Highly value-added utilization of H2S in Na2SO3solution over Ca-CdS nanocrystal photocatalysts

Article abstract of DOI:10.1039/d0cc05894g

Alkaline-earth metal Ca2+ modified CdS nanocrystals have been designed for the first time for highly efficient H2 evolution from hydrogen sulfide (H2S) with Na2SO3 as a favourable reaction medium. The advantage of Na2SO3 was revealed by an electrochemical test, and the conversion of Na2SO3 during the reaction was carefully studied. Particularly, most of Na2SO3 was converted into Na2S2O3. Highly value-added utilization of waste H2S is therefore achieved via photocatalysis. This journal is

Full text of DOI:10.1039/d0cc05894g

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: S. Yu, F. Wu, P.
Zou, X. Fan, C. Duan, M. Dan, Z. Xie, Q. Zhang, F. Zhang, H. Zheng and Y. Zhou, Chem. Commun., 2020,
DOI: 10.1039/D0CC05894G.
Volume 54
Number
January 2018
Pages 1-112
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
1
4
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Page 1 of 5
Please d oC hn eo mt Ca do mj u ms t margins
View Article Online
DOI: 10.1039/D0CC05894G
COMMUNICATION
Highly value-added utilization of H S in Na SO solution over Ca-
2
2
3
CdS nanocrystals photocatalyst
Received 00th January 20xx,
Accepted 00th January 20xx
Shan Yu,†a,b Fan Wu, Pengkun Zou, Xiang-Bing Fan, Chao Duan, Meng Dan, Zhanghui Xie,b
†b
b
c
b
a,b
DOI: 10.1039/x0xx00000x
a,b
a,b
d
a,b
Qian Zhang, Fengying Zhang, Heng Zheng and Ying Zhou*
Alkaline-earth metal Ca2+ modified CdS nanocrystals are firstly intractable oxidation products that may prevent the continuously
2
-
designed for highly efficient H
S) with Na SO
was revealed by electrochemical test and conversion of Whereas, the photo-generated S will occupy the active sites and S
during the reaction was carefully studied. Particularly, will shield the visible light absorption of photocatalyst, which
2
evolution from hydrogen sulfide stable H
2
production. For example, S and S
n
are the main by-
8
(
Na
Na
H
2
2
3
as a favourable reaction medium. Advantage of products in hydroxide and ethanolamine system, respectively.
2
-
2
SO
SO
3
n
2
3
5
b,9
most of Na
2
SO
3
was converted into Na
2 2 3 2
S O . Highly value-added greatly inhibit the H evolution performance. More importantly,
utilization of wastes H
2
S is therefore achieved by photocatalysis.
complex oxidation products make it difficult to recover sulfur
resources, and few studies have been reported on this. Therefore, it
is necessary to select the suitable reaction medium to control the
final oxidation products for efficient hydrogen production and
recovery of sulfur-containing chemicals.
With continuous increasing of energy consumption over the past
years, high acidic oil and gas reservoirs have been gradually
performed to satisfy the growing requirement of global energy.
However, the generated wastes hydrogen sulfide (H
exploitation process are seriously toxic and corrosive. At present,
1
2
S) during the
It is noted that Na
SO
production. First, Na SO
sufficiently alkaline environment to absorb quite a few amount of
is widely applied in the system of H
2
3
2
2
10
2
3
aqueous solution can provide a
2
H S is primarily treated by Claus technology in industry wherein it is
partially oxidized to yield water and element sulfur (H
2
S + 1/2 O
2
→
H
2
S. More importantly, it can play a role of scavenger to consume
3
H
2
O + S). But drawbacks like high energy consumption, toxic by-
2-
2-
2-
2-
2-
2-
the generated S or S
n
(SO
3
2-
+ S
n
→ S
2
O
3
+ Sn-1 ; S + SO
3
→
products (SO
X
) and underutilized H
2
in Claus plants are the
2- 11
S
2
O
3
). The as formed S
2
O
3
is colorless and soluble in water that
motivations for new research interests towards other available
2-
2 3
rarely influences the photocatalyst. Remarkably, S O is also a kind
4
strategies. Among them, photocatalysis technology is regarded as
of important chemicals for clinical uses, including treatment cyanide
and nitrile and heavy metal poisoning as well as that of skin
pruritus, chronic dermatitis, chronic urticaria, drug eruption and
an appealing and sustainable technology to remove toxic pollution
5
2
H S gas and obtain H
2
. Thermodynamically, hydrogen is obtained
more favourablely from H
2
S than H
2
O due to the lower splitting
S, 1.23 V or 273 kJ mol for
12
2-
scabies. Therefore, simultaneously recovery of both S
from H S in Na SO solution with photocatalytic method could be a
viable strategy that is beneficial for environment and energy.
However, there are few studies on the mechanism of using Na SO
solution as the reaction media for photocatalytic decomposition of
S to produce hydrogen. Specific influence of Na SO on hydrogen
and so on) coexist
in the system are unclear. Thereby, study on the in-
depth mechanism of photocatalytic H S splitting in Na SO solution
is essential to ultimately realize highly efficient utilization of wastes
S by obtaining H and S-containing species.
Herein, Na SO
medium for H
2 3 2
O and H
-1
-1
energy (0.14 V or 33 kJ mol for H
2
2
2
3
6
H
2
O). Therefore, photocatalytic decomposition of H
2
S to obtain H
2
has a large potential for practical applications.
Although direct conversion of H S to H
photocatalysis has been extensively investigated, this technology
for H production still encounters tremendous challenges. On the
one hand, the poisoning effect of H
2
3
2
2
and sulfur with
H
2
2
3
2-
2-
2
2 6 4
evolution and whether by-products (S O , SO
S for catalysts considerably
2-
2c
2
2 3
with S O
7
restrict the development of highly active catalysts. Furthermore,
decomposition of H S with photocatalysis meets the problem of
2
2
2
3
H
2
2
2
3
solution was proved to be an excellent reaction
a. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation,
Southwest Petroleum University, Chengdu 610500, Sichuan, China
production from H
S over a novel Ca modified CdS
2+
2
2
colloidal nanocrystals (Ca-CdS NCs), which shows a superior
b.
The Center of New Energy Materials and Technology, School of New Energy and
-1
-1
photocatalytic hydrogen production activity (56.0 mmol g h )
from H S. Electrochemical test proves that appropriate onset
potential and the weak influence of by-product sulfur on Na SO
Materials, Southwest Petroleum University, Chengdu 610500, Sichuan, China
Department of Engineering, University of Cambridge, Cambridge CB3 0FA, United
c.
2
Kingdom
d.
2
3
State key laboratory of industrial vent gas reuse, Southwest Research & Design
Institute of the Chemical Industry, No. 87 Airport Road, Chengdu, Sichuan, China
The authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: XRD, TEM images, XPS
spectra, UV-Vis and PL spectra, TA spectra, EIS, i-t curve and FT-IR spectra. See
DOI: 10.1039/x0xx00000x
solution are the important factors for effective hydrogen evolution.
Moreover, Fourier-transform infrared (FT-IR) test as well as
†
quantitative analysis confirms that Na
2 3
SO has been mostly
converted into Na after reaction. This study proves the
2 2 3
S O
Please do not adjust margins

Please d oC hn eo mt Ca do mj u ms t margins
Page 2 of 5
COMMUNICATION
Journal Name
possibility of resource utilization of H
2
S by obtaining H
2
and Na
2
S
2
O
3
of photogenerated electrons and holes may be respoVnieswibAlreticfleoOrntlhinee
2 3
in Na SO
solution, which also provides a reference for reaction higher activity (Figure S5b). This surface paDsOsivI:a1t0io.1n03w9/aDs0cCoCn0f5ir8m94eGd
mechanism study of photocatalytic H
FT-IR methods.
2
S with electrochemical and by the higher band-gap emission intensity of Ca-CdS NCs, as well as
a closer Gaussian symmetric distribution of transient absorption
Ca-CdS NCs were obtained by direct addition of inorganic Ca2+ decay curve in the time scale of several ps, which is often related to
ions into the aqueous solution of CdS NCs according to the previous the fast non-radiative process (see Figure S6 and analysis in
1
3
report. The broad diffraction peaks in XRD of Ca-CdS NCs mean a Supplementary information). Elimination of surface defects is
small size of the samples with a cubic zinc blende crystal structure beneficial for the separation of photogenerated carrier in Ca-CdS
1
3,15
type (JCPDS 75-0581) (Figure S1). No peak shift and new peaks NCs,
which is further verified by the electrochemical impedance
appeared over Ca-CdS NCs compared with CdS NCs, except that the spectroscopy (EIS) and transient photocurrent response (i-t curve)
average grain size increased from 10.8 nm to 12.5 nm (obtained by (Figure S7) with a much smaller semicircle radii and higher transient
1
6
Scherrer equation). ICP-AES elemental analysis proved that the photocurrent.
contents of Ca are 7.5 wt% in Ca-CdS NCs and over 99.9% of Cd
2 2 3
Table 1 Photocatalytic H production over Ca-CdS NCs in 0.6 M Na SO solution as
precursor was successfully maintained in Ca-CdS NCs (Table S1 and
S2), which excluded the ion exchange between Ca and Cd. All the
NCs show spherical and nanometer scale with highly irregular
shapes (Figure S2). Moreover, Zeta potential value of CdS NCs
reaction media with different treatment.
2
H production
Reaction solution
pH
-1
-1
2
+
(mmol g h )
56.0
decreased with introduction of Ca (Table S3), suggesting that the
positive Ca has combined with negative S2- on the surface of CdS
NCs. Accordingly, we believe that Ca mostly loaded on the surface
of CdS NCs. XPS indicated that the chemical states of Ca, S and Cd
were +2, -2, and +2, respectively (see Figure S3 and analysis in
2+
0
.6 M Na
.6 M Na
0.6 M Na SO -H
.6 M Na SO
No light a
No catalysts a
2
SO
SO
O-Na
-H O-HCl
3
-H
2
S
7.55
10.60
7.60
7.65
7.55
7.55
0
2
3
-H
2
O
4.85
2
3
2
2
S/HCl
10.2
1
4
supplementary information).
0
2
3
2
14.3
trace
trace
a: Reaction at 0.6 M Na
2 3 2
SO aqueous solution with 0.24 M H S. Reaction
condition: 5 mL reaction solution, 1 mg Ca-CdS NCs and 460 nm LED light.
Figure 1 Photocatalytic H
.125 mmol, 0.25 mmol, 0.5 mmol, 0.75 mmol, respectively) of Ca-CdS NCs with
error bar based on three experiments. Photocatalytic reaction condition: 5 mL 0.6
M Na SO -H S solution with 1 mg Ca-CdS NCs illuminated by 460 nm LED light.
production of different amount of Ca2+ precursor (0,
2
0
2
3
2
Photocatalytic hydrogen production ability from H
NCs were evaluated in 0.6 M Na SO
solution with saturated 0.24 M Figure 2 Photocatalytic H
based on three experiments. Blank means only H
2
2
S for Ca-CdS
2
3
2
production in different reaction media with error bar
S and no reaction media in
aqueous solution. Reaction condition: 5 mL aqueous; 1 mg Ca-CdS NCs; 460 nm
LED light.
2
+
H
(
2
S and a 460 nm LED light source. With a favorable amount of Ca
0.25 mmol), Ca-CdS NCs exhibits the highest photocatalytic activity
with H formation rate of 56.0 mmol g h , which was 2.3 times
2
-
1
-1
-1
-1
higher than that of pure CdS NCs (24.4 mmol g h ) (Figure 1).
Control experiments indicated H S is necessary for efficient H
production as it could provide both protons and sulfide Without addition of Na
simultaneously, which could be hardly achieved by extra addition of
was obtained in the H
other acid solution and Na
S (Table 1). Long time test suggests Ca- reaction media that have been reported in previous systems for
CdS NCs presents a high activity within 10 h, with hydrogen photocatalytic splitting of H S, including Na S, Na S/Na SO and
evolution rate decreased by 25.2 mmol g h after reaction for 3 h KOH solution, were also conducted over Ca-CdS NCs for comparison
Figure 2 reveals the influence of different reaction media on the
hydrogen evolution efficiency of photocatalytic H
SO in the system, only a trace amount of
S-saturated solution. Besides, other
2
S splitting.
2
2
2
3
H
2
2
2
2
2
2
2
3
-
1
-1
8
a,17
(
Figure S4). It turns out that light absorption ability is possibly not in the present work.
2
Reaction system with 0.1 M Na S alone
the main factor for the improved photocatalytic activity of Ca-CdS exhibited poor photocatalytic activity (15.5 mmol g h-1) owing to
-1
NCs due to the blue-shift of the absorption spectrum of Ca-CdS NCs the sulfur formed has not been efficiently consumed in the reaction
in contrast to that of CdS NCs (Figure S5a). Instead, surface progress. Besides, photocatalytic H
passivation of CdS NCs by Ca and hence a more efficient collection solution (56.0 mmol g h ) is dramatically higher than that in 0.1 M
2
evolution rate in 0.6 M Na
2 3
SO
2
+
-1 -1
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
Please d oC hn eo mt Ca do mj u ms t margins
Journal Name
COMMUNICATION
−
Na
(
2
S, 0.1 M Na
2
S/0.6 M Na
2
SO
3
(35.4 mmol g-1 h-1) or 0.5 M KOH
Photocatalyst + hv → e CB +h+VB
(2)
(3)
(4)
(5)
View Article Online
DOI: 10.1039/D0CC05894G
46.4 mmol g-1 h ) solution after irradiation of 5 h by 460 nm LED
-1
HS + 2 h VB → H + S
−
+
+
+
−
light. We found that the pH value of these solutions were dropped
to a similar value with 7.55 for Na SO solution, 7.65 for KOH
solution and 7.60 for Na S/Na SO solution after bubbling H S, even HS was firstly produced in the basic Na
though the initial pH were much discrepant (Table S4). In addition, introduction of H S (Eq. 1). Photogenerated holes from valence
2 H + 2 e CB → H
2
2-
↑
2
-
2
3
S + SO
3
2 3
→ S O
-
2
2
3
2
2 3
SO solution after
2
the concentration of H
Na S/Na SO -H
for Na SO -H
hydrogen evolution trend of the reaction system. This proves that photogenerated electrons on the conduction band of Ca-CdS
2
S was determined to be 0.42 M for band of Ca-CdS NCs under light irradiation were effectively
-
2
2
3
2
2
S solution, 0.3 M for KOH-H S solution and 0.24 M consumed by HS to generate hydrogen ions and sulfur, and
2
3
2
S solution (Table S4), which was mismatched with the the reduction of protons took place simultaneously with
2
-
the superior activity of the Na
of a higher concentration of H
As described before, the oxidation reaction of H
influence reduction of protons to some extent. Accordingly,
electrochemical liner sweep voltammetry (LSV) curves were
2
SO
3
solution system is not the result NCs (Eqs. 2-4). Then, SO
3
reacted with sulfur on the catalysts
2
S in the system.
surface to avoid the deposition of S (Eq. 5).
2
S to sulfur may
2
-
3 2 3 4 2 8
Table 2 Assignment of characteristic peaks about S , SO O O
2-, S 2-, SO 2-, S
2-
Assignment
S2-
Wavenumber/cm-1
1418.7
Reference
18a
2 3 2
recorded over the Na SO -H S solution with addition of a certain
amount of sulfur to study its possible influence for hydrogen
5
evolution. As shown in Figure 3, the onset potential of hydrogen
2-
SO
3
627.2, 955.8
18a,18b
18a,18c
18c
production in Na
intercept of the plot tangents on horizontal axis. With addition of
sulfur, proton reduction is only slightly influenced in Na SO -H
2 3 2
SO -H S is -0.86 V vs SCE, calculated through the
2
-
2
S O
3
675.8, 998.7, 1134.3
606.6, 1114.9
1062.8, 1289.2
2
-
2
S
SO
4
2
3
solution with the onset potential shift from -0.86 V to -0.87 V and
well-maintained current. This indicates problems of sulfur
2-
2
S O
8
-
accumulation in the Na
splitting of H
S could be well solved. In contrast, LSV curves of other Na
reaction system like Na S/Na SO -H
S solution were also conducted solutions.
as a reference (Figure S8). First of all, the onset potential of
hydrogen production in Na S/Na SO -H S solution (-0.91 V vs SCE) is
more negative than Na SO -H S (-0.86 V vs. SCE). This indicates
protons are easier to be reduced in Na SO solution, which is
consistent with the result of photocatalytic test (Figure 2).
Moreover, proton reduction in Na S/Na SO -H S solution was
2
SO
3
-H
2
S solution during photocatalytic The characteristic peaks were obtained by testing FT-IR of pure Na
2 2 3
S, Na SO ,
2 2
S O
3
, Na SO and Na solution, which showed unique peaks in their mixed
2
4
2 2 8
S O
2
2
2
3
2
2
2
3
2
2
3
2
2
3
2
2
3
2
suppressed with dramatically decreased current accompanied by an
obvious negative shift of the onset potential from -0.91 V to -0.99 V
in the presence of element sulfur (Figure S8). Consequently, the
appropriate onset potential and the weak influence of sulfur on the
system altogether contribute to the unique H
2
production
performance for Na SO -H S solution.
2
3
2
Figure 4 FT-IR of the different photocatalytic reaction progresses in the 0.6
M Na SO solution with Ca-CdS NCs as photocatalyst. Blank means pure
Na SO solution without H S.
2
3
2
3
2
Notably, here we introduced FT-IR spectroscopy as an
effective tool to verify the above photocatalytic progresses in
the presence of Na SO over photocatalytic H S splitting. First
2
3
2
of all, FT-IR spectra of a series of sulfur-related species were
recorded as references (Figure S9). Table 2 shows the
2
-
-1
2-
-
characteristic peaks of S (1418.7 cm ), SO
3
2-
(627.2, 955.8 cm
(606.6, 1114.9 cm
1
2-
-1
-
)
)
, S
, S
2
O
3
(675.8, 998.7, 1134.3 cm ), SO
(1062.8, 1289.2 cm ) according to Figure S9 and
references that have been reported. FT-IR results of the real
photocatalytic system at different reaction stages are shown in
Figure 4. After bubbling H
4
1
2-
-1
2
O
8
1
8
Figure 3 Linear sweep voltammograms (LSV) of Na
2 3 2
SO -H S solution and the
2
-
-1
S in the system, the S (1418.7 cm )
S was efficiently absorbed. It is
solution with adding sulfur. All the tests were performed under a scan rate of 50
2
-1
mV s at room temperature with platinum as working and counter electrode and were detected showing H
SCE as reference electrode.
2
2-
2-
worth noting that side reaction of S
2
O
3
formation (4 SO
3
+ 4
-
2-
H
2
S →2 HS + 3 H
2 2 3
O + 3 S O ) in darkness occurs with IR peaks
It is generally accepted that the mechanism for photocatalytic
-1
at 675.8, 998.7 and 1134.3 cm appeared in the progress of
H S bubbling, which consumed a considerable part of SO .
2 3
1
a,17
H
2
S splitting in Na
2
SO
3
-
solution can be described as following:
2
-
-
2
H S + OH → HS + H
2
O
(1)
2
-
2-
With light on, SO
3
continued to convert to S
O
2 3
with the
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please d oC hn eo mt Ca do mj u ms t margins
Page 4 of 5
COMMUNICATION
complete disappearance of peaks at 627.2 and 955.8 cm after
Journal Name
-1
Appl. Surf. Sci., 2018, 433, 329-335.
View Article Online
3
(a) O. A. Habeeb, R. Kanthasamy, G. A. M. Ali, S. Sethupathi and
DOI: 10.1039/D0CC05894G
3
SO
h. No characteristic peaks of other sulfur related species like
R. B. M. Yunus, Rev. Chem. Eng., 2018, 34, 837-854; (b) M. Sassi
and A. K. Gupta, Am. J. Environ. Sci., 2008, 4, 502-511; (c) A.
Vrachnos, G. Kontogeorgis and E. Voutsas, Ind. Eng. Chem. Res.,
2006, 45, 5148-5154.
2
-
-1
2-
-1
4
(606.6, 1114.9 cm ), S
O
2 8
(1062.8, 1289.2 cm ) were
2
-
detected in the real reaction system, demonstrating that SO
3
2
-
2 3
could efficiently convert into S O . Similar result was also
4
5
S. V. Tambwekar and M. Subrahmanyam, Int. J. Hydrogen
Energy, 1997, 22, 959-965.
(a) K. Maeda, K. Teramura, D. Lu, T. Takata, N. Saito, Y. Inoue
and K. Domen, Nature, 2006, 440, 295. (b) U. V. Kawade, R. P.
Panmand, Y. A. Sethi, M. V. Kulkarni, S. K. Apte, S. D. Naik and B.
B. Kale, RSC Adv., 2014, 4, 49295-49302.
(a) Z. H. Xie, S. Yu, X.-B. Fan, S. Q. Wei, L. Yu, Y. Zhong, X.-W.
Gao, F. Wu and Y. Zhou, J. Energy Chem., 2021, 52, 234-242; (b)
S. Yu, Z. H. Xie, M. X. Ran, F. Wu, Y. Q. Zhong, M. Dan and Y.
Zhou, J. Colloid Interface Sci., 2020, 573, 71-77; (c) X. Zong, J. F.
Han, B. Seger, H. J. Chen, G. M. Lu, C. Li and L. Z. Wang, Angew.
Chem. Int. Ed., 2014, 53, 4399-4403.
obtained by other photocatalysts including CdS NCs,
commercial CdS and Pt-loaded commercial CdS (Figure S10).
Iodometry analysis indicates that a total amount of 67.0 ± 0.4
-1
2-
mg mL S
which is close the theoretical value (67.2 mg mL ). XRD test
Figure S11) confirms that only Na could be discerned
from the reaction solution. This result indicates that it is
possible to collect Na as an important sulfur chemical in
the reaction system of Na SO solution during photocatalytic
splitting of H S for H evolution, which is often ignored by
2 3
O existed in the system after 3h of photocatalysis,
-1
9
6
(
2 2 3
S O
2 2 3
S O
2
3
2
2
7
8
Y. Li, S. Yu, D. E. Doronkin, S. Q. Wei, M. Dan, F. Wu, L. Q. Ye, J.-
D. Grunwaldt and Y. Zhou, J. Catal., 2019, 373, 48-57.
(a) B. B. Kale, J. O. Baeg, S. M. Lee, H. Chang, S. J. Moon and C.
W. Lee, Adv. Funct. Mater., 2006, 16, 1349-1354; (b) B. B. Kale,
J.-O. Baeg, K.-J. Kong, S.-J. Moon, L. K. Nikam and K. R. Patil, J.
Mater. Chem., 2011, 21, 2624-2631; (c) S. A. Naman and M.
Grätzel, J. Photochem. Photobiol. A: Chem., 1994, 77, 249-253.
M. Dan, Q. Zhang, S. Yu, A. Prakash, Y. H. Lin and Y. Zhou, Appl.
Catal. B: Environ., 2017, 217, 530-539.
0 (a) A. Prakash, M. Dan, S. Yu, S. Q. Wei, Y. Li, F. Wang and Y.
Zhou, Sol. Energy Mater. Sol. Cells, 2018, 180, 205-212; (b) Q.
Wang and K. Domen, Chem. Rev., 2020, 120, 919-985.
1 (a) K. Hara, K. Sayama and H. Arakawa, Appl. Catal. A: Gen.,
previous work. Nevertheless, it should be noted that a small
amount of polysulfide could be detected from the system in
2
-
3
UV-Vis spectra due to the lack of SO , which was all
1
9
consumed within 3 h (Figure S12).
In summary, photocatalytic splitting of H
2 2 3
S in Na SO
solution was carefully investigated with Ca-CdS NCs as the
photocatalyst. An excellent photocatalytic hydrogen evolution
9
1
-1
-1
rate of 56.0 mmol g
amount of Ca in the NCs. Na
better choice for H evolution over Ca-CdS NCs compared to
h
could be achieved with an optimal
2
SO solution was proved to be a
3
2
1
1
other previously reported reaction media by direct
photocatalytic tests and LSV tests. Moreover, FT-IR spectra
1
999, 189, 127-137; (b) N. Bühler, K. Meier and J.-F. Reber, J.
Phys. Chem. B, 1984, 88, 3261-3268.
indicated that Na
This work simultaneously collects clean energy H
chemicals (Na ) from H
presence of Na , which achieves the highly value-added
utilization of toxic H S.
2
SO
3
could convert into Na
S O
2 2 3
effectively.
2 (a) A. H. Hall, R. Dart and G. Bogdan, Ann. Emerg. Med., 2007,
4
2
and sulfur
9, 806-813; (b) B. R. Sperber, J. Allee, R. Elenitsas and W. D.
S O
2 2 3
2
S by photocatalysis in the
James, Contact Dermatitis, 2003, 48, 204-208; (c) L. Strazzula, S.
U. Nigwekar, D. Steele, W. Tsiaras, M. Sise, S. Bis, G. P. Smith
and D. Kroshinsky, JAMA Dermatol., 2013, 149, 946-949.
SO
2 3
2
1
3 X.-B. Fan, S. Yu, H.-L. Wu, Z.-J. Li, Y.-J. Gao, X.-B. Li, L.-P. Zhang,
C.-H. Tung and L.-Z. Wu, J. Mater. Chem. A, 2018, 6, 16328-
This work was supported by the National Natural Science
Foundation of China (U1862111 and 22002123), Cheung Kong
1
6332.
Scholars Programme of China and Chinese Academic of 14 (a) J. J. Ding, S. Sun, W. H. Yan, J. Bao and C. Gao, Int. J.
Hydrogen Energy, 2013, 38, 13153-13158; (b) M. Dan, J. L.
Xiang, F. Wu, S. Yu, Q. Cai, L.Q. Ye, Y.H. Ye, Y. Zhou, Appl. Catal.
B: Environ., 2019, 256, 117870; (c) Z. J. Sun, H. F. Zheng, J. S. Li
and P. W. Du, Energy Environ. Sci., 2015, 8, 2668-2676.
Science “light of west China” Program, Provincial International
Cooperation Project 2020YFH0118, Sichuan, China), Open
Fund (PLN201802 and 201928) of State Key Laboratory of Oil
and Gas Reservoir Geology and Exploitation (Southwest
Petroleum University), Open Fund of State Key Laboratory of
Industrial Vent Gas Reuse (SKLIVGR-SWPU-2020-05).
1
1
5 A. Nag, D. S. Chung, D. S. Dolzhnikov, N. M. Dimitrijevic, S.
Chattopadhyay, T. Shibata and D. V. Talapin, J. Am. Chem. Soc.,
2
012, 134, 13604-13615.
6 (a) Y. Xu and M. A. A. Schoonen, Am. Mineral, 2000, 85, 543-
56; (b) X. Q. Hao, J. Zhou, Z. W. Cui, Y. C. Wang, Y. Wang and Z.
5
G. Zou, Appl. Catal. B: Environ., 2018, 229, 41-51; (c) Y. B. Chen,
J.-F. Li, P.-Y. Liao, Y.-S. Zeng, Z. Wang and Z.-Q. Liu, Chinese
Chem. Lett., 2020, 31, 1516-1519.
Conflicts of interest
There are no conflicts to declare.
1
1
7 (a) J. L. Xiang, M. Dan, Q. Cai, S. Yu and Y. Zhou, Appl. Surf. Sci.,
2
019, 494, 700-707; (b) M. Dan, S. Yu, Y. Li, S. Q. Wei, J. L. Xiang
and Y. Zhou, J. Photoch. Photobio. C, 2020, 42, 100339.
Notes and references
8 (a) J. Yota, V. A. Burrows, J. Vac. Sci Technol. A, 1993, 11, 1083-
1
088; (b) I. V. Pekov, N. V. Chukanov, S. N. Britvin, Y. K. Kabalov,
1
(a) M. Dan, S. Q. Wei, D. E. Doronkin, Y. Li, Z. Y. Zhao, S. Yu, J.-D.
J. Göttlicher, V. O. Yapaskurt, A. E. Zadov, S. V. Krivovichev, W.
Schüller and B. Ternes, Mineral. Mag., 2012, 76, 1133-1152; (c)
S.-M. Chen, S.-W. Chiu, Electrochim. Acta, 2000, 45, 4399-4408.
9 M. Zhang, J. Guan, Y. C. Tu, S. M. Chen, Y. Wang, S. H. Wang, L.
Yu, C. Ma, D. H. Deng and X. H. Bao, Energy Environ. Sci., 2020,
Grunwaldt, Y. H. Lin and Y. Zhou, Appl. Catal. B: Environ., 2019,
2
43, 790-800; (b) X. Zhang, Y. Y. Tang, S. Q. Qu, J. W. Da and Z.
P. Hao, ACS Catal., 2015, 5, 1053-1067. (c) C. L. Geng, J. Gu, Y.
Xu and D. Weng, Mater. Rev., 2011, 25, 119-122.
1
2
(a) M. S. Shah, M. Tsapatsis and J. I. Siepmann, Chem. Rev.,
1
3, 119-126.
2
017, 117, 9755-9803; (b) A. P. Reverberi, J. J. Klemeš, P. S.
Varbanov and B. Fabiano, J. Clean. Prod., 2016, 136, 72-80; (c)
G. J. Ma, H. Y. Yan, J. Y. Shi, X. Zong, Z. B. Lei and C. Li, J. Catal.,
2
008, 260, 134-140; (d) G. Liu, J. Ji, P. Hu, S. Lin and H. Huang,
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/D0CC05894G
Highly efficient utilization of wastes H S by obtaining H and Na S O species was
2
2
2 2 3
implemented through photocatalytic technology in Na SO solution over novel
2
3
Ca-CdS nanocrystals.