Issue 5, 2020

Substituent effect of conjugated microporous polymers on the photocatalytic hydrogen evolution activity

Abstract

The construction of a donor–acceptor (D–A) organic photocatalyst is a facile approach to improve photocatalytic performances because of the efficient separation of light-generated electrons and holes. The rational design of molecular skeletons and the selection of functional groups are of great importance to an organic photocatalyst with a high photocatalytic activity. Herein, we designed two D–A conjugated microporous polymers (CMPs) with different substituent groups of fluorine atoms and methyl groups on the acceptor unit of dibenzothiophene-dioxide (DBTDO). This study reveals that the introduction of fluorine atoms with strong electron-withdrawing ability onto the acceptor unit can further enhance the electron acceptability of the DBTDO unit, leading to the efficient separation of light-generated electrons and holes, while the introduction of methyl with electron-pushing ability decreases the electron acceptability of the acceptor unit, suppressing the separation of light-generated charge carriers. As a result, the polymer PyDF with fluorine atoms shows an excellent photocatalytic activity compared to PyDM with methyl groups. Under UV/Vis light irradiation, PyDF shows an attractive photocatalytic hydrogen generation rate of 18.93 mmol h−1 g−1, which is much higher than that of PyDM (3.96 mmol h−1 g−1), implying that the functional group acts as a vital role in the catalytic activity of polymer semiconducting photocatalysts.

Graphical abstract: Substituent effect of conjugated microporous polymers on the photocatalytic hydrogen evolution activity

Supplementary files

Article information

Article type
Paper
Submitted
02 Dec 2019
Accepted
27 Dec 2019
First published
30 Dec 2019

J. Mater. Chem. A, 2020,8, 2404-2411

Substituent effect of conjugated microporous polymers on the photocatalytic hydrogen evolution activity

X. Gao, C. Shu, C. Zhang, W. Ma, S. Ren, F. Wang, Y. Chen, J. H. Zeng and J. Jiang, J. Mater. Chem. A, 2020, 8, 2404 DOI: 10.1039/C9TA13212K

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