Molten salt construction of core-shell structured S-scheme CuInS2@CoS2 heterojunction to boost charge transfer for efficient photocatalytic CO2 reduction

doi:10.1016/S1872-2067(24)60066-5

Abstract

Abstract:

Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO₂ photoreduction. To tackle this challenge and enhance the CO₂ photoconversion efficiency, fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies. In pursuit of this goal, a core-shell structured CuInS₂@CoS₂ S-scheme heterojunction was meticulously engineered through a two-step molten salt method. This approach over the CuInS₂-based composites produced an internal electric field owing to the disparity between the Fermi levels of CoS₂ and CuInS₂ at their interface. Consequently, the electric field facilitated the directed migration of charges and the proficient separation of photoinduced carriers. The resulting CuInS₂@CoS₂ heterostructure exhibited remarkable CO₂ photoreduction performance, which was 21.7 and 26.5 times that of pure CuInS₂ and CoS₂, respectively. The S-scheme heterojunction photogenerated charge transfer mechanism was validated through a series of rigorous analyses, including in situ irradiation X-ray photoelectron spectroscopy, work function calculations, and differential charge density examinations. Furthermore, in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS₂@CoS₂ heterojunction substantially lowered the formation energy of *COOH and *CO. This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of addressing carbon-related environmental issues.

Key words: S-scheme heterojunction, Molten salt, CuInS₂, CoS₂, CO₂photoreduction

Fulin Wang, Xiangwei Li, Kangqiang Lu, Man Zhou, Changlin Yu, Kai Yang. Molten salt construction of core-shell structured S-scheme CuInS₂@CoS₂ heterojunction to boost charge transfer for efficient photocatalytic CO₂ reduction[J]. Chinese Journal of Catalysis, 2024, 63: 190-201.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60066-5

https://www.cjcatal.com/EN/Y2024/V63/I8/190

Figures/Tables 6

Scheme 1. Schematic illustration of the synthesis procedure for CuInS2@CoS2.

Fig. 1. (a) XRD patterns of all samples. (b) Enlarged spectra of the region enclosed by green rectangle in (a). (c) FT-IR spectra of all samples. SEM images of CoS2 (d), CuInS2 (e), and CIS-CS (40) (f). TEM (g) and HRTEM (h) images of CIS-CS(40). (i) Elemental distribution mappings of CIS-CS(40).

Fig. 2. (a) (αhν)2 vs. hν plot of CoS2 and CuInS2. (b) Mott-Schottky plot of CoS2. (c) Mott-Schottky plot of CuInS2. (d) Energy band structure of CuInS2 and CoS2. (e) Surface potential of CuInS2. (f) Surface potential of CIS-CS(40). (g) Transient photocurrents of the samples. (h) Steady-state fluorescence spectra of samples. (i) Contact angle between the sample surface and reaction solution.

Fig. 3. (a) Product yields of CuInS2, CoS2, and CIS-CS (40). (b) Photocatalytic CO2 activity diagram of all samples. (c) Photocatalytic experiments under various conditions. (d) Mass spectrum of products obtained using 13CO2 instead of CO2. (e) Performance cycling tests of CIS-CS (40). (f) XRD patterns before and after the reaction over CIS-CS(40).

Fig. 4. Density of states of CoS2 (a), CuInS2 (b), and CIS-CS(40) (c). Work functions over CoS2 (d) and CuInS2 (e). (f) CIS-CS(40) differential charge density diagram. Cu 2p (g), In 3d (h), S 2p (i) XPS spectra of the samples.

Fig. 5. In situ FT-IR spectra (a) and the corresponding 3D color mapping surface with projection (b) over CIS-CS(40). (c) Reaction energy barrier of CO2 reduction on CoS2, CuInS2, and CIS-CS(40). (d) S-scheme heterojunction charge transfer path.

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Molten salt construction of core-shell structured S-scheme CuInS₂@CoS₂ heterojunction to boost charge transfer for efficient photocatalytic CO₂ reduction

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