Dual O2 reduction centers of COFs boosting H2O2 photosynthesis

doi:10.1016/S1872-2067(25)64740-1

Abstract

Abstract:

The two-electron oxygen reduction reaction (ORR) for H₂O₂ photosynthesis is often hindered by sluggish charge kinetics and a limited number of activation sites. Theoretical predictions based on dipole moment analysis indicate that introducing pyrazine units enhances charge migration, leading to increased accumulation of photoinduced electrons on these units, thereby facilitating the two-site, two-electron ORR. Inspired by these theoretical insights, this work designed and fabricated a triazine-pyrazine-based covalent organic framework materials (TTDN-COFs) for H₂O₂ photosynthesis via a polarity-functionalization strategy. The TTDN-COFs demonstrate a significant improvement in the photocatalytic H₂O₂ production rate, reaching 2757.6 μmol h^-1 g^-1 in pure water-3.2 times higher than that of the triazine-based COFs (TTPH-COFs). Experimental results and theoretical calculations confirm that the incorporation of pyrazine units not only enhances polarization, promoting the separation and migration of charge carriers, but also facilitates the formation of endoperoxide at both the triazine and pyrazine units. The dual adsorption activation sites lower the activation energy barrier for O₂, thereby accelerating the overall reaction kinetics. These findings highlight the potential of functional-group-mediated polarization engineering as a promising strategy for developing COFs-based H₂O₂ photosynthesis with dual activation sites.

Key words: H₂O₂ photosynthesis, Triazine-pyrazine-based COFs, Dual activation sites, Polarization

Chongbei Wu, Feihong Chu, Yongchao Hao, Xuan Li, Xiaoyue Jia, Yifan Sun, Jiaxuan Gu, Pengfei Jia, Aobing Wang, Jizhou Jiang. Dual O₂ reduction centers of COFs boosting H₂O₂ photosynthesis[J]. Chinese Journal of Catalysis, 2025, 74: 329-340.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64740-1

https://www.cjcatal.com/EN/Y2025/V74/I7/329

Figures/Tables 8

Fig. 1. (a) The synthetic routes schematics and DFT calculated dipole moments of TTPH-COFs, TTPN-COFs and TTDN-COFs. The D index (D index refers to the distance between the two centers of mass of electrons or holes) (b) and the O2 molecule adsorption energies (c) of COFs.

Fig. 2. FT-IR spectra (a), and solid-state 13C NMR spectra (b) of COFs. UV-vis absorption spectra (c) and electronic band structure (d) of COFs.

Fig. 3. (a) Time-dependent formation of H2O2 under O2-saturated pure water for COFs under illumination of a 300W Xe lamp. (b) Wavelength-dependent H2O2 yield and (c) the stability toward producing H2O2 of TTDN-COFs. (d) The H2O2 production performance of COFs under different sacrificial agent conditions. (e) The EPR spectra of TTDN-COFs recorded in ultrapure water under O2 atmosphere. (f) Photocatalytic yield of ?O2- by COFs detected by NBT method.

Fig. 4. The SPV spectroscopy (a), PL spectroscopy (b), and time-resolved PL decay measurements (c) of COFs. (d) Femtosecond transient absorption spectra of TTDN-COFs and TTPH-COFs. (e) Time profiles of normalized transient absorption kinetics of at 455 nm of TTDN-COFs and 515 nm of TTPH-COFs.

Fig. 5. (a) In-situ XPS spectra of N 1s spectra in TTDN-COFs photocatalysts. (b,c) In-situ DRIFT spectra of TTDN-COFs.

Fig. 6. PDOS plots of C 2p, N 2p in TTPH-COFs (a), TTPN-COFs (b) and TTDN-COFs (c). TDDFT-calculated absorption spectra for EDD of TTPH-COFs (d), TTPN-COFs (e) and TTDN-COFs (f).

Fig. 7. Electron and hole distribution for TTPH-COFs (a,d), TTPN-COFs (b,e), and TTDN-COFs (c,f).

Fig. 8. The weight difference index of fragments in (a) TTDN-COF, (b) TTPN-COF and (c) TTDN-COF. Calculated free energy diagrams of 2e- ORR pathway toward H2O2 production on different activation sites: (d) triazine sites in TTPH-COF, (e) pyrazine sites in TTPN-COF, (f) triazine sites in TTDN-COF and (g) pyrazine sites in TTDN-COF.

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Dual O₂ reduction centers of COFs boosting H₂O₂ photosynthesis

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