Fabricating covalent organic framework/CdS S-scheme heterojunctions for improved solar hydrogen generation

doi:10.1016/S1872-2067(21)63869-X

Abstract

Abstract:

The fabrication of S-scheme heterojunctions has received considerable attention as an effective approach to promote the separation and migration of photoexcited electron/hole pairs and retain strong redox abilities. Herein, an imine-based porous covalent organic framework (COF-LZU1) is integrated with controllably fabricated CdS hollow cubes, resulting in the formation of an S-scheme heterojunction. When the COF content reaches 1.5 wt%, the COF/CdS heterostructure (1.5%COF/CdS) achieves the highest hydrogen generation rate of 8670 μmol·h ^-1·g ^-1, which is approximately 2.1 times higher than that of pure CdS. The apparent quantum efficiency (AQE) of 1.5%COF/CdS is approximately 8.9% at 420 nm. Further systematic analysis shows that the intimate contact interface and suitable energy band structures between CdS and COF can induce the formation of an internal electric field at the heterojunction interface, which can effectively drive the spatial separation of photoexcited charge carriers and simultaneously maintain a strong redox ability, thus enhancing the photocatalytic H₂ evolution performance.

Key words: S-scheme, Covalent organic framework, CdS, Photocatalytic H₂ production

Long Sun, Lingling Li, Juan Yang, Jiajie Fan, Quanlong Xu. Fabricating covalent organic framework/CdS S-scheme heterojunctions for improved solar hydrogen generation[J]. Chinese Journal of Catalysis, 2022, 43(2): 350-358.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63869-X

https://www.cjcatal.com/EN/Y2022/V43/I2/350

Figures/Tables 8

Fig. 1. XRD (a) and FT-IR (b) spectra of COF, pure CdS, and 1.5%COF/CdS.

Fig. 2. (a) SEM image of CdS (inset: HAADF-STEM image); SEM (b) and TEM (c) images of COF; SEM (d), TEM (e), and HRTEM (f) images of 1.5%COF/CdS nanocomposite; (g-k) Elemental mappings of 1.5%COF/CdS.

Fig. 3. (a) XPS survey profile of 1.5%COF/CdS; High-resolution in situ and ex situ XPS profiles of Cd 3d (b), S 2p (c), and N 1s (d) of CdS, COF, and 1.5%COF/CdS.

Fig. 4. (a) Comparison of H2 generation rate of as-prepared samples and (b) evaluation of 1.5%COF/CdS stability in photocatalytic H2 production under visible light (λ ?≥ 420 nm).

Fig. 5. (a) The UV-vis DRS spectra (b) PL spectra with an excitation wavelength of 380 nm of the synthesized samples (c) TRPL spectra with corresponding fitting results of COF, CdS and 1.5%COF/CdS.

Fig. 6. N2 adsorption-desorption isotherms (a) and TGA thermograms (b) of COF, CdS, and 1.5%COF/CdS.

Fig. 7. Mott-Schottky plots of CdS (a) and COF (b) at 4 and 5 kHz; Transient photocurrent response (c) and EIS curves (d) of CdS, COF, and 1.5%COF/CdS.

Fig. 8. (a) S-scheme charge transfer between CdS and COF under irradiation; (b) TEM image of 1.5%COF/CdS after in situ photodeposition of Pt; inset: HRTEM image of Pt.

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