The promotional effects on photocatalytic hydrogen production of Cu _x O clusters deposited using atomic layer deposition (ALD) on P25 TiO₂ are presented. The structural and surface chemistry study of Cu _x O/TiO₂ samples, along with first principles density functional theory simulations, reveal the strong interaction of ALD deposited Cu _x O with TiO₂, leading to the stabilization of Cu _x O clusters on the surface; it also demonstrated substantial reduction of Ti⁴⁺ to Ti³⁺ on the surface of Cu _x O/TiO₂ samples after Cu _x O ALD. The Cu _x O/TiO₂ photocatalysts showed remarkable improvement in hydrogen productivity, with 11 times greater hydrogen production for the optimum sample compared to unmodified P25. With the combination of the hydrogen production data and characterization of Cu _x O/TiO₂ photocatalysts, we inferred that ALD deposited Cu _x O clusters have a dual promotional effect: increased charge carrier separation and improved light absorption, consistent with known copper promoted TiO₂ photocatalysts and generation of a substantial amount of surface Ti³⁺ which results in self-doping of TiO₂ and improves its photo-activity for hydrogen production. The obtained data were also employed to modify the previously proposed expanding photocatalytic area and overlap model to describe the effect of cocatalyst size and weight loading on photocatalyst activity. Comparing the trend of surface Ti³⁺ content increase and the photocatalytically promoted area, calculated with our model, suggests that the depletion zone formed around the heterojunction of Cu _x O-TiO₂ is the main active area for hydrogen production, and the hydrogen productivity of the photocatalyst depends on the surface coverage by this active area. However, the overlap of these areas suppresses the activity of the photocatalyst.

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