Regulation of d-band center of TiO2 through fluoride doping for enhancing photocatalytic H2O2 production activity

doi:10.1016/S1872-2067(23)64645-5

Abstract

Abstract:

Titanium dioxide (TiO₂) has received extensive attention for photocatalytic hydrogen peroxide (H₂O₂) production, with the d-band center related to the adsorption performance, which affects the photocatalytic reaction process. Herein, an ingenious strategy to lower the antibonding-orbital occupancy in the Ti 3d orbital by fluoride ion (F^‒) doping is proposed, with density functional theory calculations predicting that F-doping into TiO₂ induces a non-uniform charge distribution and enables an upshift of the d-band center in F/TiO₂. This manipulation provides accessible active centers with favorable d-band energy levels, which can improve the charge-transfer behavior, strengthen the interaction between the adsorbed oxygen and the photocatalyst, and reduce the adsorption energy of oxygen, eventually promoting the photocatalytic H₂O₂ production rate. The experimental results further confirm that a lower antibonding-orbital occupancy can intensify the adsorption of atomic oxygen at the Ti sites. Electron paramagnetic resonance experiment reveals that the presence of F^‒ ions in the lattice induces the formation of Ti³⁺ centers that localize the extra electron needed for charge compensation. Femtosecond transient absorption (fs-TA) spectroscopy suggests that photogenerated electrons are transferred from the conduction band of F/TiO₂ to the Ti³⁺ surface states and surface F^‒ ions, expediting the separation of electrons and holes. Consequently, with F^‒ doping in TiO₂, the photocatalytic H₂O₂ production yields improved from 277 to 467 μmol·g^‒1·h^‒1, with ethanol as a sacrificial reagent. This study provides a new strategy for regulating the d-band center to optimize the adsorption strength between the photocatalyst and oxygen atoms and achieve enhanced photocatalytic H₂O₂ production performance.

Key words: Antibonding orbital, d-Band center, Oxygen adsorption, Charge transfer, Hydrogen peroxide production

Yanyan Zhao, Shumin Zhang, Zhen Wu, Bicheng Zhu, Guotai Sun, Jianjun Zhang. Regulation of d-band center of TiO₂ through fluoride doping for enhancing photocatalytic H₂O₂ production activity[J]. Chinese Journal of Catalysis, 2024, 60: 219-230.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64645-5

https://www.cjcatal.com/EN/Y2024/V60/I5/219

Figures/Tables 10

Fig. 1. Graphical illustration of regulation of d-band center over F/TiO2.

Fig. 2. (a) Preparation processes of F/TiO2. TEM image (b) and the corresponding HRTEM image (c) of F/TiO2. (d) HAADF image of F/TiO2 and the EDS mapping images of F, O, and Ti elements.

Fig. 3. XPS depth profiling spectra for F/TiO2 at different sputtering times with C 1s peak at 284.6 eV as a reference. Atomic percentage (at%) distribution of Ti, O, and F (a), and high-resolution spectra of Ti 2p (b), O 1s (c), and F 1s (d). Here, 0 s is equivalent to a standard surface scan without ion sputtering, with spectra obtained after 60-180 s of sputtering corresponding to the elemental composition of the pellet bulk. Strength of the ion gun: 1000, 2000 eV.

Fig. 4. (a) EPR and (b) DRS spectra of TiO2 and F/TiO2.

Fig. 5. Calculated electronic band structure of TiO2 before (a) and after (b) fluorination. Work functions of TiO2 (c) and F/TiO2 (d).

Fig. 6. DOS for TiO2 (a) and F/TiO2 (b). (c) Calculated Ti d orbital DOS for both TiO2 and F/TiO2 surface phases. (d) Schematic diagram illustrating the optimization of antibonding-orbital occupancy of Ti?Oads for strengthening the adsorption of active Ti sites toward atomic oxygen.

Fig. 7. (a) Zeta potential of the as-prepared TiO2 and F/TiO2 in DI water. (b) O2-TPD patterns of TiO2 and F/TiO2. In situ DRIFTS spectra of O2 adsorption over TiO2 (c) and F/TiO2 (d).

Fig. 8. Photocatalytic H2O2 production performance of the as-prepared samples with ethanol as the sacrificial reagent (a) and in pure water without sacrificial reagent (b), with the H2O2 production rates summarized in (c). (d) Cycling experiments over F/TiO2 photocatalyst. (e) Photocatalytic H2O2 (1 mmol·L?1) decomposition over the as-prepared samples. (f) Comparison of ORR for H2O2 production over F/TiO2 in O2, air, and N2 with ethanol as the sacrificial agent.

Fig. 9. (a) DMPO spin-trapping EPR spectra for superoxide radical (·O2?). (b) Amount of ·O2? over TiO2 and F/TiO2 photocatalyst. PL spectra (c), TRPL spectra (d), TPR experiments (e), and EIS analysis (f) of the as-prepared TiO2 and F/TiO2. Rs, Rct, and CPE represent the electrode solution resistance, interfacial charge transfer resistance, and constant phase element, respectively.

Fig. 10. Pseudocolor plots of TiO2 (a) and F/TiO2 (b). fs-TA spectra signals at indicated delay times measured with 325 nm pump pulse excitation over TiO2 (c) and F/TiO2 (d). (e) Normalized decay kinetic curves of GSB peaks in fs-TA spectra of TiO2 and F/TiO2. (f) Schematic diagrams for electrons transfer pathway and improved photogenerated carrier separation efficiency over F/TiO2.

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Regulation of d-band center of TiO₂ through fluoride doping for enhancing photocatalytic H₂O₂ production activity

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