Achieving Multiswitchable Phases to Govern Enhanced Photocatalysis in Staggered In₂Se₃/SnSe Heterostructure

Abstract

Two-dimensional staggered heterostructures, featuring by the intrinsically facilitate charge separation, provide promising platforms for efficient photocatalytic water splitting. However, their carrier dynamics generally follow two competing pathways: type II and Z-scheme, with the distinct governing mechanisms in photocatalysis remain elusive. Here, through stacking or sliding ferroelectric control, we realize three switchable phases within an In₂Se₃/SnSe heterostructure, and uncover how interlayer polarization governs carrier dynamics for enhanced photocatalytic activities and efficiencies. First-principle results show that transitions between type II and Z-scheme models can be driven by the reversal of interlayer electric fields (E_int) or donor–acceptor band edge exchanges, which will further modulate their carrier separation, redox potential alignment, interlayer carrier lifetime, carrier dynamics, spontaneous thermodynamic feasibility, and energy conversion efficiency. Compared with the inactive type II (↑ Se⁻) phase, strengthened E_int in the type-II (↓ Se⁻) phase suppresses interlayer e–h recombination to prolonged carrier lifetimes, while the Z-scheme (↓ Sn⁺) accelerate this recombination, forming new active band edges. Thereby, both yield higher redox potentials for superior photocatalytic activities and efficiencies. These results uncover how stacking-induced polarization defines carrier-dynamics in staggered heterostructures, establishing interlayer engineering as an effective route toward next generation of switchable and high efficient 2D photocatalysts.

Keywords

first-principle calculations / In₂Se₃/SnSe heterostructure / multi-phases switch / photocatalytic activity / solar-to-hydrogen efficiency / type-II (Z-scheme) carrier dynamics

References

[1] Y. L. Liu, J. M. Wu, Nano Energy 2019, 56, 74.

[2] J. Kiwi, M. Grätzel, Nature 1979, 281, 657.

[3] A. Fujishima, K. Honda, Nature 1972, 238, 37.

[4] N. Lu, M. Y. Zhang, X. D. Jing, P. Zhang, Y. A. Zhu, Z. Y. Zhang, Energy Environ. Mater. 2023, 6, e12338.

[5] G. Q. Ma, Y. L. Liu, Y. L. Zhao, W. K. Zhao, C. L. Yang, J. Colloid Interface Sci. 2025, 701, 138747.

[6] L. Ju, J. Shang, X. Tang, L. Z. Kou, J. Am. Chem. Soc. 2019, 142, 1492.

[7] S. S. Emadian, S. Varagnolo, A. Kumar, P. Kumar, P. Ranjan, V. Pyeshkova, N. Vangapally, N. P. Power, S. Pitchaimuthu, A. Chroneos, Energy Environ. Mater. 2025, 8, e12881.

[8] M. Yoon, Y. Park, H. Sim, H. R. Kwon, Y. Lee, H. W. Jang, S. Y. Choi, J. Son, Adv. Mater. 2025, 37, 2413062.

[9] X. H. Meng, Y. Q. Shen, X. Yang, K. P. Cai, Q. Ai, Y. Shuai, Z. X. Zhou, Phys. Rev. B 2025, 112, 104503.

[10] X. H. Meng, Y. Q. Shen, L. L. Lv, M. Zhou, X. Yang, Y. Zhang, L. Pang, Z. X. Zhou, Mater. Today Phys. 2024, 47, 101532.

[11] X. H. Meng, Y. Q. Shen, X. Yang, C. Wu, Q. Ai, Y. Shuai, Z. X. Zhou, Phys. Rev. B 2025, 112, 214507.

[12] J. Mei, T. Liao, Z. Q. Sun, Energy Environ. Mater. 2022, 5, 115.

[13] J. Wang, R. Long, Nano Lett. 2024, 24, 3476.

[14] W. N. Xing, X. S. Xu, C. K. Liu, Y. Wang, Z. T. Wan, J. G. Han, G. Y. Wu, Y. D. Huang, ACS Appl. Nano Mater. 2024, 7, 16725.

[15] M. Faraji, M. Yousefi, S. Yousefzadeh, M. Zirak, N. Naseri, T. H. Jeon, W. Choi, A. Z. Moshfegh, Energy Environ. Sci. 2019, 12, 59.

[16] J. F. Zhao, Y. L. Zhao, H. J. He, P. W. Zhou, Y. Liang, T. Frauenheim, J. Phys. Chem. Lett. 2021, 12, 10190.

[17] B. Y. Dai, Y. K. Chen, S. M. Hao, H. M. Huang, J. H. Kou, C. H. Lu, Z. Q. Lin, Z. Z. Xu, J. Phys. Chem. Lett. 2020, 11, 7407.

[18] Y. C. Fan, X. H. Song, S. Y. Qi, X. K. Ma, M. W. Zhao, J. Mater. Chem. A 2019, 7, 26123.

[19] Y. Zhang, Y. Q. Shen, L. L. Lv, M. Zhou, X. Yang, X. H. Meng, N. Zhang, K. X. Wang, B. Zhang, Z. X. Zhou, Phys. Rev. Appl. 2023, 20, 44066.

[20] K. Y. Han, D. F. Guo, Y. X. Han, P. Zhao, Y. Liang, Q. Wang, Phys. Chem. Chem. Phys. 2024, 26, 8539.

[21] K. Y. Han, Q. Wang, Y. Liang, T. Frauenheim, D. F. Guo, B. Wang, J. Mater. Chem. A 2023, 11, 22971.

[22] Q. F. Cai, C. W. Tan, J. Y. Wang, T. Tu, S. Sun, X. K. Li, B. T. Zhang, H. X. Li, X. Y. Xu, X. An, X. Zhang, R. Huang, H. L. Peng, M. He, M. Li, IEEE Electron Device Lett. 2021, 42, 871.

[23] J. Cenker, J. Fonseca, M. Nguyen, C. W. Hu, D. G. Chica, T. Taniguchi, K. Watanabe, X. Y. Zhu, X. Roy, J.-H. Chu, X. D. Xu, Nano Lett. 2025, 25, 4512.

[24] W. L. Cai, P. C. Zou, S. Q. Rong, H. Wang, X. Chen, Z. Zhang, Y. J. Wang, C. Liu, T. H. Yang, T. Q. Niu, S. Y. Jin, W. M. Tian, J. X. Yao, S. F. Liu, K. Zhao, Energy Environ. Sci. 2024, 17, 8162.

[25] J. Q. Zhang, X. L. Zhao, L. Chen, S. L. Li, H. J. Chen, Y. Z. Zhu, S. J. Wang, Y. Liu, H. Y. Zhang, X. G. Duan, M. B. Wu, S. B. Wang, H. Q. Sun, Energy Environ. Mater. 2023, 6, e12365.

[26] N. Atodiresei, V. Caciuc, P. Lazic, S. Blu, gel, Phys. Rev. Lett 2009, 102, 136809.

[27] S. Liu, L. Xu, J. L. Liu, R. Huang, M. He, 8th IEEE Electron Devices Technology & Manufacturing Conference (EDTM), IEEE, Bangalore, India 2024, pp. 1–3.

[28] J. M. Li, H. Wang, X. Xiao, Energy Environ. Mater. 2020, 3, 306.

[29] L. Ju, Y. D. Ma, X. Tan, L. Z. Kou, J. Am. Chem. Soc. 2023, 145, 26393.

[30] Y. Zhou, D. Wu, Y. H. Zhu, Y. Cho, Q. He, X. Yang, K. Herrera, Z. D. Chu, Y. Han, M. C. Downer, H. L. Peng, K. J. Lai, Nano Lett. 2017, 17, 5508.

[31] W. J. Ding, J. B. Zhu, Z. Wang, Y. F. Gao, D. Xiao, Y. Gu, Z. Y. Zhang, W. G. Zhu, Nat. Commun. 2017, 8, 14956.

[32] L. Ju, X. Tan, X. Mao, Y. T. Gu, S. Smith, A. J. Du, Z. F. Chen, C. F. Chen, L. Z. Kou, Nat. Commun. 2021, 12, 5128.

[33] Y. Tang, M. P. Liu, L. Y. Bai, Y. Y. Chen, J. B. Wang, X. L. Zhong, Int. J. Hydrog. Energy 2025, 126, 45.

[34] H. S. Kim, J. Mater. Chem. A 2021, 9, 11553.

[35] N. Urakami, S. Ozaki, Y. Hashimoto, Appl. Phys. Lett. 2024, 125, 72903.

[36] X. Q. Tian, J. Y. Duan, M. Kiani, Y. D. Wei, N. X. Feng, Z. R. Gong, X. R. Wang, Y. Du, B. I. Yakobson, Nanoscale 2020, 12, 13450.

[37] S. Y. Peng, D. Liu, Z. Q. Ying, K. Y. An, C. F. Liu, W. F. Ip, K. H. Lo, H. Pan, Carbon Energy 2025, 7, e70052.

[38] S. Q. Zheng, Y. L. Sun, Y. Q. Shen, S. Z. Du, H. B. Chen, Y. M. Jing, Y. H. Yuan, F. Yao, H. M. Li, X. C. Liu, Y. C. Cheng, J. Sun, Adv. Mater. 2025, 37, e02784.

[39] C. Y. Hong, Y. Tao, A. M. Nie, M. H. Zhang, N. Wang, R. P. Li, J. Q. Huang, Y. Q. Huang, X. M. Ren, Y. C. Cheng, X. L. Liu, ACS Nano 2020, 14, 16803.

[40] C. X. Xia, J. Du, M. Li, X. P. Li, X. Zhao, T. X. Wang, J. B. Li, Phys. Rev. Appl. 2018, 10, 54064.

[41] F. Mouhat, F.-X. Coudert, Phys. Rev. B 2014, 90, 224104.

[42] A. K. Sahu, M. Pokhriyal, D. Banerjee, T. E. Ruford, S. Upadhyayula, Chem. Eng. J. 2024, 487, 150716.

[43] Y. Yuan, J. A. Pan, W. N. Yin, H. X. Yu, F. S. Wang, W. F. Hu, L. L. Wang, D. F. Yan, Chin. Chem. Lett. 2024, 35, 108724.

[44] H. P. Chen, N. Chen, C. P. Feng, Y. Gao, J. Colloid Interface Sci. 2018, 515, 119.

[45] C. Liu, S. Guan, H. B. Yin, W. H. Wan, Y. X. Wang, Y. Zhang, Appl. Phys. Lett. 2019, 115, 252903.

[46] Q. Wang, Y. Liang, H. Yao, J. W. Li, T. W. Liu, T. Frauenheim, B. Wang, J. Wang, J. Mater. Chem. C 2022, 10, 1048.

[47] P. Feng, S. X. He, Z. Zeng, C. C. Dang, M. Li, L. C. Zhao, D. B. Wang, L. M. Gao, Adv. Mater. Technol. 2024, 9, 2301355.

[48] D. Y. Bai, Y. H. Nie, J. Shang, J. X. Liu, M. H. Liu, Y. Yang, H. F. Zhan, L. Z. Kou, Y. T. Gu, Nano Lett. 2023, 23, 10922.

[49] H. L. Guo, C. Y. Zhao, Q. J. Zheng, Z. G. Lan, O. V. Prezhdo, W. A. Saidi, J. Zhao, J. Phys. Chem. Lett. 2018, 9, 3485.

[50] K. G. Reeves, A. Schleife, A. A. Correa, Y. Kanai, Nano Lett. 2015, 15, 6429.

[51] C. F. Fu, J. Y. Sun, Q. Q. Luo, X. X. Li, W. Hu, J. L. Yang, Nano Lett. 2018, 18, 6312.

[52] Q. Wang, K. Y. Han, Y. Liang, X. S. Lv, X. R. Meng, S. Wang, T. Frauenheim, D. F. Guo, B. Wang, J. Mater. Chem. A 2025, 13, 9469.

[53] B. Y. Liu, X. Wang, Y. J. Zhang, M. S. Zhu, C. X. Zhang, S. B. Li, Y. H. Ma, W. Huang, S. C. Wang, Nat. Commun. 2025, 16, 2792.

[54] A. Nakada, S. Nishioka, J. J. M. Vequizo, K. Muraoka, T. Kanazawa, A. Yamakata, S. Nozawa, H. Kumagai, S.-i. Adachi, O. Ishitani, J. Mater. Chem. A 2017, 5, 11710.

[55] Q. Lu, L. L. Zhang, T. T. Xu, B. Y. Zhang, W. J. Gong, Surf. Interfaces 2023, 36, 102608.

[56] Y. Zhang, Y. Q. Shen, J. J. Liu, L. L. Lv, M. Zhou, X. Yang, X. H. Meng, Z. X. Zhou, Appl. Phys. Lett. 2023, 122, 43901.

[57] G. Kresse, D. Joubert, Phys. Rev. B 1999, 59, 1758.

[58] G. Kresse, J. Hafner, Phys. Rev. B 1993, 47, 558.

[59] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.

[60] J. Heyd, G. E. Scuseria, M. Ernzerhof, J. Chem. Phys. 2003, 118, 8207.

[61] Q. J. Zheng, W. B. Chu, C. Y. Zhao, L. L. Zhang, H. L. Guo, Y. N. Wang, X. Jiang, J. Zhao, WIREs Comput. Mol. Sci. 2019, 9, e1411.

[62] A. V. Akimov, O. V. Prezhdo, J. Chem. Theory Comput. 2013, 9, 4959.

[63] C. F. Craig, W. R. Duncan, O. V. Prezhdo, Phys. Rev. Lett. 2005, 95, 163001.

Rights & permissions

2026 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.