pubs.acs.

org/cm Article

Molecular Engineering of Robust Starburst-Based Organic

Photosensitizers for Highly Efficient Photocatalytic Hydrogen
Generation from Water
Yan-Yi Kwok, Po-Yu Ho, Ying Wei, Zhong Zheng, Sze-Chun Yiu, Cheuk-Lam Ho,*
and Shuping Huang*
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sı Supporting Information

ABSTRACT: Six donor−donor−π−acceptor (D−D−π−A) triphenyl-

amine-based starburst organic dyes with different electron-donating
moieties and thiophene-based π-linkers were synthesized and characterized.
Their photophysical and electrochemical properties, together with their
photocatalytic hydrogen evolution performance as photosensitizers (PSs),
were investigated. Distinctive and prolonged hydrogen evolution perform-
ances of these PSs under visible-light irradiation from water in their
platinized TiO2 composites were demonstrated: a turnover number (TON)
of up to 24 900 (252 h) with 1560 μmol (37.6 mL) hydrogen produced, an
initial turnover frequency (TOFi) of 1130 h−1, initial activity (Activityi) of
705 mmol g−1 h−1, and initial apparent quantum yield (AQYi) of 12.1%. To
the best of our knowledge, according to the TOF and TON values, the
designed PS system is one of the most efficient and robust photocatalytic
H2 generation systems adopting a TiO2-anchoring molecular PS in the literature. The results showed that the starburst triarylamine
donor moiety with phenothiazine functionality and the alkyl chain on the thiophene π-linker could boost the performance and
longevity of the photocatalytic system, providing a powerful strategy for the development of starburst-based highly efficient and
robust D−D−π−A organic photosensitizers in the future.

1. INTRODUCTION than the Eg of semiconductors could facilitate the process by

With the surging demand for energy and resources, the
development of sustainable, renewable, and clean energy has
been in the limelight of research in recent decades.
Photocatalytic hydrogen evolution has emerged as a promising
method to exploit alternative and sustainable energy resources.
The hydrogen generated is an ideal energy carrier that is
carbon footprint-free and inexhaustible.1,2 The water-splitting
process involves two redox half-reactions, namely, proton
reduction into a hydrogen molecule at the cathode and water
oxidation at the anode. Our research focuses on hydrogen
production efficiency, which can be assessed by investigating
the reduction part of the water-splitting process independ-
ently.3
The cleavage of water into hydrogen and oxygen using
platinum nanoparticles combined with TiO2 has been receiving
much attention since 1972, as this is a simple way to utilize
visible light for photocatalytic hydrogen generation.4,5 It works
when the energy of the absorbed photon is larger than the
band energy of the semiconductor photocatalyst. However, as
the band gap (Eg) of TiO2 is larger than 3 eV, its light-
harvesting region is restricted to the UV region. Introducing
PSs with the highest occupied molecular orbital (HOMO)−
lowest unoccupied molecular orbital (LUMO) gap smaller
extending the capacity of spectral response and improving the
visible-light-induced activities. Sacrificial electron donors
(SEDs) are often employed as additives in the photocatalytic
water-splitting reactions to scavenge the photogenerated holes
(the radical cation PS•+ return to PS, regeneration of dye) and
suppress the recombination of charge carriers.6−10
Different types of light-harvesting chromophores, including
metal complexes and organic compounds, have been exploited
as PSs for the water-splitting process. An ideal PS should be
able to resist water corrosion and have broad spectral
absorption and high charge carrier mobility to achieve effective
charge separation.8,11,12 Metalated PSs anchoring on TiO2,
especially ruthenium and iridium complexes, have been used in
photocatalysis due to their attractive performance and effective
metal-to-ligand charge transfer.9,13−15 From the viewpoint of
Received: February 21, 2022
Revised: May 27, 2022
Published: June 9, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acs.chemmater.2c00556

5522 Chem. Mater. 2022, 34, 5522−5534
Chemistry of Materials
Figure 1. Molecular structures of dyes P1−P6.
reducing the energy costs that are required to fabricate solar
water-splitting devices, metal-free organic dyes have emerged
as an attractive cost-effective alternative over metal complexes
for photocatalysis. Organic dyes offer structural versatility to
tune the absorption wavelengths with superior molar extinction
coefficients (ε) and charge-transfer ability as compared with
the conventional metalated dyes.13,16−18 In particular, π-
conjugated molecules with electron donor−acceptor moieties
for effective intramolecular charge transfer (ICT) exhibit
noticeable photovoltaic conversion efficiencies (PCEs) for dye-
sensitized solar cell (DSSC) applications. Due to such
convenient ICT modulation, large capacity and cross section
for absorption, and efficient charge separation upon photo-
excitation, organic PSs are also applicable to water split-
ting.9,19−21 However, most of the reported rod-shaped organic
PSs are prone to aggregate on the TiO2 surface and induce
intermolecular quenching.22 To further strengthen the stability
against aggregation and prevent charge recombination, the
dyes discussed herein were designed with a starburst donor
moiety with conjugated linkers. The bulky and nonplanar
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starburst donor moieties were recorded as effective blockers to
prevent direct contact between electrolyte/aqueous media and
TiO2 through steric hindrance, hence decelerating charge
recombination in the charge-separated state.23−25 The large
surface area occupied by the starburst donor moieties on TiO2
could improve dyes’ regeneration rate and was proven to
improve the photovoltaic efficiency in DSSCs with the positive
charge localized on the dye.7,23,26 On the other hand,
triphenylamine (TPA)-based dyes are known for their high
stabilities and photovoltaic activities.27 Attributed to TPA’s
nonplanarity and exceptional hydrophobicity, the aggregation
of dyes on the semiconductors’ interface and charge
recombination of the dye layer interface could be inhibited
by blocking out water molecules from approaching to the
TiO2−carboxylate interface, while the molar extinct coefficient
and broadness of the absorption spectrum of PS could be
enhanced. Incorporating the electron-donating substituents at
the para-position of the phenyl groups of TPA, which are
electrochemically active, would enhance the electron richness
and energy/transfer efficiency, stabilize the cationic radicals of
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Chemistry of Materials
TPA, and decrease its oxidation potential, such that the
stability of the PSs could be enhanced drastically upon the
electron injection.7,16,28−31 Phenothiazine, fluorene, and
carbazole, which were selected to incorporate as electron-
donating functionalities on TPA in the present study, are all
redox-active chromophores, with significant redox cyclability,
persistent radical cation formation, and electron-donating
ability.9,32−34 The electron-rich sulfur and nitrogen atoms in
phenothiazine can enhance the delocalization of electrons from
the donor to the acceptor and are highly stable in the cationic
radical form; hence, an extra stability would be provided for
the photo-induced electron transfer to the semiconductor.
Phenothiazine’s nonplanarity can also prevent dyes from
aggregation.35−38
Cyanoacetic acid, which has an electron-withdrawing cyano
group, is the most commonly used acceptor. The carboxylate
group in cyanoacetic acid forms an ester linkage with the
semiconductor to provide effective charge injection as its
energy level overlaps well with the CB of TiO2.39−41 The
selected thiophene and its derivatives are usually used as
conjugated electron-donating linkers that can extend electronic
conjugation and facilitate the charge transfer over the donor
and acceptor cores of PSs.42−44 The hydrophobic alkyl linkers
can defend the interface from the attack by water and prevent
dye aggregation, thus stabilizing dye−TiO2 nanocomposites
under aqueous conditions.45−47 Meanwhile, the hexyl group on
the thiophene unit may impair the molecular coplanarity to
prevent the π-aggregation on the TiO2 surface and, more
importantly, to restrain the charge recombination. Moreover,
the hexylthiophene group was also introduced to evaluate the
effect of molecular planarity on optical, electrochemical, and
photocatalytic properties.
Based on such structural consideration, starburst-based
metal-free organic PSs P1−P6 that exploited the D−D−π−A
framework with different starburst triarylamine donor moieties
were synthesized in this study (Figure 1). These molecules
matched well with the prerequisites of PSs in photocatalytic H2
generation. Light-driven hydrogen generation studies from
aqueous media were carried out. The results revealed that the
starburst framework could effectively prevent the π-aggregation
on the TiO2 surface and restrain the charge recombination.
Remarkably, P4 attained an active and robust H2 generation
system with a turnover number (TON) of up to 24 900 in 252
h with 1560 μmol (37.6 mL) hydrogen produced. The initial
turnover frequency (TOFi) was 1130 h−1, the initial activity
(Activityi) was 710 mmol g−1 h−1, and the initial apparent
quantum yield (AQY i ) was 12.1% under visible-light
irradiation from water. The performance of our photocatalytic
water-splitting systems is, to the best of our knowledge, one of
the highest reported thus far for three-component systems
utilizing PS-anchoring Pt-TiO2 nanoparticle composites
(Tables S3−S6).9,34,48,49 This report provides a logical strategy
for the development of efficient PSs for water splitting and
other photocatalytic applications.
2. EXPERIMENTAL SECTION
2.1. Materials and Reagents. All chemical reactions were
conducted under a nitrogen atmosphere with Schlenk link techniques.
All glassware were cleaned and dried in an oven before use. The
commercially available reagents were used without further purifica-
tion, unless otherwise specified. These reagents were purchased from
Sigma-Aldrich, Acros Organics, Tokyo Chemical Industry Co. Ltd.,
Dieckmann, J&K Scientific, and Macklin. Solvents were dried by
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distillation with respective drying agents. All of the reactions were
monitored by thin-layer chromatography (TLC) using silica-gel-
coated aluminum plates from Merck. Column chromatography with
silica gel (230−400 mesh) from DAVISIL was used for material
purification.
2.2. Instrumentation. 1H and 13C nuclear magnetic resonance
(NMR) spectra were measured in methanol-d4, DMSO-d6, or
chloroform-d, with tetramethylsilane (TMS) used as an internal
standard for chemical shift calibration on a Bruker Avance-III 400
MHz FT-NMR system. The integration and labeling of peaks were
performed by a Bruker NMR software Suite-TopSpin. Mass spectra
were collected by an Agilent 6540 liquid chromatography-electrospray
ionization quadrupole-time-of-flight (ESI-QTOF) mass spectrometer.
Ultraviolet−visible spectra were obtained by a Varian Cary 4000 of a
UV−visible spectrophotometer at 293 K, with the samples dissolved
in dichloromethane. Photoluminescence spectra were acquired by an
Agilent G9800AA Cary Eclipse (type II) fluorescence spectropho-
tometer at 293 K, with the samples dissolved in dichloromethane.
Fluorescence lifetimes of the PSs were determined by a Photon
Technology International (PTI) QuantaMaster 50 steady-state
spectrofluorometer at 293 K. The Marquardt-based nonlinear least-
squares fitting routine was adopted for analyzing the decay curves.
Those curves were presented in a biexponential function, regarding
the equation I(t) = A1 exp (−t/τ) + A2 exp (−t/τ 2). Cyclic
voltammetry was performed on a CHI 630C electrochemical
analyzer/workstation, with a scan rate of 100 mV s−1. The
experiments were performed in dichloromethane solution, using a
three-electrode cell with a 3 mm glassy carbon working electrode, an
aqueous Ag/AgCl reference electrode, and a platinum counter
electrode. Tetrabutylammonium hexafluorophosphate (0.1 M) was
used as the supporting electrolyte, and ferrocene was applied as an
internal standard, so that the corresponding one-electron oxidation
potential could be measured. Electrochemical impedance spectrosco-
py (EIS) was operated in a three-electrode system, in which the
carbon rod and Ag/AgCl electrode were used as counter and
reference electrodes, respectively, and 0.1 M KCl solution was used as
an electrolyte. The samples were dispersed in a mixture solvent of 1
mL of methanol and 0.1 mL of Nafion solution with a mass of 1 mg.
The prepared samples were dropped on the platinum carbon
electrode, and EIS data were collected by applying a sine wave with
an amplitude of 50 mV over a frequency range from 100 000 to 0.01
Hz on a CHI 760 electrochemical workstation.
2.3. Preparation of Platinized Titanium (IV) Oxide (Pt-TiO2).
The 0.5 wt% platinized TiO2 was prepared by adding 1.6 g of TiO2
nanopowder (anatase, 99.7% trace metal basis, particle size <25 nm
from Sigma-Aldrich) and 0.1 mL of H2PtCl6 (8 wt %) solution into 40
mL of methanol. The gray slurry was stirred vigorously under the
radiation from a mercury-coated lamp (300 W, HF300PD, EYE
Lighting) for 24 h. The grayish crude product was purified by washing
with methanol and centrifuged (3500 rpm, 5 min) thrice. Pt-TiO2 was
then dried in a vacuum oven at 60 °C for 8 h.
2.4. Preparation of the Dye-Loaded Platinized Titanium(IV)
Oxide. The prepared Pt-TiO2 (20 mg) was added to 2.5 mL (50 μM)
of PS-dissolved dichloromethane solution, followed by sonication
thoroughly at 20 °C for 30 min. TiO2 nanoparticles would turn from
gray to pale purple-red and would be distributed in the colored milky
solution. The solution mixture was then centrifuged at 3500 rpm for
10 min to reclaim the nanoparticles by removing the colorless
supernatant and drying under vacuum in the dark overnight. The
dried pellet would be directly used for the photocatalytic hydrogen
evolution experiment. The collected supernatant was used for
estimating the dye-loading percentage for each PS separately by
comparing absorbance differences before and after the dye adsorption
of their low-energy peaks. These carboxylate-anchoring dyes were
favorably attached onto the TiO2 surfaces and yielded close to 100%
adsorption. The corresponding UV/vis absorption spectra of P1−P6
in CH2Cl2 before and after dye adsorption are illustrated in Figure
S52 for dye-loading percentage calculation.
2.5. Photocatalytic Hydrogen Evolution Studies. The experi-
ments were conducted by adding the dye-loaded TiO2-Pt pellet (∼20
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Chem. Mater. 2022, 34, 5522−5534
Chemistry of Materials
Scheme 1. Synthetic Scheme of P1−P3a
a
(i) Pd(PPh3)4, THF/H2O, K2CO3; (ii) N-bromosuccinimide, dry THF; (iii) Pd(PPh3)4, THF/H2O, K2CO3; and (iv) piperidine, cyanoacetic
acid, dry chloroform.
mg) and 5 mL of aquatic ascorbic acid (AA, 0.8M) solution at pH 4.0,
the latter of which acted as the SED for regenerating the PSs, into a
25 mL pear-shaped flask. AA was chosen because of its well-studied
relationship between hydrogen generation efficiency and pH and its
illustrious redox reactions.50 The sealed pear-shaped flask was then
purged with a gas mixture of nitrogen/methane (80:20 mol %) for 10
min. The presence of methane was important and served as the
internal standard for the gas chromatography (GC) analysis for every
trial. The reaction mixture would be stirred rapidly at 19 °C with the
blue (ca. 472 nm) or green (ca. 520 nm) light-emitting diodes
(LEDs) under a just-fit container, which blocked out the environ-
mental stray light and prevented the loss of scattered light from the
LEDs. Powers of the LEDs were measured by a power meter (model:
BIM-7001, Hangzhou Brolight Technology Co., Ltd.) with a thermal
sensor (model: BIM-7203-0100F). The measured power was ∼80
mW for each reaction flask. At each time point, the headspaces of
each flask were detected by GC (Shimadzu GC-8A with 5 Å
molecular sieve column and a thermal conductivity detector) to
determine the volume of hydrogen produced based on the peak area
ratio of hydrogen/methane with reference to the calibration curve
(Figure S48). The time points taken were 5, 21, 26, 42, 47, 63, 68, 84,
89, 105, 126, 147, 168, 189, 210, 231, and 252 h from 14 independent
reaction flasks (duplicate for each sample) for P1−P6 and blank (Pt−
TiO2). The blue/green LED irradiation was assumed to be
monochromatic with a maximum emission intensity at 472/520 nm
for calculating the initial apparent quantum yield (AQYi%) for each
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sample dye. The water-splitting performance was also presented in
terms of turnover number (TON), turnover frequency (TOF), initial
turnover frequency (TOFi), and initial photocatalytic activity
(Activityi).
2.6. Theoretical Calculation. To gain insights into the energy
levels and electronic transition processes upon photoexcitation and
conformational relaxation, density functional theory (DFT) and time-
dependent density functional theory (TD-DFT) calculations and the
molecular geometries of five dyes at the first excited singlet states were
optimized by Gaussian 09 program51 at the B3LYP/6-311G(d,p) and
MPWPW91/6-311G(d,p) levels, respectively. The PBE0 hybrid
functional and the 6-31G* basis set were used. The solvent effects
in CH2Cl2 media were taken into account by performing the self-
consistent reaction field (SCRF) calculations using the polarizable
continuum model (PCM).52,53 The optimized geometries were
confirmed with all real frequencies.
3. RESULTS AND DISCUSSION
3.1. Synthesis and Characterization. The molecular
structures of the newly synthesized organic PSs are displayed
in Figure 1, while their synthetic routes are illustrated in
Schemes 1 and 2. The key dibromo intermediates, 5-(4-(bis(4-
bromophenyl)amino)phenyl)thiophene-2-carbaldehyde (3)
and 5-(4-(bis(4-bromophenyl)amino)phenyl)-4-hexylthio-
phene-2-carbaldehyde (10), were prepared by palladium-
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Scheme 2. Synthetic Scheme of P4−P6a

a
(i) n-Butyllithium, dimethylformamide, dry THF; (ii) N-bromosuccinimide, dimethylformamide; (iii) Pd(PPh3)4, THF/H2O, K2CO3; (iv) N-
bromosuccinimide, dry THF; (v) Pd(PPh3)4, THF/H2O, K2CO3; and (vi) piperidine, cyanoacetic acid, dry chloroform.

catalyzed Suzuki coupling reactions, followed by dibromination
with N-bromosuccinimide (NBS). The Suzuki coupling
reaction was then applied again with corresponding aromatic
boronic acids, followed by Knoevenagel condensation with
cyanoacetic acid to yield the final products P1−P6. All of the
organic precursors were characterized by 1H and 13C NMR
spectroscopies. The singlet peak found at around δ 10.0 ppm
in the aldehyde precursors corresponds to the proton of the
aldehyde functional group. All of the target organic PSs were
5526
characterized by electrospray ionization quadrupole-time-of-
flight mass spectrometry and 1H NMR spectroscopy. The
specific downfield singlet peaks observed at around δ 8.5 ppm
on their 1H NMR spectra imply the presence of the CC
double bond of cyanoacetic acid. The success of the
aforementioned final Knoevenagel condensation could be
supported by the disappearance of the aldehyde peaks at δ
10.0 ppm and the rise of those at δ 8.5 ppm regarding the
conversion of aldehyde to cyanoacrylic acid. However,
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acquisition of good quality of the 13C NMR spectra of P1−P6 Table 1. Data of UV/Vis Absorption, Emission, and
was difficult due to their partial solubilities in common organic Lifetimes of P1−P6 in CH2Cl2
solvents. All spectra could be found in Figures S1−S47.
λmax [nm] λem [nm] (excited at
3.2. Photophysical Properties. The UV−visible absorp- dye (ε[ M−1 cm−1)]) 400 nm) τ [ns] (χ2)
tion and photoluminescence spectra of P1−P6 were measured
P1 360 (37 000) 588 2.87 (1.12)
in dichloromethane and are presented in Figure 2. The
500 (23 500)
P2 359 (43 800) 641 1.54 (1.29)
488 (23 000)
P3 345 (45 700) 626 2.62 (1.27)
494 (21 900)
P4 363 (77 100) 619 3.06 (1.17)
471 (30 400)
P5 363 (70 200) 598 3.93 (1.03)
466 (24 200)
P6 340 (88 800) 646 2.42 (1.25)
474 (28 500)

ruthenium dyes.56 In general, the absorption bands of the

Figure 2. (a) UV/vis absorption spectra and (b) photoluminescence
spectra (excitation wavelength = 400 nm) of P1−P6 in CH2Cl2 at 293
K.
corresponding data are tabulated in Table 1. All of the organic
PSs display two major broad absorption bands from 300 to 650
nm. The absorption bands with a shorter wavelength (centered
at around 350 nm) are attributed to the localized π−π*
transitions throughout the electron-rich aromatic rings, while
those with a longer wavelength (centered at around 470−500
nm) are attributed to the intramolecular charge transfer (ICT)
from the electron-donating moieties to the electron-with-
drawing anchoring group. The molar extinction coefficients (ε)
(25 000−90 000 mol −1 cm −1 ) of the target dyes are
comparable to those of reported D−π−A starburst donor-
based PSs26,30,48,54,55 and much higher than those typical
5527
π−π* transition maxima are influenced by the nature of
electron-donating moieties on the TPA rings in P1−P6, with a
bathochromic shift following the order of carbazole (λmax =
345 and 340 nm for P3 and P6, respectively) < fluorene (λmax
= 359 and 363 nm for P2 and P5, respectively) ∼
phenothiazine (λmax = 360 and 363 nm for P1 and P4,
respectively). Besides, the optical properties of P1−P6 were
also affected by the π-conjugation bridge to a considerable
extent. The peak absorption wavelengths of the ICT bands
showed substantial hypsochromic effects when comparing P1
(λmax = 500 nm) to P4 (λmax = 471 nm), P2 (λmax = 488 nm)
to P5 (λmax = 466 nm), and P3 (λmax = 494 nm) to P6 (λmax =
474 nm), after the substitution of a hexyl moiety into the
thiophene linker. This was probably due to the planarity
difference of the dyes. The introduction of a hexyl unit in the
thiophene ring increased the dihedral angles between π-bridge
and triphenylamine planes, which were calculated at their
optimized geometries at the ground singlet states by the
Gaussian 09 program. The calculated dihedral angles of P1−
P6 were 20.11, −20.69, 19.63, 39.36, −39.57, and 38.26°,
respectively (Table S1). This meant that the introduction of
the hexyl unit twisted the π-conjugation system and disrupted
the planarity to induce a light blue shift on the absorption band
and hinder the ICT process from the donor to the acceptor.57
On the other hand, the electron-donating strength of 3-
hexylthiophene was obviously larger than thiophene, which
should induce a stronger ICT process within the dye. The
altered planar conjugation of thiophene by the vibrations of the
malleable hexyl chain involved a trade-off among the
characteristics of their light absorption.27 In addition, a
significant increment of almost twice was observed in ε of
the PSs in π−π* transitions with hexylthiophene groups than
those with thiophene, implying that the hexyl chain at the β-
position of thiophene was beneficial to the light-harvesting
capability in the near UV region. The calculated absorption
spectra for P1−P6 (Figure S51) were obtained by the PBE0
functional. The positions of the calculated absorption peaks of
the dyes were consistent with the experimental ones.
All of the dyes demonstrated photoluminescence in
dichloromethane at room temperature, showing structureless
broad peaks with emission maxima (λem) ranging from 588 to
646 nm. The emission spectra over the measured spectral
window presented no band from the triplet excited state, and
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the lifetimes (τ) of P1−P6 were measured in 1.54−3.93 ns LUMO energy level differences could be calculated (ranging
(Table 1), thus fluorescent in nature.58 from 2.12 to 2.22 eV). The values of those dyes with
3.3. Electrochemical Properties. To figure out the hexylthiophene were larger than those with thiophene as the π-
impact of molecular engineering on energy levels, cyclic linker, proving that changes in the π-linker in a D−π−A
voltammetry (CV) was used to investigate the electrochemical framework were influential to the separation between the
properties of these starburst PSs, including the optimal energy HOMO and LUMO, while a trend showed that the donor
levels of the highest occupied molecular orbital (HOMO) and moieties would have little effect to the electrochemical band
the energy offsets of the synthesized PSs. P1−P6 were added gap (dihexylfluorene > hexylcarbazole > hexylphenothiazine).
into the supporting electrolyte (0.1 M tetrabutylammonium Owing to the better planarity of thiophene, the E0‑0 values of
hexafluorophosphate) in dichloromethane solution at a P1−P3 were determined to be 2.12, 2.14, and 2.13 V,
scanning rate of 100 mV s−1. The reference electrode was respectively, which were slightly narrower than those of P4−
Ag/AgCl calibrated with ferrocene−ferrocenium (Fc+/Fc) as P6 (2.21, 2.22, and 2.20 V, respectively). Besides, the PSs’
an internal reference. The cyclic voltammograms in Figure S49 ELUMO were calculated to be ranged from −2.63 to −2.94 eV,
showed that the dyes displayed either reversible or quasi- which were more positive than the conduction band of TiO2
reversible electron transfer at the oxidative potentials (E vs Ag/ (−4.0 eV).15 The much larger negativity of TiO2 than that of
Ag+ > 0 V). Referring to the results illustrated in Table 2 and the LUMO of the dyes would be favorable to the rapid
electron injection because of the larger charge separation, thus
Table 2. Electrochemical Data and Energy Levels for P1−P6 the stronger driving force.16,61 It is worthy to note that the
dye Eox, Va EHOMO, eVb E0−0, eVc Eox*, Vd ELUMO, eVe LUMO energy level of P4 is more positive than the conduction
P1 0.05 −4.85 2.12 −2.07 −2.73
band of TiO2, compared to the other four compounds,
P2 0.28 −5.08 2.14 −1.86 −2.94
indicating a stronger driving force for electron injection. This
P3 0.25 −5.05 2.13 −1.88 −2.92
was the reason for the outstanding performance of P4. The
P4 0.04 −4.84 2.21 −2.17 −2.63
HOMO levels of the dyes with the same donor moieties were
P5 0.28 −5.08 2.22 −1.94 −2.86 measured, and the results showed that they had to be almost
P6 0.27 −5.07 2.20 −1.93 −2.87 the same values (P1 vs P4, P2 vs P5, and P3 vs P6) (Figure
3). This means the planarity adjustment of the π-linker could
a
Onset of first oxidation potentials was measured by cyclic
voltammetry in dichloromethane (CH2Cl2) solution containing 0.1 effectively tune the LUMO level nearly without any influence
M of NBu4PF6 against the Ag/Ag+ reference electrode, with a glassy of the HOMO level of the dye, showing a quite promising
carbon working electrode and platinum wire auxiliary electrodes. strategy to selectively optimize energy levels of the dye. The
b
Calculated from −(Eox + 4.36), as reversible oxidation of ferrocene experimental energy levels for P1−P6 (Table 2) generally
was E1/2 = 0.44 V and the EHOMO of ferrocene is equal to −4.80 eV vs agreed with the calculated values (Table S2).
to vacuum level. cE0−0 was determined from the onset of the Electrochemical impedance spectroscopy (EIS) was per-
absorption spectrum at the corresponding lowest energy absorption formed to evaluate the charge recombination and the
maxima. dEox* = Eox + E0−0. eELUMO = EHOMO + E0−0. resistance of charge transfer of the selected photosensitizers
based on the line model of typical transmission.62,63 The
Figure 3, the first oxidation potentials (Eox) of the PSs P1−P6, Nyquist plots of dyes P1−P4 and P6 are shown in Figure S50.
which coincided with the HOMO energy levels, were found to The arc radii of P2 > P3 > P1 > P6 ∼ P4 further confirm that
be 0.05, 0.28, 0.25, 0.04, 0.28, and 0.27 V, respectively. the incorporation of hexylthiophene as the spacer could
Therefore, the calculated EHOMO values of P1−P6 were found effectively reduce the charge transport resistance and enhance
to be ranged from −4.84 to −5.08 eV, which were more the interfacial electron transfer.63−66 This also supports the
negative than the redox potential energy level of ascorbic acid performance of dyes in the photocatalytic hydrogen
(−4.65 eV at pH 4).59 This confirms that the dye regeneration production.
from the oxidation state could occur expeditiously by the 3.4. Theoretical Calculation. Investigation of frontier
thermodynamic driving force during the photocatalytic water molecular orbitals of dye molecules is essential for studying the
splitting.48,60 The absorption spectra showed the zero−zero charge-separated states. The molecular orbital diagram in
excitation energies (E0−0) of the dyes, and thus the HOMO− Figure 4 shows that the lowest unoccupied molecular orbital

Figure 3. Illustration of the energy levels (HOMO and LUMO) of P1−P6.

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Chem. Mater. 2022, 34, 5522−5534
Chemistry of Materials
Figure 4. Surface plots of P1−P6 estimated from DFT calculations
using the B3LYP/6-311G(d,p) basis set.
(LUMO) of all dyes was mainly localized at the π-bridge and
acceptor units (thiophene and 2-cyanoacrylic acid). The
carboxylic acid anchoring group of the five dyes had a
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substantial contribution to the LUMO, which facilitated a
significant electronic coupling with the TiO2 surface and
electron injection efficiency. On the contrary, the highest
occupied molecular orbital (HOMO) for the compounds was
delocalized along the donor units, mainly at the triphenylamine
for all compounds. It is worth noting that the HOMOs of P1
and P4 were more localized at one of the phenothiazine units
and they were not found at all in the electron-accepting units,
while those of P3 and P6 were distributed among the carbazole
and triphenylamine units with little HOMOs located at the
thiophene unit. The difference in HOMO and LUMO orbitals
for P4 > P1 > P6 > P3 > P5 > P2 indicated that the electrons
in TiO2 had the last tendency to recombine with the holes in
phenothiazine of P4.67 Although they had different electron
donors extended from the triphenylamine center, their
HOMOs were still distributed along triphenylamine, resulting
in the almost the same HOMO energy levels (around −5.15
eV) except P2 (−5.38 eV) and P5 (−5.34) from Table S2.
The LUMO energy levels of the six compounds varied from
−2.44 to −2.60 eV (Table S2), resulting in different energy
gaps (P2 (2.86 eV) > P5 (2.80 eV) > P3 (2.72 eV) > P1 ∼ P6
(2.60 eV) > P4 (2.55 eV)).
3.5. Photocatalytic Hydrogen Production. On account
of the outstanding light-harvesting ability of the PSs in the
400−600 nm region, it is foreseeable that P1−P6 would have
great potential for effective photocatalytic water splitting. It has
been previously reported by other works that platinum-
containing dyads used as PSs enabled unprecedentedly
efficient and steady H2 production from water after attaching
to platinized TiO2 nanoparticles.16,68 Herein, we carry out the
light-driven H2 generation studies by adopting the same
photocatalytic system for our organic PSs. In short, the H2
generation experiments were conducted in aqueous solutions
at pH 4.0, with AA (0.8 M) serving as the hole scavenger.
Similar to previous reports, GC analysis based on a methane
internal standard calibration method was used to measure the
amount of H2 produced at the end of the irradiation. The
percentage of dye loading on TiO2 was measured by changes in
absorbance of the dyes’ solution after the adsorption (Figure
S52), which are inversely related to the bulkiness of the PSs
because of the size-matching effect.69,70 The dye-loading
percentages found for our dyes laid between 96 and 98%
(Table 3) due to their similar molecular volumes. The detailed
procedures of platinizing TiO2 and dye loading onto TiO2 are
stated in Section 2.
The hydrogen generation fitting curves for the five dyes are
presented in Figure 5, and the corresponding data (TON,
TOF, TOFi, Activityi, and AQYi%) are tabulated in Table 3.
P1−P6 PSs facilitated the photocatalytic hydrogen evolution
(ranging from 5.0 to 37.6 mL) when compared with the
control bare Pt−TiO2 (4.9 mL) under blue-light irradiation
(472 nm) for more than 105 h (Figure 5a). The H2 production
increment was quite drastic for all PSs in the first 21 h, except
for P4, which had the ability to sustain that to up to 47 h. The
system with P4 had the highest and most remarkable
photocatalytic activity, with 37.6 mL of hydrogen and TON
of 24 900 over 252 h, while the TON values of P1−P3, P5,
and P6 were 11 500, 3320, 6560 (over 169 h), 6980 (over 171
h), and 15 800 (over 105 h), respectively, under blue light
irradiation. To compare the performances equitably with other
reported dyes, the initial hydrogen production activity
(activityi) and the initial apparent quantum yield (AQYi) of
our PSs were also calculated. It is worthy to note that P4
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Chemistry of Materials pubs.acs.org/cm Article

Table 3. Light-Driven H2 Generation Data With and Without PSs P1−P6 on Pt−TiO2
dye DL%a H2 (mL) TONb TOF (h−1)c TOF (h−1) optimal values at plateau TOFi (h−1)d activityi (mmol g−1 h−1)e AQYi%f
Irradiation under Blue LED (472 nm) for 169 h
P1 97 17.3 11 500 68.1 124 (84 h) 1020 636.1 11.1
P2 98 5.01 3320 19.7 35.3 (84 h) 315 197.0 3.53
P3 98 9.90 6560 38.8 73.0 (84 h) 607 379.1 6.29
P4 97 37.6 (252 h) 24 900 98.9 218 (105 h) 1130 704.5 12.1
P5 96 10.5 (171 h) 6980 40.8 221 138.0 2.36
P6 97 23.9 (105 h) 15 800 151 333 (47 h) 943 589.6 10.1
Pt-TiO2 4.90 106.6 1.77
Irradiation under Green LED (520 nm) for 169 h
P1 97 6.53 4330 25.6 33.0 (84 h) 151 94.3 2.41
P2 98 1.34 888 5.26 6.74 (84 h) 51.2 32.0 0.936
P3 98 5.17 3430 20.3 27.4 (84 h) 134 83.9 2.38
P5 96 5.19 (171 h) 3440 20.1 132 82.8 1.42
Pt-TiO2 1.03 20.9 0.478
210 h
P4 97 6.18 4090 19.5 26.7 (147 h) 170 106.3 2.80
P6 97 3.78 2510 11.9 16.3 (147 h) 121 75.6 1.99
a
Dye-loading percentage. bTurnover number of H2 is calculated as 2 × number of moles of H2 produced divided by the number of moles of PS
attached to platinized TiO2. cTurnover frequency is calculated per hour. dInitial turnover frequency in the first 5 h. eInitial photocatalytic activity of
the system is defined as the number of micromoles of H2 evolved per gram of platinum loaded per hour. fInitial apparent quantum yield percentage
(AQYi%) of the system.

achieved exceptionally high Activityi of 705 mmol g−1 h−1 and
AQYi of 12.1%, and P6 came the second with decent Activityi
of 590 mmol g−1 h−1 and AQYi of 10.1% after irradiating for 5
h. By comparing their TOF, TON, and Acitivtyi values, the
system with P4 is certainly one of the most capable and robust
photocatalytic water-splitting systems using organic-PS/TiO2/
Pt under visible light. 3,48,71 The durability was also
considerably strong, as the H2 evolution reactivity and TOF
of P4 could sustain beyond 250 h, suggesting superior
photostability of the P4-sensitized system. Most of the
metal-free PSs for photocatalytic H2 generation reported in
the literature suffer from instability (only active within 10 h)
and/or poor activity (TOF < 100 h−1),9 and our results show
that P4 has the ability to retard dye degradation or desorption
from TiO2 over the prolonged irradiation.72−74 Besides, a
comparison between the reaction mixture prior and after the
irradiation (Figure S54) showed that the aquatic AA solution
turned from colorless to orange-yellow due to the oxidation of
ascorbic acid to dehydroascorbic acid to regenerate PS during
the water splitting.
On the other hand, after the green-light irradiation (520
nm) for 169 h, P1 remained active as shown in Figure 5b. With
6.5 mL of hydrogen generated by P1 with TON of 4330, the
performances of our dyes in green light were in the order of P1
> P4 > P3 ∼ P5 > P6 > P2 in terms of the final amount of H2
produced. However, the Activityi and AQYi of P5 were
significantly higher than those of P2, while those of P4 were
slightly higher than those of P1. Such a phenomenon was not
observed between P3 and P6. It should be noted that the six
PSs exhibited a different pattern of activity under different light
irradiation. The higher TON and volume of H2 produced by
P4−P6 than P1−P3 under blue-light irradiation (472 nm)
could be attributed to the blue shift and much more
pronounced absorbance of P4−P6 in the shorter wavelength
region. More blue light photons could be absorbed by P4−P6
for dyes’ excitation, so more electrons could be transferred to
Pt−TiO2 for water reduction. With the narrower HOMO−
LUMO energy gap of P1 and P3 than that of P2, P1, and P3
5530
could have more effective excitation. Hexylphenothiazine (in
P1) and hexylcarbazole (in P3) are, therefore, better electron-
donating moieties than dihexylfluorene (in P2). Although the
energy gap of P1 (and P4) is similar to P3 (and P6), the
ELUMO of P1 (and P4) is much smaller than that of P3 (and
P6), which is more favorable for expeditious electron injection
to TiO2;71−73 thus, better performance of P1 (and P4) than
P3 (and P6) under both blue- and green-light irradiation could
be observed.
During the photocatalytic process, decomposition of PS may
occur upon light irradiation due to the formation of the
reduced dyes (PS−) via the reductive quenching pathway,9,75
which is commonly observed in most of the reported
metallated76 and metal-free PSs.34,71,77 To strengthen their
longevity, therefore, a hydrophobic, bulky, and electron-rich
starburst donor structure was adopted in the PS, so that the
excited species PS* would be unfavorably reduced by the SED
and any unfavorable chemical quenchers, thus shielding the
formation of PS− on the TiO2 surface.46 The large surface area
provided by the starburst donor in our dyes could bolster the
dye regenerating process, such that the decomposition of the
metastable oxidized PS+ species was hindered.78−80
By their steric hindrance, adding alkyl groups on the
electron-rich moieties and thiophene rings could prevent dye
aggregation and modify the orientation of the dyes to become
favorable for electron injection to TiO2 and suppress charge
recombination.44,81−84 The adventurous effect of dye regener-
ation and precluding undesirable charge recombination could
be further enhanced by introducing the hydrophobic alkyl
group at the central moieties of the scaffold, for instance,
hexylthiophene in the π-spacers of P4−P6, as the SED can
contact with PS better and more surface of TiO2 could be
covered, respectively, compared to adding the alkyl chains only
to the donors.85−88 This structural design helped P1−P6 to get
better endurance as compared with other PSs that were
without the starburst donor moiety, and they could stay active
over the long period of light irradiation time (over 100 h in
general and over 200 h under blue-light irradiation for P4).
https://doi.org/10.1021/acs.chemmater.2c00556
Chem. Mater. 2022, 34, 5522−5534
Chemistry of Materials
Figure 5. Kinetic traces of hydrogen generation with respect to
different PSs (P1−P6 and Pt−TiO2) under the irradiation of (a) blue
LED (472 nm) and (b) green LED (520 nm) at 50 mW. Each sample
flask contained 0.8 M ascorbic acid (5 mL) in water (pH 4.0) and 20
mg of PS−TiO2−Pt composite sample.
4. CONCLUSIONS
A series of novel D−D−π−A metal-free triphenylamine
starburst donor-based PSs with different donating moieties
on triphenylamine and thiophene/hexylthiophene as the π-
linkers were designed and synthesized in this work. This design
with different donating substituents and combinations would
allow the structural studies on some essential properties like
the HOMO−LUMO gap and absorbance on the water-
splitting performances. Introducing the hexyl chain onto the
thiophene π-spacer could significantly enhance the absorption
properties of P4 and P6 and double molar extinction
coefficients at around 350 and 470 nm.
P1−P6-sensitized Pt−TiO2 photocatalysts showed impres-
sive hydrogen productivity in aqueous ascorbic acid at pH 4.0
under blue and green lights, compared to the blank TiO2−Pt,
over the exceptionally long irradiation. Specifically, the most
remarkable one is attributed to P4, yielding 1560 μmol (37.6
mL) of hydrogen produced over 252 h under blue light with a
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pubs.acs.org/cm Article
TON of 24 900, TOFi of 1130 h−1, and AQYi% of 12.1.
Notably, the hydrophobic and electron-rich starburst-based
structure, with the introduction of the alkyl group(s) to the
thiophene π-spacer, could potentially boost the stability and
robustness and suppress the charge recombination of the
organic PSs in the photocatalytic hydrogen evolution system.
We expect that further structural optimization for the
absorption of longer wavelengths would provide an oppor-
tunity for the organic dyes to exhibit much higher performance
in photocatalysis.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.chemmater.2c00556.
Synthesis and characterizations of intermediates and
P1−P6, computational studies and all other spectra data
(PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Cheuk-Lam Ho − Department of Applied Biology and
Chemical Technology, The Hong Kong Polytechnic
University, Hong Kong, P. R. China; PolyU Shenzhen
Research Institute, Shenzhen 518057, P. R. China;
orcid.org/0000-0001-8596-0307; Email: cheuk-
lam.ho@polyu.edu.hk
Shuping Huang − College of Chemistry, Fuzhou University,
Fuzhou 350108 Fujian, P. R. China; orcid.org/0000-
0003-4815-1863; Email: huangshp@gmail.com
Authors
Yan-Yi Kwok − Department of Applied Biology and Chemical
Technology, The Hong Kong Polytechnic University, Hong
Kong, P. R. China; PolyU Shenzhen Research Institute,
Shenzhen 518057, P. R. China
Po-Yu Ho − Department of Applied Biology and Chemical
Technology, The Hong Kong Polytechnic University, Hong
Kong, P. R. China; PolyU Shenzhen Research Institute,
Shenzhen 518057, P. R. China; Present Address: Biological
Inorganic Chemistry Laboratory, Francis Crick Institute, 1
Midland Road, London NW1 1AT, United Kingdom;
Present Address: Department of Chemistry, King’s
College London, Britannia House, Trinity Street, London
SE1 1DB, United Kingdom
Ying Wei − College of Chemistry, Fuzhou University, Fuzhou
350108 Fujian, P. R. China
Zhong Zheng − Department of Applied Biology and Chemical
Technology, The Hong Kong Polytechnic University, Hong
Kong, P. R. China; PolyU Shenzhen Research Institute,
Shenzhen 518057, P. R. China; Department of Materials
Science and Engineering, City University of Hong Kong, Hong
Kong, P. R. China
Sze-Chun Yiu − Department of Applied Biology and Chemical
Technology, The Hong Kong Polytechnic University, Hong
Kong, P. R. China; PolyU Shenzhen Research Institute,
Shenzhen 518057, P. R. China; orcid.org/0000-0002-
3001-365X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemmater.2c00556
https://doi.org/10.1021/acs.chemmater.2c00556
Chem. Mater. 2022, 34, 5522−5534
Chemistry of Materials
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
C.-L.H. thanks the Hong Kong Research Grants Council
(PolyU 123021/17P), the Science, Technology, and Innova-
tion Committee of Shenzhen Municipality
(JCYJ20180306173720000), Environment and Conservation
Fund (ECF 79/2020) from the Government of HKSAR, and
the Hong Kong Polytechnic University (ZVVU and ZVXU)
for their financial support.
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