improves its stability: the color centers (seques-
°C (sample SILI-10). tered indigo monomers) are protected against fading pro-

2314 VOL. 2 • NO. 8 • 2308–2316 • 2010 Dejoie et al. www.acsami.org

 piolite clays with indigo. In the recent past, Domenech et
al. (67) discovered an oxidized form of indigo, dehydroin-
digo, as a result of the formation process. This is discussed

ARTICLE
by different groups (68, 69) and could account for the
characteristic turquoise shade of Maya Blue. We did not
notice such a transformation during the indigo@silicalite
synthesis. Nevertheless, the silicalite matrix is really different
from the clays used to obtain the archeological pigment, in
particular its chemical composition (pure SiO2), with no
possibility of inducing any oxidative reaction. We also
compared the high thermal stability of sorbed indigo in
FIGURE 7. TGA/DSC curves recorded on the raw silicalite and SILI-8 silicalite (Figure 7) with that of of the Maya Blue pigment.
sample. Ovarlez et al. (70) recently reported the high-temperature
stability of indigo molecules trapped in sepiolite tunnels
(>380 °C), which is in agreement with our result using the
silicalite matrix.

V. CONCLUSION
We have engineered an original indigo@zeolite hybrid
composite and studied its structural and spectroscopic
properties, which demonstrates a procedure to obtain a
durable and resistant pigment. The indigo@silicalite system
contains two distinct species of indigo: one is aggregated
indigo in contact with the surface of the zeolite, and the
FIGURE 8. Fluorescence spectra of the SILI-3 sample after irradiation second consists of entrapped indigo monomers. The stability
(5 min) by a laser (λex ) 488 nm) at different power levels (P0
corresponds to a power of 1 µW). of the hybrid pigment is monitored by controlling the initial
dye loading and the temperature. The color and color
stability directly depend on control of these factors and on
the amount of trapped indigo inside the silicalite channels.
The indigo pigment in our study can be thought of as an
analogue of the historical pigment Maya Blue (5). The present
investigation also suggests that the studied indigo@zeolite
hybrid could find applications as a natural, low-cost, and
easy-to-make painting material for industrial and artistic use.

Acknowledgment. The TGA experiments were carried out

with the help of P. Odier from Institut Néel. J. Kreisel from
LMGP provided assistance and support for the fluorescence
measurements. N. Boudet, J.-F. Bérar, S. Arnaud, and B.
Caillot are thanked for their strong support and advice at the
Beamline ESRF/CRG-BM02 for the diffraction measure-
FIGURE 9. Schematic diagram of the silicalite@indigo phase com-
position as a function of the heating temperature (150-300 °C) and
ments. Elemental analyses were performed with the help of
indigo concentrations (0.5-10 wt %). Ph. De Parseval at the Laboratory of the Mechanisms and
Transfers in Geology, Paul Sabatier University, Toulouse,
France. This project is supported by the Région Rhône-Alpes
duced by high temperature (Figure 7) and light (Figure 8). (France) through the CIBLE programme and the Materials
The positions of the diffuse-reflectance and fluorescence for Sustainable Development (MACODEV) consortium.
bands attributed to monomers of indigo inside the zeolite
channels, compared with those of indigo in solution, do not REFERENCES AND NOTES
emphasize the formation of any strong organic-inorganic (1) Holderlich, W.; Lauth, G.; Wagenblast, G.; Albert, B.; Lamm, G.;
interaction. We believe the high thermal resistance of the Reichelt, H.; Grund, C.; Gruettner-Merten, S. (assigned to W.
Holderlich). German Patent DE 4207745, 1992.
indigo@silicalite pigment is related to a particular location (2) Holderlich, W.; Lauth, G.; Muller U.; Brode, S. (assigned to BASF).
of the indigo molecules inside the channels, with the ability German Patent DE 4131447, 1992.
to lock the high-temperature phase at room temperature and (3) Jones, F. N.; Mao, W.; Ziemer, P. D.; Xiao, F.; Hayes, J.; Golden,
M. Prog. Org. Coat. 2005, 52, 9 –20.
without the possibility of diffusing out. (4) Diebold, M. P.; Bettler, C. R.; Mukoda, D. M. J. Coat. Technol. 2003,
The UV-vis diffuse-reflectance spectrum (Figure 5a) ac- 75, 29 –36.
counts for the light-blue color as long as the indigo concen- (5) Van Olphen, H. Science 1966, 154, 645–646.
(6) Lima, E.; Bosch, P.; Loera, S.; Ibarra, I. A.; Laguna, H.; Lara, V.
trations are adequate (1 wt %). This color recalls that of Appl. Clay Sci. 2009, 42, 478 –482.
ancient Maya Blue, formed by heating palygorskite or se- (7) Gómez-Romero, P.; Sánchez, C. New J. Chem. 2005, 29, 57–58.

www.acsami.org VOL. 2 • NO. 8 • 2308–2316 • 2010 2315

 (8) Sánchez, C.; Ribot, F. New J. Chem. 1994, 18, 1007–1047. Cremer, G.; De Kloe, R.; Hofkens, J.; De Vos, D. E.; Sels, B. F.
(9) Sánchez, C.; Julian, B.; Belleville, P.; Popall, M. J. Mater. Chem. J. Am. Chem. Soc. 2008, 130, 13516 –13517.
2005, 15, 3559 –3592. (40) Guth, J. L.; Kessler, H.; Weg, R. Proceedings of the 7th lnternational
ARTICLE
(10) Gettens, R. J. Am. Antiq. 1962, 27, 557–564. Zeolite Conference; Elsevier: Amsterdam, The Netherlands, 1986;
(11) Kleber, R.; Masschelein-Kleiner, R.; Thissen, J. Stud. Conserv. pp 137-142.
1967, 12 (2), 41–56. (41) Chézeau, J. M.; Delmotte, L.; Guth, J. L.; Gabelica, Z. Zeolites 1991,
(12) Kuang, W.; Facey, G. A.; Detellier, Ch.; Casal, B.; Serratosa, J. M.; 11, 598–606.
Ruiz-Hitzky, E. Chem. Mater. 2003, 15, 4956 –4967. (42) Chézeau, J. M.; Delmotte, L.; Guth, J. L.; Soulard, M. Zeolites 1989,
(13) Chiari, G.; Giustetto, R.; Ricchiardi, G. Eur. J. Mineral. 2003, 15, 9, 78 –80.
21–33. (43) Aubert, E.; Porcher, F.; Souhassou, M.; Petříček, V.; Lecomte, C.
(14) Chiari, G.; Giustetto, R.; Druzik, J.; Doehne, E.; Ricchiardi, G. Appl. J. Phys. Chem. B 2002, 106, 1110 –1117.
Phys. A: Mater. Sci. Process. 2008, 90, 3–7. (44) Weidenthaler, C.; Fischer, R. X.; Shannon, R. D.; Medenbach, O.
(15) Sánchez del Rı́o, M.; Boccaleri, E.; Milanesio, M.; Croce, G.; van J. Phys. Chem. 1994, 98, 12687–12694.
Beek, W.; Tsiantos, C.; Chyssikos, G. D.; Gionis, V.; Kacandes, (45) Sánchez del Río, M.; Martinetto, P.; Reyes-Valerio, C.; Dooryhée,
G. H.; Suárez, M.; Garcı́a-Romero, E. J. Mater. Sci. 2009, 44, 5524 – E.; Suárez, M. Archaeometry 2006, 48, 115–130.
5536. (46) Domenech, A.; Domenech-Carbo, M. T.; Sánchez del Río, M.;
(16) Hurry, J. B. The woad plant and its dye; Oxford University Press: Vasquez de Agredos Pascual, M. L.; Lima, E. New J. Chem. 2009,
London, 1939. 33, 2371–2379.
(17) Christie, R. M. Biotech. Histochem. 2007, 82, 51–56. (47) Weidner, V. R.; Hsia, J. J. J. Opt. Soc. Am. 1981, 71, 856 –861.
(18) Seixas de Melo, J.; Moura, A. P.; Melo, M. J. J. Phys. Chem. A 2004, (48) Kubelka, P.; Munk, F. Z. Tech. Phys. 1931, 12, 593–601.
108, 6975–6981. (49) http://www.esrf.eu/UsersAndScience/Experiments/CRG/BM02.
(19) Kokotailo, G. T.; Lawton, S. L.; Olson, D. H.; Meier, W. M. Nature
(50) Rodríguez-Carjaval, J. Physica B 1993, 192, 55–69.
1978, 272, 436 –437.
(51) Palancher, H.; Pichon, C.; Rebours, B.; Hodeau, J. L.; Lynch, J.;
(20) Marra, G. L.; Tozzola, G.; Leofanti, G.; Padovan, M.; Petrini, G.;
Bérar, J. F.; Prevot, S.; Conan, G.; Bouchard, C. J. Appl. Crystallogr.
Genoni, F.; Venturelli, B.; Zecchina, A.; Bordiga, S.; Ricchiardi,
2005, 38, 370 –373.
G. Stud. Surf. Sci. Catal. 1994, 84, 559 –566.
(52) Sánchez del Rı́o, M.; Dejus, R. J. SPIE Proc. 2004, 5536, 171–174.
(21) Degnan, T. F.; Chitnis, G. K.; Schipper, P. H. Microporous Meso-
porous Mater. 2000, 245, 35–36. (http://ftp.esrf.fr/pub/scisoft/xop2.3/).
(22) Wu, E. L.; Lawton, S. L.; Olson, D. H.; Rohrman, A. C., Jr.; (53) Van Koningsveld, H.; Tuinstra, F.; Jansen, J. C.; Van Bekkum, H.
Kokotailo, G. T. J. Phys. Chem. 1979, 83, 2777–2781. Zeolites 1989, 9, 253–256.
(23) Artioli, G.; Lamberti, C.; Marra, G. J. Acta Crystallogr. 2000, B56, (54) Mentzen, B. F.; Sacerdote-Peronnet, M. Mater. Res. Bull. 1993,
2–10. 28, 1017–1024.
(24) Mentzen, B. F. Mater. Res. Bull. 1992, 831–838. (55) Marinkovic, B. A.; Jardim, P. M.; Saavedra, A.; Lau, L. Y.; Baehtz,
(25) Van Koningsveld, H.; Jansen, J. C.; Van Bekkum, H. Zeolites 1990, C.; de Avillez, R. R.; Rizzo, F. Microporous Mesoporous Mater.
10, 235–242. 2004, 71, 117–124.
(26) Van Koningsveld, H.; Van Bekkum, H.; Jansen, J. C. Acta Crystal- (56) Hubbard, B.; Kuang, W.; Moser, A.; Facey, G. A.; Detellier, C. Clays
logr., Sect. B 1987, 43, 127–132. Miner. 2003, 51, 318 –326.
(27) Goyal, R.; Fitch, A. N.; Jobic, H. J. Phys. Chem B 2000, 104, 2878 – (57) Bauer, H.; Kowski, K.; Kuhn, H.; Lüttke, W.; Rademacher, P. J.
2884. Mol. Struct. 1998, 445, 277–286.
(28) Klemm, E.; Wang, J.; Emig, G. Microporous Mesoporous Mater. (58) Perpete, E. A.; Preat, J.; Andre, J. M.; Jacquemin, D. J. Phys. Chem.
1998, 26, 11–21. A 2006, 11, 5629 –5635.
(29) Van Koningsveld, H.; Jansen, J. C. Microporous Mater. 1996, 6, (59) Jacquemin, D.; Preat, J.; Wathelet, V.; Fontaine, M.; Perpete, E. A.
159 –167. J. Am. Chem. Soc. 2006, 128, 2072–2083.
(30) Van Koningsveld, H.; Koegler, J. H. Microporous Mater. 1997, 9, (60) Jacquemin, D.; Preat, J.; Wathelet, V.; Perpete, E. A. J. Chem. Phys.
71–81. 2006, 124, 074104/1-074104/12.
(31) Gao, F.; Zhu, G.; Li, X.; Li, B.; Terasaki, O.; Qiu, S. J. Phys. Chem. (61) Miliani, C.; Romani, A.; Favaro, G. Spectrochim. Acta 1998, A54,
2001, B105, 12704 –12708. 581–588.
(32) Gao, F.; Zhu, G.; Chen, Y.; Li, Y.; Qiu, S. J. Phys. Chem. B 2004, (62) Yasarawan, N.; Van Duijneveldt, J. Langmuir 2008, 24, 7184 –
108, 3426 –3430. 7192.
(33) Van Koningsveld, H.; Jansen, J. C.; Van Bekkum, H. Acta Crystal- (63) Wille, E.; Lüttke, W. Angew. Chem., Int. Ed. Engl. 1971, 10, 803–
logr., Sect. B 1996, 52, 140 –144. 804.
(34) Nishi, K.; Kamiya, N.; Yokomori, Y. Microporous Mesoporous (64) Wyman, G. M. EPA News Lett. 1994, 50, 9 –13.
Mater. 2007, 101, 83–89. (65) Monahan, A. R.; Kuder, J. E. J. Org. Chem. 1972, 37, 4182–4184.
(35) Megelski, S.; Lieb, A.; Pauchard, M.; Drechsler, A.; Glaus, S.; (66) Johnson-Buck, A.; Kim, G.; Wang, S.; Jin Hah, H.; Kopelman, R.
Debus, C.; Meixner, A. J.; Calzaferri, G. J. Phys. Chem. B 2001, 105, Mol. Cryst. Liq. Cryst. 2009, 501, 138 –144.
25–35. (67) Doménech, A.; Doménech-Carbó, M. T.; Vázquez de Agredos
(36) Busby, M.; Blum, C.; Tibben, M.; Fibikiar, S.; Calzaferri, G.; Pascual, M. L. J. Phys. Chem. B 2006, 110, 6027–6039.
Subramaniam, V.; De Cola, L. J. Am. Chem. Soc. 2008, 130, (68) Tilocca, A.; Fois, E. J. Phys. Chem. C 2009, 113 (20), 8683–8687.
10970 –10976. (69) Rondao, R.; Seixas de Melo, J. S.; Bonifacio, V. D. B.; Melo, M. J.
(37) Seebacher, C.; Rau, J.; Deeg, F. W.; Braüchle, C.; Altmaier, S.; J. Phys. Chem. A 2010, 114 (4), 1699 –1708.
Jäger, R.; Behrens, P. Adv. Mater. 2001, 13, 1374 –1377. (70) Ovarlez, S.; Giulieri, F.; Chaze, A. M.; Delamare, F.; Raya, J.;
(38) Karwacki, L.; Stavitski, E.; Kox, M. H. F.; Kornatowski, J.; hirschinger, J. Chem.sEur. J. 2009, 15 (42), 11326 –11332.
Weckhuysen, B. M. Stud. Surf. Sci. Catal. 2008, 174, 757–762.
(39) Roeffaers, M. B. J.; Ameloot, R.; Bons, A. J.; Mortier, W.; De AM100349B

2316 VOL. 2 • NO. 8 • 2308–2316 • 2010 Dejoie et al. www.acsami.org