Synergistic band and electronic engineering in cyano-oxygen co-functionalized carbon nitride for efficient photocatalytic H2O2 synthesis

doi:10.1016/S1872-2067(25)64912-6

Abstract

Abstract:

Photocatalytic hydrogen peroxide (H₂O₂) synthesis via the two-electron oxygen reduction reaction (2e^- ORR) offers a sustainable alternative to industrial methods. However, conventional carbon nitride photocatalysts suffer from rapid charge recombination, limited visible-light utilization, and insufficient 2e^- ORR selectivity. Herein, we report a novel precursor-molten salt synergistic strategy. Using the oxygen-containing precursor itself, the spontaneous oxygen doping of the carbon nitride skeleton was initiated by a one-step heat-induced condensation process, and the O-doped cyano-functionalized carbon nitride (MCN-N15) was further synthesized by molten salt-assisted synthesis. Under visible light, MCN-N15 achieves an exceptional H₂O₂ production rate of 950.14 μmol·g^-1·h^-1 in ethanol. O-doping induces n → π* electronic transitions, broadening the visible-light absorption range. Simultaneously, the introduced cyano groups (-C≡N) facilitate charge separation and enhance 2e^- ORR selectivity. Crucially, this approach not only realizes the self-doping of O, but also mitigates the conduction band downshifting typically caused by conventional molten salts, yielding a more negative conduction band potential (E_CB = -0.84 V vs. NHE) that provides a strong thermodynamic driving force for 2e^- ORR. The results of density functional theory calculations show that the synergistic modification strategy of oxygen doping and cyano modification effectively reduces the Gibbs free energy change (∆G) of the rate-determining step (* + O₂ → *O₂) and promotes the formation of intermediate *OOH, thereby significantly improving the selectivity and reaction rate of H₂O₂ synthesis. The synergistic modification optimizes the electronic and band structure of carbon nitride, providing a novel "energy band engineering-surface functionalization" co-regulation strategy for designing efficient photocatalytic H₂O₂ generation systems.

Key words: Carbon nitride, O-doping, Cyano group, Photocatalytic, H₂O₂

Rongxing Chen, Yongkang Quan, Weilong Cai, Yun Hau Ng, Jianying Huang, Yuekun Lai. Synergistic band and electronic engineering in cyano-oxygen co-functionalized carbon nitride for efficient photocatalytic H₂O₂ synthesis[J]. Chinese Journal of Catalysis, 2026, 84: 250-260.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64912-6

https://www.cjcatal.com/EN/Y2026/V84/I5/250

Figures/Tables 6

Fig. 1. (a) Schematic illustration for the synthesis of MCN-N15. TEM images of CN (b), MCN (c), and MCN-N15 (d). SEM images of CN (e), MCN (f), and MCN-N15 (g). (h-k) The elemental mapping (C, N, O, Na) of MCN-N15.

Fig. 2. XRD patterns (a), N2 adsorption-desorption isotherms (b), pore size distribution (c), FT-IR spectra (d), Solid-state 13C NMR spectra (e), XPS spectra (f), C 1s spectra (g), N 1s spectra (h), O 1s spectra (i) of CN, MCN, and MCN-N15.

Fig. 3. UV-vis absorption spectra (a), Tauc plots (b), PL spectra (c), TRPL spectra (d), transient photocurrent response (e), EIS (f), Valence band spectra (g), and band structures (h) of CN, MCN, MCN-N15.

Fig. 4. Photocatalytic hydrogen peroxide production performance (a) and corresponding reaction rate (b). (c) Cyclic stability test of MCN-N15. Photocatalytic performance of MCN-N15 under different atmospheres (d) and different sacrificial reagents (e). (f) On-site utilization of the produced H2O2 for degradation of methyl blue solution.

Fig. 5. (a) Scavenger effects on H2O2 yield. (b) The Koutecky-Levich diagrams of CN, MCN, MCN-N15. (c) EPR spectra of DMPO-?O2- signal of CN, MCN, and MCN-N15. (d) In-situ DRIFT spectra of MCN-N15 photocatalytic reaction.

Fig. 6. HOMO (a) and LUMO (b) of CN, MCN and MCN-N15. Surface electrostatic potential: CN (c), MCN (d), and MCN-N15 (e). (f) Gibbs free energy of H2O2 was generated on the CN, MCN and MCN-N15 optimization models, * represents the adsorption state.

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Synergistic band and electronic engineering in cyano-oxygen co-functionalized carbon nitride for efficient photocatalytic H₂O₂ synthesis

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