Constructing Metal–Organic Framework Films with Adjustable Electronic Properties on Hematite Photoanode for Boosting Photogenerated Carrier Transport

Hematite (α‐Fe2O3) has become a research hotspot in the field of photoelectrochemical water splitting (PEC‐WS), but the low photogenerated carrier separation efficiency limits further application. The electronic structure regulation, such as element doping and organic functional groups with different electrical properties, is applied to alleviate the problems of poor electrical conductivity, interface defects, and band mismatch. Herein, α‐Fe2O3 photoanodes are modified to regulate their electric structures and improve photogenerated carrier transport by the bimetallic metal–organic frameworks (MOFs), which are constructed with Fe/Ni and terephthalate (BDC) with 2‐substitution of different organic functional groups (─H, ─Br, ─NO2 and ─NH2). The α‐Fe2O3 photoanode loaded with FeNi‐NH2BDC MOF catalyst exhibits the optimal photocurrent density (2 mA cm−2) at 1.23 VRHE, which is 2.33 times that of the pure α‐Fe2O3 photoanode. The detailed PEC analyses demonstrate that the bimetallic synergistic effect between Fe and Ni can improve the conductivity and inhibit the photogenerated carrier recombination of α‐Fe2O3 photoanodes. The ─NH2 group as an electron‐donor group can effectively regulate the electron distribution and band structure of α‐Fe2O3 photoanodes to prolong the lifetime of photogenerated holes, which facilitates photogenerated carrier transport and further enhances the PEC‐WS performance of α‐Fe2O3 photoanode. The introduction of bimetallic MOFs with different organic functional groups can regulate the electronic and band structure of α‐Fe2O3 photoanodes to improve the photoelectrochemical conversion performance. The ─NH2 group as an electron‐donor group significantly prolongs the decay lifetime of photogenerated holes, which enhances the photoelectrochemical water oxidation of the α‐Fe2O3 photoanode along with the bimetallic synergistic effect.