Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339

Contents lists available at ScienceDirect

Journal of Photochemistry and Photobiology C:

Photochemistry Reviews
journal homepage: www.elsevier.com/locate/jphotochemrev

Hydrogen sulfide conversion: How to capture hydrogen and sulfur by

photocatalysis
Meng Dan a,b , Shan Yu a,b,∗ , Yi Li a,b , Shiqian Wei a,b , Jianglai Xiang a,b , Ying Zhou a,b,∗
a
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, China
b
The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Chengdu, 610500,
China

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 notorious gas widely generated in the petrochemical industry. How to handle H2 S effectively
Received 18 June 2019 and convert it into highly-valued products is vital. Photocatalysis is promising in this field, as it could
Received in revised form directly utilize solar light and convert H2 S into H2 and S. In this review, the properties of hydrogen
10 November 2019
sulfide (H2 S) is overviewed first, and conventional techniques (Claus process, thermolysis, non-thermal
Accepted 23 December 2019
Available online 24 December 2019
plasma, electrochemistry and other methods) for H2 S conversion are simply introduced. Basic knowledge
of photocatalysis and general strategies for enhancing the activities of photocatalysts are presented as
well. Then typical work for photocatalytic conversion of H2 S in gas phase and liquid phase are introduced
Keywords:
Photocatalysis case by case, with the generated H2 as the main product in these systems. Furthermore, methods for
H2 S conversion extraction of elemental sulfur from H2 S by photocatalysis-related methods were discussed, with specific
H2 evolution attention on photoelectrochemical cells and photovoltaic-electrochemical cells. In the end, current status
sulfur extraction of the research on photocatalytic conversion of H2 S is summarized, and challenges in this field is put
forward. In addition, some other possible strategies for photocatalytic conversion of H2 S into highly-
valued chemicals instead of hydrogen and elemental sulfur will be discussed, which is aimed to inspire
researchers interested in this field.
© 2019 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. General methods for H2 S conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Claus process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Thermolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Plasma technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.4. Electrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.5. Other methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.6. Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Design strategy of photocatalysts for conversion of H2 S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Thermodynamic requirement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Influencing factors and optimization strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.1. Band gap engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.2. Micro/nano engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.3. Interface engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.4. Crystal facet engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

∗ Correspondence author at: The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Chengdu,
610500, China.
E-mail addresses: yushan@mail.ipc.ac.cn (S. Yu), yzhou@swpu.edu.cn (Y. Zhou).

https://doi.org/10.1016/j.jphotochemrev.2019.100339
1389-5567/© 2019 Elsevier B.V. All rights reserved.
2 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339

4. Photocatalytic conversion of H2 S in various media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

4.1. Gas-phase photocatalytic conversion of H2 S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2. Liquid-phase photocatalytic conversion of H2 S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2.1. Ethanolamine system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2.2. Hydroxide system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2.3. Sulfite system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5. Extraction of sulfur in H2 S by photocatalysis-related methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
5.1. Particulate / homogeneous catalytic system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
5.2. Photoelectrochemical (PEC) / Photovoltaic electrochemical (PV-EC) cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.2.1. Brief introduction of PEC cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.2.2. PEC cells for direct conversion of H2 S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.2.3. PEC cells for indirect conversion of H2 S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5.2.4. PV-EC cells for conversion of H2 S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
6. Conclusion and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

Meng Dan received his BSc degree from Baoji University of Jianglai Xiang is currently a master degree candidate
Arts and Sciences in 2014 and MSc degree from Southwest under the supervision of Prof. Ying Zhou of South-
Petroleum University, China in 2017. Currently he is a PhD west Petroleum University, China. His current research is
candidate at Southwest Petroleum University with Prof. mainly focused on the design and synthesis of metal sul-
Ying Zhou. His present research interest focuses on the fide/2D material composites for photocatalytic utilization
design and synthesis of metal sulfides for photocatalytic of H2 S.
H2 S resource utilization.

Shan Yu received her BSc and MSc from Lanzhou

Ying Zhou received his BSc and MSc from Central South
University in 2009 and Technical institute of Physics
University and Chinese Academy of Sciences, respec-
and Chemistry, Chinese Academy of Sciences in 2014,
tively. In 2010, he received his PhD at the University
respectively. Currently, she is an associate professor in
of Zurich (UZH) under the supervision of Prof. Greta R.
Southwest Petroleum University. She was a guest Post-
Patzke. He then continued his work with a postdoctoral
doc from 2016 to 2017 at the University of Zurich in
Forschungskredit grant from UZH. He was also awarded
the group of Prof. Greta R. Patzke. Her research inter-
a fellowship by the Alexander von Humboldt Foundation
ests include photocatalytic decomposition of H2 S for H2
at Karlsruhe Institute of Technology with Prof. Jan-Dierk
production, and synthesis and spectroscopic studies of
Grunwaldt and was a visiting professor at Kyoto Uni-
traditional semiconductor-based as well as carbon-based
versity. He currently holds a professorship at Southwest
quantum dots.
Petroleum University. His research interest is in the clean
utilization of oil and gas and environmental remediation
Yi Li received BSc and MSc degree from Southwest materials as well as the related in situ characterization
Petroleum University, China, in 2016 and 2019, respec- techniques.
tively. His research is mainly focused on the design and
synthesis of metal sulfide for photocatalytic H2 production
from H2 S.
1. Introduction

Hydrogen sulfide (H2 S) is a common gas in natural environ-

ment and industrial exploration process [1–3]. Generally, H2 S in
low-concentration has a disgusting rotten egg odor and it can be
easily identified from smell. However, H2 S in high concentration
can rapidly paralyze human’s nerve, which means it is hard to
Shiqian Wei received BSc degree from Jingdezhen notice the danger because H2 S will immediately kill people.
Ceramic Institute, China, in 2014, and she received her H2 S mainly attacks the mitochondrial cytochrome c oxidases
PhD degree under the supervision of Prof. Ying Zhou in the cell of animals by complex bonding with iron ions which
from Southwest Petrolum University, China, in 2019. Her
research is mainly focused on the reaction mechanism of then stops the cellular respiration. The first report for H2 S toxicity
H2 S based on the density functional theory calculations. was proposed in 1713 [1], and according to the latter surveys, it
is believed H2 S of 50 ppm can lead to obvious hurt on human’s
body while 320 ∼ 700 ppm H2 S will be lethal [2,3]. Due to its
higher density (1.19) than air, H2 S is easily aggregated in an air-
tight space which usually caused the difficulty to evacuate the gas.
More importantly, H2 S molecule is very active. It can corrode a lot
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
of metal-made facilities and sometimes, cause explosions if the air
mixed with H2 S is burnt [4].
Modern medicine found that a certain amount of H2 S existed in
the brain and blood vessel of human to work as a signal molecule,
because of the metabolic functions of biological enzymes to trans-
form cysteine [5]. Hence, in the process of biomass decomposition,
H2 S can be produced although its quantity is not high. Secondly,
natural geological activity can also contribute to the releasing of
H2 S into air, like volcano eruption and earthquake. But as they are
the common natural phenomena, most of the produced H2 S were
eliminated by biosphere. In some special areas, for example, the
Black sea, due to its special anaerobic environment, H2 S is largely
stored at nearly 150 m below the surface and it is estimated there
are approximately 4.6 × 109 tons of H2 S in all, which has an impor-
tant influence on the exploitation of this area [6,7]. Nevertheless,
the majority of H2 S comes from the frequent human activities for
economic developments at present. Oil and gas exploitation, crude
oil desulfuration, refining and upgrading usually result in a great
deal of H2 S production [8]. The worldwide annual H2 S produc-
tion has reached approximately 10 million tons and is expected
to increase further [9]. These waste gas, in most of cases, cannot be
bore by the nature. Hence, artificial means are necessarily required
to handle these poisonous H2 S.
As H2 S is chemically composed of H element and S element, it
is theoretically feasible to convert H2 S into hydrogen (H2 ) and ele-
mental sulfur (S). Hydrogen is a necessary additive in petroleum
industry for desulfurization of heavy oil [10]. More importantly, it is
a widely-recognized clean energy source with high energy density.
Meanwhile, S is also an important chemical material for produc-
tion of sulfuric acid in industry. Accordingly, it is of great benefit to
decompose highly-toxic H2 S into hydrogen and elemental sulfur.
In this review, we first briefly introduce the currently existed
methods for conversion of H2 S. Then we will mainly focus on pho-
tocatalytic conversion of H2 S, from the aspects of extraction of H2
and elemental S respectively. Due to the length limitation of review,
we mainly discussed systems in which H2 S gas (instead of sulfide
solution) are directly involved. Separation and purification of H2 S,
which is necessary before disposal of H2 S, is beyond the scope of
this review and readers can refer to a recent comprehensive review
for relevant study [11].
2. General methods for H2 S conversion
Numerous efforts have been made for removal of H2 S during
exploitation of oilfield and natural gas reservoir. In most cases,
H2 S gas is collected through Claus process for production of ele-
mental sulfur [12,13]. Meanwhile, with respect to shortcomings of
Claus process, other methods including thermolysis [14–21], non-
thermal plasma technology [22–28], electrochemistry [29–35],
photocatalysis [36–45] and other methods [46–49] were proposed
accordingly. A brief introduction of these techniques is exhibited
as follows.
2.1. Claus process
As the most mature technology for H2 S removal, Claus process
is widely used in tail gas treatment of gas exploitation, oil desul-
furization, and coal purification with its reputation for safety and
efficiency for H2 S disposal and sulfur extraction [50,51]. Claus pro-
cess was first brought up by the German scientist C. F. Claus (with
English patent) in 1883 and later significantly modified by the Ger-
man chemical and pharmaceutical conglomerate IG Farben in 1938
[12]. Usually, Claus process is a combination of partial oxidation
of H2 S in the presence of O2 to SO2 at high temperature (thermal
step, Eq. 1) and reaction of H2 S with SO2 in the presence of cat-
3
alyst (catalytic step, Eq. 2) [13]. The specific chemical equation is
summarized as follows:
ThermalStep : H2 S + 3/2O2 → SO2 +H2 O (1)
Catalyticstep : H2 S + 1/2SO2 → 3/2S + H2 O (2)
Overallreaction : H2 S + 1/2O2 → S + H2 O (3)
For the thermal step, H2 S is oxidized in the presence of air in furnace
at 1000−1200 ◦ C. The feed ratio of air to H2 S must be well controlled
in the furnace to ensure that approximately 1/3 H2 S is converted
into SO2 . Therefore, stoichiometric reaction between H2 S and SO2
could happen in the following catalytic step [12,13]. In the pres-
ence of activated aluminum (III) or titanium (IV) oxide operated
at a relative low temperature (200−350 ◦ C), the sulfur yield from
H2 S and SO2 generated from thermal step was boosted. Reaction
temperature must be above the dew point of sulfur so that gaseous
elemental sulfur was obtained in the catalytic bed to avoid catalyst
fouling.
With suitable catalyst and multiple reaction beds during the
thermal step, about 97% of H2 S at most could be converted to ele-
mental sulfur for Claus process because of thermodynamic limit
[9]. This indicates that a small amount (3% at least) are still left
in the tail gas. Further purification of H2 S is necessary in medium
to large Claus plants and three kinds of technologies are mainly
adopted: low-temperature (sub-dew point) Claus reaction technol-
ogy, reduction-absorption technology, and H2 S selective catalytic
technology. After these processes, the sulfur yield could be fur-
ther increased to 98.5–99.5% or even higher than 99.8% for the
reduction-adsorption process particularly [25].
Claus process is now the industry standard for removal of H2 S
in oilfield chemistry and one major technique to produce sulfur.
Nevertheless, one big drawback of Claus process is that it only
focuses on the recovery of element sulfur and ignores the extraction
of hydrogen energy hidden in H2 S, which is converted into water
with low added-value in the end. Hydrogen is not only potential as
environmental-benign energy source in our daily life, but also indis-
pensable during the hydrodesulfurization (HDS) to remove sulfur
species from natural gas and from refined petroleum products.
In principle, it is viable to produce hydrogen and sulfur
simultaneously judging from the chemical composition of H2 S.
Accordingly, techniques different from Claus process were devel-
oped.
2.2. Thermolysis
To make up the drawback of Claus process, direct thermolysis
was proposed to recycle hydrogen and sulfur from H2 S in 1970s
[14]. It is demonstrated the generation of S and H2 when H2 S gas
was treated at around 1000 ◦ C [15].
H2 S  H2 + SG0 = 33.3 kJ/mol; H0 = 20.4 kJ/molat298 K (4)
The overall reaction is a reversible reaction while the forward
reaction can only happen at high temperature (Eq. 4) [16]. Usually,
increasing reaction temperature and decreasing pressure can facil-
itate the forward reaction of H2 S thermolysis reaction. However, it
is insufficient to offset the serious influence of the reverse reaction.
It is reported that only 14% of H2 S was converted into H2 and S at
1000 ◦ C, and further decrease of the reaction pressure can slightly
improve it to 26% [17]. In practice, the timely separation of prod-
ucts from raw materials can promote the conversion of H2 S, but the
overall efficiency cannot be improved significantly.
Introduction of catalyst can dramatically decrease the activation
energy of this reaction and reduce the time to reach the equilibrium.
Among various catalysts (FeS, CoS, NiS, MoS2 , Al2 O3 , Fe2 O3 , V2 O5 )
[18,19], MoS2 shows a relatively good performance than other
4 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
materials. It is mentioned that 95% of H2 S can be converted into H2
and S with continuous extraction of products by MoS2 at 800 ◦ C [20].
To further facilitate the forward reaction, a microwave-assisted
method was introduced in recent years. In particular, microwave
can selectively accelerate the forward reaction (H2 S → H2 + S) at
a relatively low temperature, because of the polar property of H2 S
molecule (which can absorb microwave effectively) and non-polar
nature of the products H2 and Zhou’s group reported a catalytic
efficiency of 66.9% at 750 ◦ C for H2 S transformation in the presence
of microwave irradiation with CoS-MoS2 /␥-Al2 O3 catalyst [21].
Overall, thermolysis is a relatively facile and direct method com-
pared to most of techniques. However, due to the limitation of
inevitable reverse reaction as well as harsh requirements for heat
and products separation, thermolysis is restricted to some specific
areas.
2.3. Plasma technology
Plasma, which is regarded as the fourth existence form distinc-
tive from gas, liquid and solid state, was used to dissociate H2 S
as a result of its high-energy and non-equilibrium properties [22].
Plasma is usually produced in the capacitor by adjusting the voltage
between two electrode plates to the breakdown voltage. Generally,
plasma consists of numerous charged atoms, molecules and radi-
cals, and hence it is very unstable. Through atoms collision and
energy transfer, plasma can drive many reactions which are unfa-
vorable in normal conditions [22–25]. The active plasma can rapidly
react with H2 S, and H2 and S steam will be obtained in tail gas in
most of cases.
However, because different gas owns different dielectric
strength, the corresponding breakdown voltage varies so much.
Pure H2 S gas can hardly become conductive unless a very high
voltage is applied, which absolutely causes a high temperature in
reaction chamber [26]. Therefore, it results in a tremendous energy
consumption and obvious security risks. To low down the dielectric
strength of H2 S gas, additional carrier gas (N2 , O2 , and Ar) is mixed
with H2 S [27]. Although the diluted H2 S gas leads to a decrease
processing efficiency, the energy required to break down capacitor
is significantly decreased, and temperature of chamber can main-
tain at an accepted level (2000 ∼ 4000 ◦ C), which hence is called
non-thermal plasma [9,28].
Plasma is thought to have great potential in removal of H2 S
because of the low energy it requires. Usually, increasing the spe-
cific input energy and reaction time in the chamber can further
improve H2 S conversion rate. Nevertheless, H2 S has to be diluted in
advance, and plasma is hence not suitable for large-scale industrial
application.
2.4. Electrochemistry
Direct decomposition of H2 S was adopted in the early time
by electrochemistry technique (Eq. 5) [29,30]. Usually, reduction
reaction (hydrogen production) is conducted on cathode (Eq. 6).
Meanwhile, sulfide ions will migrate to the anode for oxidation
reaction (sulfur production, Eq. 7). However, the aggregation of sul-
fur can lead to serious passivation of anode. Hence, heat is applied in
electrochemical system to transfer solid sulfur into sulfur steam in
some cases, although there are some undesired secondary reactions
[29,30]. Besides, organic vapour (C6 H6 , C6 H5 CH3 , cycloparaffins) is
introduced in H2 S steam to take away S anchored on electrode [9].
Overallreaction : H2 S → H2 +S
Reductionreaction : H2 S + 2e− → H2 +S2−
Oxidationreaction : S2− −2e− → S
The indirect electrochemical decomposition of H2 S was then
developed with the introduction of specific redox couples (like
Fe3+ /Fe2+ [31], VO2 + /VO2+ [32], I3 − /I− [33] and etc.) as the inter-
mediate reaction relay. Taking Fe3+ /Fe2+ for instance, firstly the
oxidized species of the redox couple (Fe3+ ) would absorb and react
with H2 S to generate sulfur as a spontaneous occurred reaction (Eq.
8). Subsequently, the reduced species of the redox couple (Fe2+ ) is
oxidized during electrolysis on the anode (Eq. 9), and protons are
reduced to produce hydrogen on cathode (Eq. 10).
H2 Sabsorption : 2Fe3+ +H2 S = 2Fe2+ +2H+ +S (8)
2+ − 3+
Anode : 2Fe −2e = 2Fe (9)
+ −
Cathode : 2H +2e = H2 (10)
As indirect electrochemistry involves two steps, the reaction effi-
ciency was determined by both the H2 S absorption efficiency and
current density during electrolysis. In general, sulfur recovery of ∼
90% and high current density can be detected at 50 ∼ 60 ◦ C, which
indicates the mild operating conditions of this technique [34,35].
However, H2 S absorption and generation of S is mostly conducted
in solution, and it is troublesome in industry to separate sulfur from
the electrolyte solution.
2.5. Other methods
Learning from Bunsen Reaction, which is related to sulfur-iodine
thermochemical water-decomposition cycle, a new chemical
approach for H2 S conversion is proposed. Traditionally, Bunsen
Reaction realizes the thermal decomposition of water into H2 and
O2 with the assistance of intermediates of H2 SO4 and I2 ) [46].
Similarly, H2 can be obtained from HI while oxidation product is
changed to S (Eqs. 11–13) [47].
H2 S + H2 SO4 → S + SO2 +2H2 O (11)
2H2 O + I2 +SO2 → H2 SO4 +2HI (12)
2HI → H2 +I2 (13)
In addition, UV decomposition technique was also proposed in
some reports [48]. Linkous’s group reported a quantum yield of 27%
for H2 production by irradiation of sodium sulfide solution with a
low-pressure Hg lamp [49]. The wavelength of UV light is approx-
imately 253.7 nm. In sodium sulfide solution, plenty of HS− ions
can be detected due to the hydrolysis of sulfide ions. UV light with
high energy stimulates the production of HS− * and these radicals
can rapidly react with each other to form H2 and polysulfide (Eqs.
14 and 15).
HS− +h→ HS− ∗ (14)
− − − 2−
HS ∗ + HS → [(HS)2 ] ∗ → H2 +S2 (15)
2.6. Photocatalysis
Generally speaking, the above methods for H2 S removal is con-
tinuously explored and improved. In most cases, traditional energy
source input (thermal or electrical energy) is necessary to com-
plete the reaction. In contrast, photocatalysis is intriguing if solar
light could be used as the energy source to drive the conversion
of H2 S into H2 and S directly, especially in consideration that the
traditional energy source fossil fuels will exhaust in near future.
Since Fujishima and Honda reported the photocatalytic prop-
erties of TiO2 in 1972 [36], photocatalysis has attracted a great
number of attentions due to its particular potential to convert solar
(5)
energy into chemical energy directly, which is similar to photosyn-
(6) thesis in nature. Therefore, photocatalysis is also named as artificial
photosynthesis in some literatures [37,38]. Typically, when semi-
(7) conductor is illuminated by light with energy higher than its
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Fig. 1. Principle of photocatalytic splitting of H2 S over a photocatalyst.
bandgap, the electrons on its valence band (VB) can be excited to the
conduction band (CB) and participate in reduction reactions; corre-
spondingly, holes are generated on VB and participate in oxidation
reactions. Although photocatalytic technology cannot be industri-
alized for a large scale currently, it has become one of the most
promising techniques with the profound significance for sustain-
able green chemistry. Works related to photocatalysis have been
intensively reported in the fields of hydrogen and oxygen produc-
tion from water splitting, dye degradation as well as CO2 reduction
[39,40].
Earlier reports concerning photocatalytic conversion of H2 S
were conducted in 1980s [41], with Na2 S aqueous solution as a
substitute of H2 S. Currently, various kinds of photocatalysts were
reported for conversion of H2 S. In the following, we will discuss the
factors that influence the reaction efficiency, strategies to enhance
the efficiency and examples of how photocatalytic conversion of
H2 S are fulfilled in detail.
3. Design strategy of photocatalysts for conversion of H2 S
3.1. Thermodynamic requirement
Thermodynamically, the mostly concerned H2 S splitting reac-
tion (Eq. 4) is an uphill reaction because of positive change in Gibbs
free energy (G0 = 33.3 kJ/mol at 298 K). However, the cleavage of
H2 S is much easier than that of H2 O (G0 = 237.2 kJ/mol) [52–54].
The principle of photocatalytic H2 S splitting is shown in Fig. 1.
When the semiconductor is irradiated by photons with sufficient
energy equal or larger than its bandgap (Eg ), the electrons can be
excited from the VB to the CB of the semiconductor (Eq. 16). These
electrons on the CB further transfer to the surface of the semicon-
ductor and reduces protons into hydrogen (Eq. 17), and holes on the
VB oxidizes sulfide into elemental sulfur (Eq. 18), which altogether
realize the cleavage of H2 S into H2 and S [43–45].
Photocatalyst+h→ h+ VB +e− CB
+ − 0
2H +2e → H2 (g)E = 0V
+ + 0 tion, mobility and lifetime of the charge carriers, but also narrow
H2 S + 2h → S + 2H E = 0.14V
Only when the redox potentials of the redox reaction lie between
the CB and VB edge of semiconductors, can surface reduction and
oxidation reactions be driven by the photogenerated e− and h+ ,
respectively. For H2 S splitting, the CB edge of a photocatalyst must
be more negative than that of H2 generation (H+ /H2 , 0 V vs. NHE),
and the VB edge must be more positive than that required for S
generation (S/H2 S, 0.14 V vs. NHE). Therefore, the thermodynamic
driving force in photocatalytic processes is strongly dependent on
5
the relative relationships between the CB/VB potential of the semi-
conductor photocatalysts used. The band levels for some important
semiconductor materials are shows in Fig. 2.
Generally, most semiconductors possess sufficient negative CB
potentials and positive VB potentials for realizing the H2 S split-
ting into H2 and S. Photocatalysts such as TiO2 , ZnO, MnS, In2 S3 ,
CdS, ZnS, ZnIn2 S4 and so on, are promising candidates for H2 S
removal. The more negative CB edge is, the larger driving force
for the proton reduction; similarly, the more positive VB edge is,
the larger driving force for the sulfide oxidation. However, semi-
conductors with more negative CB and more positive VB levels
generally possess much wider bandgaps, which will significantly
reduce the utilization efficiency of visible light in solar spectrum
(which accounts for about 43 % of solar energy), thus leading to
the lower solar energy conversion efficiency [55–57]. Such con-
tradiction between the redox abilities (determined by the CB/VB
levels) and absorption ability of visible light (determined by the
value of bandgaps) should be carefully balanced in the development
of effective visible-light-responded photocatalysts. In special, the
CB of sulfide photocatalysts is always composed of d and sp orbitals
of metal, while the VB is consisted of S 3p orbitals, which are much
more negative than O 2p orbitals. This not only makes the CB posi-
tion of sulfide semiconductors negative enough to reduce H2 S to
H2 , but also endows the bandgap of sulfide semiconductors narrow
enough with good response to the solar spectrum [43–45,58,59].
Hence, metal sulfide semiconductors are promising photocatalyst
for H2 S splitting.
3.2. Influencing factors and optimization strategy
Many factors can affect the photocatalytic efficiency for H2 S
conversion. Similar to all photocatalytic reactions, the photocat-
alytic H2 S conversion reaction involves three major steps: (i) solar
light harvesting, (ii) charge separation and migration, and (iii)
photocatalytic reaction on catalysts surfaces (surface reduction
and oxidation reactions). Therefore, the overall photocatalytic effi-
ciency is strongly dependent on the cumulative effects of these
three consecutive steps, which can be expressed by Eq. 19:
c =abs ×cst ×cu (19)
where c is the overall solar energy conversion efficiency, abs is the
light absorption efficiency, cst is charge migration and separation
efficiency, and cu is the charge utilization efficiency from photo-
catalytic reactions [60]. Therefore, any decrease in the efficiency
at each stage will decrease the overall photocatalytic efficiency. To
boost the photocatalytic efficiency, a series of methodologies have
been proposed according to the three aspects, such as band gap
engineering, micro/nano engineering, interface engineering, crys-
tal facet engineering and so on.
3.2.1. Bandgap engineering
The bandgap structure of photocatalysts can be manipulated
by various strategies, such as doping [61,62], defect engineering
(16)
[63,64], and formation of solid solution [65,66]. These strategies
(17) not only adjust the electronic properties, such as the concentra-
(18)
the bandgap of photocatalysts and make them active under visible
light irradiation.
Doping: Proper dopants can not only significantly enhance the
absorption of solar light owing to the formation of localized or delo-
calized electronic states, but also promote the separation efficiency
of photo-induced electron-hole pairs. Therefore, doping with metal
cations, non-metal anions or non-metal elements has been exten-
sively studied in the fields of photocatalytic during the past few
decades [61,62].
6 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Fig. 2. Relationship between band structure of semiconductor and redox potentials of H2 S splitting.
Fig. 3. Diffuse reflection spectra of (CuIn)x Zn2(1-x) S2 solid solutions; the values of
x are (a) 0, (b) 0.01, (c) 0.03, (d) 0.05, (e) 0.09, (f) 0.14, (g) 0.22, (h) 0.5, and (i) 1.
Samples were heat-treated in a quartz ampule tube at 1123 K [65].
Defect engineering: The defects have been confirmed to play
important role during photocatalytic reaction processes. Through
various defects engineering, the intrinsic properties of the semicon-
ductor materials such as microstructure, electronic structure, atom
coordination number, carrier concentration, or electrical conduc-
tivity can be adjusted [63,64].
Formation of solid solution: Both the bandgap and position of
CB and VB can be adjusted by varying the ratio of the compositions
of the narrow and the wide bandgap semiconductor in the solid
solution. For example, Kudo et al. reported that the controllable
band structure can be realized by (CuIn)x Zn2(1- x ) S2 solid solution
[65], as shown in Fig. 3. Over the past decades, various other
multi-component solid solutions, such as (CuIn)x Cd2(1-x) S2 [67],
Cd0.1 Snx -Zn0.9-2x S [68], Cdx Zn1-x In2 S4 [58], (Zn0.95 Cu0.05 )1-x Cdx S
[69], Cdx Cuy Zn1-x-y S [70], and so on have been extensively studied
as well.
3.2.2. Micro/nano engineering
The micro/nano architecture of photocatalyst can also strongly
influence the sunlight harvesting ability, charge separation and
migration efficiency, and catalytic reaction on surface of semicon-
ductors.
For sunlight harvesting ability, a flat-surfaced catalyst reflects
and scatters light into one direction, whereas for a rough catalyst
surface scattering occurs in all three directions (Fig. 4a-b) [71,72].
When small particles with a rough surface are suspended and illu-
minated with light, absorption can occur from all sides including
the scattered light, which strongly increases the light-absorption
and -harvesting efficiency (Fig. 4c). In addition, some morphologies
of the photocatalyst, such as hollow micro- and nanostructures, can
also trap the incident light, which increases the extent of reflection
and scattering, and enhance the light-harvesting efficiency.
For charge separation and migration, the advantages of hol-
low nanostructures for charge separation and transport mainly
include two aspects: 1) a thin shell of the hollow nanostructure
largely reduces the migration distance of photoexcited charge car-
riers; and 2) the directed charge separation and transfer through
the construction of hollow-nanostructures on their inner and outer
surfaces [57,73,74]. Therefore, the photocatalytic performance can
be influenced by the special micro/nano engineering.
For surface catalytic reaction, the benefits of micro/nano-
structures over surface reactions are obvious: 1) materials possess
a large surface area for reactions; and 2) the multilevel structure
can realize the separation of reaction species.
3.2.3. Interface engineering
In recent years, the interface engineering was widely applied as
one of the most promising ways for realizing highly efficient pho-
tocatalysis, because the photocatalytic process can be significantly
influenced by enhancing the solar light response and promoting the
separation of photo-induced electrons and holes due to the forma-
tion of the built-in electric field. Many strategies were proposed
to construct the interface structure such as co-catalyst loading,
semiconductor combination, and so on [60,75,76].
Co-catalyst decoration: Depositing metal particles (or single-
atom) on the surface of a photocatalyst forms either Schottky
barrier or Ohmic contact, depending on the work function of the
metals and the Fermi level of the semiconductor [77,78]. For exam-
ple, noble metal Pt nanoparticles typically form Schottky barriers
with most semiconductors and extract electrons from the semicon-
ductor to generate H2 . Correspondingly, the withdrawal of holes is
usually achieved by metal oxides or sulfides that donate electrons
into the VB of the semiconductor [79]. By this way, electrons or
holes in photocatalyst can be effectively separated.
Semiconductor combination: heterojunctions and homojunc-
tions could be formed by semiconductor combination [80,81]. The
fabrication of semiconductor heterojunctions is an important strat-
egy to enhance the photocatalytic performance as the separation
efficiency of e− -h+ pairs and solar light harvesting ability can
be simultaneously improved. Basically, four different heterojunc-
tions have been mainly investigated: type-II heterojunctions, p-n
heterojunctions, Z-scheme heterojunctions, and semiconductor-
graphene (SC-graphene) heterojunctions [66]. Compared with
heterojunction composed by two different materials, homojunc-
tion fabricated by materials with identical composition or crystal
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Fig. 4. Reflection and scattering paths on (a) a flat catalyst surface, (b) a rough catalyst surface, and (c) dispersed catalyst particles [71].
Fig. 5. SEM images of BiVO4 with deposited Pt (a) and MnOx (b) [95].
structure can provide continuity of band bonding and accelerate
the charge transfer across the interface more efficiently [82,83]. For
instance, commercial P25 (the combination of anatase and rutile
TiO2 ) displayed enhanced photocatalytic performance compared
to the pure anatase and rutile TiO2 due to the formation of homo-
junction [84].
3.2.4. Crystal facet engineering
Crystal facet engineering of semiconductors has become an
important strategy for fine-tuning the physicochemical properties
and thus optimizing the activity of photocatalysts. Among them,
the reactive facets engineering [85–87] and surface junction con-
struction [88,89] have been confirmed as most promising strategy
for realizing efficient crystal facet regulation.
Reactive facets engineering: Reactive facets engineering of
semiconductors is an important strategy for optimizing the pho-
tocatalytic activity of photocatalysts, because surface atomic
arrangement and coordination environment intrinsically deter-
mines the adsorption of reactant molecules, surface charge transfer
between photoexcited electrons and reactant molecules, and des-
orption of product molecules [90,91]. Typically, Yang and Lv et al.
developed a hydrothermal method to synthesize anatase TiO2 with
47 % of reactive high-energy {001} facets in 2008 [92], which is cru-
cial to the excellent photocatalytic performance [87]. Subsequently,
the facet engineering with highly exposed reactive facets became
an exciting direction for developing highly active photocatalysts
[93,94].
Surface junction construction: Photoexcited electrons and
holes may be driven to different crystal facets of the same semi-
conductors, which is crucial to the separation of photogenerated
charge carriers. Li et al. reported BiVO4 with co-exposed {010}
and {110} facets for the effective separation of photoinduced elec-
trons and holes [95]. The electrons and holes migrate to the {010}
and {110} facet, respectively, resulting in their spatial separation.
This is experimentally confirmed by the preferable deposition of
Pt cocatalyst and MnOx cocatalyst on the {010} facet by reduc-
tion and {110} facet by oxidation (Fig. 5), respectively. Accordingly,
the as-prepared photocatalyst exhibited a high photocatalytic
activity for water oxidation. Surface junction construction hence
becomes a novel strategy to improve the activity of photocata-
lyst.
7
4. Photocatalytic conversion of H2 S in various media
In this Section, we will present some typical work for photocat-
alytic conversion of H2 S case by case. Examples are categorized by
mainly the reaction media. Firstly, reaction occurred in gas phase
and processes related to the ad-desorption will be simply reviewed
and then we will primarily focus on the reaction occurred in solu-
tion, with the reduction of H2 S to H2 mainly discussed. Meanwhile,
typical reactors for photodecomposition of H2 S will also be men-
tioned. And later we will discuss the recovery of elemental S from
H2 S separately in the next section.
4.1. Gas-phase photocatalytic conversion of H2 S
Studies on photocatalytic conversion of H2 S in gas-phase by far
is limited and TiO2 was the most studied photocatalyst. In 1992,
Naman pointed out that under light irradiation, the conversion
of H2 S to H2 was increased by 45 % and activation energy has
decreased more than 50 % in the presence of TiO2 [96]. Later, Jardim
et al. reported that the existence of oxygen in the feeding gas is nec-
essary for effective removal of H2 S with low concentration (250
ppm) under illumination of black-light lamp, which could reach 99
% after 30 min of irradiation [97]. However, when the concentration
of H2 S increased (600 ppm), deactivation of TiO2 occurred, which
may be caused by the accumulation of product SO4 2− on the cata-
lyst. Neither H2 nor S was suggested as the products in this system.
Similar result that oxygen is necessary for photocatalytic oxidation
of H2 S was also presented by Jin and Yang when using the mix-
ture of CH4 , N2 , and H2 S as the feeding gas, but they found out that
the deposition of elemental sulfur was the main reason for deac-
tivation of TiO2 and further illumination of the deactivated TiO2
in the absence of H2 S could regenerate the photocatalyst [98]. By
in-situ Fourier transformed infrared (FT-IR) techniques, Anderson
confirmed the photocatalytic oxidation of H2 S into SO4 2− without
noticeable gaseous SO2 in the presence of TiO2 under ambient con-
ditions, with UV light below 330 nm being cut off and the tempera-
ture of the catalyst surface well controlled at 50 ◦ C by a heating tape
[99]. Furthermore, Sano pointed out deposition of Ag nanoparticle
on TiO2 film (0.67 wt‰) could improve the conversion of H2 S into
SO4 2− by 7 times under UV light irradiation from a black light bulb,
with the irradiation intensity of 2.0 mW/cm2 at the photocatalyst
surface. Ag mainly functions as the cocatalyst in the system [100].
8 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
In 2007, Sanchez and Portela has compared poly(ethylene
terephthalate) (PET), cellulose acetate (CA) and borosilicate glass as
the different supports for TiO2 to decompose H2 S [101]. It turns out
that PET is a better support than CA on account of the activity and
stability, and it can compete with borosilicate glass with a larger
volume. SO4 2− and SO2 was detected as the oxidation products.
They deduce that after the strong adsorption sites on TiO2 are satu-
rated with initial product, volatile SO2 will be released due to their
weak interaction with TiO2 . An optimal humidity was set at ca. 20
RH% for photooxidation of H2 S, which is balanced by disadvantage
from competition of H2 O adsorption on reaction site and advan-
tage by generation of active hydroxyl radicals. Later, they further
studied the mechanism of H2 S oxidation and pointed out that the
combination of TiO2 with adsorbent SiMgOx as the support could
reduce the release of SO2 and prolong the lifetime of photocatalyst
at the same time. In addition, regeneration of photocatalyst could be
realized by rinsing with water, and basic KOH solution could even
promote the activity by possible formation of basic sites [102]. In
2008, TiO2 impregnated with M-MCM-41 (M = Ce and Cr) molecu-
lar sieves was studied for photooxidation of H2 S. Incorporation of
Cr is beneficial for improving the activity of the catalyst under visi-
ble light irradiation and reducing the generation of SO2 byproduct,
but reduction of Cr6+ to Cr3+ during the process gradually induces
the deactivation of the sample. By contrast, no positive effects were
observed when Ce was incorporated into the system [103].
Keller has systematically studied the influence of the photo-
catalyst weight, the total flow rate, the relative humidity, the
temperature and the light irradiance on the photocatalytic oxi-
dation of H2 S by TiO2 [104]. On contrary to earlier studies, they
discovered that the H2 S conversion rate decreased with the relative
humidity. Even the internal layers of TiO2 that are not illuminated
by light could adsorb SO2 and retard its release and a higher sur-
face density of TiO2 is beneficial for H2 S conversion. After long time
irradiation, the saturated product sulfate could react with photo-
generated holes to yield sulfate radical, which finally causes the
complete conversion of sulfate into SO2 . Ti4+ was suggested to
be the active site for oxidation of H2 S and photogenerated holes,
sulfhydryl radicals (HS·) or hydroxyl radicals (OH·) are the active
species.
The photocatalytic activity of anatase and rutile (two most
importantly studied crystal phase of TiO2 in photocatalysis) for
conversion of H2 S was compared by Sopyan as well. Adsorption
of H2 S on anatase is weaker than that on rutile, but the final con-
version efficiency on anatase is still 1.5 times higher than that on
rutile [105]. Similarly, the different adsorption sites of H2 S and
interactions between H2 S and photocatalysts could affect the reac-
tion process. Based on the density functional theory (DFT), the
adsorption and reaction of molecule H2 S on rutile and anatase TiO2
surfaces have been investigated. For the adsorption of H2 S, the Ti5c
site was reported to be the favorable adsorption site on the rutile
and anatase TiO2 (110) surfaces [106,107], while Shahzada et al.
[108] demonstrated that O3c was the most stable adsorption sites
for H2 S. This may be caused by the different configurations used
in the calculations. Furthermore, Shahzada et al. pointed out four
factors to affect the adsorption of H2 S molecules: H2 S coverage,
presence of S, existence of oxygen vacancy and hydroxyl group
[108]. In special, we found that the presence of oxygen vacancy has
a pronounced influence on the adsorption of H2 S. Moreover, H2 S
splitting becomes much easier with the help of oxygen vacancies
because of the dissociation adsorption of H2 S on the defect TiO2
surface [109]. Given that the existence of oxygen vacancies could
also enhance the adsorption of visible-light [110], the introduction
of oxygen vacancies is a promising way to improve the performance
of TiO2 for H2 production from H2 S.
The adsorption and decomposition of H2 S on (0001) and (10 1
0) surfaces of photocatalyst ZnO have been investigated, too [111].
Fig. 6. Schematic diagram of the external side (a) and top (b) views of the multi-
channel photocatalytic reactor for gas-phase photoconversion of H2 S [117].
The bonding mechanism of H2 S on the ZnO (0001) surface involved
the donation of charge from the “s lone pairs” from S atom into
the surface and the back donation of surface electrons to H2 S.
Electrons played an important role in H2 S splitting. H2 S was dis-
sociatively adsorbed on the ZnO (0001) surface to generate HS−
and H+ species with no activation energy and high exothermic-
ity. Moreover, H2 could be easily generated with small activation
energy (3.99 kcal/mol) on the ZnO (0001) surface. In addition, dis-
sociative adsorption of H2 S was also found on the ZnO (10 1 0)
surface [112–115]. However, the final product of H2 S dissociation
was preferentially H2 O rather than H2 on the ZnO (10 1 0) surface
[114]. Similarly, oxygen vacancies could promote the dissociation
of H2 S to some extent because dissociated S atom was easier to
deposit on the oxygen-deficient ZnO (10 1 0) surface than that on
the perfect surface from a thermodynamic point of view [112].
In addition to TiO2 , natural iron-containing materials like mont-
morillonite in the iron form (FeMM) and shale were studied for
conversion of concentrated H2 S under UV and solar light irradia-
tion, and the activity is directly related to the content of Fe in the
catalyst [116]. To further figure out the potential of other photo-
catalysts for H2 S removal, Li et al. has systematically investigated
a series of catalysts including commercial TiO2 , CdS, ZnS, ZnO, and
ZnIn2 S4 . With their home-made five-channel reactor, the input H2 S
gas could react with photocatalyst thoroughly (Fig. 6) [117]. In an
anaerobic environment (5 % H2 S in Ar), ZnS outperforms all other
photocatalysts for evolution of H2 under Xe lamp irradiation. Intro-
duction of Cu into ZnS (Cu-ZnS) could significantly enhances the
efficiency to 80 ␮mol h−1 g−1 . Notably, CdS barely evolve H2 in
such gas-phase reaction, though it is widely recognized as an effi-
cient photocatalyst in liquid-phase reaction (see below). Oxidation
products in the system were not studied in detail, but they pointed
out that extraction of S is possible in the absence of oxygen. More-
over, dissociation of H2 S into H2 and S is carefully studied from
the thermodynamic point of view by Shamim et al. and an exergy
efficiency of smaller than 1 % was achieved with the present-of-art
photocatalyst Cu-ZnS with a quantum yield of 3.7 % [16].
The gas-phase photocatalytic H2 S conversion mechanism have
been widely investigated. In general, the generation of e− - h+ pairs
through light irradiation of suitable wavelength is the first step of
the photocatalytic H2 S splitting reaction (Eq. 16). Simultaneously,
H2 S molecules undergo mass transferring from the bulk of the gas
phase to the photocatalyst and are subsequently adsorbed on its
surface (Eq. 20). Under anhydrous circumstance, H2 Sads molecules
are directly oxidized by the photo-generated holes to yield sul-
fur (Eq. 21) which thereafter reacts with the prevalent oxygen
molecules to form SO2 gas (Eq. 22) [103].
H2 Sgas → H2 Sads (20)
+
H2 Sads +2h → Sads +H2 (21)
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Sads +O2 → SO2ads
For the surface with rich −OH groups, such as TiO2 -based cata-
lysts, −OH can be oxidized by photo-generated holes to OH species
(Eq. 23) by which H2 S molecules are directly oxidized into SO2 (Eq.
24) [118,119].
•
−OH + 2h+ → OH
+
H2 Sads +4OH → SO2ads +2H +2H2 Oads
Besides, Canela et al. and Kato et al. have proposed the mechanism
of complete oxidation of H2 S to sulfate under humid condition (Eqs.
25–29) [97,100]. In these works, elemental sulfur was not detected
by FTIR and XPS analysis, while the presence of SO4 2− on the surface
of catalyst was confirmed [97]. Here, the generation of SO4 2− can
be explained by two different pathways, through oxidation of H2 S
by OH· produced from H2 O (OH− ) and h+ (Eqs. 25–27), or by H2 O2
originated from O2 and H+ (Eqs. 28–29).
• H2 S in pure ethanolamine solution differs from that in aqueous
h+ +H2 O → OH +H+
+ −
h +OH → OH
2− +
H2 S + 8OH → SO4 +2H +4H2 O
− +
O2 +2e +2H → H2 O2
2− +
H2 S + 4H2 O2 → SO4 +2H +4H2 O
4.2. Liquid-phase photocatalytic conversion of H2 S
In contrast to that in gas phase, photoconversion of H2 S in liquid
phase is more popular, which may be caused by several reasons: (i)
the adsorption of H2 S by liquid reagents (basic aqueous solution
or ethanolamine) is a widely accepted strategy to collect H2 S gas
in both academia and industry; (ii) the removal of H2 S with higher
concentration and smaller volume can be fulfilled more easily in the
liquid phase with compared to gas phase system due to the high
concentration of H2 S achieved by solution adsorption. Concentra-
tion of H2 S in solution could be quantified in a unit of mmol/mL,
while that in gas phase is often in the ppm level; (iii) photocatalyst
usually needs to be fixed on a special thin-film in the gas phase
reaction, and photocatalysts in solution often existed in the form
of suspension under vigorous stirring, which probably allows the
latter to interact with the substrate and participate the reaction
thoroughly; and (iv) consequently, higher photocatalytic H2 S con-
version performance could be achieved in the liquid phase reaction
than that in gas phase.
According to the different reaction media, these systems can be
further divided into three categories: (I) ethanolamine system, (II)
hydroxide system and (III) sulfite system. It should be noted that for
safety and convenience, Na2 S aqueous solution (in the presence or
absence of Na2 SO3 ) are widely as a substitute for the source of H2 S
for evolution of hydrogen in liquid phase, too [120–129]. By con-
trast, direct introduction of H2 S gas into the reaction system could
not only provide sulfide ions, but also adjust the pH of the sys-
tem simultaneously, which is a very important factor to determine
the efficiency of H2 evolution. Due to the limitation of this review,
systems with Na2 S as the substitute of H2 S are briefly introduced
in Table 1 without detailed discussion here and people can refer
to some other reviews for relevant reports [55,58,60,71,130–132].
We here mainly discuss the above mentioned three categories here
below with H2 S directly introduced.
4.2.1. Ethanolamine system
Benefited from its alkalinity and low cost, ethanolamine is
extensively used as an efficient adsorbent of H2 S gas in petrochem-
ical industry [11]. Accordingly, ethanolamine was directly adopted
as the reaction medium for H2 S conversion. Naman et al. obtained
9
(22) H2 form dissolved H2 S in the aqueous solutions of ethanolamine
(20%, monoethanolamine (MEA), diethanolamine (DEA) and tri-
ethanolamine (TEA)) [133,134]. Initially, Vx Sy was used as the
visible-light responsive photocatalysts. It turns out that MEA has a
higher photocatalytic H2 S splitting performance and is more stable
than DEA and TEA, which are assigned to that MEA has the lowest
(23) molecular weight and hence greatest carrying ability for acidic H2 S
on the basis of weight or volume. Later, TiO2 , CdSe and CdS were
(24) tried as well, and aqueous solution of DEA is proved to be better
reaction medium at room temperature. But at high temperature
(60 ◦ C), MEA was still better than DEA and TEA for TiO2 and CdSe.
Similarly, the photocatalytic conversion of H2 S was also per-
formed with Pt modified CdS as the photocatalyst in pure
ethanolamine solution by Li et al. [135]. However, the highest
activity was observed for DEA and the average hydrogen produc-
tion activity can be as high as 44.64 mmol g−1 h−1 , as shown
in Fig. 7a. This result implies that the photocatalytic removal of
(25) ethanolamine solution. Control experiments show that hydroxyl
(26) group of the ethanolamine is crucial for hydrogen production. As
shown in Fig. 7b, the oxidation process can be roughly divided into
(27) three steps: (1) diffusion of sulfide ions from bulk solution to the
CdS surface, (2) photo-oxidation of sulfide ions to polysulfide ions
(28)
by holes on CdS, and (3) diffusion of polysulfide ions from the CdS
(29) surface to bulk solution. Diffusion of sulfide or polysulfide ions dur-
ing the oxidation process is proved as the rate-determining step
(RDS) in the photocatalytic decomposition of H2 S, which provides a
clue for further improvement of the photocatalytic H2 S conversion
performance. More importantly, H2 S can be split stoichiometrically
into H2 and S under visible light irradiation using ethanolamine as
the H2 S absorbent and reaction medium at room temperature.
In addition, the photocatalytic mechanism in ethanolamine
solution was studied. H2 S firstly reacts with DEA to form HS− and
HDEA+ (Eq. 30), which is then oxidized by holes and reduced by
electrons to yield Sn 2− and H2 with recovery of DEA, respectively
(Eqs. 31–32) [135]. Raman spectra and electrochemical analysis
confirmed that the produced sulfur existed as Sn 2− after pho-
tocatalytic reaction, which is attributed to a free-radical-related
one-electron oxidation process in the H2 S–DEA solution (Eq. 33).
The sulfhydryl radicals (HS·) readily produces polysulfide ions
(Sn 2− ) or polysulfide radicals (Sn − ) by deprotonation and/or dimer-
ization in basic H2 S-DEA solution [136], rather than producing
elemental sulfur.
H2 S + DEA → HS− +HDEA+ (30)
+ − 2- +
2h +HS → Sn +H (31)
− +
2e +2HDEA → H2 +2DEA (32)
− −
HS → HS + e (33)
4.2.2. Hydroxide system
Although ethanolamine can effectively adsorb H2 S for liquid
phase photocatalyic reaction, the high viscosity of ethanolamine
may be not conducive to the diffusion of reactant during reaction.
Alternatively, hydroxide solution like KOH and NaOH aque-
ous solution was used as reaction media for H2 S processing.
Under such circumstance, metal oxides (TiO2 [137], FeGaO3
[138], CuGa2 O4 [139], PbCrO4 [140]), metal sulfides (CdS [141],
Bi2 S3 [142], CdIn2 S4 [143], ZnIn2 S4 [144]) and metal phosphates
(Ag3 PO4 ) [145] has been reported as the photocatalysts. For exam-
ple, Kale et al. reported that TiO2 -based semiconductors has
realized high-efficiency H2 S decomposition in KOH solution, as
shown in Fig. 8a-b. The N doped TiO2 (N-TiO2 ) marigold flower
nanostructures shows a remarkable photocatalytic H2 produc-
tion performance (8.80 mmol g−1 h−1 ) from H2 S waste, owing
to its high surface area and excellent sunlight response [146].
 10
Table 1
Photocatalytic H2 production in the different reaction systems.

M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Photocatalyst Light source Aqueous reaction solution pH value Cocatalyst/H2 Catalyst mass (g) Year Quantum yield (%) Ref.
activity (mmol· h −1 )

CdS/ZnS:Ag 900-W Xe 0.24 M Na2 S+0.35 M Na2 SO3 13.2 Pt/16.3839 0.4 1986 37 at 450 nm [120]
CdS 300-W Xe, ␭>420 nm 0.5 M Na2 S+0.5 M Na2 SO3 13.6 Pt–PdS/8.77 0.3 2009 93 at 420 nm [121]
ZnS-In2 S3 -CuS 300-W Xe, ␭>420 nm 0.1 M Na2 S+1.2 M Na2 SO3 – 3.6 0.01 2010 22.6 at 420 nm [122]
ZnIn2 S4 300-W Xe, ␭>420 nm 0.43 M Na2 S+0.5 M Na2 SO3 – MoS2 /0.153 0.05 2014 – [123]
Cd0.5 Zn0.5 S Visible light, ␭ ≥ 430 nm 0.35 M Na2 S+0.25 M Na2 SO3 12.87 NiSx /4.2 0.1 2016 65 at 425 nm [125]
MoS2 -graphene/ZnIn2 S4 300-W Xe, ␭>420 nm 0.25 M Na2 S+0.25 M Na2 SO3 – 0.21 0.05 2016 – [124]
P-doped CdS NRs 280-W Xe, ␭>420 nm 1.0 M Na2 S+1.0 M Na2 SO3 – 0.19 0.001 2017 > 7.90 at 420 nm [127]
Mnx Cd1-x S 300-W Xe, ␭>420 nm 0.1 M Na2 S+0.1 M Na2 SO3 – NiS/0.42 0.05 2017 5.21 at 420 nm [126]
CDs-CdS 350-W Xe, ␭>420 nm 0.25 M Na2 S+0.35 M Na2 SO3 13.56 NiS/0.14 0.1 2018 – [128]
Znx Cd1-x S 300-W Xe, ␭>420 nm 0.35 Na2 S+0.25 M Na2 SO3 – NiS/0.84 0.05 2018 – [129]
VS 100-W Iod H2 S+20% MEA 10.5 0.124 0.015 1994 – [133]
CdS 300-W Xe, ␭>420 nm H2 S + DEA – Pt/1.19 0.025 2008 30 at 420 nm [135]
ZnBiVO4 450-W Hg, ␭>325 nm H2 S+0.5 M KOH 8.5 5.48 1 2005 – [157]
CdS/TiO2 500-W Hg, ␭ ≥ 420 nm H2 S+1 M NaOH 7.96 Pt/0.98 0.1 2007 – [150]
RuO2 /Pb2 Ga2 Nb2 O10 450-W Xe, ␭ ≥ 420 nm H2 S+0.5 M KOH 8.5 4.28 0.5 2008 17.2 at 430 nm [158]
NiOx /FeGaO3 450-W Xe, ␭ ≥ 420 nm H2 S+0.5 M KOH – 2.94 0.5 2008 9.3 at 550 nm [158]
ZnBiGaO4 450-W Xe, ␭ ≥ 420 nm H2 S+0.5 M KOH – 3.02 0.5 2010 – [159]

CdIn2 S4 450-W Xe, ␭ ≥ 420 nm H2S+0.5 M KOH – 3.48 0.5 2006 17.1 at 550 nm [143]
Q-CdS–glass powder 450-W Xe, ␭ ≥ 420 nm H2 S+0.5 M KOH 8.5 3.57 0.5 2007 17.5 at 470 nm [141]
CdLa2 S4 450-W Xe, ␭ ≥ 420 nm H2 S+0.5 M KOH – 2.55 0.5 2011 11.6 [148]
CdIn2 S4 300-W Xe, ␭ ≥ 420 nm H2 S+0.5 M KOH – 3.24 0.5 2011 – [147]
ZnIn2 S4 300-W Xe, ␭ ≥ 420 nm H2 S+0.5 M KOH – 5.29 0.5 2011 – [144]
N-TiO2 300-W Xe, ␭ > 420 nm H2 S+0.25 M KOH – 2.2 0.5 2013 – [146]
Bismuth QDs–glass nanocomposites 450-W Xe, ␭ > 420 nm H2 S+0.5 M KOH – 5.77 0.5 2013 – [160]
6,13-Pentacenequinone 300-W Xe, ␭>420 nm H2 S+0.25 M KOH – 2.42 0.5 2014 6.8 [149]
Bi2 S3 normal solar light H2 S+0.5 M KOH – 4.44 0.5 2014 – [142]
N-TiO2 /Graphene 300-W Xe H2 S+0.25 M KOH – 5.94 0.2 2015 – [137]
Ag3 PO4 300-W Xe, ␭ > 420 nm H2 S+0.5 M KOH – 3.92 1 2016 5.51 [145]
H2 S+0.1 M Na2 S+0.6 M Na2 SO3 0.029 34.5 at 450 nm
0.1 M Na2 S+0.6 M Na2 SO3 +0.35 M KHC8 H4 O4 0
MnS/In2 S3 300-W Xe, ␭ ≥ 420 nm 7.5-8.0 0.0025 2017 –
[45]
0.1 M Na2 S+0.6 M Na2 SO3 +0.35 M HCl 0
0.1 M Na2 S+0.6 M Na2 SO3 +0.16 M H2 SO4 0.0004
In2 S3 /CuS 300-W Xe, ␭ ≥ 420 nm H2 S+0.1 M Na2 S+0.6 M Na2 SO3 7.5-8.0 0.037 0.0025 2018 9.2 at 420 nm [152]
Cdx In1-x S 300-W Xe, ␭ ≥ 420 nm H2 S+0.1 M Na2 S+0.6 M Na2 SO3 7.5-8.0 0.041 0.0025 2019 26.7 at 420 nm [43]
MnS/(Inx Cu1-x )2 S 300-W Xe, ␭ ≥ 420 nm H2 S+0.1 M Na2 S+0.6 M Na2 SO3 7.5-8.0 0.073 0.0025 2019 65.2 at 420 nm [44]
MnS/In2 S3 /PdS 300-W Xe, ␭ ≥ 420 nm H2 S+0.1 M Na2 S+0.6 M Na2 SO3 7.5-8.0 0.057 0.0025 2019 34.1 at 400 nm [155]
MnS/In2 S3 -MoS2 300-W Xe, ␭ ≥ 420 nm H2 S+0.1 M Na2 S+0.6 M Na2 SO3 7.5-8.0 0.124 0.0025 2019 72 at 400 nm [156]
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339 11

Fig. 7. a) Photocatalytic H2 production under visible light irradiation over Pt/CdS (0.20 wt % Pt) in different solutions. DEA: diethanolamine, TEA: triethanolamine, MEA:
monoethanolamine. Reaction conditions: volume of solution, 100 ml; concentration of H2 S, 0.30 M; amount of catalyst, 0.025 g; reaction temperature, 30 ◦ C; light source,
300 W Xe lamp with a cutoff filter (␭ > 420 nm); b) Photocatalytic process of H2 S splitting in DEA [135].

Fig. 8. Schematic presentation of a) the formation of N–TiO2 spheres and marigold flowers; b) N–TiO2 sphere and marigold flower with its photocatalytic phenomenon; c)
Time verses volume of H2 evolution of N-TiO2 /Gr composites. d) photocatalytic mechanism of N-TiO2 /Gr composite [137,146].

To further improve the photocatalytic ability, N-TiO2 /Graphene
(Gr) composites were successfully prepared by a facile in-situ wet
chemical method, which shows excellent photocatalytic activity
(29.71 mmol g−1 h−1 ) for the hydrogen production under solar light
irradiation (Fig. 8c) [137]. A suitable mechanism of the catalytic pro-
cess is proposed (Fig. 8d) and the enhancement of photocatalytic
activity was attributed to N doping as well as high specific surface
area and good charge carrier separation ability of graphene. These
studies are crucial to understand the H2 S splitting process in the
hydroxide solution.
Metal sulfides are also widely studied in the hydroxide
solution. Kale et al. reported the fabrication of Bi2 S3 single-
crystalline nanorods and hierarchical nanostructures by a simple
one-pot solvothermal method, as shown in Fig. 9a-c [142]. The
maximum hydrogen evolution rate (8.88 mmol g−1 h−1 ) was
obtained using hierarchical nanostructured Bi2 S3 . The hierar-
chical nanostructure suppresses charge carrier recombination
resulted from defects, which is ultimately responsible for the
higher activity (Fig. 9d). Additionally, some ternary chalco-
genide, such as CdIn2 S4 [147], CdLa2 S4 [148], ZnIn2 S4 [144] have
been utilized to realize photodecomposition of H2 S. As a typ-
ical example, the ZnIn2 S4 was successfully constructed by a
facile reaction-surfactant-controlling strategy (Fig. 9e) [144]. The
possible growth mechanism of ZnIn2 S4 was shown in Fig. 9f.
As a result, the ZnIn2 S4 nanoplate exhibits a highest visible-
light photocatalytic H2 evolution activity (10.57 mmol g−1 h−1 ),
which is attributed to the high crystalline and special morphol-
ogy.
In addition, the organic semiconductor 6,13-pentacenequinone
(PQ) is also proved to be suitable photocatalysts for H2 S conver-
sion. PQ with good crystallinity was obtained by single step solvent
free solid-state reaction at room temperature (Fig. 10a), and the
as-prepared PQ exhibited superior photocatalytic H2 production
performance (48.48 mmol g−1 h−1 ), which is the highest one under
the visible-light irradiation in the hydroxide solution for H2 S split-
ting (cf. Fig.10b and Table 1). Such a high activity is mainly ascribed
12 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339

Fig. 9. SEM images of the Bi2 S3 samples prepared by the solvothermal method at 150 ◦ with different solvents: a) water, 24 h (S1); b) water–ethylene glycol (EG) (1: 3),
24 h (S2); and c) water–EG (1: 3) 30 h (S3); d) hydrogen evolution using S1, S2 and S3 for H2 S decomposition; e) XRD patterns of ZnIn2 S4 synthesized without surfactant
triethanolamine (TEA), and with TEA of 0.005 mol, 0.01 mol and 0.015 mol (from bottom to top); f) schematic illustration of the possible growth mechanism of ZnIn2 S4
[142,144].

Fig. 10. a) XRD pattern of 6,13-pentacenequinone; b) time dependent H2 evolution by 6,13-pentacenequinone for photodecomposition of H2 S; c) photocatalytic process of
decomposition H2 S over 6,13-pentacenequinone in the hydroxide solution [149].
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Fig. 11. Mass spectra of gases produced from photocatalytic H2 evolution from H2 S
dissolved in (A) H2 O as the baseline case, (B) D2 O, (C) 1 M NaOH/D2 O. Catalysts:
CdS(bulk)/TiO2 composite (0.1 g loaded 1 wt% Pt), light source: Hg-arc lamp (450
W) equipped with UV cut-off filter (␭ > 420 nm) [150].
to the delocalized ␲ electron system of PQ, which can effectively
absorb sunlight, generate and transport charge carriers (Fig. 10c)
[149].
Recently, Lee et al. investigated the photocatalytic mecha-
nism of H2 S splitting by the isotope experiment with D2 O as
the solvent [150]. As shown in Fig. 11, the produced gas was
mainly H2 (90%) even in the environment populated predomi-
nately with deuterium. Therefore, it can be concluded that H2
gas produced from the system H2 S dissolved in D2 O mainly
comes from H2 S (90%) and D2 from D2 O is a minor component
(10%). However, after introduction of NaOH, the main hydrogen
source (90%) come from D2 O in the system of H2 S/NaOH/D2 O,
and H2 S contributes about 10 % for the evolved H2 . Consider-
ing the dominant presence of D2 O in the solution relative to H2 S
(55.5:1), it can be concluded that, unlike in pure water, both
H2 S and D2 O become hydrogen sources in H2 S/NaOH/D2 O sys-
tem. In the presence of a strong base, hydroxyl ion reacts with
H2 S to generate and H2 O and sulfide ion (Eq. 34), which is fur-
ther oxidized by the photogenerated holes on the surface of
the photocatalyst (Eq. 35). Meanwhile, photogenerated electrons
reduce H2 O to H2 (Eq. 36):
− 2−
H2 S + 2OH → S +2H2 O (34)
2− +
S +2h → S (35)
2H2 O + 2e− → H2 +2OH− (36)
Because H2 O in the reaction (Eq. 36) could be either the one formed
via the reaction (Eq. 34) or the one present initially in the reaction
solution, this mechanism predicts both H2 S and H2 O as hydrogen
sources. Note that the concentration of OH− is preserved through
the above reactions (Eqs. 34 and 36). Such a mechanism is consis-
tent with the isotope experiment results in the presence of NaOH.
In contrast, in the absence of the strong base, H2 S directly disso-
ciates to HS− and H+ (Eq. 37). HS− is oxidized by holes to sulfur
(Eq. 38), while H+ is reduced by photoelectrons to H2 (Eq. 39). This
mechanism predicts H2 S as the sole source of hydrogen. Water
could be involved through the reaction (Eq. 39), but its effect should
be insignificant due to the low concentration of proton in neutral
water.
H2 S → HS− +H+ (37)
13
2h+ +HS− → S0 +H+ (38)
− +
2e +2H → H2 DDD (39)
Devices for the liquid-phase photocatalytic conversion of H2 S in
hydroxide solution are also explored. For instance, Preethi et al has
constructed specific photocatalytic reactor for H2 S splitting (Fig. 12)
[151]. This photocatalytic reactor of 500 mL was irradiated with a
pen-type tungsten halogen lamp. The reactor has two tubes, one
for purging with N2 gas and the other for collecting H2 gas. In a
typical experiment, 400 mL of 0.5 M aqueous KOH was vigorously
stirred and purged with H2 S and N2 for 1 h and then with bubbling
H2 S gas for 1 h (sulfide concentration 16 g/L). Then 0.2 g of the cat-
alyst was added and H2 S was bubbled at a flow rate of 2.5 mL/min,
with excess gas trapped in NaOH solution. The aqueous slurry was
irradiated with visible light and the evolved H2 was collected in a
water displacement jar and was analyzed by gas chromatograph
(GC).
In summary, H2 production from H2 S decomposition can be eas-
ily realized by using hydroxide solution as the reaction medium.
Nevertheless, the low photostability is a major obstacle due to the
severe photo-corrosion in hydroxide medium, which restricts its
wide application. Moreover, current studies mainly focus on the
efficiency of H2 production in hydroxide systems; whether H2 and
S (or the related oxidative products) are yielded in stoichiometric
ratio is not discussed.
4.2.3. Sulfite system
Recently, a series of studies have been published with sulfite and
sulfide-containing (Na2 S/Na2 SO3 ) solution as the reaction medium
for photocatalytic H2 production from H2 S [43–45,152–154]. In
specific, Na2 S/Na2 SO3 solution plays three roles in improving the
photocatalytic performance of H2 S splitting: (i) Providing suffi-
cient HS− ions for the photocatalytic reaction as absorbent (Eq.
40); (ii) promoting the separation of photo-generated electrons
and holes as electron donors (Eqs. 41,42 and 45); (iii) improving
the long-term stability of catalysts, because SO3 2- can prevent the
formation of yellow solid S or S2 2- (Eqs. 43 and 44), which has been
proved by the formation of S2 O3 2- detected by the S 2p XPS spectra
of MnS/In2 S3 composite after photocatalysis [45]. These benefits
make Na2 S/Na2 SO3 solution a good reaction medium for H2 S con-
version.
H2 S + OH− ↔ HS− +H2 O (40)
2− + 2−
2S +2h VB → S2 (41)
HS− +2h+ VB → H+ +S (42)
SO3 2− +S2 2− → S2 O3 2- +S2− (43)
S + SO3 2− → S2 O3 2− (44)
SO3 2− +S2- +2h+ VB → S2 O3 2− (45)
A series of metal sulfide based photocatalysts have been explored
and investigated for achieving excellent H2 S splitting performance
in Na2 S/Na2 SO3 solution. We discovered that the metastable state
␥-MnS showed better photocatalytic H2 evolution performance
(23.38 ␮mol g−1 h−1 ) than the stable ␣-MnS (4.24 ␮mol g−1 h−1 )
under visible light irradiation (␭ > 420 nm) due to the special
wurtzite structure (Fig. 13a-b) [153]. In addition, bismuth sulfide
(Bi2 S3 ) film with a special rod-like morphology was also used for
H2 S splitting (Fig. 13c-d) [154]. However, these single-phase metal
sulfides as photocatalysts suffer from low photocatalytic efficiency
due to the poor solar light absorption and fast recombination rate
of photo-generated excitons.
In 2017, our group reported a novel MnS/In2 S3 heterojunction
with Z-scheme by the simple solvothermal method for the first
time (Fig. 14a-b) [45]. It was found that MnS/In2 S3 composites
14 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339

Fig. 12. Schematic diagram showing liquid-phase photocatalytic reactor for H2 production from H2 S absorbed in hydroxide solution [151].

Fig. 13. a) XRD patterns of MnS sample; b) photocatalytic H2 production by MnS; c) UV–vis absorption spectra of ␤-Bi2 O3 , Bi2 S3 -6 h, Bi2 S3 -24 h and Bi2 S3 -48 h; d) photocatalytic
H2 production under light irradiation over different Bi2 S3 samples [153,154].

are very active for visible light driven photocatalytic H2 produc-
tion from H2 S. The photocatalytic activity is strongly related to
their compositions. A maximum H2 production rate of 8.36 mmol
g−1 h−1 was achieved over MnS/In2 S3 with a molar ratio of 7/3,
which was approximately 360 times higher than that of bare ␥-MnS
and 50 times higher than that of ␤-In2 S3 alone. The correspond-
ing quantum yield reaches 34.2% at 450 nm in the absence of any
noble-metal co-catalysts. The reaction system exhibits outstanding
long-term stability, which is assigned to the stability of MnS/In2 S3
itself and the Na2 S/Na2 SO3 reaction medium. The optimized con-
centration of H2 S for H2 production was determined as 3 M in this
system.
The photocatalytic activity and stability of the MnS/In2 S3 het-
erojunction can be further improved and novel MnS/(Inx Cu1-x )2 S3
composites were successfully fabricated via a “Solid solution-
Heterojunction” strategy [44]. Benefited from the synergistic effect
of solid solution and heterojunction, MnS/(Inx Cu1-x )2 S3 compos-
ites exhibit excellent sunlight response up to 599 nm and superior
charge separation and transfer efficiency. As a result, a maximum
H2 production rate of 29.25 mmol h−1 g−1 under visible-light irra-
diation (␭ > 420 nm) is obtained (Fig. 14c-d), which was 3.5 times
higher than that of the pristine MnS/In2 S3 (8.36 mmol h−1 g−1 ) and
1400 times higher than that over the CuS (0.021 mmol h−1 g−1 )
alone. The corresponding quantum yield at 420 and 450 nm was
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Fig. 14. Comparison of the visible-light photocatalytic activity of MnS/In2 S3 samples; b) photocatalytic process of H2 S splitting over MnS/In2 S3 composite in 0.6 M Na2 SO3
/ 0.1 M Na2 S / 3 M H2 S solution; c) photocatalytic H2 production over MnS/(Inx Cu1-x )2 S3 (MIC) samples under visible-light irradiation (␭ > 420 nm); d) recycling test over
MIC1.2 for hydrogen production [44,45].
65.2% and 62.6%, respectively. Notably, the existence of Cu could
promote desorption of sulfur from the surface of photocatalyst and
hence avoid the block of active sites on surface, which is crucial to
the long-term photostability of the system.
As the existence of Cu plays crucial roles to promote the photo-
conversion of H2 S, In2 S3 /CuS composite was also constructed [152].
It turns out that In2 S3 /CuS composite exhibited higher H2 evo-
lution rate (14.95 mmol g−1 h−1 ) with comparison to MnS/In2 S3
composites (8.36 mmol g−1 h−1 ). Existence of Cu in the compos-
ite can promote the absorption of sunlight and the separation of
photo-generated excitons (Fig. 15a-b).
Cdx In1-x S solid solutions were also constructed by Energy-Band-
Controlling strategy performed for H2 S splitting [43]. Visible-light
response range of Cdx In1-x S could be orderly tuned from 550 to 600
nm with simultaneous changes of CB and VB position (Fig. 15c).
The optimized Cdx In1-x S solid solution exhibits outstanding long-
term stability for at least 15 h and a remarkable H2 production rate
of 16.35 mmol g−1 h−1 under visible light irradiation. The corre-
sponding quantum efficiency at 420 nm is 26.7 %. The combination
of experiments and DFT calculation confirms that the formation of
Cdx In1-x S solid solution has three advantages for H2 S splitting: (i)
mitigating the photocorrosion of CdS-based catalytsts, (ii) promot-
ing the further oxidation of sulfur adsorbed on the catalyst surface,
and (iii) enhancing the charge-separation efficiency.
Furthermore, introduction of cocatalyst were also adopted to
boost the H2 production efficiency for photoconversion of H2 S. Typ-
ically, PdS and MoS2 has been loaded on MnS/In2 S3 composites. In
special, highly dispersed PdS is found preferably loaded on In2 S3 of
MnS/In2 S3 through chemical Pd-S-In bond and it is beneficial for
hole extraction from In2 S3 [155]. The as-obtained MnS/In2 S3 /PdS
exhibited a remarkable hydrogen production rate of 22.7 mmol g−1
h−1 with an apparent quantum yield of 34.1% at 395 nm (Fig. 16a-b).
Meanwhile, due to the corrosion-resistant nature of PdS in H2 S-rich
reaction medium, MnS/In2 S3 /PdS present good stability as well.
Correspondingly, to realized effective extraction of photogenerated
electrons, MnS/In2 S3 /MoS2 composite was also prepared by defect-
induced growth strategy [156]. The composite shows a superior
photocatalytic H2 evolution activity (49.56 mmol g−1 h−1 ), which
15
is almost 4.5 times higher than that of the MnS/In2 S3 composite
(Fig. 16c). The corresponding apparent quantum efficiency at 400
nm is as high as 72% (Fig. 16d), which is so far the highest among
all non-noble-metal photocatalysts for visible-light-driven photo-
catalytic H2 S splitting. MoS2 with rich unsaturated-sulfur-edge can
selectively grow on the MnS of MnS/In2 S3 composites, resulting in
the formation of a typical double-interface-structure. Accordingly,
the enhanced photocatalytic performance was mainly ascribed to
its efficient charge separation ability and abundant exposed edges.
In summary, the sulfite involved (Na2 S/Na2 SO3 ) system could
be more suitable for excellent photocatalytic H2 production from
H2 S in contrast to ethanolamine system and hydroxide system. To
date, the highest visible-light-driven photocatalytic H2 evolution
rate from H2 S splitting is realized over MnS/In2 S3 /MoS2 compos-
ite (49.56 mmol g−1 h−1 , see Table 1). However, sulfur stored in
H2 S is not reclaimed during photocatalysis in the sulfite medium,
and conversion of H2 S to produce H2 and S simultaneously is more
desirable.
5. Extraction of sulfur in H2 S by photocatalysis-related
methods
5.1. Particulate/homogeneous catalytic system
Most reports on the photocatalytic conversion of H2 S in Sec-
tion 4 only focused on the collection of hydrogen energy, while the
extraction of sulfur product is ignored. However, elemental sulfur
is also a very important industrial precursor to many other chem-
icals such as sulfuric acid. Notably, sulfur is still mainly produced
from petroleum and natural gas in industry, by Claus process, as we
mentioned in Section 1.2. Therefore, during the process of devel-
oping new technology for green and efficient utilization of H2 S,
extraction of sulfur must be seriously considered and well realized.
Only under this premise can Claus process be possibly replaced in
industry.
Unfortunately, separation of elemental sulfur could be
extremely difficult in the particulate photocatalytic system for H2 S
splitting in liquid phase, as sulfur and photocatalysts both dis-
16 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339

Fig. 15. a) Long time stability test of In2 S3 /CuS composite for photocatalytic H2 evolution from H2 S; b) photocatalytic process of H2 S splitting over In2 S3 /CuS composites
under visible light irradiation; c) the energy band structure of Cdx In1-x S solid solutions and photocatalytic H2 evolution from H2 S in Na2 SO3 /Na2 S/H2 S solution [43,152].

Fig. 16. a) Photocatalytic H2 production over MnS/In2 S3 /PdS (MI-Pd) under visible light irradiation (␭ > 420 nm); b) long-term performance over MI-Pd 1.5 % for photocatalytic
H2 S splitting; c) photocatalytic H2 production over all MnS/In2 S3 /MoS2 (MI-M) samples under visible light irradiation (␭ > 420 nm); d) wavelength-dependent apparent
quantum yield of photocatalytic H2 evolution over MI-M4.5 together with its UV–vis diffuse reflectance spectra (DRS) [155,156].

perse in the system in powder form after reaction. Moreover, the
accumulation of sulfur in the system would significantly decrease
the activity of photocatalyst due to light shielding effect from
yellow sulfur and the blocking of active sites on photocatalyst.
Consequently, in particulate photocatalytic system, sulfite is often
introduced to react with the initial oxidative product elemental sul-
fur, which has been demonstrated in Section 4.2.3. That’s also the
reason why extraction of sulfur is barely studied in these systems.
Using CdS/Pt as the photocatalyst, Linkous et al. studied the
possibility to recover sulfur by taking advantage of the easy-
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Fig. 17. a–c) Three kinds of typical PEC cells with photoanode a), photocathode b) and c) both photoanode and photocathode; d) band-bending of n-type semiconductors in
PEC cell before and after light illumination [163–165].
decomposition nature of thiosulfate and polysulfide under acidic
conditions and the acidic property of H2 S itself (Eqs. 46 and 47)
[161].
− −
S2 O2−
3 + H2 S → S + HS + HSO3 pH < 4.2
− in the system.
S2−
2 + H2 S → S + 2HS pH < 10
According to the configuration of the author, photocatalytic reac-
tion fluid in the photoreactor are pumped to the other reactor to
encounter H2 S and recover sulfur, and fresh reaction solution is
pumped into photoreactor all the time. Therefore, colloidal photo-
catalyst is better immobilized in the photoreactor. It is worth noting
that acid titration experiment shows that sulfur was generated
by decomposition of thiosulfate only when the pH of the system
was smaller than 4.2. However, photocatalytic test indicated that
CdS/Pt could barely evolve hydrogen under light illumination at
pH 4. In contrast, sulfur was released from polysulfide when the
pH of system was lowered to 10; at this pH, CdS/Pt maintained a
good activity for hydrogen evolution. Such results urge us to recon-
sider the necessity to introduce SO3 2− for recovery of sulfur: though
SO3 2− are often introduced into sulfide related photocatalytic sys-
tems to interact with sulfur and avoid the generation of yellowish
polysulfide ions (which would compete with CdS for visible light
and hence decreases the light utilization of the photocatalyst), it
is hard to regenerate sulfur from the as-obtained thiosulfate under
the photocatalytic conditions. The author further pointed out that
if the depth of solution in the photoreactor is smaller enough (for
example, 0.1 cm), the formation of polysulfide is acceptable. In addi-
tion, development of photocatalyst which mainly response visible
light in the region that would not be absorbed by yellowish poly-
sulfide may also be a choice.
In spite of the difficulty to recovery sulfur in colloidal solu-
tions, homogeneous system to directly split H2 S into H2 and S
was reported recently [162]. Nickel complex based octahedral cage
(Ni-TFT) could function as the catalyst for hydrogen evolution;
meanwhile, it could encapsulate neutral molecular photosensi-
tizer fluorescein (FL). After light absorption, oxidative quenching
of excited FL and subsequent hydrogen evolution occurs inside the
cage, while recovery of oxidized FL (water soluble) to neutral by
electron donor S2− occurs outside the cage; elemental sulfur was
generated by further bubbling H2 S into the system and lowering
17
the pH of the system. In contrast, without the formation of the cage,
reductive quenching is the dominant process and no elemental sul-
fur could be obtained. Nevertheless, the author didn’t give further
detailed information on how the host-guest chemistry could pro-
(46) mote the extraction of sulfur and whether polysulfide was avoided
(47)
5.2. Photoelectrochemical (PEC)/Photovoltaic electrochemical
(PV-EC) cell
In contrast to particulate photocatalyst in solution system, in
photoelectrochemical (PEC) cells, oxidation of H2 S and reduction
of H2 S occurred at the anode and cathode separately; this would
facilitate the separation of the products, especially for S from
the particulate photocatalyst. Moreover, additional bias could be
exerted into the system if necessary, which could help overcome
the overpotential for H2 S splitting.
5.2.1. Brief introduction of PEC cells
In specific, PEC cells are similar to electrolytic cells but the bias
could be partially or totally provided by semiconductors under
light illumination. To some extent, the particulate photocatalyst
dispersed in water could also be considered as a short-circuit PEC
cells, in which oxidative and reductive reaction occurred together
on photocatalyst. Typically, there are three kinds of PEC cells
(Fig. 17a–c): single photoanode (usually n-type semiconductors),
single photocathode (usually p-type semiconductors), and pho-
toanode and photocathode tandem cells. In these cells, physics of
semiconductor/liquid contacts is of great importance, which is the
prerequisite to build an effective cells: band bending of semicon-
ductor occurs after it is brought into contact with the electrolyte,
due to the different Fermi levels of redox couple in solution and
semiconductor [163,164].
Taken n-type semiconductor for example, when there’s no con-
tact between the semiconductor and the electrolyte solution, the
CB and VB of semiconductor keep flat and no charge flow occurs
(Fig. 17d) [165]. When they come into touch, electrons flow from
the semiconductor to the solution as the original Fermi level of
semiconductor is more negative than that of the redox couple; dur-
ing this process, built-in electric field is formed. Such a process
continues until the built-in electric field potential could counteract
18 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339

the potential energy barrier from the Fermi level of the two before
their contact; equilibrium has hence been reached. As the elec-
trons of n-type semiconductor near the solid/solution junction are
depleted, a depletion layer is formed and the energy band near the
junction shift upwards. The built-in electric field could further drive
the minority charge carrier holes to migrate to the surface/liquid
junction and consequently oxidative reactions occur on the surface
of n-type semiconductor; meanwhile the majority charge carrier
electrons flows to the back of the electrode and further to the cath-
ode through the external circuit, where reductive reaction happens.
Therefore, it is minority charge carriers that participate in the sur-
face redox reaction on the semiconductor side.
Under light illumination, the concentration of electrons in the
CB and holes in the VB increases; consequently, band bending at
the junction is alleviated due to the movement of photogenerated
Fig. 18. Conversion efficiency of light to chemical energy (䊏), electrical energy (䊉)
electrons and holes driven by the built-in electric field. Meanwhile,
and total energy () as a function of cell voltage [167].
the single Fermi level of the semiconductor at the junction splits
into separate quasi-Fermi levels for holes and electrons. In n-type
therefore decrease the efficiency of the cell. Unfortunately, sulfur
semiconductors, the quasi-Fermi level for electrons are almost kept
could only precipitate out after polysulfide reaches its solubility
the same with the original Fermi level; nevertheless, quasi-Fermi
limit. Therefore, most of the elemental sulfur actually existed in
level for holes drops significantly. When there’s no net current in
polysulfide and was not completely extracted.
the PEC cell, the energy difference between the electron and hole
As mentioned in Section 5.1, sulfur can further precipitate out
quasi-Fermi level is the open-circuit voltage (VOC ) of the semicon-
by decreasing pH of the polysulfide solution. Studies shows that
ductor. Typical semiconductors used in PEC cells including TiO2 ,
a low S2− /S ratio in polysulfide is beneficial for the extraction of
Fe2 O3 , WO3 , BiVO4 and n-Si as photoanodes, and Cu2 O, InP and
elemental sulfur [168]. However, disproportion of polysulfide may
p-Si as photocathodes.
occur after the introduction of H2 S and S2− /S would increase (see
For traditional water splitting without external bias, photovolt-
Eqs. 49 and 50), which is not conducive for S precipitation.
age generated by semiconductors under light illumination must be
greater than 1.23 V plus the kinetic overpotentials for hydrogen H2 S + xSx+1 S2− + 2OH− → (x + 1) Sx S2− + 2H2 O (49)
reduction and oxygen evolution and other potential loss caused by
SH− + xSx+1 S2− + OH− → (x + 1) Sx S2− + H2 O (50)
a series of resistance across the cell [166]. This is the case for p-type
semiconductors as the photocathode, too. In tandem cells, the total Experiments was carried out accordingly in electrochemical cells
photovoltage is the sum of the two. In contrast, for photoconver- and it turns out that passing H2 S into the polysulfide solution does
sion of H2 S, the photovoltage is largely decreased, as the potential yield sulfur when the concentration of sulfur species in the solution
needed for H2 S splitting itself thermodynamically is much less (0.17 is suitable. When the concentration of total sulfur species is low, the
V). In addition, the overpotential for the anode reaction (oxidation disproportion of polysulfide may predominate. When the concen-
of sulfide) could be almost neglected in contrast to that of oxygen tration was high, the generated elemental sulfur is in a form of gel,
evolution. which are hardly to collect and polysulfide may be encapsulated as
well. At middle concentration (8−11 M) and a S2− /S ratio smaller
5.2.2. PEC cells for direct conversion of H2 S than 0.15 in polysulfide, crystalline sulfur could be extracted eas-
Early in 1980s, PEC cells for direct H2 S decomposition was built ily at room temperature. O2 gas, as an oxidant for polysulfide, was
based on chemically deposited CdSe films on Ti substrate as the passed into the system too; however, no sulfur was detected.
photoanode [167]. H2 S gas was directly bubbled into 1 M solution Another problem for direct precipitation of sulfur from polysul-
of NaOH for 1 h. An open circuit photovoltage of 0.62 V and short fide is that during electrolysis process with constant potential (like
circuit photocurrent of 8.82 mA cm−2 was achieved. Polysulfide in PV-EC cells), when the polysulfide has a chain length larger than
was formed during the process, and sulfur could only precipitate 2, the anode current density will decrease significantly. However,
out from the system after polysulfide reaches its solubility limit. By in consideration that the subsequent extraction of sulfur from poly-
varying the external resistance between the cell terminals, differ- sulfide is in favor of long chain lengths, further oxidation of sulfide
ent amount of chemical energy or electrical energy can be stored must be carried out even at low current density.
through incident light conversion. The overall energy conversion
efficiency could be calculated by the following equation (Eq. 48): 5.2.3. PEC cells for indirect conversion of H2 S
More often than direct splitting of H2 S, indirect splitting of
(0.171I + IVcell )
ε (%) = × 100% (48) H2 S are usually adopted in PEC/PV-EC cells, in which redox couple
Wlight
are introduced to recover elemental sulfur by thermodynamically
in which 0.171I is the chemical energy stored considering the favorable reaction between the oxidative species and hydrogen sul-
splitting of H2 S into H2 and S, IVcell is the output electrical energy, fide. Such strategy is the same as indirect conversion of H2 S in
and Wlight is the input light energy. According to Fig. 18, the max- electrochemical cells (Section 2.4). Typically, the most widely used
imum light to chemical energy or electrical energy was 1.5% at 0 redox pairs are Fe3+ /Fe2+ and I− /I3 − (Table 2). Other species, like I-
V and 1.8% at 0.3 V, respectively; and the maximum total energy /IO3 - [33], VO2+ /VO2 + [32], H5 (PMo2 V Mo10 VI O40 ) /H3 (PMo12 VI O40 )
conversion efficiency reaches 2.85% at 0.275 V. The cells presented [52] and derivatives of Fe3+ /Fe2+ [169] are developed as well. On
good stability over 2 weeks, with a drop of short-circuit current less the one hand, the introduction of redox pairs could avoid the pas-
than 10%. In addition, the author pointed out that cation selective sivation of anode by sulfur from direct splitting of H2 S, in which
membrane between the anodes and cathodes is necessary to pre- organic solvent or a high temperature is used to extract sulfur. On
vent the migration of polysulfide from anode to cathode and hence the other hand, overoxidation of sulfide could be largely prevented.
compete with protons for reductive reaction. However, introduc- Recently, Li’s group has developed PEC cells for conversion of
tion of membrane could increase the cell internal resistance and H2 S with the assistance of redox couples (Fig. 19a) [170]. Func-
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Table 2
Standard reduction potential of typical redox couples applied in indirect conversion of H2 S in electrochemical and photoelectrochemical cells.
Redox couple Standard Reduction Potential / V vs NHE
Fe3+ /Fe2+ 0.77
I3 − /I− 0.53
IO3 − /I− * 0.26
VO2 + /VO2+ 0.99
*Note: The reduction potential of this redox couple is obtained under basic condition.
Fig. 19. Schematic illustration of a) photoelectrochemical (PEC)-chemical loop for H2 S conversion on a p-type photocathode linked with redox couples (A/A+ ), b) the selective
production of H2 O2 and S from O2 and H2 S on n-type photoanode, and c) simultaneous extraction of S and degradation of CBZ with the assistance of I− /I3 − and Fe3+ /Fe2+ on
photoanode-based PEC cells [170–172].
tionalized p-type Si and n-type Si was used in the cells as the
photocathode and photoanode, respectively. Long-term stability is
still a big challenge for the cell. Under optimal conditions, a sat-
uration photocurrent of 24 mA cm−2 was achieved at an applied
potential of 0 V vs. RHE. At a potential of 0.2 V, the cathodic pho-
tocurrent kept quite stable within 3 h. H2 evolved from the system
measured by GC is quite close to the calculation amount according
to the photocurrent; however, the amount of Fe3+ or I− generated
from the system (detected by UV–vis absorption analysis) is only
80% of the theoretical value, and the reason behind is still unclear.
Besides of the redox couple (Fe3+ /Fe2+ or I3 − /I− ) in the
anode side, they further introduced an additional redox cou-
ple anthraquinone/anthrahydroquinone (AQ/H2 AQ) in the cathode
compartment (Fig. 19b) [171]. Thermodynamically, the reduction
of AQ to H2 AQ (0.25 vs NHE) could be carried out more easily than
hydrogen evolution, and experiments confirms that reduction of
AQ to H2 AQ, instead of proton reduction, occurred exclusively in
the PEC cell. H2 AQ could further react with O2 in the air to regener-
ate AQ and H2 O2 is obtained. Meanwhile, I− is oxidized into I3 − on
the anode. The photon energy absorbed by the photoelectrode was
stored simultaneously in the form of H2 AQ and I3 − . They further
react with O2 or H2 S spontaneously and hence the net reaction of
the PEC becomes (Eq. 51):
H2 S + O2 → S + H2 O2 (51)
Still, modified p-Si and n-Si was studied as the photoanode or
photocathode, respectively. The author pointed out that p-Si pho-
tocathode didn’t work well at zero bias, which may be attributed
to the inefficient oxidation power of the photogenerated holes.
Instead, modified n-Si exhibit a photocurrent of ca. 8 mA cm−2
when carbon plate was used as the counter electrode under unbi-
ased condition. In consideration of the energy stored in the form
of H2 AQ and I3 − , the solar-to-chemical conversion (STC) efficiency
of the system is calculated to be 1.1%. Nevertheless, it should be
pointed out that for the net reaction, the STC efficiency should be
much lower due to the energy loss in the spontaneous reaction.
Similarly, Li and Lam et al. has proposed a novel PEC sulfur
recovery process coupled with electrochemical oxidation of organic
pollutant carbamazepine (CBZ) (Fig. 19c) [172]. Carbon paper with
directly brushed titanium oxide (TiO2 ) powder was used as the
photoanode and bare carbon paper was used as the cathode. For
19
Reaction with H2 S for S extraction
H2 S + 2Fe3+ → S ↓ +2Fe2+ + 2H+
H2 S + I−
3
→ S ↓ +3I− + 2H+
3H2 S + IO−
3
→ 3S ↓ +3H2 O + I−
H2 S + 2VO+2
+ 2H+ → S ↓ +2VO2+ + 2H2 O
recovery of sulfur, I− /I3 − redox couple was used, while Fe3+ /Fe2+
was introduced to promote the oxidation of CBZ. Nafion membrane
was used to separate the anodic and cathodic chamber. Though
reaction between Fe3+ and I− is thermodynamically favorable in the
dark, more efficient interplay between I− /I3 − and Fe3+ /Fe2+ couples
was observed under light illumination. H2 S was bubbled into the
anodic chamber to mediate the precipitation of sulfur. The author
pointed out that I− /I3 − couple in the system played triple roles in
favoring S recovery: (i) more efficient removal of S2- , (ii) mitiga-
tion of electrode fouling with sulfur nanoparticle mainly formed
in the bulk solution, and (iii) production of higher-purity S with
less overoxidation into SO3 2− /SO4 2− species. Similarly, oxidation
of CBZ was also promoted in the presence of Fe3+ /Fe2+ couples in
the cathodic chamber. However, the overall efficiency of the system
was not clearly presented and stability of the system in long-term
operation were not evaluated in this system.
Besides of single photoanode and photocathode, tandem PEC
cells was also introduced by Zhou et al. in 2017 (Fig. 20a) [53]. WO3
nanoplate and Pt-decorated Si photovoltaic cell Pt/Si PVC were cho-
sen as the photoanode and photocathode. Similarly, I− /I3 − couple
was used for extraction of sulfur after H2 S was bubbled into cell and
H2 SO4 was used as the anode electrolyte. Due to mismatched Fermi
levels of the two electrodes, self-driven PEC cells were achieved.
VOC of the cell gradually increased with the increased concentra-
tion of KI in the solution and it reaches 0.36 V at a KI concentration
of 0.2 M, which is close to the theoretical value of the system (0.53
V). Faraday efficiency for H2 was calculated to be 99% and light
energy conversion efficiency was estimated to be 0.56. Potential
risks of further oxidation of S into SO4 2− existed, if it is not filtered
out from the system in time. Notably, a constant generation rate of
H2 and S with stoichiometric ratio was maintained over 7 h in this
PEC cell.
Furthermore, they have constructed self-biased photoanode
with WO3 as the front photoanode for indirect collection of S from
H2 S in the existence of I− /I3 − , and commercial Si cell as rear PVC
(Fig. 20b) [173]. A microporous gas diffusion electrode (GDE) com-
posed of graphite and nickel foam was introduced as the cathode
for direct oxygen reduction into H2 O2 . The total reaction is the same
as that presented in Eq. 51, which is a spontaneous reaction ther-
modynamically. However, no additional intermediate AQ/H2 AQ is
necessary due to the high efficiency of the GDE electrode. S and
20 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
Fig. 20. Schematic illustration of self-biased PEC system for a) conversion of H2 S for S and H2 recovery [53] and b) production of H2 O2 and S from O2 and H2 S [173].
Fig. 21. Schematic illustration of PV-EC for a) conversion of H2 S for S and H2 recovery and b) simultaneous extraction of S from H2 S and reduction of CO2 into CO [52,169].
H2 O2 could be generated at a rate of 0.60 and 0.08 mmol h−1 ,
respectively, and the author speculate the relative inefficiency for
H2 O2 production may be caused by the competitive reaction of oxy-
gen reduction into H2 O. In addition, electricity could be generated
in the system, and a maximum power density of 0.19 mW cm−2
was obtained.
5.2.4. PV-EC cells for conversion of H2 S
Recently, photovoltaic electrochemical (PV-EC) cell has received
increased interest: it can be viewed as the coupling of photovoltaic
solar cells with electrolytic cell. Compared with PEC cells, the
biggest advantage of PV-EC is a wider choice of electrode materi-
als. For the former cell, photoelectrodes should be semiconductors
which present suitable bandgap for effective light harvesting and
matched CB and VB position to drive the redox reaction. In addition,
photoelectrode should stand the long-term light illumination. But
these are not the limitations in PV-EC cells. Moreover, PV-EC cells is
more advantageous for H2 S splitting, in consideration that the out-
put voltage from PV cells demand for H2 S splitting is much lower
than that for water splitting and hence there are more choices for
PV cells, too. Besides, negative light filtration effect caused by the
absorption of polysulfide or mediator couples like Fe3+ /Fe2+ and
I3 − /I− in PEC cells for H2 S removal can also be avoided, as the elec-
trolytic cell is separated from the light absorption unit. However,
cost of the cells increases correspondingly.
Li’s group has first introduced CH3 NH3 PbI3 perovskite solar cells
based PV EC cell for H2 S conversion in 2016 (Fig. 21a) [52]. Using
molybdenum-tungsten phosphide (Mo-W-P) as the cathode cat-
alyst for hydrogen evolution reaction (HER) and graphite carbon
sheet as the anode for oxidation of redox mediator (Fe3+ /Fe2+ , or
H5 (PMo2 V Mo10 VI O40 )/H3 (PMo12 VI O40 ), a net STC efficiency of 3.5%
could be achieved. In particular, the solar-to-electric power con-
version efficiency (PCE) of the perovskite solar cell reaches 16.4%
with an VOC of 1.02 V, ISC of 21.58 mA cm−2 and fill factor (FF) of
0.745. After coupled with ECs, STC efficiency drops a little bit to
13.5%. Further bubbling of H2 S into the system yield a stoichio-
metric ratio of H2 and S, and STC efficiency decreases obviously
due to the chemical energy loss during the spontaneous reac-
tion between Fe3+ and H2 S. Though Nafion membrane was used
in the system, it is noticed that crossover of Fe3+ /Fe2+ through
the membrane to the cathode is serious. Therefore, large volume
and negatively charged H5 (PMo2 V Mo10 VI O40 ) /H3 (PMo12 VI O40 )
redox couple was introduced to alleviate the possible detrimen-
tal effect. Accordingly, the stability of the system has been greatly
improved while the efficiency of the system was mostly main-
tained.
PV-EC was further utilized to realize the simultaneous con-
version of CO2 and H2 S into CO and S from the point view of
exploitation of acid nature gas field (Fig. 21b) [169]. CO2 dissolved in
1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid with
a small amount of water was reduced to CO in the cathode com-
partment directly in the PV-EC, and a small amount of H2 could be
detected as well; meanwhile, ␣-sulfur, confirmed by XRD, was gen-
erated as yellowish precipitate in the presence of redox mediator in
the anode compartment after bubbling of H2 S. In this system, par-
tially reduced zinc oxide nanoparticles encapsulated by a graphene
layer (rZnO@G) was used as the cathode and graphene modified
commercial graphite carbon sheet (G/GCS) as the anode. In order
to avoid the serious crossover of Fe3+ /Fe2+ through Nafion mem-
brane and maintain the stability of the system in neutral and basic
conditions, EDTA-Fe3+ /EDTA-Fe2+ was used in the system. A single
three-junction commercial planar silicon solar cell with VOC of 1.72
V and PCE of 10.1% was used to drive the anode and cathode reac-
tion simultaneously, and a STC efficiency of 7.5% could be reached.
Notably, after simulated nature gas (Ar: CH4 : CO2 : H2 S 60: 20: 19:
1% v/v) was bubbled into the solar driven electrochemical system,
CO and S was obtained. This positive result has therefore provided
us a conceptually new avenue for conversion of negative value
waste product into value-added product during the exploitation
of acid natural gas.
 M. Dan, S. Yu, Y. Li et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 42 (2020) 100339
6. Conclusion and outlook
Though H2 S could be split more easily both thermodynamically
and dynamically than H2 O in photocatalysis, the gaseous nature of
H2 S at room temperature and the high toxicity of H2 S makes it dif-
ficult for wide-spread study. Security of the experiment should be
seriously considered and highly specialized lab equipment is neces-
sary for study. In addition, the corrosive nature of H2 S on apparatus
and poisonous effect of sulfide species on catalyst has further lim-
ited its study. Currently, photocatalytic disposal of H2 S are mainly
carried out in bench scale, few studies in pilot scale was reported,
let alone commercial scale.
Due to the higher conversion efficiency of H2 S in liquid phase
photocatalytic systems than that in gas-phase photocatalytic sys-
tems, photocatalytic splitting of H2 S in liquid phase are more
popular. In specific, in particulate photocatalytic liquid phase
systems, strategies for optimization of photocatalyst are mainly
inherited from that adopted in water splitting, with more concern
on sulfide semiconductors due to their superior response ability
to visible light in contrast to traditional oxides and their relative
stability in sulfur species-rich environment. Theoretical calcula-
tion based on first-principles could be helpful for rational design
of photocatalyst. Moreover, interaction mode between the catalyst
and H2 S could be modeled, and possible reaction mechanism for
H2 S conversion could be predicted.
Right now, attentions are mostly paid to boost the hydrogen
evolution efficiency in these systems, and there is much less con-
cern on the exact oxidative products of sulfide species. How to
extract elemental S from polysulfide or thiosulfate in particulate
photocatalyst based systems is still a big challenge and successful
examples in experiments are very limited. Besides, sulfur species
existed in the form of polysulfide or thiosulfate are still large threats
to environment.
In PEC cells, separation of sulfur from the reaction system
become easier. However, sulfur deposit on anode would passivate
the electrode and significantly decrease the efficiency in direct H2 S
splitting. Accordingly, indirect H2 S splitting was developed. With
the assistance of redox couple, H2 and S could be simultaneously
obtained without remarkable decrease of the current in the long
run, but we should be aware of the energy loss in the reaction
between the redox mediator and H2 S. For example, to make the
reaction between the oxidative species and H2 S occur thermody-
namically, the reduction potential of the redox couple must be more
positive than the reduction potential of H2 S to S (0.17 V). Therefore,
a higher power input is necessary for indirect splitting of H2 S. The
more positive value of the reduction potential of the redox cou-
ple, the higher energy is needed for the recovery of sulfur. Besides,
it was reported in earlier literatures that sulfur product was often
generated in a colloidal state for indirect splitting, and recrystal-
lization are often needed for purification [35]. Moreover, whether S
(or relevant oxidative products) is extracted in stoichiometric ratio
should also be considered in future studies.
In addition to H2 S conversion with H2 and elemental S as the
main product highlighted in this review, we can go further and
explore more possibilities of H2 S involved reactions. In natural gas
reservoir, CO2 is often separated simultaneous with H2 S by the cur-
rent separation process based on liquid absorbents alkanolamines.
As CO2 is the most important greenhouse gas and utilizing pho-
tocatalysis to convert CO2 into CO, CH4 or CH3 OH has gained
great interest in recent years, we can combine CO2 reduction and
H2 S oxidation together. Under such circumstances, carbon com-
pounds, instead of hydrogen was obtained. Initial attempts has
been reported, in which CO and S was successful detected as the
final products in PV-EC cells [169].
Besides of CO2 associated in natural gas, H2 S could also react
with the major component of natural gas, CH4 , to yield high value-
21
added chemicals carbon disulfide CS2 , which is mainly used for
the manufacture of viscose rayon and cellophane film as well as
chemical synthesis [174]. If the concentration of H2 S in natural gas
reserves is high, the reaction is viable and called as hydrogen sul-
fide reformation of methane (H2 SRM) [9,175]. During this process,
two molecules of H2 S react with one molecules of CH4 to yield 4
molecules of H2 and one molecule of CS2 (Eq. 52). Preliminary study
of this reaction has been carried out with thermal methods. But the
possibility of this reaction with photocatalytic technology has not
been explored yet.
2H2 S + CH4 → CS2 +4H2 (52)
As elemental S (approximately 85 %) is mainly converted to sulfuric
acid in industry, we can directly oxidize H2 S into H2 SO4 in the pres-
ence of water and oxygen. In fact, such a concept has been proposed
in thermochemical conversion of H2 S as H2 S-H2 O conversion cycle,
in which iodine and hydrogen iodide are involved and cycled [46].
Overall reaction was depicted as follows (Eq. 53):
H2 S + O2 + 2H2 O → H2 SO4 + 2H2 (53)
2−
Theoretically, oxidation of H2 S into SO4 is possible in photocatal-
ysis, if sulfide was firstly oxidized to elemental S (0.17 V), then to
SO2 (0.50 V) and finally to SO4 2− (0.17 V), and SO4 2− was indeed
detected in gas-phase based photocatalytic conversion of H2 S [99].
However, no relevant work is reported in liquid-phase based pho-
tocatalytic systems to the best of our knowledge, which may be
due to the fact that eight electrons are necessary to complete the
reaction in solution and many competitive side reactions occurs
instead.
Undeniably, conversion of H2 S with photocatalytic technology is
not ready for industrial uses and it can hardly replace the widely-
accepted Claus process in near future. However, with the call for
development of clean and renewable energy and high value-added
utilization of associated gas in the oilfield exploration worldwide,
photocatalytic conversion of H2 S will definitely gain more inter-
ests. More novel systems will be developed effectively and more
details will be revealed carefully in the reaction, which should bring
the real-life application of photocatalytic conversion of H2 S much
closer to fulfillment in the future.
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgements
This work was financially supported by National Natural Science
Foundation of China (U1862111 and U1232119), Sichuan Provincial
International Cooperation Project (2017HH0030), the Innovative
Research Team of Sichuan Province (2016TD0011), Open Fund (PLN
201802PLN201802, PLN201928) of State Key Laboratory of Oil and
Gas Reservoir Geology and Exploitation (Southwest Petroleum Uni-
versity), Open Fund of State Key Laboratory of Industrial Vent Gas
Reuse (SKLIVGR-SWPU-2020-05), and Graduate Student Scientific
Research Innovative Project of SWPU (2019cxzd009).
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