Citation: Liu Ruxue, He Xiaoyan, Niu Litong, Lv Bolin, Yu Fei, Zhang Zhe, Yang Zhiwang. Hierarchical In₂S₃/CdIn₂S₄ Heterostructured Nanohybrids as Photocatalyst for Coupling of Benzyl Amines under Visible Light[J]. Acta Chimica Sinica, ;2019, 77(7): 653-660. doi: 10.6023/A19040113 shu

Hierarchical In₂S₃/CdIn₂S₄ Heterostructured Nanohybrids as Photocatalyst for Coupling of Benzyl Amines under Visible Light

Liu Ruxue ^a ,
He Xiaoyan ^b ,
Niu Litong ^a ,
Lv Bolin ^a ,
Yu Fei ^a ,
Zhang Zhe ^a ,
Yang Zhiwang ^a,,

a.
College of Chemistry and Chemical Engineering, Northwest Normal University Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, Lanzhou 730070
b.
Pingliang No.7 Middle School, Gansu Pingliang 744000

Corresponding author: Yang Zhiwang, yangzw@nwnu.edu.cn
Received Date: 4 April 2019
Available Online: 5 July 2019
Fund Project: the National Natural Science Foundation of China 21563026the Program for Changjiang Scholars and Innovative Research Team in University IRT15R56Project supported by the National Natural Science Foundation of China (No. 21563026), the Program for Changjiang Scholars and Innovative Research Team in University (No. IRT15R56), and the Innovation Team Basic Scientific Research Project of Gansu Province (No. 1606RJIA324)the Innovation Team Basic Scientific Research Project of Gansu Province 1606RJIA324

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It is a more attractive strategy that the selective oxidation of amines to the corresponding imines driven by visible light and photocatalyst. However, it is still necessary to look further into the mechanism of the transformation. In order to advance a new green photocatalysts system under milder conditions, hierarchical In₂S₃ nanotubes, which maintained the mother skeleton of NH₂-MIL-68(In), was prepared from NH₂-MIL-68(In) and thiourea, and a cation exchange method was used to synthesize hierarchical In₂S₃/CdIn₂S₄ heterostructured composites. The structure, morphology and photoelectric properties of the catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), fluorescence spectroscopy (PL) and electrochemical impedance spectra (EIS) analysis. The results showed that the existence of heterojunction between In₂S₃ and CdIn₂S₄ could minimize the recombination rate of photogenerated electron-hole pairs, which made the In₂S₃/CdIn₂S₄ show superior catalytic activity. The results of the evaluated experiments under visible light illumination showed that lots of synergy existed between the hierarchical structure, and the heterostructure could help to enhance the efficiency of carriers transfer and separation, which resulting in a high photocatalytic efficiency of In₂S₃/CdIn₂S₄ nanohybrids for the oxidation coupling of benzyl amines to imines under visible light irradiation. Interestingly, the further investigation concerned to the reaction condition revealed that the product could be detected not only in air but also in N₂ conditions, which burst out of the restriction of the reported reaction conditions and made the condition of the conversion become milder. The possible photocatalytic mechanism for the transformation was investigated by a series of experiments which concerned to the catching of the active species. The results showed that the reason for the occurring of the reaction was initiated by the presence of the nitrogen-centered radical cations and the carbon-centered radicals which were induced by the photogenerated hole (h⁺) in the photocatalyst. As for these situations, the conditions for the conversion of benzyl amines to imines were milder than the reported ones ever. What's more, from our experiments, the catalysts can be recycled five times at least, which indicated good reusability of hierarchical In₂S₃/CdIn₂S₄ nanohybrids.
- NH₂-MIL-68(In),
- hierarchical structure,
- visible-light photocatalysis,
- coupling of benzyl amines,
- heterostructure
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Hierarchical In₂S₃/CdIn₂S₄ Heterostructured Nanohybrids as Photocatalyst for Coupling of Benzyl Amines under Visible Light