Unveiling the pathway of water activation and proton transfer in photocatalytic lignin biomass hydrogenolysis over Mo vacancy and Mo-S bond engineered Bi2Mo1-xO6/ZnIn2S4 S-scheme heterojunction

doi:10.1016/S1872-2067(26)65164-9

Abstract

Abstract:

Utilizing water as a green and abundant proton source for the photocatalytic hydrogenolysis of lignin under mild conditions represents a promising approach for biomass conversion. However, the microscopic mechanism of water activation and subsequent proton transfer remains unclear, hindering the rational design of efficient catalytic system. Herein, Mo vacancy-engineered S-scheme Bi₂Mo_1-_xO₆/ZnIn₂S₄ heterojunction was constructed via a facile in-situ solvothermal process. Combining density functional theory calculations, in-situ electron paramagnetic resonance and X-ray photoelectron spectroscopy analyses reveal that the presented Mo vacancies play a dual role; they not only induce the formation of interfacial Mo-S bonds, creating atomic-level charge-transfer channels, but also drive hole localization, promoting water dissociation and generating protons for the selective hydrogenolysis of lignin C_β-O bonds. Crucially, isotope labeling experiments directly confirm that the protons generated from water dissociation serve as the direct hydrogen source for the lignin hydrogenolysis reaction. Under visible light exposure (λ > 420 nm) and an air atmosphere, the developed catalyst achieves over 90% photoconversion of 2-phenoxy-1-phenylethanol (PP-ol) lignin with a quantum yield of 5.71%, outperforming the most reported photocatalysts. Through synergistic engineering of Mo vacancies and interfacial bonds in S-scheme heterojunctions, this study provides key insights into the water-driven proton transfer mechanism in photocatalytic hydrogenolysis of lignin, highlighting an efficient biomass photoconversion strategy.

Key words: Photocatalytic hydrogenolysis, Mo vacancies, Water activation, S-Scheme heterojunction, Proton transfer

Jiangyushan Liang, Abdelkader Labidi, Chuanyi Wang. Unveiling the pathway of water activation and proton transfer in photocatalytic lignin biomass hydrogenolysis over Mo vacancy and Mo-S bond engineered Bi₂Mo_1-_xO₆/ZnIn₂S₄ S-scheme heterojunction[J]. Chinese Journal of Catalysis, 2026, 89: 279-291.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65164-9

https://www.cjcatal.com/EN/Y2026/V89/I10/279

Figures/Tables 6

Fig. 1. SEM images of Bi2Mo1-xO6 (a), ZIS (b), and the Bi2Mo1-xO6/ZIS composite (c). HRTEM image (d) and corresponding magnified HRTEM image (e) of the Bi2Mo1-xO6/ZIS composite. (f) Intensity profiles from the blue and orange rectangles in (e). XRD patterns (g) and Raman spectra (h) of Bi2MoO6, ZIS, and the Bi2Mo1-xO6/ZIS composite. (i) EPR spectra of Bi2Mo1-xO6 and Bi2Mo1-xO6/ZIS.

Fig. 2. (a) Bi 4f, (b) Mo 3d, (c) O 1s XPS spectra of Bi2Mo1-xO6/ZIS and Bi2Mo1-xO6. S 2p (d), In 3d (e), and Zn 2p (f) XPS spectra of Bi2Mo1-xO6/ZIS and ZIS.

Fig. 3. (a) Schematic illustration of electron flow in the S-scheme heterojunction compared to a conventional type-II junction. In-situ EPR spectra of the Bi2Mo1-xO6/ZIS composite for the detection of ?OH (b) and ?O2- (c) radicals. In-situ irradiated high-resolution XPS spectra of the Bi2Mo1-xO6/ZIS composite: Zn 2p (d) and Mo 3d (e) regions.

Fig. 4. (a) Calculated PDOS for the Bi2Mo1-xO6/ZIS interface. (b) Charge density difference at the Bi2Mo1-xO6/ZIS interface. Blue and yellow regions represent electron accumulation and depletion, respectively. (c) Calculated interfacial charge density difference of the Bi2Mo1-xO6/ZIS heterojunction. Work functions of Bi2Mo1-xO6 (d) and ZIS (e). (f) Schematic illustration of the S-scheme formation mechanism under light irradiation.

Fig. 5. (a) Investigation of hydrogenation and hydrogen transfer in the reaction. (b) Photocatalytic conversion of PP-ol on various samples. (c) Photocatalytic depolymerization of PP-ol over the Bi2Mo1-xO6/ZIS heterojunction photocatalyst under different gas atmospheres. (d) Extent of PP-ol depolymerization at different reaction times. Scavenger experiments (e) and trapping studies (f) for the photocatalytic conversion of PP-ol under distinct atmospheres.

Fig. 6. (a) Proposed pathways for the photocatalytic depolymerization of PP-ol under different atmospheres. In-situ EPR spectra of RO? (b), 1O2 (c), and ?Cα radicals (d) obtained with Bi2Mo1-xO6/ZIS under dark and light conditions. (e) Calculated free energy profiles for the water dissociation pathway on the Bi2MoO6 and Bi2Mo1-xO6 surfaces. The insets display the optimized atomic configurations of the initial state (IS), transition state (TS), and final state (FS).

References

[1]	D. Dai, J. Qiu, J. Xu, G. Xia, Y. Li, B. Fang, J. Yao, ACS Catal., 2025, 15, 16513-16521.
[2]	C. Suo, J. Yu, J. Zhang, W. Li, S. Luo, C. Ma, S. Liu, Biomass Bioenergy, 2024, 190, 107394.
[3]	Y. Liu, C. Li, W. Miao, W. Tang, D. Xue, J. Xiao, T. Zhang, C. Wang, Green Chem., 2020, 22, 33-38.
[4]	J. Dai, A. F. Patti, G. N. Styles, S. Nanayakkara, L. Spiccia, F. Arena, C. Italiano, K. Saito, Green Chem., 2019, 21, 2005-2014.
[5]	Y. Li, J. Qiu, J. Xu, Y. Tang, D. Dai, G. Xia, B. Fang, J. Yao, J. Catal., 2025, 446, 116076.
[6]	S. Shao, K. Wang, Y. Zhang, J. B. Love, Z. Yue, W. Li, L. Huang, Y. Wang, X. Yao, T. Chang, X. Fan, Chem Catal., 2024, 4, 101066.
[7]	Z. Yue, G. Lu, W. Wei, Y. Huang, Z. Chen, F. Dingwall, S. Shao, X. Fan, ACS Appl. Mater. Interfaces, 2024, 16, 47724-47740.
[8]	K. Jing, W. Ma, Y. Ren, J. Xiong, B. Guo, Y. Song, S. Liang, L. Wu, Appl. Catal. B, 2019, 243, 10-18.
[9]	Q. Tian, Y. Zhu, K. Shen, H. Yin, A. Pan, F. Zhang, G. Fang, Z. He, Y. Ni, Ind. Crops Prod., 2025, 232, 121263.
[10]	Q. Tian, Q. Yang, W. Guo, X. Li, G. Fang, Y. Ge, X. Liu, H. Yin, A. Pan, N. Li, Ind. Crops Prod., 2023, 191, 115966.
[11]	X. Nie, J. Li, G. Dong, Y. Li, X. Zhang, W. Zhang, Q. Fu, T. Xiao, L. Bai, J. Environ. Chem. Eng., 2025, 13, 116928.
[12]	Y. Wu, Y. Liu, Z. Shen, M. Song, Build. Environ., 2025, 282, 113297.
[13]	G. Liu, Y. Dai, X. Sun, J. Ma, T. Xian, H. Yang, Sep. Purif. Technol., 2025, 361, 131622.
[14]	J. Di, X. Zhao, C. Lian, M. Ji, J. Xia, J. Xiong, W. Zhou, X. Cao, Y. She, H. Liu, K. P. Loh, S. J. Pennycook, H. Li, Z. Liu, Nano Energy, 2019, 61, 54-59.
[15]	H. Chen, R. Xu, D. Chen, T. Lu, H. Li, M. Wang, ACS Catal., 2024, 14, 1977-1986.
[16]	J.-P. Tang, Y. Chen, Z.-Y. Wang, Y.-H. Hu, J.-H. Wang, L. Bao, Z.-Y. Zhao, Y.-J. Yuan, ACS Catal., 2025, 15, 265-274.
[17]	J. Liang, A. Labidi, B. Lu, A. O. T. Patrocinio, A. Sial, T. Gao, S. I. Othman, A. A. Allam, C. Wang, Appl. Catal. B, 2025, 367, 125092.
[18]	X. Xu, Y. Su, Y. Dong, X. Luo, S. Wang, W. Zhou, R. Li, K. P. Homewood, X. Xia, Y. Gao, X. Chen, J. Hazard. Mater., 2022, 424, 127685.
[19]	F. D. Hardcastle, I. E. Wachs, J. Phys. Chem., 1991, 95, 5031-5041.
[20]	T. Ma, R. Li, Y.-C. Huang, Y. Lu, L. Guo, M. Niu, X. Huang, R. Ali Soomro, J. Ren, Q. Wang, B. Xu, C. Yang, F. Fu, D. Wang, ACS Catal., 2024, 14, 6292-6304.
[21]	X. Yang, X. Li, B. Zhang, T. Liu, Z. Chen, ACS Sustainable Chem. Eng., 2024, 12, 6519-6528.
[22]	W. He, Y. Wei, J. Xiong, Z. Tang, Y. Wang, X. Wang, H. Xu, X. Zhang, X. Yu, Z. Zhao, J. Liu, J. Energy Chem., 2023, 80, 361-372.
[23]	Y. Cui, H. Yang, W. Zhou, S. Pal, J. Briscoe, G. Shen, X. Tao, J. Colloid Interface Sci., 2026, 703, 139211.
[24]	H. Su, H. Lou, Z. Zhao, L. Zhou, Y. Pang, H. Xie, C. Rao, D. Yang, X. Qiu, Chem. Eng. J., 2022, 430, 132770.
[25]	J. He, J. Lin, Y. Zhang, Y. Hu, Q. Huang, G. Zhou, W. Li, J. Hu, N. Hu, Z. Yang, Chem. Eng. J., 2024, 480, 148036.
[26]	T. Wang, C. Zhao, L. Meng, Y. Li, H. Chu, F. Wang, Y. Tao, W. Liu, C.-C. Wang, Chem. Eng. J., 2023, 451, 138624.
[27]	S. Li, C. You, F. Yang, G. Liang, C. Zhuang, X. Li, Chin. J. Catal., 2025, 68, 259-271.
[28]	J. Hu, F. Zhang, Y. Yang, Q. Han, Z. Li, Q. Shen, Y. Zhang, Y. Zhou, Z. Zou, Catal. Sci. Technol., 2020, 10, 3843-3847.
[29]	Q. Xu, L. Zhang, B. Cheng, J. Fan, J. Yu, Chem, 2020, 6, 1543-1559.
[30]	J. Lin, J. He, J. Hu, J. Dong, A. Liu, Y. Yang, L. Tang, L. Li, Y. Zhou, Z. Zou, Catal. Sci. Technol., 2021, 11, 3885-3893.
[31]	P. Zhang, Y. Li, Y. Zhang, R. Hou, X. Zhang, C. Xue, S. Wang, B. Zhu, N. Li, G. Shao, Small Methods, 2020, 4, 2000214.
[32]	X. Liu, Z. Jiang, X. Cao, Z. Shen, W. Zhao, F. Wang, M. Cui, C. Liang, ACS Sustainable Chem. Eng., 2023, 11, 14947-14959.
[33]	L. Yue, J. Zhang, Z. Zeng, C. Zhao, X. Hu, L. Zhao, B. Zhao, Y. He, Langmuir, 2023, 39, 13267-13278.
[34]	S. Yuan, J. Wang, C. Zhao, L. Yue, X. Ren, Z. Zeng, X. Hu, Y. Wu, Y. He, Sep. Purif. Technol., 2023, 325, 124665.
[35]	Y. Wang, X. Liu, J. Liu, B. Han, X. Hu, F. Yang, Z. Xu, Y. Li, S. Jia, Z. Li, Y. Zhao, Angew. Chem. Int. Ed., 2018, 57, 5765-5771.
[36]	F. Xu, K. Meng, B. Cheng, S. Wang, J. Xu, J. Yu, Nat. Commun., 2020, 11, 4613.
[37]	W. Song, K. C. Chong, G. Qi, Y. Xiao, G. Chen, B. Li, Y. Tang, X. Zhang, Y. Yao, Z. Lin, Z. Zou, B. Liu, J. Am. Chem. Soc., 2024, 146, 3303-3314.
[38]	B. He, Z. Wang, P. Xiao, T. Chen, J. Yu, L. Zhang, Adv. Mater., 2022, 34, 2203225.
[39]	N. Luo, M. Wang, H. Li, J. Zhang, H. Liu, F. Wang, ACS Catal., 2016, 6, 7716-7721.
[40]	X. Liu, Z. Jiang, X. Cao, Z. Shen, W. Zhao, F. Wang, M. Cui, C. Liang, Green Chem., 2024, 26, 1935-1948.
[41]	H. Chen, K. Wan, F. Zheng, Z. Zhang, Y. Zhang, D. Long, Renew. Sustain. Energy Rev., 2021, 147, 111217.
[42]	S. Shao, K. Wang, J. B. Love, J. Yu, S. Du, Z. Yue, X. Fan, Chem. Eng. J., 2022, 435, 134980.
[43]	Y. Wu, C. Liu, C. Wang, S. Lu, B. Zhang, Angew. Chem. Int. Ed., 2020, 59, 21170-21175.
[44]	S. Zhao, X. Wu, N. Wang, X. Zhou, X. Chen, Y. Tang, X. Tang, L. Lin, S. Yao, ACS Catal., 2025, 15, 19374-19384.
[45]	Q. Su, J. Li, B. Wang, Y. Li, L.-A. Hou, Appl. Catal. B, 2022, 318, 121820.
[46]	J.-Y.-S. Liang, H.-T. Ren, A. Labidi, Q.-H. Zhu, Q.-B. Dong, A. A. Allam, A. Rady, C.-Y. Wang, Rare Met., 2024, 43, 3758-3770.
[47]	N. Luo, M. Wang, H. Li, J. Zhang, T. Hou, H. Chen, X. Zhang, J. Lu, F. Wang, ACS Catal., 2017, 7, 4571-4580.
[48]	J. D. Nguyen, B. S. Matsuura, C. R. J. Stephenson, J. Am. Chem. Soc., 2014, 136, 1218-1221.
[49]	S. Feng, P. T. T. Nguyen, X. Ma, N. Yan, Angew. Chem. Int. Ed., 2024, 63, e202408504.
[50]	S. Xu, Q. Gao, Z. Hu, Y. Lu, Y. Qin, Y. Li, ACS Catal., 2023, 13, 13941-13954.
[51]	J. Liang, A. Labidi, H. Liang, Y. Tao, E. Kowalska, Y. Xue, Y. Wang, A. O. T. Patrocinio, C. Wang, Chem. Eng. J., 2025, 525, 170107.
[52]	L. Chen, J. Duan, P. Du, W. Sun, B. Lai, W. Liu, Water Res., 2022, 221, 118747.
[53]	C. Jiang, S. Zhang, S. Chen, X. Yao, H. Ji, Y. Tong, J. Colloid Interface Sci., 2025, 686, 430-437.
[54]	X. Wu, X. Fan, S. Xie, J. Lin, J. Cheng, Q. Zhang, L. Chen, Y. Wang, Nat. Catal., 2018, 1, 772-780.
[55]	Y. Xu, Q. Chu, D. Chen, A. Fuentes, Front. Mech. Eng., 2021, 7, 744001.
[56]	A. Kołodziejczyk, M. Błaziak, K. Podgórniak, A. Jezierska, K. Błaziak, Phys. Chem. Chem. Phys., 2023, 25, 21448-21455.

Unveiling the pathway of water activation and proton transfer in photocatalytic lignin biomass hydrogenolysis over Mo vacancy and Mo-S bond engineered Bi₂Mo_1-_xO₆/ZnIn₂S₄ S-scheme heterojunction

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