Polarization-enhanced piezo-photocatalysis over hollow-sphere Bi4Ti3O12: Structure-property relationship and degradation mechanism

doi:10.1016/S1872-2067(25)64758-9

Abstract

Abstract:

Tetracycline hydrochloride (TCH) exists in various forms in aqueous solution due to pH changes, which not only alters the reactivity of TCH, but also affects the process of reactive oxygen species (ROS) attacking the molecule. Therefore, the rational design of piezo-photocatalytic materials coupled with a comprehensive understanding of the degradation mechanisms of various TCH species constitutes a critical approach to addressing tetracycline antibiotic contamination. In the design and preparation of piezo-photocatalysts, controlling the oxygen vacancy concentration is crucial as it governs the coupling efficiency between piezoelectric response and photocatalytic activity, as well as the strength of spontaneous polarization. Meanwhile, the morphology of the material is a key factor influencing the migration pathways of charge carriers. In this work, hollow spherical Bi4Ti3O12 was synthesized using an inorganic titanium source, demonstrating exceptional piezo-photocatalytic activity. The degradation rate was 1.57 and 5.29 times higher than that of traditional spherical and plate-like morphologies, with a rate constant of k = 0.127. In an innovative approach, density functional theory calculations of local softness and hyper-softness were employed to analyze the reactivity changes of TCH in its different deprotonated states toward reactive oxygen species. Combined with molecular electronegativity analysis, the factors influencing the degradation efficiency were identified. This study provides a solid foundation for developing efficient and environmentally friendly piezo-photocatalysts and offers new insights into the degradation mechanism of TCH.

Key words: Piezo-photocatalysis, Morphology regulation, Spontaneous polarization, Deprotonated tetracycline hydrochloride, Local softness

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: 133-145.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64758-9

https://www.cjcatal.com/EN/Y2025/V76/I9/133

Figures/Tables 8

Fig. 1. SEM (a) and TEM (b) images of iBTO. SEM (c) and TEM (d) images of BTOC. SEM (e) and TEM (f) images of BTOS. HR-TEM of BTOS (g) with corresponding IFFT (h). (i) XRD Rietveld refinement of BTOS. (j) EPR spectra. BTOS XPS high-resolution spectra of O 1s (k), Ti 2p (l) and Bi 4f (m).

Fig. 2. AFM morphology image (a), PFM amplitude (b) and phase image (c) of BTOS. (d) P-E hysteresis loop. KPFM surface potential difference of BTO (e), BTOC (f) and BTOS (g). Finite element simulations of piezoelectric potential distribution and displacement in BTO (h), BTOC (i), and BTOS (j).

Fig. 3. (a) Carrier concentration. (b) CV loop of BTOS and active site density of Bi4Ti3O12 with different morphology. (c) EIS Nyquist plot. (d) Transient photocurrent and internal electric field intensity. (e) Charge separation efficiency. (f) LSV plot. (g) Open circuit voltage decay test. (h) Minority carrier lifetime plot. (i) TRPL spectroscopy.

Fig. 4. Degradation performance of piezocatalysis (a), photocatalysis (b) and piezo-photocatalysis (c). (d) Pseudo first order rate constant. (e) Piezo-photocatalysis performance of BTOS with different inorganic ion coexistence. (f) Piezo-photocatalysis performance of BTOS under different pH conditions. (g) Five-cycle piezo-photocatalytic performance of BTOS. Reactive oxygen species quenching test of piezocatalysis (h), photocatalysis (i) and piezo-photocatalysis (j). (k) ESR spectra of TEMPO-1O2 under different illumination conditions.

Scheme 1. Catalytic mechanism.

Fig. 5. Structural formula and deprotonation site (1), condensed local softness and condensed local hyper-softness (2) and iso-surface map (3) of HOMO, s2, s- and s0 of TCH3+ (a), TCH2 (b), TCH (c), TC2- (d), and TC3- (e).

Fig. 6. Surface electrostatic potential map of TCH3+ (a), TCH2 (b), TCH- (c), TC2- (d), and TC3- (e).

Fig. 7. (a) Optimized structure of TCH. Iso-surface maps of HOMO (b) and LUMO (c). Iso-potential maps of f- (d), f0 (e) and f+ (f). (g) Possible degradation pathways. (h) T.E.S.T. toxicity test.

References

[1]	H. Du, R. Huo, A. Liu, Y. Hui, B. Shen, N. Li, Y. Ji, Q. Jin, B. Zheng, G. Yang, Z. Zhang, Q. Wang, Appl. Catal. B, 2024, 357, 124283.
[2]	M. Arif, T. Muhmood, M. Zhang, M. Amjad Majeed, H. Yan, X. Liu, X. Wang, Chem. Eng. J., 2022, 434, 134491.
[3]	M. Cai, Y. Liu, K. Dong, X. Chen, S. Li, Chin. J. Catal., 2023, 52, 239-251.
[4]	S. Li, C. Wang, K. Dong, P. Zhang, X. Chen, X. Li, Chin. J. Catal., 2023, 51, 101-112.
[5]	L. Sun, X. Yu, L. Tang, W. Wang, Q. Liu, Chin. J. Catal., 2023, 52, 164-175.
[6]	H. Li, B. Sun, T. Gao, H. Li, Y. Ren, G. Zhou, Chin. J. Catal., 2022, 43, 461-471.
[7]	M. Ran, B. Du, W. Liu, Z. Liang, L. Liang, Y. Zhang, L. Zeng, M. Xing, Proc. Natl. Acad. Sci. U. S. A., 2024, 121, e2317435121.
[8]	Z. Lu, J. Gao, S. Rao, C. Jin, H. Jiang, J. Shen, X. Yu, W. Wang, L. Wang, J. Yang, Q. Liu, Appl. Catal. B, 2024, 342, 123374.
[9]	R. Chen, W. Gan, J. Guo, Y. Lu, S. Ding, R. Liu, M. Zhang, Z. Sun, Chem. Eng. J., 2024, 489, 151260.
[10]	L. Jing, Y. Xu, M. Xie, Z. Li, C. Wu, H. Zhao, J. Wang, H. Wang, Y. Yan, N. Zhong, H. Li, J. Hu, Nano Energy, 2023, 112, 108508.
[11]	H. Shi, Y. Li, L. Zhang, G. Liu, Q. Zhang, X. Ru, S. Zhong, Appl. Catal. B, 2025, 361, 124581.
[12]	X. Chen, A. Li, L. Xing, J. Wang, Y. Sun, Y. Wang, G. Chen, T. Xing, L. Xu, J. Water Process. Eng., 2024, 59, 105015.
[13]	J. Zhen, J. Sun, X. Xu, Z. Wu, W. Song, Y. Ying, S. Liang, L. Miao, J. Cao, W. Lv, C. Song, Y. Yao, M. Xing, Angew. Chem. Int. Ed., 2024, 63, e202402669.
[14]	Z. Li, S. Lan, M. Zhu, Environ. Sci. Ecotechnol., 2024, 18, 100329.
[15]	E. E. Mojica, E. Nguyen, M. Rozov, F. V. Bright, J. Fluoresc., 2014, 24, 1183-1198.
[16]	K. Wang, Y. He, Chin. J. Catal., 2024, 61, 111-134.
[17]	X. Ren, Y. Chu, S. Yuan, Y. Zheng, Z. Zeng, C. Xia, L. Zhao, Y. Wu, Y. He, J. Environ. Manag., 2024, 370, 122776.
[18]	D. Zhang, Y. Li, P. Wang, J. Qu, S. Zhan, Y. Li, Angew. Chem. Int. Ed., 2023, 62, e202303807.
[19]	S. Tu, H. Huang, T. Zhang, Y. Zhang, Appl. Catal. B, 2017, 219, 550-562.
[20]	H. Sun, Z. Xu, X. Xie, J. Niu, M. Wang, X. Zhang, X. Chen, J. Han, J. Alloys Compd., 2021, 882, 160609.
[21]	J. He, Z. Li, P. Feng, G. Lu, T. Ding, L. Chen, X. Duan, M. Zhu, Angew. Chem. Int. Ed., 2024, 63, e202410381.
[22]	W. Liu, P. Wang, Y. Ao, J. Chen, X. Gao, B. Jia, T. Ma, Adv. Mater., 2022, 34, 2202508.
[23]	Y. Chen, Y. Ji, J. Fang, D. Wang, R. Dong, B. Dai, Int. J. Hydrogen Energy, 2024, 95, 83-97.
[24]	H. Yu, J. Li, Y. Zhang, S. Yang, K. Han, F. Dong, T. Ma, H. Huang, Angew. Chem. Int. Ed., 2019, 58, 3880-3884.
[25]	J. Yang, M. Zhang, M. Chen, Y. Zhou, M. Zhu, Adv. Mater., 2023, 35, 2209885.
[26]	P. Wang, X. Li, S. Fan, X. Chen, M. Qin, D. Long, M. O. Tadé, S. Liu, Appl. Catal. B, 2020, 279, 119340.
[27]	F. Bai, J. Liao, J. Yang, Y. Jiang, X. Tang, Q. Liu, Z. Tang, Y. Zhou, NPJ Comput. Mater., 2023, 9, 219.
[28]	W.-G. Yang, B.-P. Zhang, N. Ma, L. Zhao, J. Eur. Ceram. Soc., 2012, 32, 899-904.
[29]	L. Zhang, X. Fan, X. Yi, X. Lin, J. Zhang, Acc. Chem. Res., 2022, 55, 3150-3161.
[30]	Q. Han, X. Bai, J. Chen, S. Feng, W. Gao, W. Tu, X. Wang, J. Wang, B. Jia, Q. Shen, Y. Zhou, Z. Zou, Adv. Mater., 2021, 33, 2006780.
[31]	Y. Yang, H. Jia, N. Hu, M. Zhao, J. Li, W. Ni, C.-Y. Zhang, J. Am. Chem. Soc., 2024, 146, 7734-7742.
[32]	J. Yuan, W. Feng, Y. Zhang, J. Xiao, X. Zhang, Y. Wu, W. Ni, H. Huang, W. Dai, Adv. Mater., 2024, 36, 2303845.
[33]	A. Xu, X. Chen, D. Wei, B. Chu, M. Yu, X. Yin, J. Xu, Small, 2023, 19, 2302253.
[34]	Y. Liu, M. Zhang, Z. Wang, J. He, J. Zhang, S. Ye, X. Wang, D. Li, H. Yin, Q. Zhu, H. Jing, Y. Weng, F. Pan, R. Chen, C. Li, F. Fan, Nat. Commun., 2022, 13, 4245.
[35]	J. Gao, X. Duan, K. O’Shea, D. D. Dionysiou, Water Res., 2020, 171, 115394.
[36]	L. Wu, Y. Yu, Q. Zhang, J. Hong, J. Wang, Y. She, Appl. Surf. Sci., 2019, 480, 717-726.
[37]	K. Wang, C. Han, J. Li, J. Qiu, J. Sunarso, S. Liu, Angew. Chem. Int. Ed., 2022, 61, e202110429.
[38]	W. Zuo, N. Li, B. Chen, C. Zhang, Q. Li, M. Yan, Sci. Total Environ., 2020, 726, 138432.
[39]	M. Torrent-Sucarrat, F. De Proft, P. W. Ayers, P. Geerlings, Phys. Chem. Chem. Phys., 2010, 12, 1072-1080.
[40]	J. I. Martínez-Araya, J. Math. Chem., 2024, 62, 461-475.
[41]	W. Guo, Y. Dai, X. Chu, S. Cui, Y. Sun, Y.-F. Li, H. Jia, Ecotoxicol. Environ. Saf., 2021, 213, 111983.

Polarization-enhanced piezo-photocatalysis over hollow-sphere Bi₄Ti₃O₁₂: Structure-property relationship and degradation mechanism

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 8

References

Related Articles 2

Recommended Articles

Metrics

[1]	Linghui Meng, Chen Zhao, Hongyu Chu, Yu-Hang Li, Huifen Fu, Peng Wang, Chong-Chen Wang, Hongwei Huang. Synergetic piezo-photocatalysis of g-C₃N₄/PCN-224 core-shell heterojunctions for ultrahigh H₂O₂ generation [J]. Chinese Journal of Catalysis, 2024, 59(4): 346-359.
[2]	Yangrui Xu, Xiaodie Zhu, Huan Yan, Panpan Wang, Minshan Song, Changchang Ma, Ziran Chen, Jinyu Chu, Xinlin Liu, Ziyang Lu. Hydrochloric acid-mediated synthesis of ZnFe₂O₄ small particle decorated one-dimensional Perylene Diimide S-scheme heterojunction with excellent photocatalytic ability [J]. Chinese Journal of Catalysis, 2022, 43(4): 1111-1122.