chemengineering

Article
Hydrogen and Oxygen Evolution in a Membrane
Photoreactor Using Suspended Nanosized Au/TiO2
and Au/CeO2
Tiziana Marino 1, *, Alberto Figoli 1 , Antonio Molino 2 , Pietro Argurio 3 and
Raffaele Molinari 3, *
1 Institute on Membrane Technology (ITM), National Research Council of Italy (CNR), Via P. Bucci Cubo 17C,
I-87036 Rende (CS), Italy; a.figoli@itm.cnr.it
2 Research Centre of Portici, Italian National Agency for New Technologies, Energy and Sustainable Economic
Development (ENEA), Piazzale Enrico Fermi 1, Portici, 80055 Napoli, Italy; antonio.molino@enea.it
3 Department of Environmental and Chemical Engineering, University of Calabria, Via P. Bucci, 44/A,
I-87036 Rende (CS), Italy; pietro.argurio@unical.it
* Correspondence: t.marino@itm.cnr.it (T.M.); raffaele.molinari@unical.it (R.M.)




Received: 8 October 2018; Accepted: 4 January 2019; Published: 10 January 2019


Abstract: Photocatalysis combined with membrane technology could offer an enormous potential for
power generation in a renewable and sustainable way. Herein, we describe the one-step hydrogen
and oxygen evolution through a photocatalytic membrane reactor. Experimental tests were carried
out by means of a two-compartment cell in which a modified Nafion membrane separated the
oxygen and hydrogen evolution semi-cells, while iron ions permeating through the membrane
acted as a redox mediator. Nanosized Au/TiO2 and Au/CeO2 were employed as suspended
photocatalysts for hydrogen and oxygen generation, respectively. The influence of initial Fe3+
ion concentration, ranging from 5 to 20 mM, was investigated, and the best results in terms of
hydrogen and oxygen evolution were registered by working with 5 mM Fe3+ . The positive effect of
gold on the overall water splitting was confirmed by comparing the photocatalytic results obtained
with the modified/unmodified titania and ceria. Au-loading played a key role for controlling the
photocatalytic activity, and the optimal percentage for hydrogen and oxygen generation was 0.25 wt%.
Under irradiation with visible light, hydrogen and oxygen were produced in stoichiometric amounts.
The crucial role of the couple Fe3+ /Fe2+ and of the membrane on the performance of the overall
photocatalytic system was found.

Keywords: water splitting; Z-scheme; photocatalysis; photocatalytic membrane reactor

1. Introduction
Photocatalytic water splitting to generate hydrogen from solar light is a process that can play
an important role for the future development of clean and renewable energies alternative to fossil
fuels [1–8]. The combination of photocatalysis, which allows converting solar energy into chemical
energy, and membrane-based operations could offer the possibility to achieve one-step hydrogen
generation from water splitting at ambient temperature without needing further energy inputs.
Hydrogen attracted increasing interest as a valid candidate for fossil-fuel substitution, enough to
give rise to create the so-called “hydrogen economy” in 1970 [9–12].
From a thermodynamic point of view, hydrogen oxidation can offer three times the energy per
gram in comparison to fossil fuels as gasoline. Moreover, hydrogen oxidation leads to the formation of
water, making it a zero-emission fuel. Hydrogen also finds applications in the chemical industry as a
reagent in fine-chemical synthesis [12].

ChemEngineering 2019, 3, 5; doi:10.3390/chemengineering3010005 www.mdpi.com/journal/chemengineering

ChemEngineering 2019, 3, 5 2 of 12

Since Fujishima and Honda discovered photocatalytic water splitting by means of TiO2 electrodes
in 1972 [13], noticeable works were carried out in order to investigate photocatalytic-based hydrogen
generation from water via both photocatalysis and photoelectrochemistry [14]. Particular attention was
paid to semiconductor oxides, due to their simple preparation through calcination and their stability
toward oxygen generation [15–19]. The water-splitting pathway involves a series of radical reactions
initiated by light-driven photocatalyst activation, as deeply described in the literature [3].
Among the well-known semiconductors, nanosized TiO2 is attracting more and more interest,
due to its unique properties of physico-chemical stability and inertness, low cost, biocompatibility,
durability, long-term photo-stability, and potent oxidative power under ultraviolet (UV)-light
irradiation [20–22]. Despite its numerous advantages, the use of TiO2 still presents a limitation,
i.e., only UV light, representing ~4% of total solar energy, can be absorbed by titania nanoparticles.
Therefore, extending TiO2 light absorption to the visible fraction represents a challenging target
for photocatalysis applications. Various techniques, such as noble-metal and non-metal doping,
dye sensitization, and coupling with carbon materials were adopted in order to modify the electronic
band of titania [23].
In a previous work, we reported that gold nanoparticles supported on titania (Au/TiO2 )
represent a suitable photocatalyst for the generation of hydrogen with visible light using methanol
and ethylenediaminetetraacetic acid (EDTA) as sacrificial electron donors [14]. A remarkable
overall efficiency of approximately 5% measured at 560 nm was determined [14]. In this system,
gold nanoparticles act as a durable and stable photosensitizer, absorbing visible light and injecting
electrons in the conduction band of the TiO2 . Using 0.25 wt% gold loading on titania and methanol as
a sacrificial agent, ~98 µmol of hydrogen was obtained (catalyst content 2 g/L) after 4 h of irradiation
with visible light [14].
Also, we showed that ceria of small average particle size can behave as a semiconductor with
a remarkably high efficiency for the photocatalytic generation of oxygen from water using Ag+ or
Ce3+ as a sacrificial electron acceptor [24]. The best performing CeO2 sample was that prepared
using a biopolymer “alginate” as a templating agent to synthesize about 5 nm of average particle size
with a Brunauer-Emmett-Teller (BET) surface area of 93 m2 ·g−1 [24]. Also, in this case, visible-light
photocatalytic activity was implemented by depositing gold nanoparticles on CeO2 (Au/CeO2 ),
which allowed achieving ~50 µmol of oxygen when the aqueous suspension containing 0.25 wt% gold
deposited on CeO2 was irradiated for 4 h with visible light in the presence of AgNO3 as a sacrificial
agent [24].
Considering the above precedents and the visible-light photocatalytic activity for independent
hydrogen and oxygen generation using Au/TiO2 or Au/CeO2 , respectively, in the presence of an
appropriate sacrificial agent, it occurs that these two photocatalysts could also work in a system to
perform the simultaneous generation of hydrogen and oxygen in the absence of sacrificial agents
using a Z-scheme [25–28]. In this Z-scheme methodology, hydrogen and oxygen are generated
photocatalytically in different cells that are irradiated and separated by a membrane [5,29–34].
An electrolyte is used to ensure the electroneutrality in each cell and to allow charge transfer from one
compartment to the other.
Li et al. [5] reported concomitant hydrogen generation and phenol degradation in a photocatalytic
twin reactor under simulated solar light. In the proposed system, Pt/STO:Rh was used as a
photocatalyst for hydrogen evolution, while WO3 was chosen for phenol oxidation. A Nafion
membrane separated the two compartments of the cell. Fe3+ /Fe2+ pairs were used for electron
transfer. The obtained data evidenced a hydrogen generation rate of 1.90 µmol·g−1 ·h−1 . Moreover,
by employing a phenol initial concentration of 200 µmol·L−1 , hydrogen yield reached a value of
11.37 µmol·g−1 after 6 h of irradiation, corresponding to an increase of 20% compared to that of
pure water splitting. Fujihara et al. [35] studied water splitting in a two-compartment cell using
Pt/TiO2 -anatase as a catalyst for hydrogen generation suspended in a Br2 /Br− aqueous solution and
Pt/TiO2 -rutile for simultaneous oxygen evolution in an Fe3+ /Fe2+ redox couple solution. Yu et al. [33]
ChemEngineering 2019, 3, 5 3 of 12

also reported the experimentation of a twin reactor for the synchronized formation of hydrogen,
through the photocatalytic activity of BiVO4 , and oxygen using Pt/SrTiO3 :Rh. A Nafion membrane
was inserted in the two-side system to assure the separate generation of the two gases. Similarly to the
above mentioned works, the Fe3+ /Fe2+ redox couple was also selected in this case as a redox mediator.
Hydrogen and oxygen in a stoichiometric ratio (2:1) were obtained, with a maximum hydrogen
formation rate of 0.65 µmol·g−1 ·h−1 . Lo et al. [31] investigated the water-splitting process for the
one-step H2 and O2 generation by means of a membrane twin reactor under visible-light irradiation.
Pt/SrTiO3 :Rh and WO3 were designated as hydrogen- and oxygen-evolution semiconductors,
respectively. The formation of the two gases reflected their stoichiometric ratio, with an average
hydrogen evolution rate equal to 1.59 µmol·g−1 ·h−1 .
Nafion represents a valid choice as a membrane material, since it is characterized by outstanding
chemical and physical resistance [36] and an affinity for iron species. Ramirez et al. [37] investigated
the uptake characteristics of different cations (Fe3+ , Cu2+ , and Ni2+ ) by Nafion 117, which is commonly
used as a separator for different chemical processes. The membrane exhibits its affinity in the order
Fe3+ ≥ Ni2+ ≥ Cu2+ , similar to that reported in a previous study [38]. In another study [39], it was
reported that a Nafion/Fe membrane was resistant to the attack of the highly oxidative radical •OH
(E◦ •OH/–OH = 1.90 eV vs. normal hydrogen electrode (NHE)) and did not allow leaching of the
Fe exchanged on the sulfonic groups within the 3000-h testing period. Kiwi et al. [40] demonstrated
that iron compounds supported on a Nafion membrane gave good results in a photo-Fenton water
treatment process, where the Fe ions were fixed and remained active in H2 O2 decomposition.
In the present work, we studied the overall photocatalytic water splitting using Au nanoparticles
as a sensitizer of TiO2 and CeO2 semiconductors irradiated with visible light in combination, a Nafion
film as a membrane separating two cells, and ferric sulfate as the electrolyte. Diffusion tests on the
iron-modified Nafion membrane were performed to determine its ability to allow diffusion of iron
species. The influence on system performance of initial Fe3+ concentration and of Au loading on the
O2 and H2 evolution photocatalysts was determined. Finally, the photocatalytic activity of the pairs
(Au/TiO2 and Au/CeO2 ) for the photocatalytic water splitting through a Z-scheme under visible light
was demonstrated.

2. Materials and Methods

TiO2 (particle size: 20 nm; rutile/anatase: 85:15, 99.9%) was a commercial P25 sample supplied by
Degussa. CeO2 was prepared starting from an aqueous solution of alginate that was flocculated with
cerium nitrate followed by calcination as previously reported [24]. Gold nanoparticles were deposited
on TiO2 and CeO2 via the deposition–precipitation method starting from AuHCl4 and maintaining
pH = 10 as described in Reference [14]. TEM images were recorded with a Jeol 200 Cx microscope
operating at 200 kV.

2.1. Photocataytic Tests

The photocatalytic membrane reactors (PMRs) experimented in the present work for simultaneous
generation of hydrogen and oxygen from water splitting mimic the Z-scheme mechanism used by
plants for natural photosynthesis. The Z-scheme (Figure 1a) basically includes two photocatalysts:
(i) the oxygen evolution photocatalyst (Au/CeO2 in this study) leading to O2 formation via water
oxidation, and (ii) the hydrogen evolution photocatalyst (Au/TiO2 in this study) which promotes H2
formation via water reduction. The aqueous suspensions containing the two photocatalysts need to
be separated by a membrane able to transports electrons via a redox couple (Fe3+ /Fe2+ in this study)
acting as an electron redox mediator.
The experimental set-up (Figure 1b) consisted of a two-compartment Pyrex cell, each with a
volume of 50 mL, separated by a Nafion modified membrane with an exposed membrane surface
area of 3.14 cm2 . Each compartment, containing 60 mg of photocatalyst suspended in 30 mL of
Milli-Q water (corresponding to 2 g·L−1 photocatalyst concentration), was irradiated with a 125-W
ChemEngineering 2019, 3, 5 4 of 12

medium-pressure mercury lamp (DLU, HDLM E27) equipped with a Pyrex glass jacket which allows
maintaining the
ChemEngineering system
2019, at a temperature
3 FOR PEER REVIEW of 20 ◦ C. The suspensions were purged with argon flow for 4
at least 30 min before irradiation in order to remove dissolved air. For polychromatic visible-light
irradiation, an Fe22(SO44))33solution
solution(3% w/v),circulated
(3%w/v), circulatedinto
intothe
thePyrex
Pyrexglass
glassjacket
jacketof
ofthe
the lamp,
lamp, was
was used
used
as a cut-off filter (λ >> 400
400 nm).
nm). Hydrogen
Hydrogen andand oxygen
oxygen generation
generation was
was determined
determined by by injecting
injecting 0.1
0.1 mL
mL
of each
each Pyrex
Pyrexcell
cellheadspace
headspace gasgas
in aingas
a chromatograph
gas chromatograph(GC; Agilent 7890A)7890A)
(GC; Agilent equipped with a thermal
equipped with a
conductivity
thermal detector.detector.
conductivity The GC determination was carried
The GC determination wasout by operating
carried out by in isothermal
operating conditions
in isothermal
(50 ◦ C), with
conditions (50 a°C),
capillary column (CP-PoraPLOT
with a capillary Q, molecular
column (CP-PoraPLOT sieve, 530
Q, molecular sieve,
µm530inner diameter,
μm inner 15 m
diameter,
length)
15 and argon
m length) as a carrier
and argon gas. gas.
as a carrier

(a)

(b)
Figure
Figure 1. (a) Diagram of the
the Z-scheme
Z-scheme overall
overall water
water splitting
splitting using
using Au/CeO
Au/CeO22 asas aa photocatalyst
photocatalyst for
for
oxygen
oxygen generation, Au/TiO22 for
generation, Au/TiO for hydrogen generation,
generation,and
andFe 3+
Fe /Fe
3+ 2+
/Fe asasaaredox
2+
redoxcouple.
couple. (b)
(b)Conceptual
Conceptual
scheme
scheme of the set-up used for photocatalytic experiments.

2.2. Membrane Modification

The Nafion 117 membrane (Aldrich, thickness of 178 μm) was modified using the procedure
described herein before its use. In the first step, the membrane was boiled in a 1 M HNO3 solution for
2 h to remove any contaminant; then, it was washed with Milli-Q water, immersed in a 1 M NaOH
solution, and subsequently in a 1 M H2SO4 solution for 4 h, each for conditioning the membrane [41].
ChemEngineering 2019, 3, 5 5 of 12

2.2. Membrane Modification

The Nafion 117 membrane (Aldrich, thickness of 178 µm) was modified using the procedure
described herein before its use. In the first step, the membrane was boiled in a 1 M HNO3 solution for
ChemEngineering 2019, 3 FOR PEER REVIEW
2 h to remove any contaminant; then, it was washed with Milli-Q water, immersed in a 1 M NaOH5
solution, and subsequently in a 1 M H2 SO4 solution for 4 h, each for conditioning the membrane [41].
Finally, the Nafion membrane was immersed in a 0.5 M Fe2(SO4)3 solution for 24 h to change its
Finally, the Nafion membrane was immersed in a 0.5 M Fe2 (SO4 )3 solution for 24 h to change its
functional groups (H++) with Fe3+3+ions.
functional groups (H ) with Fe ions.
2.3.
2.3. Iron
Iron Spectrophotometric
Spectrophotometric Determination
Determination
Spectrophotometric
Spectrophotometric analyses
analyses were
were performed
performed using 1,10-phenanthroline (Fluka,
using 1,10-phenanthroline (Fluka, Aquanal
Aquanal Plus
Plus
kit)
kit) and potassium thiocyanate (Aldrich), for total iron (λ = 510 nm) and ferric ion (λ = 477 nm)
and potassium thiocyanate (Aldrich), for total iron (λ = 510 nm) and ferric ion (λ = 477 nm)
determinations,
determinations, respectively. Ferrous iron
respectively. Ferrous iron ion
ion concentration
concentration present
present in
in solution
solution was
was calculated
calculated by
by the
the
difference between total and ferric iron concentration.
difference between total and ferric iron concentration.

3.
3. Results
Results and
and Discussion
Discussion

3.1. Diffusion Test

iron-containing modified
The iron-containing modified Nafion membrane
membrane was was tested
tested to determine
determine its ability to allow
diffusion of iron species.
species. Similar
Similar concentrations
concentrations of Fe2+
ofFe 2+ and Fe3+ as that
3+ as that utilized
utilized in
in the
the photocatalytic
experiments were
experiments wereused
usedininone
onecompartment
compartment and,
and,then,
then,thethe
presence
presenceof corresponding
of correspondingiron iron
species over
species
time was
over timedetermined in the other
was determined in thecompartment. The corresponding
other compartment. profiles of
The corresponding iron species
profiles of irondiffusing
species
through the
diffusing membrane
through are provided
the membrane are in Figure 2.
provided in Figure 2.

Figure 2. 2+ () and Fe

Fe2+
2. Fe 3+ () transport over time through the Nafion membrane in the compartment
Figure (■) and Fe3+ (□) transport over time through the Nafion membrane in the compartment
cell with
cell with no
no initial
initial salt.
salt.

It was
was observed
observed that, 3+ diffusion could be fitted by a straight line, i.e., the concentration
It that, while
while Fe
Fe3+ diffusion could be fitted by a straight line, i.e., the concentration
of Fe 3+
Fe3+ ininthe
thechamber
chamber without it grew linearly 2+ salt
of without it grew linearly overover
time,time, similar
similar experiments
experiments with Fe with Feclearly
2+ salt
clearly revealed
revealed two regimes.
two regimes. These results
These results might might be explained
be explained considering
considering that,
that, in theinfirst
the first regime,
regime, ion
ion exchange 3+
of3+Feandand 2+
exchange of Fe Fe2+Feoccurred
occurred in the
in the Nafion
Nafion membrane
membrane concomitantlytotothe
concomitantly thediffusion.
diffusion. InIn the
the
second regime, the Nafion membrane behaved essentially as a Fe 2+ exchanger.
second regime, the Nafion membrane behaved essentially as a Fe2+ exchanger.
The iron
The ironcontent
contentin in
thethe
membrane
membrane before and after
before and its use its
after wasuseestimated by SEM energy
was estimated by SEM dispersive
energy
X-ray
dispersive X-ray spectroscopy (EDX) analysis. The results showed an iron weight loadingthis
spectroscopy (EDX) analysis. The results showed an iron weight loading of ~1.3% and value
of ~1.3%
did not change after using the membrane (Figure 3).
and this value did not change after using the membrane (Figure 3).
ChemEngineering 2019, 3, 5 6 of 12
ChemEngineering 2019, 3 FOR PEER REVIEW 6

SEM picture
Figure 3. SEM picture of
of Nafion
Nafion membrane
membrane used
used for
for the
the photocatalytic
photocatalytic test
test (A)
(A) and
and energy-dispersive
energy-dispersive
X-ray spectroscopy (EDX) analysis of ferric ion-modified
ion-modified membrane
membrane (B).
(B).

Figure 44reports
Figure reportsTEM
TEMpictures
pictures
of of
thethe Au/TiO
Au/TiO 2 and and Au/CeO
2 Au/CeO 2 photocatalysts.
2 photocatalysts. The average
The average particle
particle size of photocatalyst nanoparticles, determined by considering a statistically
size of photocatalyst nanoparticles, determined by considering a statistically relevant number ofrelevant number
of particles
particles in thein TEM
the TEM images
images of theofsamples,
the samples, resulted
resulted in 2.7
in 2.7 and 5.0 and
nm for5.0 Au/TiO
nm for2 and
Au/TiO 2 and
Au/CeO 2,
Au/CeO ,
respectively.
2 respectively.

Figure4.4.TEM
Figure TEMimages
imagesof
ofAu/TiO
Au/TiO22 (A) and Au/CeO
Au/CeO22(B).
(B).

3.2. Photocatalytic
3.2. Photocatalytic Tests
Tests
For the
For theirradiation
irradiationofofthe the suspensions,
suspensions, a 125-W
a 125-W medium-pressure
medium-pressure mercury
mercury lamplamp was used.
was used. This
This lamp exhibited emission peaks at a discrete wavelength, mostly in
lamp exhibited emission peaks at a discrete wavelength, mostly in the visible region (total irradiationthe visible region (total
irradiation 2
2133 mW/m2133 2 with mW/m
61% in with 61% inrange).
the visible the visible range).
The inset The inset
of Figure of Figure
5 shows 5 shows the
the emission peaksemission
in the
peaks in the spectrum
spectrum of the lamp used. of the lamp used.
Preliminary photocatalytic
Preliminary photocatalytic tests tests were
were carried
carried outout evidencing
evidencing the the crucial
crucial role
role ofof the
the couple
couple
3+
Fe3+/Fe
/Fe 2+
2+ onon both hydrogen
Fe both hydrogen and and
oxygenoxygen generation.
generation. Indeed,Indeed, by starting
by starting the working the working
of the cellofwith
the
cell with Fe 2+ ions in the cell containing Au/TiO3+ and Fe3+ ions in the cell containing Au/CeO ,
Fe ions in the cell containing Au/TiO2 and Fe 2 ions in the cell containing Au/CeO2, oxygen2
2+

oxygen generation
generation in both
in both cells was cells was during
observed observed theduring
first 30 the
min.first
We30 min. We
suggest thatsuggest
the reason that
whytheoxygen
reason
3+
was generated in Au/TiO2 cell instead of the expected hydrogen was because Fe was formed by was
why oxygen was generated in Au/TiO 2 cell instead of the expected hydrogen was
3+ because Fe Fe2+
formed by Fe 2+ oxidation, in the presence of oxygen by air, during the preparation of the work-up
oxidation, in the presence of oxygen by air, during the preparation of the work-up cell. Analysis of
cell.FeAnalysis of the Fe 3+ concentration in the Au/TiO cell confirmed that about of Fe2+
the 3+ concentration in the Au/TiO2 cell confirmed that2 about 22% of Fe2+ ions were22% oxidized to ions
Fe3+
were oxidized to Fe 3+ during this stage. The formed Fe 3+ quenched the generation of hydrogen and
during this stage. The formed Fe quenched the generation of hydrogen and promoted the formation
3+

promoted
of oxygen, the owing formation of oxygen,reduction
to the preferential owing to of theFepreferential of Fe3+ by
reductionelectrons
3+ by photogenerated photogenerated
with respect to the
electrons with respect
photoreduction of water. to As
the aphotoreduction
consequence, during of water.the As
firsta 30
consequence,
min, oxygenduring the first
generation 30 min,
(instead of
oxygen generation (instead of hydrogen) was observed
hydrogen) was observed into the Au/TiO2 cell before changing to continuous into the Au/TiO 2 hydrogen generation.to
cell before changing
continuous
On the hydrogen
basis of thesegeneration.
preliminary results, to avoid the presence of Fe3+ ions in the Au/TiO2 cell,
the iron ions were initially added to the system only in the form of Fe3+ at different concentrations, as
reported in Table 1, in the cell containing Au/CeO2, while, in the Au/TiO2 cell, the initial iron
ChemEngineering 2019, 3, 5 7 of 12

On the basis of these preliminary results, to avoid the presence of Fe3+ ions in the Au/TiO2 cell,
the iron ions were
ChemEngineering 2019, 3initially
FOR PEER added
REVIEW to the system only in the form of Fe3+ at different concentrations,7
as reported in Table 1, in the cell containing Au/CeO2 , while, in the Au/TiO2 cell, the initial iron
concentrationwas
concentration waszero.
zero.Figure
Figure55showsshowsthe thetemporal
temporalevolution
evolutionof ofhydrogen
hydrogenininthe theAuAu(0.25
(0.25wt%)/TiO
wt%)/TiO22
cell and
cell and oxygen
oxygen in inthetheAuAu(0.25
(0.25wt%)/CeO
wt%)/CeO22 cell cell when
when 55 mM mMFe Fe3+3+ was
was added
added in in the
theAu/CeO
Au/CeO22 cell.
Operating under
Operating under these
these conditions,
conditions,the thereaction
reactionstarted
startedon onAu/CeO
Au/CeO22 with oxygen evolution via water
oxidation coupled with the reduction
oxidation reduction of Fe3+3+totoFe
of Fe Fe2+2+
. The
. The so-produced
so-produced Fe2+ 2+ ions
Feions permeated
permeated across the
across
Nafion modified membrane starting hydrogen evolution
the Nafion modified membrane starting hydrogen evolution in the Au/TiO2 compartment. As aa in the Au/TiO 2 compartment. As
consequence, during
consequence, during thisthisearly
earlystage
stageofof thethe
reaction
reaction (approximately
(approximately 5 min), the ratio
5 min), H2:O2Hwas
the ratio 2 :O2about
was
1:1 (see
about Figure
1:1 5) and5)
(see Figure evidenced
and evidencedthat H2that generation was promoted
H2 generation was promoted by Fe2+permeated
by Fe2+ which through
which permeated
the membrane.
through After this
the membrane. initial
After thisstage,
initialtwo regimes
stage, can be observed:
two regimes a first one,
can be observed: until
a first one,60until
min,60and min, a
second
and one, from
a second one,60fromto 300
60 min.
to 300 This
min. trend
This can be explained
trend considering
can be explained that, in Figure
considering 2, Figure
that, in a similar 2,
atrend with
similar the with
trend samethe twosame
regimes
two can be observed
regimes for Fe2+ permeation
for Fe2+ permeation
can be observed through the membrane.
through It could
the membrane.
becould
It deduced that Fe2+that
be deduced ion Fe 2+ ion diffusion
diffusion during the first the
during regimefirst was
regime faster
wasthan
fasterthat during
than the second
that during the
regime regime
second (0.043 vs. 0.022
(0.043 vs.μmol minFe
0.022Fe2+µmol −1)2+
andmin −1 )behavior
this affected the
and this behavior photocatalytic
affected reaction.reaction.
the photocatalytic Indeed,
the Fe2+the
Indeed, ionsFe2+
produced
ions producedin theinAu/CeOthe Au/CeO2 cell permeated
2 cell permeated across the the
across membrane
membrane andandpromoted
promoteda
ageneration
generationofofhydrogen
hydrogenininthe theAu/TiO
Au/TiO 2 cell.
2 cell.After
After300300min,min,aa very
very low hydrogen production was was
detected,probably
detected, probablybecause
becauseofofthe thenegligible
negligiblepermeation
permeation ofof 2+2+ions
FeFe ionsacross
acrossthethe membrane
membrane (see
(see Figure
Figure 2)
2) which blocked the Z-scheme mechanism. However, it should
which blocked the Z-scheme mechanism. However, it should be observed that both photocatalysts be observed that both photocatalysts
efficientlyworked
efficiently workedduringduringthese
thesetwo tworegimes
regimes(slopes
(slopesofof1.251.25µmol
μmol ·min−−11 during
H2H·2min during the first regime and and
0.41 μmol H2·min −
−1 1
during the second regime), promoting
0.41 µmolH2 ·min during the second regime), promoting the simultaneous the simultaneous generation of hydrogen
hydrogen
and oxygen
and oxygen in in aastoichiometric
stoichiometricamount amountininthe theAu/TiO
Au/TiO22 and and Au/CeO
Au/CeO22 cells, cells, respectively, and that that
blocking was
blocking was only
only caused
caused by Fe2+
by Fe 2+ ion permeation through the membrane.
ion permeation

Figure 5. Hydrogen
Figure 5. production ((
Hydrogen production ■)) using
using Au
Au (0.25
(0.25wt%)/TiO and oxygen
wt%)/TiO22 and oxygen production
production ((□ )) using
using Au
Au
(0.25 wt%)/CeO2 compared with hydrogen production ( ) using TiO2 and oxygen production (#) using
(0.25 wt%)/CeO2 compared with hydrogen production (●) using TiO2 and oxygen production (○)
CeO2 only (initial Fe3+ concentration was 5 mM in the Au/CeO2 cell and initial Fe2+ concentration
using
was CeO
zero onlyAu/TiO
in2 the (initial Fecell).
3+ concentration was 5 mM in the Au/CeO2 cell and initial Fe2+ concentration
2
was zero in the Au/TiO2 cell).
The initial concentration of Fe3+ ions in the Au/CeO2 cell varied in the range from 2 to 50 mM,
and itThe
wasinitial
foundconcentration of Fe 3+ ions in the Au/CeO2 cell varied in the range from 2 to 50 mM,
that 5 mM gave the best photocatalytic performance with the highest initial reaction
and (Table
rate it was found
1). that 5 mM gave the best photocatalytic performance with the highest initial reaction
rate (Table 1).
ChemEngineering 2019, 3, 5 8 of 12

Table 1. Photocatalytic activity (initial reaction rate, r0 , evolved hydrogen and oxygen at 7 h) of the
series of ferric aqueous solutions (initial Fe3+ concentration, C0 ) under study, using Au (0.25 wt%)/TiO2
and Au (0.25 wt%)/CeO2 for hydrogen and oxygen generation, respectively.

C0 Fe3+ Evolved H2,7h Evolved O2,7h H2 r0 × 102 O2 r0 × 102

(mM) (µmol) (µmol) (µmol·min−1 ) (µmol·min−1 )
2 56.2 28.1 34.2 20.7
5 166.1 75.6 114.0 53.4
10 86.2 43.0 96.3 32.5
20 43.2 24.2 34.8 21.1
50 25.5 16.3 33.4 23.5

Au/CeO2 was selective for oxygen generation as it was found to be unable to generate hydrogen.
The reason for this behavior might be related to the energy of the electrons in the conduction band of
Au/CeO2 , which was not sufficient for water reduction (see Figure 1). In contrast, these electrons were
able to reduce Fe3+ to Fe2+ .
The influence of gold on the photocatalytic performance of the Z-scheme overall water splitting
by TiO2 and CeO2 was determined by comparing the photocatalytic activity of the gold-containing
semiconductors in comparison with the same semiconductors without gold (Figure 5).
As expected, despite the irradiation source used not permitting exclusively visible-light emission,
a positive effect of the presence of gold was observed.
The gold loading plays an important role in the photocatalytic efficiency of the system.
To demonstrate this point, we performed some photocatalytic tests with equal gold loading on titania
and ceria varying from 0.25 to 1.0 wt%. By measuring the initial rate of hydrogen generation, it was
concluded that the optimum gold loading under these conditions was the lowest (0.25 wt%) (Table 2).

Table 2. Photocatalytic activity (initial reaction rate, r0 , evolved hydrogen and oxygen at 7 h) of the
series of gold-containing samples under study, using a 5 mM ferric solution and TiO2 and CeO2 as
photocatalysts for hydrogen and oxygen generation, respectively.

Au Loading Evolved H2,7h Evolved O2,7h H2 r0 × 102 O2 r0 × 102

(wt%) (µmol) (µmol) (µmol·min−1 ) (µmol·min−1 )
0.25 166.1 75.6 114.0 53.4
0.6 152.0 61.3 112.1 70.8
1.0 71.0 25.1 67.0 32.2

Au content in the aqueous reacting environment after the reaction was below the detection limit
(0.1 ppm).
In a precedent work it was also observed that Au loading is a key parameter controlling the
photocatalytic activity of Au/TiO2 and that an optimal Au percentage exists. Since the presence
of Au nanoparticles is detrimental for the efficiency of TiO2 photocatalysis under UV irradiation,
but enhances the photocatalytic efficiency for visible-light irradiation, the observed beneficial effect
of Au might be explained considering that, by operating under our conditions, visible light gave the
largest contribution to the total photocatalytic water splitting. In view of the above data, we propose
the water-splitting mechanism shown in Figure 6.
Upon light absorption (mostly visible), electrons (in the conduction band) and holes (in the
valence band) were generated in Au/CeO2 . It was found that electrons in Au/CeO2 were inefficient to
generate hydrogen and, therefore, they were captured by Fe3+ , forming Fe2+ ions that diffused through
the Nafion membrane to the Au/TiO2 cell. The holes located on Au of the Au/CeO2 photocatalyst had
sufficient oxidation power to generate oxygen via water oxidation as previously proven [42]. In the
Au/TiO2 cell, similar charge separation as in the Au/CeO2 cell would occur upon photon absorption;
however, in this case, the reduction potential of the TiO2 conduction band had enough energy to form
ChemEngineering 2019, 3, 5 9 of 12

hydrogen via 2019,

ChemEngineering water reduction.
3 FOR The holes on Au were, in this case, quenched by oxidation of Fe2+9
PEER REVIEW
ChemEngineering
diffusing 2019, the
through 3 FOR PEER REVIEW
Nafion membrane from the Au/CeO2 cell. 9

Figure 6. Elementary steps occurring in the photocatalytic reaction upon irradiation of a gold-
Figure 6. Elementary steps occurring in the photocatalytic reaction upon irradiation of a
Figure 6. Elementary
containing steps
photocatalyst occurring
sample in the photocatalytic
under ultraviolet reaction
(UV) irradiation: upon absorption;
(1) photon irradiation (2)
of electron
a gold-
gold-containing photocatalyst sample under ultraviolet (UV) irradiation: (1) photon absorption;
containing photocatalyst sample under ultraviolet (UV) irradiation: (1) photon absorption; (2)
migration from Au to semiconductor conduction band; (3) electron quenching by P; (4) Q oxidation electron
(2) electron migration from Au to semiconductor conduction band; (3) electron quenching by P;
migration
by Q from Au
mediated
H+oxidation to semiconductor conduction band; (3) electron quenching by P; (4) Q oxidation
byHAu.
(4) by + mediated by Au.
by H mediated by Au.
+

To demonstrate
To demonstrate the thephotocatalytic
photocatalyticactivity
activityofofthe
thepair Au/TiO
pair Au/TiO 2 andand
2
Au/CeO 2 for the
Au/CeO overall water
2 for the overall
To demonstrate
splitting through a the photocatalytic
Z-scheme under activity
visible oflight,
the pair Au/TiO2 photocatalytic
analogous and Au/CeO2 for the overall water
experiments were
water splitting through a Z-scheme under visible light, analogous photocatalytic experiments were
splitting
performed through
by a Z-scheme
filtering light to undercompletely
almost visible light, analogous
remove the photocatalytic
irradiation wavelengthexperiments
below 400were
nm
performed by filtering light to almost completely remove the irradiation wavelength below 400 nm
performed
(Figure 7). by
7). Underfiltering light to almost completely remove the irradiation wavelength below 400 nm
Under thesethese conditions,
conditions, thethe irradiance
irradiance decreased
decreased from
from 21332133 mW·m
mW·m−2 toto570 570mW·m m.−In
−2
− 2 −2 2.
(Figure mW·−2
(Figure
Figure 7).
7, 7, Under
thethetwo these
regimes conditions, the irradiance decreased from 2133 mW·m to 570 mW·m . In
In Figure two regimespreviously
previouslyobserved
observedininFigure
Figure55were
werenot not present.
present. This
This can
can be
be ascribed
ascribed to to
Figure
the 7, the
lower two regimes
irradiance (3.6 previously
times lowerobserved
for theinvisible
Figurelight
5 were not present.
compared to Thisirradiation),
UV can be ascribedwhich to
the lower irradiance (3.6 times lower for the visible light compared to UV irradiation), which decreased
the lower irradiance
decreased the H2/O2 (3.6 times lower (slopes
generation for the of visible light Hcompared to 0.04
UV−μmol
irradiation), which
rate (slopes rate 0.08−1μmol 2·min
−1 and 1 O2·min−1), thus
the H2 /O2 generation of 0.08 µmolH2 ·min and 0.04 µmol O2 ·min ), thus requiring a
decreased
requiring 2+ a the H
lower 2 /O
Fe 2 generation rate
2+ ion diffusion rate. (slopes of 0.08 μmol H 2 ·min −1 and 0.04 μmol O 2·min −1), thus
lower Fe ion diffusion rate.
requiring a lower Fe2+ ion diffusion rate.

Figure 7. Hydrogen
Figure 7. production ((
Hydrogen production ■)) using
usingAu Au(0.25
(0.25wt%)/TiO
wt%)/TiO22 and and oxygen production ((
oxygen production □)) using
using Au
Au
(0.25
Figurewt%)/CeO
7. Hydrogen , under
production (■
visible-light) irradiation
using Au (initial
(0.25 Fe 3+ concentration was 5 mM in the Au/CeO
wt%)/TiO 2 and oxygen production (□) using Au
(0.25 wt%)/CeO2,2+under visible-light irradiation (initial Fe concentration was 5 mM in the Au/CeO22
2 3+
cell
(0.25and initial Fe2, 2+under
wt%)/CeO concentration was zero in the(initial
visible-light Au/TiO cell).
cell and initial Fe concentration wasirradiation
zero in the Au/TiO Fe223+cell).
concentration was 5 mM in the Au/CeO2
cell and initial Fe2+ concentration was zero in the Au/TiO2 cell).
Also under these conditions, hydrogen and oxygen generation was observed in stoichiometric
Also under these conditions, hydrogen and oxygen generation was observed in stoichiometric
amounts
Alsoin the Au/TiO
under 2 and Au/CeO
these conditions, 2 cells,and
hydrogen respectively (Table 3). was observed in stoichiometric
oxygen generation
amounts in the Au/TiO 2 and Au/CeO2 cells, respectively (Table 3).
amounts in the Au/TiO2 and Au/CeO2 cells, respectively (Table 3).
Table 3. Photocatalytic activity (initial reaction rate, r0, evolved hydrogen and oxygen at 7 h) of the
Table 3. Photocatalytic
Au (0.25 wt%)/TiO2 andactivity
Au (0.25(initial reaction
wt%)/CeO rate, r0, evolved hydrogen and oxygen at 7 h) of the
2 samples using a 5 mM ferric solution for hydrogen and
Au (0.25generation,
oxygen and Au (0.25 under
wt%)/TiO2 respectively, wt%)/CeO 2 samples using a 5 mM ferric solution for hydrogen and
visible-light irradiation.
oxygen generation, respectively, under visible-light irradiation.
Au Loading (wt%)Evolved H2,7h (μmol)Evolved O2,7h (μmol)H2 r0 × 102 (μmol·min−1)O2 r0 × 102 (μmol·min−1)
Au Loading
0.25 (wt%)Evolved30.36H2,7h (μmol)Evolved14.89O2,7h (μmol)H2 r0 × 10211.0
(μmol·min−1)O2 r0 × 102 (μmol·min
4.2
−1)

0.25 30.36 14.89 11.0 4.2

ChemEngineering 2019, 3, 5 10 of 12

Table 3. Photocatalytic activity (initial reaction rate, r0 , evolved hydrogen and oxygen at 7 h) of the Au
(0.25 wt%)/TiO2 and Au (0.25 wt%)/CeO2 samples using a 5 mM ferric solution for hydrogen and
oxygen generation, respectively, under visible-light irradiation.

Au Loading Evolved H2,7h Evolved O2,7h H2 r0 × 102 O2 r0 × 102

(wt%) (µmol) (µmol) (µmol·min−1 ) (µmol·min−1 )
0.25 30.36 14.89 11.0 4.2

4. Conclusions
In the present article, we combined the high activity of Au/TiO2 to photocatalytically generate
hydrogen with the high activity of Au/CeO2 to promote oxygen evolution from water. Thus,
overall water splitting was obtained by operating through a Z-scheme using a Nafion membrane and
Fe3+ /Fe2+ as an electrolyte.
The obtained results showed the following:

— The employed photocatalysts promoted simultaneous hydrogen and oxygen generation;

— The optimal content of ferric ions in the Au/CeO2 compartment was 5 mM;
— Gold operated as a photosensitizer allowing photocatalytic hydrogen and oxygen formation
under visible light;
— A gold loading of 0.25 wt% led to the best results in terms of hydrogen and oxygen evolution
(166.1 and 75.6 µmol, respectively, after 7 h of UV-visible-light irradiation);
— Hydrogen and oxygen were produced in stoichiometric amounts, i.e., 30.36 and 14.89 µmol,
respectively, after 7 h of irradiation with visible light;
— The decrease in permeation rate of iron ions through the Nafion membrane affected the
photocatalytic performance, slowing the generation rates of both hydrogen and oxygen.

Author Contributions: T.M. and R.M. conceived and designed the experiments; T.M. performed the experiments;
T.M., R.M., P.A. and A.M. analyzed the data; R.M. and P.A. contributed reagents/materials/analysis tools; T.M.,
R.M., P.A., A.M., A.F. wrote the paper.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Bamwenda, G.R.; Tsubota, S.; Nakamura, T.; Haruta, M. Photoassisted Hydrogen-Production from a
water-ethanol solution—A Comparison of activities of Au-TiO2 and Pt-TiO2 . J. Photochem. Photobiol. A-Chem.
1995, 89, 177–189. [CrossRef]
2. Khan, S.U.M.; Al-Shahry, M.; Ingler, W.B. Efficient photochemical water splitting by a chemically modified
n-TiO2 . Science 2002, 297, 2243–2245. [CrossRef] [PubMed]
3. Loddo, V.; Palmisano, L.; Marino, T.; Molinari, R. Membranes for photocatalysis in water and wastewater
treatment. In Advanced Membrane Science and Technology for Sustainable Energy and Environmental Applications;
Basile, A., Nunes, S.P., Eds.; Woodhead Publishing: Sawston, UK, 2011; pp. 746–768.
4. Maeda, K.; Domen, K. New non-oxide photocatalysts designed for overall water splitting under visible light.
J. Phys. Chem. C 2007, 111, 7851–7861. [CrossRef]
5. Li, D.; Yu, J.C.; Nguyen, V.; Wu, C.S.; Wang, X. A dual-function photocatalytic system for simultaneous
separating hydrogen from water splitting and photocatalytic degradation of phenol in a twin-reactor.
Appl. Catal. B Environ. 2018, 239, 268–279. [CrossRef]
6. Argurio, P.; Fontananova, E.; Molinari, R.; Drioli, E. Photocatalytic Membranes in Photocatalytic Membrane
Reactors. Processes 2018, 6, 162. [CrossRef]
7. Iglesias, O.; Rivero, M.J.; Urtiaga, A.M.; Ortiz, I. Membrane-based photocatalytic systems for process
intensification. Chem. Eng. J. 2016, 305, 136–148. [CrossRef]
ChemEngineering 2019, 3, 5 11 of 12

8. Rahimpour, M.R.; Mahmoodi, L. Performance of Reactors With PMs; Elsevier Inc.: Amsterdam, The
Netherlands, 2018; ISBN 9780128135495.
9. Molino, A.; Migliori, M.; Blasi, A.; Davoli, M.; Marino, T.; Chianese, S.; Catizzone, E.; Giordano, G. Municipal
waste leachate conversion via catalytic supercritical water gasification process. Fuel 2017, 206, 155–161.
[CrossRef]
10. Marbán, G.; Valdés-Solís, T. Towards the hydrogen economy? Int. J. Hydrog. Energy 2007, 32, 1625–1637.
[CrossRef]
11. Armaroli, N.; Balzani, V. The hydrogen issue. ChemSusChem 2011, 4, 21–36. [CrossRef]
12. Ball, M.; Wietschel, M. The future of hydrogen—Opportunities and challenges. Int. J. Hydrog. Energy 2009,
34, 615–627. [CrossRef]
13. Fujishima, A.; Honda, K. Electrochemical photolysis of water at a semiconductor electrode. Nature 1972, 238,
37–38. [CrossRef] [PubMed]
14. Silva, C.G.; Juárez, R.; Marino, T.; Molinari, R.; García, H. Influence of excitation wavelength (UV or visible
light) on the photocatalytic activity of titania containing gold nanoparticles for the generation of hydrogen
or oxygen from water. J. Am. Chem. Soc. 2011, 133, 595–602. [CrossRef] [PubMed]
15. Galiano, F.; Song, X.; Marino, T.; Boerrigter, M.; Saoncella, O.; Simone, S.; Faccini, M.; Chaumette, C.; Drioli, E.;
Figoli, A. Novel Photocatalytic PVDF/Nano-TiO2 Hollow Fibers for Environmental Remediation. Polymers
2018, 10, 1134. [CrossRef]
16. Molinari, R.; Caruso, A.; Palmisano, L. Photocatalytic Processes in Membrane Reactors. In Comprehensive
Membrane Science and Engineering; Drioli, E., Giorno, L., Eds.; Elsevier Science B.V.: Oxford, UK, 2010;
Volume 3, pp. 165–193, ISBN 9780080932507.
17. Hoffmann, M.R.; Martin, S.T.; Choi, W.; Bahnemann, D.W. Environmental Applications of Semiconductor
Photocatalysis. Chem. Rev. 1995, 95, 69–96. [CrossRef]
18. Schneider, J.; Matsuoka, M.; Takeuchi, M.; Zhang, J.; Horiuchi, Y.; Anpo, M.; Bahnemann, D.W.
Understanding TiO2 Photocatalysis: Mechanisms and Materials. Chem. Rev. 2014, 114, 9919–9986. [CrossRef]
[PubMed]
19. Kudo, A.; Miseki, Y. Heterogeneous photocatalyst materials for water splitting. Chem. Soc. Rev. 2009, 38,
253–278. [CrossRef] [PubMed]
20. Marino, T.; Boerigter, M.; Faccini, M.; Chaumette, C.; Arockiasamy, L.; Bundschuh, J.; Figoli, A.
Photocatalytic activity and synthesis procedures of TiO2 nanoparticles for potential applications in
membranes. In Application of Nanotechnology in Membranes for Water Treatment; Hoinkis, J., Figoli, A.,
Altinkaya, S.A., Bundschuh, J., Eds.; CRC, Taylor and Francis Group: Boca Raton, FL, USA, 2017; ISBN
9781138896581.
21. Figoli, A.; Marino, T.; Simone, S.; Boerighter, M.; Faccin, M.; Chaumette, C.; Drioli, E. Application of
nano-sized TiO2 in membrane technology. In Application of Nanotechnology in Membranes for Water Treatment;
Hoinkis, J., Figoli, A., Altinkaya, S.A., Bundschuh, J., Eds.; CRC, Taylor and Francis Group: Boca Raton, FL,
USA, 2017; ISBN 9781138896581.
22. Fujishima, A.; Rao, T.N.; Tryk, D.A. Titanium dioxide photocatalysis. J. Photochem. Photobiol. C Photochem.
Rev. 2000, 1, 1–21. [CrossRef]
23. Kumar, S.G.; Devi, L.G. Review on modified TiO2 photocatalysis under UV/visible light: Selected results and
related mechanisms on interfacial charge carrier transfer dynamics. J. Phys. Chem. A 2011, 115, 13211–13241.
[CrossRef]
24. Primo, A.; Marino, T.; Corma, A.; Molinari, R.; Garcia, H. Efficient visible-light photocatalytic water splitting
by minute amounts of gold supported on nanoparticulate CeO2 obtained by a biopolymer templating
method. J. Am. Chem. Soc. 2011, 133, 6930–6933. [CrossRef]
25. Marino, T.; Primo, A.; Corma, A.; Molinari, R.; Garcia, H. Photocatalytic overall water splitting by combining
gold nanoparticles supported on TiO2 and CeO2 . In Proceedings of the 2nd European Symposium on
Photocatalysis, Bordeaux, France, 19 October 2011; p. 76.
26. Higashi, M.; Abe, R.; Ishikawa, A.; Takata, T.; Ohtani, B.; Domen, K. Z-scheme Overall Water Splitting on
Modified-TaON Photocatalysts under Visible Light (λ < 500 nm). Chem. Lett. 2008, 37, 138–139. [CrossRef]
27. Maeda, K.; Higashi, M.; Lu, D.; Abe, R.; Domen, K. Efficient nonsacrificial water splitting through two-step
photoexcitation by visible light using a modified oxynitride as a hydrogen evolution photocatalyst. J. Am.
Chem. Soc. 2010, 132, 5858–5868. [CrossRef] [PubMed]
ChemEngineering 2019, 3, 5 12 of 12

28. Chiarello, G.L.; Tealdi, C.; Mustarelli, P.; Selli, E. Fabrication of Pt/Ti/TiO2 Photoelectrodes by RF-Magnetron
Sputtering for Separate Hydrogen and Oxygen Production. Materials 2016, 9, 279. [CrossRef] [PubMed]
29. Selli, E.; Chiarello, G.L.; Quartarone, E.; Mustarelli, P.; Rossetti, I.; Forni, L. Photocatalytic water splitting
device for separate hydrogen and oxygen evolution. Chem. Commun. 2007, 47, 5022–5024. [CrossRef]
[PubMed]
30. Xu, Q.; Zhang, L.; Yu, J.; Wageh, S.; Al-ghamdi, A.A.; Jaroniec, M. Direct Z-scheme photocatalysts: Principles,
synthesis, and applications. Mater. Today 2018, 21, 1042–1063. [CrossRef]
31. Lo, C.; Huang, C.; Liao, C.; Wu, J.C.S. Novel twin reactor for separate evolution of hydrogen and oxygen in
photocatalytic water splitting. Int. J. Hydrog. Energy 2010, 35, 1523–1529. [CrossRef]
32. Seger, B.; Kamat, P.V. Fuel cell geared in reverse: Photocatalytic hydrogen production using a TiO2 /Nafion/Pt
membrane assembly with no applied bias. J. Phys. Chem. C 2009, 113, 18946–18952. [CrossRef]
33. Yu, S.-C.; Huang, C.-W.; Liao, C.-H.; Wu, J.C.S.; Chang, S.-T.; Chen, K.-H. A novel membrane reactor
for separating hydrogen and oxygen in photocatalytic water splitting. J. Membr. Sci. 2011, 382, 291–299.
[CrossRef]
34. Kitano, M.; Tsujimaru, K.; Anpo, M. Decomposition of water in the separate evolution of hydrogen and
oxygen using visible light-responsive TiO2 thin film photocatalysts: Effect of the work function of the
substrates on the yield of the reaction. Appl. Catal. A Gen. 2006, 314, 179–183. [CrossRef]
35. Fujihara, K.; Ohno, T.; Matsumura, M. Splitting of water by electrochemical combination of two
photocatalytic reactions on TiO2 particles. J. Chem. Soc. Faraday Trans. 1998, 94, 3705–3709. [CrossRef]
36. Kraytsberg, A.; Yair, E.-E. Review of Advanced Materials for Proton Exchange Membrane Fuel Cells.
Energy Fuels 2014, 28, 7303–7330. [CrossRef]
37. Ramírez, J.; Godínez, L.A.; Méndez, M.; Meas, Y.; Rodriguez, F.J. Heterogeneous photo-electro-Fenton
process using different iron supporting materials. J. Appl. Electrochem. 2010, 40, 1729–1736. [CrossRef]
38. Feng, J.; Hu, X.; Yue, P.L.; Zhu, H.Y.; Lu, G.Q. Discoloration and mineralization of Reactive Red HE-3B by
heterogeneous photo-Fenton reaction. Water Res. 2003, 37, 3776–3784. [CrossRef]
39. Sabhi, S.; Kiwi, J. Degradation of 2,4-dichlorophenol by immobilized iron catalysts. Water Res. 2001, 35,
1994–2002. [CrossRef]
40. Kiwi, J. Innovative immobilized Fenton systems useful in the abatement of industrial pollutants.
In Proceedings of the Third Asia-Pacific Conference on Sustainable Energy and Environmental Technologies,
Hong Kong, China, 3–6 December 2000; p. 562.
41. Goswami, A.K.; Acharya, A.; Pandey, A.K. Study of self-diffusion of monovalent and divalent cations in
Nafion-117 ion-exchange membrane. J. Phys. Chem. B 2001. [CrossRef]
42. Silva, C.G.; Bouizi, Y.; Fornés, V.; Garcia, H. Layered Double Hydroxides as Highly Efficient Photocatalysts
for Visible Light Oxygen Generation from Water. J. Am. Chem. Soc. 2009, 131, 13833–13839. [CrossRef]
[PubMed]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).