Unveiling the Hydration Structure of Ferrihydrite for Hole Storage in Photoelectrochemical Water Oxidation. Issue 12 (10th February 2021)

• Record Type: Journal Article
• Authors: Wang, Pengpeng; Li, Deng; Chi, Haibo; Zhao, Yongle; Wang, Junhu; Li, Dongfeng; Pang, Shan; Fu, Ping; Shi, Jingying; Li, Can
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 12(2021)
• Page Start: 6691
• Page End: 6698
• Publication Date: 2021-02-10
• Subjects: crystal water -- FeO6 polyhedra -- ferrihydrite -- hole storage -- photoelectrochemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202014871
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : The [FeO6 ] polyhedral hydration structure of ferrihydrite is responsible for its hole storage function. With the continuous loss of three molecules of crystal water, the quantity of stored photogenerated holes for PEC water oxidation gradually decreases, accompanied by the destruction of the hydration structure.