Highly efficient S2--adsorbed MoSx-modified TiO2 photocatalysts: A general grafting strategy and boosted interfacial charge transfer

doi:10.1016/j.jmst.2020.02.031

Abstract

Abstract:

Exploiting efficient and low-cost cocatalyst with a facile grafting strategy is of critical importance for significantly boosting the photocatalytic H₂-evolution activity. In this study, S^2--adsorbed MoS_x nanoparticle as a superior H₂-evolutoin cocatalyst was successfully grafted on the TiO₂ surface to greatly boost its photocatalytic activity via one-step lactic acid-induced synthesis strategy. Herein, the lactic acid can induce the homogeneous production of amorphous MoS_x (a-MoS_x) nanoparticles from MoS₄^2- precursor, while the symbiotic S^2- ions can be easily and availably self-adsorbed on the a-MoS_x surface, resulting in the formation of S^2--adsorbed a-MoS_x nanoparticles with a small size of 0.5-3 nm. Photocatalytic results manifested that the S^2--adsorbed MoS_x nanoparticles could dramatically facilitate the H₂-generation rate of TiO₂ photocatalysts (3452 μmol h^-1 g^-1, AQE = 16.5 %). In situ irradiated XPS in conjunction with transient-state PL and photoelectrochemical tests reveal that the improved H₂-generation activity can be ascribed to the synergistic effect of boosted interfacial charge transfer from TiO₂ to S^2--adsorbed MoS_x and the superior H₂-evolution reaction on self-adsorbed S^2- ions. In addition, the S^2--adsorbed MoS_x nanoparticles can also act as the general H₂-generation cocatalyst to obviously promote the activity of other typical host photocatalysts such as g-C₃N₄ and CdS. This work provides an innovative approach to develop high-efficiency MoS_x-based cocatalyst with boosted interfacial charge transfer toward highly efficient photocatalytic materials.

Key words: In situ irradiated XPS, S²-adsorbed MoSx, Cocatalyst, Photocatalysis, H₂-generation

Duoduo Gao, Ranran Yuan, Jiajie Fan, Xuekun Hong, Huogen Yu. Highly efficient S^2--adsorbed MoS_x-modified TiO₂ photocatalysts: A general grafting strategy and boosted interfacial charge transfer[J]. J. Mater. Sci. Technol., 2020, 56: 122-132.

Figures/Tables 13

Fig. 1. (A) Schematic diagram illustrating lactic acid-induced synthesis and (B) their corresponding color change of S2--adsorbed MoSx nanoparticle-modified TiO2 photocatalyst; (C) schematic illustration for electrostatic self-assembly process between S2--adsorbed MoSx nanoparticles and TiO2 photocatalyst.

Fig. 2. (A) XRD patterns of various samples: (a) TiO2, (b) a-MoSx/TiO2(0.1 wt%), (c) a-MoSx/TiO2(3 wt%), (d) a-MoSx/TiO2(8 wt.%), and (e) a-MoSx/TiO2(3 wt.% HCl).

Fig. 3. (A) TEM and (B) HRTEM images, (C) HAADF-STEM and EDS mapping images of a-MoSx/TiO2(3 wt.%) photocatalyst.

Fig. 4. (A) XPS survey spectra and high-resolution spectra of Mo 3d (B, D), S 2p (C, E) for (a) TiO2, (b) a-MoSx/TiO2 (0.1 wt.%), (c) a-MoSx/TiO2 (3 wt.%) and (d) a-MoSx/TiO2 (8 wt.%).

Table 1 Composition (wt.%) of various samples according ICP-OES results.

Sample	TiO₂	a-MoS_x/TiO₂ (0.1 wt.%)	a-MoS_x/TiO₂ (3 wt.%)	a-MoS_x/TiO₂ (8 wt.%)	a-MoS_x/TiO₂ (3 wt.% HCl)
Mo (wt. %)	0	0.01	0.97	2.10	1.04
S (wt. %)	0	0.15	2.25	4.82	2.19

Fig. 5. UV-vis spectra of various samples: (a) TiO2, (b) a-MoSx/TiO2 (0.1wt.%), (c) a-MoSx/TiO2 (3 wt.%), (d) a-MoSx/TiO2 (8 wt.%) and (e) a-MoS2/TiO2 (3 wt.% HCl).

Fig. 6. (A) Photocatalytic H2-evolution activities of various samples: (a) TiO2, (b) a-MoSx/TiO2 (0.05 wt.%), (c) a-MoSx/TiO2 (0.1 wt.%), (d) a-MoSx/TiO2 (0.5 wt.%), (e) a-MoSx/TiO2 (1 wt.%), (f) a-MoSx/TiO2 (3 wt.%), (g) a-MoSx/TiO2 (5 wt.%), (h) a-MoSx/TiO2 (8 wt.%) and (i) a-MoSx/TiO2 (3 wt.% HCl); (B) Cycling runs of a-MoSx/TiO2 (3 wt.%) sample.

Fig. 7. Proposed photocatalytic H2-generation mechanism of a-MoSx/TiO2.

Fig. 8. In situ and ex situ XPS spectra of Ti 2p (A) and O 1s (B) for TiO2 and a-MoSx/TiO2; Mo 3d (C) and S 2p (D) for a-MoSx and a-MoSx/TiO2 in dark and under UV-light irradiation; Schematic diagram for electron transfer pathway before contact (E), after contact (F) and after contact under irradiation (G) of S2--adsorbed MoSx and TiO2.

Fig. 9. Comparison of photocatalytic H2-evolution activity for a-MoSx/TiO2 (3 wt.%) before (a) and after (b) washing with distilled water.

Fig. 10. (A) Transient-state photoluminescence spectras of TiO2 (a) and a-MoSx/TiO2 (3 wt.%) (b); (B) Linear sweep voltammetry curves, (C) transient photocurrent responses and (D) electrochemical impedance spectra for various samples: (a) TiO2, (b) a-MoSx/TiO2 (0.1 wt.%) and (c) a-MoSx/TiO2 (3 wt.%).

Fig. 11. (A-D) FESEM/EDS results and (E, F) Diffuse reflectance spectra of (A) g-C3N4, (B) a-MoSx/g-C3N4, (C) CdS and (D) a-MoSx/CdS.

Fig. 12. Photocatalytic activity of typical photocatalysts before and after S2--adsorbed MoSx loading: (a) g-C3N4, (a′) a-MoSx/g-C3N4 (3 wt.%); (b) TiO2, (b′) a-MoSx/TiO2 (3 wt.%); (c) CdS, (c′) a-MoSx/CdS (3 wt.%).

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Highly efficient S^2--adsorbed MoS_x-modified TiO₂ photocatalysts: A general grafting strategy and boosted interfacial charge transfer

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