π–d Electron-Coupled PBDIT/CdS Heterostructure Enables Hole Extraction for Efficient Photocatalytic Hydrogen Production

Construction of heterostructures is one of the most promising strategies for designing photocatalysts for highly efficient solar hydrogen (H2) production because the introduction of an electron-donating counterpart contributes to more effective photon absorption, while the heterostructures benefit spatial carrier separation. However, the hole-transfer rate is usually 2–3 orders of magnitude slower than that of the electron-transfer rate within the heterostructures, ensuing serious charge recombination. Here, we find the energy band offset-driven charge-transfer behavior in a donor–acceptor (D–A)-conjugated polymer/CdS organic/inorganic heterostructure and realize hole-transfer improvement in cooperation with a further hole removal motif of poly­(3,4-ethylenedioxythiophene) polystyrene sulfonate. The photocatalytic H2 production activity is increased by nearly 2 orders of magnitude with the apparent quantum yield hitting ca. 80% at 450 nm without co-catalysts. Ultrafast transient absorption together with surface photovoltage characterizations consolidates the hole extraction mechanism. The intimate bond formed at the interface between the polymer and the inorganic semiconductor acts as an interpenetrating network at the nanoscale level, thus providing a charge-transfer freeway for boosting charge separation.