Undesired photoelectronic dormancy through active species decay is adverse to photoactivity enhancement. An insufficient extrinsic driving force leads to ultrafast deep charge trapping and photoactive species depopulation in carbon nitride (g-C 3 N 4 ). Excitation of shallow trapping in g-C 3 N 4 with longlived excited states opens up the possibility of pursuing high-efficiency photocatalysis. Herein, a near-field-assisted model is constructed consisting of an In 2 O 3 -cube/g-C 3 N 4 heterojunction associated with ultrafast photodynamic coupling. This In 2 O 3 -cube-induced near-field assistance system provides catalytic "hot areas", efficiently enhances the lifetimes of excited states and shallow trapping in g-C 3 N 4 and this favors an increased active species density. Optical simulations combined with time-resolved transient absorption spectroscopy shows there is a built-in charge transfer and the active species lifetimes are longer in the In 2 O 3 -cube/g-C 3 N 4 hybrid. Besides these properties, the estimated overpotential and interfacial kinetics of the In 2 O 3 -cube/g-C 3 N 4 hybrid co-promotes the liquid phase reaction and also helps in boosting the photocatalytic performance. The photocatalytic results exhibit a tremendous improvement (34-fold) for visible-light-driven hydrogen production. Near-fieldassisted long-lived active species and the influences of trap states is a novel finding for enhancing (g-C 3 N 4 )-based photocatalytic performance.

Ultrafast excited‐state decay and intrinsic charge carrier recombination restrain the photoactivity enhancement for solar‐to‐H2 production. Here, a CdS‐fullerene/graphene (CdS‐F/G) photocatalyst is synthesized for enhancing visible‐light‐driven hydrogen generation from earth‐abundant water. The CdS‐F/G shows ultrafast interfacial electrons/holes transfer and holes self‐trapping process in photocatalysis. The in‐situ dynamic study from transient absorption spectroscopy reveals the sub‐microsecond‐lived excited states (≈172.6 ns), interfacial electron transfer (≈30.3 ps), and hole trapping (≈44.0 ps) in the CdS‐F/G photocatalyst. The efficient active species transportation and prolonged lifetime significantly enhance the charge separation state survival, increasing the photoactivity and photostability. Consequently, visible‐light activity enhancement (>400%) of H2 evolution reaction (HER) is obtained at the CdS‐F/G photocatalyst with high stability (>36 h). The 127.2 µmol h−1 g−1 performance corresponding to a quantum efficiency of 7.24% at 420 nm is not only higher than the case of pristine CdS (29.2 µmol h−1 g−1) but also much higher than that of CdS‐Pt photocatalyst (73.8 µmol h−1 g−1). The cost‐effective CdS‐F/G photocatalyst exhibits a great potential for sustainable and high‐efficiency photocatalytic water splitting into clean energy carriers. Moreover, the optimized electronic structure associated with interfacial electrons/holes transfer and holes self‐trapping promotes overall water splitting for H2 and O2 generation.

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