Enhanced photocatalytic production of hydrogen and benzaldehyde over a dual-function ZnxCd1-xSy/FePS3 S-scheme heterojunction

doi:10.1016/S1872-2067(25)64830-3

Abstract

Abstract:

Photocatalysis is deemed a green approach to sustainable energy conversion with great promise for addressing future energy challenges. However, traditional photocatalytic systems are often inhibited by rapid recombination of photogenerated electron-hole pairs and low light-harvesting efficiency. To overcome these challenges, an S-scheme heterojunction integrating Zn_xCd_1-_xS_y (ZCS) nanocrystals with FePS₃ (FPS) nanosheets was designed to facilitate both photocatalytic hydrogen evolution and the conversion of benzyl alcohol to benzaldehyde (BAD). The obtained ZCS/FPS-15 (ZCSF-15) heterostructure exhibits remarkable visible-light-harvesting enhancement and charge separation efficiency, delivering a hydrogen evolution rate of 73.06 mmol g^-1 h^-1 and a BAD production rate of 46.68 mmol g^-1 h^-1, corresponding to 22.34- and 53.65-fold performance enhancements, respectively, compared with that of bare ZCS. To reveal the charge transfer dynamics and clarify the reaction mechanisms, in-situ diffuse-reflectance Fourier-transform infrared spectroscopy was used to identify key oxidation intermediates, coupled with interfacial charge transfer dynamics probed using in-situ X-ray photoelectron spectroscopy and atomic force microscopy-Kelvin probe force microscopy. This work establishes a dual-function heterojunction model, offering valuable insights into how to design S-scheme heterojunctions for simultaneous green fuel generation and selective organic synthesis.

Key words: S-scheme heterojunction, Photocatalysis, Hydrogen evolution, Solar energy conversion, Chemical valorization

Rundong Chen, Yuhang Zhang, Bingquan Xia, Xianlong Zhou, Yanzhao Zhang, Shantang Liu. Enhanced photocatalytic production of hydrogen and benzaldehyde over a dual-function Zn_xCd_1-_xS_y/FePS₃ S-scheme heterojunction[J]. Chinese Journal of Catalysis, 2026, 80: 123-134.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64830-3

https://www.cjcatal.com/EN/Y2026/V80/I1/123

Figures/Tables 10

Scheme 1. Process of synthesizing FPS nanosheets, ZCS, and the ZCS/FPS hybrid.

Fig. 1. (a) TEM image of ZCSF-15. (b) HRTEM image of ZCSF-15. (c) HAADF-STEM image of ZCSF-15. (d-h) Elemental mapping images of ZCSF-15.

Fig. 2. XRD patterns (a) and UV-vis DRS spectra (b) for FPS, ZCS, and ZCSF-x hybrids. PL spectra (c), TRPL spectra (d), EIS spectra (e), and transient photocurrent responses (f) of FPS, ZCS, and ZCSF-15.

Fig. 3. Performance tests of photocatalysts: Hydrogen evolution rate (a), BAD production rate (b), and BAD selectivity (c). Cyclability tests of ZCSF-15: hydrogen evolution (d) and BAD production (e). (f) Comparison of hydrogen evolution and BAD production over ZCSF-15 in water and acetonitrile.

Fig. 4. XPS spectra of Fe 2p (a), Cd 3d (b), Zn 2p (c), S 2p (d), and P 2p (e) for ZCSF-15 before and after the reaction. (f) XRD patterns of ZCSF-15 before and after the reaction.

Fig. 5. XPS spectra of Zn 2p (a) and Cd 3d (b) for pristine ZCS under dark conditions and ZCSF-15 under dark/illuminated conditions. (c) Fe 2p3/2 spectra for pristine FPS under dark conditions and ZCSF-15 under dark/illuminated conditions. (d) Differential charge density plot of the ZCSF interface. The blue and yellow regions denote electron accumulation and depletion, respectively.

Fig. 6. KPFM images of ZCS (a), FPS (d), and ZCSF-15 (g) in darkness. KPFM image of ZCS (b), FPS (e), and ZCSF-15 (h) under Xe lamp irradiation. Contact potential differences of ZCS (c), FPS (f), and ZCSF-15 (i) in darkness and under Xe lamp irradiation.

Fig. 7. (a) Schematic of charge transfer mechanism in ZCSF-x S-scheme heterojunctions before contact, after contact, and under illumination. EPR spectra of ?OH radicals (b) and ?O2? radicals (c) for ZCSF-15 and ZCS under light and dark conditions.

Fig. 8. (a) In-situ DRIFTS spectra of ZCSF-15 during photocatalytic H2 production coupled with BA oxidation. (b) Proposed oxidation steps of BA on ZCSF-15. In-situ DRIFTS spectra of ZCSF-15 in the ranges of 1150-1460 cm-1 (c), 1600-1750 cm-1 (d), and 650-760 cm-1 (e). (f) Calculated ΔGH* of ZCS at different sites. (g) Gibbs free energy of BA on FPS at each reaction stage.

Fig. 9. Proposed mechanism of the cooperative photoredox reaction for the production of H2 and BAD over the ZCSF-x S-scheme heterojunction.

References

[1]	J. Luo, C. Zhu, J. Li, J. Jin, N. E. Soland, P. W. Smith, Y. Shan, A. M. Oddo, A. L. Maulana, L. Jayasinghe, X. Chen, T. Wang, J.-A. Lin, E. Lu, B. Schaefer, M. Schmalzbauer, R. Zhang, F. Seeler, C. Lizandara-Pueyo, J. Guo, P. Yang, J. Am. Chem. Soc., 2025, 147, 3428-3437.
[2]	Z. Lin, H. Saito, H. Sato, T. Sugimoto, J. Am. Chem. Soc., 2024, 146, 22276-22283.
[3]	H. Yang, R. Zhao, J. Wang, X. Yin, Z. Lu, L. Hou, ACS Mater. Lett., 2023, 5, 2877-2886.
[4]	W. Xu, C. Zhen, H. Zhu, T. Yao, J. Qiu, Y. Liang, S. Bai, C. Chen, H.-M. Cheng, G. Liu, Chin. J. Catal., 2024, 61, 144-153.
[5]	Y. Li, J. Chen, P. Cai, Z. Wen, J. Mater. Chem. A, 2018, 6, 4948-4954.
[6]	S. Zhou, D. Wen, W. Zhong, J. Zhang, Y. Su, A. Meng, J. Mater. Sci. Technol., 2024, 199, 53-65.
[7]	W. Hiramatsu, Y. Shiraishi, S. Ichikawa, S. Tanaka, Y. Kawada, C. Hiraiwa, T. Hirai, J. Am. Chem. Soc., 2025, 147, 1968-1979.
[8]	J. Chen, S. Yan, F. Wang, F. Lin, J. Lin, R.A. Borse, Y. Wang, Angew. Chem. Int. Ed., 2025, 64, e202500924.
[9]	K. Feng, K. Wu, J. Fan, T. Sun, E. Liu, Mater. Lett., 2024, 363, 136255.
[10]	W. Yu, C. Bie, Acta Phys.-Chim. Sin., 2024, 40, 2307022.
[11]	G. Zhang, S. Huang, X. Li, D. Chen, N. Li, Q. Xu, H. Li, J. Lu, Appl. Catal. B, 2023, 331, 122725.
[12]	M. Shi, X. Wu, Y. Zhao, R. Li, C. Li, J. Am. Chem. Soc., 2025, 147, 3641-3649.
[13]	X. Shi, P. Wang, W. Li, Y. Bai, H. Xie, Y. Zhou, L. Ye, Appl. Catal. B, 2019, 243, 322-329.
[14]	N. Yao, N. Luo, S. Jiang, A. Cai, W. Pi, X. Wang, Adv. Funct. Mater., 2024, 34, 2405474.
[15]	H. Liu, L. Han, X. Duan, H. Sun, S. Wang, J. Zhang, Energy Adv., 2023, 2, 1541-1564.
[16]	C. Pan, K. Huang, Z. Zhi, Y. Yang, H. Zhang, Y. Xie, C. Zhang, Y. Liu, M. Chen, Z. Wang, Z. Jiang, D. Cao, Adv. Energy Mater., 2025, https://doi.org/10.1002/aenm.202405708.
[17]	S. Li, R. Yan, M. Cai, W. Jiang, M. Zhang, X. Li, J. Mater. Sci. Technol., 2023, 164, 59-67.
[18]	D.-E. Lee, N. Mameda, K. P. Reddy, B. M. Abraham, W.-K. Jo, S. Tonda, J. Mater. Sci. Technol., 2023, 161, 74-87.
[19]	S. Cao, B. Zhong, C. Bie, B. Cheng, F. Xu, Acta Phys.-Chim. Sin., 2024, 40, 2307016.
[20]	H. Long, X. Zhang, Z. Zhang, J. Zhang, J. Yu, H. Yu, Nat. Commun., 2025, 16, 946.
[21]	A. Kaithal, B. Chatterjee, C. Werlé, W. Leitner, Angew. Chem. Int. Ed., 2021, 60, 26500-26505.
[22]	C. Wu, K. Lv, X. Li, Q. Li, Chin. J. Catal., 2023, 54, 137-160.
[23]	Z. Lu, R. Chen, G. Liu, B. Xia, K. Fan, T. Liu, Y. Xia, S. Liu, B. You, Adv. Funct. Mater., 2025, 35, 2500944.
[24]	X.-Y. Meng, J.-J. Li, P. Liu, M. Duan, J. Wang, Y.-N. Zhou, Y. Xie, Z.-H. Luo, Y.-X. Pan, Angew. Chem. Int. Ed., 2023, 62, e202307490.
[25]	W. Li, Y. Mao, Z. Liu, J. Zhang, J. Luo, L. Zhang, Z.-A. Qiao, Adv. Mater., 2023, 35, 2300396.
[26]	J. Bai, R. Shen, G. Liang, C. Qin, D. Xu, H. Hu, X. Li, Chin. J. Catal., 2024, 59, 225-236.
[27]	L. Sun, W. Wang, T. Kong, H. Jiang, H. Tang, Q. Liu, J. Mater. Chem. A, 2022, 10, 22531-22539.
[28]	H. Zhang, Y. Gao, S. Meng, Z. Wang, P. Wang, Z. Wang, C. Qiu, S. Chen, B. Weng, Y.-M. Zheng, Adv. Sci., 2024, 11, 2400099.
[29]	X. Hu, G. Mei, X. Chen, J. Liu, B.-Y. Xia, B. You, Angew. Chem. Int. Ed., 2023, 62, e202304050.
[30]	X. Hu, Z. Sun, G. Mei, X. Zhao, B.Y. Xia, B. You, Adv. Energy Mater., 2022, 12, 2201466.
[31]	Z. Zheng, S. Tian, Y. Feng, S. Zhao, X. Li, S. Wang, Z. He, Chin. J. Catal., 2023, 54, 88-136.
[32]	X.-Y. Xu, X.-H. Liu, H.-H. Gan, D.-N. Lu, X.-M. Jiang, M.-F. Yu, S. Pan, J.-Y. Luo, H.-L. Sun, X.-H. Zhang, Rare Met., 2025, 44, 1756-1766.
[33]	G. Liu, R. Chen, B. Xia, Z. Wu, S. Liu, A. Talebian-Kiakalaieh, J. Ran, Chin. J. Catal., 2024, 61, 97-110.
[34]	R. Pan, X. Ge, Q. Liu, H. Yin, Y. Guo, J. Shen, D. Zhang, P. Chen, J. Yuan, H. Xie, C. Liu, Adv. Funct. Mater., 2024, 34, 2315212.
[35]	L. Sun, W. Wang, P. Lu, Q. Liu, L. Wang, H. Tang, Chin. J. Catal., 2023, 51, 90-100.
[36]	L. Zhang, J. Zhang, H. Yu, J. Yu, Adv. Mater., 2022, 34, 2107668.
[37]	Q. Xu, L. Zhang, B. Cheng, J. Fan, J. Yu, Chem, 2020, 6, 1543-1559.
[38]	B. Zhang, K. Li, R. Li, S. Wang, L. Kang, J. Mater. Sci. Technol., 2025, 206, 257-268.
[39]	Z. Lei, W. Wang, T. Sun, E. Liu, T. Gao, J. Mater. Sci. Technol., 2025, 216, 81-92.
[40]	X. Xu, C. Shao, J. Zhang, Z. Wang, K. Dai, Acta Phys.-Chim. Sin., 2024, 40, 2309031.
[41]	J. Cai, C. Cheng, B. Liu, J. Zhang, C. Jiang, B. Cheng, Acta Phys.-Chim. Sin., 2025, 41, 100084.
[42]	F. Li, G. Zhu, J. Jiang, L. Yang, F. Deng, Arramel, X. Li, J. Mater. Sci. Technol., 2024, 177, 142-180.
[43]	L. Sun, X. Yu, L. Tang, W. Wang, Q. Liu, Chin. J. Catal., 2023, 52, 164-175.
[44]	M. Sayed, K. Qi, X. Wu, L. Zhang, H. García, J. Yu, Chem. Soc. Rev., 2025, 54, 4874-4921.
[45]	B. Zhu, C. Jiang, J. Xu, Z. Zhang, J. Fu, J. Yu, Mater. Today, 2025, 82, 251-273.
[46]	M. Gu, J. Zhang, I. V. Kurganskii, A. S. Poryvaev, M. V. Fedin, B. Cheng, J. Yu, L. Zhang, Adv. Mater., 2025, 37, 2414803.
[47]	K. Meng, J. Zhang, B. Zhu, C. Jiang, H. García, J. Yu, Adv. Mater., 2025, 37, 2505088.
[48]	Y. Han, Y. Han, Y. Yan, Y. Zong, R. Zhao, J. Han, L. Wang, Chem. Eng. J., 2024, 500, 156864.
[49]	C. Chen, J. Zhang, H. Chu, L. Sun, G. Dawson, K. Dai, Chin. J. Catal., 2024, 63, 81-108.
[50]	H. Li, S. Tao, S. Wan, G. Qiu, Q. Long, J. Yu, S. Cao, Chin. J. Catal., 2023, 46, 167-176.
[51]	J. Lu, S. Gu, H. Li, Y. Wang, M. Guo, G. Zhou, Energy Environ. Mater., 2023, 160, 214–239.
[52]	B. Zhang, F. Liu, B. Sun, T. Gao, G. Zhou, Chin. J. Catal., 2024, 59, 334-345.
[53]	K. Huang, D. Chen, X. Zhang, R. Shen, P. Zhang, D. Xu, X. Li, Acta Phys. Chim. Sin., 2024, 40, 2407020.
[54]	J. Yan, L. Wei, Acta Phys.-Chim. Sin., 2024, 40, 2312024.
[55]	R. Samal, G. Sanyal, B. Chakraborty, C. S. Rout, J. Mater. Chem. A, 2021, 9, 2560-2591.
[56]	S. Zhang, H. Li, L. Wang, J. Liu, G. Liang, K. Davey, J. Ran, S.-Z. Qiao, J. Am. Chem. Soc., 2023, 145, 6410-6419.
[57]	R. Chen, Q. Wu, J. Luo, X. Zu, S. Zhu, Y. Sun, Acta Phys.-Chim. Sin., 2025, 41, 2308052.
[58]	L. Hao, R. Shen, C. Qin, N. Li, H. Hu, G. Liang, X. Li, Sci. China Mater., 2024, 67, 504-513.
[59]	Z. Cheng, T. A. Shifa, F. Wang, Y. Gao, P. He, K. Zhang, C. Jiang, Q. Liu, J. He, Adv. Mater., 2018, 30, 1707433.
[60]	Y. Feng, C. Lin, Y. Huang, B. Li, Y. He, J. Ma, C. Ban, L. Ruan, H. Jia, X. Tao, L. Gan, X. Zhou, Chem. Eng. J., 2025, 506, 160044.
[61]	M. Lu, X. Xiao, G. Zeng, J. Alloys Compd., 2021, 885, 160996.
[62]	L. Zhang, J. Zhang, J. Yu, H. García, Nat. Rev. Chem., 2025, 9, 328-342.
[63]	Y. Zhao, Y. Zhang, H. Tan, C. Ai, J. Zhang, J. Materiomics, 2025, 11, 100970.
[64]	M. Kou, Y. Wang, Y. Xu, L. Ye, Y. Huang, B. Jia, H. Li, J. Ren, Y. Deng, J. Chen, Y. Zhou, K. Lei, L. Wang, W. Liu, H. Huang, T. Ma, Angew. Chem. Int. Ed., 2022, 61, e202200413.
[65]	C. Cheng, M. N. Akram, O. Nilsen, N. Pryds, K. Wang, Phys. Chem. Chem. Phys., 2020, 22, 7769-7777.
[66]	B. Xia, B. He, J. Zhang, L. Li, Y. Zhang, J. Yu, J. Ran, S.-Z. Qiao, Adv. Energy Mater., 2022, 12, 2201449.
[67]	Y. Fan, X. Hao, N. Yi, Z. Jin, Appl. Catal. B, 2024, 357, 124313.
[68]	X. Bai, M. She, Y. Ji, Z. Zhang, W. Xue, E. Liu, K. Wan, P. Liu, S. Zhang, J. Li, Adv. Sci., 2023, 10, 2207250.
[69]	J. Liu, X. Li, C. Han, M. Liu, X. Li, J. Sun, C. Shao, Energy Environ. Mater., 2023, 6, e12404.
[70]	Z. Meng, J. Zhang, H. Long, H. García, L. Zhang, B. Zhu, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202505456.
[71]	M. Zhang, K. Li, C. Hu, K. Ma, W. Sun, X. Huang, Y. Ding, Chin. J. Catal., 2023, 47, 254-264.
[72]	B. Liu, J. Cai, J. Zhang, H. Tan, B. Cheng, J. Xu, Chin. J. Catal., 2023, 51, 204-215.
[73]	B. Lei, W. Cui, J. Sheng, F. Zhong, F. Dong, Small, 2024, 20, 2308088.

Enhanced photocatalytic production of hydrogen and benzaldehyde over a dual-function Zn_xCd_1-_xS_y/FePS₃ S-scheme heterojunction

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 10

References

Related Articles 15

Recommended Articles

Metrics

[1]	Qinghua Liu, Peiqing Cai, Hengshuai Li, Xue-Yang Ji, Dafeng Zhang, Xipeng Pu. Visible-light-driven hydrogen evolution over CdS/CuWO₄ S-Scheme heterojunctions: Dual synergistic enhancement via interfacial charge transfer and photothermal activation [J]. Chinese Journal of Catalysis, 2026, 81(2): 299-309.
[2]	Jiaping Lu, Chao Lin, Chao Li, Hongjie Shi, Nengyi Liu, Wandong Xing, Sibo Wang, Guigang Zhang, Teng-Teng Chen, Xiong Chen. Bipyridine-integrated bisoxazole-based donor-acceptor covalent organic framework for enhanced photocatalytic H₂O₂ synthesis [J]. Chinese Journal of Catalysis, 2026, 81(2): 185-194.
[3]	Yongsheng Hu, Shiji Du, Jihui Lang, Huilian Liu, Xuefei Li, Qi Zhang, Ming Lu, Xin Li, Binrong Li, Maobin Wei, Lili Yang. Rational construction of MXene-derived TiO₂/CoNiO₂ dual-site S-scheme heterojunction for boosting C-C coupling toward efficient photocatalytic CO₂-to-C₂H₄ conversion [J]. Chinese Journal of Catalysis, 2026, 81(2): 227-245.
[4]	Ganghua Zhou, Jie Liu, Longyun Zhang, Chuanzhou Bi, Hangmin Xu, Weiyi Jiang, Xingwang Zhu, Xin Ning, Hui Xu, Xiaozhi Wang. Atomic-level Mn incorporation into Co₃O₄ for selective CO₂ photoreduction in pure water under dilute CO₂ atmosphere [J]. Chinese Journal of Catalysis, 2026, 81(2): 216-226.
[5]	Congcong Wang, Yongkang Quan, Suili Shi, Guorong Wang, Zhiliang Jin. Self-assembling 3D/2D ZnIn₂S₄/CN-NH₄ to construct S-scheme heterojunctions for the efficient production of H₂O₂ in pure water [J]. Chinese Journal of Catalysis, 2026, 81(2): 259-271.
[6]	Zhe Zhang, Guixu Pan, Wei Zhu, Keyu Zhang, Guijie Liang, Shihan Wang, Ning Wang, Yan Xing, Yunfeng Li. Multi-intermolecular forces strengthen interfacial carrier mobility in poly (barbituric acid) all-organic heterojunction systems for efficient solar-to-hydrogen conversion [J]. Chinese Journal of Catalysis, 2026, 81(2): 284-298.
[7]	Xiong Wang, Chao Peng, Yongkang Xiao, Ziye Zhang, Huiping Zheng, Wenjie Yue, Sheng Tian, Xingsheng Hu, Weifan Shao, Guanghui Chen, Binghao Wang, Huijuan Wang, Mingming Yin, Jinxin Li, Yang Li, Lang Chen, Shuangfeng Yin. Surface engineering enhancing activity and stability of Bi₂WO_6-_x for selective C-H bond photooxidation [J]. Chinese Journal of Catalysis, 2026, 81(2): 246-258.
[8]	Na Tian, Chaofan Yuan, Tong Zhou, Wenying Yu, Yinghui Wang, Na Zhang, Yihe Zhang, Hongwei Huang. Defect-coordinated Au nanoparticles in carbon nitride for efficient piezo-photocatalytic hydrogen peroxide production [J]. Chinese Journal of Catalysis, 2026, 81(2): 272-283.
[9]	Bolin Yang, Fei Jin, Zhiliang Jin. Efficient photocatalytic hydrogen production by a heterojunction strategy with covalent organic frameworks loaded with non-precious-metal semiconductors [J]. Chinese Journal of Catalysis, 2026, 81(2): 172-184.
[10]	Miao-Miao Shi, Yue-Xuan He, Ning Zhang, Di Bao, Da-Ming Zhao, Hai-Xia Zhong, Jun-Min Yan, Qing Jiang. Direct electrochemical liquid ammonia splitting for onsite hydrogen generation under room temperature [J]. Chinese Journal of Catalysis, 2026, 81(2): 310-318.
[11]	Shuqi Liang, Zhen Xiao, Jinni Shen, Wenxin Dai, Zizhong Zhang. Tuning radical generation rate for efficient CH₄ photooxidation to CH₃OH over AgPd alloy and Co₃O₄ cascade active sites [J]. Chinese Journal of Catalysis, 2026, 80(1): 189-199.
[12]	Jinpeng Zhang, Teng Liang, Jaenudin Ridwan, Tian Chen, Elhussein M. Hashem, Meijun Guo, Amin Talebian-Kiakalaieh, Le Yu, Ping She, Jingrun Ran. Key components for realistic application of plastic photoreforming coupled with H₂ evolution [J]. Chinese Journal of Catalysis, 2026, 80(1): 20-37.
[13]	Yandong Xu, Zihui Jing, Wenhao Su, Jiale Xu, Mingliang Wang. Synergistic coupling of H₂O₂ production and furoic acid synthesis over B-TiO₂@COF S-scheme bifunctional photocatalyst [J]. Chinese Journal of Catalysis, 2026, 80(1): 135-145.
[14]	Shaodan Wang, Heng Yang, Lijun Xue, Jianjun Zhang, Shuxin Ouyang, Lili Wen. S-scheme heterojunctions of metal-doped ZnIn₂S₄/TpPa-1: Regulating H adsorption/desorption and internal electric field for boosted dual-functional photocatalysis [J]. Chinese Journal of Catalysis, 2026, 80(1): 159-173.
[15]	Xuan Zhang, Lin Zhou, Teng Yan, Xiaohu Zhang, Hao Chen. Fabrication of S-scheme heterojunction between covalent organic frameworks and Ni-ZIF-8 and its photocatalytic hydrogen production performance [J]. Chinese Journal of Catalysis, 2026, 80(1): 200-212.