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Photoelectrochemical (PEC) hydrogen production is an emerging technology that uses renewable solar light aimed to establish a sustainable carbon‐neutral society. The barriers to commercialization are low efficiency and high cost. To date, researchers have focused on materials and systems. However, recent studies have been conducted to utilize thermal effects in PEC hydrogen production. This Review provides a fresh perspective to utilize the thermal effects for PEC performance enhancement while delineating the underlying principles and equations associated with efficiency. The fundamentals of the thermal effect on the PEC system are summarized from various perspectives: kinetics, thermodynamics, and empirical equations. Based on this, materials are classified as plasmonic metals, quantum dot‐based semiconductors, and photothermal organic materials, which have an inherent response to photothermal irradiation. Finally, the economic viability and challenges of these strategies for PEC are explained, which can pave the way for the future progress in the field. [ABSTRACT FROM AUTHOR]

Solar‐driven photoelectrochemical (PEC) hydrogen production is one potential pathway to establish a carbon‐neutral society. Nowadays, quantum dots (QDs)‐sensitized semiconductors have emerged as promising materials for PEC hydrogen production due to their tunable bandgap by size or morphology control, displaying excellent optical and electrical properties. Nevertheless, they still suffer from anodic corrosion during long‐term cycling, offering poor stability. This Review discussed advancements to improve long‐term stability of QDs particularly in terms of cocatalysts and passivation layers. The working principle of PEC cells was reviewed, along with all important configurations adopted over recent years. The equations to assess PEC performance were also described. A greater emphasized was placed on QDs and incorporation of cocatalysts or passivation layers that could enhance the PEC performance by influencing the charge transfer and surface recombination processes. [ABSTRACT FROM AUTHOR]