The organic-inorganic S-scheme heterojunction with enhanced charge separation simultaneously catalyze the production of hydrogen and imine

doi:10.1016/S1872-2067(26)65073-5

Abstract

Abstract:

Photocatalytic hydrogen production coupled with value-added chemical synthesis has attracted extensive research interests as a promising route to realize efficient conversion of solar energy to chemical energy. However, the rapid charge recombination hinders the improvement of conversion efficiency. Herein, a pyrene-based conjugated polymer (PyDF)/Mn_0.2Cd_0.8S (MCS) organic-inorganic S-scheme heterojunction photocatalyst (PMCS) was reported. The incorporation of large delocalized π-conjugation system and formation of the S-scheme heterojunction significantly enhanced the charge separation and transfer. As a result, the optimal PMCS_0.5 composite exhibited a hydrogen evolution rate of 16.3 mmol h^-1 g^-1 with ascorbic acid as sacrificial agent. In the coupled system for benzylamine (BA) oxidation and hydrogen production, it delivered a hydrogen evolution rate of 3.72 mmol h^-1 g^-1, with nearly 100% conversion of 358.8 μmol BA to N-benzylidene benzylamine (NBBA) within 4 h. To elucidate the charge transfer mechanism within the S-scheme heterojunction, density functional theory calculations, in-situ X-ray photoelectron spectroscopy, and in-situ irradiated Kelvin probe force microscopy were conducted. In addition, in-situ diffuse reflectance infrared Fourier transform spectroscopy was employed to monitor the stepwise transformation of amines to imines during the photocatalytic process. This work offers a promising approach for bifunctional photocatalyst design toward simultaneous energy conversion and green synthesis.

Key words: S-scheme heterojunction, Hydrogen evolution, Imine synthesis, Bifunctional photocatalytic system, In-situ spectroscopy

Hao Wu, Xinyu Zeng, Wang Wang, Bei Cheng, Jingzhao Cheng, Jingsan Xu, Shaowen Cao. The organic-inorganic S-scheme heterojunction with enhanced charge separation simultaneously catalyze the production of hydrogen and imine[J]. Chinese Journal of Catalysis, 2026, 87: 185-196.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65073-5

https://www.cjcatal.com/EN/Y2026/V87/I8/185

Figures/Tables 7

Fig. 1. (a) Synthesis diagram of the PMCS composites. XRD patterns of PyDF (b) and MCS and PMCS composites (c).

Fig. 2. TEM (a), HRTEM (b), HAADF-STEM (c) images, and EDX mapping (d) of PMCS0.5.

Fig. 3. (a) UV-Vis DRS spectra of the prepared catalysts. UPS spectra of PyDF (b) and MCS (c). (d) Band structure diagram of PyDF and MCS.

Fig. 4. (a) Comparative analysis of hydrogen production coupling oxidation reactions over all photocatalysts within 4 h under light irradiation. (b) Comparative analysis of BA conversion amount over all photocatalysts within 4 h. (c) BA consumption, NBBA production and BA conversion rate over all photocatalysts within 4 h. (d) Photocatalytic H2 production cycling tests. (e) NBBA production and BA residual in cycling tests. (f) BA conversion rate in six cycles. TRPL spectra (g), photocurrent density curves (h), and EIS Nyquist plots (i) of the prepared catalysts.

Fig. 5. XPS survey spectra (a), and high-resolution XPS spectra of C 1s (b), Cd 3d (c), and Mn 2p (d) of PyDF, MCS and PMCS0.5.

Fig. 6. Surface morphology of PMCS0.5 under dark (a) and light (b). (c) Height map before and after light. KPFM of PMCS0.5 under dark (d) and light (e). (f) CPD changes of PMCS0.5 under dark and light conditions.

Fig. 7. The in-situ DRIFTS of PMCS0.5 under dark (a) and light irradiation for 60 min (b) in N2 atmosphere. (c) Mechanism of photocatalytic hydrogen production coupled with benzylamine oxidation of PyDF/MCS.

References

[1]	T. Hisatomi, K. Domen, Nat. Catal., 2019, 2, 387-399.
[2]	T. Takata, J. Jiang, Y. Sakata, M. Nakabayashi, N. Shibata, V. Nandal, K. Seki, T. Hisatomi, K. Domen, Nature, 2020, 581, 411-414.
[3]	P. Zhou, I. A. Navid, Y. Ma, Y. Xiao, P. Wang, Z. Ye, B. Zhou, K. Sun, Z. Mi, Nature, 2023, 613, 66-70.
[4]	Y. Wang, W. Yu, C. Wang, F. Chen, T. Ma, H. Huang, eScience, 2024, 4, 100228.
[6]	J. Cheng, S. Gao, B. Cheng, K. Yang, W. Wang, S. Cao, Acta Phys. Chim. Sin., 2024, 40, 2406026.
[7]	W. Li, Z. Ni, O. Akdim, T. Liu, B. Zhu, P. Kuang, J. Yu, Adv. Mater., 2025, 37, 2503742.
[8]	X. Yin, D. Gao, J. Zhang, H. García, J. Yu, H. Yu, J. Am. Chem. Soc., 2025, 147, 34881-34890.
[9]	F. Yin, W. Wang, J. Zhang, S. Wan, B. Cheng, G. Luo, C. Wang, J. Yu, S. Cao, Angew. Chem. Int. Ed., 2025, 64, e202513602.
[10]	A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[11]	T. Hisatomi, K. Domen, Nat. Sustain., 2024, 7, 1082-1084.
[12]	X. Xin, Y. Li, Y. Zhang, Y. Wang, X. Chi, Y. Wei, C. Diao, J. Su, R. Wang, P. Guo, J. Yu, J. Zhang, A. J. Sobrido, M.-M. Titirici, X. Li, Nat. Commun., 2024, 15, 337.
[13]	K. Sun, Y. Huang, F. Sun, Q. Wang, Y. Zhou, J. Wang, Q. Zhang, X. Zheng, F. Fan, Y. Luo, J. Jiang, H.-L. Jiang, Nat. Chem., 2024, 16, 1638-1646.
[14]	C. Tang, T. Bao, S. Li, X. Wang, H. Rao, P. She, J.-S. Qin, Appl. Catal. B, 2024, 342, 123384.
[15]	C. Shu, X. Yang, P. Xie, X. Yang, B. Tan, X. Wang, Chin. J. Catal., 2025, 73, 300-310.
[16]	M. Wei, X. Zhou, C. Cheng, J. Zhang, C. Jiang, B. Cheng, J. Mater. Sci. Technol., 2025, 232, 302-312.
[17]	Y. Liu, J. Wu, F. Wang, Appl. Catal. B, 2022, 307, 121144.
[18]	Z. Jia, R. Li, P. Ji, Z. Xu, K. P. Homewood, X. Xia, Y. Gao, J.-P. Zou, X. Chen, Appl. Catal. B, 2024, 357, 124279.
[19]	S. Wan, W. Wang, B. Cheng, G. Luo, Q. Shen, J. Yu, J. Zhang, S. Cao, L. Zhang, Nat. Commun., 2024, 15, 9612.
[20]	P. Wang, S. Fan, X. Li, J. Wang, Z. Liu, C. Bai, M. O. Tadé, S. Liu, Nano Energy, 2021, 89, 106349.
[21]	J. Cai, B. Liu, S. Zhang, L. Wang, Z. Wu, J. Zhang, B. Cheng, J. Mater. Sci. Technol., 2024, 197, 183-193.
[22]	Y. Jin, D. Zheng, Z. Fang, Z. Pan, S. Wang, Y. Hou, O. Savateev, Y. Zhang, G. Zhang, Interdiscip. Mater., 2024, 3, 389-399.
[23]	G. Han, Y.-H. Jin, R. A. Burgess, N. E. Dickenson, X.-M. Cao, Y. Sun, J. Am. Chem. Soc., 2017, 139, 15584-15587.
[24]	F. Kolahdouzan, N. Goodarzi, M. Setayeshmehr, D. S. Mousavi, A. Z. Moshfegh, Chin. J. Catal., 2025, 70, 230-259.
[25]	X. Xiang, B. Cheng, B. Zhu, C. Jiang, G. Liang, Chin. J. Catal., 2025, 68, 326-335.
[26]	S. Cao, B. Zhong, C. Bie, B. Cheng, F. Xu, Acta Phys.-Chim. Sin., 2024, 40, 2307016.
[27]	B. Liu, J. Zhang, H. Li, B. Cheng, C. Bie, Acta Phys.-Chim. Sin., 2025, 41, 100121.
[28]	J. Cheng, W. Wang, J. Zhang, Z. Liu, S. Wan, B. Cheng, G. Luo, J. Yu, J. Xu, S. Cao, Adv. Mater., 2025, 37, e12144.
[29]	G. Tang, J. Zhang, C. Bie, X. Zheng, C. Jiang, J. Yu, Adv. Mater., 2025, 37, e14576.
[30]	W. Wang, B. Cheng, G. Luo, J. Yu, S. Cao, Mater. Today, 2024, 81, 137-158.
[31]	C. Zhu, K. Zhong, B. Zhu, S. Li, H. Li, J. Yang, H. Xu, Appl. Catal. B, 2025, 371, 125200.
[32]	X. Zhang, M. Zhang, C. Luo, Y. Li, L. Zhang, C. Li, X. Zhang, J. Liao, W. Zhou, Appl. Catal. B, 2025, 371, 125288.
[33]	W. Dai, C. Wang, Y. Wang, J. Sun, H. Ruan, Y. Xue, S. Xiao, Interdiscip. Mater., 2024, 3, 400-413.
[34]	J. Cai, C. Cheng, B. Liu, J. Zhang, C. Jiang, B. Cheng, Acta Phys.-Chim. Sin., 2025, 41, 100084.
[35]	M. Sayed, K. Qi, X. Wu, L. Zhang, H. García, J. Yu, Chem. Soc. Rev., 2025, 54, 4874-4921.
[36]	M. Li, X. Li, J. B. Ghasemi, Chin. J. Catal., 2025, 73, 12-15.
[37]	Z. Wang, C. Bie, J. Mater. Sci. Technol., 2026, 243, 206-208.
[38]	Z. Meng, J. Zhang, H. Long, H. García, L. Zhang, B. Zhu, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202505456.
[39]	Y. Zhang, Y. Wang, Y. Liu, S. Zhang, Y. Zhao, J. Zhang, J. Materiomics, 2025, 11, 100985.
[40]	R. He, D. Xu, M. Sayed, J. Materiomics, 2025, 11, 100989.
[41]	Y. Zhang, S. Wang, Chin. J. Catal., 2025, 71, 1-4.
[42]	M. Gu, J. Zhang, I. V. Kurganskii, A. S. Poryvaev, M. V. Fedin, B. Cheng, J. Yu, L. Zhang, Adv. Mater., 2025, 37, 2414803.
[43]	H. Li, W. Wang, K. Xu, B. Cheng, J. Xu, S. Cao, Chin. J. Catal., 2025, 72, 24-47.
[44]	Y.-F. Yu, X.-M. You, Y. Zhang, Y. Peng, X.-L. Wang, P.-F. Liu, H.-G. Yang, Sci. China Mater., 2024, 67, 2645-2652.
[45]	X. Han, L. Zhang, X. Wang, S. Song, H. Zhang, Nano Res. Energy, 2023, 2, e9120084.
[46]	D. Zheng, Q. Wang, Z. Pan, S. Wang, Y. Hou, G. Zhang, Sci. China Mater., 2024, 67, 1900-1906.
[47]	Z. Su, Q. Huang, Q. Guo, S. J. Hoseini, F. Zheng, W. Chen, Nano Res. Energy, 2023, 2, e9120078.
[48]	H. Li, S. Tao, S. Wan, G. Qiu, Q. Long, J. Yu, S. Cao, Chin. J. Catal., 2023, 46, 167-176.
[50]	B. Liu, K. Meng, B. Cheng, L. Wang, G. Liang, C. Bie, J. Mater. Sci. Technol., 2025, 231, 286-295.
[51]	X. Dong, H. Zhao, K. Zhang, X. Lang, Coord. Chem. Rev., 2024, 513, 215902.
[53]	X. Zeng, K. Meng, W. Wang, J. Zhang, B. Cheng, S. Zhang, G. Luo, J. Yu, S. Cao, Small, 2025, 21, 2500130.
[54]	Z. Chen, S. Wan, B. Cheng, W. Wang, Y. Xiang, J. Yu, S. Cao, Sci. China Chem., 2024, 67, 1953-1960.
[55]	Y. Li, S. Wan, W. Liang, B. Cheng, W. Wang, Y. Xiang, J. Yu, S. Cao, Small, 2024, 20, 2312104.
[56]	S. Iqbal, Appl. Catal. B, 2020, 274, 119097.
[57]	Q.-Z. Huang, Z.-J. Tao, L.-Q. Ye, H.-C. Yao, Z.-J. Li, Appl. Catal. B, 2018, 237, 689-698.
[58]	J. Cheng, S. Wan, S. Cao, Angew. Chem. Int. Ed., 2023, 62, e202310476.
[59]	Z. Li, Z. Zhuang, F. Lv, H. Zhu, L. Zhou, M. Luo, J. Zhu, Z. Lang, S. Feng, W. Chen, L. Mai, S. Guo, Adv. Mater., 2018, 30, 1803220.
[60]	Z. Zhuang, Y. Li, Z. Li, F. Lv, Z. Lang, K. Zhao, L. Zhou, L. Moskaleva, S. Guo, L. Mai, Angew. Chem. Int. Ed., 2018, 57, 496-500.
[61]	J. Liu, Y. Liu, N. Liu, Y. Han, X. Zhang, H. Huang, Y. Lifshitz, S.-T. Lee, J. Zhong, Z. Kang, Science, 2015, 347, 970-974.
[62]	C. Xu, H. Liu, D. Li, J.-H. Su, H.-L. Jiang, Chem. Sci., 2018, 9, 3152-3158.
[63]	B. He, C. Bie, X. Fei, B. Cheng, J. Yu, W. Ho, A. A. Al-Ghamdi, S. Wageh, Appl. Catal. B, 2021, 288, 119994.
[64]	B. He, Z. Wang, P. Xiao, T. Chen, J. Yu, L. Zhang, Adv. Mater., 2022, 34, 2203225.
[65]	C. Zhu, C.-A. Liu, Y. Fu, J. Gao, H. Huang, Y. Liu, Z. Kang, Appl. Catal. B, 2019, 242, 178-185.
[66]	J. Wang, J. Luo, D. Liu, S. Chen, T. Peng, Appl. Catal. B, 2019, 241, 130-140.
[67]	J. Liu, X. Sun, Y. Fan, Y. Yu, Q. Li, J. Zhou, H. Gu, K. Shi, B. Jiang, Small, 2024, 20, 2306344.
[68]	B. He, P. Xiao, S. Wan, J. Zhang, T. Chen, L. Zhang, J. Yu, Angew. Chem. Int. Ed., 2023, 62, e202313172.

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