Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(24)60113-0

Abstract

Abstract:

Photocatalytic hydrogen (H₂) evolution using covalent organic frameworks (COFs) is an attractive and promising avenue for exploration, but one of its big challenges is low photo-induced charge separation. In this study, we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency, achieved through atomic modulation (O, S, and Se) of the COF monomer. Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment, thereby affecting charge separation efficiency and photostability, which in turn affects the rates of photocatalytic H₂ evolution. As a result, the newly developed TMT-BO-COF, which contains highly electronegative O atoms, exhibits the lowest exciton binding energy, the highest efficiency in charge separation and transportation, and the longest lifetime of the active charges. This leads to an impressive average H₂ production rate of 23.7 mmol g^-1 h^-1, which is 2.5 and 24.5 times higher than that of TMT-BS-COF (containing S atoms) and TMT-BSe-COF (containing Se atoms), respectively. A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations. Our findings provide new insights into the design of highly photoactive organic framework materials for H₂ evolution and beyond.

Key words: Covalent organic framework, Vinylene linkage, Electronegativity, Dipole polarization, Photocatalytic hydrogen evolution

Ming Wang, Yaling Li, Dengxin Yan, Hui Hu, Yujie Song, Xiaofang Su, Jiamin Sun, Songtao Xiao, Yanan Gao. Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2024, 65: 103-112.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60113-0

https://www.cjcatal.com/EN/Y2024/V65/I10/103

Figures/Tables 5

Fig. 1. Synthetic routes (a) and dipole polarization ability (b) of the three COFs in this study.

Fig. 2. The experimental and simulated PXRD patterns of TMT-BO-COF (a), TMT-BS-COF (b), and TMT-BSe-COF (c). (d) The solid-state 13C NMR spectra of TMT-BO-COF, TMT-BS-COF, and TMT-BSe-COF. Nitrogen adsorption isotherms (e) and pore size distributions (f) of TMT-BO-COF, TMT-BS-COF, and TMT-BSe-COF. HRTEM images of TMT-BO-COF (g), TMT-BS-COF (h), and TMT-BSe-COF (i).

Fig. 3. (a) Energy band position. Photocatalytic H2 evolution rate of TMT-BO-COF in the presence of various scavengers (b), different catalyst dosages (c), and different Pt loadings (d). (e) Catalytic activity of TMT-BO-COF under different reaction conditions. H2 evolution performance (f) and photocatalytic H2 evolution rates (g) of TMT-BO-COF, TMT-BS-COF and TMT-BSe-COF. (h) Long-term H2 production of TMT-BO-COF. (i) The photocatalytic hydrogen evolution properties of vinylene-linked COFs.

Fig. 4. EPR spectra (a), photocurrent responses (b), EIS (c), and temperature-dependent PL spectra (d-f), excited at 400 nm and Arrhenius plots determining exciton binding energies of TMT-BO-COF, TMT-BS-COF, and TMT-BSe-COF (inset). Electron (green regions)-hole (blue regions) distributions (iso-surface = 0.002 a.u.) of TMT-BO-COF (g), TMT-BS-COF (h), and TMT-BSe-COF (i) in the excited state. Surface potential of the TMT-BO-COF (j), TMT-BS-COF (k) and TMT-BSe-COF (l) examined by KPFM (green line shows the surface potential detection area).

Fig. 5. (a) Illustration of the calculated five possible active sites of TMT-BO-COF, and the adsorption Gibbs free energy diagram of hydrogen evolution reaction on five possible sites. (b) Mechanism of photocatalytic hydrogen evolution at TMT-BO-COF.

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