Visible light photo-sensitized metallo-porphyrin/TiO2 photocatalyst and its related self-cleaning effects in poly ethylene terephthalate

Article abstract of DOI:10.1166/jnn.2019.16760

Dye degrading property to exhibit self-cleaning effect in Poly Ethylene Terephthalate (PET) through photocatalytic effect by Metallo porphyrin and TiO2 has been studied in detail. PET has been modi?ed by step wise deposition of anatase TiO2 and Metallo po

Full text of DOI:10.1166/jnn.2019.16760

Article
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Nanoscience and Nanotechnology
Vol. 19, 8004–8012, 2019
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Visible Light Photo-Sensitized Metallo-Porphyrin/TiO2
Photocatalyst and Its Related Self-Cleaning
Effects in Poly Ethylene Terephthalate
Gisu Heo†, Ramalingam Manivannan†, Hyorim Kim, Ji Won Ryu, and Young-A Son∗
Department of Advanced Organic Materials Engineering, Chungnam National University, 220 Gung-dong,
Yuseong-gu, Daejeon 305-764, South Korea
Dye degrading property to exhibit self-cleaning effect in Poly Ethylene Terephthalate (PET) through
photocatalytic effect by Metallo porphyrin and TiO2 has been studied in detail. PET has been
modified by step wise deposition of anatase TiO2 and Metallo porphyrin (CuTCNPP, NiTCNPP,
ZnTCNPP), self-cleaning property of the modified PET has been studied by photo degradation of
rhodamine B (RB) by irradiation under visible light and the degrading ability and the efficiency has
been monitored using UV-Vis spectral technique by measuring the change in concentration of RB
in the PET at different time intervals. Stability of Metallo porphyrin in PET also measured by UV-
Vis spectral method. Indicating the porphyrin attached in PET are highly stable after washing the
samples with detergent, water even after irradiating under visible light for more than 5 h. The degra-
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dation effectiveness found to be in the order of PET/TiO /ZnTCNPP > PET/TiO2/CuTCNPP > PET/
Copyright: American Scien2tific Publishers
TiO2/NiTCNPP > TiO2 > PET. The modification made in the PET samples were characterized and
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confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Ultraviolet-visible
spectroscopy (UV-Vis), Field emission scanning electron microscope (FESEM) analysis and the
prepared Metallo porphyrin has been confirmed through mass analysis.
Keywords: Metallo-Porphyrin,
TiO2,
Rhodamine,
Visible
Light,
Photocatalysis,
Photodegradation.
1. INTRODUCTION
is obtained by modifying the surface chemically or geo-
metrically. Whereas, hydrophilic self-cleaning character in
fibrous material is achieved over and done with photo-
catalytic effect by photoactive material, for this polycrys-
talline semiconductor oxides exhibiting optical properties
are employed, these photoactive material works sponta-
neously to remove absorbed contaminants, dirt through
chemical decomposition in presence of light by the process
of photo oxidation and photo reduction reactions [1, 2].
Based on recent reports integrating nanosized TiO2 to
the substrate, various methods were employed in deposit-
ing TiO2 to the fibrous material by sol–gel method,
hydrothermal, impregnation, chemical spacer attachment,
sputtering [3–9]. However, attaching TiO2 on flexible sur-
face like paper, fabric and plastic is challenging because
of its low thermal and chemical resistance [10–12]. TiO2
is known to be reliable and eco-friendly photocatalyst
which is known to possess high stability towards various
Research related to functionalizing fibrous material is
of great demand in recent years, apart from the basic
property; the material should possess properties like self-
cleaning, protection against pollutant, microorganisms,
deodorization. In particular, Self-cleaning textile materials
are receiving importance in recent years due to its poten-
tial application in daily life. Self-cleaning surfaces attained
either by hydrophobic or hydrophilic modification made in
the fibrous material, for this purpose coating methods are
developing rapidly to achieve self-cleaning property in tex-
tiles. The hydrophobic nature popularly known as the lotus
effect displays water contact angle more 150ꢀ where the
dirt can be rolled off when comes in contact with water this
∗Author to whom correspondence should be addressed.
†These two authors contributed equally to this work.
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1533-4880/2019/19/8004/009
doi:10.1166/jnn.2019.16760

Heo et al.
Visible Light Photo-Sensitized Metallo-Porphyrin/TiO2 Photocatalyst and Its Related Self-Cleaning Effects in PET
chemicals and have excellent oxidizing ability, more-
over it is non-toxic and low cost. The photocatalytic
self-cleaning ceramic first discovered by Fujishima et al.
opened the space for researchers to explore numerous
self-cleaning materials like lamp covers, glasses, window-
blinds, tents. Daoud et al. first invented self-cleaning cot-
ton through nucleation and growth of anatase TiO2 at
low temperature and ambient pressure [13]. This photo-
catalytic self-cleaning surface functionalization are marked
as hydrophilic self-cleaning coating which tend to show
extraordinary photo-induced hydrophilicity after light irra-
diation [1, 14]. Significant research has been approved
to produce TiO2 nanocrystals on natural and synthetic
fibers [15] for the UV-active self-cleaning materials and
does not show the self-cleaning property under visible
light because of the wide band gap of TiO2 which is
about 3.2 eV, thus it can absorb UV light of wavelength
in the range of 385 nm [16], to spread its light absorb-
ing ability towards visible region, various strategies were
carried out such as doping metal, nonmetals [17, 18]
to TiO2. Dye-sensitization is an another approach to
induce photocatalytic activity in visible region [19]. Dye-
sensitization achieved by incorporating Porphyrin to TiO2
as it has a strong absorption peak in the range of 450 nm
region (Soret band) and weak Q bands at around 500–
700 nm [20]. Thus the surface modification attained
through this process may have the excellent self-cleaning
group that interacts with the TiO2-coated PET for the
development of hydrophilic self-cleaning material, as
shown in Scheme 1. Rhodamine-B (RB) dye degradation
also investigated in this work to prove the self-cleaning
behavior of surface modified PET.
2. EXPERIMENTAL DETAILS
All reagents and solvents were of analytical grade were
purchased and used without further purification. An
AVANCE III 300 spectrometer (Akishima company, Japan)
was operated at 600 MHz for proton NMR spectroscopy
with Alice 4.0 software for spectral analysis. 4000 Q
TRAP mass spectrometer used for the ESI mass spec-
tra. SEM analysis was conducted using a LYRA3 XMU
system. UV-Visible absorption spectra were recorded in
an Agilent 8453 instrument. Solid-state UV-Vis spectra
were recorded on a Shimadzu Solid Spec-2700 instrument.
XPS measurements done by using a Multilab 2000 spec-
trometer. XRD studies were conducted using an X-ray
diffractometer (PHILIPS, X’Pert-MPD System, Max P/N:
3 kW/40 kV, 45 Ma, Netherlands) with a CuKꢀ (ꢁ =
1.54056 Å) X-ray tube. Photodegradation of rhodamine-B
under visible-light irradiation (approximately 555 nm), it
was irradiated by a 50 W halogen lamp to simulate sun-
light and The Metallo porphyrin used in the present study
were prepared according to the literature procedures and
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property also can be able to clean themselves as soon as
comes in contact with the visible light.
Copyright: American Scientific Publishers
are shown in Scheme 2.
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In this work we developed self-cleaning Poly
Ethylene Terephthalate (PET) fabric by modifying
the surface by incorporating anatase TiO2 and Met-
allo porphyrin. Three different porphyrin deriva-
tives were prepared (Copper (II) complex of 4,4ꢁ,4ꢁꢁ,
4ꢁꢁꢁ-(porphyrin-5,10,15,20-tetrayl)tetrabenzonitrile (CuTC-
NPP), Nickel (II) complex of 4,4ꢁ,4ꢁꢁ,4ꢁꢁꢁ-(porphyrin-
2.1. Synthesis and Characterization of 4,4ꢁ,4ꢁꢁ,4ꢁꢁꢁ-
(porphyrin-5,10,15,20-tetrayl)Tetrabenzo
Nitrile (TCNPP)
To a solution of substituted 4-formylbenzonitrile (1 eqv.)
in propionic acid (50 mL) was added pyrrole (1 eqv.) and
the reaction mixture was refluxed 12 h in dark, then it was
filtered and column purified to obtain the desired product.
1H NMR (CDCl3, 600 MHz), ꢂ (ppm): −2.94 (s, 2H), 8.02
(d, 8H, J = 8.4 Hz), 8.25 (d, 8H, J = 8.4 Hz), 8.72 (s,
8H), ESI-MS (m/z) calcd. 714.2, found 715.3 (M +H+ꢃ.
5,10,15,20-tetrayl)tetrabenzonitrile
(NiTCNPP)
and
Zinc (II) complex of 4,4ꢁ,4ꢁꢁ,4ꢁꢁꢁ-(porphyrin-5,10,15,20-
tetrayl)tetrabenzonitrile (ZnTCNPP)) in which cyanate
group in the porphyrin molecule acts as an anchoring
Scheme 1. Surface modification to obtain photocatalytic self-cleaning PET by attaching TiO2 and metallo porphyrin.
J. Nanosci. Nanotechnol. 19, 8004–8012, 2019
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Visible Light Photo-Sensitized Metallo-Porphyrin/TiO2 Photocatalyst and Its Related Self-Cleaning Effects in PET
Heo et al.
Scheme 2. Synthesis of CuTCNPP, NiTCNPP and ZnTCNPP.
2.2. Synthesis and Characterization of Copper (II)
Complex of 4,4ꢁ,4ꢁꢁ,4ꢁꢁꢁ-(porphyrin-
5,10,15,20-tetrayl)Tetrabenzonitrile
(CuTCNPP)
The solvent was evaporated under reduced pressure to
yield pure ZnTCNPP.
ESI-MS (m/z) calcd. 778.1, found 779.2 (M +H+).
2.5. Preparation and Characterization of TiO2
TCNPP (0.714 g, 1 mmol) and Cu(OAc)2 · H2O (1.99 g,
10 mmol) in a mixture of dichloromethane (240 mL)
and methanol (120 mL) were vigorously stirred for
3 h at reflux temperature. Then, the reaction mixture
was quenched with addition of water and extracted by
dichloromethane. After that the combined organic layer
was washed with water and dried over anhydrous Na2SO4.
The solvent was evaporated under reduced pressure to
yield pure CuTCNPP.
Anatase TiO2 was prepared according to literature proce-
dure [5] by adding Titanium tetraisopropoxide in acetic
acid solution to the acidified water (HNO3, 1.4%) and then
ꢀ
stirred the reaction mixture at 60 C for 16 h and was
confirmed by XRD which has the characteristic diffraction
peaks at 2ꢄ = 25.3, 37.9, 47.7 and 54.4ꢀ (Fig. 2(a)).
2.6. Process of TiO2 Coating in PET
The TiO2 sol was used for the transparent coating in PET
by a dip-coating method. Then the obtained PET sample
was shown to ammonia vapour to obtain a neutral pH in
ESI-MS (m/z) calcd. 776.3, found 777.3 (M +H+).
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2.3. Synthesis and Characterization of Nickel (II)
the surface.
Complex of 4,4ꢁ,4ꢁꢁ,4ꢁꢁꢁ-(porphyrin-
5,10,15,20-tetrayl)Tetrabenzonitrile
(NiTCNPP)
2.7. Process of Porphyrin-Coating in TiO2
Imbedded PET
Metallo-porphyrin was deposited in TiO2 coated PET by
dissolving the Metallo porphyrin solution (1×10−5 M) in
dimethyl formamide (DMF), and soaked thꢀe TiO2 attached
PET, then the sample was heated at 100 C for 6 h and
washed with DMF and water to eliminate the excess of
uncoated porphyrin.
TCNPP (0.714 g, 1 mmol) and Ni(OAc)2 · 4H2O (2.48 g,
10 mmol) in a mixture of dichloromethane (240 mL)
and methanol (120 mL) were vigorously stirred for
3 h at reflux temperature. Then, the reaction mixture
was quenched with addition of water and extracted by
dichloromethane. After that the combined organic layer
was washed with water and dried over anhydrous Na2SO4.
The solvent was evaporated under reduced pressure to
yield pure NiTCNPP.
2.8. Photocatalyst Study for the Degradation of
Rhodamine (RB)
RB was dissolved in chloroform (1 × 10−3 M) solution
which was then drop casted in TiO2/Metallo-porphyrin
coated PET and dried for 1 h in dark to attain adsorption–
desorption equilibrium. The photo degradation ability of
the modified PET has been checked by measuring the
change in the intensity of RB under visible light irradi-
ation and confirmed by recording the UV-Vis absorption
spectra at different time intervals.
ESI-MS (m/z) calcd. 771.4, found 772.3 (M +H+).
2.4. Synthesis and Characterization of Zinc (II)
Complex of 4,4ꢁ,4ꢁꢁ,4ꢁꢁꢁ-(porphyrin-
5,10,15,20-tetrayl)Tetrabenzonitrile
(ZnTCNPP)
TCNPP (0.714 g, 1 mmol) and Zn(OAc)2 ·2H2O (2.20 g,
10 mmol) in a mixture of dichloromethane (240 mL)
and methanol (120 mL) were vigorously stirred for
3 h at reflux temperature. Then, the reaction mixture
was quenched with addition of water and extracted by
dichloromethane. After that the combined organic layer
was washed with water and dried over anhydrous Na2SO4.
3. RESULTS AND DISCUSSION
3.1. SEM Analysis
Surface modification of PET has been examined by
SEM analysis. Surface morphology of PET before and
after deposition of TiO2 and porphyrin are shown in
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Heo et al.
Visible Light Photo-Sensitized Metallo-Porphyrin/TiO2 Photocatalyst and Its Related Self-Cleaning Effects in PET
Figures 1(a)–(e). Figures 1(a) and (b) corresponds to PET
and TiO2 attached PET and Figures 1(c)–(e) after modi-
fying TiO2 attached PET with metallo porphyrin (CuTC-
NPP, NiTCNPP and ZnTCNPP). SEM images reveal that
the PET showed smoother surface when compared with
TiO2 and porphyrin attachment, surface aggregation can be
observed in PET/TiO2, PET/TiO2/CuTCNPP, PET/TiO2/
NiTCNPP, PET/TiO2/ZnTCNPP coated sample, but the
PET retain its integrity after modification.
observed in the TiO2/metallo porphyrin attached PET fab-
rics indicating the successful loading of TiO2. The C1s
spectra of PET/TiO2/CuTCNPP, PET/TiO2/NiTCNPP and
PET/TiO2/ZnTCNPP showed three deconvoluted peaks at
284, 285 and 288 eV related to sp2 carbon and C–O–C/C–
OH/C O or C–N, respectively. The deconvoluted O 1s
peaks at 528 and 530 is due to the existence of C–O and
C
O [21, 22] in the surface modified PET. In addition,
the presence of TiO2 in the PET sample has been con-
firmed through the peak centered at 530 eV. The pyrrole-
like nitrogen in the porphyrin ring bonded to the metal
was confirmed by the presence of a deconvoluted N 1s
peak at 399 and 400 eV. The two deconvoluted peaks in
the Ti 2p region at 457 (Ti 2p3/2) and 462 eV (Ti 2p1/2)
with the peak in the O 1s region at 530 eV, are the charac-
teristic peaks of TiO2. The two peaks of Cu 2p at 932 eV
(Cu 2p3/2) and 957 eV (Cu 2p1/2) and peak at 856 eV
(Ni 2p), 1022 eV (Zn 2p) suggest the presence of metallo
porphyrin in PET samples.
3.2. XRD Analysis
XRD analysis was carried out to confirm the pres-
ence of TiO2 in the modified PET samples. The as
prepared anatase TiO2 was confirmed by XRD which
has the characteristic diffraction peaks at 2ꢄ = 25.3,
37.9, 47.7 and 54.4ꢀ, same peaks were observed with
the coated PET samples, however no peak related to
anatase TiO2 was present in pristine PET sample, and
for PET/TiO2/CuTCNPP, PET/TiO2/NiTCNPP, PET/TiO2/
ZnTCNPP XRD showed the pattern of the characteristic
anatase peak at 2ꢄ = 25, 38, 48 and 55ꢀ (Fig. 2(b)).
3.4. UV-Vis Spectroscopy
Figures 4(a) and (b) showed the UV-Vis spectra of CuTC-
NPP, NiTCNPP and ZnTCNPP in solution as well as in
solid state. In solution phase, metallo porphyrin showed a
strong intense peak at 418, 419 and 428 nm corresponds
to soret band of CuTCNPP, NiTCNPP and ZnTCNPP
respectively and less intense peak between 500–650 nm
3.3. XPS Measurement
To obtain the experimental evidence for the surface mod-
ification in PET fabric XPS was recorded and the XPS
spectra of the PET/TiO2/CuTCNPP, PET/TiO2/NiTCNPP
and PET/TiO /ZnTCNPP were shown in Figure 3.
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2
Copyright: American Scientific Publishers
As expected, peaks of C, O, N and Ti can be clearly
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Figure 1. SEM images of (a) PET, (b) PET/TiO2, (c) PET/TiO2/
Figure 2. XRD spectra of (a) Anatase TiO2 (b) PET, PET/TiO2, PET/
CuTCNPP, (d) PET/TiO2/NiTCNPP and (e) PET/TiO2/ZnTCNPP.
TiO2/CuTCNPP, PET/TiO2/NiTCNPP and PET/TiO2/ZnTCNPP.
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Visible Light Photo-Sensitized Metallo-Porphyrin/TiO2 Photocatalyst and Its Related Self-Cleaning Effects in PET
Heo et al.
CuTCNPP, NiTCNPP and ZnTCNPP adsorbed on TiO2
coated PET is shown in Figure 4(b). UV-Vis spectra
recorded for PET and TiO2 coated PET in order to con-
firm the presence of metallo porphyrin in it and the spectra
showed no peaks above 400 nm, whereas the metallo por-
phyrin attached PET shows peaks at around 400–450 nm
which corresponds to the soret band of CuTCNPP, NiTC-
NPP and ZnTCNPP. These soret band which appeared in
solution state, red shifted to about 3 to 6 nm for the TiO2
coated PET samples which also confirms the interaction
between the anchoring groups in metallo porphyrin with
TiO2 in PET sample. Q bands appeared for CuTCNPP,
NiTCNPP and ZnTCNPP in solution state disappeared
after adsorbed to TiO2 coated PET is due to the interaction
of porphyrin with polar solvents [26], also a peak broden-
ing was observed after interaction with TiO2 coated PET
this might be due to the dye aggregation which is a typ-
ical occurrence of metallo porphyrin when assembled on
solid substrates [27, 28]. Therefore the photodegradation
and self-cleaning property has been studied further after
confirming the metallo porphyrin presence in the TiO2
coated PET.
Figure 3. XPS survey spectra of PET/TiO2/CuTCNPP, PET/TiO2/
NiTCNPP and PET/TiO2/ZnTCNPP.
(Q-bands) (Fig. 4(a)). The interaction of TiO2 with PET
has been reported in the literature [23, 24] and also
the interaction of cyanate as an anchoring group with
TiO2 also reported [25], therefore the interaction of met-
allo porphyrin with TiO2 coated PET fabric was studied
and confirmed by UV-Vis spectra. The UV-Vis spectra of
3.5. Photocatalytic Degradation of Rhodamine
The photodegradation ability and self-cleaning behavior
of metallo Porphyrin/TiO2 coated PET samples under
visible light irradiation were studied quantitatively by
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monitoring the degradation of RB through photocatalytic
Copyright: American Scientific Publishers
action by adsorbing RB to pristine PET, PET/TiO2 and
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Figure 4. UV-Vis spectra of (a) CuTCNPP, NiTCNPP, ZnTCNPP in
DMF, (b) solid-state UV-Vis spectra of PET, PET/TiO2, PET/TiO2/
CuTCNPP, PET/TiO2/NiTCNPP and PET/TiO2/ZnTCNPP.
Figure 5. Photocatalytic degradation of rhodamine by PET and surface-
modified PET under visible-light irradiation.
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Visible Light Photo-Sensitized Metallo-Porphyrin/TiO2 Photocatalyst and Its Related Self-Cleaning Effects in PET
metallo Porphyrin/TiO2 coated samples and measured the
degradation every 1 h, no degradation of RB observed in
pristine PET sample. However, photodegradation of RB
was observed for TiO2 and TiO2 with CuTCNPP, NiTC-
NPP and ZnTCNPP in PET samples under visible-light
irradiation for up to 4 h (Fig. 5), the result was further
confirmed by UV-Vis spectra and are given in Figure 6.
The Figure 7 showed a plot of normalized concentration
(C/C0ꢃ versus Time (h) and the degradation efficiency cal-
culated for PET and TiO2, TiO2 with CuTCNPP, NiTCNPP
and ZnTCNPP in PET samples shows RB degradation
up to 31%, 53%, 36% and 79% respectively. The result
obtained indicating that the RB dye degradation and
photocatalytic performance, is higher for TiO2/ZnTCNPP
coated PET thus the degradation efficiency in the order
of TiO2/ZnTCNPP > TiO2/CuTCNPP > TiO2/NiTCNPP >
TiO2 > PET. Further the visible light irradiated metallo
porphyrin/TiO2 coated sample evaluated for self-cleaning
performance, a reproducible RB photodegradation about
79% was observed for the TiO2/ZnTCNPP coated PET.
3.6. Photostability of Metallo Porphyrin on PET
Photostability and durability of metallo porphyrin are the
important requisite for th reusability and practical appli-
cation, therefore the stability of CuTCNPP, NiTCNPP and
ZnTCNPP in TiO2 attached PET samples has been mea-
sured by irradiating the sample under visible light irradi-
ation. The samples were kept under visible-light for 5 h
and then recorded by UV-Vis spectra. The change in con-
centration of metallo porphyrin was measured and shown
in Figures 8(a)–(c) corresponds to PET/TiO2/CuTCNPP,
PET/TiO2/NiTCNPP, PET/TiO2/ZnTCNPP, the intensity of
soret band is considered to check for the change in concen-
tration of metallo porphyrin before and after irradiation, a
slight degradation about 5% was observed in all the three
samples.
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Figure 6. Solid-state UV-Vis spectra of the degradation of rhodamine under visible-light irradiation by (a) PET, (b) PET/TiO2, (c) PET/TiO2/
CuTCNPP, (d) PET/TiO2/NiTCNPP, (e) PET/TiO2/ZnTCNPP.
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Visible Light Photo-Sensitized Metallo-Porphyrin/TiO2 Photocatalyst and Its Related Self-Cleaning Effects in PET
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3.7. Stability of Metallo Porphyrin/TiO2 on PET
Interaction of TiO2 and cyanate group of porphyrin
and TiO2 interaction with PET is reported in litera-
ture [23–25], therefore the hybrid material formed by
this was further analyzed for its stability by washing the
samples with detergent, water and petroleum ether for
1 h at room temperature at a constant stirring speed of
300 rpm, then the samples were dried in an oven and
the change in concentration was measured using UV-
Vis spectra (Figs. 8(d–e)). All the samples showed more
than 90% retention of CuTCNPP, NiTCNPP and ZnTC-
NPP on TiO2 coated PET, thus the samples before and
after washing indicating the modified PET samples allow
photocatalytic property equivalent to that of prewashed
PET, ensuing an effective photocatalytic self-cleaning
material.
Figure 7. Degradation of rhodamine under visible-light irradiation for
4 h by PET and surface-modified PET [error bars are the standard error
of the mean (three times)].
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Figure 8. UV-Vis spectra of (a) PET/TiO2/CuTCNPP, (b) PET/TiO2/NiTCNPP, (c) PET/TiO2/ZnTCNPP before and after 5 h irradiation under visible-
light and percentage retention of CuTCNPP, NiTCNPP and ZNTCNPP before and after washing with (d) petroleum ether, (e) water and (f) detergent
[error bars are the standard error of the mean (three times)].
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Visible Light Photo-Sensitized Metallo-Porphyrin/TiO2 Photocatalyst and Its Related Self-Cleaning Effects in PET
Figure 9.
(a) Plausible photocatalytic mIePch:a1ni9sm3.a2n0d3(b.1) 1de.g6r0adaOtionn: pTroucees,s2in5mAoudigfie2d0P2E0T. 14:10:04
Copyright: American Scientific Publishers
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3.8. Photodegradation Mechanism
4. CONCLUSIONS
Mechanism for the photodegradation ability of metallo
porphyrin, TiO2 attached hybrid PET material has been
shown in Figure 9. Since the energy gap between valence
band and conduction band is 3.2 eV therefore electron
excitation can be achieved only under UV light on the
other hand, for porphyrin, the electron excitation occurs
through UV-Visible light range. To energize the conduc-
tion band of TiO2, porphyrin has been used, by attach-
ing porphyrin to TiO2 the excited electron moved to TiO2
conduction band that is electron transfer from the ground
state of porphyrin dye [Pp] to the first excited singlet state
porphyrin 1[Pp]∗ [29]. Then the singlet excited state relax-
ation generates the triplet excited state 3[Pp]∗ through a
process of intersystem crossing. Electrons from singlet and
triplet excited states can transfer the electron to the TiO2
conduction band. Further, the conduction band electrons
reduce the O2 adsorbed on the surface of TiO2 to Oꢂ2− and
results in degrading RB. Also TiO2 holes got theꢂability to
exchꢂange the porphyrin and H2O molecules to OH, and
this OH degrades RB. Metallo porphyrins with unpaired
electrons have short lifetime of excited state and no flu-
orescent emission detected in solution [28], resulting in
less effective electron injection in conduction band of TiO2
after in slow degradation of RB when compared to that of
metal free porphyrin [30].
The visible-light active hydrophilic self-cleaning PET
through surface modification was successfully developed
by the incorporation of TiO2 and metallo porphyrin by a
simple adsorption method. Performance of the modified
PET under visible light photocatalytic activity, stability of
the dye in PET and overall photodegradation efficiency
has been discussed in detail. Self-cleaning performance,
a reproducible photodegradation about 79% of RB was
observed for the TiO2/ZnTCNPP coated PET, the stabil-
ity of porphyrin in TiO2 attached PET also confirmed
by washing the sample with aqueous and organic sol-
vent, as well as irradiating the sample under visible light.
Thus TiO2 with CuTCNPP, NiTCNPP and ZnTCNPP in
PET samples showed potential application of self-cleaning
material.
Acknowledgments: This study was supported by the
Basic Science Research Program through the National
Research Foundation of Korea (NRF) funded by the Min-
istry of Science, ICT and Future Planning (Grant No.
NRF-2017R1E1A1A01074266). This work was supported
by the industrial Fundamental Technology Development
Program (10076350) funded by the Ministry of Trade,
Industry and Energy (MOTIE) of Korea.
J. Nanosci. Nanotechnol. 19, 8004–8012, 2019
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Heo et al.
References and Notes
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8012
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