Hindawi

International Journal of Energy Research

Volume 2023, Article ID 9881469, 10 pages
https://doi.org/10.1155/2023/9881469

Research Article
Enhancing Hydrogen Production through Integration of
Electrolysis and Photocatalysis in a Cell

Yohanes Engge ,1,2 Frendi Maulana,1 Muhammad Nurhuda ,1 Istiroyah ,1

and Lukman Hakim 3
1
Physics Department, Faculty of Mathematics and Natural Sciences, Brawijaya University, Indonesia
2
Weetebula Catholic University, Indonesia
3
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Brawijaya University, Indonesia

Correspondence should be addressed to Muhammad Nurhuda; [email protected]

Received 14 June 2023; Revised 26 September 2023; Accepted 6 October 2023; Published 8 November 2023

Academic Editor: Sathish K. Kamaraj

Copyright © 2023 Yohanes Engge et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.

We present a new method for hydrogen production that combines photocatalysis and electrolysis in a cell. TiO2 was doped with
Ni and nitrogen to form Ni-TiO2 and N-Ni-TiO2 photocatalysts. XRD, UV-Vis, and SEM techniques were used to characterize the
resulting samples. The Ni-TiO2 and N-Ni-TiO2 samples had anatase structures with energy gaps of 2.77 eV and 2.03 eV,
respectively. A 50-watt UV lamp with a wavelength of 254 nm was used as the photon source. Our results indicate that this
method produces more hydrogen than the sum of hydrogen generated by separate electrolysis and photocatalysis methods.
The N-Ni-TiO2 sample produced the highest yield of HHO gas among the Ni-TiO2 and TiO2 p.a samples. The underlying
mechanisms responsible for this improvement, including the role of the Ni and nitrogen doping, are discussed and analyzed.

1. Introduction sive. For example, a simple electrolysis of water with acidic

or alkaline electrolytes yields 70% efficiency [5, 6].
Hydrogen is one of the most promising clean and sustain- Hydrogen generation via photocatalysis of water has also
able energy carriers, producing only water as the final prod- attracted the attention of many researchers [7]. Most
uct, and thus ideal for electrochemical applications in fuel photocatalysts are made from semiconducting materials
cells [1, 2]. On earth, hydrogen is generally found as compo- because they have an energy gap that allows them to create
nent of other compounds, such as water (H2O), methane gas electron-hole pairs when exposed to photons with a certain
(CH4), hydrocarbons, amino acids, and carbohydrates [3]. minimum energy. This formation of electron-hole pairs
Electrolysis process is a common method used to pro- leads to the splitting of water molecules [8]. Fujishima and
duce hydrogen from water by passing current to electrodes Honda reported the first experiments related to the splitting
immersed in water. Compared to other methods, water elec- of water into hydrogen and oxygen using heterogeneous
trolysis can produce hydrogen of high purity (99.99%), with photocatalysts. Their approach uses a photoelectrochemical
the hydrogen produced being twice that of oxygen [4]. While (PEC) cell that incorporates TiO2 as the photoanode and
the process can be sustainable and environmentally friendly platinum as the counter electrode, under exposure to UV
when renewable energy sources such as solar or wind are light and an external potential [9]. Bard then applied this
used to provide the electrical energy resources, it is often concept to design a photocatalysis system that uses semicon-
considered inefficient as it requires a significant amount of ductor particles or powders as photocatalysts [10, 11]. Along
electrical input power, which can make the process expen- with the development of it, several photocatalyst materials
2 International Journal of Energy Research

have been identified and explored, such as V2O5 nanorods for 2 hours, left to stand for 24 hours, and then oven heated
[12], CdS QDs/BiOI [13], and ZnO/CdTe [14]. To date, at 100°C for 15 hours. Finally, the product was calcined at
the field of photocatalyst technology has seen rapid progress 500°C for 2 hours, followed by crushing to obtain the pow-
and widespread use, including applications in water treat- der form of Ni-TiO2.
ment and purification [15, 16]. N and Ni dopant synthesis: initially, solution A was pre-
TiO2 is a semiconductor material that is widely used pared by mixing 30 mL of ethanol, 1 mL of acetylacetone,
owing to its several advantages such as high stability, corro- and 8 mL of 97% TTIP from Aldrich. Solution B was then pre-
sion resistance, abundance in nature, relatively low cost, and pared by combining 2 mL of glacial acetic acid, 4 mL of demi-
nontoxicity [17]. However, the large energy gap of TiO2 neralized water, and 30 mL of ethanol. Subsequently, solutions
(~3.2 eV) limits its use as a photocatalyst material for absorb- A and B were mixed and stirred for 30 minutes at room tem-
ing longer wavelengths of light. The reduced efficiency of TiO2 perature. The doping process was initiated by adding 30 mL of
in photocatalysis reactions arises not only from this energy gap demineralized water, 1.8 gram of urea (1 M), and 0.4003 g of
but also from the rapid recombination of electrons and holes Ni (II) nitrate hexahydrate to the mixture. The rest of the steps
at the photocatalyst’s surface before interacting with water were the same as those for synthesizing Ni-doped TiO2.
[18]. One way to reduce the energy gap of TiO2 and the The synthesized photocatalyst materials were character-
recombination of electrons and holes is by doping other mate- ized using X-ray diffraction (XRD), UV-Vis spectroscopy,
rials to TiO2, e.g., transition metal elements such as Mn, Cr, and SEM-EDS. XRD (Empyrean Cu LFF HR 9430 033
Ni, and Cu [19–22] and nonmetals, such as S, N, C, and P 7310x) was used to determine the crystal structure, size, and
[23–26]. Several researchers have used doubly doped non- phase of the photocatalyst materials. UV-Vis spectroscopy
metal ions and transition metals in TiO2 (see, e.g., [27]) and (SPECORD 200 PLUS-223E1117F) was used to measure the
successfully synthesized a Ni-N-TiO2 photocatalyst that pro- absorption spectrum of the samples and gather data on the
vides an energy gap of 2.4 eV. wavelength and absorbance. The data were then analyzed
Based on the above considerations, it seems interesting using the Tauc plot method to obtain the band energy values.
to combine electrolysis and photocatalysis in a single cell SEM-EDS was used to determine the morphology, particle
(reactor) to increase the efficiency. This hypothesis is based size, and elemental composition of the samples.
on previous studies that a thin layer of TiO2 on an electrode
is an ideal photocatalytic agent for water electrolysis [28]. 2.2. Electrophotocatalysis Cell Design. Figure 1 shows the
In this paper, we propose the use of photocatalyst mate- design of the reactor cell for the combined electrolysis and
rials in powder form, instead of as a thin layer on the anode photocatalysis processes. The reactor consisted of an electro-
or cathode, for two reasons. First, in powder form, the lyte solution container (1), electrodes made of SS 316 stain-
photocatalyst material has a much larger surface area, which less steel (2) and (3), an electrolyte solution (4), a magnetic
increases its interaction with water and its ability to absorb stirrer (5, 7), a UV lamp (6), an MQ-8 gas sensor (8), a con-
photons. Second, we expect a synergistic interaction between tainer to capture bubble products (9), purified water (10),
photocatalysis activity and electrolysis. When the photocata- and a hydrogen-hydrogen oxygen (HHO) gas line (11, 12).
lyst material absorbs photons, it produces electrons and holes. The process for producing hydrogen via simultaneous
The electrolysis process facilitates the transport of these elec- electrolysis and photocatalysis in a cell, hereinafter referred
trons and holes to the cathode and anode, respectively. This to as the “electrophotocatalysis,” was conducted as follows:
accelerates the water splitting process. To further accelerate first, the reactor is partially filled with 500 mL of demineralized
water splitting, we dope the TiO2 with N and/or Ni, which water, and a quantity of the synthesized photocatalyst powder
reduces the bandgap energy of the material. This allows the is dispersed in it. A small amount of methanol was then added
photocatalyst material to absorb a wider range of photons. as an electron-hole sacrificial agent, which acted as an electron
Ni- and Ni-N-doped TiO2 were synthesized using the sol-gel donor or a hole scavenger to prevent recombination of elec-
method to form a nanoparticle photocatalyst. tron holes and reverse reaction of H2 and O2 during the
photocatalysis process [29, 30]. Additionally, natrium hydrox-
2. Methods ide (NaOH) was added to the solution to facilitate the electrol-
ysis process. A 50 W/254 nm UVC lamp was used as the
2.1. Photocatalyst Preparation and Characterization. Single- photon source for photocatalysis. To keep the photocatalyst
dopant TiO2 (Ni-TiO2) and double-dopant nitrogen and suspended, the mixture was agitated during the observation
nickel (N-Ni-TiO2) photocatalyst materials were prepared process using a magnetic stirrer. The direct current (DC) sup-
using the sol-gel method according to the following steps: plying both electrodes was maintained at a constant level using
Ni dopant synthesis: first, 8.3 mL of 97% titanium iso- Buck-Boost ZK-4KX. The hydrogen gas concentration was
propoxide (TTIP) from Aldrich was mixed with 143 mL of measured using MQ-8 gas sensor.
ethanol to obtain solution A. Solution B was prepared by
adding 35 mL of ethanol and 3 mL of HNO3 into 15 mL of
demineralized water. Next, solutions A and B were mixed 3. Results and Discussion
to form solution C, which was then stirred for 30 minutes 3.1. Photocatalyst Materials
at room temperature. Subsequently, 1% Ni (II) nitrate hexa-
hydrate (precursor Ni) and 10 mL of demineralized water 3.1.1. Crystal Structure and Size. Figure 2 shows the X-ray
were added to solution C. The resulting mixture was stirred diffraction results for the TiO2 samples synthesized with
International Journal of Energy Research 3

(101)
8
2 3

(200)
12

Intensity

(004)

(211)
(105)

(204)

(215)
(112)
(103)

(116)
(220)
6
11

1 ⁎ ⁎

4
10 20 30 40 50 60 70 80
10 2� (°)
9 5
TiO2 p.a ⁎ = Rutile
7
N-Ni-TiO2 = NiTiO3
Ni-TiO2 = Brookite

Figure 2: Comparison of the diffractograms of TiO2 p.a (anatase)

Figure 1: The scheme of the reactor combining photocatalysis and with the synthesized Ni-TiO2 and N-Ni-TiO2 photocatalysts.
electrolysis (electrophotocatalysis).

single Ni and double N-Ni dopants and TiO2 proanalysis Kλ

D= , 1
(p.a) Merck for comparison. The pattern exhibits the charac- β cos θ
teristic diffraction peaks of TiO2 anatase structure at 2θ
values of 25.30°, 37.80°, 48.05°, 53.91°, 55.08°, and 62.70° cor- where D is the crystal size (nm), K is the crystal shape factor
responding to crystal planes (101), (004), (200), (105), (211), (0.9-1.0), λ is the X-ray wavelength (0.15406 nm), β is the
and (204), respectively. The absence of any additional peaks FWHM value in radian, and θ is the diffraction angle in
in the N-Ni-TiO2 sample confirms that Ni and N were degree. The results revealed that crystal sizes were
incorporated into the TiO2 lattice through substitution, 46.450 nm, 12.265 nm, and 7.120 nm for TiO2 p.a, Ni-TiO2,
replacing some O2- and Ti4+ lattice sites. This is because and N-Ni-TiO2, respectively. It suggests that doping TiO2
the ionic radii of N3- (1.46 Å) and Ni2+ (0.830 Å) are larger with N and Ni in general reduces the crystal size of the
than those of O2- (1.40 Å) and Ti4+ (0.745 Å) [31]. photocatalyst material.
In the case of the nickel-modified samples, in addition to The variation in crystal size of TiO2 samples doped with
the main anatase phase, there are minor amounts of rutile, Ni and N-Ni had a significant impact on the photocatalysis
brookite, and NiTiO3 phases. The rutile phase was observed water splitting process. Smaller crystals typically have larger
at 2θ angles of 27.44° and 36.05°, which correspond to the surface areas and higher densities of active sites [40], which
(110) and (101) planes of rutile (JCPD card No. 21-1276) provide more surface area for water molecules to adsorb and
[32]. This is due to the Ni-induced phase transformation, facilitate efficient water splitting and hydrogen production.
whereby the Ni ions disrupt the crystal structure of TiO2 and The smallest crystal size observed in the N-Ni-TiO2 sample
promote the formation of rutile [33]. The brookite phase was suggests that this photocatalyst is highly efficient for hydro-
observed at a 2θ angle of 30.83°, which corresponds to the gen production.
(121) plane of brookite (JCPDS map No. 29-1360) [32]. The The anatase crystal structure remains the dominant
NiTiO3 phase was identified at 2θ angles of 33.04°, 41.25°, structure of the photocatalyst material, even when doped
and 49.38° (ICDD File No. 04-006-6640), which is consistent with Ni and N. This can be verified using the following
with the previous reports [33–35]. two equations:
The anatase phase is the most photocatalytically active crys-
talline form of TiO2 in Ni-TiO2 and N-Ni-TiO2 samples because 2d hkl sin θ = nλ, 2
it has a wider bandgap than rutile [36]. This allows anatase to
absorb UV and visible light more readily, producing more
electron-hole pairs for the photocatalysis reaction, which 1 h 2 k2 l 2
= + + , 3
increases the efficiency of photocatalysis. Rutile is more ther- d 2hkl a2 b2 c2
mally and mechanically stable than anatase, but it has a narrower
bandgap and is therefore less photocatalytically active [37, 38]. where a, b, and c represent the lattice parameters, hkl is the
The crystal size of each synthesized sample was deter- index of the crystal planes, dhkl stands for the distance
mined using the Debye-Scherrer equation and FWHM anal- between the crystal planes, λ is the wavelength of the inci-
ysis [39], as described by the following equation: dent X-rays (1.5406 A), n is the diffraction order (chosen
4 International Journal of Energy Research

as 1), and θ denotes the diffraction angle in radians. For 3,5

60
tetragonal crystal, the value of a = b. Equation (2) was TiO2 p.a
employed to extract the value of d from XRD peaks. 3,0 Ni-TiO2
Subsequently, by applying Eq. (3), we obtained the following N-Ni-TiO2

(αhv)2 (eVm–1)2
40
lattice parameters: a = b = 0 37848 nm and c = 0 95124 nm 2,5
for TiO2 p.a, a = b = 0 37852 nm and c = 0 94988 nm for

Absorbance
2,0 20
Ni-TiO2, and a = b = 0 37858 nm and c = 0 95170 nm for
N-Ni-TiO2. These results suggest that the incorporation of 1,5 2,03 eV 2,77 eV 3,28 eV

Ni and N dopants into TiO2 does not significantly alter the 0

anatase crystal structures. 1,0 1 2
Energy (eV)
3 4

N-Ni-TiO2
3.1.2. Optical Absorption of Photocatalyst Materials. The 0,5
optical absorption spectra of TiO2 p.a and TiO2 doped with Ni-TiO2
N and Ni were analyzed using UV-Vis spectroscopy. 0,0 TiO2 p.a
Figure 3 shows the absorption spectra of the synthesized
photocatalysts at various radiation wavelengths. The UV- 400 600 800 1000 1200
Vis absorption spectra show that the absorption peak of Wavelength (nm)
the TiO2 p.a sample occurs within the wavelength range of Figure 3: UV-Vis absorption spectra of each sample, with the
350-400 nm, which is characteristic of anatase TiO2 [39]. corresponding bandgap energy shown in the inset.
In the visible light region (λ > 400 nm), the absorbance
decreased and became flat. For the Ni-TiO2 sample, the energy levels below the conduction band, while N dopants
absorption spectra shifted to the wavelength range of 350- are above the valence band [33].
550 nm, which corresponds to the UV and visible light spec-
tral regions. The double-dopant N-Ni-TiO2 sample shows 3.1.3. SEM-EDS Analysis. The analysis results using a scan-
an even greater shift towards the wavelength of visible light, ning electron microscope (SEM) in Figure 4 show changes
which is in the range of 400-600 nm. This is in line with the in the morphology and particle size of the TiO2 photocata-
expectation that the presence of metallic and nonmetallic lyst after being doped with N and Ni elements. In Figure 4
elements in TiO2 can improve its performance as a photoca- (b1) and (c1), it can be seen that there is little agglomeration
talyst material in the visible light region. in the sample, which consists of primary particles. Through
The UV-Vis absorption spectra of the N-Ni-TiO2, SEM analysis and the use of ImageJ software, we were able to
Ni-TiO2, and TiO2 p.a samples correlate with the photon measure the distribution and average diameter of the
energy required to excite the valence band electrons to the particles in each sample. The measurement results show that
conduction band. The bandgap energy of each sample was the average particle diameter is 148.57 nm for TiO2 p.a,
determined using the Tauc plotting method: 31.67 nm for Ni-TiO2, and 21.00 nm for N-Ni-TiO2, as seen
in Figure 4 (a2), (b2), and (c2). Both types of modified
αhv n
= A hv − Eg , 4 photocatalysts showed much smaller particle diameters
compared to TiO2 p.a, and the difference in diameters was
where α is the absorbance coefficient, derived from the not significant between the doped samples.
Lambert-Beer law: Energy-dispersive X-ray spectroscopy (EDS) analysis
was performed to confirm the successful doping of N and
α = 2 303 × absorbance values, 5 Ni elements in the TiO2 structure. In the single-doped sam-
ple (Ni-TiO2) shown in Figure 5(b), three Ni peaks were
where h is Planck’s constant, v is the frequency of light, Eg is detected at energies of 0.8 keV, 7.5 keV, and 8.3 keV. In the
the bandgap, and A is the proportional constant. The value of doubly doped sample (N-Ni-TiO2) shown in Figure 5(c), the
n is set to be 2 because the transition is direct, as it depends N peak was observed at 0.5 keV, while the Ni peak remained
on the nature of the electronic transitions of the semiconduc- constant. These findings confirm the presence of N and Ni
tor [21]. dopants in the TiO2 crystal structure, which could potentially
The inset of Figure 3 shows curves representing the rela- alter the photocatalytic activity of the doped samples.
tion between αhv n and photon energy hv. To obtain the
bandgap energy, we draw a straight line that represents the 3.2. Electrophotocatalysis Experiment. Experiments on the
asymptotic slope of the curve. This line is extended until it electrolysis of water in combination with a photocatalysis
intersects with the energy axis hv. We found the bandgap process or electrophotocatalysis were performed in a reactor
energy values for each sample for TiO2 p.a, Ni-TiO2, and according to the procedure described in the preceding sec-
N-Ni-TiO2 to be 3.28 eV, 2.77 eV, and 2.03 eV, respectively. tion. The photocatalyst materials used in this study were
The N-Ni-TiO2 photocatalyst exhibited the lowest bandgap TiO2 p.a, Ni-TiO2, and N-Ni-TiO2.
energy. This indicates that the double doping of metal (Ni) The instantaneous concentration of hydrogen gas pro-
and nonmetal (N) is very effective in reducing the bandgap duced was measured as a function of time using an MQ-8
energy in TiO2 photocatalysts, owing to the synergistic effect gas sensor. The total gas yield was calculated based on the
of the two dopants. Thus, Ni dopants can generate new number of bubbles released. The spitting rate of water is
International Journal of Energy Research 5

(a1) (a2)
10
TiO2 p.a TiO2 p.a
Average particle size = 148.57 nm
8

Frequency
6

0
50 100 150 200 250
Particle size (nm)
(a) TiO2 p.a
(b1) (b2)
Ni-TiO2 Ni-TiO2
10 Average particle size = 31.67 nm

Frequency
6

0
20 25 30 35 40 45
Particle size (nm)
(b) Ni-TiO2
(c1) (c2)
12 N-Ni-TiO2
N-Ni-TiO2
Average particle size = 21.00 nm
10
8
Frequency

6
4
2
0
16 18 20 22 24 26 28
Particle size (nm)
(c) N-Ni-TiO2

Figure 4: Scanning electron microscopy (SEM) images of the surface morphology and particle size distribution of each sample.

proportional to the hydrogen concentration at any given It can be seen from Figure 6 that the electrophotocatalysis
moment because the HHO gas escapes the water tank with- process exhibits the highest instantaneous hydrogen density
out accumulating and maintains a constant pressure within compared to the individual electrolysis and photocatalysis
the tank. Therefore, the total amount of hydrogen gas pro- processes. It also shows that the hydrogen production activity
duced is proportional to the number of HHO bubbles gener- noticeably increased during the first six minutes and then lin-
ated during the experiment. early progressed. This could be due to the fact that all compo-
Figure 6 shows the experimental results of photocatalysis, nents involved in the reaction process work at their peak
electrolysis, and electrophotocatalysis for three different cases: performance during the initial stages and then decline as the
(a) TiO2 p.a (as control), (b) Ni-TiO2, and (c) N-Ni-TiO2 reaction progresses (see, e.g., Cao and Piao [41]). We observed
photocatalysts. In all cases, 1 gram of photocatalyst was photocatalyst deposits on the surface of the electrodes,
suspended in an aqueous solution containing 500 mL of demi- although the difference was not significant. Furthermore,
neralized water, 5 mL of methanol, and 5 mL of 1 M NaOH agglomeration and sedimentation of the photocatalyst could
solution. The current and voltage were set to fixed values of also reduce hydrogen production in the water splitting pro-
0.5 A and 8.6 V, respectively. Each case was repeated thrice, cess [42].
and the results were averaged. During data collection, the volt- It can also be seen from Figure 6 that the highest instan-
age and current fluctuated by approximately 2.3%. taneous hydrogen density was due to the N-Ni-TiO2
6 International Journal of Energy Research

16 16 Ti
TiO2 p.a Ti Ni-TiO2
14 14
12 12
10

cps/eV
10
cps/eV

8 8
6 6 O
O
4 Ti
4 Ti
2 Ni
2 Ni Ni
0 0
0 2 4 6 8 10 0 2 4 6 8 10
keV keV
(a) (b)
16 Ti
N-Ni-TiO2
14
12
cps/eV

10
8
6 O
4 N Ti
2 Ni
Ni Ni
0
0 2 4 6 8 10
keV
(c)

Figure 5: Energy spectrum of each sample.

photocatalyst, followed by Ni-TiO2, and finally TiO2 p.a. Since the instantaneous hydrogen density only represents
This is a strong evidence that the two dopants clearly play the proportion of the yield, so it is also important to consider
a synergistic role in enhancing the photocatalysis activity the total yield of hydrogen. This was done by counting the
of TiO2 compared with that of a single dopant [33]. The syn- number of generated HHO bubbles. Since HHO gas is a mix-
ergistic role of nitrogen and nickel dopant in N-Ni-TiO2 ture of hydrogen and oxygen gases in a 2 : 1 ratio, so the por-
sample is that nitrogen dopant reduces the energy bandgap tion of hydrogen in HHO gas is 66.67%. In the inset of
of TiO2, allowing it to absorb more light energy in a wider Figure 7, we show the number of bubbles generated through
wavelength range. Correspondingly, the nickel dopant also the electrophotocatalysis process as blue bars, while the gains
contributes to energy bandgap reduction and acts as an elec- are displayed as yellow bars. The number of bubbles generated
tron trap, which helps reduce the recombination rate of for TiO2 p.a, Ni-TiO2, and N-Ni-TiO2 were 209, 220, and 250
electron-hole pairs during the water splitting reaction pro- bubbles, respectively, while the respective gains were 28, 35,
cess. As a result, N-Ni-TiO2 can produce more hydrogen and 61.
gas from the water splitting process compared to the other The origin of the enhancement of hydrogen yield in the
two materials. electrophotocatalysis reaction might be as follows: it is
The role of photocatalysts and electrolytes in electrophoto- known that water is a polar molecule, which is slightly pos-
catalysis water splitting might be described as follows: photo- itively charged on the hydrogen atoms and slightly nega-
catalysts absorb photons of light and generate electron-hole tively charged on the oxygen side. The electrons in the
pairs. The electrons then participate in the reduction of water water molecule are more concentrated around the oxygen
to produce hydrogen, while the holes participate in the oxida- atom, resulting in a partial negative charge. In contrast, the
tion of water to produce oxygen. Electrolytes facilitate the flow hydrogen atoms have a partial positive charge as a result of
of electricity between the photocatalyst and the electrodes, electron displacement towards the oxygen atom. In the pres-
promote electrochemical reactions, and maintain the stability ence of a photocatalyst material, the formation of electron-
of the solution throughout the process. The presence of a hole pairs may increase the polarity of H2O molecules. This
photocatalyst and an electrolyte creates an electrostatic equi- phenomenon is consistent with the findings of Hribar et al.,
librium that drives the overall water splitting reaction. This who reported that the structure of water is strongly affected
equilibrium could be essential for achieving high efficiency by electrostatic equilibrium when ions are present around a
in hydrogen production. water molecule [43]. Consequently, the presence of a photo-
To measure the performance of the electrophotocatalysis catalyst would also affect the electrostatic equilibrium of
process more accurately, we define “gain” as the difference water and hence reduces the dissociation energy of the water
between the instantaneous hydrogen density obtained from molecules. When an external electric field is applied through
electrophotocatalysis and the sum of the instantaneous the electrode plates, the binding energy between hydrogen
hydrogen density from photocatalysis and electrolysis. and oxygen in the polarized water affected by the photocata-
Figure 7 shows that the gain in instantaneous hydrogen den- lyst is more easily broken than that without photocatalyst
sity is highest for Ni-N-TiO2 among the three samples. activation. This is confirmed by our experiments; in the
International Journal of Energy Research 7

300

Inst. hydrogen density (ppm)

250

200

150

100

50

0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
t (s)

TiO2 p.a
Photocatalysis
Electrolysis
Electro-photocatalysis
(a)
300
Inst. hydrogen density (ppm)

250

200

150

100

50

0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
t (s)

Ni-TiO2
Photocatalysis
Electrolysis
Electro-photocatalysis
(b)

300
Inst. hydrogen density (ppm)

250

200

150

100

50

0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
t (s)

N-Ni-TiO2
Photocatalysis
Electrolysis
Electro-photocatalysis
(c)

Figure 6: Comparison of the instantaneous hydrogen density obtained through electrolysis, photocatalysis, and electrophotocatalysis
reaction with respect to different photocatalyst material.
8 International Journal of Energy Research

120 Electro-photocatalysis
300 Number of bubbles as gain
100 250 400
Inst. hydrogen density gain (ppm)

HHO bubbles

220

Inst. hydrogen density (ppm)

209
200
80
100
300
60 61
N-Ni-TiO2
28 35

40
0 Ni-TiO2
TiO2 p.a Ni-TiO2 N-Ni-TiO2 200

20 TiO2 p.a
100
0

–20
0
0 400 800 1200 1600 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
t (s) t (s)
Electro-photocatalysis
Figure 7: Instantaneous hydrogen density gain from
electrophotocatalysis for three different photocatalysts. The inset NaOH 0 mL
shows the number of hydrogen bubbles generated through NaOH 5 mL
electrophotocatalysis (blue bars) and the gain in hydrogen NaOH 10 mL
bubbles (yellow bars).
Figure 9: Evolution of instantaneous hydrogen density in the
electrophotocatalysis process using NaOH catalysts with different
350 volumes.

300 varying the amount of NaOH catalyst without addition of

Inst. hydrogen density (ppm)

methanol.
250 Figure 8 shows the results of the electrophotocatalysis
experiment obtained by varying the amount of methanol.
200 In this case, 1 gram of Ni-N-TiO2 photocatalyst and 5 mL
of NaOH solution with a concentration of 1 M were dis-
150
solved in 500 mL of demineralized water. Four different
amounts of methanol were used, i.e., 0 mL, 5 mL, 10 mL,
100
and 15 mL. The current supplied to the cell was set to
50 0.5 A, while the voltage was set 8.6 V.
We can see that adding methanol had a minimal impact
0 on hydrogen yield. Initially, the instantaneous hydrogen
0 200 400 600 800 1000 1200 1400 1600 1800 2000 density was lower without or with minimal methanol addi-
t (s) tion, but it reversed as the reaction progressed. The average
Electro-photocatalysis instantaneous hydrogen density after completing the
Methanol 0 mL Methanol 10 mL experiment was 215 ppm for 0 mL methanol addition and
Methanol 5 mL Methanol 15 mL 226 ppm for 5 mL. However, adding more methanol decreased
the instantaneous hydrogen density. This reverse trend is
Figure 8: Evolution of the instantaneous hydrogen density in the likely due to a decrease in the pH level of the solution. We
electrophotocatalysis process using different volumes of methanol. observed that the pH levels were 12, 11, 10, and 9 for the
0 mL, 5 mL, 10 mL, and 15 mL of methanol addition to solu-
absence of a photocatalyst, the dissociation by electrolysis tions, respectively.
starts at V = 2 5 eV, while in the presence of the photocata- Figure 9 shows the effect of NaOH concentration on the
lyst, the dissociation starts at V = 2 0 eV. instantaneous hydrogen density, without the addition of
methanol. Other parameters were kept the same as in the
3.3. Effect of Sacrificial Agent and Electrolyte on previous experiments. The instantaneous hydrogen density
Electrophotocatalysis Water Dissociation. It is known that the production was minimal without NaOH, indicating that
concentration of ions strongly affects the charge transport in the photocatalyst alone contributes little to hydrogen pro-
cells and determines the performance of water electrolysis. duction. As more NaOH is added, the instantaneous density
We performed a series of experiments to observe the variation of hydrogen production increases. This is likely due to the
in the NaOH catalyst and methanol as the sacrificial agent. increase in OH- ions, as a higher concentration of OH- ions
Two different treatments were performed: the first consisted results in a higher conductivity, which facilitates the flow of
of varying the concentration of methanol and keeping the electric current during electrolysis. The pH values of the
concentration of NaOH fixed, while the second consisted of solutions were 7.7, 11.9, and 13.2 for NaOH amounts of
International Journal of Energy Research 9

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