Efficient photocatalytic hydrogen production by a heterojunction strategy with covalent organic frameworks loaded with non-precious-metal semiconductors

doi:10.1016/S1872-2067(25)64904-7

Abstract

Abstract:

Rational energy band engineering and the exposure of catalytically active sites critically enhance the efficiency of the hydrogen evolution reaction. In this study, TAPT-TFPT-COF/Mn_0.2Cd_0.8S composite photocatalysts were prepared by wet impregnation. The energy bands of non-precious-metal sulfide nanorods and a covalent organic framework (COF) were interleaved for effective heterojunction construction, enabling a three-fold enhancement in hydrogen evolution compared to that of the pure Mn_0.2Cd_0.8S catalyst. The enhanced catalyst performance is attributed to the construction of heterojunctions and the synergistic photothermal dynamics of the flexible monomers under illumination, which facilitates localized charge carrier migration. Furthermore, the hydrogen evolution mechanism in the Mn_0.2Cd_0.8S/COF composites was elucidated through photoelectrochemical experiments, in-situ irradiation X-ray photoelectron spectroscopy, surface photovoltage measurements, and density functional theory. The loaded organic semiconductor materials were combined with non-precious-metal semiconductors to construct S-scheme heterojunctions with increased hydrophilicity, and the tight combination of Mn_0.2Cd_0.8S and COF optimized the photogenerated electron utilization efficiency.

Key words: S-scheme heterojunction, Metal sulfide, Photocatalytic hydrogen evolution, Covalent organic frameworks, Charge transfer, Internal electric field

Bolin Yang, Fei Jin, Zhiliang Jin. Efficient photocatalytic hydrogen production by a heterojunction strategy with covalent organic frameworks loaded with non-precious-metal semiconductors[J]. Chinese Journal of Catalysis, 2026, 81: 172-184.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64904-7

https://www.cjcatal.com/EN/Y2026/V81/I2/172

Figures/Tables 8

Fig. 1. (a) Schematic of the synthesis of the MCSC-x composite catalyst. (b) XRD patterns of Mn0.2Cd0.8S. (c) Experimental PXRD patterns of COF. (d) XRD patterns of MCSC-x (x = 10, 20, 30).

Fig. 2. Mn 2p (a), Cd 3d (b), S 2p (c), and C 1s (d) XPS spectra of Mn0.2Cd0.8S, COF, and MCSC-20 catalysts. (e) FT-IR spectrum of the TAPT-TFPT-COF catalyst. (f) Zeta potentials of Mn0.2Cd0.8S, COF, and MCSC-20 catalysts. N2 absorption-desorption curves of Mn0.2Cd0.8S (g), COF (h), and MCSC-20 (i) (the insets show the pore-size distribution curves).

Fig. 3. (a) Photocatalytic hydrogen evolution with Mn0.2Cd0.8S, COF, and MCSC-20. (b) Photocatalytic hydrogen evolution with MCSC-x catalysts (variable x represents the range of 10, 20, and 30). (c) Cyclic photocatalytic hydrogen evolution with MCSC-20. (d) TEM images of MCSC-20 after the hydrogen evolution reaction. Infrared thermography of Mn0.2Cd0.8S (g), MCSC-20 (h), and control (blank) (i) catalysts under illumination with light for 180 s.

Fig. 4. SEM images of Mn0.2Cd0.8S (a), COF (b), and MCSC-20 (c). (c-m) TEM images of MCSC-20. (e-j) EDS mapping images of MCSC-20. Water contact angles of Mn0.2Cd0.8S (o), COF (p), and MCSC-20 (q).

Fig. 5. (a) Transient photocurrent response of Mn0.2Cd0.8S, COF, and MCSC-20 catalysts. (b) LSV spectra of Mn0.2Cd0.8S, COF, and MCSC-20. (c) EIS spectra of Mn0.2Cd0.8S, COF, and MCSC-20. (d) Mott-Schottky curves of Mn0.2Cd0.8S and COF. (e) UV-vis DRS of Mn0.2Cd0.8S, COF, and MCSC-20. (f) Bandgaps of Mn0.2Cd0.8S and COF obtained from Tauc plots. (g) PL spectra of Mn0.2Cd0.8S, COF, and MCSC-20. (h) TRPL spectra of Mn0.2Cd0.8S, COF, and MCSC-20. (i) Band structure diagram of Mn0.2Cd0.8S and COF.

Fig. 6. (a,b) Optimized structural models of Mn0.2Cd0.8S and COF. (c) ΔGH* of Mn0.2Cd0.8S and Mn0.2Cd0.8S/COF. (d) ELF of the Mn0.2Cd0.8S/COF heterojunction. Band structure and state density (PDOS) of Mn0.2Cd0.8S (e-g) and COF (i-k). (h,l) Work functions of Mn0.2Cd0.8S and COF.

Fig. 7. LUMO (a) and HOMO (b) of the periodic unit of TAF-COF based on DFT calculations. (c,d) Plane-average difference density plot along the z-axis of the Mn0.2Cd0.8S/COF heterogeneous junction. (e) Diagram of the charge transfer mechanism before and after contact between Mn0.2Cd0.8S and COF.

Fig. 8. In-situ irradiation XPS spectra of Mn 2p (a), Cd 3d (b), S 2p (c), C 1s (d), N 1s (e), and O 1s (f) in Mn0.2Cd0.8S/COF. (g) Photocatalytic reaction mechanism of MCSC-x.

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