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.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

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 ɛyy 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.

References

[1]	L. Kesavan, R. Tiruvalam, M. H. A. Rahim, M. I. bin Saiman, D. I. Enache, R. L. Jenkins, N. Dimitratos, J. A. Lopez-Sanchez, S. H. Taylor, D. W. Knight, C. J. Kiely, G. J. Hutchings, Science, 2011, 331, 195-199.
[2]	L. Q. Xiong, J. W. Tang, Adv. Energy Mater., 2021, 11, 2003216.
[3]	A. Maldotti, A. Molinari, R. Amadelli, Chem. Rev., 2002, 102, 3811-3836.
[4]	J. A. Labinger, J. E. Bercaw, Nature, 2002, 417, 507-514.
[5]	G. Laudadio, Y. Deng, K. van der Wal, D. Ravelli, M. Nuño, M. Fagnoni, D. Guthrie, Y. Sun, T. Noël, Science, 2020, 369, 92-96.
[6]	Z.-J. Bai, J. Xiong, Y. Mao, S. Tian, B.-H. Wang, B. Hu, X. Wang, W. Zhou, C.-T. Au, L. Chen, S.-F. Yin, Cell Rep. Phys. Sci., 2023, 4, 101591.
[7]	M. T. Gonfa, S. Shen, L. Chen, B. Hu, W. Zhou, Z.-J. Bai, C.-T. Au, S.-F. Yin, Chin. J. Catal., 2023, 49, 16-41.
[8]	L. Yao, G. Lu, Y. Haver, Y. Hu, Z. Shen, X. Kong, Z. Li, B. Peng, G. Zhao, M. Muhler, X. Huang, Nanoscale, 2025, 17, 11502-11511.
[9]	L. Chen, J. Tang, L.-N. Song, P. Chen, J. He, C.-T. Au, S.-F. Yin, Appl. Catal. B, 2019, 242, 379-388.
[10]	X. Wang, G.-H. Chen, Y. Li, S. Tian, B.-H. Wang, B. Hu, X.-S. Hu, C. Peng, L. Chen, S.-F. Yin, Sci. China Mater., 2025, 68, 785-794.
[11]	Z.-J. Bai, Y. Mao, B.-H. Wang, L. Chen, S. Tian, B. Hu, Y.-J. Li, C.-T. Au, S.-F. Yin, Nano Res., 2023, 16, 6104-6112.
[12]	Z.-J. Bai, X.-P. Tan, L. Chen, B. Hu, Y.-X. Tan, Y. Mao, S. Shen, J.-K. Guo, C.-T. Au, Z.-W. Liang, S.-F. Yin, Chem. Eng. Sci., 2022, 247, 116983.
[13]	Z.-J. Bai, S. Tian, T.-Q. Zeng, L. Chen, B.-H. Wang, B. Hu, X. Wang, W. Zhou, J.-B. Pan, S. Shen, J.-K. Guo, T.-L. Xie, Y.-J. Li, C.-T. Au, S.-F. Yin, ACS Catal., 2022, 12, 15157-15167.
[14]	Z. Wu, K. Zhang, X. Li, G. Hai, X. Huang, G. Wang, Appl. Surf. Sci., 2021, 555, 149732.
[15]	Y. Hu, Z. Shen, Y. Chen, N. Zheng, G. Zhao, Z. Ji, X. Wang, X. Huang, M. Muhler, J. Catal., 2024, 437, 115668.
[16]	R. Yuan, S. Fan, H. Zhou, Z. Ding, S. Lin, Z. Li, Z. Zhang, C. Xu, L. Wu, X. Wang, X. Fu, Angew. Chem. Int. Ed., 2013, 52, 1035-1039.
[17]	H. Wang, C. Cao, D. Li, Y. Ge, R. Chen, R. Song, W. Gao, X. Wang, X. Deng, H. Zhang, B. Ye, Z. Li, C. Li, J. Am. Chem. Soc., 2023, 145, 16852-16861.
[18]	Y. Liu, L. Chen, Q. Yuan, J. He, C.-T. Au, S.-F. Yin, Chem. Commun., 2016, 52, 1274-1277.
[19]	B. Yuan, B. Zhang, Z. Wang, S. Lu, J. Li, Y. Liu, C. Li, Chin. J. Catal., 2017, 38, 440-446.
[20]	X. Li, L. Luo, H. Guo, B. Weng, L. Sun, G. Velpula, I. Aslam, M. B. J. Roeffaers, Q. Chen, L. Zeng, M.-Q. Yang, Q. Qian, J. Mater. Chem. A, 2024, 12, 11841-11847.
[21]	Y. Shi, P. Li, H. Chen, Z. Wang, Y. Song, Y. Tang, S. Lin, Z. Yu, L. Wu, J. C. Yu, X. Fu, Nat. Commun., 2024, 15, 4641.
[22]	R. Sun, X. Cao, J. Ma, H.-C. Chen, C. Chen, Q. Peng, Y. Li, Nat. Synth., 2025, 4, 1017.
[23]	G. Zhou, B. Lei, F. Dong, ACS Catal., 2024, 14, 4791-4798.
[24]	X. Cao, A. Huang, C. Liang, H.-C. Chen, T. Han, R. Lin, Q. Peng, Z. Zhuang, R. Shen, H.-M. Chen, Y. Yu, C. Chen, Y. Li, J. Am. Chem. Soc., 2022, 144, 3386-3397.
[25]	Y. Li, X. Wang, X.-S. Hu, B. Hu, S. Tian, B.-H. Wang, L. Chen, G.-H. Chen, C. Peng, S. Shen, S.-F. Yin, Chin. J. Catal., 2024, 59, 159-168.
[26]	J. Yi, X. Yang, L. Shen, H. Xue, M.-Q. Yang, Q. Qian, Small, 2024, 20, 2404579.
[27]	T.-Q. Zeng, B.-H. Wang, S. Tian, Z.-J. Bai, X. Wang, Y. Li, C.-T. Au, L. Chen, S.-F. Yin, Ind. Eng. Chem. Res., 2023, 62, 11573-11584.
[28]	T. Wu, J. Cui, C. Wang, G. Zhang, L. Li, Y. Qu, Y. Niu, Nanomaterials, 2022, 12, 4410.
[29]	F. Zhan, G. Wen, R. Li, C. Feng, Y. Liu, Y. Liu, M. Zhu, Y. Zheng, Y. Zhao, P. La, Phys. Chem. Chem. Phys., 2024, 26, 11182-11207.
[30]	Y. Yang, S. Zhao, F. Bi, J. Chen, Y. Li, L. Cui, J. Xu, X. Zhang, Cell Rep. Phys. Sci., 2022, 3, 101011.
[31]	J.-B. Pan, B.-H. Wang, J.-B. Wang, H.-Z. Ding, W. Zhou, X. Liu, J.-R. Zhang, S. Shen, J.-K. Guo, L. Chen, C.-T. Au, L.-L. Jiang, S.-F. Yin, Angew. Chem. Int. Ed., 2021, 60, 1433-1440.
[32]	G. Liu, J. Li, J. Fu, G. Jiang, G. Lui, D. Luo, Y.-P. Deng, J. Zhang, Z. P. Cano, A. Yu, D. Su, Z. Bai, L. Yang, Z. Chen, Adv. Mater., 2019, 31, 1806761.
[33]	J.-W. Jung, H.-S. Choi, Y.-J. Lee, Y. Kim, T. Taniguchi, K. Watanabe, M.-Y. Choi, J. H. Jang, H.-S. Chung, D. Kim, Y. Kim, C.-H. Cho, Adv. Sci., 2024, 11, 2310197.
[34]	S. Zhou, K. Chen, J. Huang, L. Wang, M. Zhang, B. Bai, H. Liu, Q. Wang, Appl. Catal. B, 2020, 266, 118513.
[35]	S. Kim, T. A. Dela Pena, S. Seo, H. Choi, J. Park, J.-H. Lee, J. Woo, C. H. Choi, S. Lee, Appl. Surf. Sci., 2021, 563, 150357.
[36]	C. Xu, Y. Pan, G. Wan, H. Liu, L. Wang, H. Zhou, S.-H. Yu, H.-L. Jiang, J. Am. Chem. Soc., 2019, 141, 19110-19117.
[37]	L. Xiao, Q. Zhang, P. Chen, L. Chen, F. Ding, J. Tang, Y.-J. Li, C.-T. Au, S.-F. Yin, Appl. Catal. B, 2019, 248, 380-387.
[38]	R. S. H. Khoo, C. Fiankor, S. Yang, W. Hu, C. Yang, J. Lu, M. D. Morton, X. Zhang, Y. Liu, J. Huang, J. Zhang, J. Am. Chem. Soc., 2023, 145, 24052-24060.
[39]	H. Zhang, S. Liu, A. Zheng, P. Wang, Z. Zheng, Z. Wang, H. Cheng, Y. Dai, B. Huang, Y. Liu, Angew. Chem. Int. Ed., 2024, 63, e202400965.
[40]	L. Zhuang, L. Ge, H. Liu, Z. Jiang, Y. Jia, Z. Li, D. Yang, R. K. Hocking, M. Li, L. Zhang, X. Wang, X. Yao, Z. Zhu, Angew. Chem. Int. Ed., 2019, 58, 13565-13572.
[41]	X. Y. Yue, L. Cheng, F. Li, J. J. Fan, Q. J. Xiang, Angew. Chem. Int. Ed., 2022, 61, e202208414.
[42]	X. Cao, Z. Chen, R. Lin, W.-C. Cheong, S. Liu, J. Zhang, Q. Peng, C. Chen, T. Han, X. Tong, Y. Wang, R. Shen, W. Zhu, D. Wang, Y. Li, Nat. Catal., 2018, 1, 704-710.
[43]	Z. R. Shen, Z. H. Luo, J. Y. Chen, Y. W. Li, Adv. Funct. Mater., 2023, 33, 2213935.
[44]	M.-L. Xu, X.-J. Jiang, J.-R. Li, F.-J. Wang, K. Li, X. Cheng, ACS Appl. Mater. Interfaces, 2021, 13, 56171-56180.
[45]	A. A. Kistanov, Y. Cai, K. Zhou, S. V. Dmitriev, Y.-W. Zhang, J. Mater. Chem. C, 2018, 6, 518-525.
[46]	Z.-J. Bai, A.-J. Yang, S. Tian, L. Chen, B.-H. Wang, B. Hu, X. Wang, T.-Q. Zeng, C. Peng, Y. Mao, M. Tulu, C.-T. Au, S.-F. Yin, Chem. Eng. Sci., 2023, 282, 119334.
[47]	Y.-X. Tan, Z.-M. Chai, B.-H. Wang, S. Tian, X.-X. Deng, Z.-J. Bai, L. Chen, S. Shen, J.-K. Guo, M.-Q. Cai, C.-T. Au, S.-F. Yin, ACS Catal., 2021, 11, 2492-2503.
[48]	X.-X. Deng, S. Tian, Z.-M. Chai, Z.-J. Bai, Y.-X. Tan, L. Chen, J.-K. Guo, S. Shen, M.-Q. Cai, C.-T. Au, S.-F. Yin, Ind. Eng. Chem. Res., 2020, 59, 13528-13538.
[49]	X. Wang, B.-H. Wan, C. Peng, H.-J. Wang, G.-H. Chen, S. Tian, L. Chen, S.-F. Yin, ACS Catal., 2025, 15, 13288-13301.
[50]	Y. Dai, C. Poidevin, C. Ochoa-Hernández, A. A. Auer, H. Tüysüz, Angew. Chem. Int. Ed., 2020, 59, 5788-5796.
[51]	I. Hermans, J. Peeters, L. Vereecken, P. A. Jacobs, ChemPhysChem, 2007, 8, 2678-2688.

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

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 7

References

Related Articles 15

Recommended Articles

Metrics

[1]	Jiaping Lu, Chao Lin, Chao Li, Hongjie Shi, Nengyi Liu, Wandong Xing, Sibo Wang, Guigang Zhang, Teng-Teng Chen, Xiong Chen. Bipyridine-integrated bisoxazole-based donor-acceptor covalent organic framework for enhanced photocatalytic H₂O₂ synthesis [J]. Chinese Journal of Catalysis, 2026, 81(2): 185-194.
[2]	Ganghua Zhou, Jie Liu, Longyun Zhang, Chuanzhou Bi, Hangmin Xu, Weiyi Jiang, Xingwang Zhu, Xin Ning, Hui Xu, Xiaozhi Wang. Atomic-level Mn incorporation into Co₃O₄ for selective CO₂ photoreduction in pure water under dilute CO₂ atmosphere [J]. Chinese Journal of Catalysis, 2026, 81(2): 216-226.
[3]	Zhe Zhang, Guixu Pan, Wei Zhu, Keyu Zhang, Guijie Liang, Shihan Wang, Ning Wang, Yan Xing, Yunfeng Li. Multi-intermolecular forces strengthen interfacial carrier mobility in poly (barbituric acid) all-organic heterojunction systems for efficient solar-to-hydrogen conversion [J]. Chinese Journal of Catalysis, 2026, 81(2): 284-298.
[4]	Na Tian, Chaofan Yuan, Tong Zhou, Wenying Yu, Yinghui Wang, Na Zhang, Yihe Zhang, Hongwei Huang. Defect-coordinated Au nanoparticles in carbon nitride for efficient piezo-photocatalytic hydrogen peroxide production [J]. Chinese Journal of Catalysis, 2026, 81(2): 272-283.
[5]	Jinpeng Zhang, Teng Liang, Jaenudin Ridwan, Tian Chen, Elhussein M. Hashem, Meijun Guo, Amin Talebian-Kiakalaieh, Le Yu, Ping She, Jingrun Ran. Key components for realistic application of plastic photoreforming coupled with H₂ evolution [J]. Chinese Journal of Catalysis, 2026, 80(1): 20-37.
[6]	Shaodan Wang, Heng Yang, Lijun Xue, Jianjun Zhang, Shuxin Ouyang, Lili Wen. S-scheme heterojunctions of metal-doped ZnIn₂S₄/TpPa-1: Regulating H adsorption/desorption and internal electric field for boosted dual-functional photocatalysis [J]. Chinese Journal of Catalysis, 2026, 80(1): 159-173.
[7]	Shuqi Liang, Zhen Xiao, Jinni Shen, Wenxin Dai, Zizhong Zhang. Tuning radical generation rate for efficient CH₄ photooxidation to CH₃OH over AgPd alloy and Co₃O₄ cascade active sites [J]. Chinese Journal of Catalysis, 2026, 80(1): 189-199.
[8]	Liyuan Xiao, Zhenlu Wang, Jingqi Guan. Advances in multinuclear metal-organic frameworks for electrocatalysis [J]. Chinese Journal of Catalysis, 2026, 80(1): 59-91.
[9]	Rundong Chen, Yuhang Zhang, Bingquan Xia, Xianlong Zhou, Yanzhao Zhang, Shantang Liu. Enhanced photocatalytic production of hydrogen and benzaldehyde over a dual-function Zn_xCd_1-_xS_y/FePS₃ S-scheme heterojunction [J]. Chinese Journal of Catalysis, 2026, 80(1): 123-134.
[10]	Wei Zhong, Aiyun Meng, Xudong Cai, Yiyao Gan, Jingtao Wang, Yaorong Su. Enhancing photocatalytic H₂ evolution by weakening S-H_ad bonds via Co-induced asymmetric electron distribution in NiCoS cocatalysts [J]. Chinese Journal of Catalysis, 2025, 76(9): 108-119.
[11]	Xiangyang Zheng, Jinwang Wu, Haifeng Shi. Double-vacancy-induced polarization and intensified built-in electric field in S-Scheme heterojunction for removal of antibiotics and Cr (VI) [J]. Chinese Journal of Catalysis, 2025, 76(9): 50-64.
[12]	Bicheng Ji, Xicheng Li, Shuai Gao, Zeping Qin, Changzheng Wang, Qiang Wang, Chong-Chen Wang. Polarization-enhanced piezo-photocatalysis over hollow-sphere Bi₄Ti₃O₁₂: Structure-property relationship and degradation mechanism [J]. Chinese Journal of Catalysis, 2025, 76(9): 133-145.
[13]	Shijie Li, Rui Li, Kexin Dong, Yanping Liu, Xin Yu, Wenyao Li, Tong Liu, Zaiwang Zhao, Mingyi Zhang, Bin Zhang, Xiaobo Chen. Self-floating Bi₄O₅Br₂/P-doped C₃N₄/carbon fiber cloth with S-scheme heterostructure for boosted photocatalytic removal of emerging organic contaminants [J]. Chinese Journal of Catalysis, 2025, 76(9): 37-49.
[14]	Bo Feng, Danning Feng, Yan Pei, Baoning Zong, Minghua Qiao, Wei Li. Cu single atoms on defective carbon nitride for photocatalytic oxidation of methane to methanol with selectivity over 92% [J]. Chinese Journal of Catalysis, 2025, 76(9): 96-107.
[15]	Xu Xinmeng, Xi Zuoshuai, Gao Hongyi, Zhao Danfeng, Liu Zhiyuan, Ban Tao, Wang Jingjing, Zhao Shunzheng, Wang Ge. Microenvironment modulation around frustrated Lewis pairs in Ce-based metal-organic frameworks for efficient catalytic hydrogenation [J]. Chinese Journal of Catalysis, 2025, 75(8): 59-72.