An Efficient Electron Donor for Conjugated Microporous Polymer Photocatalysts with High Photocatalytic Hydrogen Evolution Activity

Conjugated microporous polymers (CMPs) with donor‐acceptor (D‐A) molecular structure show high photocatalytic activity for hydrogen evolution due to the efficient light‐induced electron/hole separation, which is mostly determined by the nature of electron donor and acceptor units. Therefore, the selection of electron donor and acceptor holds the key point to construct high performance polymer photocatalysts. Herein, two dibenzo[b,d]thiophene‐S,S‐dioxide (BTDO) containing CMP photocatalysts using tetraphenylethylene (TPE) or dibenzo[g,p]chrysene (DBC) as the electron donor to investigate the influence of the geometry of electron donor on the photocatalytic activity are design and synthesized. Compared with the twisted TPE donor, DBC has a planar molecular structure with extended π‐conjugation, which promotes the charges transmission and light‐induced electron/hole separation. As a result, the polymer DBC‐BTDO produced from DBC donor shows a remarkable photocatalytic hydrogen evolution rate (HER) of 104.86 mmol h‐1 g‐1 under full arc light (λ > 300 nm), which is much higher than that of the polymer TPE‐BTDO (1.80 mmol h‐1 g‐1), demonstrating that DBC can be an efficient electron donor for constructing D‐A polymer photocatalysts with high photocatalytic activity for hydrogen evolution. A conjugated microporous polymer photocatalyst adopting dibenzo[g,p]chrysene with planar structure and extended π‐conjugation as the electron donor shows a high hydrogen evolution rate of 104.86 mmol h−1 g−1 under full arc light (λ > 300 nm).