“Electricity”‐assisted Catalytic Solar‐to‐fuel Processes

Efficient conversion of solar energy into chemical fuels is pivotal for establishing sustainable energy systems, yet persistent challenges in carrier dynamics and reaction selectivity hinder practical implementation. This review systematically examines the emerging paradigm of ”electricity”assisted solar‐to‐fuel catalysis, innovatively proposing a dual‐path framework based on distinct electrical intervention mechanisms: Cross‐Space Charge Transfer System and Local Electric Field Regulation System, elucidating their unique roles in bridging light absorption and fuel synthesis. In the cross space charge transfer system, charge transfer driven by external bias enhances separation of photogenerated charges in single photoelectrode photoelectrocatalysis (PEC), while the self‐powered dual photoelectrodes PEC‐PEC, photovoltaic‐photoelectrocatalysis (PV‐PEC), and photovoltaic‐electrocatalysis (PV‐EC) systems achieve zero energy conversion from solar energy to fuel through band matching and device integration, utilizing charge transfer driven by photogenerated potential. In the local electric field regulation system, static intrinsic electric field (spontaneous polarization and interface electric field) and dynamic electric field (piezoelectric, pyroelectric, flexoelectric and triboelectric induced transient electric field) optimize carrier transport dynamics and accelerate reactant adsorption. This article systematically summarizes promotion of diverse forms of“electricity”on solar‐to‐fuel catalysis, reveals energy conversion mechanisms, material design principles, performance bottlenecks, and solutions of different systems, providing insights into the future development direction of this field.