Plasmonic Engineering of Gold Nanoparticles Coupled Pyrene-Sulfone Polymer for Enhanced Photocatalytic Hydrogen...

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.