Facile Synthesis of Organic–Inorganic Hybrid Heterojunctions of Glycolated Conjugated Polymer-TiO_2−X for Efficient Photocatalytic Hydrogen Evolution

The utilization of the organic–inorganic hybrid photocatalysts for water splitting has gained significant attention due to their ability to combine the advantages of both materials and generate synergistic effects. However, they are still far from practical application due to the limited understanding of the interactions between these two components and the complexity of their preparation process. Herein, a facial approach by combining a glycolated conjugated polymer with a TiO_2−X mesoporous sphere to prepare high-efficiency hybrid photocatalysts is presented. The functionalization of conjugated polymers with hydrophilic oligo (ethylene glycol) side chains can not only facilitate the dispersion of conjugated polymers in water but also promote the interaction with TiO_2−X forming stable heterojunction nanoparticles. An apparent quantum yield of 53.3% at 365 nm and a hydrogen evolution rate of 35.7 mmol h⁻¹ g⁻¹ is achieved by the photocatalyst in the presence of Pt co-catalyst. Advanced photophysical studies based on femtosecond transient absorption spectroscopy and in situ, XPS analyses reveal the charge transfer mechanism at type II heterojunction interfaces. This work shows the promising prospect of glycolated polymers in the construction of hybrid heterojunctions for photocatalytic hydrogen production and offers a deep understanding of high photocatalytic performance by such heterojunction photocatalysts.