Unveiling the highly disordered NbO6 units as electron-transfer sites in Nb2O5 photocatalysis with N-hydroxyphthalimide under visible light irradiation

doi:10.1016/S1872-2067(21)64026-3

Abstract

Abstract:

Although different NbO_x units are present in Nb₂O₅-based catalysts, the correlations between these structures and activity remain unclear, which considerably hinders the further development of Nb₂O₅ photocatalysis. Herein, we utilized N-hydroxyphthalimide (NHPI) as the probe molecule to distinguish the role of different NbO_x units in the activation of C-H bond under visible light irradiation. With the addition of NHPI, Nb₂O₅ catalysts with highly disordered NbO₆ units exhibited higher activities than that with slightly disordered NbO₆ units (419‒495 vs. 82 μmol·g^-1·h^-1) in photocatalytic selective oxidation of ethylbenzene. Revealed by Raman spectra, electron paramagnetic resonance spectra, and transmission-electron-microscopy images, highly disordered NbO₆ units were confirmed to act as the active sites for the transfer of photogenerated electrons from NHPI, promoting the generation of phthalimide-N-oxyl (PINO) radicals for the enhanced conversion of ethylbenzene under visible light irradiation. This study provides guidance on the role of local NbO_x units in Nb₂O₅ photocatalysis.

Key words: Photocatalysis, Nb₂O₅, Highly disordered NbO₆ units, Charge-transfer process, N-hydroxyphthalimide

Kaiyi Su, Chaofeng Zhang, Yehong Wang, Jian Zhang, Qiang Guo, Zhuyan Gao, Feng Wang. Unveiling the highly disordered NbO₆ units as electron-transfer sites in Nb₂O₅ photocatalysis with N-hydroxyphthalimide under visible light irradiation[J]. Chinese Journal of Catalysis, 2022, 43(7): 1894-1905.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64026-3

https://www.cjcatal.com/EN/Y2022/V43/I7/1894

Figures/Tables 11

Fig. 1. The plausible process for the electron transfer from NHPI molecules into Nb2O5 under visible light irradiation.

Fig. 2. XRD patterns (a), UV-Vis diffuse reflectance spectra (b), Tauc plots (c), and the electronic structures (d) of Nb2O5-450, Nb2O5-550, Nb2O5-650, and Nb2O5-850, respectively.

Fig. 3. The photoluminescence spectra (a) and Raman spectra (b) of as-synthesized Nb2O5-x catalysts.

Fig. 4. The HRTEM images and corresponding intensity plots of the lattice of Nb2O5-450 (a,e), Nb2O5-550 (b,f), Nb2O5-650 (c,g), and Nb2O5-850 (d,h). The scale bar is 10 nm.

Fig. 5. Comparison in the results of UV-Vis DRS for NHPI molecules, as-synthesized Nb2O5-x catalysts before and after the addition of NHPI molecules (NHPI + Nb2O5-x). (a) Nb2O5-450; (b) Nb2O5-550; (c) Nb2O5-650; (d) Nb2O5-850.

Fig. 6. The results of EPR for the mixture of different Nb2O5 catalysts and NHPI in CH3CN solution (designated as NHPI + Nb2O5-x) under dark and light irradiation (450 nm). (a,b) NHPI+Nb2O5-450; (c,d) NHPI+Nb2O5-550; (e,f) NHPI+Nb2O5-650; (g,h) NHPI+Nb2O5-850.

Fig. 7. XPS results of high resolution of Nb 3d spectra for different Nb2O5-x catalysts before and after the addition of NHPI. (a) Nb2O5-450; (b) Nb2O5-550; (c) Nb2O5-650; (d) Nb2O5-850.

Fig. 8. The photocatalytic performance of different Nb2O5 catalysts in the oxidation of ethylbenzene. Reaction conditions: as-synthesized Nb2O5-x (10 mg), CH3CN solution containing ethylbenzene (0.1mmol), O2 (0.1 Mpa), blue LEDs (455 nm), 20?30 °C, reaction time 12 h. a 3 mg NHPI without any Nb2O5 catalyst. b addition of 3 mg NHPI. The conversion is the average result.

Fig. 9. The influence of different scavengers in the conversion of ethylbenzene over the mixture of NHPI and different Nb2O5-x catalysts. (a) Nb2O5-450; (b) Nb2O5-550; and (c) Nb2O5-650. Reaction conditions: Nb2O5-x catalyst (10 mg), 3 mg NHPI and 0.1 mmol of ethylbenzene dissolved in CH3CN (1 mL), O2 (0.1 Mpa), blue LEDs (455 nm), ca. 20?30 °C, reaction time 12 h. The amounts of (NH4)2C2O4, AgNO3, BQ, t-BuOH, and BHT were 0.1 mmol, 0.1 mmol, 0.1 mmol, 0.2?0.3 mmol, 0.1 mmol, respectively.

Fig. 10. Proposed charge-transfer process and the activation of ethylbenzene to acetophenone over the mixture of NHPI and Nb2O5-x catalysts (Nb2O5-450, Nb2O5-550, and Nb2O5-650) under visible light irradiation.

Fig. 11. The plausible relationship between average lattice spacing and conversion of ethylbenzene over Nb2O5-x catalysts. Reaction conditions are the same as those shown in Fig. 8 with the addition of NHPI.

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Unveiling the highly disordered NbO₆ units as electron-transfer sites in Nb₂O₅ photocatalysis with N-hydroxyphthalimide under visible light irradiation

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