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Because of very high potential barrier for thermionic emission and trap‐assisted charge recombination, photocatalytic reaction rate that determined by semiconductor‐cocatalyst interfacial electron transfer severely deviates from linearity to the photocatalyst dosage or to the light intensity. This makes it challenging to maximize utilization of practical irradiation by referring the parameters evaluated from method used in conventional catalysis. We here develop a model and predict that photocatalytic reaction rate positively correlates to photocatalyst concentration under weak illumination while the correlation becomes negative under intense irradiation. The theoretical simulation that matches the experimental values can be used to guide maximizing photocatalytic photon utilization under various intensity of irradiation. The strong correlation can rationalize photocatalytic evaluation instead of obtaining a numerically high value by excessively lowering the denominators. To realize efficient utilization of real‐time changing sunlight, we propose a reactor configuration that can optimize the amount of photocatalyst participating into the reaction.

Developing cocatalyst-free photocatalysts is highly desired because it could avoid the very slow interfacial electron transfer that makes photocatalytic photon utilization a dilemma. However, even in the optimal case, photocatalysts without the use of cocatalysts deliver comparable performance only for conventional construction. We demonstrate here that electronic doping not only provides catalytically active sites in cocatalyst-free photocatalysts but also plays certain additional roles. These electronic states can efficiently channel the trapped electrons to the semiconductor surface without suffering from time-consuming detrapping and can facilitate the extraction of photogenerated holes. These features endow our demonstrated tungsten-doped CdS with evident superiority in photocatalytic performance over conventional counterparts loaded with platinum cocatalysts.

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