Plasmonic Engineering of Gold Nanoparticles Coupled Pyrene‐Sulfone Polymer for Enhanced Photocatalytic Hydrogen Evolution

ABSTRACT A combination of semiconductors with noble metal nanoparticles is an effective way to improve photocatalytic hydrogen evolution performance via the plasmonic effect by near‐field enhancement and hot electron injection. The effectiveness of this approach to organic semiconductors is often compromised by an inefficient electron transfer process at the metal‐polymer interface that limits hot electron utilization. Herein, we rationally designed a novel pyrene‐sulfone polymer (PSP) composite system that enables firm anchoring of gold nanospheres through electrostatic interactions and coordination effects, thereby establishing efficient pathways for plasmon‐induced charge transfer. The size and loading of gold nanospheres were systematically tuned to optimize photocatalytic performance. Our investigation reveals that PSP combined with 8 wt.% 60 nm gold nanospheres exhibited the optimal hydrogen production rate of 72.41 mmol h ⁻¹ g ⁻¹ , 4.6 fold of that for pure PSP (∼15.66 mmol h ⁻¹ g ⁻¹ ). In situ XPS, ultrafast transient absorption spectroscopy, and temperature‐dependent PL measurements confirm that the synergetic effect of reduced exciton binding energy and hot electron injection effectively promotes carrier generation for the photocatalytic process.