Self-assembled S-scheme In2.77S4/K+-doped g-C3N4 photocatalyst with selective O2 reduction pathway for efficient H2O2 production using water and air

doi:10.1016/S1872-2067(24)60077-X

Abstract

Abstract:

The development of an efficient artificial H₂O₂ photosynthesis system is a challenging work using H₂O and O₂ as starting materials. Herein, 3D In_2.77S₄ nanoflower precursor was in-situ deposited on K⁺-doped g-C₃N₄ (KCN) nanosheets using a solvothermal method, then In_2.77S₄/KCN (IS/KCN) heterojunction with an intimate interface was obtained after a calcination process. The investigation shows that the photocatalytic H₂O₂ production rate of 50IS/KCN can reach up to 1.36 mmol g^-1 h^-1 without any sacrificial reagents under visible light irradiation, which is 9.2 times and 4.1 times higher than that of KCN and In_2.77S₄, respectively. The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_2.77S₄ according to density functional theory calculations, electron paramagnetic resonance and free radical capture tests, leading to an expanded light response range and rapid charge separation at their interface, as well as preserving the active electrons and holes for H₂O₂ production. Besides, the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O₂ around the active centers, the energy barriers of O₂ protonation and H₂O₂ desorption steps are effectively reduced over the composite. In addition, this system also exhibits excellent light harvesting ability and stability. This work provides a potential strategy to explore a sustainable H₂O₂ photosynthesis pathway through the design of heterojunctions with intimate interfaces and desired reaction thermodynamics and kinetics.

Key words: Photocatalysis, H₂O₂ production, K⁺-doped g-C₃N₄, In_2.77S₄, S-scheme heterojunction

Qiqi Zhang, Hui Miao, Jun Wang, Tao Sun, Enzhou Liu. Self-assembled S-scheme In_2.77S₄/K⁺-doped g-C₃N₄ photocatalyst with selective O₂ reduction pathway for efficient H₂O₂ production using water and air[J]. Chinese Journal of Catalysis, 2024, 63: 176-189.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60077-X

https://www.cjcatal.com/EN/Y2024/V63/I8/176

Figures/Tables 7

Fig. 1. (a) Schematic illustration of IS/KCN preparation. XRD patterns (b) and SEM images (c?e) of samples. Elemental mappings (f), TEM (g,h) and HRTEM (i,j) images of 50IS/KCN.

Fig. 2. XPS spectra of various samples: (a) total survey; (b) C 1s; (c) N 1s; (d) K 2p; (e) S 2p; (f) In 3d.

Fig. 3. (a,b) H2O2 production rate of various samples. H2O2 production curves (c), the effect of pH values on H2O2 production rate (d) and cycling durability (e) of 50IS/KCN. (f) Kinetic relationship of formation rate constant (Kf) and decomposition rate constant (Kd) for H2O2 production.

Fig. 4. UV-vis spectra (a), corresponding Tauc plots (b) and schematic illustration of energy levels structure (c) of samples. Transient photocurrent response curves (d), EIS Nyquist plots (e), time-resolved photoluminescence spectra (f), multi-potential steps i-t curves (g), SPV spectra (h) and linear relationship between the current density and scan rate (i) of samples.

Fig. 5. (a-c) band structures of CN and In2.63S4. Calculated electrostatic potentials (d,e), density of states (f) and free-energy diagrams (g) for the reduction of O2 to H2O2 on various samples.

Fig. 6. The water contact angle patterns of KCN (a), 50IS/KCN (b) and In2.77S4 (c). (d) Photos of samples dispersed in water.

Fig. 7. (a,d) Single-variable control experiments of species capture. (b,e) ESR spectra of DMPO-·O2?. (c,f) ESR spectra of TEMP-1O2 over KCN and 50IS/KCN. (g) Photocatalytic mechanism diagram of H2O2 production over 50IS/KCN.

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Self-assembled S-scheme In_2.77S₄/K⁺-doped g-C₃N₄ photocatalyst with selective O₂ reduction pathway for efficient H₂O₂ production using water and air

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