Constructing dual-cocatalyst-directed quantifiable electron and hole transfer for enhanced photocatalytic performance

doi:10.1016/S1872-2067(25)64729-2

Abstract

Abstract:

Photocatalysts are essential for the preparation of wanted fine chemical and biomedical intermediates via visible photocatalysis, but existing photocatalysts with low catalytic efficiency limit their wide applications. Herein, CdS/Ti₃C₂T_x/MBI nanocomposites have been successfully fabricated through anchoring reduction cocatalyst Ti₃C₂T_x with electron-drawing ability and oxidation cocatalyst 2-mercaptobenzimidazole (MBI) with hole-capturing capacity on CdS nanoparticles. The Ti₃C₂T_x and MBI of CdS/Ti₃C₂T_x/MBI nanocomposites can extract electrons and holes from CdS nanoparticles to come true electron-hole separation, respectively. Moreover, the electron-drawing and hole-capturing abilities of the CdS/Ti₃C₂T_x/MBI nanocomposites depend on Ti₃C₂T_x and MBI contents, and the quantifiable electron and hole transfers finally determine photocatalytic efficiency of the CdS/Ti₃C₂T_x/MBI nanocomposites. The transient photocurrent density of the CdS/Ti₃C₂T_x/MBI nanocomposites is 6-fold higher than that of the CdS nanoparticles. The CdS/Ti₃C₂T_x/MBI nanocomposites with strong electron-hole separation capability exhibit outstanding visible photocatalytic organic transformation properties. The CdS/Ti₃C₂T_x/MBI nanocomposites produce (E)-N-benzyl-1-phenylmethylimine in ~96% yield (~8000 μmol·g^-1·h^-1), which is 3-fold higher than the CdS nanoparticles (~2500 μmol·g^-1·h^-1, 30%). This work provides a new strategy for constructing efficient and stable photocatalysts that can be used for efficient visible light-driven organic transformations.

Key words: Redox dual cocatalyst, Electron-hole separation, Photocatalyst, Organic transformation, MXene

Wenjing Gao, Yuchan Liu, Chenyao Chen, Ziqi Lian, Rongkai Ye, Chaorong Qi, Jianqiang Hu. Constructing dual-cocatalyst-directed quantifiable electron and hole transfer for enhanced photocatalytic performance[J]. Chinese Journal of Catalysis, 2025, 74: 319-328.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64729-2

https://www.cjcatal.com/EN/Y2025/V74/I7/319

Figures/Tables 8

Fig. 1. Schematic plot of the synthesis of CdS/Ti3C2Tx/MBI nanocomposites fabricated thus.

Fig. 2. XRD patterns (A) and UV-vis absorption spectra (in water) (B) of CdS NPs and CdS/MBI, CdS/Ti3C2Tx and CdS/Ti3C2Tx-3/MBI-6 nanocomposites. (C) FT-IR spectra of MBI, CdS NPs and CdS/MBI, CdS/Ti3C2Tx and CdS/Ti3C2Tx-3/MBI-6 nanocomposites. SEM images of Ti3C2Tx (D), CdS/Ti3C2Tx (E) and CdS/Ti3C2Tx-3/MBI-6 (F) nanocomposites. TEM images of CdS/Ti3C2Tx-3/MBI-6 (G) and CdS/MBI (I) nanocomposites. (H) Element mapping images of CdS/Ti3C2Tx-3/MBI-6 nanocomposites.

Fig. 3. High-resolution XPS spectra of N 1s (A) and C 1s (B) of the CdS/Ti3C2Tx-3/MBI-6 nanocomposites and Cd 3d (C) and S 2p (D) of the CdS NPs and CdS/Ti3C2Tx and CdS/Ti3C2Tx-3/MBI-6 nanocomposites. (E) UV-vis diffuse reflectance spectra (solid) of the CdS NPs and CdS/MBI, CdS/Ti3C2Tx and CdS/Ti3C2Tx-3/MBI-6 nanocomposites. Tauc plots (F) and Mott-Schottky plots (G) of the CdS NPs. (H) Schematic plot of charge transfer of the CdS/Ti3C2Tx/MBI nanocomposites prepared by the present method.

Fig. 4. PL emission spectra (excitation wavelength: 370 nm) (A), electrochemical impedance spectroscopy Nyquist plots (B), TRPL spectra (λ = 375 nm) (C) and transient photocurrent response (D) of the CdS NPs and CdS/MBI, CdS/Ti3C2Tx and CdS/Ti3C2Tx-3/MBI-6 nanocomposites.

Fig. 5. (A) Yields and TOF of oxidative coupling of amines under different photocatalysts. (B) Reusability of the CdS/Ti3C2Tx-3/MBI-6 nanocomposites used for coupling of amines. (C) XRD patterns of the CdS/Ti3C2Tx-3/MBI-6 nanocomposites and corresponding photocatalysts after five cycles.

Table 1 Photocatalytic oxidative coupling of amines under different conditions.a

Entry	Photocatalyst	Yield^b (%)	TOF^c (μmol·g^-1·h^-1)
1	CdS	30	2500
2	CdS/MBI	47	3917
3	CdS/Ti₃C₂T_x	48	4000
4	CdS/Ti₃C₂T_x-1/MBI-4	55	4583
5	CdS/Ti₃C₂T_x-2/MBI-4	64	5333
6	CdS/Ti₃C₂T_x-3/MBI-4	80	6667
7	CdS/Ti₃C₂T_x-4/MBI-4	69	5750
8	CdS/Ti₃C₂T_x-3/MBI-2	56	4667
9	CdS/Ti₃C₂T_x-3/MBI-6	96	8000
10	CdS/Ti₃C₂T_x-3/MBI-8	76	6333

Table 2 Substrate scope of photocatalytic oxidative coupling of amines catalyzed by CdS/Ti3C2Tx/MBI nanocomposites a.

Fig. 6. (A) The catalytic activity of the CdS/Ti3C2Tx/MBI nanocomposites under various reaction conditions. (B) EPR spectra of CdS/Ti3C2Tx/MBI nanocomposites and DMPO. (C) Possible photocatalytic mechanism of CdS/Ti3C2Tx/MBI-mediated oxidative coupling of amines.

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