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Article
CdS Nanospheres Decorated with NiS Quantum Dots as Nobel-
metal-Free Photocatalysts for Efficient Hydrogen Evolution
Wuyuan Tan, Yuanli Li, Wenshuai Jiang, Chunlang Gao, and Chunqiang Zhuang
ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.0c01507 • Publication Date (Web): 03 Aug 2020
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Page 1 of 32 ACS Applied Energy Materials

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4 CdS Nanospheres Decorated with NiS Quantum Dots as
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7 Nobel-Metal-Free Photocatalysts for Efficient Hydrogen
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9 Evolution
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12 Wuyuan Tan , Yuanli Li #, Wenshuai Jiang, Chunlang Gao, and Chunqiang Zhuang
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17 ABSTRACT:
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20 Noble-metal-free photocatalysts has attracted tremendous interest in recent years.
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22 Among them, cadmium sulfide (CdS) has been considered as one of the most important
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25 photocatalysts for potential applications on hydrogen evolution. However, its efficiency
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is relatively low due to the fast recombination of photo-generated charge carriers. In
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30 this work, defective CdS nanospheres were designed. NiS quantum dots were
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33 introduced to facilitate the efficient separations of photo-generated electrons and holes.
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35 Without noble metals, the hydrogen production of CdS nanospheres with NiS quantum
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38 dots is ~ 24 times higher than that of pure CdS nanospheres, demonstrating the key role
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of NiS quantum dots in highly efficient separations of photo-generated carriers.
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43 Meanwhile, the designed photocatalysts has good stability. They can maintain ~ 90%
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46 photocatalytic ability during the stability measurement. The potential photocatalytic
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48 mechanism was proposed.
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51 KEYWORDS: CdS photocatalysts, NiS quantum dots, hydrogen production, defect,
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stability
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58 
59 These authors contributed equally to this work
Corresponding author: [email protected] (C. Zhuang)
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7 1. INTRODUCTION
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9 In recent years, ever-increasing consumption of fossil fuels has resulted in the
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12 climate changes and ambient air pollutions. Considerable endeavors have been devoted
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to developing clean, abundant, and renewable energies.1 Among them, hydrogen has
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17 attracted great attention because it is clean and renewable.2 There are many approaches
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20 to produce hydrogen. One of them is from water splitting over photocatalysts using
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22 solar energy. This method has received broad attention due to its sustainability and
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25 environmental friendliness.3, 4
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With regard to water splitting, various photocatalysts such as metal oxides,
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30 oxynitrides, metal sulphides and perovskite have been developed.5-8 In particular,
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33 cadmium sulfide (CdS) has attracted intensive attention.9 However, pure CdS has a low
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35 efficiency of hydrogen production due to the fast recombination of photo-generated
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38 carriers.10 To solve the problem, noble metals (eg. Pt11,12, Pd13, Au14) were introduced
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as cocatalysts. CdS photocatalysts loaded with noble metals generally showed an
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43 apparent improvement of hydrogen production.15,16 However, the high costs and low
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46 reserves of noble metals limit the broad applications of such kinds of photocatalysts.
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48 Thus, the exploration of non-noble metals as cocatalysts has been one of the most
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51 important issue for developing new kinds of photocatalysts for hydrogen evolution.
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Earth-abundant element-based materials have been used as cocatalysts to improve
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56 the photocatalytic activity of CdS, such as MoS2,17 NiS,18 CuS19 and WS2.20 Among
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59 them, nickel sulfide (NiS) has received increasing attention due to its easy preparation,
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4 low cost, high conversion efficiency, high electrical conductivity, and friendliness to
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7 environment.21 For CdS decorated with NiS, previous studies show that their
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9 photocatalytic properties are closely related to surface morphologies. In general, CdS
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12 with two-dimensional nanosheet, one-dimensional nanowire and nanotube has high H2
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production rates.22-25 This indicates that the morphology plays an important role in
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17 determining the photocatalytic properties of CdS materials. Indeed, zero-dimensional
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20 nanostructures have showed a high quantum yield of 51.3%26 or even higher up to
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22 60.4%.27 They are beneficial to charge separations to achieve highly photocatalytic
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25 hydrogen production.28 In addition, defects are also important in photocatalysts. Photo-
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generated electrons can move towards defects where their locations are relatively
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30 energetic which can be used as potential active sites.24
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33 In this work, zero-dimensional defective CdS nanospheres were designed, which
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35 were coupled with NiS quantum dots to achieve highly efficient separations of photo-
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38 generated electrons and holes. The photocatalytic performances were evaluated by
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hydrogen production from water splitting under full spectrum irradiation. A possible
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43 mechanism was proposed.
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48 2. EXPERIMENTAL SECTION
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51 Material preparations
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CdS nanospheres were prepared by hydrothermal method.29-31 Cadmium acetate
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56 (0.5 g) and thiourea (0.7 g) were added into a beaker with 50 ml deionized water under
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59 continuous stirring. Then the solution was transferred to a Teflon lined autoclave, and
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4 treated at 160 oC for 2 h. Afterwards, the solution was collected by centrifugation and
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7 washed by deionized water. The obtained samples were dried at 80 oC in air.
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9 In a typical synthesis of NiS@CdS photocatalysts, 200 mg CdS and 2.28 g thiourea
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12 were dispersed into a beaker with 40 ml deionized water under ultrasonic treatment.
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Then 0.2 M nickel acetate tetrahydrate was added into the solution to obtain different
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17 loading concentrations of NiS (1.5 wt.%, 3 wt.%, 5 wt.%, 7 wt.%, 10 wt.%). Afterwards,
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20 the solution was transferred into a Teflon lined autoclave, and treated at 140 oC for 4 h.
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22 Then, the particles were washed by deionized water, and dried at 60 oC in air.
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25 Material characterizations
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Powder X-ray diffraction (XRD) were collected by X-ray diffractometer with Cu-
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30 K radiation (Bruker D8 Advance). The morphologies of obtained samples were
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33 characterized by field emission scanning electron microscope (FESEM, FEI Quanta
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35 650) operated at 10 kV. Atomic-scale microstructures were characterized by high-
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38 resolution transmission electron microscopy (HRTEM, FEI, Themis) operated at 300
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kV. UV-vis diffuse reflection spectroscopy was examined by Shimadzu UV-2600
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43 spectrophotometer with BaSO4 as the benchmark. The photoluminescence (PL) spectra
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46 were collected by Hitachi F-7000 instrument with an excitation wavelength of 325 nm.
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48 The binding states were detected by X-ray photoelectron spectroscopy (XPS)
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51 measurements (Thermo, ESCALAB250). The electron paramagnetic resonance (EPR)
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was performed on EPR spectrometer (Bruker, Germany) at room temperature.
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56 Electrochemical tests were carried out by CHI760e instrument in a standard three-
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59 electrode system. Platinum wire was used as counter electrode and Ag/AgCl electrode
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4 was used as reference electrode. The working electrodes were prepared by coating
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7 prepared photocatalysts onto indium tinoxide (ITO) conductive glass. 0.1 M Na2SO4
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9 aqueous solution was used as the electrolyte.
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12 Photocatalytic measurements
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The photocatalytic activities were evaluated by hydrogen production in a Pyrex
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17 reaction cell that is connected to a gas circulation system under vacuum (Beijing Perfect
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20 Co., Ltd). 10 mg photocatalysts were dispersed into 50 mL of ultrapure water with Na2S
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22 and Na2SO3 as sacrificial agents. The suspension was then degassed and irradiated by
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25 Xe lamp (300 W). The hydrogen production was monitored by an online gas
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chromatography. The apparent quantum efficiency (AQE) was measured by using
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30 band-pass filters with specific wavelength and calculated by the following equation:
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Number of hydrogen  2
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34 Number of incident photons
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39 3. RESULTS AND DISCUSSION
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42 The microstructures of obtained samples were firstly studied by X-ray powder
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44 diffraction (XRD). As shown in Figure 1, pure CdS nanospheres (0 %) are hexagonal
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47 phase (JCPDS 80-0006).32 Diffraction peaks at 24.9o, 26.4o, 28.2o, 43.7o, 47.7o, 51.9o
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50 correspond to (100), (002), (101), (110), (103), and (112) planes, respectively. Peaks at
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52 69.5o, 70.9o, and 77.2o can be indexed to (211), (114), and (204) planes, respectively.
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55 With the incorporation of NiS nanoparticles, there are several tiny peaks, which
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57 correspond to the structural characteristic of NiS nanoparticles (JCPDS 12-0041). They
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4 are (101), (300), (021), (211), (131), (410), (300) and (012) planes at 29.8o, 31.7o, 34.9o,
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7 39.8o, 48.2o, 49.7o, 57.1o, and 59.2o, respectively.33 This indicates that the incorporation
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9 of NiS nanoparticles do not change the main structure of CdS nanospheres. This also
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12 indicates that the loading of NiS nanoparticles does not enter into the crystal lattice of
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CdS nanospheres.34 In our experiments, CdS nanospheres were prepared firstly, and
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17 then they were transferred into a Teflon lined autoclave with the addition of Ni source
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20 for the synthesis of CdS@NiS samples. In principle, NiS should not enter into the lattice
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22 of CdS. It is not like the case that Cd, S and Ni precursors are together put into Teflon
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25 lined autoclave for the preparation of CdS@NiS samples. Nevertheless, if we see
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carefully the XRD patterns in the range of 30 ~ 40 degree, some differences can be
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30 observable. The existence of NiS can be further verified by TEM as shown below.
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33 Besides, NiS quantum dots are also not fully crystallized. This is also one possible
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29 Figure 1. X-ray diffraction patterns of pure CdS (0 wt.%) and CdS with different NiS
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31 contents. The corresponding peaks were marked inside.
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37 Scanning electron microscopy (SEM) was employed to check the phase
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39 composition and surface morphology of photocatalysts. Figure 2a shows typical surface
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42 morphologies of pure CdS nanospheres. They are relatively uniform with an average
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44 size of ~ 500 nm. It can be inferred from Figure 2a that CdS nanospheres are assembled
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47 by relatively small CdS nanoparticles as indicated by plenty of grain boundaries on the
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50 surface of CdS nanospheres. These defects are not only beneficial to the loading of NiS
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52 quantum dots, but also promote the fast separations of photo-generated carriers. This
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55 will be further discussed in the following section. EDS mappings in Figure 2b-d show
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29 Figure 2. (a) A typical SEM image of CdS nanospheres. (b-d) EDS mappings of CdS
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37 Detailed structural information was further characterized by transmission electron
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39 microscopy (TEM). Figure 3a shows the typical low-magnification micrograph of CdS
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42 nanosphere with NiS quantum dots. Figure 3b shows the atomic image of CdS. The
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44 interplanar spacing of 0.36 nm and 0.32 nm corresponds to the (100) plane and the
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47 (111) plane of hexagonal CdS, respectively. This can also be evaluated by the fast
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50 Fourier transform (FFT) in Figure 3c. Figure 3d shows clearly the atomic image of CdS
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52 and NiS as marked by arrows. The TEM sample was prepared by continuously
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55 ultrasonic treatment. If NiS quantum dots adhered loosely to the surface of CdS
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4 the strong ultrasonic treatment. The observation in Figure 3d clearly shows that NiS
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7 quantum dots are tightly adhered onto CdS nanospheres. Elemental distributions were
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12 in Figure 3e-h, in which the Ni signal can be clearly captured. We can ensure that NiS
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has been successfully loaded onto the surface of CdS nanospheres. Besides, pure NiS
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17 quantum dots were also prepared by the same experimental procedure as that of
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20 CdS@NiS (7 wt.%) without the addition of CdS nanospheres. The obtained NiS
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25 observations. Figure 3i shows the low magnification TEM image, revealing the
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morphology of NiS quantum dots with the grain size of ~ 5 nm (dark dots inside).
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4 Figure 3. (a) Typical TEM image of CdS nanosphere. (b) CdS atomic image. (c) FFT
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7 image of (b). (d) Atomic images of CdS and NiS quantum dots. (e-h) EDS mapping of
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9 CdS nanosphere loaded with NiS quantum dots. (i) NiS quantum dots (black dots
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12 inside).
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17 X-ray photoelectron spectrum (XPS) was carried out to check the chemical
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20 compositions and the surface bonding states of NiS@CdS photocatalysts. Figure 4a and
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25 Ni signal is weak as observed from Figure 4b. This is probably caused by the relatively
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higher signal intensity of Cd and S, which is the similar as the case that samples were
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30 dispersed onto silicon wafer for EDS mapping by SEM, the intensity of silicon
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33 dominates the EDS signals, resulting in small peaks for other elements, especially for
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35 the elements with tiny content. The high resolution of Cd element in Figure 4c has two
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38 main peaks located at 405.1 eV and 411.8 eV. The peak at 405.1 eV can be assigned to
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Cd 3d5/2, which can be deconvoluted into two peaks located at 404.9 eV and 405.4 eV.
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43 The peak at 411.8 eV can be assigned to Cd 3d3/2, which can be deconvoluted into two
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46 peaks located at 411.6 eV and 412.3 eV.35 The high resolution of S element in Figure
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51 located at 161.4 eV and 162.8 eV. They correspond to S 2p3/2 and S 2p1/2, respectively.34
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The small amount of Ni element results in a high-noise signal of the high resolution
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56 XPS of Ni element as shown in Figure 4e. Nevertheless, the Ni main peak is observable
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59 at 856 eV, which corresponds to the binding state of NiS quantum dots. The broadening
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4 of the Ni 2p curve can be deconvoluted into two peaks at 855.9 eV and 857.7 eV, which
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7 correspond to Ni 2p3/2 and Ni 2p1/2, respectively. Our results are consistent with
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9 previous reports.36 XPS data here further prove that NiS quantum dots are successfully
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12 deposited on the surface of CdS nanospheres. As comparisons, Figure 4f shows the
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high-resolution XPS of Cd element for CdS and CdS loaded with NiS. The binding
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17 energy of Cd 3d5/2 and Cd 3d3/2 is located at 404.9 eV and 411.6 eV for pure CdS
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20 nanospheres, respectively. The two peaks shift towards higher binding energy of 405.3
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22 eV and 412.0 eV for CdS nanospheres loaded with NiS. The peak drift was corrected
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25 for each measurement by standard procedure based on carbon source, the peak shift
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indicates that the changes of binding states of Cd elements after loading NiS quantum
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37 Figure 4. Full X-ray photoelectron spectrum of pure CdS nanospheres (a) and CdS
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42 Cd, S and Ni elements. (f) Comparison of Cd 3d between pure CdS and CdS with NiS
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44 (7 wt.%).
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50 The photocatalytic activities are shown in Figure 5. The hydrogen evolution of all
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52 photocatalysts shows a nearly linear trend as a function of reaction time (Figure 5a).
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4 the low yield of hydrogen. As shown in Figure 5b, the hydrogen evolution rate is 113.2
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7 μmol g−1 for CdS nanospheres. With the incorporation of 1.5 wt.% NiS quantum dots,
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12 than that of pure CdS nanospheres. With more incorporation of NiS quantum dots, the
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H2 production rate is 953.5 μmol g−1 (3 wt.%), 1663.2 μmol g−1 (5 wt.%), 2569.3 μmol
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17 g−1 (7 wt.%) and 1117.5 μmol g−1 (10 wt.%). The H2 production rate of CdS
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20 nanospheres with 7 wt.% NiS is nearly 23 times higher that of pure CdS photocatalysts.
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25 induced electrons and holes, thus increasing H2 production. The H2 evolution can be
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comparable to previous works.37 Besides the full spectrum, we also performed the
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30 photocatalytic experiments under visible light with the ultraviolet filter ( > 420 nm).
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33 As shown in Figure 5c, the hydrogen production with filter is relatively lower
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38 hydrogen production of photocatalysts with ultraviolet filter is ~ 1770 μmol g−1 for 4 h
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as shown in Figure 5d.
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43 In addition, the cycle stability was evaluated by using CdS nanospheres with 7 wt.%
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46 NiS. As shown in Figure 5e, the H2 evolution rate in the first run is ~ 2578.2 μmol g−1,
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51 during the stability measurement. The stability can compare with previous works.38, 39
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The slightly decrease of the hydrogen production is probably from the photo-corrosion
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4 one plays the key role, the tested photocatalysts were collected after photochemical
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7 conversion process for further SEM and XRD studies. As can be seen from Figure 5f,
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9 the XRD result shows nearly no change after photocatalytic experiment comparing with
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catalysts also shows that the change of CdS morphologies is negligible as observed
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17 from in Figure 5g. Grain boundaries can still be clearly seen from the image, which are
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20 nearly the same as the catalysts before photocatalytic experiments. Based on the SEM
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25 reason of the degradation. The slight decrease of the cycling stability is probably due
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to the consumption of the sacrificial agents.
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30 The apparent quantum efficiencies (AQE) were measured by using different band-
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33 pass filters based on CdS nanospheres with 7 wt.% NiS. The trend of the AQE follows
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35 well with the UV-vis curve as shown in Figure 5h. The AQE obviously decreases as
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38 the wavelength increases. This indicates that the hydrogen production from water
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splitting is prompted by the adsorption of solar illumination. The AQE is relatively
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43 lower than previous reported results.29, 40 The AQE can be affected by many factors.
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46 For example, light power density, sacrificial agents, reactors, light sources,
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48 photocatalysts. Here the measured light power density is ~ 280 mW/cm2 for full
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51 spectrum and is ~ 220 mW/cm2 with ultraviolet cut filter. The light energy is not fully
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utilized during the photocatalytic process in our experiments. In addition, sacrificial
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56 agents are quite different from previous works.29,40 Moreover, our prepared
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59 photocatalysts are also different from the reported ones.29,40 We used CdS nanospheres
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4 decorated with NiS quantum dots, while they used one-dimensional CdS nanowires40
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7 or large-scale NiS ultrathin films together with carbon dots.29 The different
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Figure 5. photocatalytic properties of pure and hybrid CdS nanospheres. (a) The
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4 nanospheres with different concentrations of NiS quantum dots. (c) Hydrogen evolution
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7 as a function of reaction time with the ultraviolet cut filter ( > 420 nm). (d) Hydrogen
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9 production of photocatalysts with 7 wt.% NiS for 4 h with the ultraviolet cut filter. (e)
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12 The cycling stability of CdS nanospheres with 7 wt.% of NiS quantum dots. (f) XRD
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patterns of prepared photocatalysts (7 wt.% NiS) before and after photocatalytic
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17 experiments. (g) SEM image of prepared photocatalysts (7 wt.% NiS) after
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20 photocatalytic experiments. (h) Apparent Quantum efficiency of CdS nanosphere with7
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22 wt.% NiS, the corresponding UV-vis is also shown for comparisons.
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In order to unveil the mechanism of photocatalytic hydrogen production, the
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30 absorption properties were examined by UV-vis absorption spectra as shown in Figure
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33 6a. The corresponding Tauc-plot curve is shown in Figure 6b. The absorption edge is
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35 located at ~ 587 nm for CdS nanospheres. With the incorporation of NiS quantum dots,
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38 the absorption edge shifts towards ~ 560 nm. If we check the microstructures of CdS
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nanospheres as shown in Figure 2, we can observe that there are plenty of defects on
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43 the surface. These defects may result in the absorption edge of CdS nanospheres
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46 shifting towards low wavelengths. Defects are also indicated by the photoluminescence
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48 (PL) spectrum of CdS nanospheres as shown in Figure 6c. The broadened main peak
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51 and the long tail at the high wavelength can be clearly observed in the PL spectrum of
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CdS nanospheres. Moreover, defects are also detected by electron paramagnetic
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56 resonance (EPR) as shown in Figure 6d. Both CdS nanospheres and CdS with NiS have
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59 a resonance signal at g = 2.005, which is identified as electrons trapped by sulfur
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4 vacancy.41-43 With the incorporation of NiS quantum dots, the intensity of the EPR
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7 signal for CdS@NiS is lower than that of CdS nanospheres, indicating that the
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9 concentration of sulfur vacancy in CdS@NiS is decreased after loading NiS quantum
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12 dots. This is probably because the loading of NiS quantum dots onto CdS nanospheres
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fills parts of sulfur vacancy during the hydrothermal process.44
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44 Figure 6. (a) UV-vis absorbance properties of NiS and CdS nanospheres with different
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47 concentrations of NiS quantum dots. (b) Tauc-plot curves of NiS, CdS and CdS with 7
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50 wt.% NiS. (c) photoluminescence (PL) spectrum of CdS and CdS with 7 wt.% NiS. (d)
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52 Electron paramagnetic resonance (EPR) of CdS and CdS with 7 wt.% NiS.
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55 The PL intensity of CdS nanospheres in Figure 6c is clearly higher than that of
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57 CdS with 7 wt.% NiS. This indicates that the combination of photo-generated charge
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4 carriers in CdS nanospheres can be efficiently restrained by loading NiS quantum dots.
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7 NiS quantum dots play an important role in the fast separations of photo-generated
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9 carriers. To further demonstrate the transfer of photo-generated electrons and the
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12 potential mechanism, electrochemical tests were performed to examine the Mott-
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Schottky relations in NiS quantum dots, CdS nanospheres, and CdS@NiS (7 wt.%).
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17 The positive slope in Figure 7a-c indicates that they are n-type semiconductors. There
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20 is no obvious V-shape inside of Figure 7c. This indicates that the CdS@NiS (7 wt.%)
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22 is not p-n junction.45, 46 Combined UV-Vis data with Mott-Schottky plots, we can
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25 basically figure out the possible photocatalytic mechanism as shown in Figure 7d.
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Under the irradiation of light energy, photo-generated electrons are excited from VB to
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30 CB in CdS nanospheres. Electrons are separated from holes to form electron-hole pairs.
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33 Then photo-generated electrons migrate towards NiS quantum dots. NiS quantum dots
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35 are more like metallic cocatalysts. They are considered as active sites to collect photo-
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38 generated electrons from CdS nanospheres for the succeeding hydrogen evolution. In
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addition, NiS quantum dots have the dull black color, which are beneficial to enhancing
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43 the visible-light harvesting ability. The highly efficient separation of photo-generated
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46 charge carriers by NiS quantum dots thus greatly improves the photocatalytic properties
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48 of CdS nanospheres.47-50
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31 Figure 7. Electrochemical Mott-Schottky plots of NiS quantum dots (a), CdS
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34 nanospheres (b), and CdS@NiS (7 wt.%) (c). (d) The schematic description of the
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37 mechanism of hydrogen production for CdS nanospheres coupled with NiS quantum
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39 dots.
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44 In addition, we also used photo-deposition method to strengthen the proposed
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47 photocatalytic mechanism. Pt ions were used as an indicator of photo-generated
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50 electrons, which can be reduced by photo-generated electrons. Meanwhile, photo-
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52 generated holes can be consumed by the sacrificial agents of Na2S and Na2SO3. By
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55 tracking the location of reduced Pt particles, we can figure out the active sites for
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57 hydrogen evolution. In order to track clearly the active sites, we intentionally prepared
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4 one sample with large NiS particles on the surface of CdS nanospheres. Figure 8a shows
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7 the morphology of CdS with NiS by HADDF-STEM. EDS mapping in Figure 8b-e
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9 clearly shows the elemental distributions of Cd, S, Ni and Pt. We can see from Figure
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12 8e that Pt signal can be clearly observed on NiS. If the hydrogen evolution only happens
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on the surface of CdS nanospheres, Pt should not be detected on NiS. The appearance
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17 of Pt on NiS demonstrates the transition of photo-generated electrons from CdS
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20 nanospheres to NiS quantum dots. With regard to the Pt signal on CdS nanospheres, it
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22 is because the active sites on CdS nanospheres are not fully covered by the loading of
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25 small amount of NiS quantum dots. Parts of photo-generated electrons remain on CdS
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nanospheres for hydrogen evolution.
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46 Figure 8. (a) HADDF-STEM image of CdS with NiS. (b-e) EDS mapping of Cd, S, Ni
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48 and Pt elements.
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4. CONCLUSIONS
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56 In summary, defective CdS nanospheres decorated with NiS quantum dots were
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59 designed. Comparing with pure CdS, CdS nanospheres with NiS show highly efficient
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4 hydrogen evolution. The hydrogen evolution rate can reach up to 2569.3 μmol g−1,
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7 which is ~ 24 times higher than that of pure CdS nanospheres. This demonstrates that
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9 NiS quantum dots play the crucial role in the fast separations of photo-generated
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12 carriers, thus remarkably improving the photocatalytic properties of CdS nanospheres.
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The design of defective catalysts coupled with quantum-sized active sites may provide
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17 an efficient way to develop new kind of photocatalysts.
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22 AUTHOR INFORAMTION
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25 Corresponding Author
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28
Chunqiang Zhuang  Institute of Microstructure and Property of Advanced Materials,
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30 Beijing Key Lab of Microstructure and Property of Advanced Materials, Beijing
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33 University of Technology, Beijing 100124, China
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35 E-mail: [email protected] (C. Zhuang)
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Authors
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43 Wuyan Tan  Institute of Microstructure and Property of Advanced Materials, Beijing
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46 Key Lab of Microstructure and Property of Advanced Materials, Beijing University of
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48 Technology, Beijing 100124, China
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51 Yuanli Li  Institute of Microstructure and Property of Advanced Materials, Beijing
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Key Lab of Microstructure and Property of Advanced Materials, Beijing University of
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56 Technology, Beijing 100124, China
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59 Wenshuai Jiang  Beijing Key Laboratory for Green Catalysis and Separation,
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4 Department of Chemistry and Chemical Engineering, School of Environmental and
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7 Energy, Beijing University of Technology, Beijing 100124, China
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9 Chunlang Gao  Institute of Microstructure and Property of Advanced Materials,
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12 Beijing Key Lab of Microstructure and Property of Advanced Materials, Beijing
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University of Technology, Beijing 100124, China
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17
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20 Notes
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22 The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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30 This work was supported by the Basic Science Center Program for Multiphase
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33 Evolution in Hypergravity of the National Natural Science Foundation of China (No.
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35 51988101), the National Science Foundation of China (No. 11874001), the Natural
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38 Science Foundation of Beijing, China (No. 2182008), the “111” project (DB18015),
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40
and the Beijing Outstanding Young Scientists Projects (BJJWZYJH01201910005018).
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43
44
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