Over the past few years, many approaches have been developed progressively to produce hydrogen (H2) from water under solar light irradiation. This process of fuel production is clean, potentially cost-effective,...

Photocatalytic water splitting is considered one of the most important and appealing approaches for the production of green H2 to address the global energy demand. The utmost possible form of artificial photosynthesis is a two‐step photoexcitation known as “Z‐scheme”, which mimics the natural photosystem. This process solely relies on the effective coupling and suitable band positions of semiconductors (SCs) and redox mediators for the purpose to catalyze the surface chemical reactions and significantly deter the backward reaction. In recent years, the Z‐scheme strategies and their key role have been studied progressively through experimental approaches. In addition, theoretical studies based on density functional theory have provided detailed insight into the mechanistic aspects of some breathtakingly complex problems associated with hydrogen evolution reaction and oxygen evolution reaction. In this context, this critical review gives an overview of the fundamentals of Z‐scheme photocatalysis, including both theoretical and experimental advancements in the field of photocatalytic water splitting, and suggests future perspectives.

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