Surface oxygen vacancies of BiOBr regulating piezoelectricity for enhancing efficiency and selectivity of photocatalytic CO2 reduction

doi:10.1016/S1872-2067(25)64649-3

Abstract

Abstract:

Although defect engineering has been widely used to boost catalytic CO₂ photoreduction, the piezoelectric polarized properties induced by structure changes through introducing defects are always ignored. Here we report a new kind of bismuth oxybromide (BiOBr, BOB) with piezoelectric property regulated by oxygen vacancies (OVs). Compared with pure BOB, BOB with OVs (BOB-OV) could enhance photocatalytic CO₂ reduction efficiency under the ultrasonic force, achieving durable CO₂ reduction process to superior production rates of CO (54.4 µmol g^-1 h^-1) with a high selectivity (92%). Moderate OVs concentration changed the degree of Bi-Br stretching in the BOB-OV to produce strong dipole moments, which endowed BOB-OV with strong spontaneous piezoelectric polarization ability under external force. Ultrasonic piezoelectric effects were innovatively integrated into the photocatalytic reaction, which not only provided an alternating force field to modulate the spontaneous polarization of BOB-OV, thereby maintaining efficient photogenerated charge separation, but also lowered the reaction energy barrier of CO₂ by high stress, ultimately improving CO product selectivity. This study is the first to leverage OVs-induced piezoelectric polarization effects to enhance the performance and product selectivity of photocatalytic CO₂ reduction, providing new directions and insights for defect engineering to contribute to photocatalysis.

Key words: BiOBr, Oxygen vacancy, Piezoelectricity, High selectivity, Photocatlytic CO₂ reduction

Cunjun Li, Jie He, Tianle Cai, Xianlei Chen, Hengcong Tao, Yingtang Zhou, Mingshan Zhu. Surface oxygen vacancies of BiOBr regulating piezoelectricity for enhancing efficiency and selectivity of photocatalytic CO₂ reduction[J]. Chinese Journal of Catalysis, 2025, 74: 130-143.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64649-3

https://www.cjcatal.com/EN/Y2025/V74/I7/130

Figures/Tables 6

Fig. 1. (a) Design concept of the study. (b) Element mappings of BOB-OV-2. XRD patterns (c) and EPR signals (d) of BOB-OV series samples. (e) The content ratio of oxygen species in BOB-OV-2 with different etching time.

Fig. 2. (a) Raman spectra of BOB-OV series samples. (b) The dipole moment of BOB-OV series models by theoretical calculations. PFM of BOB (c), BOB-OV-0.5 (d), BOB-OV-1 (e), BOB-OV-2 (f), and BOB-OV-3 (g). (h) Relationship between piezoelectric response and OV content of BOB-OV series samples.

Fig. 3. (a) Catalytic activity and selectivity of BOB-OV series materials in photocatalytic and piezoelectric-synergistic photocatalytic CO2 reduction. Yield of CH4 and CO for CO2 reduction with different ultrasonic powers (b) and different dosages of BOB-OV-2 (c). (d) A summary of catalytic CO2 reduction performance by using different photocatalysts including BOB-OV-2 of this work. (e) Cyclic runs of piezoelectric-synergistic photocatalytic CO2 reduction by BOB-OV-2.

Fig. 4. AFM (a), in-situ KPFM under dark (b) and light (c) conditions over BOB. AFM (d), in-situ KPFM under dark (e) and light (f) conditions over BOB-OV-2. The surface potential difference of dark and light over BOB (g) and BOB-OV-2 (h).

Fig. 5. The COHP value of CO2 (a) and CO (b) with BOB-OV series models under 2 GPa. (c) In-situ FTIR of photocatalytic CO2RR over BOB-OV-2. The Gibbs free energy (ΔG) of intermediates in the catalytic CO2 reduction pathways by BOB-OV series models under 0 GPa (d) and 2 GPa (e).

Scheme 1. Schematic illustration of the piezoelectric-synergistic photocatalytic CO2 reduction by BOB-OV samples.

References

[1]	E. Gong, S. Ali, C. B. Hiragond, H. S. Kim, N. S. Powar, D. Kim, H. Kim, S.-I. In, Energy Environ. Sci., 2022, 15, 880-937.
[2]	Y. Wang, E. Chen, J. Tang, ACS Catal., 2022, 12, 7300-7316.
[3]	N. Wubulikasimu, R. Shen, L. Hao, H. He, K. Li, X. Li, J. Xie, Chem. Eng. J., 2024, 501, 157397.
[4]	M. Halmann, Nature, 1978, 275, 115-116.
[5]	C. Liu, J. Zhang, W. Wang, L. Chen, M. Zhu, Surf. Interfaces, 2023, 42(B), 103491.
[6]	H. Fu, J. Tian, Q. Zhang, Z. Zheng, H. Cheng, Y. Liu, B. Huang, P. Wang, Chin. J. Catal., 2024, 64, 143-151.
[7]	H. Huang, Q. Lin, Q. Niu, J. Ning, L. Li, J. Bi, Y. Yu, Chin. J. Catal., 2024, 60, 201-208.
[8]	C. Du, J. Sheng, F. Zhong, Y. He, V. P. Guro, Y. Sun, F. Dong, Chin. J. Catal., 2024, 60, 25-41.
[9]	R. T. Guo, J. Wang, Z. X. Bi, X. Chen, X. Hu, W. G. Pan, Small, 2023, 19, 2206314.
[10]	M. Aggarwal, S. Basu, N. P. Shetti, M. N. Nadagouda, E. E. Kwon, Y.-K. Park, T. M. Aminabhavi, Chem. Eng. J., 2021, 425, 131402.
[11]	K. Huang, G. Liang, S. Sun, H. Hu, X. Peng, R. Shen, X. Li, J. Mater. Sci. Technol., 2024, 193, 98-106.
[12]	L. Meng, Y. Qu, L. Jing, Chin. Chem. Lett., 2021, 32, 3265-3276.
[13]	H. Li, J. Liu, X. Liang, W. Hou, X. Tao, J. Mater. Chem. A, 2014, 2, 8926-8932.
[14]	Y. Zhou, H. Dong, Z. Xu, Q. Zha, M. Zhu, Y. Meng, Appl. Catal. B, 2024, 343, 123504.
[15]	J. Hu, Y. Chen, Y. Zhou, L. Zeng, Y. Huang, S. Lan, M. Zhu, Appl. Catal. B, 2022, 311, 121369.
[16]	C. Liu, S. Mao, M. Shi, F. Wang, M. Xia, Q. Chen, X. Ju, J. Hazard. Mater., 2021, 420, 126613.
[17]	X. Xue, R. Chen, H. Chen, Y. Hu, Q. Ding, Z. Liu, L. Ma, G. Zhu, W. Zhang, Q. Yu, Nano Lett., 2018, 18, 7372-7377.
[18]	M. Wu, H. Wang, B. Zhang, J. Wang, M. Fan, L. Dong, B. Li, Z. Chen, G. Chen, Surf. Interfaces, 2024, 45, 103947.
[19]	Y. Wang, W. Yu, C. Wang, F. Chen, T. Ma, H. Huang, EScience, 2024, 4, 100228.
[20]	W. Zheng, Z. Zhu, R. Sha, S. Tu, H. Huang, J. Materiomics, 2025, 11, 100928.
[21]	J. Wu, X. Li, W. Shi, P. Ling, Y. Sun, X. Jiao, S. Gao, L. Liang, J. Xu, W. Yan, Angew. Chem. Int. Ed., 2018, 57, 8719-8723.
[22]	X. Chen, X. Zhang, Y.-H. Li, M.-Y. Qi, J.-Y. Li, Z.-R. Tang, Z. Zhou, Y.-J. Xu, Appl. Catal. B, 2021, 281, 119516.
[23]	Q. Yu, J. Chen, Y. Li, M. Wen, H. Liu, G. Li, T. An, Chin. J. Catal., 2020, 41, 1603-1612.
[24]	H. Wang, D. Yong, S. Chen, S. Jiang, X. Zhang, W. Shao, Q. Zhang, W. Yan, B. Pan, Y. Xie, J. Am. Chem. Soc., 2018, 140, 1760-1766.
[25]	J. Wang, C. Hu, L. Shi, N. Tian, H. Huang, H. Ou, Y. Zhang, J. Mater. Chem. A, 2021, 9, 12400-12432.
[26]	Y. Bao, K. Xiao, S. Yue, M. Zhang, X. Du, J. Wang, W.-D. Oh, Y. Zhou, S. Zhan, Surf. Interfaces, 2023, 40, 103107.
[27]	C. Porwal, A. Gaur, V.S. Chauhan, R. Vaish, Surf. Interfaces, 2023, 42(A), 103391.
[28]	J. He, Z. Li, P. Feng, G. Lu, T. Ding, L. Chen, X. Duan, M. Zhu, Angew. Chem. Int. Ed., 2024, 63, e202410381.
[29]	H. Cai, F. Chen, C. Hu, W. Ge, T. Li, X. Zhang, H. Huang, Chin. J. Catal., 2024, 57, 123-132.
[30]	Q. Zhu, A. A. Dar, Y. Zhou, K. Zhang, J. Qin, B. Pan, J. Lin, A. O. T. Patrocinio, C. Wang, ACS ES&T Eng., 2022, 2, 1365-1375.
[31]	J. Yang, M. Zhang, M. Chen, Y. Zhou, M. Zhu, Adv. Mater., 2023, 35, 2209885.
[32]	C. Hu, H. Huang, Acta Phys.-Chim. Sin., 2023, 39, 2212048.
[33]	Z. Miao, Q. Wang, Y. Zhang, L. Meng, X. Wang, Appl. Catal. B, 2022, 301, 120802.
[34]	X.-J. Wang, Y. Zhao, F.-T. Li, L.-J. Dou, Y.-P. Li, J. Zhao, Y.-J. Hao, Sci. Rep., 2016, 6, 24918.
[35]	X. Y. Kong, W. C. Lee, W. J. Ong, S. P. Chai, A. R. Mohamed, ChemCatChem, 2016, 8, 3074-3081.
[36]	Z. Li, Y. Zhou, Y. Zhou, K. Wang, Y. Yun, S. Chen, W. Jiao, L. Chen, B. Zou, M. Zhu, Nat. Commun., 2023, 14, 5742.
[37]	Y. Ma, J. Gong, P. Zeng, M. Liu, Nano-Micro Lett., 2023, 15, 173.
[38]	Y. Zhang, Y. Luo, Y. Zhang, Y.-J. Yu, Y.-M. Kuang, L. Zhang, Q.-S. Meng, Y. Luo, J.-L. Yang, Z.-C. Dong, Nature, 2016, 531, 623-627.
[39]	J. He, Z. Yi, Q. Chen, Z. Li, J. Hu, M. Zhu, Chem. Commun., 2022, 58, 10723-10726.
[40]	J. He, X. Wang, S. Lan, H. Tao, X. Luo, Y. Zhou, M. Zhu, Appl. Catal. B, 2022, 317, 121747.
[41]	L. Liu, H. Huang, Z. Chen, H. Yu, K. Wang, J. Huang, H. Yu, Y. Zhang, Angew. Chem. Int. Ed., 2021, 60, 18303-18308.
[42]	H. Yu, F. Chen, X. Li, H. Huang, Q. Zhang, S. Su, K. Wang, E. Mao, B. Mei, G. Mul, Nat. Commun., 2021, 12, 4594.
[43]	F. Chen, Z. Ma, L. Ye, T. Ma, T. Zhang, Y. Zhang, H. Huang, Adv. Mater., 2020, 32, 1908350.
[44]	Y. Wang, K. Wang, J. Meng, C. Ban, Y. Duan, Y. Feng, S. Jing, J. Ma, D. Yu, L. Gan, X. Zhou, Nano Energy, 2023, 109, 108305.
[45]	J. Meng, Y. Duan, S. Jing, J. Ma, K. Wang, K. Zhou, C. Ban, Y. Wang, B. Hu, D. Yu, L. Gan, X. Zhou, Nano Energy, 2022, 92, 106671.
[46]	H. Yu, H. Huang, A. H. Reshak, S. Auluck, L. Liu, T. Ma, Y. Zhang, Appl. Catal. B, 2021, 284, 119709.
[47]	H. Yu, J. Li, Y. Zhang, S. Yang, K. Han, F. Dong, T. Ma, H. Huang, Angew. Chem. Int. Ed., 2019, 58, 3880-3884.
[48]	B. Lei, W. Cui, P. Chen, L. Chen, J. Li, F. Dong, ACS Catal., 2022, 12, 9670-9678.
[49]	X. Shi, X.a. Dong, Y. He, P. Yan, S. Zhang, F. Dong, ACS Catal., 2022, 12, 3965-3973.
[50]	W. Cai, X. Ma, J. Chen, R. Shi, Y. Wang, Y. Yang, D. Jing, H. Yuan, J. Du, M. Que, Appl. Surf. Sci., 2023, 619, 156773.
[51]	K. Wang, C. Han, J. Li, J. Qiu, J. Sunarso, S. Liu, Angew. Chem. Int. Ed., 2022, 61, e202110429.
[52]	J. He, X. Wang, P. Feng, Y. Zhou, K. Wang, B. Zou, M. Zhu, Appl. Catal. B, 2024, 355, 124186.
[53]	J. Ma, X. Xiong, D. Wu, Y. Wang, C. Ban, Y. Feng, J. Meng, X. Gao, J. Y. Dai, G. Han, L.-Y. Gan, X. Zhou, Adv. Mater., 2023, 35, 2300027.
[54]	Y. Zhang, Y. Li, Y. Peng, J. Liu, Appl. Surf. Sci., 2024, 642, 158623.
[55]	X. Li, B. Kang, F. Dong, Z. Zhang, X. Luo, L. Han, J. Huang, Z. Feng, Z. Chen, J. Xu, Nano Energy, 2021, 81, 105671.
[56]	R. Chen, F. Fan, T. Dittrich, C. Li, Chem. Soc. Rev., 2018, 47, 8238-8262.
[57]	S. Zhang, Z. Xu, T. Ji, Z. Chen, P. Guan, A. Li, D. Jv, T. Liang, Y. Weng, Z. Ao, Surf. Interfaces, 2023, 38, 102809.
[58]	Z. Li, J. Hu, Y. Xiao, Q. Zha, L. Zeng, M. Zhu, Anal. Chim. Acta, 2021, 1146, 174-183.
[59]	H. Xie, K. Wang, D. Xiang, S. Li, Z. Jin, J. Mater. Chem. A, 2023, 11, 14971-14989.
[60]	S. Mukasa, S. Nomura, H. Toyota, Jpn. J. Appl. Phys. 1, 2004, 43, 2833-2837.
[61]	X. Fu, T. Belwal, G. Cravotto, Z. Luo, Ultrason. Sonochem., 2020, 60, 104726.
[62]	J. Ma, S. Jing, Y. Wang, X. Liu, L. Y. Gan, C. Wang, J. Y. Dai, X. Han, X. Zhou, Adv. Energy Mater., 2022, 12, 2200253.
[63]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-1797

Surface oxygen vacancies of BiOBr regulating piezoelectricity for enhancing efficiency and selectivity of photocatalytic CO₂ reduction

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 6

References

Related Articles 15

Recommended Articles

Metrics

[1]	Pengkun Zhang, Qinhan Wu, Haoyu Wang, Dong-Hau Kuo, Yujie Lai, Dongfang Lu, Jiqing Li, Jinguo Lin, Zhanhui Yuan, Xiaoyun Chen. Z-scheme heterojunction Zn₃(OH)₂(V₂O₇)(H₂O)₂/V-Zn(O,S) for enhanced visible-light photocatalytic N₂ fixation via synergistic heterovalent vanadium states and oxygen vacancy defects [J]. Chinese Journal of Catalysis, 2025, 74(7): 279-293.
[2]	Rui Li, Pengfei Feng, Bonan Li, Jiayu Zhu, Yali Zhang, Ze Zhang, Jiangwei Zhang, Yong Ding. Photocatalytic reduction of CO₂ over porous ultrathin NiO nanosheets with oxygen vacancies [J]. Chinese Journal of Catalysis, 2025, 73(6): 242-251.
[3]	Tengfei Cao, Quanlong Xu, Jun Zhang, Shenggao Wang, Tingmin Di, Quanrong Deng. S-scheme g-C₃N₄/BiOBr heterojunction for efficient photocatalytic H₂O₂ production [J]. Chinese Journal of Catalysis, 2025, 72(5): 118-129.
[4]	Yuqing Tang, Yanjun Chen, Aqsa Abid, Zichun Meng, Xiaoying Sun, Bo Li, Zhen Zhao. Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: Double-edged oxygen vacancy [J]. Chinese Journal of Catalysis, 2025, 68(1): 272-281.
[5]	Zichao Huang, Tinghui Yang, Yingbing Zhang, Chaoqun Guan, Wenke Gui, Min Kuang, Jianping Yang. Enhancing selectivity in acidic CO₂ electrolysis: Cation effects and catalyst innovation [J]. Chinese Journal of Catalysis, 2024, 63(8): 61-80.
[6]	Xinyu Chen, Cong-Cong Zhao, Jing Ren, Bo Li, Qianqian Liu, Wei Li, Fan Yang, Siqi Lu, YuFei Zhao, Li-Kai Yan, Hong-Ying Zang. An oxygen-vacancy-rich polyoxometalate-aided Ag-based heterojunction electrocatalyst for nitrogen fixation [J]. Chinese Journal of Catalysis, 2024, 62(7): 209-218.
[7]	Zheng Wei, Guoxia Jiang, Yiwen Wang, Ganggang Li, Zhongshen Zhang, Jie Cheng, Fenglian Zhang, Zhengping Hao. Asymmetric oxygen vacancies in La₂FeMO₆ double perovskite for boosting oxygen activation and H₂S selective oxidation [J]. Chinese Journal of Catalysis, 2024, 62(7): 198-208.
[8]	Jie Wang, Yihe Chen, Yuda Wang, Hao Zhao, Jinyu Ye, Qingqing Cheng, Hui Yang. Manipulating the electronic state of ruthenium to boost highly selective electrooxidation of ethylene to ethylene glycol in acid [J]. Chinese Journal of Catalysis, 2024, 60(5): 376-385.
[9]	Miaoli Gu, Yi Yang, Bei Cheng, Liuyang Zhang, Peng Xiao, Tao Chen. Unveiling product selectivity in S-scheme heterojunctions: Harnessing charge separation for tailored photocatalytic oxidation [J]. Chinese Journal of Catalysis, 2024, 59(4): 185-194.
[10]	Jielin Huang, Jie Wang, Haonan Duan, Songsong Chen, Junping Zhang, Li Dong, Xiangping Zhang. Constructing mesoporous CeO₂ single-crystal particles in ionic liquids for enhancing the conversion of CO₂ and alcohols to carbonates [J]. Chinese Journal of Catalysis, 2024, 66(11): 152-167.
[11]	Mingjie Cai, Yanping Liu, Kexin Dong, Xiaobo Chen, Shijie Li. Floatable S-scheme Bi₂WO₆/C₃N₄/carbon fiber cloth composite photocatalyst for efficient water decontamination [J]. Chinese Journal of Catalysis, 2023, 52(9): 239-251.
[12]	Shijie Li, Chunchun Wang, Kexin Dong, Peng Zhang, Xiaobo Chen, Xin Li. MIL-101(Fe)/BiOBr S-scheme photocatalyst for promoting photocatalytic abatement of Cr(VI) and enrofloxacin antibiotic: Performance and mechanism [J]. Chinese Journal of Catalysis, 2023, 51(8): 101-112.
[13]	Xiu-Qing Qiao, Chen Li, Zizhao Wang, Dongfang Hou, Dong-Sheng Li. TiO_2-_x@C/MoO₂Schottky junction: Rational design and efficient charge separation for promoted photocatalytic performance [J]. Chinese Journal of Catalysis, 2023, 51(8): 66-79.
[14]	Jiao Wang, Fangfang Zhu, Biyi Chen, Shuang Deng, Bochen Hu, Hong Liu, Meng Wu, Jinhui Hao, Longhua Li, Weidong Shi. B atom dopant-manipulate electronic structure of CuIn nanoalloy delivering wide potential activity over electrochemical CO₂RR [J]. Chinese Journal of Catalysis, 2023, 49(6): 132-140.
[15]	Yan Zeng, Hui Wang, Huiru Yang, Chao Juan, Dan Li, Xiaodong Wen, Fan Zhang, Ji-Jun Zou, Chong Peng, Changwei Hu. Ni nanoparticle coupled surface oxygen vacancies for efficient synergistic conversion of palmitic acid into alkanes [J]. Chinese Journal of Catalysis, 2023, 47(4): 229-242.