Construction of multivariate donor-acceptor heterojunction in covalent organic frameworks for enhanced photocatalytic oxidation: Regulating electron transfer and superoxide radical generation

doi:10.1016/S1872-2067(24)60132-4

Abstract

Abstract:

Covalent organic frameworks (COFs) have attracted attention as photocatalysts, however, low electron transfer and reactive oxygen species (ROS) generation still hinder their photocatalytic application. In this work, we construct multivariate donor-acceptor (D-A) heterojunctions in the covalent organic frameworks by synchronously introducing electron-withdrawing and donating substituents. Importantly, the optoelectronic characteristics and visible-light photocatalytic performance were improved with the increase of the electron donor carbon chains in multivariate D-A COFs. Combining in-situ characterization with theoretical calculations, the charge carrier separation and transfer efficiency, •O₂^- generation and conversion, and the energy barrier of the rate determination steps related to the formation of *OH and *OOH, can be well regulated by the multivariate D-A COFs. More importantly, the ortho-carbon atom of the Br and OCH₃ group-linked benzene rings and the imine bond (-C=N-) in COF-Br@OCH₃ were activated to produce the key *OH and *OOH intermediates for effectively reducing the energy barrier of H₂O oxidation and O₂ reduction. This work provides valuable insights into the precise design and synthesis of COFs-based catalysts and the regulation of electron transfer and ROS generation by modulating the electron-withdrawing and donating substituents for highly efficient visible-light photocatalytic degradation of refractory organic pollutants.

Key words: Covalent organic framework, Charge carrier separation, Electron transfer, Multivariate donor-acceptor heterojunction, Superoxide radical

Lu Zhang, Hourui Zhang, Dongyang Zhu, Zihan Fu, Shuangshi Dong, Cong Lyu. Construction of multivariate donor-acceptor heterojunction in covalent organic frameworks for enhanced photocatalytic oxidation: Regulating electron transfer and superoxide radical generation[J]. Chinese Journal of Catalysis, 2024, 66: 181-194.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60132-4

https://www.cjcatal.com/EN/Y2024/V66/I11/181

Figures/Tables 7

Fig. 1. Synthesis of traditional D-A COFs (COF-H) (a) and multivariate D-A COFs (COF-Br@R, R = OCH3, OC3H7, and OC8H17) (b).

Fig. 2. The chemical identity of COFs. PXRD patterns (a1-a4), FTIR patterns (b1-b4), 13C CP-MAS solid-state NMR spectra (c1-c4), and SEM images (d1-d4) of COF-H and COF-Br@R (R = OCH3, OC3H7, and OC8H17).

Fig. 3. Optoelectronic characteristics of COFs. The UV-vis diffuse reflectance spectra (DRS) spectra and Tauc plot analysis (illustration of (a)) (a), band alignment (b), Photocurrents (c), LSV plot (d), EIS Nyquist plot (e), Tafel curve (f), photoluminescence spectra (g), EPR spectra (h) for detecting electron, and quantum yield (QY) (i) of COF-H, COF-Br, and COF-Br@R (R = OCH3, OC3H7, and OC8H17).

Fig. 4. Evaluation of the photocatalytic performance of COFs. The photocatalytic degradation of TC over COF-H and COF-Br@R (R = OCH3, OC3H7, and OC8H17) (a) and its reaction rate constant (b). (c) Photocatalytic degradation of TC over COF-Br@OCH3 with different Br/OCH3 ratio. (d) Photocatalytic degradation of TC over COF-Cl and COF-Cl@R (R = OCH3, OC3H7, and OC8H17). (e) Ratio to the values of COF-Br@R. (f) Comparison of the kinetic rate constants of degradation previously reported in the degradation system of TC with this work. Conditions: [TC] = 20 mg L-1, [COFs] = 0.3 g L-1.

Fig. 5. Identification of reactive species in photocatalytic degradation of TC by COFs. Photocatalytic degradation of TC over COF-H (a), COF-Br@CH3 (b), COF-Br@OC3H7 (c), and COF-Br@OC8H17 (d) with different scavengers. (e) Degradation efficiency under different scavengers in COF-H and COF-Br@R (R = OCH3, OC3H7, and OC8H17) system. (f) Photocatalytic degradation of NBT over COF-H and COF-Br@R and concentration of generated ?O2-. ESR spectrum for detecting h+ (g), ?O2- (h), and ?OH (i) in COFs photocatalytic systems. Conditions: [TC] = 20 mg L-1, [COFs] = 0.3 g L-1, [p-BQ] = [EDTA-2Na] = [tBA] = 100 mmol L-1, [NBT] = 0.05 mmol L-1.

Fig. 6. The DFT calculations. Hole (blue) and electron (green) distribution (a1-a4) and electrostatic potential calculations (b1-b4) of COF-H, COF-Br, COF-Br@OCH3, and COF-Br@OC3H7. (c) In-situ ATR-FTIR spectra of COF-Br@OCH3. The energy barrier of H2O oxidation to *OH (d) and O2 reduction to *OOH (e) on the ortho-carbon atom of the benzene ring, and O2 reduction to *O2 and *OOH (f) on the carbon atom on the imine bond in COF-H and COF-Br@OCH3.

Fig. 7. Mechanism of photocatalytic degradation of TC over traditional D-A COFs (COF-H) and multivariate D-A COFs (COF-Br@R, R = OCH3, OC3H7, and OC8H17) under visible light irradiation.

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