Hydrophilic Photocrosslinkers as a Universal Solution to Endow Water Affinity to a Polymer Photocatalyst for an Enhanced Hydrogen Evolution Rate

Abstract A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL‐R) or ethylene glycol‐based bridge chains (CL‐TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365 nm. When employing the hydrophilic CL‐TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5‐fold compared to that obtained using non‐crosslinked F8BT photocatalysts, whereas CL‐R‐based photocatalysts yield HER rates comparable to those of non‐crosslinked counterparts. Photophysical analyses including time‐resolved photoluminescence and transient absorption measurements reveal that adding CL‐TEG accelerates exciton separation, forming long‐lived charge carriers. Additionally, the in‐depth study using molecular dynamics simulations elucidates the dual role of CL‐TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high‐permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts.