Modulating electronic structure of g-C3N4 hosted Co-N4 active sites by axial phosphorus coordination for efficient overall H2O2 photosynthesis from oxygen and water

doi:10.1016/S1872-2067(25)64735-8

Abstract

Abstract:

Single-atom catalysts are promising for H₂O₂photosynthesis from O₂ and H₂O, but their efficiency is still limited by the ill-defined electronic structure. In this study, Co single-atoms with unique four planar N-coordination and one axial P-coordination (Co-N₄P₁) are decorated on the lateral edges of nanorod-like crystalline g-C₃N₄(CCN) photocatalysts. Significantly, the electronic structures of central Co as active sites for O₂ reduction reaction (ORR) and planar N-coordinator as active sites for H₂O oxidation reaction (WOR) in Co-N₄P₁can be well regulated by the synergetic effects of introducing axial P-coordinator, in contrast to the decorated Co single-atoms with only four planar N-coordination (Co-N₄). Specifically, directional photoelectron accumulation at central Co active sites, induced by an introduced midgap level in Co-N₄P₁, mediates the ORR active sites from 4e^--ORR-selective terminal -NH₂ sites to 2e^--ORR-selective Co sites, moreover, an elevated d-band center of Co 3d orbital strengthens ORR intermediate *OOH adsorption, thus jointly facilitating a highly selective and active 2e^--ORR pathway to H₂O₂ photosynthesis. Simultaneously, a downshifted p-band center of N 2p orbital in Co-N₄P₁ weakens WOR intermediate *OH adsorption, thus enabling a preferable 2e^--WOR pathway toward H₂O₂ photosynthesis. Subsequently, Co-N₄P₁ exhibits exceptional H₂O₂photosynthesis efficiency, reaching 295.6 μmol g^-1 h^-1 with a remarkable solar-to-chemical conversion efficiency of 0.32 %, which is 15 times that of Co-N₄ (19.2 μmol g^-1 h^-1) and 10 times higher than CCN (27.6 μmol g^-1 h^-1). This electronic structure modulation on single-atom catalysts offers a promising strategy for boosting the activity and selectivity of H₂O₂ photosynthesis.

Key words: Crystalline carbon nitride, Coordination engineering, Single atom Co-N₄P₁ active sites, Modulating electronic structure, Overall H₂O₂ photosynthesis

Shinuo Liang, Fengjun Li, Fei Huang, Xinyu Wang, Shengwei Liu. Modulating electronic structure of g-C₃N₄ hosted Co-N₄ active sites by axial phosphorus coordination for efficient overall H₂O₂ photosynthesis from oxygen and water[J]. Chinese Journal of Catalysis, 2025, 76: 81-95.

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Figures/Tables 12

Scheme 1. Schematic of the Co-N4P1 catalyst.

Fig. 1. SEM image of sample CCN (a), Co-N4 (b) and Co-N4P1 (c). TEM (d), HRTEM (e) and AC-HAADF-STEM (f) images of Co-N4P1. (g) HRTEM image of CCN. HAADF-STEM image (h) and the corresponding EDS elemental mappings (i-l) of the typical sample Co-N4P1.

Fig. 2. XPS and XAFS characterizations. XPS spectra of Co 2p (a) and P 2p (b). Normalized Co K-edge XANES spectra (c) and k2-weighted Co K-edge FT-EXAFS spectra (d) at R space of Co-N4, Co-N4P1 and reference samples. The k2-weighted Co K-edge EXAFS fitting curve of Co-N4 (e) and Co-N4P1 (f) at R space. (g-j) WT-EXAFS spectra of Co foil, Co-N4, CoPc, Co-N4P1.

Fig. 3. DFT optimized structure and the corresponding formation energy of the Co-N4 (a) and Co-N4P1 (b) catalysts (model (1)).

Fig. 4. PDOS plots of Co-N4 (a) and Co-N4P1 (b) obtained by DFT calculations; and corresponding LUMO and HOMO orbitals of Co-N4 (c) and Co-N4P1 (d). UV-vis diffuse reflectance spectra (e) and the illustrated band structures (f) of samples CCN and Co-N4 and Co-N4P1.

Fig. 5. The steady-state PL spectra (a), time-resolved PL spectra (b), transient photocurrent responses (c), Nyquist plots of EIS curves (d), electrochemical O2 reduction (e) and H2O oxidation (f) curves of samples CCN, Co-N4 and Co-N4P1.

Fig. 6. (a) H2O2 photosynthesis performance on CCN, Co-N4 and Co-N4P1 samples. Experimental conditions: photocatalyst (0.25 g L-1, 40 mL) under full spectrum irradiation (λ ?≥ 320?nm, 200 mW cm-2), 1?atm O2 with pure water (pH = 7) and T = 298 K. (b) The corresponding fitted formation rate constants (Kf) and decomposition rate constants (Kd). (c) Cycling stability of the Co-N4P1 catalyst. (d) AQE of Co-N4P1 as a function of wavelength. (e) H2O2 photosynthesis performance in an oxygen-free environment on CCN, Co-N4 and Co-N4P1 samples. (f) Activity comparison of Co-N4P1 with reported state-of-the-art photocatalysts under visible-light (λ? ≥ 420?nm), 1?atm O2, pure water (pH = 7) and T?=?298?K.

Fig. 7. (a) Influence of CH3OH (h+ scavenger) for the H2O2 photosynthesis on CCN, Co-N4 and Co-N4P1. (b) ESR spectra of superoxide radicals (•O2-). (c) The Koutecky-Levich plots obtained by RDE measurements at −2.0 V (vs. Ag/AgCl). (d) Influence of AgNO3 (e- scavenger) for the H2O2 generation on CCN, Co-N4 and Co-N4P1. (e) ESR spectra of hydroxyl radicals (•OH). (f) H218O isotope experiment to explore the H2O2 evolution through WOR pathway for Co-N4P1.

Fig. 8. In situ DRIFTS spectra under H2O and O2 of Co-N4 (a) and Co-N4P1 (b).

Fig. 9. The adsorption of O2 (a) and H2O (b) at different sites for Co-N4 and Co-N4P1.

Fig. 10. (a) Comparison of ∆G*OOH for the 2e?-ORR in catalytic activity volcanoes plot on Co-N4 and Co-N4P1 and other transition metal (Mn, Fe, Ni, Cu) single atom catalysts [28]. (b) Calculated free energy diagrams for WOR on Co-N4 and Co-N4P1. PDOS for Co 3d (c) and N 2p (d). COHP analyses of the Co-O bonds (e) and N-O bonds (f). (g) Schematic diagram about the optimize *OOH and *OH intermediate adsorption.

Scheme 2. Schematic illustration of reaction pathways toward H2O2 photosynthesis at the spatially separated ORR and WOR centers over Co-N4P1.

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Modulating electronic structure of g-C₃N₄ hosted Co-N₄ active sites by axial phosphorus coordination for efficient overall H₂O₂ photosynthesis from oxygen and water

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