Journal of Nanostructure in Chemistry

https://doi.org/10.1007/s40097-021-00411-y

ORIGINAL RESEARCH

Solar‑light responsive efficient ­H2 evolution using a novel ternary

hierarchical S­ rTiO3/CdS/carbon nanospheres photocatalytic system
Saikumar Manchala1,2,3,4 · Ambedkar Gandamalla1,2 · Vempuluru Navakoteswara Rao5 ·
Shankar Muthukonda Venkatakrishnan5 · Vishnu Shanker1,2 

Received: 2 November 2020 / Accepted: 5 June 2021

© Islamic Azad University 2021

Abstract
Carbon nanospheres (CNS) have tremendous potential in photocatalysis due to their unique opto-electronic properties that
facilitated effective electron transfer and high visible-light harvesting nature. The present work deals with the design and
synthesis of novel ternary hierarchical S
­ rTiO3/CdS/carbon nanospheres photocatalytic system and evaluated its photocatalytic
performance for H ­ 2 production under sunlight illumination. The ternary photocatalytic system formation is explained using
surface imaging (FE-SEM and TEM) and surface chemical analysis (XPS). At optimized conditions, the ternary S ­ rTiO3/CdS/
carbon nanospheres’ photocatalytic system has exhibited excellent H ­ 2 production of 3085 μmol ­h−1 ­gcat−1 when compared
to single and binary photocatalytic systems. The incorporation of carbon nanospheres takes part as an electron nabber and
carrier to improve the electron transfer of the ­SrTiO3/CdS photocatalytic system in the hierarchical ternary photocatalytic
system. The high ­H2 production of the ternary ­SrTiO3/CdS/carbon nanospheres’ photocatalytic system is demonstrated by
photocurrent and lifetime PL studies. Furthermore, a suitable mechanism is also proposed.

Keywords  Carbon nanospheres · SrTiO3 · CdS · Ternary hierarchical photocatalytic system · Hybrid nano-composite

Introduction However, it is not available readily in the environment suf-

Molecular hydrogen is identified as one of the clean and
green fuels often sourced from nature. In upcoming years,
hydrogen can be an alternative, attractive, and eco-friendly
energy carrier, which can replace conventional fossil fuels
because of its zero-emission and high energy density.
* Vishnu Shanker
vishnu@nitw.ac.in
1
Department of Chemistry, National Institute of Technology,
Warangal, Telangana 506004, India
2
Centre for Advanced Materials, National Institute
of Technology, Warangal, Telangana 506004, India
3
Department of Chemistry, Indian Institute of Technology,
Hauz Khas, New Delhi 110016, India
4
Department of Chemistry, Mallareddy Engineering
College (Autonomous), Maisammaguda, Dhulapally,
Secunderabad 500100, India
5
Nano Catalysis and Solar Fuels Research Laboratory,
Department of Materials Science and Nanotechnology,
Yogi Vemana University, Vemanapuram, Kadapa,
Andhra Pradesh 516005, India
ficiently and the cost of production is too high [1–5]. Among
all the possible technologies of H­ 2 production, photocatalytic
using semiconductor materials received heightened attention
because of its inexpensive and eco-friendly nature, water
splitting since the first photocatalytic water splitting (in
1972) on T ­ iO2 electrode by Fujishima and Honda [6–9]. So
far, many photocatalysts have been reported mainly includ-
ing ­TiO2-based photocatalysts [10], CdS-based photocata-
lysts [11], ZnO-based photocatalysts [12], and titanates [13].
However, these photocatalysts limited their activity under
UV light.
Like ­TiO2 and ZnO, the perovskite ­SrTiO3 (STO) is one
of the most prominently explored semiconductor materials
because of its structural flexibility, high chemical stability,
biological compatibility, and low cost. However, the larger
bandgap (3.2–3.5 eV) of S ­ rTiO3 is unfavorable for the absorp-
tion of visible light and it allows its activity under UV light.
It also suffers from the recombination of excitons [14–16]. To
tackle this problem, making binary hybrid nanocomposites
with ­SrTiO3 with narrow bandgap semiconductors would be
a productive method to allow its photocatalytic activity under
visible-light illumination [17]. On another hand, CdS (CS)

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has fascinated the attention of the research society because
of its narrow bandgap (2.0–2.4 eV) which flexible to absorb
visible light and morphologically controlled nanostructures.
CdS can also be an ideal candidate for H ­ 2 evolution with suit-
able negative conduction band (CB) potential. However, CdS
suffers from the recombination of excitons and photochemical
stability [18–22]. In this concern, it is better to make a ­SrTiO3/
CdS binary photocatalytic system to get rid of the above-raised
issues of both ­SrTiO3 and CdS. And also, it offers better charge
separation and excellent photocatalytic activity.
An artificial visible-light responsive ternary photocata-
lytic system just resembles the natural photosynthesis, and
furnishes better charge separation for the enhanced ­H2 evolu-
tion from water splitting [23, 24]. Already, several types of
ternary photocatalytic systems have been reported [25–27];
in which the interfacial electron migration of semiconduc-
tors is the crucial and rate-determining step. In this context,
the presence of a good solid electron transporter/co-catalyst
at the surface of semiconductors can play a key role to stimu-
late effective electron transfer. Until now, numerous solid
electron transporters/co-catalysts have been explored such
as reduced graphene oxide, nanocarbon, carbon quantum
dots, poly pyrrole, and metal nanoparticles like Ag and Au
[28–35]. In this context, carbon nanospheres were recog-
nized as a distinctive class of carbonaceous allotropes with
high specific surface area, mechanical stability, and good
electrical conductivity have been studied extensively owing
to their vast range of applications in fuel cells, catalysis,
supercapacitor electrodes, adsorption, and Li–S batteries
[36–38].
In the present work, carbon nanospheres were employed
as solid electron transporter to build a ternary photocata-
lytic system for the first time, where ­SrTiO3 and CdS were
selected as two photocatalysts. The ternary hierarchical
­SrTiO3/CdS/carbon nanospheres’ photocatalytic system
­(SrTiO3/CdS/CNS) was prepared by a facile hydrothermal
procedure and potentially applied for photocatalytic ­H2 evo-
lution from water splitting. The ternary hierarchical S ­ rTiO3/
CdS/CNS photocatalytic system offered excellent photocata-
lytic ­H2 evolution because of the synergistic effect between
three components compared to S ­ rTiO3, CdS, S ­ rTiO3/CdS,
­SrTiO3/CNS, and CdS/CNS. Moreover, the relevant mecha-
nisms for electron transfer of binary ­SrTiO3/CdS and ter-
nary ­SrTiO3/CdS/CNS photocatalytic systems have been
proposed.
Experimental section
Materials
Strontium nitrate (Sr(NO3)2, SRL, 99.0%), Titanium isopro-
poxide (Ti[OCH(CH3)2]4, Sigma-Aldrich, 99.9%), Pyrrole
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Journal of Nanostructure in Chemistry
­(C5H5N, SRL, 98%), Aniline (­ C6H5–NH2, SDFCL, 98%),
Triton X-100 ­(C14H22O(C2H4O)n, Merck, 98%), Cadmium
chloride monohydrate ­(CdCl2⋅H2O, Merck, 99%), Potassium
per-sulfate ­(K2S2O8, SDFCL, 99%), Citric acid monohydrate
­(C6H8O7⋅H2O, Finar, 99.5%), Lactic acid (­ CH3CHCO3H,
Thermo Fisher Scientific, 92%), and Thiourea ­(NH2CSNH2,
SRL, 99%) were used. Throughout the experiments, double-
distilled (DD) water was used.
Method
Synthesis of carbon nanospheres
CNS were synthesized by a facile self-assembly/polymeriza-
tion and carbonization of C­ 6H5–NH2 and C ­ 5H5N. First, add
aniline (400 μL) and pyrrole (300 μL) to DD water (65 mL).
Afterwards, add Triton X-100 (120 μL) to the above solu-
tion and kept for cooling. Then, add a pre-cooled 0.1 M of
­K2S2O8 solution to the above uniform solution and put at
0 °C in fridge for self-assembly overnight. During reaction,
aniline and pyrrole precursors undergo oxidation and polym-
erization in the prepared solution and form a co-polymer
of polyaniline-co-polypyrrole (PACPP). Finally, acquired
product was washed the number of times with DD water to
remove impurities and dried. The dried product was kept for
thermal treatment at 400 °C for 24 h for carbonization leads
to the development of CNS.
Synthesis of ­SrTiO3
SrTiO3 was prepared using the previously reported poly-
meric citrate precursor method [39]. In brief, added 3.26 mL
of titanium isopropoxide to the 25 mL of ethylene glycol and
stir for 30 min for complete dissolution. Subsequently, dis-
solve 20.82 g of citric acid in that solution under continuous
stirring. To this solution, add 3 g of strontium nitrate slowly.
Finally, it became transparent. Then the resultant mixture
was stirred and heated for 5 h approximately at 120 °C to
promote polymerization. After 5 h, the solvents were evapo-
rated and it gets solidify into the transparent brown resin.
The developed brown color resin was calcined for 3 h at
350 °C and then ground to obtain a black powder. Further-
more, the obtained black powder was calcined for 6 h at
800 °C. The acquired STO powder was white in color.
Synthesis of CdS
CdS was prepared by employing a facile hydrothermal pro-
cedure. In brief, stir for 15 min to dissolve 0.262 g of cad-
mium chloride in 40 mL of DD water. Then add 0.556 g of
thiourea to the above solution and stir for 30 min. Afterward,
the resultant clear solution was transferred into a 50 mL
hydrothermal autoclave and maintained at 180 °C for 24 h.
Journal of Nanostructure in Chemistry
In the end, the resultant orange color precipitate was centri-
fuged with DD water for washing 3 times and dried at 80 °C
for 12 h in the hot air oven.
Synthesis of ternary hierarchical S­ rTiO3/CdS/CNS
photocatalytic system
Hierarchical ­SrTiO3/CdS/CNS ternary heterojunction was
prepared by employing an easy hydrothermal procedure.
Briefly, take carbon nanospheres (5 mg) in the beaker con-
sist of 40 mL of DD water and stir for 15 min. Then add
1:1 ratio of synthesized S ­ rTiO3 powder and CdS powder
and stir for 30 min. The resultant solution was poured into
a 50 mL hydrothermal bomb and maintained temperature at
120 °C for 6 h. The resultant precipitate was washed with
DD water 3 times by centrifugation and dried at 80 °C for
12 h in the hot air oven. Then, the ­SrTiO3/CNS, CdS/CNS,
and ­SrTiO3/CdS binary photocatalytic systems without the
addition of CdS, S­ rTiO3, and CNS were prepared according
to a similar procedure.
Experimental particulars such as instruments used for the
analysis and photo-electrochemical study details employed
in this paper were discussed in the supplementary data.
Photocatalytic ­H2 evolution tests
The solar-light responsive photocatalytic ­H2 evolution reac-
tions are executed in the Yogi Vemana University located
in the district of Kadapa, Andhra Pradesh state, India. The
average solar light intensity (8.5 × ­104 Lx) is measured with
the help of a digital Lux meter (TES 1332A) for 1 h interval
from 11:00 A.M. to 3:00 P.M. First, 0.01 g of photocatalyst
powder is dispersed by stirring in a 185 mL quartz reactor
contains 50 mL of 25 Vol% lactic acid solution prepared by
using battery-grade distilled water under dark for 30 min.
Then, the solution is evacuated with a vacuum pump and
afterward removed the dissolved gases by passing high pure
­N2 gas. In the end, the reactor is exposed to sunlight and
the produced H ­ 2 gas is regularly collected at each 1 h and
analyzed with the offline Shimadzu GC-2014 furnished with
Molecular Sieve/5 Å and TCD, under constant N ­ 2 gas flow
at 70 °C.
Results and discussion
Characterization
The PXRD pattern shown in Fig. 1a exhibits the broad and
weak diffraction peaks at 43.7° and 26.1° which can be
inscribed to the (101) and (002) planes of prepared CNS
[40]. In addition, the broadened peaks also indicate the
amorphous nature and low graphitization degree of CNS
[41].
Figure 1b represents the FT-IR studies of as-prepared
CNS. The ‘2’ bands at 3173 and 3400 ­cm−1 imputed to
the –OH/–NH-stretching vibrations. The bands at 2860
and 2925 ­cm−1 correlated to the CH symmetric and asym-
metric stretching frequencies [42]. The bands at 1503 and
1614  ­cm−1 related to the C=C benzenoid and quinonoid
stretching frequencies. The bands at 824, 923, 1363, 1041,
1122, and 1264 ­cm−1 imputed to the pyrrole ring, C–H in-
plane, C–H out-of-plane, C–O–C, C–N, and C–O-stretching
vibrations [43, 44]. Altogether, FT-IR studies suggest that
the existence of oxygen and nitrogen-containing function-
alities (ONCFGs) on the prepared CNS. These ONCFGs
could enhance the stability and hydrophilicity of the CNS
in aqueous media. Furthermore, they can help to combine
the CNS with semiconductor materials [34]. FE-SEM and
TEM images displayed in Fig. 1c–f reveal that the formed
CNS were of spherical morphology with uniform diameter
and all CNS were randomly oriented throughout the sample.
The morphological/microstructural characteristics and
elemental composition of the prepared ternary ­SrTiO3/
CdS/CNS, pure ­SrTiO3, and pure CdS photocatalytic sys-
tems were investigated by FE-SEM, EDS, and elemental
mapping analysis. As presented in Fig. 2a, b, S ­ rTiO3 pos-
sessed a porous hollow sponge-like morphology throughout
the microstructures. As exhibited in Fig. 2c, d, CdS offered
flower-like microstructures. As revealed in Fig. S1a and S1b,
the EDS of ­SrTiO3 and CdS display the occurrence of Sr, Ti,
O, and Cd, S elements, respectively.
Figure 2e, f discloses the FE-SEM images of the ternary
hierarchical ­SrTiO3/CdS/CNS photocatalytic system com-
prise ­SrTiO3, CdS, and CNS components. Furthermore,
the EDS and respective EDS elemental mapping images of
ternary hierarchical ­SrTiO3/CdS/CNS (Fig. 2g) photocata-
lytic system comprise all the constituent elements (Sr, Ti,
Cd, S, O, N, and C) reveals the presence of a homogeneous
distribution of three components (CNS along with S ­ rTiO3
and CdS) throughout the specimen. These studies confirm
the presence of CNS in the resultant ternary photocatalytic
system.
The morphological characteristics and chemical composi-
tion of the prepared ternary hierarchical ­SrTiO3/CdS/CNS
photocatalytic system were also confirmed by TEM studies.
As exhibited in Fig. 3a–h, it was observed that the presence
of both nanostructures of the CdS (flower-like) and S ­ rTiO3.
Besides, the CNS were adhered to them. The respective
selected area electron diffraction (SAED) pattern (Fig. 3i) of
ternary hierarchical S
­ rTiO3/CdS/CNS photocatalytic system
reveals the d-spacing of about 0.2771 and 0.1938 nm were in
good agreement with the (110) and (200) planes of ­SrTiO3
[45] and the d-spacing of about 0.3560 nm was in good
agreement with the (100) plane of CdS [46], respectively.
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 Journal of Nanostructure in Chemistry

Fig. 1  PXRD pattern (a), FT-IR spectrum (b), FE-SEM images (c, d), and TEM micrographs (e, f) of prepared CNS

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Journal of Nanostructure in Chemistry
Fig. 2  FE-SEM images of prepared pure ­SrTiO3 (a, b), pure CdS (c, d), and ternary ­SrTiO3/CdS/CNS photocatalysts (e, f), EDS studies (g), and
respective elemental mapping images of ternary ­SrTiO3/CdS/CNS photocatalytic system
The crystal structures and constitution of the prepared
materials were verified by PXRD studies, as displayed in
Fig. 4a. The pristine S ­ rTiO3 sample shows the standard
diffraction peaks at 2θ = 32.5, 40.0, 46.5, 52.3, 57.7, 67.8,
and 77.1° attributed to the (110), (111), (200), (210), (211),
(220), and (310) planes of perovskite cubic phase (JCPDS
No: 79-0176). On another hand, the pure CdS displays the
standard diffraction peaks at 2θ = 24.7, 26.5, 28.2, 36.6,
43.8, 47.9, 51.9, and 53.2° ascribed to the (100), (002),
(101), (102), (110), (103), (112), and (201) planes of the
hexagonal phase of CdS (JCPDS No: 89-2944). Similarly,
all the binary and ternary composites display standard dif-
fraction peaks of all the respective constituent components.
However, CNS-based photocatalytic systems including CdS/
CNS, ­SrTiO3/CNS, and S ­ rTiO3/CdS/CNS do not show the
standard diffraction peak from CNS at 25°, due to relatively
less diffraction intensity, amorphous nature, and homogene-
ous distribution of CNS. It reveals the information about
the successful synthesis of binary CdS/CNS, ­SrTiO3/CNS,
­SrTiO3/CdS, and ternary ­SrTiO3/CdS/CNS photocatalytic
systems.
The structural vibrations and composition of the pre-
pared materials were studied by FT-IR studies, as exhib-
ited in Fig. 4b. In all pure and hybrid (both binary and ter-
nary) photocatalytic systems, the ‘2’ bands were positioned
at around 3450 and 1622 ­cm−1 because of stretching and
bending vibrations of adsorbed ­H2O molecules. The pure
­SrTiO3 displays ‘2’ strong bands approximately at 635 and
432 ­cm−1 ascribed to the characteristic Ti–O bond stretch-
ing and bending frequencies, which are generally observed
in the titanates [39]. The pure CdS exhibits a strong char-
acteristic metal-sulfide (Cd–S) bond stretching frequency
at 629 ­cm−1 indicating the formation of CdS [47]. Besides,
in all the photocatalytic systems, respective characteristic
bands were displayed according to their combination, which
directly describes the productive formation of binary CdS/
CNS, ­SrTiO3/CNS, ­SrTiO3/CdS, and ternary S ­ rTiO3/CdS/
CNS photocatalytic systems.
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Fig. 3  TEM micrographs (a–h) and SAED pattern (i) of prepared ternary ­SrTiO3/CdS/CNS photocatalytic system
Figure 4c represents the UV–Vis-DRS spectra of prepared
photocatalysts. The pure ­SrTiO3 and CdS samples show a
strong absorption edge at 406 and 619 nm in the UV and vis-
ible regions and corresponding bandgaps were determined to
be 3.05 and 2.00 eV using Tauc plots (Fig. 4d). In the case
of hybrid photocatalytic systems, S ­ rTiO3/CNS, ­SrTiO3/CdS/
CNS, and CdS/CNS, a red-shift was observed compared to
pristine ­SrTiO3 and CdS, i.e., the absorption edge shift from
UV to the visible region and S ­ rTiO3/CdS/CNS, a blue shift
was observed compared to pristine CdS, i.e., the absorption
shift towards the low visible region, attributed to the co-
existence of S­ rTiO3, CdS, and CNS together. In all cases,
the shift is due to the background absorption of CNS. The
significant improvement in the optical absorption properties
of these ­SrTiO3/CdS, ­SrTiO3/CNS, CdS/CNS, and S ­ rTiO3/
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Journal of Nanostructure in Chemistry
CdS/CNS photocatalysts can produce a huge quantity of
photo-generated excitons which are essential for the photo-
catalytic reduction of ­H+ to yield more ­H2.
The complete surface elemental profile and oxidation
state of the elements present in pure ­SrTiO3, pure CdS,
and ternary ­SrTiO3/CdS/CNS materials were explored by
XPS studies, as exhibited in Fig. 5a–h. The existence of
ONCFGs was also confirmed by XPS studies. Figure 5a
displays the survey XPS studies of prepared pure ­SrTiO3,
pure CdS, and ternary S ­ rTiO3/CdS/CNS samples reveal
the presence of respective elements such as Sr, Ti, and
O; Cd and S; and Sr, Ti, Cd, O, S, N, and C elements.
The deconvoluted XPS spectrum of ­SrTiO3, as displayed
in Fig. 5b reveals the ‘2’ peaks at 132.48 and 134.18 eV,
imputed to the standard binding energies (BEs) of Sr ­3d3/2
Journal of Nanostructure in Chemistry
Fig. 4  PXRD patterns (a), FT-IR spectra (b), UV–Vis–DRS spectra (c), and Tauc plots (d) of prepared pure S
CNS, ­SrTiO3/CNS, ­SrTiO3/CdS, and ternary ­SrTiO3/CdS/CNS photocatalytic systems
and Sr 3­ d5/2 of ­Sr2+. Figure 5c discloses the ‘2’ peaks at
458.10 and 463.90 eV, corresponding to the standard BEs
of ­Ti4+ (Ti 2­ p1/2 and Ti 2­ p3/2) [18]. As exhibited in Fig. 5d,
the high-resolution XPS spectrum of CdS represents the
‘2’ peaks at 404.55 and 411.28 eV, assigned to the stand-
ard BEs of ­Cd2+ (Cd ­3d5/2 and Cd ­3d3/2). Also, the decon-
voluted spectrum of O 1s (Fig. 5e) possesses ‘3’ peaks at
529.06, 531.73, and 533.23 eV, imputed to the standard
BEs of ­O2− ions in the STO lattice ­(Olatt), ­O2− associated
with defect/vacancy (­ Ovac) environment, and O ­ 2− adsorbed
(OH/H2O) on the surface ­(Oads) [48]. The deconvoluted
spectrum of S 2p (Fig. 5f) contains ‘2’ peaks at 161.15
and 162.35 eV, assigned to the standard BEs of ­S 2− (S
­2p3/2 and S ­2p 1/2) [49]. Figure 5g shows the very broad
peak of C 1s of ternary S ­ rTiO 3/CdS/CNS photocata-
lytic system constructs asymmetrically with ‘3’ peaks at
the BEs of 284.40, 285.92, and 288.29 eV. The intense
peak at 284.40 eV corresponding to the ­s p 2 hybridized
(C=C) carbon and the next peaks are located at 285.89
and 288.29 eV attributed to the C–N/C–O and C=N/C=O
[50]. The deconvoluted spectra of N 1s (Fig. 5h) exhibit
­ rTiO3, pure CdS, and binary CdS/
‘2’ peaks located at 399.96 and 401.13 eV imputed to the
tertiary nitrogen N–(C)3 groups, and amino N–H groups in
the ternary S­ rTiO3/CdS/CNS photocatalytic system [51].
In the ternary S­ rTiO3/CdS/CNS photocatalytic system, the
positions of the peaks of Sr 3d, Ti 2p, O­ vac, Cd 3d, and S
2p move to the lower BE side, because of strong interac-
tion and partial electron transfer among the S ­ rTiO3, CdS,
and CNS components [52]. Simultaneously, the intensity
of ­Ovac peak of the ternary hierarchical S
­ rTiO3/CdS/CNS
photocatalytic system has been increased comparably
when correlated to the intensity of ­Ovac peak of ­SrTiO3;
implies the existence of more number of oxygen defects
which directly affect the photocatalytic performance by a
decline in the recombination of excitons, efficiently [53,
54].
Moreover, XPS results could reveal ­SrTiO3, CdS, and
CNS exist together in the ternary hierarchical ­SrTiO3/CdS/
CNS photocatalytic system, which further strongly sup-
ports the FT-IR, FE-SEM, EDS elemental mapping, and
TEM results.
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 Journal of Nanostructure in Chemistry

Fig. 5  Survey XPS profile of the prepared S ­ rTiO3, CdS, and S­ rTiO3/CdS/CNS photocatalysts (a), and respective deconvoluted spectra of Sr 3d
(b), Ti 2p (c), Cd 3d (d), O 1s (e), S 2p (f), C 1s (g), and N 1s (h)

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Journal of Nanostructure in Chemistry
Photocatalytic studies
The photocatalytic ­H2 production experiments were con-
ducted for as-prepared photocatalysts under sunlight illumi-
nation. As mentioned in Fig. 6a, the pristine ­SrTiO3 shows
a trivial ­H2 production performance of 19.5 μmol ­h−1 ­gcat−1
attainable due to a high kinetic energy barrier, demonstrating
that the pristine ­SrTiO3 is inactive for solar-light respon-
sive photocatalytic ­H2 production because of its bandgap
energy in the UV region, which has also been delivered by
the previous reports [55, 56]. The pristine CdS exhibits a
low ­H2 production rate (HPR) of 935 μmol ­h−1 ­gcat−1. Upon
loading the CNS with the ­SrTiO3 and CdS, the HPRs of
the as-prepared S ­ rTiO3/CNS and CdS/CNS photocatalytic
systems were improved and show the moderate HPRs are
895 and 1629 μmol ­h−1 ­gcat−1. In contrast, when CNS were
fabricated with both S ­ rTiO3 and CdS, it can be noticed that
the formed ternary ­SrTiO3/CdS/CNS photocatalytic system
was displayed remarkably highly efficient photocatalytic
HPR as 3085 μmol ­h−1 ­gcat−1, which is nearly 158.20, 3.30,
Fig. 6  Solar-light responsive HPR (a), ­H2 production for 4 h (b) over
prepared ­SrTiO3, CdS, CdS/CNS, ­ SrTiO3/CNS, ­SrTiO3/CdS, and
­SrTiO3/CdS/CNS photocatalytic systems, photocurrent studies (c) of
3.45, 1.90, and 1.17 times higher than that of ­SrTiO3 (19.5
μmol  ­h−1 ­gcat−1), CdS (935 μmol ­h−1 ­gcat−1), ­SrTiO3/CNS
(895 μmol ­h−1 ­gcat−1), CdS/CNS (1629 μmol ­h−1 ­gcat−1), and
­SrTiO3/CdS (2644 μmol ­h−1 ­gcat−1) photocatalysts as dis-
played in Table 1. For comparison, we also investigated the
photocatalytic HPR of the as-prepared binary S ­ rTiO3/CdS
photocatalytic system, i.e., 2644 μmol ­h−1 ­gcat−1, this value is
less than that of the ternary ­SrTiO3/CdS/CNS photocatalytic
system, which implies the fabricated CNS effectively served
as electron collector and transporter to facilitate charge sep-
aration, further responsible for high HPRs under sunlight
illumination. Furthermore, the superior H ­ 2 production of the
ternary hierarchical S­ rTiO3/CdS/CNS photocatalytic system
was proved by photocurrent experiments.
The efficacious charge transfer among the ­SrTiO3, CdS,
and CNS in the ternary hierarchical ­SrTiO3/CdS/CNS pho-
tocatalytic system was observed by the photocurrent studies,
as shown in Fig. 6c. The ternary ­SrTiO3/CdS/CNS photo-
catalytic system demonstrated a high amount of photo-elec-
trochemical current compared to binary ­SrTiO3/CNS, CdS/
prepared ­SrTiO3/CNS, CdS/CNS, S ­ rTiO3/CdS, and S­ rTiO3/CdS/CNS
photocatalysts, and d ultrafast PL spectra of S
­ rTiO3/CdS and ­SrTiO3/
CdS/CNS photocatalytic systems
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Table 1  Photocatalytic HPR over as-prepared photocatalysts
S. no. Photocatalyst Amount (mg) H2 production
(μmol ­h−1 ­gcat−1)
1 SrTiO3 10 19.5
2 CdS 10 935
3 SrTiO3/CNS 10 895
4 CdS/CNS 10 1629
5 SrTiO3/CdS 10 2677
6 SrTiO3/CdS/CNS 10 3085
CNS, and S ­ rTiO3/CdS photocatalytic systems. This circum-
stance allows us to tell the data about established electron
transfer mobility among the ­SrTiO3, CdS, and CNS for fea-
sible charge separation efficiency, which subsequently rea-
son for the improved photocatalytic ­H2 evolution of ternary
hierarchical ­SrTiO3/CdS/CNS photocatalytic system.
Moreover, to reveal the reason for the potential H ­ 2 evo-
lution over the ternary and binary photocatalytic systems
of ­SrTiO3/CdS/CNS and S ­ rTiO3/CdS, ultrafast PL was exe-
cuted to know the lifetime of photo-induced charge carriers.
As displayed in Fig. 6d, for binary ­SrTiO3/CdS photocata-
lytic system, the average PL lifetime is 18.9 ns which is less
than that of ternary S
­ rTiO3/CdS/CNS photocatalytic system
(22.7 ns). The main reason for this circumstance is in the ter-
nary ­SrTiO3/CdS/CNS photocatalytic system the employed
CNS captures the photo-induced electrons, and thus, the
decay lifetime has increased. Furthermore, the fabricated
CNS in the S ­ rTiO3/CdS photocatalytic system improves the
migration and charge separation of photo-induced electrons,
which directly increase the availability of more electrons for
‘H+’ reduction; this is absent in the case of the binary photo-
catalytic system. Altogether, the ternary hierarchical S­ rTiO3/
CdS/CNS photocatalytic system can be a potential candidate
for ­H2 evolution due to an effective interfacial charge migra-
tion and less recombination of photo-induced carriers.
Furthermore, as exhibited in Fig. S2, the PXRD was
recorded after the photocatalytic H ­ 2 evolution reaction for
the ternary hierarchical S ­ rTiO3/CdS/CNS photocatalytic
system and it revealed that the structural pattern appears
to be the same, which means the used ternary photocata-
lytic system has good stability and it can be reused further.
In the end, the fabricated ternary hierarchical ­SrTiO3/CdS/
CNS photocatalytic system seems to be a stable, potential,
and affordable photocatalytic system for H ­ 2 evolution from
water splitting.
Tentative photocatalytic mechanism
To describe an enhanced HPR over the ternary S ­ rTiO3/
CdS/CNS and binary ­SrTiO3/CdS photocatalytic systems, a
possible electronic transfer mechanism has been proposed.
13
Journal of Nanostructure in Chemistry
According to Eqs. (1–2), the ECB and EVB (band edge poten-
tials) are determined and supplied in the supplementary data
[33]
ECB = X − Ee − 0.5Eg , (1)
EVB = Eg − ECB . (2)
The determined E CB and E VB values for S ­ rTiO 3 are
− 0.71 and 2.35 eV, and for CdS are − 0.21 and + 1.79 eV.
If ­SrTiO3 is composited with CdS, the developed binary
­SrTiO3/CdS photocatalytic system is enhanced its photo-
catalytic performance largely up to 2644 μmol ­h−1 ­gcat−1
compared to pure S ­ rTiO3 (19.5 μmol ­h−1 ­gcat−1) and CdS
−1 −1
(935 μmol ­h  ­gcat ). The S ­ rTiO3/CdS photocatalytic sys-
tem follows the type-I nano junction mechanism (Fig. 7a)
due to the feasible arrangement of S ­ rTiO3 and CdS VB and
CB positions [57–59]. As illustrated in Fig. 7b, the CNS
which are deposited/fabricated onto the S ­ rTiO3/CdS photo-
catalytic system able to increase the visible-light harvesting
capability and serve as the electron transfer medium to boost
the migration rates of excitons in the ternary hierarchical
­SrTiO3/CdS/CNS photocatalytic system [60, 61]. Upon sun-
light exposure, the excited electrons present in the CB of
­SrTiO3 feasibly move to the CB of CdS and then transfer to
the surface of CNS, and then finally combine with ­H+ and
reduce it into ­H2. Concurrently, the holes stemming from the
VB of S­ rTiO3 move to the VB of CdS and oxidize the lactic
acid. As a consequence, a large number of photo-generated
electrons at S­ rTiO3 readily participate in the reduction of
­H+ to ­H2. Therefore, it leads to efficacious charge transfer in
between ­SrTiO3, CdS, and CNS, which promotes the much
more amount of photocatalytic ­H2 evolution over the ternary
hierarchical ­SrTiO3/CdS/CNS photocatalytic system.
Conclusions
In summary, a ternary hierarchical S­ rTiO3/CdS/CNS pho-
tocatalytic system has been prepared hydrothermally by
fabricating CNs into the binary ­SrTiO3/CdS photocatalytic
system with close interfacial interactions. The informa-
tion obtained from PXRD, FT-IR, FE-SEM, TEM, and
XPS data revealed the formation of a ternary hierarchical
­SrTiO3/CdS/CNS photocatalytic system. The fabricated
CNS successfully improves the visible-light absorption
and charge separation properties. Notably, the ternary hier-
archical ­SrTiO3/CdS/CNS photocatalytic system displayed
a remarkable HPR of 3085 μmol ­h−1 ­gcat−1 among the other
prepared photocatalysts including pure ­SrTiO3, pure CdS,
binary ­SrTiO 3/CNS, ­SrTiO 3/CdS, and CdS/CNS photo-
catalytic systems under sunlight. Furthermore, the out-
standing enhancement in the HPR is due to the presence
Journal of Nanostructure in Chemistry
Fig. 7  Schematic illustration of solar-light responsive photocatalytic H
­ 2 production using binary S
(b) photocatalytic systems
of CNS which acts as charge transporters and improves the
interfacial charge migration in the ternary photocatalytic
system. Moreover, this work offers new prospects for the
designing of highly efficient photocatalytic systems like
the ternary hierarchical S
­ rTiO3/CdS/CNS photocatalytic
system, to realize large-scale production of solar fuels to
address environmental issues.
Supplementary Information  The online version contains supplemen-
tary material available at https://​doi.o​ rg/1​ 0.​1007/s​ 40097-0​ 21-​00411-y.
Acknowledgements  Saikumar sincerely acknowledges MHRD (Govt.
of India) for financial support and NIT-Warangal for the instrumenta-
tion facilities.
Author contributions  Conceptualization, investigation, formal analysis,
methodology, original draft preparation, and editing of the manuscript
draft: SM; investigation, methodology, and formal analysis: AG; formal
analysis, data collection, and analysis: VNR; validation of the method,
and editing of the manuscript draft: SMV; supervision, reviewing, and
editing of the manuscript draft: VS.
Funding  No funding was received from any organization for conduct-
ing this work.
Availability of data and materials/code availability  The authors confirm
that the data supporting the findings of this work are comply with the
field standards and available within the article and its supplementary
information.
­ rTiO3/CdS (a) and ternary S
­ rTiO3/CdS/CNS
Declarations 
Conflict of interest  The authors declare that they have no known com-
peting financial interests or personal relationships that could have ap-
peared to influence the work reported in this paper.
References
1. Ahmad, H., Kamarudin, S.K., Minggu, L.J., Kassim, M.: Hydro-
gen from photo-catalytic water splitting process: a review. Renew.
Sustain. Energy Rev. 43, 599–610 (2015)
2. Corbo, P., Migliardini, F., Veneri, O.: Hydrogen Fuel Cells for
Road Vehicles. Springer London, London (2011)
3. Mccay, M.H.: Hydrogen as an Energy Carrier. Springer, Berlin
(1988)
4. Rahman, S., Andrews, C.J.: Special issue on the hydrogen econ-
omy. Proc. IEEE 94, 1781–1784 (2006)
5. Manchala, S., Nagappagari, L.R., Venkatakrishnan, S.M., Shan-
ker, V.: Solar-light harvesting bimetallic Ag/Au decorated gra-
phene plasmonic system with efficient photoelectrochemical per-
formance for the enhanced water reduction process. ACS Appl.
Nano Mater. 2, 4782–4792 (2019)
6. Kalamaras, C.M., Efstathiou, A.M.: Hydrogen production technol-
ogies: current state and future developments. Conf. Pap. Energy.
2013, 1–9 (2013)
7. Manchala, S., Nagappagari, L.R., Muthukonda Venkatakrishnan,
S., Shanker, V.: Facile synthesis of noble-metal free polygo-
nal ­Zn2TiO4 nanostructures for highly efficient photocatalytic
13

hydrogen evolution under solar light irradiation. Int. J. Hydrogen
Energy. 43, 13145–13157 (2018)
8. Fujishima and Honda: © 1972 Nature Publishing Group. Nature
238, 37–38 (1972)
9. Tan, H.L., Abdi, F.F., Ng, Y.H.: Heterogeneous photocatalysts: an
overview of classic and modern approaches for optical, electronic,
and charge dynamics evaluation. Chem. Soc. Rev. 48, 1255–1271
(2019)
10. Ge, M., Li, Q., Cao, C., Huang, J., Li, S., Zhang, S., Chen, Z.,
Zhang, K., Al-Deyab, S.S., Lai, Y.: One-dimensional T ­ iO2 nano-
tube photocatalysts for solar water splitting. Adv. Sci. 4, 1600152
(2016)
11. Yuan, Y.-J., Chen, D., Yu, Z.-T., Zou, Z.-G.: Cadmium sulfide-
based nanomaterials for photocatalytic hydrogen production. J.
Mater. Chem. A. 6, 11606–11630 (2018)
12. Tso, S., Li, W., Wu, B., Chen, L.-J.: Enhanced ­H2 production in
water splitting with CdS–ZnO core-shell nanowires. Nano Energy
43, 270–277 (2018)
13. Kumar, S., Tonda, S., Baruah, A., Kumar, B., Shanker, V.: Syn-
thesis of novel and stable g-C3N4/N-doped ­SrTiO3 hybrid nano-
composites with improved photocurrent and photocatalytic activ-
ity under visible light irradiation. Dalt. Trans. 43, 16105–16114
(2014)
14. Kanhere, P., Chen, Z.: A review on visible light active perovskite-
based photocatalysts. Molecules 19, 19995–20022 (2014)
15. Jiao, Z., Zhang, Y., Chen, T., Dong, Q., Lu, G., Bi, Y.: T­ iO2 nano-
tube arrays modified with Cr-doped ­SrTiO3 nanocubes for highly
efficient hydrogen evolution under visible light. Chem. A Eur. J.
20, 2654–2662 (2014)
16. Karimi, L., Zohoori, S.: Superior photocatalytic degradation of
azo dyes in aqueous solutions using T ­ iO2/SrTiO3 nanocomposite.
J. Nanostruct. Chem. 3, 32 (2013)
17. Kanagaraj, T., Thiripuranthagan, S.: Photocatalytic activities of
novel ­SrTiO3–BiOBr heterojunction catalysts towards the deg-
radation of reactive dyes. Appl. Catal. B Environ. 207, 218–232
(2017)
18. Su, E.-C., Yeh, J.-M., Huang, B.-S., Lee, J.-T., Wey, M.-Y.: Design
of a solar light-responsive metal oxide/CdS/SrTiO3 catalyst with
enhanced charge separation for hydrogen evolution. Sol. Energy.
147, 240–247 (2017)
19. Zhang, Y., Han, L., Wang, C., Wang, W., Ling, T., Yang, J., Dong,
C., Lin, F., Du, X.-W.: Zinc-blende CdS nanocubes with coor-
dinated facets for photocatalytic water splitting. ACS Catal. 7,
1470–1477 (2017)
20. Zhai, X.-L., Liu, J., Hu, L.-Y., Bao, J.-C., Lan, Y.-Q.: Polyoxomet-
alate-Decorated g-C3N4-wrapping snowflake-like CdS nanocrystal
for enhanced photocatalytic hydrogen evolution. Chem. A Eur. J.
24, 15930–15936 (2018)
21. Lu, X., Toe, C.Y., Ji, F., Chen, W., Wen, X., Wong, R.J., Seidel, J.,
Scott, J., Hart, J.N., Ng, Y.H.: Light-induced formation of ­MoOxSy
clusters on CdS nanorods as cocatalyst for enhanced hydrogen
evolution. ACS Appl. Mater. Interfaces. 12, 8324–8332 (2020)
22. Zhao, J., Tian, S., Shi, H., Quan, Q., Xiao, C.: Encapsulated cad-
mium sulfide in silicon dioxide porous shells for enhanced pho-
tocatalytic sustainability and commendable protection of organic
carriers. Adv. Mater. Interfaces 6, 1801933 (2019)
23. Yun, H.J., Lee, H., Kim, N.D., Lee, D.M., Yu, S., Yi, J.: A combi-
nation of two visible-light responsive photocatalysts for achieving
the Z-scheme in the solid state. ACS Nano 5, 4084–4090 (2011)
24. Sun, D., Shi, J.-W., Ma, D., Zou, Y., Sun, G., Mao, S., Sun, L.,
Cheng, Y.: CdS/ZnS/ZnO ternary heterostructure nanofibers fab-
ricated by electrospinning for excellent photocatalytic hydrogen
evolution without co-catalyst. Chin. J. Catal. 41, 1421–1429
(2020)
25. Zou, Y., Shi, J.-W., Ma, D., Fan, Z., Cheng, L., Sun, D., Wang,
Z., Niu, C.: ­WS 2 /graphitic carbon nitride heterojunction
13
Journal of Nanostructure in Chemistry
nanosheets decorated with CdS quantum dots for photocatalytic
hydrogen production. Chemsuschem 11, 1187–1197 (2018)
26. Shi, J.-W., Ma, D., Zou, Y., Fan, Z., Shi, J., Cheng, L., Ji, X.,
Niu, C.: Rational construction of multiple interfaces in ternary
heterostructure for efficient spatial separation and transfer of
photogenerated carriers in the application of photocatalytic
hydrogen evolution. J. Power Sources 379, 249–260 (2018)
27. Ma, D., Shi, J.-W., Zou, Y., Fan, Z., Shi, J., Cheng, L., Sun,
D., Wang, Z., Niu, C.: Multiple carrier-transfer pathways in
a flower-like ­In2S3/CdIn2S4/In2O3 ternary heterostructure for
enhanced photocatalytic hydrogen production. Nanoscale 10,
7860–7870 (2018)
28. Iwase, A., Ng, Y.H., Ishiguro, Y., Kudo, A., Amal, R.: Reduced
graphene oxide as a solid-state electron mediator in Z-scheme
photocatalytic water splitting under visible light. J. Am. Chem.
Soc. 133, 11054–11057 (2011)
29. Shi, F., Chen, L., Chen, M., Jiang, D.: A g-C3N4/nanocarbon/
ZnIn 2S 4 nanocomposite: an artificial Z-scheme visible-light
photocatalytic system using nanocarbon as the electron media-
tor. Chem. Commun. 51, 17144–17147 (2015)
30. Zhang, C., Yu, K., Feng, Y., Chang, Y., Yang, T., Xuan, Y., Lei,
D., Lou, L.-L., Liu, S.: Novel 3DOM-SrTiO3/Ag/Ag3PO4 ter-
nary Z-scheme photocatalysts with remarkably improved activ-
ity and durability for contaminant degradation. Appl. Catal. B
Environ. 210, 77–87 (2017)
31. Yang, G., Ding, H., Chen, D., Feng, J., Hao, Q., Zhu, Y.: Con-
struction of urchin-like ­ZnIn2S4–Au–TiO2 heterostructure with
enhanced activity for photocatalytic hydrogen evolution. Appl.
Catal. B Environ. 234, 260–267 (2018)
32. Wang, X., Yin, R., Zeng, L., Zhu, M.: A review of graphene-
based nanomaterials for removal of antibiotics from aqueous
environments. Environ. Pollut. 253, 100–110 (2019)
33. Manchala, S., Gandamalla, A., Rao, V.N., Venkatakrishnan,
S.M., Shanker, V.: High potential and robust ternary L ­ aFeO3/
CdS/carbon quantum dots nanocomposite for photocatalytic ­H2
evolution under sunlight illumination. J. Colloid Interface Sci.
583, 255–266 (2021)
34. Xie, Z., Tan, H.L., Wen, X., Suzuki, Y., Iwase, A., Kudo, A.,
Amal, R., Scott, J., Ng, Y.H.: The importance of the interfa-
cial contact: is reduced graphene oxide always an enhancer
in photo(electro)catalytic water oxidation? ACS Appl. Mater.
Interfaces. 11, 23125–23134 (2019)
35. Zhao, J., Han, P., Tian, S., Shi, H., He, J., Xiao, C.: Polypyrrole/
cadmium sulfide hollow fiber with high performance contami-
nant removal and photocatalytic activity fabricated by layer-by-
layer deposition and fiber-sacrifice template approach. J. Colloid
Interface Sci. 557, 94–102 (2019)
36. Li, S., Pasc, A., Fierro, V., Celzard, A.: Hollow carbon spheres,
synthesis and applications—a review. J. Mater. Chem. A 4,
12686–12713 (2016)
37. Yang, Z.-C., Tang, C.-H., Gong, H., Li, X., Wang, J.: Hollow
spheres of nanocarbon and their manganese dioxide hybrids
derived from soft template for supercapacitor application. J.
Power Sources. 240, 713–720 (2013)
38. Li, X., Bai, S., Zhu, Z., Sun, J., Jin, X., Wu, X., Liu, J.: Hollow
carbon spheres with abundant micropores for enhanced ­CO 2
adsorption. Langmuir 33, 1248–1255 (2017)
39. Tonda, S., Kumar, S., Anjaneyulu, O., Shanker, V.: Synthesis of
Cr and La-codoped ­SrTiO3 nanoparticles for enhanced photo-
catalytic performance under sunlight irradiation. Phys. Chem.
Chem. Phys. 16, 23819–23828 (2014)
40. Wang, Y., Su, F., Wood, C.D., Lee, J.Y., Zhao, X.S.: Preparation
and characterization of carbon nanospheres as anode materials
in lithium-ion secondary batteries. Ind. Eng. Chem. Res. 47,
2294–2300 (2008)
Journal of Nanostructure in Chemistry
41. Adewumi, G.A., Inambao, F., Eloka-Eboka, A., Revaprasadu,
N.: Synthesis of carbon nanotubes and nanospheres from coco-
nut fibre and the role of synthesis temperature on their growth. J.
Electron. Mater. 47, 3788–3794 (2018)
42. Saravanan, S., Joseph Mathai, C., Anantharaman, M.R., Venka-
tachalam, S., Prabhakaran, P.V.: Investigations on the electrical
and structural properties of polyaniline doped with camphor sul-
phonic acid. J. Phys. Chem. Solids. 67, 1496–1501 (2006)
43. Cordeiro, E.R., Fernandes, A.W.C., Pereira, A.F.C., da Costa,
M.M., Nascimento, M.L.F., de Oliveira, H.P.: Staphylococcus
aureus biofilm formation on polypyrrole: an electrical overview.
Quim. Nova. 38, 1075–1079 (2015)
44. Zhang, Y., Liu, J., Zhang, Y., Liu, J., Duan, Y.: Facile synthesis
of hierarchical nanocomposites of aligned polyaniline nanorods
on reduced graphene oxide nanosheets for microwave absorbing
materials. RSC Adv. 7, 54031–54038 (2017)
45. Xing, G., Zhao, L., Sun, T., Su, Y., Wang, X.: Hydrothermal
derived nitrogen doped ­SrTiO3 for efficient visible light driven
photocatalytic reduction of chromium(VI). Springerplus 5, 1132
(2016)
46. She, H., Li, L., Zhou, H., Wang, L., Huang, J., Wang, Q.: Photo-
catalytic activation of saturated C–H bond over the CdS mixed-
phase under visible light irradiation. Front. Chem. 6, 466 (2018)
47. Thangadurai, P., Balaji, S., Manoharan, P.T.: Surface modification
of CdS quantum dots using thiols—structural and photophysical
studies. Nanotechnology 19, 435708 (2008)
48. Cheng, M., Fan, H., Song, Y., Cui, Y., Wang, R.: Interconnected
hierarchical ­NiCo2O4 microspheres as high-performance electrode
materials for supercapacitors. Dalt. Trans. 46, 9201–9209 (2017)
49. Tonda, S., Kumar, S., Gawli, Y., Bhardwaj, M., Ogale, S.:
g-C3N4(2D)/CdS(1D)/rGO(2D) dual-interface nano-composite for
excellent and stable visible light photocatalytic hydrogen genera-
tion. Int. J. Hydrogen Energy. 42, 5971–5984 (2017)
50. Zhang, Y., Cui, P., Zhang, F., Feng, X., Wang, Y., Yang, Y., Liu,
X.: Fluorescent probes for “off–on” highly sensitive detection of
­Hg2+ and L-cysteine based on nitrogen-doped carbon dots. Talanta
152, 288–300 (2016)
51. Jiang, Z., Qian, K., Zhu, C., Sun, H., Wan, W., Xie, J., Li, H.,
Wong, P.K., Yuan, S.: Carbon nitride coupled with CdS–TiO2
nanodots as 2D/0D ternary composite with enhanced photocata-
lytic ­H2 evolution: a novel efficient three-level electron transfer
process. Appl. Catal. B Environ. 210, 194–204 (2017)
52. Yang, J., Hu, R., Meng, W., Du, Y.: A novel p-LaFeO3/n-Ag3PO4
heterojunction photocatalyst for phenol degradation under visible
light irradiation. Chem. Commun. 52, 2620–2623 (2016)
53. Tan, H., Zhao, Z., Bin Zhu, W., Coker, E.N., Li, B., Zheng, M.,
Yu, W., Fan, H., Sun, Z.: Oxygen vacancy enhanced photocata-
lytic activity of pervoskite S
­ rTiO3. ACS Appl. Mater. Interfaces.
6, 19184–19190 (2014)
54. Gu, L., Wei, H., Peng, Z., Wu, H.: Defects enhanced photocata-
lytic performances in ­SrTiO3 using laser-melting treatment. J.
Mater. Res. 32, 748–756 (2017)
55. Jafari, T., Moharreri, E., Amin, A.S., Miao, R., Song, W., Suib,
S.L.: Photocatalytic water splitting—the untamed dream: a review
of recent advance. Molecules 21, 900 (2016)
56. Wang, C., Qiu, H., Inoue, T., Yao, Q.: Band gap engineering of
­SrTiO3 for water splitting under visible light irradiation. Int. J.
Hydrogen Energy. 39, 12507–12514 (2014)
57. Shi, Y., Xiao, M., Luo, L., Zhang, Y., Wang, S., Chen, Y., Long,
Y., Li, L., Jiang, F.: ­Bi2O3/BiFeO3 heterostructure: preparation,
characterization, and photocatalytic activity. Chem. Pap. 72,
1327–1337 (2018)
58. Li, H., Zhou, Y., Tu, W., Ye, J., Zou, Z.: State-of-the-art progress
in diverse heterostructured photocatalysts toward promoting pho-
tocatalytic performance. Adv. Funct. Mater. 25, 998–1013 (2015)
59. Prabhakar Vattikuti, S.V., Byon, C., Reddy, C.V.: Z ­ rO2/MoS2 het-
erojunction photocatalysts for efficient photocatalytic degradation
of methyl orange. Electron. Mater. Lett. 12, 812–823 (2016)
60. Hu, Y., Liu, Y., Qian, H., Li, Z., Chen, J.: Coating colloidal car-
bon spheres with CdS nanoparticles: microwave-assisted synthesis
and enhanced photocatalytic activity. Langmuir 26, 18570–18575
(2010)
61. Cao, L., Sahu, S., Anilkumar, P., Bunker, C.E., Xu, J., Fernando,
K.A.S., Wang, P., Guliants, E.A., Tackett, K.N., Sun, Y.-P.: Car-
bon nanoparticles as visible-light photocatalysts for efficient
­CO2 conversion and beyond. J. Am. Chem. Soc. 133, 4754–4757
(2011)
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