Self-sacrificing MOF-derived hierarchical porous In2S3 nanostructures with enhanced photocatalytic performance

doi:10.1016/S1872-2067(24)60003-3

Abstract

Abstract:

Fabrication of porous hierarchical structures is an effective method to improve the photo-absorption capability of photocatalysts by enhancing the photogenerated charge separation and transfer. In-based metal-organic frameworks (MOFs) are utilized as self-sacrificial templates to synthesize various hierarchical In₂S₃ photocatalysts including hollow nanotubes/microtubes/ spheres and dodecahedrons by the sulfidation process. The porous hierarchical structures improve multiple refraction and reflection of the incident light, provide larger surface areas, and increase the light utilization and phase separation efficiency of the photogenerated carriers. As a result, the photocatalytic efficiency is much higher than that of the bulk and commercial In₂S₃. In particular, the hollow In₂S₃ nanotubes (HNTs) have the best photocatalytic properties boosting degradation rates of organic pollutants that are 135.6 and 446.9 times than those of the bulk and commercial-grade In₂S₃, respectively. Theoretical calculations, optical/electrical characterization, and free radical trapping experiments reveal that under the condition of light, the photogenerated electron hole pairs produced in In₂S₃-HNT can effectively separate due to its hierarchical porous structure. So, the In₂S₃-HNT can accumulate more reactive oxygen radicals. This novel self-sacrificial template method has large potential in the design and fabrication of hierarchical high-efficiency photocatalysts.

Key words: In₂S₃, Metal-organic framework, Morphological control, Photocatalysis, Pollutants degradation

Tingting Yang, Bin Wang, Paul K. Chu, Jiexiang Xia, Huaming Li. Self-sacrificing MOF-derived hierarchical porous In₂S₃ nanostructures with enhanced photocatalytic performance[J]. Chinese Journal of Catalysis, 2024, 59: 204-213.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60003-3

https://www.cjcatal.com/EN/Y2024/V59/I4/204

Figures/Tables 6

Scheme 1. Schematic illustration of the synthesis of the hierarchical In2S3 structures.

Fig. 1. SEM and TEM images of In(OH)3 (a,b), In2S3-HNT (c,d), MIL-68-In (f,g), In2S3-HMT (h,i), In(OH)(2,5-PDC) (k,l), In2S3-HS (m,n), In-rho-ZMOFs (p,q), and In2S3-PD (r,s). HR-TEM images of In2S3-HNT (e), In2S3-HMT (j), In2S3-HS (o), and In2S3-PD (t).

Fig. 2. N2 adsorption-desorption isotherms (a), XRD patterns (b), XPS In 3d (c) and S 2p (d) spectra of In2S3-HNT, In2S3-HMT, In2S3-HS, and In2S3-PD. (e) Calculated DOS. (f) Band structure of In2S3. UV-vis DRS and bandgaps (g), XPS valence-band spectra (h), and Mott-Schottky plots (i) of In2S3-HNT, In2S3-HMT, In2S3-HS, and In2S3-PD.

Fig. 3. Photocatalytic properties for degradation of RhB (a) and TC (b) under visible light irradiation. (c) Reaction kinetics for degradation of RhB and TC. Interference experiments for Positive ions (d), Negative ions (e), and pH (f) for RhB degradation in the presence of In2S3-HNT. EIS spectra (g), Photocurrent curves (h), and PL spectra (i) of In2S3-HNT, In2S3-HMT, In2S3-HS, and In2S3-PD.

Fig. 4. Possible degradation routes of RhB (a) and TC (b) in In2S3-HNT. Growing situation (c) and average length (d) of mung bean seeds in deionized water as well as solution before and after photocatalytic degradation.

Fig. 5. (a-c) Comparison of the photocatalytic activities of In2S3-HNT for the degradation of RhB (a) and TC (b) with or without adding TBA, TEOA, Trp, and N2 under visible light irradiation. ESR spectra of electrons (d), holes (e), DMPO-·O2- (f), DMPO-·1O2 (g), and DMPO-·OH (h) of In2S3-HNT, In2S3-HMT, In2S3-HS, and In2S3-PD. (i) Mechanism and role of In2S3 in photocatalytic degradation.

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Self-sacrificing MOF-derived hierarchical porous In₂S₃ nanostructures with enhanced photocatalytic performance

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