Surface engineering enhancing activity and stability of Bi2WO6-x for selective C-H bond photooxidation

doi:10.1016/S1872-2067(25)64899-6

Abstract

Abstract:

Oxygen vacancies (Ov) play a pivotal role in enhancing photocatalytic C-H bond oxidation, yet their susceptibility to depletion under oxidative conditions significantly compromises catalyst stability. To address this challenge, we developed a surface engineering strategy through in-situ growth of a Bi-MOF layer on oxygen vacancy-rich Bi₂WO₆ (Bi₂WO_6-_x@Bi-MOF). This interfacial Bi-O interaction not only constructed a built-in charge transfer channel to boost electron migration from Bi₂WO_6-_x to Bi-MOF, but also shifted the Bi p-band center closer to the Fermi level (E_f) to facilitate the adsorption of oxygen molecules and toluene. This surface engineering strategy preferentially adsorbs O₂ on Bi-MOF and prevents its direct interaction with the Bi₂WO_6-_x host, thereby mitigating oxygen vacancy depletion and enhancing catalyst stability. The optimized photocatalyst achieves 96% toluene conversion and 80% benzaldehyde selectivity within 2 h of light irradiation and maintains excellent structural stability and catalytic performance over ten consecutive cycles. This study offers a new design strategy for constructing robust and efficient Ov-based photocatalytic systems and expands the potential application of MOF materials in complex interfacial reactions.

Key words: Photocatalysis, Oxygen vacancies, Surface engineering, C-H oxidation, Metal-organic framework

Xiong Wang, Chao Peng, Yongkang Xiao, Ziye Zhang, Huiping Zheng, Wenjie Yue, Sheng Tian, Xingsheng Hu, Weifan Shao, Guanghui Chen, Binghao Wang, Huijuan Wang, Mingming Yin, Jinxin Li, Yang Li, Lang Chen, Shuangfeng Yin. Surface engineering enhancing activity and stability of Bi₂WO_6-_x for selective C-H bond photooxidation[J]. Chinese Journal of Catalysis, 2026, 81: 246-258.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64899-6

https://www.cjcatal.com/EN/Y2026/V81/I2/246

Figures/Tables 7

Fig. 1. (a) Preparation process of the Bi2WO6-x@Bi-MOF. XRD patterns (b) and FTIR spectra (c) of the prepared Bi2WO6-x@Bi-MOF, Bi2WO6-x, and p-BWO. C 1s (d), Bi 4f (e), O 1s (f) XPS spectra, and EPR spectra (g) of the prepared samples.

Fig. 2. SEM (a) and TEM (b) images of Bi2WO6-x@Bi-MOF. HR-TEM images and the corresponding strain distribution of ?yy at the interface of Bi2WO6-x@Bi-MOF (c,d) and pure Bi2WO6-x (e,f). (g) EDS mapping images of Bi2WO6-x@Bi-MOF.

Fig. 3. PL emission spectra (a), time-resolved PL decay spectra (b), and electrochemical impedance spectroscopic data (c) of p-BWO, Bi2WO6-x and Bi2WO6-x@Bi-MOF. In-situ XPS spectra of Bi 4f (d), W 4f (e), and C 1s (f) of Bi2WO6-x@Bi-MOF in the dark or light irradiation conditions.

Fig. 4. (a) Photocatalytic toluene selective oxidation under 405 nm LED (1W) irradiation. (b) Time-dependent toluene photo-oxidation property over Bi2WO6-x@Bi-MOF. (c) Cycling test results for Bi2WO6-x@Bi-MOF and Bi2WO6-x. (d) EPR spectra of Bi2WO6-x and Bi2WO6-x@Bi-MOF before and after photocatalytic reaction. (e,f) In-situ EPR spectra denoting the corresponding active free radicals. (g) Photo-oxidation of other hydrocarbons over Bi2WO6-x@Bi-MOF photocatalyst.

Fig. 5. (a) The computed DOS plots of, Bi-pDOS plots of Bi2WO6-x and Bi2WO6-x@Bi-MOF. (b) The computed O-pDOS plots of free O2 and O2 adsorbed on Bi2WO6-x or Bi2WO6-x@Bi-MOF. (c) DFT-calculated O2 adsorption energies on pristine Bi2WO6-x, the Bi2WO6-x or Bi-MOF region of Bi2WO6-x@Bi-MOF. Differential charge density maps of O2 adsorption on pristine Bi2WO6-x (d), the Bi2WO6-x region of Bi2WO6-x@Bi-MOF (e), and the Bi-MOF region of Bi2WO6-x@Bi-MOF (f). Yellow and cyan isosurfaces represent electron accumulation and depletion, respectively. (g) PL intensity decay processes of Bi2WO6-x and Bi2WO6-x@Bi-MOF. (h) The time-resolved photoluminescence spectra in poor and rich oxygen reaction environments. (i) Periodic on/off photocurrent responses of Bi2WO6-x and Bi2WO6-x@Bi-MOF in electrolyte environments with different atmosphere treatments accordingly. (j) Schematic diagram illustrating the p-band of Bi in Bi2WO6-x and Bi2WO6-x@Bi-MOF and their optimized antibonding-orbital occupancy of Bi-Oads.

Fig. 6. In-situ FT-IR spectra for photocatalytic oxidation of toluene over p-BWO (a), Bi2WO6-x (b), and Bi2WO6-x@Bi-MOF (c) under dark and visible-light conditions, respectively. (d) Free-energy diagrams for C-H activation on different samples. (e) Atomic configurations for the corresponding steps in the simulation (Bi2WO6-x@Bi-MOF), bluish purple, orange-red, red, gray, and white spheres represent bismuth, tungsten, oxygen, carbon, and hydrogen atoms, respectively.

Fig. 7. Proposed toluene oxidation mechanism over Bi2WO6-x@Bi-MOF photocatalyst.

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Surface engineering enhancing activity and stability of Bi₂WO_6-_x for selective C-H bond photooxidation

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