Designs, synthesis, characterization and direct electrochemistry of zinc-porphyrin bearing pyrene noncovalent functionalized graphene oxide sheet

Article abstract of DOI:10.1002/cjoc.201200282

We have designed and synthesis a new compound of zinc-porphyrin bearing four pyrene groups (ZnP-t-P(py)₄) and prepared a new hybrid materials of ZnP-t-P(py)₄ with graphene oxide (GO) via non-covalent interactions. The ZnP-t-P(py)

Full text of DOI:10.1002/cjoc.201200282

FULL PAPER
DOI: 10.1002/cjoc.201200282
Designs, Synthesis, Characterization and Direct Electrochem-
istry of Zinc-Porphyrin Bearing Pyrene Noncovalent
Functionalized Graphene Oxide Sheet
Bi, Chun(毕纯)
Li, Yongjie(李永捷)
Chen, Haowen(陈浩文)
Yin, Gui*(尹桂)
Zhu, Junjie(朱俊杰)
Key Laboratory of Analytical Chemistry for Life Science, Ministry of Education of China, School of Chemistry and
Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093, China
We have designed and synthesis a new compound of zinc-porphyrin bearing four pyrene groups (ZnP-t-P(py)4)
and prepared a new hybrid materials of ZnP-t-P(py)4 with graphene oxide (GO) via non-covalent interactions. The
ZnP-t-P(py)4, along with four pendant pyrene entities ZnP-t-P(py)4, stacking on the (GO) surface due to π-π interac-
tions, has been revealed by AFM measurements. FTIR, UV-vis absorption confirm the non-covalent functionaliza-
tion of the GO. Raman spectral measurements revealed the electronic structure of the GO to be intact upon hybrid
formation. In this donor-acceptor nanohybrid, the fluorescence of photoexcited ZnP-t-P(py)4 is effectively quenched
by a possible electron-transfer process. The fluorescence and photoelectrical response measurements also showed
that this hybrid may act as an efficient photoelectric conversion material for optoelectronic applications.
Keywords zinc-porphyrin, graphene oxide, non-covalent interaction, optoelectronic character
Introduction
when it is combined with planar aromatic molecules
such as porphyrins and phthalocyanines. To accomplish
this, the donor, zinc porphyrin, has been functionalized
with four pendant pyrene entities (Scheme 1, ZnP-t-
P(py)4)).[19] Due to the presence of four interacting
pyrene entities on the GO' surface, stable ZnP-t-P(py)4/
GO hybrids are expected to form. As demonstrated here,
this is indeed the case; additionally, the newly formed
ZnP-t-P(py)4/GO hybrids have allowed us to investigate
the photoinduced electron transfer and photoelectro-
chemical responses of these ZnP-t-P(py)4/GO nanohy-
brids have been tested.
Recently, a lot of research effort has been devoted to
understanding the physicochemical properties of the
carbon allotrope-graphene with an atomically thin, 2D
structure that consists of sp2-hybridized carbons, and
exhibits remarkable electronic and mechanical proper-
ties.[1-4] Theoretically, the molecules of other allotropic
carbon forms can be built from graphene.[5a] For exam-
ple it can be stacked to form 3D graphite, rolled to form
1D nanotubes, and wrapped to form 0D fullerenes. Usu-
ally, graphene oxide (GO) can be easily deposited on
different substrates to produce continuous films for the
construction of transparent conductors,[5b] photovoltaic
devices,[6-8] and biosensors,[9-11] and hydroxyl groups at
the basal planes of GO sheets, which is responsible for
the formation of stable aqueous dispersions of GO.[12]
A number of types of covalently functionalized GO
have been prepared by utilizing the above functional
groups.[13,14] Such modified GO can be also applied as
electron-accepting material in organic solar cells due to
its unique structure and excellent electronic proper-
ties.[15] The interesting aspect attracting us is the non-
covalent functionalization of GO, with planar organic
molecules via π-π stacking, van der Waals, and/or elec-
trostatic forces. More importantly, this easy method can
endow GO with designed optoelectronic properties
Experimental
General conditions
NMR spectra were recorded on Bruker (300 MHz
1
for H) instruments in DMSO-d6 or CDCl3 (TMS as an
internal standard) solutions. Mass spectroscopy was
recorded with autoflex TOF/TOF-(Bruker) and High
Resolution Mass Spectra (LTQ-Orbitrap XL, Thermo-
fisher). Analytical thin-layer chromatography (TLC)
used GF254. Flash chromatography was performed on
silica gel (200—400 mesh). The morphologies of the
modified surfaces were studied using atomic force mi-
croscopy (Agilent 5500 model, USA) in tapping mode.
*
E-mail: yingui@nju.edu.cn
Received March 22, 2012; accepted May 16, 2012; published online XXXX, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200282 or from the author.
Chin. J. Chem. 2012, XX, 1—7
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Bi et al.
FULL PAPER
Scheme 1 Schematic representation of the ZnP-t-P(py)4 functionalized with four pendant pyrene entities on graphene oxide(GO)
H
N
O
O
O
O
NH
NH
O
HN
O
N
N
N
N
O
O
Zn
py
N
N
N
N
O
O
Zn
ZnP
N
H
ZnP-t-P(py)4
IR data were measured on a KBr crystal plate, using a
Bruker VECTOR 22 spectrophotometer. Resonance
Raman spectra were recorded using a Renishaw-in via
Raman spectroscopy (Renishaw, United Kingdom).
UV/Vis absorption spectra were recorded using a
Lambda 35 UV/Vis spectrometer (Perkin-Elmer instru-
ments, USA). Fluorescence spectra were recorded at
room temperature using an F900 fluorescence spec-
trometer (Edinburgh Instruments Ltd., United Kingdom).
Photoelectrical response measurement experiments were
performed using a CHI 660D electrochemical work-
station (CH Instruments Inc., USA). All experiments
were carried out at room temperature using a conven-
tional three-electrode system with an indium-tin oxide
(ITO) electrode as a working electrode, a platinum wire
as an auxiliary electrode, saturated calomel electrode as
a reference electrode, and supporting electrolyte is the
solution of 0.1 mol/L ascorbic acid (AA) in 0.1 mol/L
phosphate buffer solution (PBS, 200 mL mixture solvent
composed by 0.5928 g NaH2PO4 and 5.8019 g Na2HPO4,
pH＝7.4).
method[16-18] through the acid oxidation of flake graphite
as originally presented by Kovtyukhova et al.[19,20]
Synthesis of 5,10,15,20-tetra-4-oxy(acetic acid) phe-
nylporphyrin (TAPP)
To a solution of 5,10,15,20-tetra-4-hydroxy-phenyl-
Porphyrin (TPP)[21] (70 mg, 0.01 mmol) and ethyl bro-
moacetate (100 mg, 0.06) in 20 mL dry acetone was
added K2CO3 (110 mg, 0.08 mmol). The mixture was
heated under reflux for 24 h. After cooling to room
temperature, the solvent and excess ethyl bromoacetate
was removed via rotary evaporator. The solid was
washed with methanol-water mixture (1∶1, V∶V).[22,23]
The solid and KOH (56 mg) were dissolved in THF (20
mL), stirred and refluxed for 4 h. After cooling, 10%
HCl was added into the solvent to neutralize excess
KOH to pH＝7, then removed the solvent and washed
the residue with water. The crude product was recrystal-
lized with methanol and water. Yield obtained was 90%
1
(88 mg). H NMR (DMSO-d6) δ: 13.17 (s, 4H), 8.84 (s,
8H), 8.13 (d, J＝8.11 Hz, 4H), 8.11 (d, J＝8.11 Hz, 4H),
7.36 (d, J＝7.84, 4H), 7.34 (d, J＝7.84, 4H), 4.97 (s,
8H), －2.92 (s, 2H), autoflexTOF/TOF: m/z＝910.73.
Synthesis of graphite oxide (GO)
GO was produced by the modification of Hummers
2
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Designs, Synthesis, Characterization and Direct Electrochemistry of Zinc-Porphyrin
Scheme 2 The synthesis of ZnP-t-P(py)4: (i) ethyl bromoacetate, K2CO3, dry acetone refluxed for 24 h; (ii) KOH, THF, refluxed for 4 h;
(iii) N-methylmorphine, ethylchloroformate, 1-aminopyrene, stirred at －12 ℃ for 2 h, then stirred at room temperature for 24 h; (iv)
zinc acetate, DMF, refluxed for 3 h
HO
O
O
OH
OH
O
HO
O
NH
N
N
NH
N
N
i
iii
iv
O
OH
O
HO
ii
HN
HN
O
O
OH
TPP
OH
TAPP
H
O
O
N
NH
HN
N
N
N
N
Zn
O
O
O
O
O
O
N
H
ZnP-t-P(py)4
Synthesis of ZnP-t-P(py)4
8H), 8.38—8.10 (m, 44H), 7.59 (d, J＝7.58 Hz, 4H),
7.56 (d, J＝7.58, 4H), 5.28 (s, 8H). The mass of the
ZnP-t-P(py)4 is 1770.3235, 1771.2788, 1773.0624
[ZnP-t-P(py)4＋H＋]; 1787.1266, 1789.1896 [ZnP-t-
P(py)4＋H＋＋H2O].
TAPP (90 mg, 0.1 mmol) was dissolved in dry THF
(30 mL), stirred for 30 min. Then N-methyl morphine
(54 mg, 0.52 mmol) was added to the solution, stirred
for 40 min at －12 ℃ followed by the addition of
ethylchloroformate (56 mg, 0.52 mmol). The mixture
was stirred for 30 min at －12 ℃. 1-Aminopyrene (110
mg, 0.5 mmol) was added to the stirred solution and the
mixture solution was stirred for 24 h during which the
temperature was allowed to come to room temperature.
After completion of reaction the solution was filtered
and respectively washed with methol (50 mL), di-
chloromethane (50 mL). The residue was recrystallized
with DMF.[24] Then zinc acetate was added to the DMF
solvent of the H2P-t-P(py)4, stirred and refluxed for 3 h,
filtered and washed with water. Yield obtained was 10%
(18 mg); 1H NMR (CD3CSCD3) δ: 10.77 (s, 4H), 8.86 (s,
Preparation of ZnP-t-P(py)4/GO and ZnP-t-P(py)4/
GO/ITO
2.0 mg sample of GO was added to 5.0 mg of ZnP-t-
P(py)4 dissolved in 20 mL of dry DMSO, and the reac-
tion mixture was ultrasonic processed for 10 min and
then stirred for 48 h at room temperature. The mixture
was centrifugated for 20 min and the excess ZnP-t-
P(py)4 was washed by DMSO, followed by centrifuga-
tion at least three times, until the solution in the centri-
fuge tube turned colorless. At the end, 10 mL of fresh
solvent was added to the resulting deposit and was
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Bi et al.
FULL PAPER
sonicated for 15 min at 20 ℃. This homogeneous
brown dispersion was stable for several days and used
as mentioned in subsequent studies.[25]
GO nanohybrids. The Raman spectrum of GO (Figure 2)
shows two prominent bands at about 1330 cm－1 (D band
originating from disorder-activated Raman mode) and
1576 cm－ (G band corresponding to sp2 hybridized
1
The solution of 1 mg/mL ZnP-t-P(py)4/GO was pre-
pared for some subsequent measures. After the ITO
electrode had been cleaned with isopropanol solution of
1.5 mol/L KOH, washed with acetone and twice-
distilled water, and dried at room temperature, 20 μL
suspension of ZnP-t-P(py)4/GO was coated on the ITO
electrode of 0.25 cm2 and dried at room temperature to
obtain ZnP-t-P(py)4/GO/ITO.[28]
carbon).[29a,29b] In contrast to GO, the D and G bands of
ZnP-t-P(py)4/GO are shifted to the lower wavenumbers
－
1
by ν＝11 and 15 cm , respectively. It is worth pointing
out that Raman spectroscopy could be used to determine
the number of layers for n-layer graphene or graphene
oxide by the shift and shape of the 2D peak, because the
2D peak in graphene is attributed to two phonons with
opposite momentum in the highest optical branch.[29c]
The 2D peak of ZnP-t-P(py)4/GO appearing at 2709
Results and Discussion
－
－
1
1
cm , shifts to the higher wavenumber value by 35 cm
Characterization of the ZnP-t-P(py)4/GO complex in
solution
and becomes broader for an increasing number of
ZnP-t-P(py)4 layers with respect to single-layer gra-
The presence of GO sheets in the suspension was
confirmed by atomic force microscopy (AFM). The
AFM image in Figure 1A shows a single GO sheet cap-
tured from the suspension on a mica substrate. The av-
erage thickness of GO was measured to be about 0.8 nm
in water.[26] However, when GO was functionalized with
ZnP-t-P(py)4, the average thickness of a ZnP-t-P(py)4/
GO sheet was determined to be about 2.0 nm (Figure
1B), we assume that monolayered ZnP-t-P(py)4-
molecules covered both sides of graphene oxide sheet
with offset face-to-face orientation via π-π interactions,
by considering that the thickness of one porphyrin
molecule is about 0.5 nm.[27,28]
－
1
phene oxied (2D: 2674 cm ).[29a] The peak at 2924
cm－1 (D＋G mode) is attributed to defects, because it is
a combination of two phonons with different momen-
tum.[29d]
FT-IR spectra
Figure 3 shows FT-IR spectra of ZnP-t-P(py)4/GO,
ZnP-t-P(py)4, and GO. In the spectrum of ZnP-t-P(py)4
and ZnP-t-P(py)4/GO, the peak at 2919 cm－ corre-
1
sponds to the sp3 C—H characteristic stretching band.
These results clearly indicate that the Zn-t-P(py)4 mole-
cules had been non-covalently bonded to the grapheme
oxide by π-π stacking. The stretching band of C＝O
peak appeared at 1651 cm－1, while the band of
ZnP-t-P(py)4/GO broadened because of including the
group of —COOH (GO) and —CONH— (ZnP-t-
P(py)4).
Raman spectrum
The samples were also characterized using laser
Raman spectroscopy to obtain spectroscopic insight into
the electronic structure of the GO in the ZnP-t-P(py)4/
Figure 1 Tapping-mode AFM images and cross-sectional analyses of (A) GO and (B) ZnP-t-P(py)4/GO on mica.
4
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Designs, Synthesis, Characterization and Direct Electrochemistry of Zinc-Porphyrin
Steady-state fluorescence spectra
Figure 5 shows the steady-state fluorescence spectra
of ZnP-t-P(py)4 and ZnP-t-P(py)4/GO hybrids, observed
by the predominant excitation of the pyrene moiety (red
line), exhibiting a main peak around 390, 409 and 434
nm in DMSO. A slight peak shift from 434—437 nm
was observed for ZnP-t-P(py)4/GO, supporting interac-
tion between pyrene units and the GO surface. Under
350 nm excitation, some excited electrons of pyrene
moiety return to ground state with transferring the en-
ergy to ZnP moiety (red line at 609 nm), because the
ranges of pyrene emission cover the absorption wave-
length of ZnP moiety,[31] then the excited state electrons
of ZnP moiety transfer to GO surface. The ZnP moiety
returns to steady-state (black line at 609 nm).[32] In the
hybrids with GO, the Zn-porphyrin fluorescence inten-
sity was found to be quenched over 80% of its original
intensity around 610 nm.[5a,16]
Figure 2 The Raman spectra of GO (top), ZnP-t-P(py)4/GO
(bottom), λex＝532 nm.
Figure 3 FT-IR spectra of ZnP-t-P(py)4, ZnP-t-P(py)4/GO, and
GO.
Figure 5 Steady-state fluorescence spectra of ZnP-t-P(py)4/
GO and ZnP-t-P(py)4 (2×10－ mol/L) in DMSO, the inset is the
6
UV/vis absorption
Zn-porphyrin fluorescence intensity around 610 nm; λex＝350
The UV/vis absorption spectra of ZnP-t-P(py)4, and
ZnP-t-P(py)4/GO are shown in Figure 4. ZnP-t-P(py)4
exhibited the typical Soret absorption at 431 nm and Q
absorption at 561 and 602 nm. In the presence of GO,
the Soret band of ZnP-t-P(py)4/GO is redshifted from
431 to 433 nm, and the Q band is redshifted from 561
and 602 nm to 566 and 608 nm, which indicates the
formation of a J-type aggregate nucleated on GO
through π-π noncovalent interactions.[30]
nm.
Photoelectrical response measurement
The typical photoelectrical response of the ZnP-t-
P(py)4/GO in thin film for the on/off light illumination
cycles is shown in Figure 6. For the ZnP-t-P(py)4/GO
film on ITO substrate, a reversible rise/decay of the
photocurrent in response to the on/off illumination step
is observed. After light illumination, the photocurrent is
about 134% higher than that before illumination and
65.5 times as blank experiment. Compared with re-
ported literature[33c] which connected porphyrin and GO
via covalent, this hybrid has higher photocurrent and
lower dark current. In addition, the interaction between
porphyrin and GO via noncovalent method is conven-
ient to be prepared. Blank experiments carried out with
ITO coated with GO films[33d] produced a negligibly
small photoelectrochemical effect under similar experi-
mental conditions. Moreover, it is evident that the
photoelectrical response measured for the ZnP-t-P(py)4/
GO shows evident photocurrent stability when exposed
to several on/off cycles. According to the results re-
ported by others,[32] this phenomenon shows that there is
electron transfer from ZnP-t-P(py)4 to GO and higher
Figure 4 UV/vis absorption spectra of ZnP-t-P(py)4/GO and
ZnP-t-P(py)4 (2×10－6 mol/L) in DMSO.
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Bi et al.
FULL PAPER
ZnP-t-P(py)4, stacking on the GO surface due to π-π
interactions, has been revealed by AFM measurements.
FTIR, UV-vis absorption spectra confirm the non-
covalent functionalization of the GO. Raman spectral
measurements revealed the electronic structure of the
GO to be intact upon hybrid formation. In this donor-
acceptor nanohybrid, the fluorescence of photoexcited
ZnP-t-P(py)4 is effectively quenched by a possible elec-
tron-transfer process. Fluorescent and photoelectrical
response measurements also reveal that this hybrid may
act as an efficient photoelectric conversion material for
optoelectronic applications.
Figure 6 The typical photoelectrical response of the ZnP-t-
P(py)4/GO film on ITO substrate under white light illumination at
an applied potential of －0.4 V (solution: H2O of 0.1 mol/L AA
and 0.1 mol/L PBS, pH＝7.4).
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Conclusions
In summary, we have designed a new ZnP-t-P(py)4/
GO hybrid material via non-covalent interactions. The
ZnP-t-P(py)4, along with four pendant pyrene entities
6
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Designs, Synthesis, Characterization and Direct Electrochemistry of Zinc-Porphyrin
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