2D tris(triazolo)triazine-based covalent organic frameworks for efficient photoinduced molecular oxygen activation

doi:10.1016/S1872-2067(25)64761-9

Abstract

Abstract:

Photoinduced molecular oxygen activation is crucial for artificial photosynthesis. However, metal-free semiconductor photocatalysts with high activation efficiency are still lacking up to now. Herein, two isomorphic tris(triazolo)triazine-based covalent organic frameworks were successfully constructed under solvothermal conditions. And they possess high crystallinity, inherent porosity with large surface area and good stability. Strong electron donor-acceptor skeletons expand the visible light harvesting, also facilitate the charge separation and thus lead to their superior activity of photoinduced molecular oxygen activation including photosynthesis of tetrahydroquinolines and hydrogen peroxide. This work provides a way to improve the efficiency of molecular oxygen activation through the rational design of COFs, and also opens new avenues for the construction of highly active and metal-free photocatalysts toward sustainable solar-to-chemical energy conversion.

Key words: Covalent organic frameworks, Tris(triazolo)triazine, Superoxide radical anion, Tetrahydroquinolines, Hydrogen peroxide

Shanshan Zhu, Xinrui Mao, Zhenwei Zhang, Liuliu Yang, Jiahao Li, Zhongping Li, Yucheng Jin, Huijuan Yue, Xiaoming Liu, . 2D tris(triazolo)triazine-based covalent organic frameworks for efficient photoinduced molecular oxygen activation[J]. Chinese Journal of Catalysis, 2025, 76: 120-132.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64761-9

https://www.cjcatal.com/EN/Y2025/V76/I9/120

Figures/Tables 7

Fig. 1. (a) Syntheses of COF-JLUs. (b) Top and (c) side views of COF-JLU61. (d) Top and (f) side views of COF-JLU62 (Color code: light gray, carbon; blue, nitrogen; yellow, sulfur; red, oxygen; hydrogen is omitted for clarity).

Fig. 2. (a) The experimental and simulated PXRD profiles of COF-JLU61 and (b) COF-JLU62. (c) SEM image of COF-JLU61 and (d) COF-JLU62. (e) TEM image of COF-JLU61 and (f) COF-JLU62.

Fig. 3. FT-IR spectra of COF-JLU61 (a) and (b) COF-JLU62, and their corresponding monomers. The chemical structure and 13C CP-MAS NMR spectra of COF-JLU61 (c) and COF-JLU62 (d). N2 sorption isotherm of COF-JLU61 (e) and COF-JLU62 (f) at 77 K. Insets: the corresponding pore size distribution (solid circles for adsorption and open circles for desorption).

Fig. 4. (a) UV-vis DRS spectrum of COF-JLUs; inset: its photograph. (b) Tauc plots of COF-JLUs. (c) Band structures diagram of two COF-JLUs (the electrochemical potential at pH = 7.0). (d) Transient current density of COF-JLU61 and COF-JLU62. (e) EIS spectra of COF-JLU61 and COF-JLU62. (f) Transition photocurrents of COF-JLUs under visible-light illumination. Integrated PL emission intensity as a function of the temperature of COF-JLU61 (g) and COF-JLU62 (h). Inset: the corresponding temperature-dependent PL spectra.

Table 1 Substrate scope for photocatalytic tetrahydroquinolines.

Fig. 5. (a) The photocatalytic tetrahydroquinoline of COF-JLU61 under different conditions. (b) EPR conduction band electrons spectra of COF-JLU61 and COF-JLU62 in the dark and during visible light irradiation. (c) Calculated band structure and density of states of COF-JLU61. (d) Kohn-Sham orbitals of HOMO and LUMO of COF-JLU61. (e) Charge density difference excited states of the model compound (COF-JLU61). (f) Charge density difference excited states of the model compound (COF-JLU62). The green and blue orbitals represent electron and hole distribution, respectively.

Fig. 6. (a) Time-dependent H2O2 photogeneration using visible light for COF-JLU61 and COF-JLU62 (Conditions: 5 mg of catalyst in 50 mL of pure water, O2 atmosphere and air atmosphere, AM 1.5, average light intensity: 100 mW cm−2). (b) The H2O2 production of COF-JLU61 and COF-JLU62 under different conditions (AM 1.5, average light intensity: 100 mW cm−2). (c) The Koutecky-Levich plots obtained by RDE measurements (vs. Ag/AgCl). (d) RRDE voltammograms obtained in 0.1 mol L−1 phosphate buffer solution with a scan rate of 10 mV s−1 and a rotation rate of 1000 rpm. The potential of the Pt ring electrode is set at −0.23 V (vs. Ag/AgCl) to detect O2. (e) DRIFTS spectra of COF-JLU61 in H2O2 photosynthesis (dark and light). (f) Distributions of the photo-excited electrons and holes (yellow and blue represent electrons and holes, respectively). (g) Gibbs free energy diagrams of H2O2 photogeneration over COF-JLUs by 2e− ORR paths, and (h) Gibbs free energy diagrams of O2 photogeneration by 4e− WOR path by the DFT calculations.

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