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Fabricate Globular Flower-like CuS/CdIn2S4/ZnIn2S4 with High Visible Light Response via Microwave-assisted One– step Method and Its Multi-pathway Photoelectron Migration Properties for Hydrogen Evolution and Pollutant Degradation Xi Chen, Li Li, Wenzhi Zhang, Yixuan Li, Qiang Song, and Li Dong ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b01543 • Publication Date (Web): 19 Sep 2016 Downloaded from http://pubs.acs.org on September 22, 2016
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Fabricate Globular Flower-like CuS/CdIn2S4/ZnIn2S4 with High Visible Light Response via Microwave-assisted One–step Method and Its Multi-pathway Photoelectron Migration Properties for Hydrogen Evolution and Pollutant Degradation Xi Chen a,b
Li Li a,b,c∗ Wenzhi Zhang b
Yixuan Li b
Qiang Song b Li Dong b
a. College of Materials Science and Engineering, Qiqihar University, No.42, Wenhua Street, Qiqihar, Heilongjiang, China b. College of Chemistry and Chemical Engineering, Qiqihar University, No.42, Wenhua Street, Qiqihar, Heilongjiang, China c. College of Heilongjang Province Key Laboratory of Fine Chemicals, Qiqihar University, No.42, Wenhua Street, Qiqihar, Heilongjiang, China
Abstract: The photocatalyst CuS/CdIn2S4/ZnIn2S4 with attractive visible light absorption was prepared by microwave-assisted one–step method, and then characterized by XRD, XPS, UV–vis/DRS, N2 adsorption–desorption, SEM, TEM and HRTEM tests. The results show that there are two kinds of crystal structures, hexagonal and cubic phase in the product. Moreover, the composite has an absorption edge as high as 670 nm with a high visible light response. In addition, the composite possesses an excellent surface area of 239.3 m2/g, displays a favorable globular flower-like surface morphology, and consists mostly of three disparate shapes of crystals in microstructure. Compared to heterogeneous ZnIn2S4 and P25, as-prepared composite demonstrates the greatest photocatalytic activity under simulated sunlight and visible light by methyl orange degradation. Together with Pt loading as cocatalyst, hydrogen was achieved over CuS/CdIn2S4/ZnIn2S4 in Na2S–Na2SO3 aqueous solution, leading to hydrogen production rate of 358.4 µmol·h-1·g-1 under simulated sunlight,
*
Corresponding author at: College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006, China. Tel.: +86 4522738206. E-mail addresses:
[email protected],
[email protected] (L. Li). -1-
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high hydrogen production rate of 233.9 µmol·h-1·g-1 under visible light (λ > 420 nm). Besides, utilizing the related formulas to calculate the semiconductor energy band configuration
and
speculate
the
possible
photoreaction
mechanism
of
CuS/CdIn2S4/ZnIn2S4. Finally, the effect of multi-pathway photoinduced charges migration during photocatalysis process was explained. Key words: Microwave-assisted one–step method; CuS/CdIn2S4/ZnIn2S4; Visible light response; Hydrogen evolution; Charge transfer
Introduction Since 1972, when professor Fujishima and Honda have found that TiO2 electrode could be used to decompose water into hydrogen and oxygen under UV irradiation, photocatalytic technology has attracted much attention.1 To date, hydrogen has attracted interest as an new energy carrier that others both huge energy capacity and less environmental impact, and the development of the high-efficiency photocatalyst is an important approach to increase the production of hydrogen.2–5 Not only that, photocatalytic technology also displays a broad prospect on environment pollution treatment. The photocatalytic degradation reaction can thoroughly destroy the pollution in water and air, and mineralize them into CO2, and H2O under the light at ordinary temperature and pressure.6–9 However, most of the photocatalysts show photocatalytic activity by ultraviolet light that corresponds to 3%~5% of the sunlight. Because of the inefficient sunlight utilization, researches aimed at the preparation of photocatalytic materials with higher visible light response are topical.10–13 In the recent years, ZnIn2S4, as the only member of the AB2X4 type semiconductor with a layered structure, has attracted some interests because of its applications in various fields.14–17 Lei et al. synthesized ZnIn2S4 catalyst by hydrothermal method which shows well and stable photocatalytic activity for H2 evolution under visible light irradiation.18 Gou et al. used cetyltrimethylammonium bromide (CTAB) or poly (ethylene glycol) (PEG) to prepare the ZnIn2S4 solid or hollow microspheres via a solvothermal method.19 Among the methods for ZnIn2S4 -2-
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synthesis, microwave irradiation has great interest in chemical synthesis. Compared to conventional heating, microwave irradiation exhibits the better advantages, for instance, fast heating, short reaction time and homogeneous heating.20–27 Accordingly, CuS/CdIn2S4/ZnIn2S4 photocatalyst with high visible light absorption was achieved through microwave-assisted one–step method in this paper. On the one hand, because CdIn2S4 and CuS have narrow band gaps, they are expected to substantially increase the absorption of composite materials in the visible region and achieve high utilization rate of the sunlight.28–31 CuS/CdIn2S4/ZnIn2S4 composite is also expected to enhance the paths of photogeneration electrons migratory. This multi-way photoinduced electron migration essentially reduces the recombination rate of electron–hole pairs, and then improves the photocatalytic reaction efficiency. Moreover, the crystal structures and physicochemical properties of pure ZnIn2S4, CdIn2S4/ZnIn2S4 and CuS/CdIn2S4/ZnIn2S4 photocatalysts are studied, and their photocatalytic activities by methyl orange degradation and hydrogen generation under simulated sunlight and visible light are also investigated. Finally, the suitable photocatalytic mechanism of CuS/CdIn2S4/ZnIn2S4, and the main factor for the enhanced photocatalytic activity of composite material are discussed.
Experiment section Materials and instruments Indium nitrate (In(NO3)3·4.5H2O, 99.5%) was obtained from Sinopharm Chemical Reagent Co.Ltd., Shanghai, China. Zinc nitrate (Zn(NO3)3·6H2O, 99.0%) was purchased from Dongli Chemical Reagent Factory, Tianjin, China. Cadmium nitrate (Cd(NO3)2·4H2O, 99.0%) and thioacetamide (C2H5NS, 99.0%) were obtained from Kemiou Chemical Reagent Co.Ltd., Tianjin, China. Copper nitrate (Cu(NO3)2·3H2O, 99.5%) and sodium sulfite (Na2SO3, 97%) were purchased from Tianli Chemical Reagent Co.Ltd., Tianjin, China. Chloroplatinic acid (H2PtCl6·6H2O, 37.5%) was obtained from Aladdin Reagent Co.Ltd., Shanghai, China. Sodium sulfide (Na2S·9H2O, 98.0%) was purchased from Kaitong Chemical Reagent Co.Ltd., Tianjin, -3-
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China. All the reagents were used without further purification. MDS-8G microwave reactor was obtained from Xin Yi Co., Shanghai, China, and the BL-GHX-V photochemical reactions instrument was obtained from Bilang Biotechnology Co., Xian, China. LabSolar-ⅢAG photocatalytic on-line analysis system was purchased from Philae Technology Co., Beijing, China. Preparation of photocatalyst Typically, the corresponding reagents were dissolved in 20 mL distilled water (as shown in Table S1). After stirring for 20 min, the solution was added to a 100 mL Teflon-lined autoclave. The microwave hydrothermal reaction was maintained at 160 °C for 1.5 h. Then, the precipitate was filtered, washed with ethanol and distilled water several times, and dried at 60 °C for 12 h in oven. Characterization of photocatalyst X-ray powder diffraction (XRD) patterns of the as-prepared samples measured by with a X-ray diffractometer (Bruker-AXS(D8) using Kα radiation (λ = 0.15406 nm) from 20°−80°. X-ray photoelectron spectra (XPS) were recorded on a ESCALAB 250Xi spectrometer using Al Kα radiation at 300 W. The UV−vis diffuse reflectance spectra were recorded on an UV−vis spectrophotometer (Model TU-1901) fitted with an integrating sphere. The surface morphology was investigated by scanning electron microscopy (SEM) (HitachiS-4300) operated at 20 kV. The microstructure was examined by transmission electron microscopy (TEM) (HitachiH-7650) and high-resolution transmission electron microscopy (HRTEM) (JEM-2100F) working at 200 kV. The specific surface area and porosities of the samples were recorded by surface area instrument (Beishide Instrumentation Technologies (Beijing) Ltd., Model 3H-2000PS2) at 77 K on Brunauer-Emmett-Teller (BET) method. The amount of evolved H2 was quantitatively determined by gas chromatography spectrometry (Techcomp (Shanghai) Ltd., Model GC-7900). Photocatalytic experiment The experimental facilities for photocatalytic degradation can be seen elsewhere.32–35 The visible-light source consisted of a 400 W Xe-lamp (specially made glass filters UV light), and the simulated sunlight source consisted of a 1000 W -4-
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Xe-lamp. The corresponding product was suspended in methyl orange (MO) aqueous solution (50 mg·L-1). Before irradiation, the suspension was magnetically stirred for 30 min in darkness to ensure the adsorption−desorption equilibrium. The MO solution was collected after selected durations, and its concentration was measured with an UV−vis spectrophotometer (Model TU-1901) at λmax. The H2 evolvement was carried out in LabSolar-ⅢAG photocatalytic on-line analysis system, and the photocatalytic experimental facilities for H2 evolved can be see our group previously reported.36 Typically, 0.05g of photocatalyst was diluted by 50 mL of deionized water, and the solution was transferred to the photocatalytic vessel. Sacrificial reagent (CNa2S = 0.25 mol·L-1, CNa2SO3 = 0.25 mol·L-1, CNa2S-Na2SO3 = 0.125 mol·L-1 Na2S + 0.125 mol·L-1 Na2SO3) was added (if needed). The cocatalyst was in situ deposited as described elsewhere.37–39 H2PtCl6 is the precursor for Pt, and was just added in the solution before irradiation. The light source was a 300 W Xe lamp (Philae Technology (Beijing) Co., PLS-SXE300/300UV) equipped with a 420 nm filter (if needed), and the illumination time was 6 hours. The reactant solution was stirred and maintained at room temperature by a flow of cooling water during the photocatalytic process. The amount of evolved H2 was determined with online gas chromatography (Techcomp (Shanghai) Ltd., GC-7900, MS-5 A column, TCD, N2 carrier).
Results and discussion Crystal structure and XPS analysis XRD analysis was performed to investigate the crystal structure of the obtained samples. From Figure 1, the diffraction peaks of as-prepared samples both well correspond to hexagonal ZnIn2S4 phase (JCPD standard card No.65-2023) and cubic ZnIn2S4 phase (JCPD standard card No. 48-1778), which indicates the products have the hybrid crystal structure, and their main phase are hexagonal phase (See Fig. S1).40, 41 Moreover, the diffraction peak marked by ▼ corresponds to the crystal face (220) of cubic CdIn2S4 (JCPD standard card No. 27-0060).42 In addition, the diffraction peaks of CuS can not be observed from XRD patterns. This result is
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attributed to the low amount of Cu doping which can not be detected. The grain sizes of different products were estimated by Scherrer equation, and the values are shown in Table 1.43, 44 d=Kλ/(Bcosθ)
(1)
Where d is the crystallite size diameter, K takes a value of 0.89, λ is the wavelength of X-ray, B represents full width at half-maximum of the X-ray diffraction peak, and θ represents the diffraction angle in XRD. It is noted that the diffraction peaks correspond to the crystal planes (006), (104), (108) and (116) of hexagonal ZnIn2S4 were significantly reduced while the diffraction peaks correspond to the crystal planes (111), (400) and (511) of cubic ZnIn2S4 were obviously enhanced, which shows that a portion of the hexagonal ZnIn2S4 has translated into cubic ZnIn2S4 in the composites. However, we believe that this conversion is beneficial. Because cubic ZnIn2S4 has a less band gap than that of hexagonal ZnIn2S4,45 thus, the increase of cubic ZnIn2S4 can expand the
(110)
Hexagonal ZnIn2S4 Cubic ZnIn2S4 Cubic CdIn2S4
(116) (022)
(108)
(511)
(104)
▼
(400)
(111)
(006)
(102)
visible light response of composites.
Intensity/a.u.
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ZnIn2S4 ▼
CdIn2S4/ZnIn2S4 CuS/CdIn2S4/ZnIn2S4
10
20
30
40
50
2 Theta Degree
60
70
80
Fig.1 XRD patterns of the products. To further investigate the surface compositions and chemical states of the CuS/CdIn2S4/ZnIn2S4, XPS measurements were carried out. From Figure 2, the signals of Zn2p3/2 and Zn2p1/2 at 1022.6 and 1045.6 eV (Figure 2a) reveal that zinc is in the state of Zn2+.46 The XPS signals for Cd3d5/2 and Cd3d3/2 at binding energys of 405.3 eV and 412.3 eV (Figure 2b) correspond to the Cd2+ cation.47 The peaks at binding energies of 932.3 and 952.3 eV (Figure 2c) are the split signals of Cu2p3/2 and -6-
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Cu2p1/2, reveal that Cu species in composite is in the states of Cu2+.48 In addition, the XPS quantitative analysis of CuS/CdIn2S4/ZnIn2S4 indicates the mole ratio of Cu to
a
7000
Zn2p3/2
b
Cd3d5/2
60000
40000
Cd3d3/2
6000
20000 1030
1040 Eb/eV
1050
c
Cu2p3/2
404
408
412
Cu2p1/2
27200 twice the content of Cu
26800
23600
5000
1020
27600
In tensity/a.u .
Intensity/a.u.
Zn2p1/2
In tensity/a.u .
Cd to Zn is about 1: 6.5: 155.5.
Intensity/a .u.
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Cu2p3/2
Cu2p1/2
23200 22800
416
Eb/eV
930
940
Eb/eV
950
960
Fig.2 XPS spectra of Zn2p (a), Cd3d (b), and Cu2p (c).
Optical properties The optical absorption properties of the catalysts were characterized by UV−vis spectrometer. Figure 3 shows the UV−vis absorption spectra of heterogeneous ZnIn2S4, CdIn2S4/ZnIn2S4 and CuS/CdIn2S4/ZnIn2S4. Compared to ZnIn2S4, the absorption edges of composite materials shift to longer wavelengths, and the visible light absorption has a certain increase in the range of 400~520 nm. From figure S2, we found that CuS has good absorption in visible light region.49, 50 The introduction of CuS increases the light absorption of composite materials in the range of visible light region. Moreover, the appearance of red shift becomes more obvious which attributes to SPR effect of Cu in CuS/CdIn2S4/ZnIn2S4 composite, leads to an enhanced visible light absorption in the range of 450~650 nm.51 The results display that CuS/CdIn2S4/ZnIn2S4 composite performs a favorable absorption in visible light region.
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0.6
0.4 A bs
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0.2 ZnIn2S4 CdIn2S4/ZnIn2S4 CuS/CdIn2S4/ZnIn2S4
0.0 300
400
500
600
700
800
Wavelength(nm)
Fig.3 UV-vis/DRS spectra of different samples. Table 1 The crystallite sizes, BET surface areas, average pore diameters and pore volumes of as-prepared catalysts. Products
d/nm
SBET/(m2/g)
D/nm
Vtotal/(cm3/g)
Heterogeneous ZnIn2S4
9.2
215.2
18.45
0.993
CdIn2S4/ZnIn2S4
11.0
226.1
15.34
0.867
CuS/CdIn2S4/ZnIn2S4
8.5
239.3
11.51
0.689
N2 adsorption–desorption isotherms To investigate the physicochemical properties of different samples, the heterogeneous ZnIn2S4, CdIn2S4/ZnIn2S4 and CuS/CdIn2S4/ZnIn2S4 were detected by N2 adsorption–desorption analysis. Figure 4 shows the type of Ⅳ isotherms with a H3 type hysteresis loop.52 This type of isotherms indicates better uniform mesopores, and all of the samples exhibit mesoporous distribution. In particular, CuS/CdIn2S4/ZnIn2S4 composite presents uniform pore size distribution, means that most of the particles are packed tightly, and the distribution of semiconductors is homogeneous in composite materials (as seen in Fig.S3). In addition, compared with other photocatalysts, CuS/CdIn2S4/ZnIn2S4 has small average pore diameter which increases collision times of organic molecular and the pore wall, and then enhances the rate of photocatalytic reaction. As can be seen from Table 1, all of the samples have large specific surface areas. In general, the greater specific surface area represents the larger adsorption
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capacity of organic molecules, which corresponds to a higher photocatalytic activity. Thus, the results imply that CuS/CdIn2S4/ZnIn2S4 composite performs an excellent photocatalytic activity. 600
V olum e A bsorb ed /m lg -1
400
200
ZnIn2S4
0 0.0
0.2
0.4
P/P0
0.6
0.8
C
450
400
300
200
150
CdIn2S4/ZnIn2S4
0
1.0
600
b
V olum e A bsorb ed /m lg -1
a
600 V o lum e A b so rb ed/m lg -1
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0.0
0.2
0.4
P/P0
0.6
0.8
1.0
CuS/CdIn2S4/ZnIn2S4
0 0.0
0.2
0.4
P/P0
0.6
0.8
1.0
Fig.4 N2 adsorption–desorption isotherms of ZnIn2S4 (a), CdIn2S4/ZnIn2S4 (b), and CuS/CdIn2S4/ZnIn2S4 (c).
Surface morphology and microstructure analysis The
surface
morphology,
microstructure
and
crystal
phase
of
CuS/CdIn2S4/ZnIn2S4 were confirmed by SEM, TEM and HRTEM, respectively, and the results are shown in Figure 5. As one can see from Figure 5a-b, the composite presents a regular globular flower-like structure with a diameter approximate 600 nm of each sphere which has a well dispersity among the others. Simultaneously, the result from Figure 5c-d shows that it consists of a large amount of irregular massive crystals and a small amount of long-rod-like crystals with the length of 100-200 nm. Moreover, there are plenty of nanoparticles with ~5 nm in diameter uniformly distribute on the irregular massive crystals and long-rod-like crystals. The HRTEM images of CuS/CdIn2S4/ZnIn2S4 composite are shown in Figure 5e-f, and their fast Fourier transform (FFT) images on different selected areas were inserted. In addition, Figure 5g-j display their magnifying HRTEM images on different selected areas in composite. The distinct lattice spacing of 0.32 nm attributes to the (102) face of hexagonal ZnIn2S4, the distinct lattice fringes of 0.27 nm corresponds to the (400) face of cubic ZnIn2S4, the lattice fringes of 0.19 nm corresponds to the (440) face of cubic CdIn2S4, and the lattice fringes of 0.19 nm corresponds to the (110) face of hexagonal CuS were also observed, respectively.53–56 From Figure 5g-j, because of the
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different crystalline phases, the interfacial angles also represent certain contrast (as seen in Fig. S4). These results prove that irregular massive crystals is composed of hexagonal ZnIn2S4 and cubic ZnIn2S4, long-rod-like crystals is composed of cubic CdIn2S4, and the nanoparticles with ~5 nm in diameter is hexagonal CuS which uniformly distribute on the irregular massive crystals and long-rod-like crystals.
(a)
(b)
500 nm
(c)
1 µm
(d)
CuS
ZnIn2S4 CdIn2S4
(e)
(f) cubic ZnIn2S4
hexagonal CuS
hexagonal ZnIn2S4
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cubic CdIn2S4
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(g) hexagonal ZnIn S
2 4
(h)
cubic ZnIn2S4
(102) 0.32 nm
(i)
(400) 0.27 nm
(j)
hexagonal CuS
(440) 0.19 nm
90° 0.5 nm
60°
cubic CdIn2S4
90°
0.5 nm
0.5 nm
(110) 0.19 nm 0.5 nm
60°
Fig.5 SEM (a-b), TEM (c-d), HRTEM (e-f) and magnifying HRTEM (g-j) images of the CuS/CdIn2S4/ZnIn2S4
Photocatalytic performance To understand the photocatalytic performance of catalysts, the photocatalytic degradation MO and decomposition of water into hydrogen tests were carried out, and the results are shown in Figure 6. Figure 6a-b show that the photocatalytic activity of CuS/CdIn2S4/ZnIn2S4 composite was the highest of all under simulated sunlight and visible light, even better than that of commercial P25. To study the degradation rate of MO by synthesized products, the analysis of kinetics-experiments is shown in Figure 6c. Base on the experiment, the kinetics equation can be denoted as follows: -ln(Ct/C0) = kt + b
(2)
where Ct represents the concentration at reaction time t (mg•L-1), C0 is the initial MO concentration (mg•L-1) stirred for 30 min in darkness, k is the rate constant (min-1), and b is the intercept.35 It is seen from Figure 6c, the linear relationship illustrates the photodegradation follow the pseudo-first-order kinetics model. The obtained rate constants
of
direct
photolysis,
P25,
ZnIn2S4,
CdIn2S4/ZnIn2S4
and
CuS/CdIn2S4/ZnIn2S4 under visible light irradiation are 5.67×10-5, 4.95×10-4, 5.34×10-3, 6.20×10-3 and 8.96×10-3 min-1, respectively. The simulated sunlight photocatalytic activity of water splitting H2 production over different samples in Na2S aqueous solution was shown in Figure 6d. It turned out that CuS/CdIn2S4/ZnIn2S4 composite has an outstanding capability of H2 evolution, even surpasses fifteen times than P25. Figure 6e illustrates that CuS/CdIn2S4/ZnIn2S4 performs the highest H2 evolution rate in Na2S–Na2SO3 aqueous solution than in any other single sacrifice agent aqueous solution, which implies the synergistic effect between Na2S and Na2SO3 during photocatalytic process. To further improve the - 11 -
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capability of CuS/CdIn2S4/ZnIn2S4 to H2 evolution, Pt serves as cocatalyst to in situ loaded on the surface of photocatalyst by photo-reduction method, as shown in Figure 6f. After 0.2% wt Pt loaded, the H2 evolution rate of CuS/CdIn2S4/ZnIn2S4 was raised to 358.4 µmol·h-1·g-1, equivalently six times higher than the unloaded one. After 420 nm cut-off filter was employed, Pt loaded CuS/CdIn2S4/ZnIn2S4 still maintains a well H2 evolution rate of 233.9 µmol·h-1·g-1, which presents a high response in visible region. To investigated the photocatalytic stability of Pt loaded CuS/CdIn2S4/ZnIn2S4, the experiment was carried out in Na2S–Na2SO3 aqueous solution under visible light (λ > 420 nm) for 24 h. As shown in Figure S5, the photocatalyst remains a good stability, and there is no significant change in the crystal structures of CuS/CdIn2S4/ZnIn2S4 after illuminated for 24 h (Figure S6). In addition, the decline of the H2 evolution rate over composite can be attributed to the decrease of sacrificial agent concentration and the photocorrosion effect in composite.57–59 1.0
1.0
b
a 0.8
0.6 C t /C 0
0.8
C t /C 0
0.9
Direct photolysis P25 ZnIn2S4 CdIn2S4/ZnIn2S4
0.7 0.6
0.4
Direct photolysis P25 ZnIn2S4
0.2
CdIn2S4/ZnIn2S4
CuS/CdIn2S4/ZnIn2S4
0.5
0
60
120
CuS/CdIn2S4/ZnIn2S4
180
240
0.0
300
0
30
60
Η ydrogen evolution rate / µ m olh -1 g -1
c
CdIn2S4/ZnIn2S4 CuS/CdIn2S4/ZnIn2S4
1.0
0.5
0.0 0
30
60
90
t/min
120
150
180
40
d
Direct photolysis P25 ZnIn2S4
1.5
90 t/min
t/min
-In(C t/C 0 )
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120
150
180
CuS/CdIn2S4/ZnIn2S4
30
20 CdIn2S4/ZnIn2S4
10
ZnIn2S4 P25
0
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e Na2S-Na2SO3 CuS/CdIn2S 4/ZnIn2S4
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Na 2SO3
Na2S 0
20
40
Ηydrogen evolution rate / µmolh-1g-1
Fig.6
60
Η ydrogen evolution rate / µ m olh -1 g -1
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400 Pt cocatalyst
f 300
Pt cocatalyst
200
420 nm cutoff filter
100 CuS/CdIn2S4/ZnIn2S4
0
Simulated sunlight photodegradation MO over different photocatalysts (a);
Visible-light photodegradation MO over different photocatalysts (b); Visible-light photodegradation MO kinetics over different photocatalysts (c); Simulated sunlight photocatalytic activity of water splitting H2 production over different samples in Na2S aqueous solution (d); simulated sunlight photocatalytic activity of water splitting H2 production over CuS/CdIn2S4/ZnIn2S4 in different sacrificial agent aqueous solution (e); Photocatalytic activity of water splitting H2 production over CuS/CdIn2S4/ZnIn2S4 loaded with Pt cocatalyst (0.2% wt) in Na2S–Na2SO3 aqueous solution (f).
Possible photocatalytic mechanism To understand the migration pathway of photogenerated charges in CuS/CdIn2S4/ZnIn2S4 composite, the formula (3) and (4) were used for calculation, the results are shown in Table 2.35 ECB = X – EC – 0.5Eg
(3)
EVB = ECB + Eg
(4)
Where X is the electronegativity of the semiconductor, and manifested as the geometric mean of the absolute electronegativity of the combine atoms, EC refers to the energy of free electrons (EC = -4.5 eV for NHE). ECB represents the conduction band edge potential (CB), EVB is the valence band edge potential (VB), and Eg refers to the band gap of the semiconductor. Table 2 The electronegativity (eV), energy band gaps (eV), conduction band edge and valence band edge potential E/(eV) of ZnIn2S4, CdIn2S4 and CuS. - 13 -
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Semiconductor
X/eV
Eg/eV
ECB/eV
EVB/eV
Hexagonal ZnIn2S4
4.77
2.560
-0.98
1.52
Cubic ZnIn2S4
4.77
2.360
-0.88
1.42
CdIn2S4
4.79
2.142
-0.76
1.34
CuS
4.85
2.261
-0.75
1.45
Photocatalytic degradation for methylic orange. As we seen in Figure 7, it is found that the conduction band of ZnIn2S4, CdIn2S4 and CuS are all negative than that of E(O2/O2•-) (-0.33 eV vs NHE), and the valence band of ZnIn2S4, CdIn2S4 and CuS are less positive than that of E(•OH/OH-) (2.38 eV vs NHE).60 Therefore, photoinduced electrons from the conduction band of semiconductors can reduce the dissolved oxygen to produce the strong oxidizing superoxide radicals (•O2-) on the surface of the catalysts. The photogenerated holes from the valence band of semiconductors are not able to oxidize (OH-) to give (•OH), but they can directly oxidize MO. Moreover, the strong oxidbillity of •O2- and •OH can transform MO into CO2 and H2O in the end.
Fig.7 The photocatalytic reaction mechanism of degradation MO over CuS/CdIn2S4/ZnIn2S4 composite. Hydrogen evolved by light energy in Na2S–Na2SO3 aqueous solution. As we seen in Figure 8, from the conduction band of the semiconductors, Pt cocatalyst can capture the photogenerated electrons which generate in the conduction band of CuS/CdIn2S4/ZnIn2S4, leads to the decrease of recombination of electrons and holes.
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Afterwards, those photogenerated electrons which captured by Pt cocatalyst, reduce the water to form H2. From the valence band of the semiconductors, holes can be captured by S2- in the composite. Then the production of S22- ion, which act as an optical filter and compete with reduction of protons, is effciently suppressed by SO32ions, consequently forms S2- and S2O32- (See the following formulas 5-7). In addition, the presence of excessive S2- in the reaction solution not only captures the holes, but also suppresses the formation of sulfur defects and stabilizes the CuS/CdIn2S4/ZnIn2S4 composite. The production of S2O32- is colorless and does not compete with the composite for light absorption. This is the reason why water splitting H2 production in Na2S–Na2SO3 aqueous solution is higher than that in Na2S or Na2SO3 aqueous solution.57, 62 2S2- + 2hVB+ → S22-
(5)
S22- + SO32- → S2O32- + S2-
(6)
SO32- + S2- + 2hVB+ →S2O32-
(7)
Fig.8 The photocatalytic reaction mechanism of water splitting H2 production over CuS/CdIn2S4/ZnIn2S4 composite loaded with Pt cocatalyst in Na2S–Na2SO3 aqueous solution In general, when CuS/CdIn2S4/ZnIn2S4 is exposed to the sunlight, the electrons can be excited from valence band to conduction band, and leave the corresponding species holes in valence band. Simultaneously, the electrostatic interaction brings about the combination of photogenerated electron–hole pairs which suppresses the - 15 -
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photocatalytic reaction. Because this type of electrostatic interactions can make the photoinduced electrons come back to the valence band. Compared to the usual semiconductor, ZnIn2S4, CdIn2S4 and CuS semiconductors all have narrow band gaps which can obtain higher visible light response, but result in the easier recombination of photoinduced electron and hole. However, this type of band configuration can inhibit the combination of electrons–holes pairs substantially. The reason is photoinduced electrons can transfer from the more negative conduction band of the semiconductor to the less negative conduction band of another semiconductor. Similarly, holes can transfer from the more positive valence band of the semiconductor to the less positive valence band of another semiconductor.35, 62, 63 That is photoinduced electrons transfer from heterogeneous ZnIn2S4 crystals to rodlike CdIn2S4 crystals, then to CuS crystals, as shown in Figure 9. In summary, different composite materials exhibit different energy band structures, results in diverse migration manners of photoinduced electrons. Moreover, the contrast of potentials between semiconductors determines the migration manners of photoinduced electrons. This type of migration manners efficiently prevents the recombination of photoinduced electrons and holes, thus, improves the photocatalytic activity of the composite materials. heterogeneous ZnIn2S4
ecubic CdIn2S4
ehexagonal CuS
Fig.9 Multi-pathway photoelectron migration in CuS/CdIn2S4/ZnIn2S4 composite.
Conclusion The CuS/CdIn2S4/ZnIn2S4 photocatalyst with high visible light absorption was - 16 -
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successfully synthesized via microwave-assisted one–step method. The composite consists of heterogeneous ZnIn2S4, cubic CdIn2S4 and hexagonal CuS, which displays a favorable globular flower-like surface morphology with excellent surface area. Moreover, the presence of CdIn2S4 and CuS improves the absorption of composite material under the visible light, and makes the red-shift become more obvious. Compared to P25, CuS/CdIn2S4/ZnIn2S4 presents more outstanding photocatalytic activity to degrade MO under simulated sunlight and visible light. In addition, CuS/CdIn2S4/ZnIn2S4 loaded with Pt cocatalyst performs the highest water splitting H2 production under visible light (λ > 420 nm) in Na2S–Na2SO3 aqueous solution. Moreover, CdIn2S4 and CuS enlarge the range of the composite under the visible light response, and increase the pathways for photogenerated electrons migration, which inhibits the combination of photoelectrons and holes, thus, enhanced the photocatalytic activity of composite.
Acknowledgements This study are supported by the National Natural Science Foundation of China (21376126), Natural Science Foundation of Heilongjiang Province, China (B201106), Scientific Research of Heilongjiang Province Educaton Department (12511592), Government of Heilongjiang Province Postdoctoral Grants, China (LBH-Z11108), Open Project of Green Chemical Technology Key Laboratory of Heilongjiang Province College, China (2013 year), Postdoctoral Researchers in Heilongjiang Province of China Research Initiation Grant Project (LBH-Q13172), Innovation Project of Qiqihar University Graduate Education (YJSCX2014-009X) and Qiqihar University in 2015 College Students Academic Innovation Team Funded Projects.
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For Table of Contents Use Only
Fabricate Globular Flower-like CuS/CdIn2S4/ZnIn2S4 with High Visible Light Response via Microwave-assisted One–step Method and Its Multi-pathway Photoelectron Migration Properties for Hydrogen Evolution and Pollutant Degradation Xi Chen, Li Li, Wenzhi Zhang, Yixuan Li, Qiang Song, Li Dong
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ACS Paragon Plus Environment
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ACS Sustainable Chemistry & Engineering
Synopsis: Globular flower-like CuS/CdIn2S4/ZnIn2S4 with photoelectronic multi-way migration characteristic performed the high photocatalytic activitiy to evolve H2 under visible light.
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ACS Paragon Plus Environment
