Carbon dots mediated excitons dissociation in defect engineering for high-efficient visible-light-driven overall H2O2 photosynthesis from pure water

doi:10.1016/S1872-2067(25)64865-0

Abstract

Abstract:

The pursuit of an efficient photocatalytic pathway for hydrogen peroxide (H₂O₂) synthesis from pure water without adding additional sacrifice agents poses a formidable research endeavor and remains a pivotal challenge. Herein, we demonstrate that incorporating hexaketocyclohexane-derived carbon dots (H-CDs) and S vacancies into ZnIn₂S₄ weakens the exciton effect, leading to the dissociation into free carriers that participate in the dual pathways of oxygen reduction reaction and water oxidation reaction, thereby achieving efficient photocatalytic H₂O₂ production with a high H₂O₂ yield of 17.8 mM/g/h under visible light in pure water. Experimental results combined with theoretical calculations clearly illustrate that the presence of H-CDs and S vacancies modulates the local charge density of ZnIn₂S₄, markedly diminishing the exciton binding energy and facilitating the occurrence of exciton dissociation. Moreover, S vacancies and H-CDs effectively capture free electrons and extract free holes, respectively, significantly inhibiting the recombination of photogenerated electron-hole pairs. By optimizing the electronic structure and optical properties of ZnIn₂S₄, they thermodynamically satisfy the conditions for oxygen reduction and water oxidation reactions. Additionally, the synergy between H-CDs and S vacancies in ZnIn₂S₄ enhances the adsorption of oxygen and intermediate products, increasing their participation in the reaction and facilitating the conversion to H₂O₂. This work offers novel insights into catalyst design from the perspective of excitons dissociation, and underscores the distinct roles that free charge carriers play in various pathways for photocatalytic H₂O₂ production.

Key words: Photosynthesis, H₂O₂, Exciton dissociation, Carbon dots, Defect engineering

Kaiqu Sun, Zixuan Guo, Jun Luo, Xueying Wang, Haoyuan Qin, Lijing Wang, Nan Zhao, Changyu Lu, Weilong Shi. Carbon dots mediated excitons dissociation in defect engineering for high-efficient visible-light-driven overall H₂O₂ photosynthesis from pure water[J]. Chinese Journal of Catalysis, 2026, 80: 174-188.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64865-0

https://www.cjcatal.com/EN/Y2026/V80/I1/174

Figures/Tables 8

Fig. 1. (a) Schematic illustration for the preparation process of H-CDs/ZIS-Vs photocatalyst. SEM (b), TEM (c), and HRTEM (d) images of H-CDs/ZIS-Vs-4. XRD patterns (e), high-resolution S 2p XPS spectra (f), and EPR spectra (g) of as-prepared samples.

Fig. 2. UV-vis DRS (a), band gap energies (inset shows VB-XPS spectra) (b) and the corresponding energy band structures (c) of ZIS, ZIS-Vs and H-CDs/ZIS-Vs-4. Concentration of photocatalytic H2O2 production curves (d) and photocatalytic H2O2 evolved rate (e) of various catalysts under visible light irradiation. (f) Repeated photocatalytic H2O2 production over H-CDs/ZIS-Vs-4 under visible light irradiation. (g) Photocatalytic H2O2 production of various catalysts under different conditions. (h) Summary of recently reported photocatalytic H2O2 production under visible light irradiation.

Fig. 3. (a) Charge density difference (CDD) calculation results of ZIS, ZIS-Vs and H-CDs/ZIS-Vs-4. Steady-state PL spectra with a function of temperature of ZIS (b), ZIS-Vs (c) and H-CDs/ZIS-Vs-4 (d). Low-temperature steady-state PH spectra (77 K) (e), and low-temperature time-resolved PH spectra (77 K) (f) of ZIS, ZIS-Vs and H-CDs/ZIS-Vs-4. (g) Illustration of the excitonic behaviors in H-CDs/ZIS-Vs.

Fig. 4. Steady-state SPV spectra (a) and TPV spectra (b) of ZIS, ZIS-Vs and H-CDs/ZIS-Vs-4. Maximum extraction rate (tmax) of charge (c), maximum charge extraction efficiency (A) (d), electron attenuation constants (τ) (e) of charge recombination process and the number of effective charges (Aeff) (f) for ZIS, ZIS-Vs and H-CDs/ZIS-Vs-4 based on TPV spectra.

Fig. 5. Pseudo-colored TAS spectra of ZIS (a), ZIS-Vs (d) and H-CDs/ZIS-Vs-4 (g). TAS spectra with different delay times of ZIS (b), ZIS-Vs (e) and H-CDs/ZIS-Vs-4 (h) under the pump excitation of 320 nm. Fitting curves of TAS decay dynamics of ZIS (c), ZIS-Vs (f) and H-CDs/ZIS-Vs-4 (i) at 553 nm.

Fig. 6. PL spectra (a), TRPL spectra (b), photocurrent response curves (c) and EIS Nyquist plots (d) of ZIS, ZIS-Vs and H-CDs/ZIS-Vs-4. (e) RRDE polarization curves at different rotation rates (ω = 600, 900, 1200 and 1600 rpm) over H-CDs/ZIS-Vs-4 sample. H2O2 selectivity (f) and the corresponding number of electron transfer (g) over ZIS, ZIS-Vs and H-CDs/ZIS-Vs-4. (h) TPD-O2 profiles of ZIS, ZIS-Vs and H-CDs/ZIS-Vs-4.

Fig. 7. (a) Theoretical calculation of adsorbed O2 environment charge density difference (CDD) for ZIS, ZIS-Vs and H-CDs/ZIS-Vs. (b) Adsorption energy of H+, O2, *O2 and *OOH of ZIS, ZIS-Vs and H-CDs/ZIS-Vs. Calculated free-energy diagrams of oxygen reduction (c) and water oxidation (d) processes linked to H2O2 production. (e) In-situ DRIFT spectra of H-CDs/ZIS-Vs-4 recorded during the photoreaction.

Fig. 8. Schematic illustration of the photocatalytic H2O2 production mechanism based on H-CDs/ZIS-Vs composite photocatalyst.

References

[1]	Y. Kondo, Y. Kuwahara, K. Mori, H. Yamashita, Chem, 2022, 8, 2924-2938.
[2]	Y. Wu, Y. Yang, M. Gu, C. Bie, H. Tan, B. Cheng, J. Xu, Chin. J. Catal., 2023, 53, 123-133.
[3]	R. He, D. Xu, X. Li, J. Mater. Sci. Technol., 2023, 138, 256-258.
[4]	H. Lv, Z. Li, P. Yin, P. Wan, M. Zhu, Chin. Chem. Lett., 2025, 36, 110457.
[5]	M. Xu, Z. Li, R. Shen, X. Zhang, Z. Zhang, P. Zhang, X. Li, Chin. J. Catal., 2025, 70, 431-443.
[6]	H. Zhang, J. Liu, Y. Zhang, B. Cheng, B. Zhu, L. Wang, J. Mater. Sci. Technol., 2023, 166, 241-249.
[7]	B. Xia, G. Liu, K. Fan, R. Chen, X. Liu, L. Li, Chin. J. Catal., 2025, 69, 315-326.
[8]	X. Fang, X. Huang, Q. Hu, B. Li, C. Hu, B. Ma, Y. Ding, Chem. Commun., 2024, 60, 5354-5368.
[9]	T. Tian, W. Wang, Y. Wang, K. Li, Y. Li, W. Fu, Y. Ding, Chin. J. Catal., 2024, 67, 176-185.
[10]	X. Fang, B. Li, J. Huang, C. Hu, X. Yang, P. Feng, X. Dong, J. Wu, Y. Li, Y. Ding, Energy Environ. Sci., 2025, 18, 6202-6213.
[11]	Y.-Y. Tang, X. Luo, R.-Q. Xia, J. Luo, S.-K. Peng, Z.-N. Liu, Q. Gao, M. Xie, R.-J. Wei, G.-H. Ning, D. Li, Angew. Chem. Int. Ed., 2024, 63, e202408186.
[12]	L. Zheng, Z. Wang, H. Zhang, Y. Shi, F. Wang, Z. Wang, D. Lin, J. Yue, Q. Wang, Appl. Catal. B, 2024, 347, 123811.
[13]	B. Zhu, J. Liu, J. Sun, F. Xie, H. Tan, B. Cheng, J. Zhang, J. Mater. Sci. Technol., 2023, 162, 90-98.
[14]	T. Hu, P. Feng, H. Chu, T. Gao, F. Liu, W. Zhou, Chin. J. Catal., 2025, 69, 123-134.
[15]	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.
[16]	C. Ai, B. Luo, C. Zhang, Y. Wang, B. Wang, L. Ma, D. Jing, J. Mater. Sci. Technol., 2024, 196, 237-247.
[17]	W. Zhang, Z. Li, X.-F. Yu, K. Zhang, S. Liu, Y. Du, Q. Guo, L. Zhang, X. Ding, H. Tang, Y. Peng, X. Yang, Inorg. Chem., 2024, 63, 2954-2966.
[18]	H. Mao, Y. Liu, Z. Xu, Z. Bian, Chin. J. Catal., 2024, 61, 247-258.
[19]	W. Han, H. Zhang, D. Li, W. Qin, X. Zhang, S. Wang, X. Duan, Appl. Catal. B, 2024, 350, 123918.
[20]	L. Zdražil, A. Cadranel, M,. Medved‘, M. Otyepka, R. Zbořil, D. M. Guldi, Chem, 2024, 10, 2700-2723.
[21]	W. Ren, N. Li, Q. Chang, J. Wu, J. Yang, S. Hu, Z. Kang, Chin. J. Catal., 2024, 62, 178-189.
[22]	Z. Wu, X. Li, Y. Zhao, Y. Li, K. Wei, H. Shi, T. Zhang, H. Huang, Y. Liu, Z. Kang, ACS Appl. Mater. Interfaces, 2021, 13, 60561-60570.
[23]	T. He, J. Wu, Y. Li, K. Wei, Y. Liu, H. Huang, Y. Liu, Z. Kang, Chem. Eng. J., 2023, 451, 138551.
[24]	K. Sun, H. Yuan, Y. Yan, H. Qin, L. Sun, L. Tan, F. Guo, X. Du, W. Shi, J. Water Process. Eng., 2024, 58, 104803.
[25]	J. Chen, S.-J. Wu, W.-J. Cui, Y.-H. Guo, T.-W. Wang, Z.-W. Yao, Y. Shi, H. Zhao, J. Liu, Z.-Y. Hu, Y. Li, J. Colloid Interface Sci., 2022, 608, 504-512.
[26]	C. Long, S. Liu, X. Li, J. Zhu, L. Zhang, T. Qing, P. Zhang, B. Feng, Chem. Eng. J., 2022, 432, 134315.
[27]	H. Peng, H. Yang, J. Han, X. Liu, D. Su, T. Yang, S. Liu, C.-W. Pao, Z. Hu, Q. Zhang, Y. Xu, H. Geng, X. Huang, J. Am. Chem. Soc., 2023, 145, 27757-27766.
[28]	X. Wu, G. Chen, L. Li, J. Wang, G. Wang, J. Mater. Sci. Technol., 2023, 167, 184-204.
[29]	Y. Zhao, L. Xu, X. Wang, Z. Wang, Y. Liu, Y. Wang, Q. Wang, Z. Wang, H. Huang, Y. Liu, W.-Y. Wong, Z. Kang, Nano Today, 2022, 43, 101428.
[30]	Q. Si, W. Guo, H. Wang, B. Liu, S. Zheng, Q. Zhao, H. Luo, N. Ren, T. Yu, Appl. Catal. B, 2021, 299, 120694.
[31]	X. Li, G. Zhang, N. Li, Q. Xu, H. Li, J. Lu, D. Chen, Adv. Funct. Mater., 2024, 34, 2316773-2316784.
[32]	H. Jia, X. Shao, Y.-N. Wang, J. Zhang, R. Li, T. Peng, Appl. Catal. B, 2024, 353, 124090.
[33]	H. Yuan, W. Shi, J. Lu, J. Wang, Y. Shi, F. Guo, Z. Kang, Chem. Eng. J., 2023, 454, 140442.
[34]	J. Wang, D. Liu, M. Li, X. Gu, S. Wu, J. Zhang, Chin. J. Catal., 2024, 63, 202-212.
[35]	D. Yang, Y. Li, R. Chen, X. Wang, Z. Li, T. Xing, L. Wei, S. Xu, P. Dai, M. Wu, J. Mater. Sci. Technol., 2024, 183, 23-31.
[36]	T. Tang, J. Zhao, Y. Shen, F. Yang, S. Yao, C. An, Appl. Catal. B, 2024, 346, 123721.
[37]	C. Shao, Q. He, M. Zhang, L. Jia, Y. Ji, Y. Hu, Y. Li, W. Huang, Y. Li, Chin. J. Catal., 2023, 46, 28-35.
[38]	Y. Yang, C. Wang, Y. Li, K. Liu, H. Ju, J. Wang, R. Tao, J. Mater. Sci. Technol., 2024, 200, 185-214.
[39]	Z. Yu, D. Zhang, C. Ai, J. Zhang, Q. Xiang, Chin. J. Catal., 2024, 67, 71-81.
[40]	Y. Huang, M. Shen, H. Yan, Y. He, J. Xu, F. Zhu, X. Yang, Y.-X. Ye, G. Ouyang, Nat. Commun., 2024, 15, 5406.
[41]	H. Zhang, Z. Wang, J. Zhang, K. Dai, Chin. J. Catal., 2023, 49, 42-67.
[42]	W. Zhang, W. Huang, B. Wu, J. Yang, J. Jin, S. Zhang, Coord. Chem. Rev., 2023, 491, 215235.
[43]	L. Xia, K. Zhang, X. Wang, Q. Guo, Y. Wu, Y. Du, L. Zhang, J. Xia, H. Tang, X. Zhang, Y. Peng, Z. Li, X. Yang, Appl. Catal. B, 2023, 325, 122387.
[44]	M. Xu, R. Wang, H. Fu, Y. Shi, L. Ling, Proc. Natl. Acad. Sci. USA, 2024, 121, e2318787121.
[45]	Y. Shi, Z. Yang, L. Shi, H. Li, X. Liu, X. Zhang, J. Cheng, C. Liang, S. Cao, F. Guo, X. Liu, Z. Ai, L. Zhang, Environ. Sci. Technol., 2022, 56, 14478-14486.
[46]	W. Xu, B. Wang, S. Liu, W. Fang, Q. Jia, J. Liu, C. Bo, X. Yan, Y. Li, L. Chen, Nat. Commun., 2024, 15, 4415.
[47]	X. Fang, Y. Tang, Y.-J. Ma, G. Xiao, P. Li, D. Yan, Sci. China Mater., 2023, 66, 664-671.
[48]	H. Wang, S. Jiang, S. Chen, D. Li, X. Zhang, W. Shao, X. Sun, J. Xie, Z. Zhao, Q. Zhang, Y. Tian, Y. Xie, Adv. Mater., 2016, 28, 6940-6945.
[49]	Z. Li, Z. Zhang, X. Zhu, C. Meng, Z. Dong, S. Xiao, Y. Wang, Y. Wang, X. Cao, Y. Liu, Appl. Catal. B, 2023, 332, 122751.
[50]	F. Qin, Y. Kang, X. San, Y.-L. Tang, J. Li, X. Zhang, K. Zhang, G. Liu, J. Am. Chem. Soc., 2025, 147, 12897-12907.
[51]	H. Yuan, H. Sun, Y. Shi, J. Wang, A. Bian, Y. Hu, F. Guo, W. Shi, X. Du, Z. Kang, Chem. Eng. J., 2023, 472, 144654.
[52]	Q. Chen, Y. Liu, B. Mao, Z. Wu, W. Yan, D. Zhang, Q. Li, H. Huang, Z. Kang, W. Shi, Adv. Funct. Mater., 2023, 33, 2305318.
[53]	I. H. M. van Stokkum, C. C. Jumper, J. J. Snellenburg, G. D. Scholes, R. van Grondelle, P. Malý, J. Chem. Phys., 2016, 145, 174201.
[54]	C. Xu, K. Lin, D. Hu, F.-L. Gu, M. F. Gelin, Z. Lan, J. Phys. Chem. Lett., 2022, 13, 661-668.
[55]	W. Wang, Y. Tao, L. Du, Z. Wei, Z. Yan, W. K. Chan, Z. Lian, R. Zhu, D. L. Phillips, G. Li, Appl. Catal. B, 2021, 282, 119568.
[56]	W. Li, Z. Wei, K. Zhu, W. Wei, J. Yang, J. Jing, D. L. Phillips, Y. Zhu, Appl. Catal. B, 2022, 306, 121142.
[57]	X.-J. Li, M.-Y. Qi, J.-Y. Li, C.-L. Tan, Z.-R. Tang, Y.-J. Xu, Chin. J. Catal., 2023, 51, 55-65.
[58]	J. Hu, M. Zhu, Z. Ali Ghazi, Y. Cao, Chin. J. Catal., 2025, 71, 319-329.
[59]	K. Zhang, M. Dan, J. Yang, F. Wu, L. Wang, H. Tang, Z. Q. Liu, Adv. Funct. Mater., 2023, 33, 2302964.
[60]	M. Cai, Y. Liu, K. Dong, X. Chen, S. Li, Chin. J. Catal., 2023, 52, 239-251.
[61]	M. Song, X. Song, X. Liu, W. Zhou, P. Huo, Chin. J. Catal., 2023, 51, 180-192.
[62]	Z. G. Tai, G. T. Sun, X. H. Zhang, X. B. Yang, T. Wang, Z. Y. Fang, Q. Ye, L. C. Jia, H. Q. Wang, J. Mater. Sci. Technol., 2023, 166, 113-122.
[63]	Y. Cheng, J. Jin, H. Yan, G. Zhou, Y. Xu, L. Tang, X. Liu, H. Li, K. Zhang, Z. Lu, Angew. Chem. Int. Ed., 2024, 63, e202400857.
[64]	Y. Xu, X. Hu, Y. Chen, S. Lin, C. Wang, F. Gou, X. Yang, W. Zheng, D.-K. Ma, Adv. Sci., 2024, 11, 2304948.
[65]	A. Meng, X. Ma, D. Wen, W. Zhong, S. Zhou, Y. Su, Chin. J. Catal., 2024, 60, 231-241.
[66]	C. Zhao, X. Wang, Y. Yin, W. Tian, G. Zeng, H. Li, S. Ye, L. Wu, J. Liu, Angew. Chem. Int. Ed., 2023, 62, e202218318.
[67]	J.-Z. Xiao, Z.-H. Zhao, N.-N. Zhang, H.-T. Che, X. Qiao, G.-Y. Zhang, X. Chu, Y. Wang, H. Dong, F.-M. Zhang, Chin. J. Catal., 2025, 69, 219-229.

Carbon dots mediated excitons dissociation in defect engineering for high-efficient visible-light-driven overall H₂O₂ photosynthesis from pure water

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 8

References

Related Articles 15

Recommended Articles

Metrics

[1]	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.
[2]	Shinuo Liang, Fengjun Li, Fei Huang, Xinyu Wang, Shengwei Liu. Modulating electronic structure of g-C₃N₄ hosted Co-N₄ active sites by axial phosphorus coordination for efficient overall H₂O₂ photosynthesis from oxygen and water [J]. Chinese Journal of Catalysis, 2025, 76(9): 81-95.
[3]	Li Yuanrui, Zhang Xiaolei, Li Tong, Hu Cheng, Chen Fang, Cai Hao, Huang Hongwei. Few-layer oxygen vacant Bi₂O₂(OH)NO₃ for dual-channel piezocatalytic H₂O₂ production from H₂O and air [J]. Chinese Journal of Catalysis, 2025, 75(8): 105-114.
[4]	Chongbei Wu, Feihong Chu, Yongchao Hao, Xuan Li, Xiaoyue Jia, Yifan Sun, Jiaxuan Gu, Pengfei Jia, Aobing Wang, Jizhou Jiang. Dual O₂ reduction centers of COFs boosting H₂O₂ photosynthesis [J]. Chinese Journal of Catalysis, 2025, 74(7): 329-340.
[5]	Han Li, Wang Wang, Kaiqiang Xu, Bei Cheng, Jingsan Xu, Shaowen Cao. Solar-driven H₂O₂ production by S-scheme heterojunction photocatalyst [J]. Chinese Journal of Catalysis, 2025, 72(5): 24-47.
[6]	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.
[7]	Shuhao Wei, Guojun Lan, Yiyang Qiu, Di Lin, Wei Kong, Ying Li. Advances in metal-free carbon catalysts for acetylene hydrochlorination: From heteroatom doping to intrinsic defects over the past decade [J]. Chinese Journal of Catalysis, 2025, 70(3): 8-43.
[8]	Mingyang Xu, Zhenzhen Li, Rongchen Shen, Xin Zhang, Zhihong Zhang, Peng Zhang, Xin Li. Constructing S-scheme heterojunction between porphyrinyl covalent organic frameworks and Nb₂C MXene for photocatalytic H₂O₂ production [J]. Chinese Journal of Catalysis, 2025, 70(3): 431-443.
[9]	Hongfen Li, Yihe Zhang, Jianming Li, Qing Liu, Xiaojun Zhang, Youpeng Zhang, Hongwei Huang. Boosting H₂O₂ evolution of CdS via constructing a ternary photocatalyst with earth-abundant halloysite nanotubes and NiS co-catalyst [J]. Chinese Journal of Catalysis, 2025, 69(2): 111-122.
[10]	Jian-Zhou Xiao, Zhi-Hao Zhao, Nan-Nan Zhang, Hong-Tu Che, Xiu Qiao, Guang-Ying Zhang, Xiaoyu Chu, Ya Wang, Hong Dong, Feng-Ming Zhang. Linkage engineering in covalent organic frameworks for overall photocatalytic H₂O₂ synthesis from water and air [J]. Chinese Journal of Catalysis, 2025, 69(2): 219-229.
[11]	Bingquan Xia, Gaoxiong Liu, Kun Fan, Rundong Chen, Xin Liu, Laiquan Li. Boosting hydrogen peroxide photosynthesis via a 1D/2D S-scheme heterojunction constructed by a covalent triazine framework with dual O₂ reduction centers [J]. Chinese Journal of Catalysis, 2025, 69(2): 315-326.
[12]	Lihong Tan, Xinhe Wu, Jiachao Xu, Mahmoud Sayed, Guohong Wang. Na₂CO₃-assisted synthesis of Na-doped crystalline/amorphous g-C₃N₄ S-scheme homojunction photocatalyst for enhanced H₂O₂ production [J]. Chinese Journal of Catalysis, 2025, 79(12): 174-185.
[13]	Qianqian Shen, Chenlong Dong, Shilong Feng, Xueli Zhang, Qiurong Li, Jinbo Xue. The synergistic effect of non-compensated Cu/N co-doping and graphene enhances the dual-channel generation of H₂O₂ over TiO₂ photocatalysts [J]. Chinese Journal of Catalysis, 2025, 78(11): 252-264.
[14]	Wenhui Qi, Xiuyan Li, Shaonan Gu, Bin Sun, Yinan Wang, Guowei Zhou. Electronic structure modulation of metal based organic catalysts for photocatalytic H₂O₂ production [J]. Chinese Journal of Catalysis, 2025, 77(10): 45-69.
[15]	Xianglin Xiang, Bei Cheng, Bicheng Zhu, Chuanjia Jiang, Guijie Liang. High-entropy alloy nanocrystals boosting photocatalytic hydrogen evolution coupled with selective oxidation of cinnamyl alcohol [J]. Chinese Journal of Catalysis, 2025, 68(1): 326-335.