Bifunctional citrate-Ni0.9Co0.1(OH)x layer coated fluorine-doped hematite for simultaneous hole extraction and injection towards efficient photoelectrochemical water oxidation

Abstract

Surface modification by loading a water oxidation co-catalyst (WOC) is generally considered an efficient means to optimize the sluggish surface oxygen evolution reaction (OER) of a hematite photoanode for photoelectrochemical (PEC) water oxidation. However, the surface WOC usually exerts little impact on the bulk charge separation of hematite. Herein, an ultrathin citrate-Ni_0.9Co_0.1(OH)_x [Cit-Ni_0.9Co_0.1(OH)_x] is conformally coated on the fluorine-doped hematite (F-Fe₂O₃) photoanode for PEC water oxidation to simultaneously promote the internal hole extraction and surface hole injection of the target photoanode. Besides, the conformally coated Cit-Ni_0.9Co_0.1(OH)_x overlayer passivates the redundant surface trap states of F-Fe₂O₃. These factors result in a superior photocurrent density of 2.52 mA cm⁻² at 1.23 V versus a reversible hydrogen electrode (V vs. RHE) for the target photoanode. Detailed investigation manifests that the hole extraction property in Cit-Ni_0.9Co_0.1(OH)_x is mainly derived from the Ni sites, while Co incorporation endows the overlayer with more catalytic active sites. This synergistic effect between Ni and Co contributes to a rapid and continuous hole migration pathway from the bulk to the interface of the target photoanode, and then to the electrolyte for water oxidation.