Chemical Engineering Journal 489 (2024) 151215

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Chemical Engineering Journal

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

Self-powered photoelectric sensors based on hydrogel diodes doped

with photoacid
Liwei Wu a, 1, Jinfan Qi a, 1, Lingling Zhang a, *, Lei Yu b, Hongfei Gao b, Jun Gao b, Jie Ju a, *,
Xi Yao a, *
a
Key Lab for Special Functional Materials of Ministry of Education, Henan University, Kaifeng 475004, Henan Province, China
b
Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 266101 Qingdao, China

A R T I C L E I N F O A B S T R A C T

Keywords: Artificial retina requires photo-sensory units that convert light into electric signals without relying on any
Hydrogel diode external power supply. Recent development on hydrogel diodes paves a new avenue for creating photo-electric
Photoacid signals that can be picked up by human optic nerves. Here, we report a self-powered photoelectric sensor based
Photoelectric sensor
on hydrogel diodes doped with photoacid, which produces electric signal relying on no external power supply.
Artificial retina
The photoelectric sensor is self-powered due to the fact that the photoacid-released protons are mobilized under
the influence of the built-in electric field in the hydrogel PN junction. The photo-induced open-circuit voltage
reaches to 1.6 mV under 50 mW cm− 2. We found that the highest electric response occurred when photoacid was
presented at the cationic side of the hydrogel PN junction. A prototype consisting 9-element sensor array is
prepared, and we have demonstrated its potential for spatially resolved visualization upon light irradiation.

1. Introduction
Biomimetic sensors transfer signals of external stimuli to either
human or machines, following mechanisms analogous to the human
counterparts [1–6]. Among all sorts of specialty sensors, artificial photo-
receptors hold great potentials in restoring lost functions or providing
augmentation to human vision [7,8]. Many biomimetic sensors are
hydrogel-based so as to fit in application in human bodies in terms of
both mechanics and biocompatibility [6,9–11]. In previous attempts,
hydrogel-based photo receptor might use to photo-thermal effect to
change the impedance [12] or transparency [13] of hydrogel. Others
might combine organic photodiodes with hydrogels [14].
Nonetheless, external power supply is often involved to generate or
transfer electric signals, which makes it inconvenient for biomedical
applications [4,5,15]. Self-powered refers to a strategy that involves
battery-free operation and long-lasting power approaches. This means
that the devices are designed to generate their own power without the
need for external batteries or frequent recharging [16,17]. Recently, Y.
Yu et al. reported a high-voltage output photoelectric sensor based on
photo-deformable liquid crystal polymers and piezo-material, poly­
vinylidene fluoride trifluoroethylene (P(VDFTrFE)) [18]. The high open-
circuit voltage can be picked up by human optic nerve system [19]. More
importantly, the signal formation is based on the photo-mechanical­
–electrical stimulus–response route, so that the entire device was self-
powered [20–22]. However, the nature of transient electric response
by piezo-materials makes the output signal unsustainable, which poses a
dilemma between adding signal sustaining modules and keeping the
whole setup self-powered. Aside from piezoelectric devices, the func­
tioning of ionotronics relies on transfer of mobile ions, which offers an
opportunity to devise photo receptor with sustainable output signal.
Among many existing ionotronic materials and devices, hydrogel
diodes are an emerging species, receiving more and more research in­
terests [23]. For instance, Z. Suo and co-worker built up an elastomeric
PN junction structure based on oppositely charged polyelectrolytes
[24,25]. The intrinsic built-in electric field might provide an internal
electric force to mobilize ions in a photo receptor [14]. Herein, we
developed a self-powered photoelectric sensor system based on hydrogel
diode doped with photoacid. Photoacids are a wide species that
deprotonate/reprotonate in presence/absence to light irradiation [26].
The absorption spectra of photoacids can vary depending on their spe­
cific chemical structures (Table S1). For instance, HPTS (8-Hydrox­
ypyrene-1, 3, 6-trisulfonic acid, trisodium salt) has an absorption range

* Corresponding authors.
E-mail addresses: zll2021@henu.edu.cn (L. Zhang), jujie@henu.edu.cn (J. Ju), yaoxi@henu.edu.cn (X. Yao).
1
These authors contributed equally.

https://doi.org/10.1016/j.cej.2024.151215
Received 30 January 2024; Received in revised form 19 March 2024; Accepted 10 April 2024
Available online 10 April 2024
1385-8947/© 2024 Published by Elsevier B.V.
L. Wu et al.
of 290–420 nm, making it sensitive to ultraviolet and visible light in that
wavelength range [27]. Spiropyran, another type of photoacid, dem­
onstrates absorbance between 420–460 nm [28]. Azoniaanthracene
[29], 2-Hydroxyazobenzenes [30], and other photoacids also possess
unique absorption spectra, allowing them to respond to particular
wavelengths of light. These distinct absorption characteristics make
photoacids suitable candidates for various applications, including the
development of self-powered artificial retinas based on hydrogel diodes
doped with photoacid. By carefully selecting the appropriate photoacid
and tailoring its integration within the hydrogel diodes, researchers can
optimize the light-responsive properties of the artificial retina system.
We investigated on the mechanism photoelectric response based on
proton release and transfer in the network of hydrogel PN junction.
Furthermore, we demonstrated the concept of artificial retina as a 9-
element prototype. The hydrogel diode unit successfully picked up
patterns of light irradiation.
2. Experimental sections
2.1. Materials
2-Acrylamido-2-methylpropane sulfonic acid (AMPS, 98 %, Mack­
lin), (2-Acryloyloxyethyl)-N,N,N-trimethylammonium chloride
(DMAEA-Q, 80 %, Sigma-Aldrich), N,N’-Methylenebis (acrylamide)
(MBAA, 99 %, J&K), Ammonium persulphate (APS, 98 %, Sigma-
Aldrich), N,N,N’,N’-Tetramethylethylenediamine (TEMED, 99 %,
Macklin), 8-Hydroxypyrene-1, 3, 6-trisulfonic acid, trisodium salt
(HPTS, > 98.0 %, Aladdin), Sodium Hypochlorite (NaClO, 6–14 %,
Macklin) were all used as received. Silver strings were purchased from
online a retailer on Taobao.com. All chemicals were used as received
without further purification. Deionized water was used in all the
experiments.
2.2. Synthesis of hydrogel diodes
Anionic hydrogel: Monomer 2-Acrylamido-2-methylpropane sul­
fonic acid (3 M), crosslinker N, N’-Methylenebis (acrylamide) (4 mol%
to monomer), initiator ammonium persulphate (0.35 mol% to mono­
mer) and Initiator promoter TEMED (0.17 mol% to monomer) were add
to 10 mL of deionized water and mixed by vortex mixer (Vortex 2-IKA)
for 1–3 min and subject to ultrasound degassing for 1 min. The resulting
transparent solution was cast into glass molds (two glass plates spaced
by 500-µm-thick scotch taminpe). The molds were heated in an oven at
60 ◦ C for one hour until the hydrogel was fully cured. Cationic hydrogel:
the AMPS was replaced by DMAEA-Q, and the polycationic hydrogel
with DMAEA-Q were prepared following the same protocol as preparing
the cationic hydrogel.
2.3. Fabrication of the photo-sensing hydrogel diode
To introduce photoacid in hydrogels, the desired amount of 8-
Hydroxypyrene-1, 3, 6-trisulfonic acid, trisodium salt (HPTS, photo­
acid) was first dissolved in deionized water (1 wt%, 5 wt%, 10 wt%, 20
wt%, 30 wt%). The pre-dried hydrogel was sealed in a zip-lock bag with
equal amount of HPTS aqueous solution as that of water in the hydrogel
before drying. In the zip-lock bag, HPTS aqueous solution was fully
absorbed by the dry gel, and HPTS-containing hydrogel was
accomplished.
Hydrogel diodes: polycationic hydrogel and polyanionic hydrogel
were cut into 1 × 2 cm2 pieces. A piece of polyanionic hydrogel was
stack together with a piece of polycationic hydrogel to form a hydrogel
PN junction. According to specific experiments, HPTS might or might
not be introduced to both or either side of the PN junction.
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Chemical Engineering Journal 489 (2024) 151215
2.4. Fabrication of photoelectric sensors based on hydrogel diodes
The proof-of-concept prototype of photoelectric sensor array was
assembled and sandwich-sealed in between two polyimide (PI)-based
printed circuit board (PCB) films. In the 9-element sensor, each unit was
connected to respective copper electrodes attached to the PCB on PI
films. A schematic representation of the layout was shown in Fig. S16.
The signal generated by the photoelectrical units was collected and
processed by the collector and then uploaded to the computer for
display. The collector uses a 24-bit Analog-to-digital converters (ADC)
with a voltage range of ± 1.2 V and a sampling resolution of 0.143 µV.
This ADC performance was sufficient to capture the millivolt-level
voltage changes that occur in photoelectrical sensor upon presence or
absence of light.
3. Results and discussion
Visible light travels through the lens of an eye, and arrives at the
retina, where the column cells trigger cross-membrane transport of ions
as a start of signal transmission to the brain (Fig. 1A) [31].
In our design, the main structure of the photoelectric sensor is
composed by the hydrogel diode, which is a bilayer of polyelectrolytes
carrying positive (2-Acryloyloxyethyl)-N,N,N-trimethylammonium
chloride, DMAEA-Q) and negative (2-acrylamide-2-methyl­
propanesulfonic acid, AMPS) charges. The photoacid used here is 8-
Hydroxypyrene-1,3,6-trisulfonic acid, trisodium salt (HPTS), which is
of fair solubility in water, because it carries multiple groups of strong
electrolytes [32]. The obtained hydrogel diode is verified by Fourier
transform infrared spectrometry (FT-IR) (Fig. S1), scanning electron
microscope (SEM) and energy-dispersive X-ray spectroscopy (EDS)
(Fig. S2). Results are in agreement with our design structure. The hy­
droxyl group in HPTS can rapidly deprotonate/reprotonate in presence/
absence to light irradiation (Fig. 1C). The HPTS with adsorption peaks in
290 nm − 420 nm (Fig. S3) is introduced to polycationic side of the PN
junction by swelling (Fig. 1B). To keep constant volume of materials, we
first evaporate certain amount of water and swell equal amount of HPTS
solution to the gel. After loading HPTS, the polycationic hydrogel is
directly attached to the polyanionic hydrogel. The interfacial adhesion is
automatically secured by electrostatic interaction [33–35]. By light
irradiation of the polycationic gel side, HPTS is deprotonated, releasing
protons to the surroundings. When light is absent, the generate protons
gradually recombine (Fig. 1C). The very nature of the onset of voltage
and current of HPTS upon light irradiation is based on the fact that after
deprotonation, the anionic and cationic counterparts are of different
sizes and thus different mobility in an aqueous media [36,37]. The
resulting electric current and voltage is interpreted as the photoelectric
response of the self-powered photoelectric sensor.
The ability for HPTS to release protons in response to light irradia­
tion is crucial to the design. In experiments, the HPTS aqueous solution
gradually changed from fluorescent green to dark brown as increasing
HPTS concentration (Fig. 1D). As irradiation went on, the pH of HPTS
solution gradually decreased, and the largest shift of pH (3.71 ± 0.7 to
3.07 ± 0.13) occurs at the HPTS concentration of 5 wt% (Fig. 1E). Lower
pH drops at higher HPTS concentration, we speculate that the higher
concentration of HPTS in solution blocks penetration of light and limits
the release of protons. As such, 5 wt% HPTS is used for all later exper­
iments except otherwise mentioned. As shown in Fig. 1F, the as-
prepared hydrogel PN junction is transparent and soft. And the excel­
lent interfacial adhesion capability of hydrogel PN junction is proved
through the optical microscope image of the cross section [25].
We conduct an experiment to investigate the rectification charac­
teristics of hydrogel diodes and photo-sensing hydrogel diodes. In
Fig. S4, we utilize 1 mm thick poly(dimethylsiloxane) (PDMS) spacers
with a 0.5 mm diameter hole. Cylindrical slabs of polyelectrolyte
hydrogels are inserted into the PDMS spacers to secure the gels, creating
a gel interface. Contact between the polyelectrolyte hydrogels and 5 μm
L. Wu et al. Chemical Engineering Journal 489 (2024) 151215

Fig. 1. Self-powered photoelectric sensor based on hydrogel diodes. (a) in human eyes, photoreceptor cells in the retina conduct ion transport upon receiving light
irradiation. (b) in the current photoelectric sensor, polyelectrolytes carrying opposite charges (amps and dmaea-q) stack together to form a hydrogel diode. the
photoacid are introduced to the cationic side. (c) in the diode, there is a built-in potential. the photoacid exert protons upon receiving light, which increases the
potential difference, similar to the ion movement in retina cells. (d) aqueous solution with different hpts contents. (e) the ph response according to light irradiation on
hpts solution with various concentration (100 mw cm− 2). (F) Optical microscope image of the cross section of hydrogel PN junction loaded with 5 wt% HPTS. The
inset images are the appearance of the as-prepared hydrogel PN junction.

tungsten filament probe is established, as shown in Fig. 2A. Current-
voltage curves are generated for the hydrogel diodes, as depicted in
Fig. 2B. The junction formed by oppositely charged polyelectrolyte
hydrogels exhibit pronounced current rectification. It is observed that
the desalination procedures, achieved by soaking the gel for varying
periods of time in water, do not affect the rectification characteristics of
the diode but decrease the conductivity (Fig. S5). Conversely, when two
hydrogels with the same charge are adhered together, weaker current
rectification is observed (Fig. S6). Notably, hydrogel diodes containing
photoacid demonstrate enhanced rectification in the presence of light
irradiation (Fig. 2B). This enhancement is attributed to an increased
availability of counterions for conducting the current (Fig. S7) [23].
To understand the transport behavior of photo-released ionic parti­
cles in a hydrogel diode, we consider four situations, where HPTS might
exist at different positions of the PN junction (Fig. 2C). When the two
polyelectrolytes are brought into contact, the dissociated cationic and
anionic ions diffuse into opposite sides as a result of the entropy of
mixing. This entropic depletion of mobile ions leads to an accumulation
of excess polyanionic and polycationic chains on the respective sides.
These excess fix charges generate a built-in electric field, as illustrated in
Fig. 2D. It is important to note that in the absence of light, the positive
and negative charges in the photoacid molecules remain in a stable
combined state. When HPTS exist in the polycationic side (N), there are
significant changes in voltage and current, 11.31 ± 0.34 mV and 730 ±

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L. Wu et al. Chemical Engineering Journal 489 (2024) 151215

Fig. 2. Hydrogel diodes characteristic and photoelectric response of hydrogel sensors. (A) Schematic of the current density experiment. (B) Current density as a
function of applied bias for junctions prepared from different hydrogel diodes. Each gel layer was 0.5-mm thick, and 365 nm light (80 mW cm− 2). (C) Photoelectric
response of hydrogel diodes with photoacid, HPTS in different positions. Addition of HPTS to the polyanionic side P-junction only, both sides add HTPS at the same
time, the P-junction side receives light, both sides add HTPS at the same time, N junction side receives light, and the polycationic side N-junction only, the largest
response are measured when HPTS presented in the polycationic side. (HPTS aqueous solution concentration: 5 wt%, optical power density: 2000 mW/cm2). (D) The
process of the two polyelectrolytes forms heterojunction. (E) Under the influence of built-in potential, the charges from photoacid are transferred to the polycationic
hydrogel side under irradiation. (F) Plot showing the open-circuit voltage and short-circuit current of self-powered photoelectric sensors within 30 min irradiation
(Optical power density: 35 mW/cm2, λ = 405 nm). (G) Plot showing the open-circuit voltage of the self-powered photoelectric sensors during twelve cycles. (H) Plot
showing the short-circuit current of the self-powered photoelectric sensors during twelve cycles. The duration of illumination and interval are 5 and 5 s, respectively.
(I) The short-circuit current output curve upon illumination for 5 s shows the response time within 120 ms. The intensity of 365 nm light is 50 mW cm− 2.

30nA, respectively (Fig. S9D). In this case, light irradiation leads to the
photoacid deprotonation (Fig. 2E). Under the influence of built-in po­
tential, the protons transfer from the cationic side, travel across the
depletion region and arrive at the anionic side. The opposite motion of
anions is considerably weak due to their larger sizes (Fig. 2E). When
HPTS is at the polyanionic side (P), the results are comparable to those of
the blank group (~2.5 mV and ~ 30nA) (Fig. S8), with no significant
electric signals (Fig. S9A). Such small amplitude of electric response can
be considered a reverse case to the first one, with the larger-sized anions
traveling through the bilayer structure under built-in potential. Whereas
in the case of HPTS existing in both sides (Figs. S9B, C), moderate
electric signals are detected, which is in accordance with the uniform
distribution of mobile ions.
To examine the photo responsiveness in a single duration, the
responsive voltage and current under 30 min irradiation (with the light
intensity of 35 mW cm− 2) are studied. As shown in Fig. 2F, when the
incident light is given, the sensor generates a response voltage, which
gradually increases with the extension of the irradiation time, and after
the irradiation time is greater than 25 min, the response voltage in­
creases slowly and gradually tends to be stable. This indicates that the
migration of ions is almost in equilibrium. The response current in­
creases within 5 min of irradiation, reaches the maximum value at 5
min, and then gradually decreases with the extension of irradiation time,
and tends to stabilize at 30 min. Since the visual persistence time of the
human eye is generally in the second level, we use 5 s or 30 s of light to
carry out related experiments in subsequent experiments.
The open-circuit voltage and short-circuit current of the self-
powered photoelectric sensors are detected during twelve cycles
(Fig. 2G, H). The significate changes of photo-induced voltage and
current under 50 mW cm− 2 are 1.6 mV and 60nA, respectively. The
magnitude of the bioelectrical signals in optical nerve system resides in a
level of millivolts [38]. Our results show that the electrical signal output
of the current material also lies in the same range, which would be
beneficial for direct signal pick up in human–machine interfaces [39].
The photoelectric sensors generate electric voltage and current signal
(Fig. 2G, H), and at the moment of turning on and off the 365 nm light,
the responsive voltage and current show rapidly response. When the
short-circuit current is amplified, we find that the current of photo­
electric sensor increases rapidly within 120 ms (Fig. 2I), which is com­
parable to the response time of human eyes (ranging from 50 to 150 ms)

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L. Wu et al. Chemical Engineering Journal 489 (2024) 151215

[40]. The rapidly response ability (120 ms) are observed at the moment
of turning off the 365 nm light. The rapid response time is attributed to
the fast photo-induced deprotonation of photoacid [41]. The short-
circuit current continues to increase gradually under light irradiation,
which reflects the migration rate of ions [42].
In later experiments we examine the electric response influenced by
photoacid concentration, light input energy density, wavelength of
incident light, and monomer concentration of the hydrogels (Fig. 3). As
changing the concentrations of photoacid, the open-circuit voltage and
short-circuit current first increase then decrease, with the peak
appearing at 5 wt% (Fig. 3A). The result is consistent with the most
significant shifting of pH for the HTPS solution shown in Fig. 1E. As
increasing the optical power density, the voltage-current response are
showing an increasing trend (Fig. 3B). Apart from full range light, we
carefully examine the current and voltage response to incident light with
different wavelengths (Fig. S10A). We chose 50 mW/cm2 for the light
intensity, throughout the test to avoid interferences from possible heat
irradiation. The initial point in Fig. 3C represents irradiation light with
full range from the used lamp. Maximum response occurred at ~ 365 nm
wavelength, which is in accordance with the intrinsic spectrum absor­
bency of HPTS [27]. Here, it is important to mention that the photoacid
we chose for our experiment is a mere embodiment for the proposed
concept. There might be better choices in terms of proton release rate.
More importantly, HPTS is not necessarily the best candidate when other
photoacids might possess more suitable ranges of light spectrum in
alignment with human visions.
Moreover, we take monomer concentration into account, as it may
affect the ion transport behavior in the hydrogel network. In this section,
we take same monomer concentrations for both sides of the hydrogel
diodes to create similar network environment for the mobile ions. As
shown in Fig. S10B, at 3 M (mol/L) monomer concentration, the pho­
toelectric sensor shows the highest current–voltage variation under 700
mW/cm2 and full-spectrum light irradiation. The low electric response
at monomer concentrations higher than 3 M is due to the denser network
lead by higher polymer fraction in this formula. Interestingly, monomer
concentration lower than 3 M also results in weaker response. This may
be a result of the weak built-in electric field bias, which also explains the
lowest voltage generated in this condition.
In Fig. 3C, a flexible sensor device is shown being bent to a thickness
of 1 mm to evaluate its photoelectric performance under incident light at
different angles. The corresponding electrical signal output of the sensor
is presented in Fig. 3D. The sensor exhibits excellent photoelectric per­
formance when exposed to 405 nm light with an intensity of 35 mW/cm2
for a duration of 30 s. As the incident light angle increases, the photo­
electric response capability initially increases and then decreases,
reaching its peak value at 90◦ . The maximum values for current–voltage

Fig. 3. Photoelectric response of hydrogel PN junction self-powered photoelectric sensor device. (A) Photoelectron sensing response of different HPTS quantitative
solvated PN junction hydrogels. (Optical power density: 2000 mW/cm2) (B) Photoelectric sensing response of PN junction hydrogels at different optical power
densities. (50 mW/cm2, 100 mW/cm2, 400 mW/cm2, 700 mW/cm2). (C, D) Schematic of flexible photoelectric sensor under different direction of light (C) and the
corresponding electric response results (D). The duration of illumination and interval are 30 s and the size of the sample is 2 cm (length) × 2 cm (width) × 0.5 mm
(thickness) (Optical power density: 35 mW/cm2, λ = 405 nm). Unless specifically mentioned, all the test conditions are conducted under full-spectrum light
irradiation.

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L. Wu et al.
variation are 6.0 mV and 55nA, respectively. This is because the area of
the sample exposed to light reaches its maximum at 90◦ incident light,
and the photoacid deprotonation reaches maximum at this time, and
therefore exhibits the maximum response voltage and current at this
incident light angle.
To verify the stability of the sensor, we tested the photoelectric
performance of the sensor in the flat and bent state respectively. As
shown in Fig. S11, the electrical signals of the sensor have good stability
and no obvious attenuation phenomenon after 5 cycles. In addition, the
electric signals of the bent sensor are slightly weaker than that of the
unbent photoelectric sensor (1 mV reduction in voltage and 10nA
reduction in current). The slight reduction of output signal is due to the
reduction of projection area receiving light when the diode is bent. The
photoelectric sensors demonstrate ultimate strain of 37 % and ultimate
stress of 58.4 kPa before illumination (Fig. S12). There are no significant
changes observed in the ultimate strain (39 %) and stress (50.9 kPa)
after illumination. Moreover, the excellent structural stability of the
photoelectric sensor is demonstrated by the lack of significant changes
in morphology throughout the entire light cycle, as illustrated in
Fig. S13. Moreover, we investigated the variations in electrical signals of
the hydrogel diode within the range of fluctuations in eye pressure and
temperature. The voltage and current response of the sensor under
different external pressures shows a stable corresponding, as shown in
Fig. S14. It can be seen that the electrical signal output is negatively
correlated with the pressure change, decreasing from 1.52 mV and 0.11
μA at zero pressure to 1.11 mV and 0.06 μA at 3000 Pa. This is due to the
fact that the force-induced deformation reduces the cross-sectional area
of hydrogel, impeding the ion mobility that affects the electronic signal
[43,44]. The performance of the hydrogel diode shows no significant
attenuation with temperature variation from 20 ◦ C to 30 ◦ C (Fig. S15).
The similarities between optoelectronic materials and visual re­
ceptors in terms of signal transmission, ion transport, and time resolu­
tion inspire us to the design of optoelectronic device that could
potentially interact with the optic nerve system. As a proof of concept,
we design a prototype of sensory array (Fig. 4A). A unit sensor comprises
a piece of photoacid-loaded hydrogel PN junction sandwiched between
two polyimide (PI)-based printed circuit board (PCB) (Fig. 4B). The
copper wires at the polyanionic side are grounded, whereas the wires
connecting the individual polycationic surfaces are inducted to a visual
receptor, respectively. Before light irradiation, each unit averages the
Fig. 4. A 9-element photoelectric sensor array based on hydrogel diodes. (A) Schematics showing the array structure and (B) a zoom-in view of the scheme showing a
single unit of the sensory device. (C) Photograph and (E) corresponding voltage bar plot of the photoelectric sensor array detecting a single point receiving light. (D)
Photograph and (F) corresponding voltage bar plot of the photoelectric sensor array detecting multiple points receiving light.
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Chemical Engineering Journal 489 (2024) 151215
voltages from the previous few seconds. Applying light (light power
density: 700 mW/cm2) to the polycationic side results in the release of
protons from the photoacid. The generated ions with opposite charges
on both sides exert a significant potential bias. Consequently, the light-
exposed units show changes of voltage that can be immediately plotted
and mapped. It is worth noting that without photoacid, there is no
response to light irradiation (Fig. S8). As shown in Fig. 4C, when the
Unit (2, 2) is shone upon, the voltage increases most significantly at the
corresponding position on the map (Fig. 4E). The units on the left and
behind are exposed to weak light, so there is a relatively small voltage
change. When the units (1, 1), (1, 2), (1, 3) and (2, 2) are exposed, we
observe rise of voltage in correct positions on the map (Fig. 4D, F).
4. Conclusions
In summary, our study focused on the self-powered light respon­
siveness of hydrogel diodes doped with photoacid. The photoacid, HPTS,
undergoes deprotonation upon light irradiation, generating an electric
signal that can be detected by the visual receptor. The light-induced
protons are driven by the built-in electric field of the hydrogel PN
junction, making the photoelectric sensor self-powered. We discovered
that the output signal is optimized when HPTS is present on the poly­
cationic side of the hydrogel diodes, which can be understood through
the ionic transfer efficiency of protons in the polymer network with a
finite built-in electric field. The prototype design for a photoelectrocal
sensor consisting of 9-element (3 × 3) array of sensing units successfully
proves the idea that the self-powered light sensor might be possible for
visually challenged people. In our design prototype, HPTS is chosen as a
representation of the proposed concept, but there are potentially better
options available in terms of proton release rate and broader or more
specific spectrum responsiveness for various research and application
purposes. Moreover, visual augmentation, e.g. infrared or UV visuali­
zation can be expected in the future, when we consider introducing
functional photosensitive molecules [45–48] to our current design.
CRediT authorship contribution statement
Liwei Wu: Methodology, Investigation. Jinfan Qi: Investigation,
Data curation. Lingling Zhang: Writing – original draft, Data curation,
Conceptualization. Lei Yu: Software. Hongfei Gao: Resources. Jun
L. Wu et al.
Gao: Conceptualization. Jie Ju: Visualization, Funding acquisition,
Conceptualization. Xi Yao: Writing – review & editing, Project admin­
istration, Funding acquisition, Conceptualization.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
The authors are grateful for the financial support from National
Natural Science Foundation of China (22172045, U23A20122,
21905076, 21905077), Key Science Foundation Project of Henan
Province (232300421146), China Postdoctoral Science Foundation
(2023M740990), and the Key Scientific Research Project of Colleges and
Universities in Henan Province (22B150001).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2024.151215.
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