A New Approach to Sensing H+ Using SBA-15 Grafted with Fluorene di-ammonium Groups and Theoretical study

Article abstract of DOI:10.1002/jccs.201500382

Fluorene-di-ammonium-functionalized mesoporous silica (FDMS) was prepared through post synthesis grafting method of SBA-15. The obtained material was characterized by means of small and wide angle X-ray diffraction, nitrogen adsorption-desorption, Fourier transform infrared spectroscopy, Raman spec- troscopy, thermo gravimetric analysis and elemental analysis. The results showed that the original structure of SBA-15 is preserved after the post grafting procedure. Surface area, pore size and pore volume de- creased by attaching functional groups to the pore surface. The grafted amount of fluorene on the surface of SBA-15 was 0.50 mmol with yield about 40.6 %. The emission spectra of FDMS was studied in acid me- dia and discussed in details. Computational studies were performed in order to obtain a detailed electronic description of the mechanism of FDMS fluorescence by H⁺ as well as studying the structure and bonding in the (FDMS)H⁺. The structural change between FDMS and protonated form can serve as an effective candidate for pH-indicator, and might be used as acid-dependent molecular-sensor models for advanced applications in optical sensors in the future.

Full text of DOI:10.1002/jccs.201500382

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
A New Approach to Sensing H+ Using SBA-15 Grafted with Fluorene di-ammonium
Groups and Theoretical Study
Alireza Badiei,a,b* Marzieh Yadavi,a Alireza Shayesteh,a Maryam Jafaria and
Ghodsi Mohammadi Ziaranic
aSchool of Chemistry, College of Science, University of Tehran, Tehran, Iran
bNanobiomedicine Centra of Excellence, Nanoscience and Nanotechnology Research Centra, University of Tehran,
Tehran, Iran
cDepartment of Chemistry, Faculty of Science, Alzahra University, Tehran, Iran
(Received: Sept. 16, 2015; Accepted: Nov. 11, 2015; Published Online: Apr. 5, 2016; DOI: 10.1002/jccs.201500382)
Fluorene-di-ammonium-functionalized mesoporous silica (FDMS) was prepared through post synthesis
grafting method of SBA-15. The obtained material was characterized by means of small and wide angle
X-ray diffraction, nitrogen adsorption–desorption, Fourier transform infrared spectroscopy, Raman spec-
troscopy, thermo gravimetric analysis and elemental analysis. The results showed that the original struc-
ture of SBA-15 is preserved after the post grafting procedure. Surface area, pore size and pore volume de-
creased by attaching functional groups to the pore surface. The grafted amount of fluorene on the surface
of SBA-15 was 0.50 mmol with yield about 40.6%. The emission spectra of FDMS was studied in acid me-
dia and discussed in details. Computational studies were performed in order to obtain a detailed electronic
description of the mechanism of FDMS fluorescence by H+ as well as studying the structure and bonding
in the (FDMS)H+. The structural change between FDMS and protonated form can serve as an effective
candidate for pH-indicator, and might be used as acid-dependent molecular-sensor models for advanced
applications in optical sensors in the future.
Keywords: Mesoporous silica; SBA-15; Fluorene.
INTRODUCTION
Since the last decade, organically functionalized me-
investigations were dedicated to surface modification of
different mesoporous silicas using aminoalkoxysilanes for
their application in sensors.8,9
soporous silica materials such as MCM-41, SBA-15 and
HMS established great attention in the literature and nu-
merous review papers were published in this field.1-6 The
interest of such materials is strongly related to their regu-
larly ordered pore arrangement, narrow pore size distribu-
tion, and high specific surface area. These materials tender
more advantages over other porous solids due to hydrother-
mal stability. Such properties are adequate for applications
involving adsorption, catalysis, chromatography, sensor
technology and sequestration. However, these applications
need modification of the surface of the mesoporous ma-
terials by several strategies to assign specific properties
and reactivity. The surface functionalization via reining of
organic functional groups attracted much notice as it al-
lowed to introduce a number of functionalities on the inter-
nal pore surfaces.5 Thus, organic functional groups such as
amine, thiol, carboxylic, alkyl chloride, and aromatic
groups have been incorporated into the structure of meso-
porous material via post-synthesis grafting or co-conden-
sation.7 Among all these organic functional groups, several
Fluorene derivatives are used in applications of
thermo and light sensitisers and organometallic complexes.
Zheng et al. reported on absorption and fluorescence pH
sensors based on 9-(cyclo heptatrienylidene) fluorene (9-
CHF) derivatives.10 These compounds are used not only as
an absorption sensor in strong acidic media, they act as
fluorescence sensors in mildly acidic environments.11-13
Egelhaaf et al. were reported that fluorene was attached co-
valently to organic–inorganic hybrid polymers as a fluores-
cence model compound for a matrix-bound active centre.14
In principle, molecular construction with photoinduced
electron transfer (PET)15 between fluorophore and receptor
systems is one of the most frequently used pathways for
building useful sensors.16 When its receptor is combined
with the analytes, the molecule can display enhanced or
quenching fluorescence emission upon various analytes.
Aromatic amines are typical examples of pH fluorescent
sensors because their fluorescent spectra can be changed
by protonation.17
* Corresponding author. Tel: +982161112614; Fax: +9821 66405141; Email: abadiei@khayam.ut.ac.ir
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SBA-15 Grafted with Fluorene di-ammonium Groups
Previously, we reported the synthesis of the fluorene
functionalized mesoporous silica based on mono amine
functionalized SBA-15 and studied its photo luminescence
behavior in acidic media.18 In this paper [1-(2-amino-
ethyl)-3-aminopropyl]trimethoxy-silane (TMPED) with
two amine groups is selected as the linkage units. The
fluorene group was grafted in to the nanochannels of
SBA-15 via two steps: (i) attachment of [1-(2-amino
ethyl)-3-aminopropyl] trimethoxy-silane on SBA-15, then
(ii) covalent linkage of fluorene. By reaction substitution
into the SBA-15 surface between amino groups on the sur-
face of the functionalized SBA-15 and 9-bromofluorene
derivative, fluorene as a fluorophore group could be at-
tached on the surface of the mesoporous silica. However
the nitrogen groups with a lone pair as a Bronsted base can
exhibit unique properties. The interaction of H+ with this
material was studied using fluorescence spectroscopy. The
FDMS has photo induced electron transfer (PET), demon-
strated potential applications in molecular devices. The ob-
tained materials were characterized by small and wide
angle X-ray diffraction, nitrogen adsorption–desorption,
Fourier transform infrared spectroscopy, Raman spectros-
copy thermogravimetric analysis and elemental analysis.
The quantum mechanical calculations were performed in
order to provide more detailed information. The change in
the fluorescence emission of fluorene functionalized meso-
porous silica (FDMS) in acidic media might be an effective
candidate for pH-dependent molecular-sensor models for
advanced applications of optical sensors.
without any pore wall collapse during the modification of
the surface. The larger wall thickness of the functionalized
SBA-15 is consistent with grafting the organic groups onto
the pore walls within the porous network (Table 1).
Nitrogen adsorption–desorption
The textural properties of the samples were evaluated
by the nitrogen adsorption-desorption isotherms (Figure
2). All materials exhibit a irreversible type IV nitrogen ad-
sorption isotherm with an H1 hysteresis loop as defined by
IUPAC.22 There is a shift of the hysteresis position toward
low relative pressures and a slight decreasing trend in over-
all nitrogen adsorption volume due to the grafting of di-
aminopropyl groups and fluorene. This indicates some
modification of the tubular channels of the parent SBA-15
silica material. The nitrogen adsorption at low relative
pressures is accounted for by monolayer adsorption of N2
on the pore walls, and does not essentially involve the pres-
ence of micropores. The sharp inflection in the P/P0 range
from 0.50 to 0.70 of the isotherm is related to the capillary
condensation within mesopores, the position of which is
clearly correlated to a diameter in the mesopore scale. The
pore size distribution was calculated from BJH method
RESULTS AND DISCUSSION
X-ray diffraction patterns
Figure 1 shows the low angle XRD patterns of
SBA-15, DMS and FDMS. All samples have a single inten-
sive reflection around 2q = 0.87° similar to the typical
SBA-15 material that is generally recognized characteristic
of the long-range periodic.19 For the SBA-15 material, two
additional peaks related to the higher ordering (110) and
(200) reflections can also be observed around 2q = 1.4° and
2q = 1.7° respectively, which are associated with a two-di-
mensional hexagonal (p6mm) structure.20 However, in the
case of functionalized SBA-15 materials, the peak (100) in-
tensity was decreased after functionalization steps due to
the difference in the scattering of the pores and the walls,
and due to the irregular coverage of organic groups on the
nanochannel surface.21 This observation indicates that the
hexagonal structure of the original SBA-15 is maintained
Fig. 1. Small angle XRD patterns a) SBA-15, b) DMS
and c) FDMS.
Table 1. Texture properties of prepared compoundsa
Molecular
sieves
DBJH
(nm)
SBET
Vtotal
wtb
(nm)
d100
(nm)
(m2/g)
(cm3/g)
SBA-15
DMS
FDMS
6.2
5.4
4.2
587
218
152
0.780
0.373
0.225
6.7
7.5
8.4
8.06
9.02
9.07
a SBET is the BET surface area; V is the total pore volume; DBJH is
the average pore diameter calculated using BJH method.
2
b Wall thickness =
– pore diameter.
3d(100)
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Badiei et al.
based on the desorption branch of the nitrogen adsorption
isotherm. As it demonstrated in Figure 2, BJH plot of DMS
and FDMS show a narrow pore size distribution. The uni-
formity of the mesopores in this modified SBA-15 is com-
parable to the SBA-15, indicating that the integrity of the
original wall structure of the SBA-15, is retained. In com-
parison with SBA-15, decreasment in the pore diameter
value by about 0.8 and 2 nm are observed for DMS and
FDMS, respectively. The textural parameters including
specific surface areas, pore diameters and total pore vol-
umes are given in Table 1, which shows a trend of decreas-
ing in surface area, pore volume and pore diameter due to
functionalization inside the channels of SBA-15.
spectively.23 There is an abundance of silanol groups pre-
sent in the parent SBA-15 silica in the surface of the
mesoporous channels. After grafting TMPED on the sur-
face of SBA-15, the intensity of the band at 3434 cm-1 is de-
creased. Meanwhile, the DMS showed the new adsorption
bands at 1598 cm-1 and 1465 cm-1 due to N-H bending vi-
brations. The band at 2930 cm-1 is assigned to the C-H
stretching vibrations of the methylene groups. These re-
sults indicated that the di-amino group was attached on the
surface of SBA-15. In the case of FDMS, the strong peak of
741 cm-1 was observed which due to the C=C ring skeletal
vibrations. The weak peaks at 1608 and 1449 cm-1 are also
related to the same type of vibrations.
FT-IR and Raman measurements
Figure 3 shows FT-IR spectra of SBA-15, DMS and
FDMS. In the FT-IR spectrum of the SBA-15 silica the
band at 3434 cm-1 can be assigned to the stretching vibra-
tion of OH groups. The bands at 804 and 1086 cm-1 are at-
tributed to the Si-O-Si and Si-O stretching vibrations, re-
Fig. 2. Nitrogen adsorption-desorption isotherms of
(a) SBA-15, (b) DMS, (c) FDMS (inset: BJH
pore size distribution curves of (a) SBA-15, (b)
DMS, (c) FDMS).
Fig. 3. FT-IR spectra of (a) SBA-15 (b) DMS (c)
FDMS.
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SBA-15 Grafted with Fluorene di-ammonium Groups
Figure 4 shows the Raman spectra of SBA-15, DMS
and FDMS. The band at 2900 cm-1 is attributed to C-H
stretching vibrations in the propyl chain in DMS and
FDMS. In the Raman spectra of FDMS, the strong bands at
1610 cm-1, 1484 cm-1 and 1024 cm-1 are clearly related to
the C-C and C=C ring skeletal vibrations of fluorene. The
bands at 3100 and 1350 cm-1 are attributed to the C-H ring
and C-N vibrations, respectively, confirming that the
fluorene was attached onto the surface of SBA-15.
tion of the weights loss could possibly confirmed that two
functional groups located on the surface of SBA-15. A mi-
nor weight loss due to silanol condensation at high temper-
ature was observed.25 The experimental and the theoretical
C/N molar ratio of DMS and FDMS were calculated from
the elemental analysis data (Table 2) which confirms that
di-amino propyl groups and fluorene are grafted onto the
surface. The amount of fluorene in FDMS was calculated
from the variation of the carbon percentage in DMS and
FDMS. With comparing data, it can be concluded that the
Conversion efficiency of DMS to FDMS is about 40.6%.
The amount of organic content determined by elemental
analysis is in approximate agreement with the value ob-
tained by TGA.
Thermogravimetric analysis
Thermogravimetric analysis and elemental analysis
were carried out to further verify the grafting of organic
groups onto the surface SBA-15. The TGA profiles of the
samples are illustrated in Figure 5. The weight loss aruond
100 °C corresponded to desorption of physisorbed water,
which is about 3.18% and 1.33% for DMS and FDMS, re-
spectively.24 The weight loss 18.67% between 340 °C and
700 °C is mainly due to the decomposition of aminopropyl
groups in DMS. The weight loss 33.21% between 200 °C
and 750 °C is due to the decomposition of organic groups in
FDMS. The breakage in the around 470 °C and the varia-
Fluorescence
The fluorescence spectrum of FDMS in water is illus-
trated in Figure 6. It exhibits two fluorescence emission at
305 nm and 410 nm followed by maximum excitation
wavelength of 260 nm. The blue shift was observed for
FDMS in comparison to fluorene (310 nm), due to, interac-
tion the p structure of the fluorene ring system with lone
pair of di-amino group. As the solution was acidified, two
changes in the emission spectra were observed. The first
change is appearing a new peak at 350 nm as the ground
state or the excited state is strongly destabilized by pro-
tonation of amine groups.16 The intensity of this peak was
increased with increase in [H+] from 0.16 mM to 1.5 mM by
titration with HCl 0.02 M. The second change is peak in-
Fig. 4. Raman spectra of (a) SBA-15, (b) DMS and (c)
FDMS.
Fig. 5. TGA analysis of (a) DMS (b) FDMS.
Table 2. The elemental analysis
Sample C% N% C/NExperimental C/NTheoretical Aminopropyl (mmol/g) Fluorene (mmol/g)
DMS 7.4 2.7 2.74 2.5
1.23a
FDMS 18.23 2.6 7.01 1.23
a Amount di-aminopropyl (mmol/g) = 1000C%/5(WC) 100.
b Fluorene(mmol/g) = 1000(C%FDMS - C%DMS)/18(WC) 100.
-
9
0.50b
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tensity decreasing in 410 nm with increasing of [H+] val-
ues. The first emission arises from the lowest excited sin-
glet state. In that state, the bridging carbon atom in the
9-position is tetrahedrally hybridized; the di-amino group
interacts simply with the p structure of the fluorene ring
system.26 The new emission could be observed between
360 nm to 410 nm for fluorene that depends on the media.27
This emission is attributed to a novel kind of twisted
intermolecular charge transfer (TICT) conformer within
the life time of the lowest excited singlet state.26 The elec-
tron donating nitrogen atom of FDMS inhibits the photo in-
duced electron transfer (PET) process between six and five
membered rings. Figure 7 display the protonation of the ni-
trogen atom enhancing the PET process due to the electron
withdrawing nature of the ammonium cations.10 In fact, the
failure of the protonated amino fluorene to demonstrate the
long-wave length fluorescence indicates the importance of
the availability of the lone pair of the di-amino group in the
occurrence of the long-wave length component. This mate-
rial can be introduced as a pH sensor based on fluorescence
measurements.
Computational detail
In order to have better insight on the electronic pro-
perties of FDMS, quantum mechanical calculations were
carried out with the density functional theory (DFT) and
time-dependent density functional theory (TD-DFT) in wa-
ter using the ORCAprogram. We have chosen PBE0 hybrid
functional for all DFT and TD-DFT calculations combined
with the def2-TZVPP basis set for all atoms. The PBE0
functional has been reported to be one of the most accurate
density functionals for TD-DFT calculations. All geome-
tries were optimized both in the gas phase and in water us-
ing the COSMO solvation model implemented in ORCA.
The vertical excitation energies were calculated using the
TD-DFT method.28-30 In order to find an explanation for
fluorescence and to investigate the chemical transforma-
tion of receptor from neutral (FDMS) to cationic forms, ab-
sorption spectra of the predicted structures were calcu-
lated, and the results are presented in Table 3.
According to calculated results, when the concentra-
tion of H+ increases and (FDMS) becomes protonated, the
lowest elecronic excitation energy increases, resulting in a
smaller l for the S1 ® S0 transition. This is consistent with
the experimental observation of fluoresence shift from 410
to 350 nm. Although the wavelengths for the S1 ® S0 tran-
sitions of all protonated forms of (FDMS) are very similar,
the oscillator strength (fosc) for (FDMS) H+ that contains a
proton on the terminal amine group is larger than the others
by a factor of two, and perhaps this form has the dominant
contribution in the observed fluorescence at 350 nm. The
HOMO and LUMO orbitals of (FDMS) and (FDMS) H+
are displayed in Figure 8. We have repeated our calcula-
tions with a few other density functionals, and the results
are presented in the Table 3.
Fig. 6. Fluorescence emission spectrum FDMS (0.1
g/L), (l = 260 nm) pH dependence of the PL
ex
CONCLUSIONS
spectra as a function of pH in water in the
presence of H+ from 0.16 to 1.5 Mm.
The work has shown that how the fluorene grafted to
the inner surface of mesoporous silica (FDMS), prepared
by a post synthesis. The fluorene reacts with di-amino-
modified surfaces. The products were characterized with
different techniques. Low angle X-ray analysis showed
that the mesoporous structure was preserved during the
functionlization processes. The nitrogen adsorption-de-
sorption isotherms displaied opening pores. The FT-IR and
Raman spectra demonstrated the incorporation of di-amino
functional groups and fluorene on the surface of SBA-15.
The grafted amount of organic moietes and the chemical
composition were determinated by elemental analysis and
Fig. 7. Fluorescence emission of FDMS and (FDMS)H+.
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SBA-15 Grafted with Fluorene di-ammonium Groups
media might be applied as a pH sensor. Also, its derivatives
may be effective candidate acid dependent molecular-sen-
sor models for advanced applications in optical sensors.
EXPERIMENTAL
Materials: P123 (EO20PO70EO20, MW = 5800) was ob-
tained from Aldrich. Fluorene, bromine, carbon tetrachloride, tet-
raethyl orthosilicate (TEOS), [1-(2-aminoethyl)-3-aminopropyl]
trimethoxysilane (TM PED), p-toluenesulfonic acid and hydro-
choloric acid were obtained from Merck. Toluene was dried ac-
cording to the standard purification methods.31
Fig. 8. Frontier molecular orbitals for (a) (FDMS) and
(b) (FDMS)H+ calculated in aqueous solution at
the PBE0/ def2-TZVPP.
Synthesis of di-aminopropyl functionlized SBA-15 (DMS):
SBA-15 material was synthesized by following the procedure re-
ported in the literature.18-32 A typical post-synthesis method, en-
tailed refluxing in a nonpolar solvent in the presence of organo-
silanes, was employed.33 Adetailed experimental description is as
follows: 0.5 g of SBA-15 was dispersed in 80 mL of toluene for 30
min at 50 °C with stirring. The p-toluenesulfonic acid (3.5 mg,
0.02 mmol) and TMPED (0.222 g, 1.0 mmol) were then added.
The mixture was reflux and maintained for 2 h with stirring. Then,
the solid product was filtered, washed with ethanol three times,
and was dried at 100 °C over night. (Figure 9)
TGA, respectively. The grafted amount of fluorene onto the
surface of SBA-15 was 0.50 mmol with yield about 40.6%.
The results demonstrated that during this grafting process
about half of the di-amino groups on the surface were re-
acted with fluorene. The emission spectra FDMS was
changed with addition of H+ that was showing the interac-
tion of H+ with this material. The computational studies
helped us to go further in determination of electronic struc-
tures. The fluorescence emission change of FDMS in acid
Synthesis of 9-Bromofluorene: 9-Bromofluorene was
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Badiei et al.
synthesized according to the other literature.18,34 To the solution
of fluorene (4.15 g, 25 mmol) in 50 ml of carbon tetrachloride un-
der a strong mercury arc (ultraviolet lamp) that emits a strong blu-
ish light as electric current passes through mercury vapor, 50 ml
of a molar solution of bromine in carbon tetrachloride was added
drop wisely, until the brown color was disappeared. The solvent
was evaporated under air and the residue was recrystallized from
hot ethanol. White needles of 9-Bromofluorene, m.p. 102-104 °C.
IR data: nmax/cm-1 3033 (C-H, arom), 1738, 1300 (C=C, ring), 629
(C-Br), MS data: m/e 82 (HBr+, 11.8), 246 (C13H10Br+, 47.2), 165
Brunauer-Emmett-Teller (BET) method, pore size distributions
were calculated from the nitrogen isotherms by Barret-Joyner-
Halenda (BJH) method. Thermogravimetric analysis (TGA) was
performed on a TA Q50 instrument. The scans were performed
between 25 and 900 °C at 10 °C min-1 in air atmosphere. Elemen-
tal analysis was carried out by a Rapid elemental analyzer. Emis-
sion spectra were recorded on Perkin Elmer LS-50B model fluo-
rescence spectrofluorometer and a dilute suspension of com-
pounds in water solvent (0.1 g/L) was used for fluorescence in-
vestigation. Calcinations were carried out in a box furnace under
conditions of flowing air. Mass spectra were measured using an
Agilent Technologies 5973 Net Work spectrometer. Melting
points were determined by the capillary method on electro ther-
mal 9100 apparatus.
+
(C13H9 , 100). The synthesis procedure was depicted in Figure 9.
Synthesis of fluorene functionalized mesoporous silica
(FDMS): 0.4 g DMS was vacuumed for 15 min, then 70 ml dried
toluene was added and mixture was stirred for 15 min. After
wards, 9-Bromofluorene (0.245 g, 1 mmol) was added to the
above mixture under inert atmosphere (Ar) and reflux for 4 h.
Then, it was cooled to the room temperature and toluene was re-
moved by filtration under vacuum. The obtained product was
refluxed with dry toluene and dried over night. (Figure 9)
ACKNOWLEDGEMENTS
The authors wish to thank the University of Tehran
for financially supporting this work.
Characterization Techniques: FT-IR spectra were ob-
tained on Equinox 55 spectrometer. Raman spectra were obtained
on a SENTERRA spectrometer. Low angle X-ray scattering pat-
terns were recorded on a model Hecus S3-MICROpix SAXS
diffractometer (Graz, Austria, X516/8910-980), with a one-di-
mensional PSD detector using Cu Ka radation (50 KV, 1 mA) at a
wave length of 1.542 Å. Nitrogen adsorption-desorption iso-
therms were obtained on a BELSORP mini-II at liquid nitrogen
temperature (77 K). Surface area was measured using the
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