Accepted Manuscript

Full Length Article

Fabrication of CdSe/CaTiO3 nanocomposties in aqueous solution for improved

photocatalytic hydrogen production

Jishu Han, Ying Liu, Fangxu Dai, Ruiyang Zhao, Lei Wang

PII: S0169-4332(18)32142-1
DOI: https://doi.org/10.1016/j.apsusc.2018.08.026
Reference: APSUSC 40063

To appear in: Applied Surface Science

Received Date: 15 June 2018

Revised Date: 23 July 2018
Accepted Date: 3 August 2018

Please cite this article as: J. Han, Y. Liu, F. Dai, R. Zhao, L. Wang, Fabrication of CdSe/CaTiO3 nanocomposties
in aqueous solution for improved photocatalytic hydrogen production, Applied Surface Science (2018), doi: https://
doi.org/10.1016/j.apsusc.2018.08.026

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 Fabrication of CdSe/CaTiO3 nanocomposties in aqueous solution for

improved photocatalytic hydrogen production

Jishu Hana, Ying Liua, Fangxu Daia, Ruiyang Zhaob, Lei Wanga*

a
Key Laboratory of Eco-chemical Engineering, Ministry of Education, College of Chemistry

and Molecular Engineering, Qingdao University of Science and Technology, Qingdao

266042, P.R.China. bCollege of Chemical Engineering, Qingdao University of Science and

Technology, Qingdao 266042, P.R.China. E-mail: jishu_han@163.com, yingl_qust@163.com,

dfx_qust@163.com, zhaoruiyang1985@163.com, inorchemwl@126.com.

*Corresponding author e-mail: inorchemwl@126.com; Fax: +86 532 84023927; Tel: +86

532 84022681.
Abstract

Novel CdSe/CaTiO3 nanocomposites are prepared in aqueous phase and used for

photocatalytic hydrogen production. The modification of CdSe QDs on the surface of CaTiO 3

sheet-like structure effectively increases visible light absorption of nanocomposites, improves

the separation and transfer of photoinduced electrons and prevents the recombination of

electron-hole pairs. Experimental results show that obtained CdSe/CaTiO 3 nanocomposites

possess significantly enhanced photocatalytic hydrogen production performance. The

photocatalytic hydrogen production amount of CdSe/CaTiO3 is 48 times higher than that of

pure CaTiO3 and 4.14 times higher than that of CdSe QDs. Meanwhile, CdSe/CaTiO3

nanocomposites display high stability and recyclability, which is beneficial for photocatalytic

hydrogen production application.

Keywords: nanocomposite, CdSe, photocatalysis, hydrogen production

1. Introduction

To date, the natural energy such as coal and fossil oil are faced with growing depletion. At

the same time, the environmental pollution and greenhouse effect caused by the burning of

fossil fuels also forced us to look for a clean, sustainable and renewable source of energy to

replace natural energy [1]. Hydrogen as a kind of clean energy has been widely concerned in

recent years since it possesses many advantages, such as high calorific value, non-toxic and

clean combustion production. Therefore, hydrogen is gradually accepted to be an alternative

to conventional fossil fuels [2]. But the methods of large-scale production of hydrogen still

have some shortcomings such as large energy consumption and environmentally unfriendly,

so it is necessary to find a more economical and green method to produce hydrogen. When the

method of water splitting into hydrogen by TiO2 electrodes was reported [3], the

semiconductor photocatalytic hydrogen production technology becomes one of the most

important approaches to solve global energy and environmental issues [4].

Now semiconductor materials for photocatalytic hydrogen evolution reaction have been

widely researched and developed [5], such as TiO2 [6-9], g-C3N4 [10-12], MoS2 [13-15],

CaTiO3 [16-19] and so on. Among, CaTiO3 is well known as one of the most important

perovskites and shows excellent photocatalytic performance in degradation of organic and

inorganic pollutants and the photolysis of water into hydrogen and oxygen [20]. On the other

hand, the superiorities of simple synthesis method, low cost and acid resistance also make

CaTiO3 to be one of the promising photocatalysts [21]. However, the wide band gap of

CaTiO3 leads to the low visible-light utilization and the high recombination rate of

photoinduced electrons and holes, thus resulting in the decrease of photocatalytic activity.

Therefore, the faced challenge is fabricating highly active CaTiO3 photocatalyst through
various modification. In comparison, the formation of nanocomposites could effectively alter

the band gap, restrain the photoinduced electron-hole pair recombination and further improve

the photocatalytic activity.

Among numerous nanomaterials, colloidal semiconductor quantum dots (QDs), especially

metal chalcogenide QDs such as CdS [22], CdSe [23-25], CdTe [26], have appeared at the

forefront. It is because their unique properties are quite different from the bulk materials [27],

such as the size-dependent optical properties, quantum confinement effects and large

surface-to-volume ratios [28,29]. And they have been used in various applications, such as

bio-labeling, solar cell, light-emitting diodes and so on [30-32]. Moreover, metal

chalcogenide QDs have been recently demonstrated as ideal candidates for solar H 2 evolution

due to their outstanding advantages in visible-light harvesting [33], charge separation, rich

surface binding properties [27]. Recently, CdSe QDs [34], CdSe/CdS QDs [35,36], CdSe/ZnS

QDs/1T-MoS2 [37] were reported to be used in photocatalytic hydrogen production

successively. CdSe QDs possess suitable band gap and conduction band edge [38-40], which

is beneficial for the transfer of excited electrons. Therefore, utilizing CdSe QDs to modify

CaTiO3 would be a promising approach to improve the photocatalytic hydrogen production

performance of CaTiO3.

In this work, we report a novel type of CdSe/CaTiO3 nanocomposites as photocatalyst for

hydrogen production. Here CaTiO3 are synthesized through hydrothermal method and CdSe

QDs are synthesized in aqueous solution capped by mercaptopropionic acid (MPA), avoiding

the use of organic solvent and further phase transition [41]. Then CaTiO3 are composited with

water soluble CdSe QDs. The results demonstrate that CdSe/CaTiO3 nanocomposites show

distinctly enhanced visible light photocatalytic activity for hydrogen production.

2. Experimental Section

2.1 Materials

Selenium powder (99%), NaBH4 (96%), NaOH (99%), mercaptopropionic acid (MPA,

99%), Cd(NO3)2·4H2O (99%), Ca(NO3)2·4H2O, tetrabutyl titanate (99%), Na2SO3 (99%),

Na2S·9H2O (99%) and K2PtCl4 (99%) were purchased from aladdin. Other chemicals are of

analytical grade without further purification unless otherwise noted.

2.2 Synthesis of CdSe /CaTiO3 nanocomposites

The preparation of CdSe QDs was improved based on previous reports [42]. In brief, 0.315

g of selenium powder, 6 mL of chilled water and 0.34 g of NaBH4 were added to a glass vial.

The reaction showed intense bubbling and lasted for approximately 90 min. Finally, the black

selenium was reduced and transparent NaHSe was obtained. Aqueous colloidal CdSe QDs

solution was prepared by mixing a solution of Cd(NO3)2·4H2O and MPA at pH 11.0, and then

adding a certain volume of the as-prepared NaHSe solution. The reaction was deaerated with

N2 bubbling in a three-necked flask, and refluxed for 2.0 h at 100 oC to promote the growth of

CdSe QDs. CdSe QDs with different concentration (0.001 M, 0.01 M, 0.1 M referring to Cd)

were obtained through above method.

CaTiO3 were synthesized according to the reported methods [20]. CaTiO3 particles were

synthesized through the hydrothermal method. In a typical process, solid Ca(NO3)2·4H2O

(2.362 g) was dissolved by deionized water (30 mL) in the 50 mL Teflon-lined stainless steel

vessel. Tetrabutyl titanate (3.4 mL) was dropwise added into the solution under vigorous

stirring. Then, solid NaOH (0.8 g) was introduced as the mineralization reagent. The mixture

was continuously stirred at ambient temperature for 1.0 h. Subsequently, the hydrothermal

treatment was carried out for 24 h at 200 oC. The precipitates were centrifuged and washed for
several times with ethanol and deionized water, and then dried for 12 h at 80 oC.

As-prepared CaTiO3 (0.3 g) was dissolved in 50 mL CdSe QDs solution under vigorous

stirring at room temperature for 24 h in the dark. The products were collected, washed several

times with ethanol and deionized water, and then dried at 60 oC in vacuum for further usage.

For comparison, the CdSe QDs with different concentration (0.001 M, 0.01 M, 0.1 M

referring to Cd) were composited with CaTiO3 and the corresponding products were denoted

CdSe/CaTiO3-1, CdSe/CaTiO3-2 and CdSe/CaTiO3-3, respectively.

2.3 Photoelectrochemical measurements

Electrochemical impedance spectroscopy (EIS) was carried out on an electrochemical

workstation (Gamry 35119) with a glassy carbon electrode, a carbon rod and Hg/HgCl

electrode (SCE, saturated KCl) as the working electrode, counter and reference electrode,

respectively. In the EIS tests, the photocatalysts were modified on working electrodes and the

measurement was carried out with the amplitude of 10 mV and a frequency range from 100

kHz to 0.1 Hz in 0.35 M Na2S and 0.25 M Na2SO3 aqueous solution. The photocurrent

response tests were carried out on a CHI 660D workstation with a three-electrode model,

which was composed of a FTO slice as working electrode, a Pt electrode as the counter

electrode and an Ag/AgCl electrode as the reference electrode. Then the working electrodes

were modified with 10 mg of the photocatalyst and A 300 W Xe lamp served as a light source.

2.4 Photocatalytic hydrogen evolution

The photocatalytic hydrogen evolution experiments were carried out in a closed quartz

reactor flask. During the photocatalysis, a 300W Xe lamp was used as the light sources, which

was positioned 10 cm away from the reactor. Typically, 25 mg of the as-obtained catalysts

was dispersed in 100 mL of an aqueous solution containing 0.35 M Na 2S and 0.25 M Na2SO3
as sacrificial agent and 1 mL K2PtCl4 (0.32 mg/mL) as the co-catalyst. Before irradiation, the

system was bubbled with nitrogen for 15 min to remove the air. The produced hydrogen was

analyzed by an online gas chromatograph system equipped with a thermal conductivity

detector.

2.5 Characterization

X-ray powder diffraction (XRD) investigation was collected using X’Pert PRO MPD

diffractometer. The catalysts morphologies were observed using a scanning electron

microscope (SEM, JSM-7500F), Transmission electron microscopy (TEM, Tecnai-G20) and

high-resolution transmission electron microscope (HRTEM, Tecnai-G2-F30 (FEI, USA)).

X-ray photoelectron spectroscopy (XPS) was recorded using Escalab 250Xi spectrometer

(Thermo Fisher Scientific) equipped with a monochromatic Al-Kα X-ray source (1486.6 eV).

UV-visible diffuse reflectance spectra (DRS) were recorded using a Lambda 750

UV/VIS/NIR spectrometer. A F-4500 fluorescence spectrophotometer was used to determine

the photoluminescence (PL) spectra.

3. Results and Discussion

Aqueous CaTiO3 and CdSe/CaTiO3 nanocomposites are synthesized as mentioned in

experimental section. As shown in Fig. 1a and b, the morphology of as-obtained CaTiO3 is a

sheet-like shape and the surface of CaTiO3 is very smooth. When CaTiO3 is composed with

CdSe QDs, the smooth surface of CaTiO3 is covered with CdSe (Fig. 1c). The size of CdSe on

the surface is about 20 nm. Monodispersed CdSe QDs are observed in Fig. S1a, and the

diameters of CdSe QDs are mainly distributed in the narrow range of 6−11 nm, with an

average size of 8 nm (Fig. S1b). For avoiding the size influence of three different

concentration CdSe QDs on the reactivity of the nanocomposites, three kinds of CdSe QDs
with nearly same size distribution are synthesized through controlling their reflux time

(Figure S1c and d). After compositing with CaTiO 3, the size of the CdSe QDs becomes lager,

due to the occurrence of QD aggregation. The HRTEM image in Fig. 1d presents the

interplanar distances are 0.24 and 0.378 nm, which are consistent with the spacing of the (220)

plane of CdSe and (110) plane of CaTiO3 respectively, indicating that CdSe QDs are loaded

on the surface of the CaTiO3. To investigate the composition of the as-prepared

nanocomposites, the XRD patterns of CaTiO3, CdSe QDs and CdSe/CaTiO3 are characterized

in Fig. 2. It can be seen that all the diffraction peaks of CaTiO3 can be indexed to the

orthorhombic phase of CaTiO3 (JCPDS No.22-0153). The sharp diffraction peaks indicate

CaTiO3 is well crystallized. And all the peaks in the XRD pattern of CdSe QDs are fitted well

to the zinc blende structure of bulk CdSe crystal (JCPDS No. 19-0191). When forming the

CdSe/CaTiO3 nanocomposites, the main characteristic diffraction peaks do not shift compared

to CaTiO3. And the diffraction peaks of CdSe QDs are not observed obviously. This may be

resulted from that the diffraction peaks of CdSe QDs are relative weaker and could not be

detected when coexisting with CaTiO3. Moreover, there is no impure phases detected,

indicating that the as-prepared CdSe/CaTiO3 nanocomposites photocatalysts are two-phase

hybrids.

The XPS analysis is performed to further investigate the surface chemical composition of

the CdSe/CaTiO3. The XPS survey spectrum (Fig. S2) show the existence of Ca, Ti, Cd, and

Se elements in the composite, further confirming the coexistence of CaTiO 3 and CdSe. The

high-resolution XPS spectra of Cd 3d, Se 3d, Ca 2p and Ti 2p are shown in Fig. 3. The XPS

spectrum (Fig. 3a) of Cd 3d can be resolved into two peaks at around 404.9 eV and 411.7 eV

respectively. In the Se 3d XPS spectrum (Fig. 3b), the peak is observed at around 53.8 eV,
which is consistent with selenium in selenide. The XPS spectrum of Ca 2p (Fig. 3c) can be

resolved into two peaks with the binding energy of 349.7 eV and 346.2 eV, which are assigned

to the characteristic spectrum of Ca2+ in CaTiO3. As shown in Fig. 3d, the XPS spectrum of Ti

2p can be resolved into two peaks at around 458.1 eV and 463.9 eV, attributed to the

characteristic spectra of Ti4+ in CaTiO3. According to the XPS data (Table S1), the atomic

ratio of Ca and Ti is 1:1.1. And the atomic ratio of Cd and Se is approximately 1.8:1. It is

because excessive Cd2+ is added in the preparation process, thus leading to more Cd atoms

bonded on the surface of nanocrystal than Se atoms. The molar ratio of CaTiO3 and CdSe is

calculated to be 4.8:1 based on the XPS measurement.

For investigating the visible light absorption performance of as-prepared photocatalyst, the

UV-vis diffuse spectra of CdSe QDs, CaTiO3 and CdSe/CaTiO3 with different concentration

of CdSe are presented in Fig. 4a. The pure CaTiO3 exhibits a weak absorption with the

absorption edge at around 348 nm, whereas CdSe QDs possess a broad and intense visible

light absorption with the absorption edge at around 612 nm. After CdSe QDs modified on the

surface of CaTiO3, the visible light absorption significantly enhances with the increase of

CdSe QDs concentration. This result indicates that the addition of CdSe QDs significantly

enlarges the absorption wavelength range and light trapping capability. The bandgap energies

of CaTiO3 and CdSe QDs are estimated in Fig. 4b. The bandgap energy can be obtained from

the extrapolated values of the tangents to the x axis. Therefore the bandgap energies of

CaTiO3 and CdSe QDs are 3.27 eV and 1.6 eV respectively. The specific calculation process

of the band positions of CaTiO3 and CdSe QDs as shown in Table S2.

In order to further demonstrate the charge transfer of the prepared nanocomposites, EIS is

investigated in Fig. 5a and S3. In general, the semicircle in the high-frequency region is
attributed to charge transfer resistance (Rct) [43]. The semicircle diameter of CaTiO3 is largest,

illustrating its poor conductivity. With the increase of CdSe QDs concentration, the

electrochemical impedance of CdSe/CaTiO3 nanocomposites gradually decreases, and

CdSe/CaTiO3-3 displays the smallest Rct value among these four samples. It indicates the

modification of CdSe QDs could improve the conductivity of nanocomposite and accelerate

charge transfer, as well as reduces the recombination rate of photoinduced electron-hole pairs.

The photocurrent responses of CaTiO3, CdSe QDs and CdSe/CaTiO3-3 nanocomposites are

also demonstrated in Fig. 5b. The CdSe/CaTiO3-3 nanocomposites with smallest Rct value

exhibits the highest photocurrent density (0.494 μA/cm−2) compared with pure CaTiO3 (0.227

μA/cm2) and pure CdSe QDs (0.364 μA/cm2). It suggests that the modification of CdSe QDs

effectively improves the photo-response of CdSe/CaTiO3 nanocomposites and the separation

and transfer of photoinduced charge carriers. Namely, the formation of CdSe/CaTiO3

nanocomposites would avoid the high recombination rate of photoinduced electron-hole pairs

and enhance its photocatalytic activity obviously.

Due to the improvement of photocatalytic performance, CdSe/CaTiO3 nanocomposites are

applied in photocatalytic hydrogen production in the presence of Na2S and Na2SO3 as

sacrificial agent. As shown in Fig. 6, the photocatalytic H2 evolution amount of CaTiO3 and

CdSe QDs are 500.8 μmol/g and 5822.2 μmol/g in 8 hours, indicating CaTiO3 and CdSe QDs

are not very active under this condition. In comparison, the H2 evolution significantly

increases after compositing with CdSe QDs. Among these CdSe/CaTiO3 nanocomposites,

CdSe/CaTiO3-3 exhibits highest photocatalytic activity. The H2 production amount reaches to

24111.5 μmol/g in 8 hours, which is 48 times higher than that of pure CaTiO3 and 4.14 times

higher than that of CdSe QDs. The result reveals that the modification of CdSe QDs on the
surface efficiently enhances the photocatalytic activity of H2 production. In addition, the

effect of 0.6 wt % Pt co-catalyst on the H2 evolution amount is compared in Figure S4a. The

H2 evolution amount without Pt co-catalyst is nearly same to that with 0.6 wt % Pt co-catalyst

at the first 1.5 hours and about 80% of that with Pt co-catalyst from 1.5 hours to 8 hours.

Although the H2 evolution amount of CdSe/CaTiO3 nanocomposites without Pt co-catalyst

decreased slightly, it is still 38.5 times higher than that of pure CaTiO3 and 3.3 times higher

than that of CdSe QDs. So the reactivity of the composite photocatalysts without using Pt

co-catalyst for electron sinks is still high. And the addition of K2PtCl4 facilitates

photocatalytic hydrogen production, rather then is the determinant of the increase of

photocatalytic H2 evolution amount. The visible-light-induced reactivity for H2 evolution by

CdSe/CaTiO3 nanocomposites is also compared in Figure S4b. The H2 evolution amount of

CdSe/CaTiO3 nanocomposites with cutoff filter (λ=420-785 nm) is 21253.5 μmol/g in 8 hours,

about 90% of that without cutoff filter (λ=350-785 nm). Because the light absorption of

CdSe/CaTiO3 nanocomposites in visible region is remarkably improved, CdSe/CaTiO3

nanocomposites mainly utilize the visible light to catalyze hydrogen production. Furthermore,

the stability and reusability of CdSe/CaTiO3 is investigated through the cycling experiments

in Fig. 6b. The H2 production amount of CdSe/CaTiO3-3 increases rapidly in each cycle, after

four cycles the H2 production amount remains over 93%. Moreover, the XPS spectra of

CdSe/CaTiO3 nanocomposites after the photocatalytic reaction are measured in Figure S5.

The peaks in the XPS spectra of Cd 3d, Se 3d, Ca 2p and Ti 2p are no shift and change

compared with those before the reaction (Figure 3), indicating no change in the oxidation state

of metal elements of the nanocomposites before and after the reaction. The CdSe/CaTiO3

displays good stability and could be reused for photocatalytic hydrogen production.
 Fluorescence intensity of CdSe/CaTiO3 nanocomposites is also characterized because high

fluorescence intensity represents facile recombination of photoinduced electron-hole pairs,

thus influencing the photocatalytic hydrogen production. As shown in Fig. S6, both CdSe

QDs and pure CaTiO3 show relatively strong fluorescence in Na2S/Na2SO3 solution. As the

amount of CdSe QDs increases in the nanocomposites, the fluorescence intensity of

CdSe/CaTiO3 decreases and CdSe/CaTiO3-3 possesses lowest fluorescence intensity,

indicating the occurrence of charge transfer between CdSe and CaTiO3 and effectively

suppression of photoinduced electron-hole recombination. The time-resolved fluorescence

emission decay curves of CaTiO3, CdSe QDs and CdSe/CaTiO3-3 are also analysed and

demonstrated in Fig. S7 and Table S3. The intensity-weighted average lifetime (τavg) of

CdSe/CaTiO3-3 decays obviously compared with CaTiO3 and CdSe QDs, indicating the

efficient charge transfer between CdSe QDs and CaTiO3 [36,44]. Based on biexponential

fitting data, τ1 corresponds to the near-band-edge emission, and τ2 originates from the spatially

localized states. The reduction in the recombination lifetime of τ1 results from the fast electron

migration between CaTiO3 and CdSe. And the reduction in the recombination lifetime of τ2

attributes to the suppression of undesired charge migration to the trap states [44]. So the

formation of CdSe/CaTiO3 nanocomposites results in the efficient charge transfer for the

photocatalytic reaction, thus enhancing H2 production efficiency significantly.

Based on the above measurements, the high photocatalytic H2 production activity of

CdSe/CaTiO3 nanocomposites would be attributed to the enhancement of light absorption, the

increase of CdSe QDs as reaction active sites, and the formation of interface between CdSe

QDs and CaTiO3 which improves the separation and transfer of photoinduced charge carriers.

The proposed photocatalytic mechanism of CdSe/CaTiO3 nanocomposites for photocatalytic

hydrogen evolution is illustrated in Figure 7. The conduction band and valence band

potentials of CaTiO3 and CdSe QDs have been calculated in Table S2. When the as-prepared

CdSe/CaTiO3 nanocomposites are irradiated, the electrons could be excited from the valence

band to the conduction band, thus generating the electron-hole pairs. Since the conduction

band potential of CaTiO3 (-1.095 eV) is more negative than that of CdSe QDs (-0.25 eV), the

photoinduced electrons would be driven and transfer from CaTiO3 to CdSe QDs, thus

facilitating the separation of electrons and holes. Especially, CdSe QDs possess high

photocatalytic H2 production performance (Fig. 6a). The accumulation of more electrons in

the CB of CdSe QDs would be beneficial to react with the adsorbed H + to generate more H2.

So the CdSe/CaTiO3 nanocomposites obviously increases photocatalytic H2 production rate.

In addition, the photoinduced holes in the valence band of CaTiO3 would transfer to the

valence band of CdSe to react with S2-/SO32-, which could also inhibit the recombination of

photoinduced electron-hole pairs.

4. Conclusions

In summary, novel CdSe/CaTiO3 nanocomposites with improved photocatalytic activities

have been fabricated by aqueous synthesis and hydrothermal method. The modification of

CdSe QDs on the surface of CaTiO3 effectively increases visible light absorption, improves

the separation and transfer of photoinduced electrons and prevents the recombination of

electron-hole pairs, thus significantly enhancing the photocatalytic hydrogen production

performance. Moreover, CdSe/CaTiO3 nanocomposites display high stability and recyclability,

which is beneficial for photocatalytic hydrogen production application.

Supporting Information
 TEM images and size distributions histogram of the CdSe QDs, XPS survey spectrum of

CdSe/CaTiO3 nanocomposites, Atomic content of the prepared CdSe/CaTiO3 nanocomposites

based on the XPS data, Calculation of X, Eg, ECB and EVB of CaTiO3 and CdSe QDs, EIS

Nyquist plots of CdSe QDs, The effect of Pt co-catalyst on the H2 evolution amount, The H2

evolution amount of the CdSe/CaTiO3-3 nanocomposites under different light irradiation,

XPS spectra of CdSe/CaTiO3 nanocomposites after the photocatalytic reaction, PL spectra of

CaTiO3, CdSe QDs, CdSe/CaTiO3 nanocomposites in Na2S/Na2SO3 solution, Time-resolved

fluorescence emission decay curves and photoluminescence lifetime of CaTiO3, CdSe QDs,

CdSe/CaTiO3-3.

Acknowledgements

This work was supported by National Natural Scientific Foundation of China [grant

numbers 51703112, 51772162, 21571112, 51572136, 21601103], the Taishan Scholars

program, Natural Science Foundation of Shandong Province, China [grant numbers

ZR2016BQ28, ZR2017BEM040], China Postdoctoral Science Foundation [grant numbers

2017M622152], Open Fund of the State Key Laboratory of Luminescent Materials and

Devices [South China University of Technology, No. 2017-skllmd-10] and the Scientific

Research Foundation of Key Laboratory of Eco-chemical Engineering, Ministry of Education

Qingdao University of Science and Technology [KF1701].

Notes

Declarations of interest: none.

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Fig. 1. SEM image (a) and TEM image (b) of CaTiO3, SEM image (c) and HRTEM image (d)
of CdSe/CaTiO3 nanocomposites.

Fig. 2. XRD patterns of the as-synthesized CaTiO3, CdSe QDs and CdSe/CaTiO3
nanocomposites.
Fig. 3. XPS spectra of the CdSe/CaTiO3 nanocomposites, (a) Cd 3d, (b) Se 3d, (c) Ca 2p, (d)
Ti 2p.

Fig. 4. UV-visible diffuse spectra (a) of CaTiO3, CdSe QDs, CdSe/CaTiO3-1, CdSe/CaTiO3-2
and CdSe/CaTiO3-3 nanocomposites, Plots of (Ahν)1/2 versus photon energy (hν) for the band
gap energies of CaTiO3 (b) and Plots of (Ahν)2 versus photon energy (hν) for the band gap
energies of CdSe QDs (c).
Fig. 5. EIS Nyquist plots (a) of CaTiO3, CdSe/CaTiO3-1, CdSe/CaTiO3-2 and CdSe/CaTiO3-3,
PEC current response spectra (b) of CaTiO3 , CdSe QDs and CdSe QDs/CaTiO3-3
nanocomposites.

Fig. 6. (a) The stereogram of H2 evolution amount of the CaTiO3, CdSe QDs, CdSe/CaTiO3-1,
CdSe/CaTiO3-2 and CdSe/CaTiO3-3 nanocomposites in 8 hours, (b) Photocatalytic H2
evolution amount of CdSe/CaTiO3-3 nanocomposites for 4 cycles.
Fig. 7. Schematic diagram of the proposed photocatalytic mechanism of CdSe/CaTiO3
nanocomposites for photocatalytic hydrogen evolution.
Highlights:

 CdSe modified CaTiO3 nanocomposites exhibit high photocatalytic activity for hydrogen

production.

 The nanocomposites improve the separation and transfer of photoinduced electrons.

 High stability and recyclability is beneficial for hydrogen production application.

Graphical abstract: