Recent advances in g-C3N4-based S-scheme photocatalyst

doi:10.1016/S1872-2067(26)65252-7

Chinese Journal of Catalysis ›› 2027, Vol. 92: 37-64.DOI: 10.1016/S1872-2067(26)65252-7

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Recent advances in g-C₃N₄-based S-scheme photocatalyst

Shike Wang^a^,¹, Man Lang^a^,¹, Feng Wang^b^,^*(), Pengfei Xia^a^,^*(), Dieqing Zhang^a^,^*()

^a The Education Ministry Key Laboratory of Resource Chemistry,Joint International Research Laboratory of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, College of Chemistry and Materials Science, Shanghai Normal University, Shanghai 200234, China
^b Electronics and Photonics Materials, Department of Physics, Chemistry, and Biology (IFM), Linköping University, Linköping 58183, Sweden

Received:2026-08-11 Accepted:2026-08-21 Online:2027-01-02 Published:2026-10-30
Contact: *E-mail: dqzhang@shnu.edu.cn (D. Zhang),
forsky@shnu.edu.cn (P. Xia),
feng.wang@liu.se (F. Wang).
About author:Feng Wang received his PhD from The Chinese University of Hong Kong. Since 2023, he has been an Associate Professor in the Department of Physics, Chemistry and Biology at Linköping University, Sweden. He has previously been awarded a VINNMER Fellowship (Sweden, 2017), a Marie Skłodowska-Curie Fellowship (European Commission, 2018), and an Åforsk Entrepreneurship Scholarship (Sweden, 2023). His research has been supported by funding from the Swedish Research Council, STINT, the Formas Network Grant, Olle Engkvists Stiftelse, Carl Tryggers Stiftelse, and the Swedish Government Strategic Research Area in Materials Science at Linköping University. His research interests focus on developing novel materials for sustainable energy technologies, particularly solar cells and photocatalytic hydrogen production through water splitting. Feng Wang has co-authored more than 100 peer-reviewed publications in high-impact journals, which have received over 11,000 citations with an h-index of 49.
Pengfei Xia (College of Chemistry and Materials Science, Shanghai Normal University) holds a Ph.D. degree and is currently engaged in teaching and research at Shanghai Normal University. Prior to joining Shanghai Normal University, He worked at the University of Electronic Science and Technology of China. His research mainly focuses on semiconductor photocatalysis and solar-energy conversion, particularly photocatalytic H₂ evolution and CO₂ conversion, with emphasis on the design of heterojunction photocatalysts, regulation of interfacial charge transfer, and elucidation of photocatalytic reaction mechanisms. He has led research projects supported by the National Natural Science Foundation of China, the National Postdoctoral Program for Innovative Talents, and the China Postdoctoral Science Foundation. His research has been published in leading journals including Advanced Materials, Angewandte Chemie International Edition, Advanced Functional Materials, and Nanoscale. His recent work focuses on regulating interfacial electronic structures and charge-transfer pathways to improve the efficiency and selectivity of photocatalytic energy conversion.
Dieqing Zhang (College of Chemistry and Materials Science, Shanghai Normal University) received her Ph.D. degree from The Chinese University of Hong Kong. She has been awarded the National Science Fund for Excellent Young Scholars and the Shanghai Eastern Talent Leading Project, and has received multiple honors, including the March 8th Red-Banner Pacesetter of the Shanghai Education System, Shanghai Young Top Talent, the Pujiang Talent Program, Shuguang Scholar, and Young Science and Technology Rising Star. Her research focuses on environmental chemistry and atmospheric pollution control chemistry, with particular emphasis on the deep purification and resource utilization of nitrogen oxide pollutants. Her work centers on the precise design of catalysts and the elucidation of conversion mechanisms, providing fundamental and applied support for the development of self-purifying and intelligent cities in alignment with the “Beautiful China” initiative. She has published more than 100 SCI-indexed papers as first or corresponding author in leading journals, including Nature Communications, Journal of the American Chemical Society, Angewandte Chemie International Edition, Advanced Materials, Advanced Energy Materials, Advanced Functional Materials, and Environmental Science & Technology. She serves as an Editorial Board Member in the field of Environmental Chemistry for Chinese Chemical Letters. As a key contributor, she has received several major awards, including the First Prize of the “Industry-University-Research Cooperative Innovation Achievement Award” from the China Association for Promoting Industrial-University-Research Cooperation, the First and Second Prizes of the Shanghai Natural Science Award, and the Third Prize of the Shanghai Science and Technology Progress Award.
First author contact:
¹ Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22376142);National Natural Science Foundation of China(22305157);National Natural Science Foundation of China(22022608);National Natural Science Foundation of China(22176127);Shanghai Eastern Talent Plan Leading Project(LJ2024115);Shanghai Engineering Research Center of Green Energy Chemical Engineering(18DZ2254200);“111” Innovation and Talent Recruitment Base on Photochemical and Energy Materials(D18020)

Abstract

Abstract:

Benefiting from Fermi level equilibration, interfacial band bending, and built-in electric fields, S-scheme heterostructures achieve efficient interfacial charge separation while preserving the robust redox capability of photogenerated charge carriers. This review systematically clarifies the evolutionary logic of heterojunction charge transfer models, spanning from conventional type-II and diverse Z-scheme configurations to advanced S-scheme heterostructures, and elaborates the core interfacial semiconductor physics governing S-scheme systems. A comprehensive overview is provided on the experimental characterization and theoretical verification techniques for identifying S-scheme charge transfer pathways, including density functional theory simulations, Kelvin probe force microscopy, in-situ X-ray photoelectron spectroscopy, femtosecond transient absorption spectroscopy, and electron paramagnetic resonance. On this basis, the unique superiority of graphitic carbon nitride (g-C₃N₄) as a reduction photocatalyst (RP) in S-scheme systems is thoroughly analyzed from the perspectives of thermodynamic band structure, interfacial charge redistribution, layered structural compatibility, and flexible surface modification. Furthermore, this paper summarizes the state-of-the-art advances of g-C₃N₄-based S-scheme photocatalysts for typical catalytic reactions, including photocatalytic H₂ evolution, H₂O₂ production, photoreductive CO₂ conversion, bacterial disinfection, and organic pollutant degradation. Corresponding reaction-oriented structural optimization strategies are also categorized and discussed, involving dimensional matching engineering, active site regulation, homojunction construction, and bifunctional redox coupling design. Finally, the key bottlenecks that restrict the practical application of g-C₃N₄-based S-scheme photocatalysts are highlighted.

Key words: Photocatalysis, g-C3N4, S-scheme heterojunction, Structure-activity relationship, Applications

Shike Wang, Man Lang, Feng Wang, Pengfei Xia, Dieqing Zhang. Recent advances in g-C₃N₄-based S-scheme photocatalyst[J]. Chinese Journal of Catalysis, 2027, 92: 37-64.

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Figures/Tables 22

Fig. 1. Schematic illustration of the band alignment at the OP/RP interface. The opposite curvature of Ec/v(x) on the two sides is determined by the sign of ρ(x), leading to negative charge accumulation in the OP side and positive charge accumulation in the RP side, with depletion widths of dOP and dRP, respectively, and a built-in electric field E(x) < 0.

Fig. 2. Development of charge-transfer mechanisms in heterojunction photocatalysis, including conventional liquid-phase Z-scheme (a), single-component semiconductor (b), type-II heterojunction (c), all-solid-state Z-scheme (d), direct Z-scheme (e), and S-scheme heterojunction (f).

Fig. 3. Charge transfer route in an S-scheme heterojunction.

Fig. 4. Band-edge positions of g-C3N4 and relevant redox potentials at pH = 7 (vs. NHE).

Fig. 5. Representative schematics related to the structural features of g-C3N4. (a) Surface/interface active sites of g-C3N4, showing different nitrogen species and surface-modified structures. (b) Schematic illustration of Au anchored on amino-group-enriched g-C3N4 and its subsequent photocatalytic reaction process. (c) Hybrid structure and π-conjugated structure of the tri-s-triazine unit of g-C3N4. Adapted from Refs. [101-103], respectively, with permission from Springer Nature, Wiley, and Elsevier, 2019, 2020, and 2019.

Fig. 6. (a) Research history of defective g-C3N4 photocatalysts for solar applications [108]. (b) Strategies for tuning the electronic structure and surface properties of g-C3N4 [108]. (c) Schematic synthesis process of g-C3N4 via thermal polymerization of different precursors [99]. Panel (a) is adapted from Springer Nature, 2023; panel (b) is adapted from Springer Nature, 2016; and panel (c) is adapted from ACS.

Fig. 7. Schematic band structure of representative photocatalytic materials at pH = 7 vs. NHE. Cyan, gray, and red bars denote the conduction band minimum, Fermi level, and valence band maximum, respectively. The numbers 1-20 indicate WO3 [16], N-doped-MoS2 [112], CeO2 [113], BiOI [114], I-doped-BiOBr [115], TiO2, sulfur-deficient In2.77S4 [116], N-doped-Nb2O5 [117], Bi2O4 [113], Cu2O [118], B-doped g-C3N4 [119], Mn0.25Cd0.75S [120], ZnIn2S4 [121,122], oxygen-vacancy TiO2 [123], alpha-Fe2O3 [124], ZnCdS, S-doped g-C3N4, FCN [125], TD-COF [126], and g-C3N4 [127], respectively.

Fig. 8. Schematic summary of the evidence chain for probing the interfacial charge-transfer mechanism. DFT, KPFM, XPS/TAS, and EPR respectively provide theoretical insight, interfacial evidence, mechanistic evidence, and functional evidence, thereby establishing a complete framework for understanding carrier migration and redox behavior.

Fig. 9. Three-dimensional isosurface and planar-averaged charge density difference of the BP/g-C3N4 heterojunction. Pink, blue, and gray spheres represent P, N, and C atoms, respectively. Yellow and blue isosurfaces denote electron accumulation and depletion, respectively; positive and negative values in the planar-averaged Δρ profile indicate charge density increase and decrease, respectively. Reproduced from Ref. [136] with permission from Acta Phys.-Chim. Sin., 2021.

Fig. 10. AFM and KPFM characterization of the CdS/BiOBr heterojunction, including morphology, contact potential difference in the dark and under illumination, and surface photovoltage analysis. Reproduced from Ref. [144] with permission from Wiley. Copyright 2025 Wiley-VCH GmbH.

Fig. 11. XRD patterns (a) and high-resolution XPS spectra of TiO2, ZnIn2S4, and TiO2@ZnIn2S4, showing the Ti 2p (b), O 1s (c), Zn 2p (d), In 3d (e), and S 2p (f) signals. Reproduced from Ref. [158] with permission from Wiley. Copyright 2021 Wiley-VCH GmbH.

Fig. 12. Two-dimensional fs-TAS maps and corresponding transient absorption spectra of pure TiO2 (a,b), pristine CdIn2S4 (c,d), 15TCIS heterojunction (e,f), and 15TCIS (g,h) in the presence of AgNO3 as an electron scavenger. Adapted from Ref. [169], with permission from Elsevier, 2025.

Fig. 13. Schematic summary of dimensional engineering in heterostructure design. The upper panel shows typical 0D/2D, 1D/2D, and 2D/2D coupling modes, while the lower panel presents representative hierarchical architectures, including hollow concave-shell, hierarchical floral assembly, and laminated puff-pastry structures.

Fig. 14. SEM and TEM characterizations of representative g-C3N4-based heterostructures. (a,b) SEM images of BiOBr/g-C3N4. (c,d) TEM images of BiOBr/g-C3N4. (e,f) SEM and TEM images of ZnIn2S4/g-C3N4/Ti3C2. SEM images of g-C3N4 NS (g), TpPa-1-COF NS (i), and TPCNNS-2 (k). TEM images of g-C3N4 NS (h), TpPa-1-COF NS (j), and TPCNNS-2 (l). (m‒p) TEM-EDS mapping images of TPCNNS-2 (scale bar: 500 nm). Adapted from Refs. [236,237,240] with permission from Elsevier. Copyright 2022, 2020, and 2022, respectively.

Fig. 15. Schematic illustrations of the material design and synthesis strategies for Au/α-Fe2O3@g-C3N4 nanoreactor [124] (a), Pd SAs-modulated g-C3N4/CdS heterostructure [242] (b), and p-CNQDs/Vo-ZnO heterojunction [243] (c). Adapted from Refs. [124,242] with permission from Wiley. Copyright 2024 Wiley-VCH GmbH, and from Ref. [243] with permission from Elsevier, 2022.

Fig. 16. (a) Atomic percentages of C and N in CN-C with increasing depth after successive ion etching; the secondary y-axis (right) shows the atomic C/N ratio. (b) Corresponding atomic percentages of C in C-rings and g-C3N4 in CN-C; the secondary y-axis (right) shows the atomic ratio of C-t-tri to N. (c‒e) Surface morphologies and potential maps of CN under dark and light irradiation. (f) CPD profile of CN before and after irradiation. (g‒i) Surface morphologies and potential maps of SBCNKNa under dark and light irradiation. (j) CPD profile of SBCNKNa before and after irradiation. (k‒m) Surface morphologies and potential maps of SBCNNH4KNa under dark and light irradiation. (n) CPD profile of SBCNNH4KNa before and after irradiation. Adapted from Refs. [247] and [119] with permission from Elsevier, 2023 and 2026, respectively.

Fig. 17. Schematic illustrations of the S-scheme charge-transfer process for C3N4/Cd0.5Zn0.5S heterojunction (a), MCS/HCN composite (b), and band structure alignment (c) of TCMX. Panels (a)-(c) are adapted from Refs. [248] (2024), [120] (2023), and [249] (2025), respectively, with permission from Elsevier.

Fig. 18. Representative illustrations of free-energy diagrams for the reduction of O2 to H2O2 on Vr-CNS and Vp-CNS (a), adsorption of *OOH on B-BSO, g-CN and B-BSO/g-CN for H2O2 generation (b), Gibbs free energy of the OOH intermediate on C3N4 and Na-C3N4 (c), and precise control of electronic band structures by structural design (d). Panels (a)‒(d) are adapted from Refs. [267] (2026), [268] (2025), [271] (2025), and [270] (2025), respectively, with permission from Elsevier.

Fig. 19. Classification of oxidation reactions coupled with photocatalytic H2O2 production, including pollutant degradation, value-added oxidation, sacrificial oxidation, and biomass oxidation.

Fig. 20. (a) Representative illustrations of DFT calculation on CO2 adsorption at three possible active sites, namely, the terminal ‒NH site (left), lateral Cu2+ site (middle), and interfacial Cu-NH site (right) on CCN/CuPc [285]. (b) Gibbs free-energy diagram of the CO2 reduction pathway, showing the facilitated COOH formation on the PCN/ZnIn2S4 S-scheme heterojunction [286]. Adapted from Refs. [285,286], with permission from Elsevier, 2025. (c) Schematic illustration of the formation of surface CN-H+ species and proton-ligand-assisted growth of ZnIn2S4 on protonated g-C3N4 [286].

Fig. 21. (a‒f) Interfacial distribution of CO2 and H2O, H2O adsorption behavior, and DORI analysis on WS/o-CN and WS/CN. Adapted with permission from Ref. [289]. Copyright 2025 American Chemical Society. (g‒l) Wettability, H2O/CO2 adsorption behavior, and optimized adsorption configurations in the g-C3N4/CuFe2O4/ZnIn2S4 self-supporting three-phase system. (m,n) Gibbs free energy profiles for photocatalytic CO2 reduction and HER over g-C3N4, CuFe2O4, ZnIn2S4, and CNCZ(x) heterojunctions. Adapted with permission from Ref. [290]. Copyright 2024, American Chemical Society.

Fig. 22. Antibacterial performance and reactive oxygen species generation of the CeO2/PCN heterojunction under visible-light irradiation, including representative colony images under dark and illuminated conditions, corresponding fluorescence images, quantitative bacterial counts/removal efficiency, and EPR spectra of DMPO-•OH and DMPO-•O2-. Adapted from Ref. [295] with permission from Wiley, 2020.

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Recent advances in g-C₃N₄-based S-scheme photocatalyst

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