In-situ Construction of 2D/3D ZnIn2S4/TiO2 with Enhanced Photocatalytic Performance

doi:10.6023/A21060265

Abstract

To study the influence of the construction of heterojunction on the visible-light response range and the photo-generated charge carriers separation efficiency of TiO₂, two dimensional/three dimensional (2D/3D) ZnIn₂S₄/TiO₂ heterojunctions were synthesized by high-temperature calcination followed by a facile oil bath method, and were investigated for the photodegradation of Rhodamine B (RhB) and tetracycline (TC). X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were applied to investigate the composition, crystal structure, and morphology of the as-prepared specimens. UV-visible diffuse reflectance spectra (UV-vis DRS), electrochemical impedance spectroscopy (EIS), photocurrent measurement, photoluminescence (PL) spectra, and first-principles calculation were also performed to investigate the photoelectric property. The results showed TiO₂ maintains the morphology of metal-organic frameworks (MOFs) with narrow visible-light response range and high photo-generated charge recombination efficiency. After coupling with ZnIn₂S₄ nanosheets, a larger specific surface area was obtained with offering more active sites for photocatalytic reaction. The band gap of the composite was reduced from 3.23 eV of TiO₂ to 2.52 eV of ZnIn₂S₄/TiO₂-II, and thus obtaining an extended visible-light response range and enhancing visible light utilization rate. The energy band structure acquired from the UV-vis DRS and XPS valence band spectra indicated a construction of type II heterojunction in the ZnIn₂S₄/TiO₂composite, and thus improving the separation and transfer efficiency of photo-generated carrier pairs, which was confirmed by the PL, EIS and photocurrent test results. Under the visible light, ZnIn₂S₄/TiO₂ displayed signiﬁcantly enhanced photocatalytic activity than bare TiO₂and ZnIn₂S₄. Among of ZnIn₂S₄/TiO₂photocatalysts, ZnIn₂S₄/TiO₂-II possessed the highest photocatalytic degradation efficiency (93%) of RhB solution within 60 min, which was nearly 18 and 2 times higher than pristine TiO₂and ZnIn₂S₄, respectively. Besides, the ZnIn₂S₄/TiO₂-II photocatalyst also showed enhanced photocatalytic activity for TC degradation than pure TiO₂and ZnIn₂S₄. The cycle experiment showed that the ZnIn₂S₄/TiO₂-II photocatalyst could maintain good reusability, and it could still photodegrade 83% RhB after 5-cycle test. This work demonstrates that constructing 2D/3D ZnIn₂S₄/TiO₂ heterojunction based on MOFs-derived TiO₂ is an efficient strategy for significantly enhancing the photocatalytic activity of TiO₂.

Key words: photocatalysis, titanium dioxide, metal-organic frameworks, heterojunction, visible-light response

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Huan Liu, Li Li, Ping Li, Guangzhi Zhang, Xun Xu, Hao Zhang, Lingfang Qiu, Hui Qi, Shuwang Duo. In-situ Construction of 2D/3D ZnIn₂S₄/TiO₂ with Enhanced Photocatalytic Performance[J]. Acta Chimica Sinica, 2021, 79(10): 1293-1301.

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Fig. & Tab. 12

Figure 1. The XRD patterns of the specimens

Figure 2. SEM images of (a) MIL-125, (b) TiO2, (c) ZnIn2S4 and (d) ZnIn2S4/TiO2-II; TEM (e) and HRTEM (f) images of ZnIn2S4/TiO2-II

Figure 3. N2 adsorption-desorption isotherms (a) and corresponding pore diameter distribution (b) of TiO2, ZnIn2S4, and ZnIn2S4/TiO2-II

Figure 4. XPS spectra of ZnIn2S4/TiO2-II: (a) survey scan spectrum and high resolution spectra of O 1s (b), Ti 2p (c), S 2p (d), In 3d (e) and Zn 2p (f)

Figure 5. UV-visible DRS spectra of TiO2, ZnIn2S4 and ZnIn2S4/TiO2-II (a) as well as the corresponding optical band gap (b); the XPS valence band spectra (c) and band edge positions (d) of TiO2 and ZnIn2S4

Figure 6. PL spectra (a), photocurrent responses (b), EIS plots (c) and Zeta potential (d) of the TiO2, ZnIn2S4 and ZnIn2S4/TiO2-II

Figure 7. (a) Photocatalytic degradation curves of RhB by different photocatalysts; (b) photocatalytic degradation curves of TC in the presence of TiO2, ZnIn2S4 and TiO2/ZnIn2S4-II; (c) the comparison of photocatalytic activities between light-dark cycles (grey squares) and continuous irradiation (red dots) under visible light

Figure 8. The photodegradation kinetic curves of RhB

Figure 9. Photocatalytic degradation cycle experiments of ZnIn2S4/ TiO2-II

Figure 10. The capture experiments of active species (a) and corresponding photodegradation rates (b) in the presence of different scavengers

Figure 11. Schematic of the photocatalytic mechanism for RhB photodegradation on ZnIn2S4/TiO2 photocatalyst

Figure 12. Schematic diagram of preparation process of ZnIn2S4/TiO2

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2D/3D ZnIn₂S₄/TiO₂复合物的原位构筑及其提高的光催化性能

In-situ Construction of 2D/3D ZnIn₂S₄/TiO₂ with Enhanced Photocatalytic Performance

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2D/3D ZnIn2S4/TiO2复合物的原位构筑及其提高的光催化性能