Sensors and Actuators B 190 (2014) 93100

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Sensors and Actuators B: Chemical

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

Synthesis, characterization, and oxygen sensing properties of

functionalized mesoporous silica SBA-15 and MCM-41 with a
Pt(II)porphyrin complex
Binbin Wang a,b , Liming Zhang c , Bin Li c , Yao Li b , Yuhua Shi a , Tongshun Shi a,
a

College of Chemistry, Jilin University, Changchun 130021, PR China

College of Chemistry, Changchun Normal University, Changchun 130032, PR China
c
Key Laboratory of Excited State Processes, Changchun Institute of Optics Fine Mechanics and Physics, Changchun 130033, PR China
b

a r t i c l e

i n f o

Article history:
Received 27 December 2012
Received in revised form 16 July 2013
Accepted 7 August 2013
Available online 30 August 2013
Keywords:
Platinum(II) complex
Oxygen sensing
Mesoporous silica
High response

a b s t r a c t
A
novel
luminescent
platinum(II)
complex
platinum
5,10,15,20-tetra{4-[(Ncarbazyl)butyloxyphenyl]}porphyrin (PtTCBPyP) has been synthesized and characterized by 1 H
NMR, elemental analysis, IR and UVvis. The platinum porphyrin is assembled with mesoporous silica
SBA-15 and MCM-41 resulting in the assembly materials PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41.
The luminescence of platinum porphyrin complex/silicate assemble materials can be quenched
by molecular oxygen with very high response (I0 /I100 > 8700 for PtTCBPyP/SBA-15(20 mg/g) and
I0 /I100 > 3800 for PtTCBPyP/MCM-41(20 mg/g)), indicating that platinum porphyrin complex/silicate
systems can be employed to develop high performance oxygen sensors. Among this assembly system,
PtTCBPyP/SBA-15(20 mg/g) exhibits the highest response of platinum porphyrin complex/silica.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Over the past decades, luminescence-based optical oxygen sensors have been largely developed because the determination of
molecular oxygen both in the gas and in the liquid phase is very
important in many different elds such as analytical chemistry,
medical chemistry, environmental monitoring and industrial applications [14]. These sensors are based upon the principle that
oxygen is a powerful quencher of the luminescent intensity and
lifetime of luminescent complexes. The optical oxygen sensing systems consists of various complexes such as polypyridyl transition
metal complexes [5,6] and metalloporphyrins [7,8] owing to their
high quantum yields, large Stokes shifts, long luminescent lifetimes
and short response times, and they can be used for measuring oxygen concentration in gas, aqueous, and organic phase [5,6,810].
The host materials used to encapsulate the luminescent complexes
are solgel and polymer lms. Some interesting systems based on
solgel or polymer immobilized transition metal complexes have
been reported [1115].
After the discovery of mesoporous silicas prepared by the cooperative organization of surfactant and inorganic species in 1992
[16,17], the synthesis, characterization, and applications of the
supramolecular-templated mesostructured materials have been

of widespread interest in materials science. Ordered mesoporous

materials continue to be widely and extensively used as excellent host materials due to their unique properties such as high
surface area, ordered pore structure of varying morphologies,
and controllable pore size over wide ranges [1822]. Mesoporous
materials are able to physically encapsulate and immobilize the
functional molecules into the pores, while the solvent and other
small molecules or ions are allowed into the interior of the mesoporous silicas through channels. In order to obtain excellent optical
oxygen sensors, high response is necessary for some transition
metal complex based oxygen sensing materials [2327]. However,
few of these oxygen sensors display high response. The design and
assembly of high performance oxygen sensors based on luminescent transition metal complexes remain a challenge for chemists. To
obtain more efcient oxygen sensing materials, in this contribution,
we report the synthesis of a novel luminescent platinum(II) complex (PtTCBPyP) and the assembly of PtTCBPyP with mesoporous
silica SBA-15 and MCM-41. The optical oxygen sensing properties of
assembly materials PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41 also
will be presented.

2. Experimental
2.1. Materials

Corresponding author. Fax: +86 431 85168898.

E-mail address: tsshi163@163.com (T. Shi).
0925-4005/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2013.08.036

Analytical grade solvents and compounds were used for preparations. Pyrrole, 1, 4-dibromobutane and platium(II) chloride were

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B. Wang et al. / Sensors and Actuators B 190 (2014) 93100

Scheme 1. Synthesis procedure of the porphyrin ligand and its complex.

purchased form Aldrich. 4-hydroxybenzaldehyde and carbazole

were obtained from Acros. All the other chemicals were obtained
from Tianjin Tiantai Pure Chemicals Co., Ltd. 5, 10, 15, 20-tetra(4hydroxyphenyl)porphyrin [28] and N-(8-bromooctyl)carbazole
[29] were synthesized according to the literature procedures.
Mesoporous silica (SBA-15 and MCM-41) [30,31] was hydrothermally prepared following literature procedures. Then the template
was removed from the mesoporous silicate by calcinations at
560 C for 8 h. The solvent dichloromethane (CH2 Cl2 ) was used
after desiccation with anhydrous calcium chloride. Dimethyl formamide (DMF) was pre-dried over activated 4 A molecular sieves
and vacuum distilled from calcium hydride (CaH2 ) prior to use. Dry
benzonitrile was obtained by distillation from CaH2 . Anhydrous
potassium carbonate was dried under vacuum at 80 C for half an
hour.
2.2. Synthetic procedures
The synthesis procedures for the porphyrin derivatives were
illustrated in Scheme 1.
2.2.1. Synthesis of 5,10,15,20-tetra{4-[(Ncarbazyl)butyloxyphenyl]}porphyrin(TCBPyP)
Under nitrogen, 5, 10, 15, 20-tetra(4-hydroxyphenyl)porphyrin
(0.80 g, 1 mmol) was added to 250 mL of DMF with K2 CO3 (1.4 g,
10 mmol). The mixture was heated to reux for 1 h, and then N(8-bromobutyl)carbazole (2.4 g, 8 mmol) was added. Heating the
mixture to reux for 24 h was continued. After distilling off DMF,
the residue was puried by column chromatography using silica
gel with dichloromethane as eluent (yield 25%). 1 H NMR (300 MHz,
CDCl3 , 25 C, TMS): = 8.835 (s, 8H, pyrrole ring), 8.4318.478 (t, 8H,
-C6 H4 ), 8.1428.168(d, 8 H, carbazole ring C1 H), 8.0698.096(d,
8 H, m-C6 H4 ), 7.545 (t, 16H, carbazole ring C2,3 H), 7.2367.276
(t, 8H, carbazole ring C4 H), 4.5484.569 (t, 8H, O CH2 ),
4.2214.261 (t, 8H, N CH2 ), 2.2592.309 (m, 8H, N C CH2 ),
2.0272.073 (m, 8H, O C CH2 ), 2.785 (s, 2H, pyrrole N H). MS
m/z (%): found [M+ ] 1563.8, calcd. 1563.9.
2.2.2. Synthesis of platinum
5,10,15,20-tetra{4-[(N-carbazyl)butyloxyphenyl]}porphyrin
(PtTCBPyP)
Under nitrogen, PtCl2 (50 mg, 0.2 mmol) and TCBPyP (30 mg,
0.02 mmol) were suspended in 100 mL of benzonitrile. The mixture was then heated to reux for 10 h. The mixture was cooled
to room temperature, and the solvent was removed by vacuum
distillation. The crude product was puried by column chromatography using silica gel with dichloromethane as the eluent (yield
99%). 1 H NMR (300 MHz, CDCl3 , 25 C, TMS): = 8.764 (s, 8H, pyrrole

ring), 8.3178.336 (t, 8H, o-C6 H4 ), 8.1408.162(d, 8 H, carbazole

ring C1 H), 8.0638.090(d, 8 H, m-C6 H4 ), 7.539 (t, 16H, carbazole
ring C2,3 H), 7.2337.274 (t, 8H, carbazole ring C4 H), 4.5484.569
(t, 8H, O CH2 ), 4.2124.257 (t, 8H, N CH2 ), 2.2382.292 (m,
8H, N C CH2 ), 2.0012.056 (m, 8H, O C CH2 ). Anal. Calcd.
for C108 H88 N8 O4 Pt: C, 73.83; H, 5.05; N. 6.38. Found: C, 73.79; H,
5.09; N, 6.35. IR (KBr pellets): 3050, 2925, 2854, 1599, 1459, 1328,
1245, 1174, 1008, 811, 725 cm1 .
2.2.3. Synthesis of PtTCBPyP/SBA-15
PtTCBPyP was immobilized into SBA-15 by the following procedure. In a typical preparation, 1 mg PtTCBPyP was added into
10 ml dichloromethane and the mixture was stirred for 5 min. Then
SBA-15 (0.1 g) was added into the dichloromethane solution of
PtTCBPyP. The resulting mixture was stirred for 1 h at room temperature, and ltrated. The obtained white powder was washed several
times with the solvent until no PtTCBPyP existed in the ltrate. The
powder was dried in air, and the target sample PtTCBPyP/SBA-15
was obtained. The samples with different loading levels (10, 20 and
40 mg/g SBA-15) were prepared by altering the concentrations of
initial solution of PtTCBPyP.
2.2.4. Synthesis of PtTCBPyP/MCM-41
The samples with different loading levels (10, 20 and 40 mg/g
MCM-41) were prepared with procedure similar to that described
above.
2.3. Apparatus and measurements
1H

NMR spectra were acquired on a Varian Clnity 300 MHz

spectrometer by using standard pulse sequences. Spectra were
recorded at 25 C in CDCl3 unless otherwise stated. Chemical shifts
were reported on the scale relative to tetramethylsilane (TMS).
Elemental analyses were measured by a PerkinElmer 240C auto
elementary analyzer. The excited state lifetime was detected by
a systemequipped with a TDS 3052 digital phosphor oscilloscope
pulsed Nd:YAG laser with a THG 355 nm output and a computercontrolled digitizing oscilloscope. UVvis spectra were collected on
a Shimadzu UV-365 spectrometer. Infrared spectra were recorded
on a Nicolet 5PC-FT-IR spectrometer in the region 4000400 cm1 .
Mass spectra were obtained using a VG-Quattro mass spectrometer.
Thin layer chromatography was performed on glass micro-plates
coated with silica gel G. The photoluminescence (PL) spectrawere
obtained by a Hitachi F-4500 uorescence spectrophotometer
equipped with a monochromator (resolution: 0.2 nm) and a 150 W
Xe lamp as the excitation source. The photoluminescence quantum yield was dened as the number of photons emitted per
photon absorbed by the system and was measured with an

B. Wang et al. / Sensors and Actuators B 190 (2014) 93100

Fig. 1. UVvis absorption spectra of TCBPyP and PtTCBPyP in dichloromethane solution.

integrating sphere by literature method. The powder X-ray

diffraction (XRD) data were collected on a Bruker D2 PHASER
diffractometer equipped with CuK1 target ( = 0.15405 nm). The
scanning range is 0.210 with 0.02 step and scanning speed is
1 s/step.
The oxygen-sensing properties of our samples were discussed
based on the uorescence intensity quenching. The excitation
wavelength of all samples was 421 nm. In the measurement of
SternVolmer plots, oxygen and nitrogen were mixed at different concentrations via gas ow controllers and passed directly
into the sealed gas chamber at 25 C, 45% relative humidity (Oxygen response properties almost remain unchanged on the different
relative humidity, see supplementary le). We typically allowed
1 min between changes in the N2 /O2 concentration to ensure that
a new equilibrium point had been established. Equilibrium was
evident when the luminescence intensity remained constant. The
sensor response curves were obtained using the similar method.
The experiments were carried out in the dark at room temperature.
3. Result and discussion
3.1. UVvis absorption spectra
UVvis absorption bands of the porphyrins are due to electronic transitions from the ground state (S0 ) to the two lowest
singlet excited states S1 (Q state) and S2 (Soret state) [28]. The
S0 S1 transition gives the weak Q bands in the visible region while
S0 S2 transition produces the strong Soret band in the near UV
region [32,33]. The absorption spectra of TCBPyP and PtTCBPyP in
dichloromethane solution are shown in Fig. 1. The UVvis spectrum
of TCBPyP showed a maximum peak at 421 nm which is typical
for Soret band, and four Q-bands were appeared at 518, 554, 593,
650 nm. The Q band consists of four absorptions typical of Qx (0,0),
Qx (0,1), Qy (0,0), Qy (0,1) transitions. The relative intensities of these
bands are: 421 > >518 > 554 > 593 > 650 nm. These intensities are
similar to those observed for TPP [34]. The absorption peaks and
relative intensities of porphyrin ligand is almost identical, indicating that covalent linking of carbazole side groups to TPP has little
effect on the -electron system of the porphyrin. The absorption
bands of PtTCBPyP are almost identical too, which appear at 429,
523, 560 nm. Compared with the porphyrin ligand, the number of
the absorption bands of the metalloporphyrin complex decrease,
the most remarkable difference is the absence of some Q bands.
When the metal ions substitute the protons on the N atoms in

95

Fig. 2. UVvis absorption spectra of PtTCBPyP in dichloromethane solution (a),

PtTCBPyP/SBA-15(20 mg/g) (b) and PtTCBPyP/MCM-41 (20 mg/g) (c).

pyrrole rings, the symmetry of the molecule was changed from

D2h to D4h , therefore their absorption spectra are changed to some
extent.
UVvis absorption spectra of PtTCBPyP in dichloromethane
PtTCBPyP/SBA-15(20 mg/g)
and
PtTCBPyP/MCMsolution,
41(20 mg/g) are shown in Fig. 2. UVvis absorption spectra of
PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41 are similar to that
of PtTCBPyP in dichloromethane solution, indicating that the
luminophors incorporated in composite systems remain intact
and keep their photochemical properties unchanged during the
process of encapsulation.
3.2. Photoluminescence spectra
Luminescence quantum yield is dened as the ratio of the number of photons emitted to the number of photons absorbed. The
room-temperature luminescence quantum yield of TCBPyP and
PtTCBPyP in degassed dichloromethane solution have been conrmed by comparing with the known luminescence quantum yield
from platinum meso-tetrakis(phenyl)porphyrin (PtTPP, = 0.046)
[35]. Sample and standard solutions are degassed with no less than
four freezepumpthaw cycles. Quantum yield is identied according to the following Eq (1):
sample =

Fsample
FPtTPP

APtTPP
PtTPP
Asample

(1)

where Fsample and FPtTPP are measured photoluminescence integral areas (under the photoluminescence spectra) of the sample
and the reference PtTPP, respectively, Asample and APtTPP are the
absorbances of the sample and the reference, sample and PtTPP are
the quantum yields of the sample and the reference PtTPP at same
excitation wavelength. The S1 S0 quantum yield depends on the
relative rates of the radiative process S1 S0 and two radiationless
processes S1 S0 and S1 Tn . The photoluminescent quantum
yields of TCBPyP and PtTCBPyP in solution are 0.246 and 0.202 at
a concentration of 1.0 105 mol/L, which are much more than
that of TPP and PtTPP. This indicates fairly certainly that the radiative process S1 S0 is predominant for S1 S0 in these porphyrin
compounds and TCBPyP and PtTCBPyP possess good luminescence
properties in anaerobic surroundings. The raise of luminescence
quantum yield can be explained by the insert of the strong hole
transport carbazole group.

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B. Wang et al. / Sensors and Actuators B 190 (2014) 93100

Fig. 3. Solid-state emission spectra of PtTCBPyP in air, pure nitrogen and pure oxygen. ex = 420 nm, slit widthex/em = 5.0/2.5 nm.

The emission spectra in solid-state have been obtained in air,

pure nitrogen and oxygen, respectively, and the data indicate that
the emission intensity of PtTCBPyP is signicantly inuenced by
the concentration of oxygen, as shown in Fig. 3. The striking difference in emission intensity under different oxygen concentration is
noteworthy, because it indicates that PtTCBPyP probably possesses
oxygen-sensing properties.
Excited-state lifetime of PtTCBPyP, PtTCBPyP/SBA-15 and
PtTCBPyP/MCM-41 in air is measured (see Table 1). All of the data
are found to be well-t by the double exponential. Where and
 are the pre-exponential factors and the excited-state lifetime
of the related decay prole, respectively. The subscripts 1 and 2
denote the assigned lifetime components. Longer lifetime values
can be observed from PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41
samples than PtTCBPyP. This result can be attributed to the fact
that the PtTCBPyP/MCM-41 and PtTCBPyP/SBA-15 samples avoid
self-quenching efciently compare with solid state Pt (II) complex.
Such lifetime values also can be explained on the basis of the suppression of the vibrational deactivation and the restriction on the
mobility of the Pt (II) complex in an excited state due to the rigidity
of the silica matrix [36].

Fig. 4. (A) Powder XRD patterns of SBA-15 (a) and PtTCBPyP/SBA-15

(B) Powder XRD patterns of MCM-41 (a) and PtTCBPyP/MCM-41 (b).

oxygen, which is accompanied by the formation of singlet oxygen. As a result, the complex could be commonly used to develop
oxygen-sensing materials. The oxygen concentration dependent
emission spectra of PtTCBPyP/SBA-15(20 mg/g) are shown in
Fig. 5. The emission maximum of PtTCBPyP/SBA-15(20 mg/g) is
at 651 nm and is constant under different oxygen concentrations.

3.3. Oxygen-sensing properties

Powder XRD patterns of SBA-15, PtTCBPyP/SBA-15, MCM-41
and PtTCBPyP/MCM-41 are shown in Fig. 4. It shows three Bragg
reections in the low angle indexed to d100 , d110 , and d200 , which
are characteristic peaks of highly ordered hexagonal mesostructure
[37,38]. Powder XRD measurement results indicate that the hexagonal arrangement of channels in mesoporous molecular sieves
remains unchanged after the incorporation of PtTCBPyP.
The luminescence of platinum porphyrin complex could be
quenched efciently by molecular oxygen. The mechanism of the
quenching process consists of the exchange energy transfer from
the lowest triplet excited state of metalloporphyrin to molecular
Table 1
Excited-state lifetime of PtTCBPyP, PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41 in air.
sample

 1 (s) 2

PtTCBPyP
0.08
4.23
0.35 10.00
PtTCBPyP/SBA-15(20 mg/g)
4.96
PtTCBPyP/MCM-41 (20 mg/g) 0.58

 2 (s) <> (s) r2

0.02 10.00
0.60
3.72
0.02 18.20

6.37
7.55
6.45

0.9987
0.9972
0.9960

Fig. 5. Emission spectra of PtTCBPyP/SBA-15(20 mg/g) under different oxygen concentrations: (a) 0; (b) 0.1; (c) 10; (d) 100% oxygen.

B. Wang et al. / Sensors and Actuators B 190 (2014) 93100

97

Fig. 7. SternVolmer plot for PtTCBPyP/SBA-15 at different concentrations of oxygen. (I0 and I are luminescent intensities in the absence and in the presence of
oxygen).
Fig. 6. Emission spectra of PtTCBPyP/MCM-41 (20 mg/g) under different oxygen
concentrations: (a) 0; (b) 0.1; (c) 10; (d) 100% oxygen.

However, the relative intensity decreases markedly upon increasing oxygen concentration. The variations of the emission spectra
of PtTCBPyP/SBA-15(10 or 40 mg/g) display similar trends to that
of PtTCBPyP/SBA-15(20 mg/g). The relative luminescent intensities of PtTCBPyP/SBA-15(10 mg/g), PtTCBPyP/SBA-15(20 mg/g), and
PtTCBPyP/SBA-15(40 mg/g) decrease by 99.94%, 99.99% and 99.98%,
respectively, upon changing from pure nitrogen to pure oxygen
conditions. PtTCBPyP/SBA-15(20 mg/g) is more sensitive compared
with PtTCBPyP/SBA-15(10 mg/g) and PtTCBPyP/SBA-15(40 mg/g),
suggesting that the optimum loading level is 20 mg/g. The oxygen
concentration dependent emission spectra of PtTCBPyP/MCM41 (20 mg/g) are shown in Fig. 6. The emission maximum of
PtTCBPyP/MCM-41 (20 mg/g) is at 646 nm and the emission intensity drops quickly. For PtTCBPyP/MCM-41 (20 mg/g), similar results
are observed by comparing the emission spectra under different concentrations of oxygen. Upon changing from pure nitrogen
to pure oxygen conditions, the relative luminescent intensities
of PtTCBPyP/MCM-41 (10 mg/g), PtTCBPyP/MCM-41 (20 mg/g) and
PtTCBPyP/MCM-41 (40 mg/g) decrease by 99.77%, 99.97% and
99.92%, respectively, and the optimum loading level is 20 mg/g. The
two opposite factors probably affect the sensing properties of the
composite systems. When the loading level is 10 mg/g, the emission
from the complex is comparatively weak which results in the low
response. When the loading level is 40 mg/g, concentration quenching existing among the platinum porphyrin molecules in the pores
of mesoporous silica may become stronger.
Luminescent molecule quenching in homogeneous media with
negligible matrix effects are expected to show single-exponential
excited state decay and the emission intensity or decay time with
oxygen concentration can be described by the SternVolmer (SV)
Eq. (2):
I0 /I = 0 / = 1 + KSV [Q ] = 1 + Kq 0 [Q ]

Figs. 7 and 8 present the SternVolmer plots for PtTCBPyP/SBA15 and PtTCBPyP/MCM-41, respectively. The plots are nonlinear
within a wide range of oxygen concentrations. The deviation
from linearity is attributed to a distribution of slightly different quenching environments for the luminophore molecules. It is
believed that there are two sites of platinum porphyrin complex
micro-environments within the ormosil matrix: one site is oxygeneasy accessible and the others are oxygen-difcult accessible sites
[4245]. Platinum porphyrin complex may exhibits characteristic
quenching constants within each distinct platinum porphyrin complex site, and the overall SternVolmer expression becomes Eq. (3):
I0
=
I

1
f01
1+KSV1 [Q ]

f02
1+KSV2 [Q ]

(3)

Here, f01 and f02 denote the fractional contributions of the total
intensity from the platinum porphyrin complex located at two different sites that exhibit two discrete SternVolmer constants KSV1
and KSV2 , respectively. This two-site model accounts for nonlinearity commonly observed for SternVolmer plots. The I0 /I100 ratio
has been used as an indicator of the response of the sensing device,
and a sensor with I0 /I100 more than 3.0 is a suitable oxygen sensing device [46]. The value of I0 /I100 of PtTCBPyP/SBA-15(20 mg/g)
is 8779.8. To our knowledge, it is the highest value for optical oxygen sensors based on platinum porphyrins that have been achieved

(2)

where I and  are the luminescence intensity and the excited-state

lifetime of the related decay prole, respectively, the subscript 0
denotes the absence of oxygen, KSV is the SternVolmer constant,
Kq is the bimolecular rate constant describing the efciency of the
collisional encounters between the luminophore and the quencher,
and [Q] is the O2 concentration. In the idea case, the plot of I0 /I or
 0 / versus oxygen concentration should give a straight-line relationship with slope KSV . However, non-linear SternVolmer plots
are often obtained when quenching takes place in a solid matrix
[3941].

Fig. 8. SternVolmer plot for PtTCBPyP/MCM-41 at different concentrations of oxygen. (I0 and I are luminescent intensities in the absence and in the presence of
oxygen).

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B. Wang et al. / Sensors and Actuators B 190 (2014) 93100

Fig. 9. Response time and relative intensity change and reproducibility for
PtTCBPyP/SBA-15(20 mg/g) on switching between 100% nitrogen (a) and 100% oxygen (b).

until now. It can be seen from the SternVolmer plots that high
response is obtained at low oxygen concentrations (less than 10%,
I0 /I10 ). Even when the concentration is only 10%, for PtTCBPyP/SBA15(10, 20 and 40 mg/g) the quenching of luminescence can
reach 99.81% (I0 /I10 = 526.9), 99.96% (I0 /I10 = 2634.6) and 99.89%
(I0 /I10 = 1881.8), for PtTCBPyP/MCM-41(10, 20 and 40 mg/g) the
quenching of luminescence can reach 99.24% (I0 /I10 = 131.7), 99.80%
(I0 /I10 = 1038.3) and 99.73% (I0 /I10 = 376.4), respectively. Even when
the concentration is only 0.1%, for PtTCBPyP/SBA-15(20 mg/g) the
quenching of luminescence can reach 96.14% (I0 /I0.1 = 25.9), for
PtTCBPyP/MCM-41 (20 mg/g) the quenching of luminescence can
reach 95.42% (I0 /I0.1 = 21.8), respectively. It is important that the
measurement, so PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41 has a
great potential for application in oxygen sensors.
The response time and recovery time are also very important factors in evaluating an oxygen sensor. Traditionally, 95%
response time, i.e. t (95%, N2 O2 ) refers to the time required
for the luminescent intensity to decrease by 95% on changing from 100% nitrogen to 100% oxygen, and 95% recovery
time, i.e. t (95% N2 O2 ), is dened as the time required for
the luminescent intensity to reach 95% of the initial value
recorded under 100% nitrogen on changing from100% oxygen
to 100% nitrogen. Figs. 9 and 10 show the response property
of PtTCBPyP/SBA-15(20 mg/g) and PtTCBPyP/MCM-41 (20 mg/g).
The emission intensity of the samples drops quickly with the
increasing of oxygen concentration, and recovers when 100%
nitrogen replacing oxygen. The samples are repeatedly exposed
to an alternating atmosphere of nitrogen and oxygen and the
emission intensity changes with the oxygen concentration are

Fig. 10. Response time and relative intensity change and reproducibility for
PtTCBPyP/MCM-41 (20 mg/g) on switching between 100% nitrogen (a) and 100%
oxygen (b).

reversible. The values of response (I0 /I100 ), t, t and Demas model

oxygen-quenching tting parameters are compiled in Table 2.
Oxygen sensing materials based on PtTCBPyP/SBA-15 have good
response (I0 /I100 > 1700), especially PtTCBPyP/SBA-15(20 mg/g)
with an excellent response (I0 /I100 > 8700). Oxygen sensing materials based on PtTCBPyP/MCM-41 (20 mg/g) have fast recovery
time (t < 15.0 s), response time (t < 2.0 s) and good response
(I0 /I100 > 3800). The oxygen sensing property of this kind of material
is much better than that of other Ptporphyrin based sensing materials reported previously [4750]. These results provide possible
explanation as follows: Even though some PtTCBPyP molecules are
encapsulated in the pores of mesoporous silica, there is still excess
space to allow oxygen molecules to transport freely, so oxygen
molecules can easily diffuse into/out of the pores of PtTCBPyP/silica.
The molecular dimensions of PtTCBPyP are bigger than those of
other Ptporphyrin, but the conjugacy of PtTCBPyP is weaker. At
the concentration of 20 mg/g, the distribution of PtTCBPyP is better than other Ptporphyrin in the pores of mesoporous silica.
The long alkyl-carbazole arms of PtTCBPyP can avoid concentration quenching among the platinum porphyrin molecules, which
make the energy can transfer from excited porphyrin molecule to
the ground state oxygen more effectively but not transfer among
the platinum porphyrin molecules. Bigger molecular dimensions
and weaker conjugated structure could make the luminescence of
PtTCBPyP/silica quenched by oxygen molecules efciently [51,52].
The results illustrate that the recovery time is signicantly longer
than the response time. Since small molecules such as oxygen are
well known to be adsorbed strongly on silica surfaces, we suggest
that the longer recovery time may be attributed to slow desorption

Table 2
Values of response (I0 /I100 ), t, t, and Demas modela oxygen-quenching tting parameters of PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41.
PtTCBPyP/SBA-15

I0 /I100
t(s)
t(s)
KSV1 (O2 %1 )
KSV2 (O2 %1 )
f 01 b
r2
a
b

PtTCBPyP/MCM-41

10 mg/g

20 mg/g

40 mg/g

10 mg/g

20 mg/g

40 mg/g

1756.0
4.5
15.5
0.00338 0.00059
71.7061 3.05388
0.00057 0.00003
0.99958

8779.8
3.0
17.0
0.00339 0.00059
359.18093 15.32362
0.00011 0.00001
0.99958

6271.3
3.0
19.0
0.00338 0.00059
256.51536 10.94195
0.00016 0.00001
0.99958

439.0
2.5
16.0
0.00335 0.00059
17.80357 0.75323
0.00226 0.00012
0.99959

3853.0
1.5
14.5
0.00029 0.00037
131.50852 3.44677
0.00019 0.00001
0.99974

1254.3
1.5
17.5
0.00338 0.00059
51.17177 2.17744
0.00079 0.00004
0.99958

Terms are from Eq. (3).

f 01 + f 02 = 1.

B. Wang et al. / Sensors and Actuators B 190 (2014) 93100

of oxygen from the silica surface in the support. PtTCBPyP/SBA-15

and PtTCBPyP/MCM-41 show similar recovery times and response
times, but their response is obviously different, which is explained
in detail by the difference of pore structure between the two
kinds of mesoporous oxygen sensing materials. It is well-known
that comparing with the MCM-41, the porous structure of SBA15 has much larger pore volume [18], which causes the change of
O2 desorption rate and N2 desorption rate of PtTCBPyP/SBA-15 is
faster than that of PtTPyP/MCM-41. Therefore the luminescence of
PtTCBPyP/SBA-15 could be quenched efciently on changing from
100% nitrogen to 100% oxygen and recovered completely on changing from 100% oxygen to 100% nitrogen.
4. Conclusions
In conclusion, A novel luminescent platinum(II) complex
PtTCBPyP has been synthesized and characterized. The luminescence of PtTCBPyP is easily quenched by oxygen and exhibits strong
oxygen dependent characteristic. The oxygen-sensing properties
of PtTCBPyP have been tested by incorporating it into mesoporous SBA-15 and MCM-41 with three different loading levels.
We demonstrate that PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41
are oxygen sensing materials with a high response. The response
(I0 /I100 = 8779.8) of the optimal loading level system is the highest
value for optical oxygen sensors of platinum porphyrin complex/silica. PtTCBPyP/SBA-15 and PtTCBPyP/MCM-41 has a great
potential for application in oxygen sensors.
Acknowledgements
This work was supported by the National Natural Science Foundation of Peoples Republic of China (Grant No. 20801022) and
Changchun Normal University Natural Science Foundation.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2013.08.036.
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Biographies
Binbin Wang Received his BSc in 2004 and MSc in 2007 in inorganic chemistry from
Northeast Normal University (NNU), and then he began his PhD student experience
in inorganic chemistry, Jilin University under the supervising of Prof. Tongshun Shi.
He has been a lecturer since 2010 at Changchun Normal University. His research
interest is the synthesis of porphyrin metal complexes. He is also interested in the
exploration of porphyrin metal complexes as gas sensors.
Liming Zhang Received his BSc degree in 2005 from NNU and PhD in 2010 in condensed state physics from Changchun Institute of Optics Fine Mechanics and Physics
(CIOMP). He has been a research assistant at the CIOMP. He has been working on
luminescence materials.
Bin Li Received his BSc in 1986 and MSc in 1991 in inorganic chemistry from NNU,
and PhD in 1997 in inorganic chemistry from Changchun Institute of Applied Chemistry of Chinese Academy of Sciences. He has been an associate professor since 1999
at NNU and a professor since 2003 at CIOMP. His current research interests are the
study of application of transition metal complex as gas sensors, and the organic light
emitting devices (OLED).
Yao Li Received her BSc in 2005 and MSc in 2008 in inorganic chemistry from NNU,
and then she began her PhD student experience in inorganic chemistry, Beijing
Institute of Technology. Her research interest is luminescent materials.
Yuhua Shi Received her BSc in 1996 and PhD in 2001 in analytical chemistry from
Jilin University, and then she became an associate professor at Jilin University. Her
research interest is luminescent materials.
Tongshun Shi Received his BSc degree in 1969 from Jilin University. He has been
an associate professor since 1992 and a professor since 1998 at Jilin University.
His current research interests are the synthesis and application of porphyrin metal
complexes.