Journal of Hazardous Materials 345 (2018) 10–17

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Journal of Hazardous Materials

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

Photocatalytic degradation of H2 S aqueous media using sulfide

nanostructured solid-solution solar-energy-materials to produce
hydrogen fuel
Mohsen Lashgari a,b,∗ , Majid Ghanimati a
a
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran
b
Center for Research in Climate Change and Global Warming: Hydrogen and Solar Division, Zanjan 45137-66731, Iran

h i g h l i g h t s

• Synthesis of alloy photocatalyst nanoparticles through a facile hydrothermal route.

• Simultaneous photo-degradation of H2 S solutions and production of hydrogen fuel.
• HS− plays a crucial role in photo-redox processes, serves as e/h scavenger species.
• Mechanism of pH influence on the photocatalyst performance in H2 S media.

a r t i c l e i n f o a b s t r a c t

Article history: H2 S is a corrosive, flammable and noxious gas, which can be neutralized by dissolving in alkaline media
Received 20 May 2017 and employed as H2 -source by utilizing inside semiconductor-assisted/photochemical reactors. Herein,
Received in revised form 30 October 2017 through a facile hydrothermal route, a ternary nanostructured solid-solution of iron, zinc and sulfur was
Accepted 31 October 2017
synthesized in the absence and presence of Ag-dopant, and applied as efficient photocatalyst of hydrogen
Available online 6 November 2017
fuel production from H2 S media. The effect of pH on the photocatalyst performance was scrutinized and
the maximum activity was attained at pH = 11, where HS− concentration is high. BET, diffuse reflectance
Keywords:
and photoluminescence studies indicated that the ternary solid-solution photocatalyst, in comparison to
H2 S photocatalytic degradation
pH effect
its solid-solvent (ZnS), has a greater surface area, stronger photon absorption and less charge recombina-
Alloy semiconductor nanoparticles tion, which justify its superiority. Moreover, the effect of silver-dopant on the photocatalyst performance
Hydrogen solar fuel was examined. The investigations revealed that although silver could boost the absorption of photons
Water photosplitting and increase the surface area, it could not appreciably enhance the photocatalyst performance due to its
weak influence on retarding the charge-recombination process. Finally, the phenomenon was discussed
in detail from mechanistic viewpoint.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Hydrogen sulfide (H2 S) is a toxic, corrosive (Eq. (1)) and
flammable (Eq. (2)) gas [1–5]; its emission to the environment is
harmful and could be lethal at concentrations above 500 ppm [6].
This hazardous material has the stench of rotten eggs, and can be
easily produced by acidification of sulfide media (Eq. (3)) [7,8].
H2 S + Fe → FeS + H2 (1)
∗ Corresponding author at: Department of Chemistry, Institute for Advanced Stud-
ies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran.
E-mail address: Lashgari@iasbs.ac.ir (M. Lashgari).
3
H2 S + O2 → SO2 + H2 O (2)
2
H+ H+
S2− ↔HS− ↔H2 S (3)
This noxious gas is biologically generated via microbial activities
of sulfur reducing bacteria (SRB), by degradation of sulfur-
containing compounds in sewage environments [9]. Hydrogen
sulfide is also recognized as by-product of sour gas and oil,
which is the main cause of severe corrosion and hydrogen
damage/embrittlement in petroleum and gas industries [10,11].
Therefore, the deactivation of this noxious/devastating gas is not
only important from environmental but also crucial from corro-
sion as well as industrial standpoints. Beside these aspects, the
elimination of H2 S is highly interesting from energy/fuel per-

https://doi.org/10.1016/j.jhazmat.2017.10.062
0304-3894/© 2017 Elsevier B.V. All rights reserved.
 M. Lashgari, M. Ghanimati / Journal of Hazardous Materials 345 (2018) 10–17
spective; here, by photocatalytic decomposition of H2 S solutions,
without needing external hole-scavenger additives, hydrogen fuel
can be effectually produced [12,13] upon appropriate semicon-
ductor photocatalyst/solar-energy materials [14]. The method of
photocatalytic utilization of H2 S media is deemed to be economi-
cal and efficient [15–17]. This is because, a vast amount of H2 S gas
is annually generated during various industrial/natural processes,
including hydrodesulfurization of crude oil, acid leaching of sul-
fide ores, sewage treatment, geothermal activities, etc. [18–20].
Therefore, using low-cost, efficient, solar-energy materials, this
hazardous feed could be economically/effectually converted into
hydrogen clean fuel.
Concerning photocatalytic production of hydrogen fuel, it is
worth noting that zinc sulfide (ZnS) is a non-toxic, photostable,
semiconductor material with a proper (high) conduction-band
energy-level [21,22]; this is a reason why ZnS is usually selected
as a good photocatalyst base for photochemical reduction of pro-
tons and production of hydrogen solar fuel [23,24]. This compound
(Eg ∼ 3.5 eV [25]) however is only active in the UV region–which
forms a small portion of sunlight (∼5% [26]). To absorb photons in
the visible region (∼43% of sunlight [26]), therefore, it is crucial to
decrease the bandgap of the semiconductor/solar-energy material
without noticeable lowering its conduction-band energy-level [27].
To this end, one of the effective methods is the application of dopant
to synthesize a solid solution or alloy semiconductor material
[24,27]. For ZnS semiconductor, the use of cadmium [28], indium
[29], and copper [30] alloying components has been reported in the
literature; albeit the toxicity as well as the abundancy of dopants
should also be taken into account.
In this paper, we focused on Fe dopant and synthesized the
(III) (II)
ternary Fe0.2 Zn0.7 S solid-solution (IZS) through a facile hydrother-
mal route [24], and applied it for the first time as an effective
photocatalyst of hydrogen fuel production from H2 S aqueous
(III) (II)
media. We synthesized Fe0.2 Zn0.7 S because this composition
exhibited the greatest extent of photon absorption [31]. Concern-
ing the selection of iron dopant, it is also worth noting that Fe is an
eco-friendly abundant element which can combine with sulfur and
produce FeS. This compound is relatively stable (Ksp = 8 × 10−19 )
and being industrially applied as a high temperature (550–900 ◦ C)
catalyst of H2 S decomposition to produce hydrogen gas [32]:

FeS + H2 S→FeS2 + H2
In the present work, instead of oxide semiconductor materials,
we employed sulfide one. The choice was based on the ability of
sulfide materials to form a chemical bond with proton species (Eq.
(3)), which in turn could result in the facilitation of electron trans-
port from the photoexcited semiconductor solar-energy-material
to proton species on the photocatalyst surface [14].
The effect of pH of medium on the photocatalyst performance
was another interesting issue, which was scrutinized in this article.
Due to the ability of silver atoms to exhibit surface Plasmon reso-
nance and enhance the photocatalyst performance [27,4], we also
examined the effect of silver on the photocatalyst activity.
2. Experimental
2.1. Synthesis of solid-solution photocatalyst/solar-energy
materials
(III) (II)
The ternary solid-solution photocatalyst, viz. Fe0.2 Zn0.7 S (IZS)
was synthesized through a hydrothermal procedure using appro-
priate molar ratio of the precursor ions [24]; here, we first prepared
a 50 ml aqueous solution containing 0.36 M zinc acetate (Fluka;
98%), 0.08 M iron (III) nitrate (Sigma-Aldrich; 99.98%) and 0.4 M
thioacetamide (Scharlau; 98%). The solution was then poured into
11
a handmade stainless steel (SS 316) autoclave reactor with an inter-
nal vessel made of polytetrafluoroethylene (PTFE) and heated for
12 h at 433 K. After cooling the reactor, the obtained precipitate
was decanted and washed several times with distilled water and
finally was dried overnight at 343 K. The product was a rust color
IZS powder. For the synthesis of zinc sulfide (ZS; a milky-white
color photocatalyst material), the same procedure was applied in
the absence of iron precursor. In the case of silver-doped photo-
catalyst (IZSS), we repeated the synthesis of IZS in the presence of
Ag+ cation (0.008 M), by adding 0.067 gr of AgNO3 (Merck; 99.8%)
to the reaction medium (the product color was burnt umber).
2.2. Photocatalyst characterization
For the characterization of the solar-energy-materials syn-
thesized here, we employed different techniques including
X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS),
Brunauer-Emmett-Teller (BET), scanning electron microscopy
(SEM), diffuse reflectance (DR) spectroscopy, and photolumines-
cence (PL) spectroscopy. XRD patterns of the materials were
determined using a Philips X’Pert Pro X-ray powder diffractome-
ter (␭ = 1.54 Å; Cu K␣ beam). XPS spectra were recorded via an
8025-BesTec (Germany) spectrometer with monochromatic Al
K␣ radiation source (1486.6 eV). Peak deconvolution was per-
formed using MATLAB software [33]. N2 adsorption-desorption
(BET isotherm) and porosimetry experiments were conducted
at 77 K on a BELSORB-max (BEL, Japan) instrument. The field
emission SEM images of the solar-energy-materials were taken
by a ZEISS SIGMA VP electron microscope. DR spectra were
recorded by applying a Varian Cary 5 UV–vis-NIR spectrometer
(BaSO4 was used as the blank). To record PL spectra of the solar-
energy-materials, we utilized a fluorescence Avantes spectrometer
(AvaSpec-ULS2048 × 64 TEC) with excitation wavelength 350 nm.
2.3. Photoreactor setup, hydrogen measurement, and
photocatalyst performance
Similar to our previous report [14], the hydrogen evolution
(4) experiments were carried out in a double-walled 50 ml cylindrical
glass vessel equipped with a T-controlling bath circulator (exposed
surface area: 10 cm2 and T = 298 K). During the tests, the photo-
catalyst powder (0.2 g in 50 ml solution [27]) was continuously
dispersed using a magnetic stirrer, and the reactor was illumi-
nated by a 500-W power-tunable Xe-lamp (Ushio Xenon Short
Arc Lamp). We applied xenon light source, because its spectrum
is close to that of Sun and the intensity of incident photons was
set at 100 mW/cm2 , similar to that coming directly from the Sun
to the Earth’s surface under non-cloudy/standard conditions [24].
The quantity of photogenerated gas was measured through a vol-
umetric method, described in detail elsewhere [27]. The reaction
medium was an H2 S saturated solution (containing ∼16 g/L of sul-
fide [34,16]), prepared by conducting H2 S gas into a 0.5 M NaOH
solution. Due to safety issues, H2 S gas was not purchased but pro-
vided in the laboratory through the reaction between FeS and HCl
feed, using a Kipp generator setup [35]. Alternatively, the reaction
medium (H2 S solution) can be directly prepared by acidifying a
sodium sulfide solution (0.5 M Na2 S, the optimum concentration
of sulfide reported in literature [34]; Eq. (3)). To prohibit the dis-
charge of un-reacted H2 S into the atmosphere, the excess gas was
de-neutralized by passing the outflow through a sodium hydroxide
solution (H2 S + 2NaOH → Na2 S + 2H2 O). To adjust the pH at con-
sidered values, appropriate quantities of HCl were added to the
medium.
12 M. Lashgari, M. Ghanimati / Journal of Hazardous Materials 345 (2018) 10–17

Table 3
Surface area and porosimetry data of the semiconductor photocatalysts obtained
from N2 adsorption-desorption isotherms (BET measurements).

Semiconductor Surface area (m2 g−1 ) Mean pore diameter (nm)

ZS 12.1 7.2
IZS 20.9 22.0
IZSS 60.8 10.1

be present in both metallic and cationic forms (the peaks at 373.7

and 374.2 eV correspond to Ag+ and Ag◦ , respectively [39,40]). The
presence of Ag+ was already expectable, because we used silver
(I) nitrate precursor in the synthesis of photocatalyst material (see
Experimental). The production of metallic silver is also rationalized
Fig. 1. X-ray diffraction (XRD) patterns of the ternary solid-solution photocatalyst to thioacetamide, serving not only as a sulfur source but as a weak
(solar-energy-material) in the absence (IZS) and presence (IZSS) of Ag dopant (the
reducing agent, which partially converts silver cations to metallic
solvent is zinc sulfide, ZS).
element [24]. Besides XPS evidence, the presence of Ag metal is indi-
rectly verified by the observation of surface plasmon resonance effect
Table 1
Energy dispersive X-ray spectroscopy (EDS/EDX) data (wt.%) obtained for the solid- in diffuse reflectance spectra of the Ag-doped photocatalyst/solar-
solution photocatalysts. energy material [27,41] (see next section; Fig. 5).
The surface area of photocatalysts was determined using BET
Photocatalyst Fe Ag Zn S
studies (Fig. 2) and the results are summarized in Table 3. The
ZS – – 68.4 31.6 observation of a hysteresis loop in BET diagrams indicates that all
IZS 18.3 – 54.2 27.5
IZSS 15.0 6.2 52.1 26.7
photocatalyst materials synthesized here are mesoporous (the size
of pores is in the range of 2–50 nm) [24]. Moreover, data listed in
Table 3 show that the presence of alloying element (dopant/solute)
Table 2 causes an increase in the surface area of the resulting photocatalyst
XPS results of the solid-solution photocatalyst (containing all atoms).
material.
Element Spectral line Binding energy (eV) Oxidation state References The porous structure of the photocatalyst/solar-energy mate-
Fe 2p1/2 723.4 +3 [31] rials was also confirmed by SEM studies (Figs. 3 and 4). The SEM
2p3/2 710.8 image of ZS (Fig. 3) exhibited a gravel-like nanostructure for this
Zn 2p1/2 1044.1 +2 [36] solar-energy material –which consists of some fine and coarse
2p3/2 1021.2 nanoparticles (Fig. 3b) and their aggregation constructs greater size
S 2p1/2 162.5 −2 [38,39]
microspheres (Fig. 3a). The addition of iron and silver dopants to ZS
2p3/2 161.3
Ag 3d3/2 (373.7a , 374.2b ) 0, +1 [39,40] makes the size of nanoparticles to be more diminutive (see Fig. 4).
3d5/2 ∼368c The spherical shape and porous structure recognized here seem to
a,b
Data are standing for cationic and metallic silver, respectively. be the characteristics of hydrothermal route for the synthesis of
Owing to negligible shift in binding energy of Ag 3d5/2 between Ag+ and Ag◦
c ZnS-based solid-solution materials, which were also observed in
(0.2 eV [40]), as compared with that of Ag 3d3/2 (0.5 eV), the deconvolution was just our previous study [27].
successfully attained for Ag 3d3/2 peak.

3.2. Optical response (DR, PL)

3. Results and discussion
3.1. Synthesis and characterization (XRD, EDS, XPS, BET, SEM)
XRD patterns of the ZnS-based solid-solution materials are pre-
sented in Fig. 1. Here, three intense peaks observed at 2 = 28.8, 47.7
and 56.6◦ are the characteristic peaks of zinc sulfide (ZS), indicating
a cubic structure (zinc blende; JCPDS 77-2100) for the synthesized
solid-solution materials [24,36]. In these solid-solution materials,
ZnS has the role of solvent and the addition of solute (Fe/Ag dopant)
has no noticeable effect on shifting the position of the character-
istic peaks mentioned above. The existence of weak peaks around
24, 36, 41, 50, 54, 62.5, and 64◦ indicate that besides the synthesis
of solid-solution material, a negligible amount of impurity (Fe2 S3
and Fe7 S8 [37]) could also be co-synthesized by the present facile
approach. The addition of silver to IZS, because of its low quantity
(the molar ratio of Ag+ to Fe3+ is 1:10), has no definite influence on
XRD pattern [see Fig. 1; the XRD patterns of IZS and IZSS are quite
similar].
The presence of Ag and Fe dopants in the synthesized solid-
solution materials was approved by EDS/EDX and XPS studies
(Tables 1 and 2). XPS investigation also revealed that the oxidation
state of Fe is +3. This result was predictable because in the synthe-
sis of photocatalyst, we used Fe3+ cations as precursor. Moreover,
deconvolution of Ag 3d spectrum indicated that Ag in IZSS could
Diffuse reflectance spectra of the photocatalyst/solar-energy
materials synthesized here are plotted in Fig. 5. This figure indi-
cates that ZS absorbs photons only in the ultraviolet (UV) region.
By adding Fe and Ag dopants (alloying elements) to ZS and syn-
thesizing IZS and IZSS, the absorption of photons is boosted and
extends toward longer wavelengths (visible domain). Concerning
the prerequisites of a good photocatalyst material, it is worth not-
ing that besides its ability to absorb a greater number of incident
photons in a broad range of wavelengths, an efficient photocatalyst
should also exhibit a low recombination [14]. Under this condition,
the photogenerated e/h pairs would have a greater opportunity to
participate effectually in the photo-redox reaction, prior to being
−
annihilated via charge recombination process (eCB + h+ VB
→ null);
here, the less recombination is normally recognized as a decrease
in the PL emission intensity of the photocatalyst material [14].
Based on PL spectra depicted in Fig. 6, a noticeable extinction is
observed in the PL spectrum of IZS, when Fe-dopant is added to
ZS photocatalyst material. Thus, a greater photocatalytic activity is
anticipated for IZS as compared with ZS. The less recombination of
IZS is attributed to the presence of Fe3+ cations–which act as elec-
tron traps [42], delaying the annihilation (recombination) of the
transiently photogenerated e/h pairs. Fig. 6 also reveals that the
addition of silver to IZS does not exhibit an appreciable influence
on improving the charge separation process (notice, the PL spectra
 M. Lashgari, M. Ghanimati / Journal of Hazardous Materials 345 (2018) 10–17 13

Fig. 2. Nitrogen adsorption-desorption isotherms of the photocatalysts/solar-energy materials synthesized through facile hydrothermal route.

Fig. 3. SEM images of ZS (zinc sulfide) solar-energy-material taken at two different magnifications (a: the scale bar is 1 ␮m, b: the scale bar is 200 nm).

of IZS and IZSS are almost identical). Therefore, despite the ability of
Ag to augment the absorption of photons (see Fig. 5), the presence of
Ag could not effectively boost the photocatalyst performance [this
prediction is confirmed by Fig. 7].
3.3. Photocatalysts performance
The ability of photocatalyst/solar-energy materials to produce
hydrogen fuel from H2 S solutions is presented in Fig. 7. This
figure shows that the lowest photocatalytic activity is result-
ing for ZS, having the widest bandgap (∼3.5 eV) as well as the
greatest PL-emission. By adding Fe-dopant and synthesis of IZS
solid-solution, not only the bandgap of the resulting photocat-
alyst material decreases (∼2.04 eV), but the PL emission is also
notably diminished. This explains how IZS can effectively harvest
the incident photons and produce more fuel. In the presence of Ag,
although extra photons can be absorbed by IZSS [refer to Fig. 5], no
substantial enhancement on the photocatalyst performance was
achieved. As mentioned beforehand, this behavior is rationalized
to the weak ability of Ag on improving the charge separation pro-
cess. Since, both IZS and IZSS solar-energy materials displayed a
significant photocatalytic activity, their long-term action was also
investigated. The diagrams depicted in Fig. 8 approved that both
solar-energy materials synthesized here have a good photostability
for prolonged application in H2 S media.
14 M. Lashgari, M. Ghanimati / Journal of Hazardous Materials 345 (2018) 10–17
Fig. 4. SEM images of IZS (a) and IZSS (b) solid-solution solar-energy materials.
Fig. 5. Diffuse reflectance (DR) UV–vis spectra of the photocatalyst/solar-energy
materials.
Fig. 6. Photoluminescence (PL) spectra of the photocatalyst/solar-energy materials.
3.4. pH effect on the photocatalyst activity and mechanistic
understanding of the phenomenon
A glance at the literature indicates a pH-dependence for the
amount of H2 gas being photocatalytically evolved from H2 S media
[43–45,34]. To scrutinize the effect of pH on the photocatalyst per-
formance, it is essential to respond these queries: 1- At a given
pH, which form of H2 S (sulfide, bisulfide, or hydrogen sulfide) is
dominant? 2- In H2 S solutions, how does the hydrogen photo-
evolution process take place? 3- What can we declare about the
stability of photocatalyst at different pHs? Concerning the first
query, by using dissociation constant data of H2 S and mass bal-
Fig. 7. The volume of hydrogen gas being photocatalytically produced as a function
of irradiation time (data were recorded every 10 min under atmospheric pressure
at 298 K; the reaction chamber contained 0.2 g photocatalyst/solar-energy material
(powder) dispersed in a 50-mL H2 S alkaline solution at pH 11).
     
ance law ( S2− = S2− + HS− + [H2 S]) [46], the concentration
◦
of sulfureous species were calculated at different pHs for a 0.5 M
sodium sulfide solution; the results are illustrated in Fig. 9. Using
this figure, the following points can be deduced:
1. By acidifying the sulfide medium (pH < 9), the concentration
of H2 S increases substantially. Under this situation, if [H2 S]
exceeds the saturation limit (ca. 0.103 M [47]), the excess quan-
tity escapes as H2 S gas. Moreover, it is worth noting that by
bubbling H2 S gas into the alkaline solution (0.5 M NaOH), the
minimal pH that could be practically attained under atmospheric
pressure, is ∼7.3 (to get less pHs, extra pressures or lower tem-
peratures are required).
2. Under high alkaline conditions (pHs greater than 11), both sul-
fide and bisulfide are simultaneously existing in the reaction
medium; at slightly lower pHs, between 9–11, however, the pro-
tonated form of sulfide, viz. bisulfide (HS− ) becomes the sole
dominant species.
As mentioned above, by decreasing the pH, sulfide anions
get unstable; in aqueous solutions with moderate alkalinity
(9 ≤ pH ≤ 11), sulfide anions are predominantly transformed to
their protonated form (HS− ). Under such a condition, if the sul-
fide semiconductor (SC) is irradiated by photons (h + SC  e + h
[27]), the photogenerated electrons can be transferred to the proton
 M. Lashgari, M. Ghanimati / Journal of Hazardous Materials 345 (2018) 10–17 15

By recombination of the H atoms, H2 gas is consequently evolved

[14]:

H + H → H2 ↑ (6)

With consumption of the photogenerated electrons and pro-

duction of hydrogen gas (Eqs. (5) and (6)), to satisfy the charge
neutrality (e− + h+ = 0), the photogenerated holes must also be syn-
chronously used up via an oxidative process [49]. In the present
system, both sulfide and bisulfide (HS− ) anions play the role of hole-
scavenger; they are oxidized to disulfide (S2− 2 ) anions as follows
[50]:

S2− + 2h+ → S

S2− + S → S2−
2 (7)
− − − − − − −−
2S2− + 2h+ → S2−
2

and [43,32,34],

HS− + h+ → HS ·

2HS · → H2 S2 → 2H+ + S2−

2
(8)
− − − − − − − − − − −−
2HS− + 2h+ → 2H+ + S2−
2

 As implicitly pointed above, the concentration of proton

( H+ = 10−pH ) can directly (H+ + e− → H; Eq. (7)) or indirectly (by
Fig. 8. The ability of IZS and IZSS solid-solution photocatalyst/solar-energy materi-
affecting on [HS− ]; Fig. 9) influence on both photo-redox processes
als to evolve hydrogen gas, examined for 3 successive runs (each run lasted 3 h and (Eqs. (5) and (8)), and hence alter the quantity of H2 gas (Fig. 10).
the volume of gas was recorded every 10 min; the pH was 11). Moreover, since HS− plays a pivotal role [51] in photochemical pro-
duction of hydrogen fuel (it participates in both photo-reduction
and −oxidation processes; see Eqs. (5) and (8)), where [HS− ] is high
(9 ≤ pH ≤ 11; Fig. 9), it is predicted H2 gas being more effectively
species already attached to the sulfide anions at the photocatalyst
evolved (see Fig. 10).
surface, and produce H atoms and S2− anions [48,14]:
Concerning the effect of pH on photocatalyst performance, it
should be noted that there are some controversial reports in the lit-
HS−  H+ + S2− erature [44,45,38,51–54]. Some researchers reported that the best
photocatalytic activity is achieved at pH 7.8, whereas the oth-
H+ + e− → H (5) ers witnessed the greatest performance at pH 12.8 [38,54,51].
−−−−−−−−−
Therefore, in addition to these values, extra pHs were also selected
HS− + e− → H + S2− from Fig. 9 and examined in the present study; see Fig. 10. From

Fig. 9. Concentration of sulfide (S2− ), bisulfide (HS− ) and hydrogen sulfide (H2 S) species determined theoretically as a function of pH in a 0.5 M sodium sulfide aqueous
solution.
16 M. Lashgari, M. Ghanimati / Journal of Hazardous Materials 345 (2018) 10–17
Fig. 10. Volume of hydrogen gas evolved from the H2 S solution at different pHs;
data were measured after 90 min operation of the photoreactor containing 0.2 g of
the ternary solid-solution photocatalyst/solar-energy material.
comparison of the diagrams of pH 7.8 and pH 12.8, a greater activ-
ity (hydrogen evolution) is observed at the second pH (12.8). This
observation could be rationalized to the greater stability of metal
sulfides in alkaline media [55]. Through a similar argument, we can
justify why a greater activity is achieved at pH 11 as compared with
that of pH 10 and 9. The less gas evolution at pH 12.8 in comparison
to that of pH 11 is also rationalized to low concentration of bisulfide
as well as proton at this pH. Furthermore, we should declare that at
pHs less than 9, the level of H2 S increases with acidification of the
medium (see Fig. 9); correspondingly, Fig. 10 demonstrates that by
increasing H2 S, a greater volume of hydrogen gas is evolved. The
greater hydrogen gas being evolved at higher H2 S concentration
is obviously attributed to the facile dissociation of H2 S as com-
pared with that of H2 O molecules (GH dis.
S
= 33.4kJmol−1 , GH
dis.
O
= Kolekar, B. Kale, Confinement of Ag3 PO4 nanoparticles supported by surface
2 2
237kJmol−1 [56]).
4. Conclusion
Based on the present study, we can conclude that:
• Using a facile hydrothermal route, one could easily synthesize
efficient solid-solution solar-energy-materials and apply them to
generate hydrogen solar fuel from H2 S solutions.
• The ternary solid-solution photocatalyst synthesized here (IZS) is
able to serve as an efficient solar-energy material in H2 S media
to produce hydrogen gas.
• By doping Ag to IZS, the photocatalyst performance is slightly
enhanced; therefore, the use of this element is not recommended
for the present system, due to its high price.
• The maximum photocatalyst performance was attained at pH 11,
where HS− species is dominant in the reaction medium; during
the photocatalytic degradation of H2 S solutions, this anion plays
a crucial role in both photo-redox processes.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at https://doi.org/10.1016/j.jhazmat.2017.10.
062.
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