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.

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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.

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

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