Alkali-cyano dual-tailored g-C3N4/BiOCl S-scheme heterojunctions for highly efficient visible-light-driven H2O2 photosynthesis in pure water

doi:10.1016/S1872-2067(25)64893-5

Abstract

Abstract:

Efficient and sustainable photocatalytic hydrogen peroxide (H₂O₂) synthesis is crucial due to its role as an eco-friendly oxidant and the limitations of conventional industrial methods. Graphitic carbon nitride (g-C₃N₄) is a promising photocatalyst but suffers from inefficient charge separation and limited visible light absorption. This study introduces a dual-modified g-C₃N₄, incorporating Na⁺/K⁺ ions and cyano groups, coupled with ultrathin BiOCl nanosheets to form an S-scheme heterojunction (CN-NH-NaK/BiOCl). The modification enhances the electronic structure, visible light absorption, and charge separation. The CN-NH-NaK/BiOCl photocatalyst achieved an outstanding H₂O₂ production rate of 33.15 mmol·g^‒1·h^‒1 under visible light (λ ≥ 400 nm), outperforming pristine g-C₃N₄ (118-fold) and BiOCl (83-fold), and surpassing all previously reported g-C₃N₄- and BiOCl-based photocatalysts. Even in pure water, the production rate reached 5.18 mmol·g^‒1·h^‒1, exceeding that of most previously reported catalysts. Comprehensive characterization revealed an efficient S-scheme charge transfer mechanism, enabling selective 2e^‒ oxygen reduction reaction (94.06% selectivity) and water oxidation. The heterojunction demonstrated excellent stability, reusability, and enhanced degradation of tetracycline hydrochloride. This work provides a promising strategy for advanced S-scheme photocatalysts in sustainable H₂O₂ production and environmental remediation.

Key words: S-scheme heterojunction, H₂O₂ photosynthesis, g-C₃N₄, BiOCl

Ziyi Liao, Lan Jiang, Yang Yang, Lin Wang, Weiyou Yang, Huilin Hou. Alkali-cyano dual-tailored g-C₃N₄/BiOCl S-scheme heterojunctions for highly efficient visible-light-driven H₂O₂ photosynthesis in pure water[J]. Chinese Journal of Catalysis, 2026, 83: 143-161.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64893-5

https://www.cjcatal.com/EN/Y2026/V83/I4/143

Figures/Tables 9

Fig. 1. (a) Schematic diagram of the preparation process for CN-NH-NaK/BiOCl. SEM (b), TEM (c), and HRTEM (d) images of CN-NH-NaK/BiOCl. XRD patterns (e), FT-IR spectra (f), and N2 adsorption-desorption isotherms (g) of the as-prepared photocatalysts.

Fig. 2. (a) XPS survey spectra of the as-prepared photocatalysts. High-resolution XPS spectra of C 1s (b), N 1s (c), Bi 4f (d), O 1s (e), and Cl 2p (f).

Fig. 3. UV-vis DRS (a) and the corresponding Tauc plots (b) of BiOCl and CN-NH-NaK. VB-XPS spectra of BiOCl (c) and CN-NH-NaK (d). UPS spectra of BiOCl (e) and CN-NH-NaK (f). Work functions of BiOCl (g) and CN-NH-NaK (h) calculated based on the DFT theory.

Fig. 4. (a-e) Quasi-in-situ XPS spectra of CN-NH-NaK/BiOCl catalysts under dark and light illumination conditions. (f) Schematic diagram of the electron-transfer process between CN-NH-NaK and BiOCl. (g-i) Schematic diagram of the S-scheme heterojunction formed by BiOCl and CN-NH-NaK.

Fig. 5. (a) Photocatalytic H2O2 production by the photocatalyst in the presence of isopropanol as a sacrificial agent. (b) Comparison of H2O2 production rates among different photocatalysts. (c) Wavelength-dependent H2O2 evolution rate and the corresponding AQY values. (d) Cyclic stability of H2O2 generation over the CN-NH-NaK/BiOCl photocatalyst. (e) Photocatalytic decomposition of H2O2 by the photocatalyst. (f) Comparison of the H2O2 production rate (Kp) and decomposition rate (Kd). (g) Photocatalytic H2O2 production over CN-NH-NaK/BiOCl photocatalysts tested under different light condition. (h) Photocatalytic H2O2 production by the photocatalyst in pure water. (i) Comparison of H2O2 production rates in pure water among different photocatalysts. (j) Comparison of the photocatalytic H2O2 performance of the CN-NH-NaK/BiOCl photocatalyst with that of other reported photocatalysts.

Fig. 6. KPFM of BiOCl (a), CN-NH-NaK (b), and CN-NH-NaK/BiOCl (c); EIS Nyquist plots (d) and photocurrent responses (e) of as-prepared photocatalysts. (f,g) PL spectra and TRPL spectra of the as-prepared photocatalysts. (h-k) Proposed structural models for BCN, CN-NH-NaK, BiOCl, and CN-NH-NaK/BiOCl.

Fig. 7. EPR trapping experiments under dark (a) and light (b) conditions of BCN, BiOCl, CN-NH-NaK and CN-NH-NaK/BiOCl, respectively. H2O2 selectivity as a function of the applied potential (c) and the calculated average number of transferred electrons (n) (d) of the catalyst.

Fig. 8. (a,b) In-situ infrared spectroscopy monitoring of the photocatalytic H2O2 production process on CN-NH-NaK/BiOCl. (c) Optimized adsorption configurations for CN-NH-NaK, BiOCl and CN-NH-NaK/BiOCl. (d) Comparison of the Gibbs free energy changes for each step of the photocatalytic 2-electron ORR. (e-g) Charge density differences between the adsorbed *OOH intermediate and each sample. (h) Proposed mechanism of photocatalytic H2O2 production on CN-NH-NaK/BiOCl in pure water.

Fig. 9. (a) Degradation activity of different synthesized samples for the coupled photocatalytic production of hydrogen peroxide for the degradation of TH. (b) The corresponding first-order kinetic curves. (c) Comparison of corresponding degradation rates. (d) Photocatalytic coupled hydrogen peroxide production degradation of TH by CN-NH-NaK/BiOCl compared with the experiment of photocatalytic degradation of TH alone. (e) The corresponding first-order kinetic curves. (f) Comparison of corresponding degradation rates.

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Alkali-cyano dual-tailored g-C₃N₄/BiOCl S-scheme heterojunctions for highly efficient visible-light-driven H₂O₂ photosynthesis in pure water

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