Synthesis of novel porphyrin derivatives and their self-assemblies to enhance photocatalytic performance

Article abstract of DOI:10.1039/d0nj05297c

Three new porphyrin derivatives were synthesized from tetra (4-aminophenyl) porphyrin (TAPP), namely tetra[p-(4-cyanophenylmethylene imino)]phenyl porphyrin (TCyPPP), tetra[p-(P-benzylidene)]phenyl porphyrin (TbePPP) and tetra[p-(4-pyridylimethylene imino)]phenyl porphyrin (TPyPPP). Based on the principle of self-assembly, three kinds of porphyrin derivatives were self-assembled to prepare three kinds of monomers. The structures were characterized clearly by UV-vis, FT-IR, 1H NMR and SEM. The photocatalytic performance study shows that the self-assemblies of the three porphyrin derivatives have stronger photocatalytic performance than their monomers. Moreover, the self-assemblies and their monomers have good photocatalytic stability. This journal is

Full text of DOI:10.1039/d0nj05297c

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Synthesis of novel porphyrin derivatives and
their self-assemblies to enhance photocatalytic
Cite this: New J. Chem., 2021,
performance†
45, 3454
a
ab
a
a
Jinghe Pei, Bo Gao,
*
Yanhui Li
and Qian Duan
*
Three new porphyrin derivatives were synthesized from tetra (4-aminophenyl) porphyrin (TAPP), namely
tetra[p-(4-cyanophenylmethylene imino)]phenyl porphyrin (TCyPPP), tetra[p-(P-benzylidene)]phenyl
porphyrin (TbePPP) and tetra[p-(4-pyridylimethylene imino)]phenyl porphyrin (TPyPPP). Based on the
principle of self-assembly, three kinds of porphyrin derivatives were self-assembled to prepare three
Received 28th October 2020,
Accepted 18th January 2021
1
kinds of monomers. The structures were characterized clearly by UV-vis, FT-IR, H NMR and SEM. The
photocatalytic performance study shows that the self-assemblies of the three porphyrin derivatives
have stronger photocatalytic performance than their monomers. Moreover, the self-assemblies and their
monomers have good photocatalytic stability.
DOI: 10.1039/d0nj05297c
rsc.li/njc
photochemistry, photophysics, electrochemistry and other
excellent properties.
Self-assembly is based on the interaction forces between
Introduction
1
3–17
Porphyrin, as a natural aromatic cyclic compound, has unique
physical properties and can be used in catalytic energy storage porphyrin molecules (such as hydrogen bonds, p–p stacking,
and optoelectronic devices for energy conversion, photody- hydrophilic or hydrophobic interactions, ligand coordination, etc.)
1
–5
namic therapy, sensors and photonics.
Unfortunately, the to achieve accumulation and arrangement between molecules in
18–20
absorption range of the porphyrin monomer in the visible light order to form porphyrin self-assembled nanoparticles.
region is relatively narrow and it is easily corroded by light. It recent years, the self-assembly of porphyrins has been more and
is shown that the design of the porphyrin molecular structure more popular, and self-assembled nanoparticles of porphyrins
and the accumulation of porphyrin molecules can effectively have been synthesized by many methods.
affect the ability to separate photogenic carriers.
In
6
21–27
Yong Zhong et al.
7
prepared porphyrin self-assembled nanostructures with lamellar,
In recent years, a large amount of wastewater containing octahedral and microsphere morphologies, and investigated
organic pollutants has been discharged into the natural the effect of the porphyrin self-assembled morphologies on the
8
,9
28
water system, causing serious water pollution problems.
photocatalytic performance.
Peipei Guo prepared a one-
As an economical and environmentally friendly technology, dimensional supramolecular ZnTPyP nanometer assembly using
photocatalytic technology is more and more popular. The idea the surfactant-assisted self-assembly method and using GO as the
of eliminating organic pollutants by using solar energy makes surfactant, which shows superior photocatalytic activity compared
29
photocatalytic technology a potential technology to solve the with the conventional surfactant preparation method. Duong
1
0
environmental problems faced by human beings. For the Duc La et al. assembled a TiO @porphyrin hybrid material
2
self-assembly of porphyrin, more and more applications in photo- by means of collaborative self-assembly, and the material exhib-
1
1,12
catalytic degradation have been seen in recent years.
ited highly efficient photocatalytic activity under simulated
30,31
Porphyrin self-assembly is widely used in sensing, photocollec- sunlight.
Dong Wang et al. also used tetrapyridine zinc
tion and photocatalytic degradation due to its excellent porphyrin as the assembly unit to self-assemble ZnTPyP@NO
porphyrin nanoparticles by an acid–base neutralization-micellar
a
limited self-assembly method, which significantly enhanced the
antibacterial activity.
School of Materials Science and Engineering, Changchun University of Science and
Technology, 7989 Weixing Road, Changchun 130022, China.
E-mail: gaobo@ciac.ac.cn, duanqian88@hotmail.com; Fax: +86-431-85583015;
Tel: +86-431-85583015
32
Since the discovery of Schiff base chemistry and its impor-
tant application in catalyst science, it has been widely used
b
Engineering Research Center of Optoelectronic Functional Materials, Ministry of
Education, Changchun 130022, China
3
3
in the modification of porphyrin compounds. Based on
these results, tetra(4-aminophenyl)porphyrin (TAPP) was com-
bined with p-cyanobenzaldehyde benzaldehyde and 4-pyridinyl
†
Electronic supplementary information (ESI) available. See DOI: 10.1039/
d0nj05297c
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Fig. 1 (A) UV-vis spectra of TAPP, TCyPPP, TbePPP and TPyPPP. (B) UV-
vis spectra of TAPP, TCyPPP, TbePPP and TPyPPP in the range of 500–
7
00 nm. (C) Self-assembly of TCyPPP, TbePPP and TPyPPP. (D) The FT-IR
spectra of TAPP and TCyPPP, TbePPP and TPyPPP.
Scheme 1 Synthesis routes of TCyPPP, TbePPP and TPyPPP.
1
(
Fig. 1A). H NMR (500 MHz, CDCl ), d ppm: 8.90 (s, 8H, C–H,
3
formaldehyde in the form of a Schiff base, and three new pyrrole), 7.99 (d, 8H, Ar-H), 7.08 (d, 8H, Ar-H), 5.29 (s, 8H,
porphyrin–Schiff base conjugates were synthesized, as shown PH-NH ), ꢀ2.72 (s, 2H, –NH– pyrrole) (Fig. S2, ESI†).
2
in Scheme 1. Finally, the three porphyrin derivatives were self-
Synthesis of porphyrin derivatives TCyPPP, TbePPP and
assembled based on the principle of self-assembly, and the TPyPPP. 0.5 g (0.7 mmol) TAPP, 60 mL ethanol and 3.5 mmol
monomer and its self-assembly were used in a photocatalytic aldehyde were stirred and dissolved. A little glacial acetic acid
degradation experiment of rhodamine B in visible light, their was added as a catalyst. The solution was refluxed at 90 1C for
photocatalytic performance was evaluated, and the corres- 8 h, and left to rest until the reaction was over. It was then
ponding photocatalytic mechanism was proposed.
filtered and washed with anhydrous ethanol until the filtrate
was colorless and vacuum dried.
Tetra[p-(4-cyanophenylmethylene imino)]phenyl porphyrin
TCyPPP). According to the above method, 0.5 g (0.7 mmol)
TAPP and 0.46 g (3.5 mmol) p-cyanobenzaldehyde were taken to
Experimental
Materials and characterization
(
The TNPP used was prepared in the laboratory with pyrrole and prepare compound TCyPPP.
ꢀ1
p-nitrobenzaldehyde as raw materials, and pyrrole had to be
FT-IR (KBr, cm ): 3364 (nN–H, pyrrole), 2229 (n–CN, phenyl),
distilled prior to use. All other chemicals were purchased from 1613 (nCQN, –NQCH–), 1467 (nCQC, phenyl), 1179 (nCQN, pyr-
1
Sinopharm Chemical Reagent Co. and were used as received. role) are the skeletal vibrations of pyrrole (Fig. 1D). H NMR
1
H NMR spectra were recorded on a Bruker Avance 500 MHz (500 MHz, CDCl ), d ppm: 10.06 (s, 8H, C–H, pyrrole), 8.94 (s,
3
3
spectrometer using CDCl as a solvent at ambient temperature. 4H, –NQCH–), 8.27–8.25 (d, J = 8.0 Hz, 8H, phenyl), 7.94–7.96
FT-IR measurements were performed on KBr pellets on a (d, J = 8.0 Hz, 8H, phenyl), 7.62–7.64 (d, J = 8.0 Hz, 8H, phenyl),
Shimadzu-8400SIR spectrometer. UV-vis spectra of the samples 7.08–7.10 (d, J = 8.0 Hz, 8H, phenyl), ꢀ2.74 (s, 2H, –NH– pyrrole)
were recorded over different irradiation time intervals using a (Fig. S3, ESI†).
Thermo Scientific Evolution 220 spectrophotometer. SEM was
performed using a JEM-6701F with an Oxford INCA PentaFET-
x3 EDS system. X-Ray diffraction (XRD) patterns were recorded According to the above methods, 0.5 g (0.7 mmol) TAPP and
on a RigakuUltima VI diffractometer using Cu-Ka radiation. 360 mL (3.5 mmol) benzaldehyde were used to prepare com-
Synthesis of 5,10,15,20-tetra(4-aminophenyl)-21h,23h-porphyrin pound TbePPP.
TAPP). 500 mg TNPP, 2.6 g Na S and 160 mg NH Cl were dissolved FT-IR (KBr, cm ): 3313 (nN–H, pyrrole), 1623 (nCQN, Schiff
in 50 mL DMF and reacted at 70 1C for 8 h. After cooling, they were base), 1471 (nCQC, phenyl), 1175 (nCQN, pyrrole) (Fig. 1D).
Tetra[p-(P-benzylidene imino)]phenyl porphyrin (TbePPP).
ꢀ
1
(
2
4
1
filtered, washed with deionized water, and dried in a vacuum. After
purification by column chromatography, the purple powder solid 8.95 (s, 4H, –NQCH–), 8.81–8.79 (d, J = 8.0 Hz, 8H, phenyl),
TAPP was obtained (Fig. S1, ESI†). 8.24–8.22 (d, J = 8.0 Hz, 8H, phenyl), 8.07–8.05 (d, J = 8.0 Hz, 8H,
H NMR (500 MHz, CDCl ), d ppm: 10.03 (s, 8H, C–H, pyrrole),
3
ꢀ
1
FT-IR (KBr, cm ): 3440 (nvs N–H, amino), 3348 (nN–H, pyrrole), phenyl), 7.56–7.54 (d, J = 8.0 Hz, 8H, phenyl), 7.03 (s, 8H,
350 (nN–H, amino), 1470 (nCQN, pyrrole), 1285 (nC–N, amino) phenyl), ꢀ2.70 (s, 2H, –NH– pyrrole) (Fig. S4, ESI†).
1
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Tetra[p-(4-pyridylimethylene imino)]phenyl porphyrin (TPyPPP).
Paper
The UV-vis absorption spectra of the TAPP, TCyPPP, TbePPP
According to the above method, 0.5 g (0.7 mmol) TAPP and and TPyPPP porphyrin derivatives in dichloromethane solution
36 mL 4-pyridyl formaldehyde (3.5 mmol) were used to prepare are shown in Fig. 1(A and B). The three self-assemblies were
3
compound TPyPPP.
studied using the UV-vis spectra, as shown in Fig. 1(C). Com-
ꢀ1
FT-IR (KBr, cm ): 3308 (nN–H, pyrrole), 3029 (nC–H, pyridyl), pared with the monomers, the self-assemblies have better
1
603 (nCQN, –NQCH–), 1471 (nCQC, phenyl), 1171 (nCQN, pyr- optical properties. After self-assembly of the three monomers,
1
role) (Fig. 1D). H NMR (500 MHz, CDCl
3
), d ppm: 10.05 (s, 8H, the Soret band showed a significant red shift from about
C–H, pyrrole), 8.81 (s, 4H, –NQCH–), 8.27–8.25 (d, J = 8.0 Hz, 426 nm to about 460 nm, and a slight split occurred at
H, phenyl), 8.76–7.74 (d, J = 8.0 Hz, 8H, phenyl), 7.61–7.59 434 nm in the Soret band. The Q band for the three monomers
d, J = 8.0 Hz, 8H, phenyl), 7.05–7.03 (d, J = 8.0 Hz, 8H, phenyl), appeared in the 500–680 nm visible region, while the Q band
2.71 (s, 2H, –NH– pyrrole) (Fig. S5, ESI†). for the three self-assemblies appeared at 630–780 nm, and the
Self-assembly of TCyPPP, TbePPP and TPyPPP monomers. Q band also showed a significant red shift. In addition, whether
8
(
ꢀ
Three monomers of TCyPPP, TbePPP and TPyPPP were self- it is the Soret band or the Q band, the peak position is obviously
assembled by a simple solution method. Three monomers of widened and the intensity is also significantly stronger. These
1
mg were respectively put into three small beakers and features indicate that the self-assemblies of TCyPPP, TbePPP
dissolved with tetrahydrofuran. The concentrated sulfuric and TPyPPP are J-aggregates, which results in a red shift in the
acid-coated slides were then placed in a small beaker to allow absorption spectrum to improve the light absorption in the
the solution to submerge the slides. The beakers were placed in visible light absorption spectrum. For the Q band, Q has four
a fume hood and tetrahydrofuran was allowed to evaporate small absorption peaks in the three monomers, and, after self-
slowly. In the process of volatilization, the three monomers are assembly, four small absorption peaks disappeared obviously,
self-assembled on the glass sheet, and the self-assembly is while a strong absorption peak appeared at 630–780 nm. This
attached to the slide during the process of self-assembly. After may be because the absorption range of the Q band becomes
tetrahydrofuran was completely evaporated, the self-assembly wider and the absorption intensity becomes larger, so the
attached to the slide was carefully scraped and collected.
absorption bands overlap, showing only one strong absorption
band at the macro level.
Photocatalytic degradation measurement
FT-IR spectra of the TAPP and TCyPPP, TbePPP and TPyPPP
porphyrin derivatives are shown in Fig. 1(D). The characteristic
A rhodamine B solution was prepared at a concentration of
ꢀ1
ꢀ
5
ꢀ1
peak of –NH was observed at 3348 cm in TAPP, which was
2
1
ꢁ 10 mol L , 40 mL was taken out and put into a xenon
lamp reactor, about 1 mL of hydrogen peroxide was added, and
mg of photocatalyst was added. The photocatalytic degrada-
basically consistent with the known literature. However, there
was no corresponding absorption peak in the three porphyrin
derivatives of TCyPPP, TbePPP and TPyPPP, indicating that
5
tion of rhodamine B solution was performed by using a xenon
lamp of 300 W as the visible light source. The rhodamine B
solution was stirred with a magnetic stirrer for 60 min in the
dark before visible light illumination to ensure that an adsorp-
tion–desorption equilibrium was established between the
photocatalyst and rhodamine B. Then, the light source was
turned on for visible light irradiation, and samples were taken
every 30 min, and studied using a spectrophotometer to mea-
sure the absorbance of the rhodamine B solution.
–
2
NH disappeared in TCyPPP, TbePPP and TPyPPP. In the
infrared spectrum of TCyPPP, TbePPP and TPyPPP, three
characteristic stretching vibration peaks were generated at
ꢀ1
1
613, 1623 and 1603 cm , respectively. It indicates that the
expected TCyPPP, TbePPP and TPyPPP porphyrin derivatives
were successfully coupled with p-cyanobenzaldehyde, benzal-
dehyde and 4-pyridinyl formaldehyde in the form of a Schiff
base through TAPP. In addition, in the infrared spectrum of
TCyPPP, the stretching vibration peak of –CN appears at 2229
ꢀ
1
ꢀ1
cm . Similarly, in the infrared spectrum of TbePPP, 3021 cm
is the C–H absorption peak located on the aromatic ring, and
Results and discussion
Synthesis and characterization
ꢀ1
there are three weak absorption peaks nearby, and 1573 cm is
the stretching vibration peak of the aromatic ring CQC skele-
In this work, three new porphyrin derivatives TCyPPP, TbePPP ton. In the infrared spectrum of TPyPPP, the C–H absorption
ꢀ
1
and TPyPPP were successfully prepared by means of Schiff base peak on the pyridine ring is at 3029 cm and the vibration
ꢀ1
connection. The structures of the porphyrin derivatives and peak of the CQC skeleton is at 1552 cm . The appearance of
their self-assemblies were characterized via FT-IR, UV-vis, these characteristic absorption peaks fully indicates that the
1
SEM and H NMR. The synthesis routes of 5,10,15,20-tetra expected aldehyde groups in the three aldehydes are success-
(
[
5
(
4-aminophenyl)-21h,23h-porphyrin (TAPP), 5,10,15,20-tetra fully linked to the amino group on TAPP, and the three TCyPPP,
p-(4-cyanophenylmethylene imino)]phenyl porphyrin (TCyPPP), TbePPP and TPyPPP porphyrin derivatives are successfully
,10,15,20-tetra[p-(P-benzylidene imino)]phenyl porphyrin synthesized.
TbePPP) and 5,10,15,20-tetra[p-(4-pyridylimethylene imino)]- The TAPP and TCyPPP, TbePPP and TPyPPP porphyrin
phenyl porphyrin (TPyPPP) are shown in Scheme 1. On the derivatives were studied using the H NMR spectra using CDCl
basis of the prepared monomers, three monomers were self- as a solvent. Since the porphyrin compound is a conjugated
1
3
assembled.
system having 18 p electrons, it can generate an opposite
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induced magnetic field under the action of an external mag-
netic field. Therefore, the N atom with a high electron cloud
density on the porphyrin ring is in strong shielding, and finally
the N–H proton signal peak appears at about ꢀ2.70 ppm. For
TAPP, the proton signal peak of b-H on the porphine ring
appears at 8.88 ppm, which belongs to the characteristic peak
of typical porphyrin compounds. For the three porphyrin
derivatives, as the conjugation range becomes larger, the over-
all electron cloud density is relatively small, so the shielding
effect is reduced, the descreening effect is increased, and the
chemical shift of b-H is larger, which appears at 10.06, 10.03
and 10.05 ppm, respectively.
For TAPP, a sharp single peak appeared at 5.30 ppm,
attributed to the chemical shift of the H in the amino group,
while no corresponding chemical displacement peak was
observed in the three porphyrin derivatives TCyPPP, TbePPP
and TPyPPP. In contrast, for the three TCyPPP, TbePPP and
TPyPPP porphyrin derivatives, a singlet peak appeared at 8.94,
8.95, and 8.81 ppm. This corresponds to the chemical shift of
the azo protons (–CHQN–) in the three conjugates, indicating
that the three porphyrin derivatives were successfully synthe-
sized. In addition, the H NMR spectrum of the coupled TPyPPP; and self-assemblies of (D) TCyPPP, (E) TbePPP and (F) TPyPPP.
TCyPPP has multiple peaks at 7.08–7.62 ppm, which is attrib-
Fig. 2 SEM images of the monomers of (A) TCyPPP, (B) TbePPP and (C)
1
uted to the chemical shift of protons on the benzene ring
connected to the cyanide group. Similarly, the protons on the
benzene ring of coupled TbePPP and the pyridine protons of
The degradation degree D of RhB is calculated by the following
formula (1):
t
TPyPPP show multiple peaks in the range of 7.56–8.07 ppm and
A0 ꢀ At
1
D ¼
ꢁ 100%:
(1)
t
7.05–7.61 ppm. The H NMR of TAPP and TCyPPP, TbePPP and
A0
TPyPPP showed a weak singlet peak around ꢀ2.70 ppm, which
is attributed to the proton characteristic peak in the porphyrin Here, A
0
is the initial absorbance of rhodamine B at the 554 nm
is the absorbance at time t. According to the
results of four kinds of photocatalytic degradation, the absor-
ring. All these proved that the three porphyrin derivatives were absorption and A
synthesized successfully.
t
In order to more objectively observe the morphology of the bance measured for RhB at different illumination times was
three self-assemblies after self-assembly, the three types of plotted as shown in Fig. 3.
monomers and their self-assemblies were studied by scanning
The change curve of the degradation rate of the RhB dye
electron microscopy (SEM), as shown in Fig. 2(A–C). In Fig. 2 with time by TAPP and the three porphyrin derivatives is shown
are scanning electron microscope images of the three mono- in Fig. 5(A). In the absence of a photocatalyst, RhB self-
mers, TCyPPP, TbePPP, and TPyPPP, respectively. From the degraded by about 10.9% in 3.5 h, as shown in curve 5 in
electron microscope image, it can be seen that all three mono- Fig. 5(A), which can be ignored. It is believed that RhB cannot
mers have irregular shapes and appear in a disordered state. In degrade itself under visible light, or it takes a long time to
Fig. 2(D–F) are respectively the scanning electron microscope degrade itself. However, the degradation rate of RhB was
images of the three self-assembled bodies TCyPPP, TbePPP accelerated after a photocatalyst was added and the degrada-
and TPyPPP. It can be clearly seen from the electron microscopy tion amount was greatly increased. After 3.5 h or even less, the
that, after the process of self-assembly, the three kinds of degradation rate of RhB reached more than 85%, which is
self-assembly have formed a good shape. The self-assembly basically considered to achieve complete degradation. There-
of TCyPPP has a regular petal-shaped structure. The self- fore, for the degradation of RhB, it is necessary to help the
assembly of TbePPP has a spherical morphology, and the self- photocatalyst to achieve the purpose of degradation under
assembly of TPyPPP has a layered structure with layers of visible light.
accumulation. All three self-assemblies have a good regular
After the addition of the TAPP catalyst, the degradation rate
morphology compared to the monomer, indicating the success- of RhB reached 88.3% after 3.5 h, and substantially complete
ful preparation of the self-assemblies.
degradation was achieved, as shown by curve 1 in Fig. 5(A).
Under the same experimental conditions, the degradation rate
and degradation time of RhB were significantly accelerated
Photocatalytic performance
The photocatalytic properties of the TAPP and TCyPPP, TbePPP after the addition of the three porphyrin derivative photocata-
and TPyPPP porphyrin derivatives under visible light were studied lysts, and the degradation rate reached over 85% within
with the organic pollutant rhodamine B as a representative. 2.5 h. For catalyst TCyPPP, as shown in curve 2 of Fig. 5(A),
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Fig. 5 (A) Degradation efficiency of RhB for TAPP, TCyPPP, TbePPP and
TPyPPP. (B) Degradation efficiency of RhB for the self-assembly of
TCyPPP, TbePPP and TPyPPP.
Fig. 3 UV-vis of RhB solution at different illumination times with (A) TAPP,
(
B) TCyPPP, (C) TbePPP and (D) TPyPPP (the initial concentration of RhB
ꢀ5
ꢀ1
is 1 ꢁ 10 mol L ).
the degradation rate reached 86.4% at 2.5 h. For catalyst
TbePPP, as shown in curve 3 of Fig. 5(A), the degradation rate Fig. 6 (A) First order kinetic fitting curve of RhB degradation by TCyPPP,
TbePPP and TPyPPP. (B) First order kinetic fitting curve of RhB degradation
reached 88.3%. The degradation rate of catalyst TPyPPP also
reached 85.8%, as shown in curve 4 of Fig. 5(A). After TAPP is
by the self-assemblies of TCyPPP, TbePPP and TPyPPP.
coupled with three aldehydes via a Schiff base, the photocata-
lytic efficiency can be greatly improved, indicating that the
the three self-assemblies have a good degradation effect on
three porphyrin derivatives of TCyPPP, TbePPP and TPyPPP
RhB, and substantially complete degradation is achieved in
have higher photocatalytic efficiency.
about two hours.
The photocatalytic experiments of RhB were carried out on
First-order kinetics was used to evaluate the degradation of
the three self-assemblies. According to the results of the three
the RhB dye, and its first-order kinetics equation was expressed
porphyrin self-assemblies of photocatalytic degradation, the
by formula (2):
absorbance measured for rhodamine B under different illumi-
ꢀ
ꢁ
nation times was plotted as shown in Fig. 4. The curve of the
absorbance measured for RhB under different illumination
time conditions as a function of time is shown in Fig. 5(B). It
can be seen from the ultraviolet absorption curve of RhB that Here, ka is the rate constant (min ). The change curve of
ln(C /C ) with time t (C is the initial concentration of the
ct
ln
¼ ꢀkat:
(2)
c0
ꢀ
1
t
0
0
solution, and c
t
is the concentration of the solution at time t)
was plotted to study the photocatalytic reaction kinetics, as
shown in Fig. 6(A). The rate constants of TAPP and TCyPPP,
TbePPP and TPyPPP for RhB under visible light irradiation were
ꢀ
3
ꢀ1
ꢀ3
ꢀ1
ꢀ3
ꢀ1
8
.12 ꢁ 10 min , 11.66 ꢁ 10 min , 13.64 ꢁ 10 min
ꢀ3 ꢀ1
and 13.10 ꢁ 10 min , respectively. It can be seen from the
rate constant that the degradation rate of the three new
porphyrin derivatives, TCyPPP, TbePPP and TPyPPP, is signifi-
cantly higher than that of TAPP, indicating that the catalytic
performance of the three new porphyrin derivatives is much
higher than that of TAPP. As for the self-degradation of rhoda-
ꢀ3
ꢀ1
mine B, its degradation rate constant is only 0.58 ꢁ 10 min
,
which is much lower than the catalytic rate constant of the
three catalysts, so the self-degradation of RhB can be ignored.
Similarly, Fig. 6(B) shows the first order kinetic fitting curve of
self-assembled TCyPPP, TbePPP and TPyPPP degradation of RhB.
ꢀ
3
ꢀ1
ꢀ3
ꢀ1
The rate constants were 18.8 ꢁ 10 min , 14.4 ꢁ 10 min
Fig. 4 UV-vis absorption spectra of RhB aqueous solution at different
illumination time intervals with the self-assembly of (A) TCyPPP, (B) TbePPP
and (C) TPyPPP (the initial concentration of RhB is 1 ꢁ 10ꢀ5 mol Lꢀ1).
ꢀ
3
ꢀ1
and 24.2 ꢁ 10 min , respectively. The photocatalytic degrada-
tion rate constants were also greater than those of the monomers
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Table 1 Comparison of the photocatalytic properties for RhB pollutant degradation of the three porphyrin derivatives and their self-assemblies and
other similar studies
ꢀ3
ꢀ1
Photocatalysts
Dyes
Photocatalytic rate constant (10 min
)
References
Graphene@TCPP porphyrin
RhB
RhB
MB
RhB
RhB
RhB
RhB
RhB
RhB
RhB
6.5
9.4
5.22
1.2
11.66
13.64
13.10
18.8
14.4
24.2
34
36
37
Graphene@TiO
Porphyrin dicarboxylic acid–TiO
2
@porphyrin
2
(PORBP–TiO
2
)
P-25 Degussa TiO
TCyPPP
2
30 and 36
This study
This study
This study
This study
This study
This study
TbePPP
TPyPPP
Self-assembly of TCyPPP
Self-assembly of TbePPP
Self-assembly of TPyPPP
under the same conditions. In addition, these rate constants are
Studies have shown that after the J-aggregation of organics
significantly higher than the photocatalytic performance of por- with a p-conjugated structure, electrons in the aggregate can fill
34–37
phyrin derivatives reported previously,
as well as the p-25 the entire aggregate across a single molecule, resulting in a
Degussa TiO
2
photocatalyst (the relative rate constant is only 1.2 ꢁ strong p–p interaction, making it a semiconductor material.
ꢀ
3
ꢀ1
30,36
10
min ), as shown in Table 1.
Therefore, the self-assembled porphyrin can be used as a
Compared with the three monomers, the self-assemblies photocatalyst to collect light energy by using visible light
have higher catalytic efficiency. The catalytic degradation of irradiation and generate electron–hole pairs. These electron–
RhB in the three self-assemblies reached more than 90% within hole pairs play an oxidation–reduction role in the degradation
2
2
h, while the degradation rate of RhB was only about 85% after of rhodamine B. It also has better photocatalytic efficiency due
.5 h of the three monomers, indicating that the catalytic time to its higher charge separation ability.
of the self-assemblies for RhB is shorter and the catalytic
efficiency is higher.
Reproducibility of the photocatalytic activity
In order to further explore the photocatalytic activity of the
three self-assembled compounds, we took TCyPPP as an exam-
ple to test the photocatalytic efficiency of a blank (only RhB),
TCyPPP, H O and TCyPPP + H O (Fig. 7). As can be seen from
The photostability and repeatability of the photocatalyst are
important factors that affect the practical application of the
photocatalyst. Therefore, the photostability of the TAPP and
TCyPPP, TbePPP and TPyPPP porphyrin derivatives was tested.
The photocatalytic degradation rate changes of the TAPP and
TCyPPP, TbePPP and TPyPPP porphyrin derivatives after five
repeated experiments are shown in Fig. 8(A). Whether it is TAPP
or the TCyPPP, TbePPP and TPyPPP porphyrin derivatives, the
2
2
2 2
the figure, the degradation rates of RhB by TCyPPP and H O
2
2
reached 41.8% and 54.7%, respectively. When TCyPPP and
acted together to catalyze degradation, the degradation
2 2
H O
rate reached 96.9% within 140 min, indicating that the two
cooperated in the catalytic engineering and significantly
improved the photocatalytic degradation effect.
Fig. 8 (A) Difference in the photocatalytic degradation rate of TAPP and
TCyPPP, TbePPP and TPyPPP before and after the cycling test. (B) Stability
test of the photocatalytic activity of the TCyPPP self-assembly. (C) The
XRD and (D) the FT-IR tests of the monomers TCyPPP, TbePPP and
TPyPPP before and after the photocatalytic cycle experiment.
Fig. 7 The RhB degradation rates of various catalytic conditions under
visible light irradiation in water at room temperature.
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photocatalytic activity decreased by about 10% after 5 cycles of
experiments, indicating that the photocatalytic activity gradu-
ally decreased with the cycle period. Taking self-assembled
TCyPPP as an example, a photocatalytic cycle experimental test
was carried out, and the results are shown in Fig. 8(B). After five
cycles of experiments, the photocatalytic degradation rate of
self-assembled TCyPPP decreased from 93.5% to 83.2%. Basi-
cally, it can be considered that self-assembled TCyPPP also has
good photocatalytic stability.
In addition, the monomers TCyPPP, TbePPP and TPyPPP
were respectively tested by XRD and FT-IR before and after the
photocatalytic cycle experiment. The results are shown in
Fig. 8(C and D). The results showed that the monomers
TCyPPP, TbePPP and TPyPPP maintained good original frame-
work connectivity during photodegradation, thus demonstrat-
ing the good cyclability and high stability of the monomers
during photocatalytic degradation.
Fig. 10 Reasonable photocatalytic mechanism for RhB under visible light
irradiation.
In addition, we took self-assembled TCyPPP nanoparticles
as an example to capture active species during rhodamine B
3
8–44
photocatalytic degradation.
was found that ethylenediaminetetraacetic acid disodium salt
EDTA-2Na), isopropanol (IPA) and benzoquinone (BQ) were
Through a literature review, it
and the valence band (VB) of the photocatalyst is more likely to
excite light generation. The electrons are directed to their
conduction band (CB). Secondly, electrons in the VB are mainly
distributed in the orbital of the photocatalyst before visible
(
+
ꢂ
ꢂ
2ꢀ
45–47
utilized as the scavengers of h , OH and O , respectively.
Fig. 9 shows the RhB degradation process under different
conditions (without H ). The experimental results showed
light exposure. Under visible light irradiation, visible light absorbed
O
2
+
2
by the photocatalyst transfers energy to H
2
O
2
to form h . O
2
can
that the addition of the EDTA-2NA, IPA and BQ scavengers
seriously affected the degradation of RhB. This indicates that
ꢂ
ꢀ
get excited electrons and form O . At the same time, the
same number of photogenerated holes (h ) as photogenerated
2
+
+
ꢂ
ꢂ
2ꢀ
h , OH and O produced in the photocatalytic process are
important active species and play a very important role in RhB
degradation.
+
ꢂ
ꢂ
ꢀ
electrons is left in the VB. h , OH and O2 can effectively
degrade rhodamine B molecules, thereby achieving the purpose
of catalytic degradation. Finally, since the three porphyrin
derivatives have a larger conjugation range, the charge transport
speed will be faster, thereby promoting the separation of photo-
generated carriers and effectively improving the photocatalytic
activity of the catalyst.
By referring to the references and the above experimental
results, we proposed a possible photocatalytic degradation
4
8–51
reaction mechanism, as shown in Fig. 10.
Firstly, the
electronic structure of the porphyrin derivatives was adjusted
by coupling TAPP with three aldehydes. The band gap of the
three porphyrin derivatives was narrower than that of TAPP,
Conclusions
Three new porphyrin derivatives, TCyPP, TbePPP and TPyPPP,
were synthesized successfully and the three derivatives were
self-assembled by the principle of self-assembly. Photocatalytic
degradation experiments of rhodamine B were carried out and
the photocatalytic activities of the three derivatives and their
self-assembled components were evaluated. The photocatalytic
experiments show that the catalytic efficiency of the self-
assemblies is higher than that of the three monomers and
TAPP because of their higher charge separation ability. In
addition, the three kinds of self-assembly have good reusability.
Author contributions
Conceptualization: B. Gao and Y. Li. Investigation: J. Pei. Con-
tent analysis: J. Pei. Experiments and writing – original draft:
J. Pei. Writing – review & editing: B. Gao. All others contributed
Project administration: Y. Li and Q. Duan.
Fig. 9 Photogenerated carrier trapping in the system of photodegrada-
tion of phenol by self-assembly of TCyPP under visible light irradiation.
3460 | New J. Chem., 2021, 45, 3454ꢀ3462
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Conflicts of interest
20 J. Wang, Y. Zhong, L. Wang, N. Zhang, R. Cao, K. Bian,
L. Alarid, R. E. Haddad, F. Bai and H. Fan, Nano Lett., 2016,
There are no conflicts to declare.
16, 6523–6528.
21 J. Wang, Y. Zhong, L. Wang, N. Zhang, R. Cao, K. Bian,
L. Alarid, R. E. Haddad, F. Bai and H. Fan, Nano Lett., 2016,
Acknowledgements
16, 6523–6528.
2
2 A. F. Molina-Osorio, D. Cheung, C. O’Dwyer, A. A. Stewart,
M. Dossot, G. Herzog and M. D. Scanlon, J. Phys. Chem. C,
This work was supported by the Jilin Province Science and
Technology Development Program (No. 20180101189JC).
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23 J. Hou, P. Lei, T. Meng, F. Zhao, H. Xu, X. Li, K. Deng and
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