Mechanistic Insights into S-Doped g-C3N4 for Enhanced Photocatalytic Performance: A Theoretical Study

doi:10.1007/s40242-025-5187-5

Chemical Research in Chinese Universities ›› 2025, Vol. 41 ›› Issue (5): 1067-1075.doi: 10.1007/s40242-025-5187-5

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Mechanistic Insights into S-Doped g-C₃N₄ for Enhanced Photocatalytic Performance: A Theoretical Study

YANG Yufei^1,2, ZHAO Yi², YIN Lifang², ZHAO Jiaying², GAO Qiang², SU Tan², ZHANG Heyang², YIN Yajun², SU Zhongmin¹, ZOU Luyi²

1. School of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Changchun 130012, P. R. China;
2. Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, P. R. China

Received:2025-08-31 Accepted:2025-09-09 Online:2025-10-01 Published:2025-09-26
Contact: SU Zhongmin, E-mail: zmsu@nenu.edu.cn;ZOU Luyi, E-mail: zouly@jlu.edu.cn E-mail:zmsu@nenu.edu.cn;zouly@jlu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (No. 22573039) and the International Science and Technology Cooperation Project of Jilin Provincial Department of Science and Technology, China (No. 20240402047GH).

Abstract

Abstract: Non-metal doping is an effective strategy to modulate the electronic structure of graphitic carbon nitride (g-C₃N₄) and optimize its photocatalytic activity. Based on first-principles density functional theory, this work calculated the formation energy, electronic properties, and optical performance of S-doped monolayer g-C₃N₄. The results demonstrate that S atoms preferentially occupy interstitial sites, as characterized by low formation energy and thermodynamic spontaneity, which leads to stabilization, followed by the edge N2-sites. After introducing S impurities via the N2 and interstitial doping sites, the band gap of g-C₃N₄ is narrowed from 2.63 eV (calculated by the HSE06 functional) to 2.35 eV (for N2-site doping) and 1.99 eV (for interstitial-site doping), respectively. Both C₃N₄-N2 and S-interstitial doping enhance the delocalization of the highest occupied molecular orbital and the lowest unoccupied molecular orbital. Specifically, interstitial S atoms act as "bridges" to connect adjacent structural units, significantly improving carrier mobility and facilitating the separation of photogenerated electron-hole pairs. Furthermore, S-interstitial doping reduces the work function of g-C₃N₄ from 4.16 eV to 3.64 eV, which strengthens visible light absorption. This work provides theoretical support for the design and preparation of non-metal-doped modified g-C₃N₄ photocatalysts.

Key words: Sulfur doping, g-C₃N₄, Photocatalytic mechanism, First-principles calculation, Doping site

YANG Yufei, ZHAO Yi, YIN Lifang, ZHAO Jiaying, GAO Qiang, SU Tan, ZHANG Heyang, YIN Yajun, SU Zhongmin, ZOU Luyi. Mechanistic Insights into S-Doped g-C₃N₄ for Enhanced Photocatalytic Performance: A Theoretical Study[J]. Chemical Research in Chinese Universities, 2025, 41(5): 1067-1075.

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Mechanistic Insights into S-Doped g-C₃N₄ for Enhanced Photocatalytic Performance: A Theoretical Study

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