Ferrihydrite (Fh) has been demonstrated acting as a hole-storage layer (HSL) in photoelectrocatalysis system. However, the intrinsic structure responsible for the hole storage function for Fh remains unclear. Herein, by dehydrating the Fh via a careful calcination, the essential relation between the HSL function and the structure evolution of Fh material is unraveled. The irreversible and gradual loss of crystal water molecules in Fh leads to the weakening of the HSL function, accompanied with the arrangement of inner structure units. A structure evolution of the dehydration process is proposed and the primary active structure of Fh for HSL is identified as the [FeO6 ] polyhedral units bonding with two or three molecules of crystal water. With the successive loss of chemical crystal water, the coordination symmetry of [FeO6 ] hydration units undergoes mutation and a more ordered structure is formed, causing the difficulty for accepting photogenerated holes as a consequence.
Keywords: FeO6 polyhedra; crystal water; ferrihydrite; hole storage; photoelectrochemistry.
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