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Strong ultra-broadband near-infrared

photoluminescence from bismuth-
embedded zeolites and their
derivatives
Minoru Mizuhata

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Strong Ultra-Broadband Near-Infrared
Photoluminescence from Bismuth-Embedded Zeolites
and Their Derivatives
By Hong-Tao Sun,* Akinobu Hosokawa, Yuji Miwa, Fumiaki Shimaoka,
Minoru Fujii,* Minoru Mizuhata, Shinji Hayashi, and Shigehito Deki
Zeolites are crystalline aluminosilicates with pores of molecular
dimensions.[1a] Due to their microporosity, zeolites have very
high surface areas and have been widely used in applications
such as catalysis, ion exchange, and separations.[1] Their potential
as host materials for luminescent guest species has only
been evaluated in recent years, and the corresponding results
prove that appropriately functionalized zeolites and related
structures are a promising new class of luminophores.[2] At
present, visible luminescence with very high efficiencies from
rare-earth-functionalized zeolites has been reported, rendering
them eligible for application as phosphors and lasers.[2] However,
the efficiency of the emitters becomes problematic in the
near-infrared (NIR) region due to the fast relaxation of the
excitation energy through nonradiative vibrational deactivation.
To avoid this, usually two strategies reported in the pioneering
work of Wada, Yanagida, Kynast and coworkers were used.[3,4]
For example, Wada and Yanagida demonstrated enhanced NIR
emission of Nd3þ by ligating it to bis(perfluoromethylsulfonyl)-
aminate in cages of large-pore zeolites. This method consists of
complicated fabrication processes and the final products always
have to be kept in a vacuum. Its notable advantage is that emission
with increased efficiency can be realized owing to suppression of
the relaxation of the excitation energy of Nd3þ arising from the
low-vibrational environment.[3] In 2006, Kynast et al. showed that
strong NIR emission of Nd3þ can be realized by collapsing the
open zeolitic materials into more dense aluminosilicates, such as
sodalites, combined with sufficient space filling.[4b] That is, not
enough room is left for the admission of water. Essentially, this
method is based on phase transition at the expense of the zeolite
structure, and additional compounds, such as WO3, have to be
used to act as auxiliaries to realize it. The similarity of the
above strategies is that Nd3þ ions were used as active centers, and
the full-width at half-maximum (FWHM) of the emission spectra
is less than 50 nm.
[*] Dr. H.-T. Sun, Prof. M. Fujii, Y. Miwa, F. Shimaoka, Prof. S. Hayashi
Department of Electrical and Electronic Engineering
Kobe University
Kobe 657-8501 (Japan)
E-mail: timothyhsun@gmail.com; fujii@eedept.kobe-u.ac.jp
A. Hosokawa, Prof. M. Mizuhata, Prof. S. Deki
Department of Chemical Science and Engineering
Kobe University
Kobe 657-8501 (Japan)
DOI: 10.1002/adma.200900573
3694 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
Herein, we report a facile and novel strategy to realize strong,
air-stable, long-lived, ultra-broadband (with a FWHM larger than
160 nm) tunable NIR photoluminescence (PL) from bismuth-
compound-embedded faujasite (FAU)-type zeolites and their
derived amorphous nanoparticles. This method consists of a
simple ion-exchange process and subsequent high-temperature
annealing under Ar atmospheric conditions. All the samples
obtained were exposed to the laboratory atmosphere prior to
measurements. We demonstrate that ‘‘blocking’’ of the small
pores of zeolites using bismuth compounds with low melting
points is an excellent approach to achieve strong NIR emission
from bismuth active centers. Bismuth ions not only act as
ultra-broadband NIR luminescence centers, but also as blocks for
selectively closing down the ‘‘in–out windows’’ of water
molecules, that is, bismuth active centers can be sealed in a
low-vibrational environment by bismuth agglomerates even when
the sample still contains a large amount of water. We also show
that further enhanced emission can be realized by a zeolite
amorphization strategy.
Figure 1 shows X-ray diffraction (XRD) results for bismuth-
embedded zeolites annealed at different temperatures. The
zeolite structure is well maintained after thermal treatment at
950 8C, and its crystallinity was estimated from the ratio of the
sums of the intensities of the peaks (111), (311), (331), (511),
(440), (533), and (642) of the annealed zeolites and the reference
material (bismuth-embedded zeolites annealed at 600 8C), by
following a usual procedure.[5,6] The results show a slight
decrease in crystallinity as the annealing temperature increases
(see Supporting Information, Table S1). A total amorphization
of this material is observed at 1000 8C. Figure 2 displays the
corresponding field-emission scanning electron microscopy
(FE-SEM) images of the samples. The morphology and
monodispersity of the annealed zeolites remain almost
unchanged from 800 to 950 8C. Further increase of the
temperature results in the disappearance of smaller particles,
which indicates that an Ostwald-ripening-like process takes place
(Fig. 2d). Energy-dispersive X-ray spectroscopy (EDS) confirms
that the amorphous particles are composed of Si, Al, O, and Bi
(Fig. S1, Supporting Information).
Figure 3a shows the NIR PL spectra of zeolites annealed at
different temperatures under the excitation of a 514.5 nm laser
line at a power of 0.014 mW. All samples show strong
ultra-broadband emission from 930 to 1630 nm with a FWHM
of 160 nm. The peak wavelength is at 1145 nm. With increasing
temperature, the PL intensity monotonously increases
Adv. Mater. 2009, 21, 3694–3698
www.advmat.de
Figure 1. XRD patterns of bismuth-embedded zeolites annealed at the
indicated temperatures in an Ar atmosphere.
(Fig. 3a and d). We also found that the PL shows spectral
tunability: the peak wavelength and shape of PL closely depend on
the excitation wavelength (Fig. 3a and b, and Fig. S2, Supporting
Information). The FWHMs of the PL spectra shown in Figure 3b
are 268 and 221 nm under 632.8 and 800 nm excitation,
respectively. In the mother zeolites, we did not detect any NIR
PL under the same excitation conditions. Thus, we conclude that
the PL is from bismuth-related infrared-active (BiIRA) centers
instead of intrinsic structure defects of zeolites. Figure 3c
demonstrates the fluorescence-decay curves of the annealed
products. The 1/e lifetime at 300 K increases from 80 ns to 430 ms
from 800 to 1000 8C (Fig. 3d). The quantum efficiency (QE) is also
dependent on the annealing temperature; at 950 and 1000 8C, it is
38.1 and 72.8%, respectively (Table S2, Supporting Information).
Figure 2. FE-SEM images of zeolites annealed at a) 800, b) 900, c) 950,
and d) 1000 8C in an Ar atmosphere. Scale bars: 1 mm.
Adv. Mater. 2009, 21, 3694–3698 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
The finding of temperature-dependent decay curves at 1145 nm
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reveals that the 1/e lifetime keeps an almost constant value of
225 ms from 5 K to as high as 300 K for the sample annealed at
950 8C, which indicates that the emission has strong resistance
to thermal quenching (Fig. S3, Supporting Information). It is
necessary to note that the PL enhancement factors show different
excitation-wavelength dependence; at 514.5 nm, larger factors can
be obtained. We will discuss the origin and enhancement
mechanism of PL in detail below.
It is well known that bismuth can exist in materials in different
valence states, such as 0, þ1, þ2, þ3, and þ5, or even mixed
valence states of þ1 and þ5.[7] In the past few decades, the
luminescence properties of Bi3þ- or Bi2þ-doped crystals and
glasses have been investigated. The emission peaks of Bi3þ occur
in the ultraviolet, green, or even red wavelength regions with
variation of host material, while the emission of Bi2þ is observed
in the range of 600–700 nm.[7] Up to now, no infrared
luminescence from Bi3þ- and Bi2þ-doped materials has been
reported. In recent years, NIR emission has been observed in
bismuth-doped multicomponent glasses.[8] However, the origin
of the NIR PL is still unclear and controversial.[7b,8] Interestingly,
the properties of NIR emission of bismuth-doped glasses are
similar to the results reported here, except that the PL property of
bismuth-embedded zeolites is dependent on the annealing
atmospheric conditions; the BiIRA centers can be destroyed when
the zeolites are annealed in air or in a H2/N2 atmosphere (Fig. S4,
Supporting Information). In Bi-doped zeolites annealed in air,
Bi3þ ions form in the matrix, whereas in a H2/N2 atmosphere,
bismuth metal preferentially forms.[9a,b] Since Bi2þ ions are not
infrared active, we suggest tentatively that the NIR luminescence
derives from subvalent bismuth of Biþ. In general, the energy
level of main-group ions with nsnp configuration can be affected
by multiple factors of spin–orbit interaction, the crystal field, and
the additional electrostatic interaction.[9] These ions can show
multiple valence states, depending on their chemical environ-
ments. Notably, results from X-ray photoelectron spectroscopy
(XPS) cannot present more information related to the distribution
of bismuth valence states in the annealed zeolites (Fig. S5,
Supporting Information). Since there is no other approach to
prove the existence of Biþ, optical spectroscopy may be an
effective way to study the unusual NIR emission from bismuth
ions.
Figure 4a shows the absorption spectra of zeolites annealed
under different conditions. The zeolites annealed at 900 and
950 8C display three strong and broad bands with maxima at
around 430, 540, 710 nm and a weak band at 630 nm, while that
annealed at 800 8C only displays two broader bands with maxima
at 530 and 715 nm. The bands at >490 nm can be assigned to
the electronic transitions of Biþ,[10a,b] and that at 430 nm to
the transition of cationic bismuth clusters.[10c] In contrast, the
amorphous product obtained by annealing at 1000 8C shows one
superwide band from 420 to 650 nm, and a very weak band at
705 nm. The different absorption properties of Biþ in these
samples lead to the dependence of PL enhancement factors on the
excitation wavelength. In comparison, the zeolites annealed in
air and under H2/N2 atmospheric conditions do not show
Biþ-related absorption bands in the range of 400–800 nm (Fig. S6,
Supporting Information). These results reveal that BiIRA
centers are more closely related to Biþ ions than to other forms
3695
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710 nm in Figure 4a, can be assigned to the

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3
P0 ! 1S0, 3P0 ! 1D2, and 3P0 ! 3P2 transi-
tions, respectively. The log–log dependence of
the infrared emission intensity on excitation
power is nearly linear, which indicates that one
incident photon is involved in this infrared
emission (Fig. S7, Supporting Information).
Thus, the NIR emission can be assigned to
the electronic transition of 3P1 ! 3P0.[8b,d]
The FAU structure can be viewed as being
built from cubooctahedral dodecahedra (soda-
lite cages or b cages) linked together at four of
the eight six-ring windows. This creates
three different types of cages in the structure:
supercages (or a cages), with large pore
openings of 7.4 Å, which are interconnected
via 12-ring windows to four other supercages;
sodalite cages, with large pore openings of
2.6 Å, which are connected via six-ring open-
ings to four adjoining supercages; and finally
double six-ring hexagonal prisms, with a
smaller opening than that of the sodalite cage,
which link the sodalite cages together. It was
revealed before by Hong et al. that for
Tb3þ-doped FAU-type zeolites, Tb3þ ions can
migrate into small cages, such as sodalite
cages and hexagonal prisms, depending on
Figure 3. a) Ultra-broadband NIR PL spectra of zeolites annealed at the indicated temperatures the treatment temperature and zeolite compo-
in an Ar atmosphere, which were excited by the 514.5 nm line of an Arþ laser at a power of sition: the cations in high-silica FAU-type
0.014 mW. b) Normalized NIR PL of the sample annealed at 1000 8C under 514.5, 632.8, and zeolites (Si/Al ¼ 3.4) migrate first to sodalite
800 nm excitation. c) Fluorescence-decay curves of the annealed samples at 300 K. The detected cages at 100 8C, and in turn to hexagonal
wavelength is 1145 nm. d) Left axis: annealing temperature dependence of enhancement factor of prisms at temperatures higher than 100 8C.[11]
PL when excited at 514.5, 632.8, and 800 nm. Enhancement factors at different excitation
In contrast, our bismuth-embedded FAU-type
wavelengths were calculated by dividing integrated PL intensities at different temperatures by
that at 800 8C. Right axis: temperature dependence of 1/e lifetime at 1145 nm. zeolites (Si/Al ¼ 7.0) were thermally treated at
temperatures of
800 8C. In view of the
similarity of the ionic diameters of bismuth
of bismuth, which confirms, in a sense, our supposition that Biþ and terbium ions, it is reasonable to assume that the bismuth ions
ions are the origin of NIR emission. The ground configuration of can migrate into the sodalite cages and hexagonal prisms from
Biþ is 6s26p2. The mutual electrostatic interaction of two 6p the supercages.[12a] On the other hand, high-temperature
electrons splits the ground-state configuration into three terms: annealing in an inert atmosphere is a necessary process to
3
P, 1D, and 1S. Spin–orbit interaction further splits the create Biþ ions, because in the as-ion-exchanged zeolites, no NIR
3 3 3
ground-state term of P into fine-structure levels of P0, P1, PL is observed; at the same time, non-infrared-active compounds
and 3P2. Three absorption bands, centered at 540, 630, and also form in this process (Fig. 5a–c). Owing to the extended
nature of the 6p orbitals of Biþ, the crystal field plays an important
role in the luminescence properties.[12b,c] According to previous
work by Mortier on the ideal symmetry of various cation sites
present in the FAU structure, site I in hexagonal prisms has the
ideal Oh symmetry, whereas both sites I’ and II’ in sodalite cages
have the ideal point symmetry of C3v.[13] This will result in the
difference of orbital energy of Biþ ions in different sites owing to
the different crystal-field stabilization energy, that is, polytype Biþ
ions instead of single-type ones contribute to the emission, thus
leading to excitation-wavelength-dependent emission of Biþ ions.
Usually, coordinated water in optically activated materials can
strongly affect the NIR emission efficiency of the emitters.
Thermogravimetric (TG) analysis reveals that the water content in
Figure 4. a) Absorption spectra of bismuth-embedded zeolites annealed the annealed zeolites decreases notably with increasing annealing
at different temperatures in an Ar atmosphere. b) TG analysis of these temperature (Fig. 4b). Note that the zeolites annealed at 900 and
samples. 950 8C contain much less water than that annealed at 800 8C.

3696 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2009, 21, 3694–3698
www.advmat.de
Figure 5. a–c) Schematic illustration of the structure transformation of
the zeolites annealed at different temperatures. d) 2D representation of the
structure of an aluminosilicate network. Note that ‘‘loose’’ and ‘‘dense’’
just represent small and large possibilities of sealing the pores of the
zeolites with bismuth agglomerates.
The crystallinity of the zeolites annealed 800, 900, and 950 8C
does not show a large difference (Table S1, Supporting
Information), which indicates that there should be other reasons
for the decrease in water content. This becomes understandable
if we further consider the physical properties, especially the
thermal parameters, of bismuth compounds. The melting points
of all inorganic bismuth compounds are below 820 8C.[14] When
the exchanged zeolites are annealed at high temperatures, on
the one hand, bismuth-related dissociation reactions can easily
take place;[15] on the other hand, bismuth compounds have a
chance to form agglomerates owing to bismuth migration into
zeolite pores, which can partially block or totally seal the pores of
the zeolites when the samples are suddenly cooled down. The
higher the annealing temperature, the higher the possibility of
sealing the pores of the zeolites (Fig. 5b and c). This leads to a
decrease of water content in the zeolites annealed at a relatively
higher temperature. Most possibly, partial Biþ ions can be held in
captivity totally in the sodalite cages and hexagonal prisms if the
annealing temperature is high enough and water molecules have
little chance to interact with them, which results in strong and
long-lived NIR emission. Owing to the much larger pore
openings of the supercages, the chance to seal them totally is
much smaller (Fig. 5b and c) than for sodalite cages and
hexagonal prisms. Therefore, the zeolites annealed at 950 8C still
contain 12 wt% coordinated water. All water can be removed by
collapse of the zeolite structure when annealed at 1000 8C for 1 h,
which results in the strongest NIR emission and the longest PL
lifetime (Figs. 3 and 5d).
Adv. Mater. 2009, 21, 3694–3698 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
In conclusion, we have successfully realized ultrabroadband
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NIR emission from bismuth-embedded zeolites and their
derivatives through a simple ion-exchange process and sub-
sequent controlled annealing. The advantages of this finding can
be summarized as follows: i) the PL from these annealed
zeolites is strong and air-stable; ii) the PL lifetime can reach up
to several hundred microseconds, which is much longer than
that of rare-earth ions in zeolites; iii) the PL displays
spectral tunability by tailoring the excitation wavelength; and
iv) the broad NIR PL with a FWHM of more than 160 nm covers
the whole telecommunication windows of O (1260–1360 nm),
E (1360–1460 nm), and S (1460–1530 nm) bands, and even the
C (1530–1565 nm) and L (1565–1625 nm) bands, being much
broader than those of rare-earth ions. Most importantly, we
demonstrate that even in samples containing a large amount of
water, it is possible to achieve efficient NIR emission if active ions
can be effectively separated from coordinated water. Additional
studies will be performed in the near future to further elucidate
the exact origin of the NIR emission in these materials. Owing to
the peculiar optical properties of these activated zeolites and the
mature zeolite assembly techniques developed,[16,17] we believe
that these materials are promising for applications as the active
media of broadly tunable micro- or nanooptical sources and
devices.
Experimental
Synthesis: FAU-type zeolites in the NH4 form were purchased from
Tosoh Co., Japan (Zeolite Y, SiO2/Al2O3 ¼ 7, grain size 700–1000 nm).
Zeolite was stirred in a 0.04 M aqueous solution of Bi3þ prepared from
Bi(NO3)3  5H2O at 80 8C for 144 h to exchange the NH4 ions with Bi3þ
ions. The products were isolated by centrifugation, then washed with
deionized water, and dried in air at 120 8C. The Bi3þ-exchanged zeolites
were calcined at 800–1000 8C for 1 h in an Ar atmosphere. For comparison,
the exchanged zeolites were also calcined at 900 8C for 1 h in air and under
H2/N2 atmospheric conditions. All samples were exposed to the laboratory
atmosphere prior to measurements.
Characterization: The prepared products were first characterized by
X-ray diffractometry (Rigaku-TTR/S2, l ¼ 1.54056 Å). The morphologies of
the prepared products were characterized using a FE-SEM instrument
(JEOL, JSM-6335F) operating at an accelerating voltage of 15 kV. Bismuth
concentrations were measured by EDS. The atomic ratios of Bi/(SiþAlþO)
for the products annealed in an Ar atmosphere were determined to be 2%.
Luminescence measurements were carried out at room temperature with
excitation by the 514.5 nm line of an Arþ laser, 632.8 nm line of a He–Ne
laser, and 800 nm line of a Ti:sapphire laser. The signal was analyzed by a
single-grating monochromator and detected by a liquid-nitrogen-cooled
InGaAs detector. Time-resolved luminescence measurements were
performed by detecting the modulated luminescence signal with a
photomultiplier tube (Hamamatsu, R5509-72) and then analyzing the
signal with a photon-counting multichannel scaler. The excitation source
for the time-resolved PL measurements was the 514.5 nm light from an
optical parametric oscillator pumped by the third harmonic of a Nd:YAG
laser. For temperature-dependent time-resolved luminescence measure-
ments, the sample was cooled by a closed-cycle He cryostat. The PL QE was
measured using an integrating sphere following the procedure
reported[18]. Here, we used bismuth-doped infrared-active aluminosilicate
glasses in thin pieces as a reference to determine the emission QE of
bismuth-embedded zeolites, because the measured QE for powder
samples can be strongly affected by the sample preparation parameters,
such as powder concentration in solution, solution type, and so on[18b].
Bismuth-doped infrared-active aluminosilicate glasses were prepared by
a melt-quenching technique. Measurements were carried out at 300 K
3697

with excitation by 727 nm light from a Ti:sapphire laser. The signal
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was analyzed by a single-grating monochromator and detected by a
liquid-nitrogen-cooled InGaAs detector. For all the spectra, the spectral
response of the detection system was corrected by the reference spectrum
of a standard tungsten lamp. Note that the glass showed similar NIR
emission to that of bismuth-embedded zeolites, and the 1/e lifetime at
1145 nm taken at 300 K was determined to be 170 ms (Fig. S8, Supporting
Information), which indicates that the same type of BiIRA centers
contribute to the NIR emission. Assuming that the radiative lifetime of
BiIRA centers is the same in bismuth-doped zeolites and glass, the QEs
for the annealed zeolites can be estimated based on:
t Zeolite
QEZeolite ¼ QEGlass  (1)
t Glass
where QEZeolite and QEGlass are the QEs of bismuth-doped zeolites and
glass, respectively, while tZeolite and tGlass are the 1/e lifetime at 1145 nm
taken at 300 K for zeolites and glass, respectively. QEGlass was determined
to be 28.8%, and the calculated QEs for the annealed zeolites are listed in
Table S2 (Supporting Information). Absorption spectra were recorded
using a UV–vis spectrophotometer (JASCO, V7200) with a diffuse
reflectance attachment. TG analysis was carried out using a Rigaku
Thermo Plus TG-DTA series (TG 8120) apparatus. The chemical states of Bi
and O in the annealed samples were analyzed by XPS (JEOL JPS-9010MC).
Acknowledgements
This work was supported by the Japan Society for the Promotion of Science
(JSPS) and a Grant-in-Aid for Scientific Research from the Ministry of
Education, Culture, Sports, Science, and Technology, Japan (Grant No.
19007322). H.-T.S. is grateful for the support from JSPS in the form of a
fellowship. The authors are grateful to J. Ruan for preparing bismuth-doped
infrared-active aluminosilicate glasses. Supporting Information is available
online from Wiley InterScience or from the author.
Received: February 18, 2009
Revised: March 6, 2009
Published online: May 26, 2009
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