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The interaction mechanism between the reacting species and the active site of α‐Fe2O3‐based photoanodes in photoelectrochemical methanol conversion reaction is still ambiguous. Herein, a simple two‐step strategy is demonstrated to fabricate a porous α‐Fe2O3/CoFe2O4 heterojunction for the methanol conversion reaction. The influence of the electronic structure of active site and interfacial effect on the reaction are investigated by constructing two different FeO6 octahedral configurations and heterogeneous structures. The optimal sample ZnFeCo‐2 affords high photocurrent density of 1.17 mA cm−2 at 0.5 V vs Ag/AgCl, which is 3.2 times than that of ZnFe (0.37 mA cm−2). Meanwhile, the ZnFeCo‐2 also exhibits 97.8% Faraday efficiency of CH3OH to HCHO, and long‐term stability over 40 h. Furthermore, density functional theory calculations reveal that the heterostructured α‐Fe2O3/CoFe2O4 with favorable electron transfer effectively lowers methanol adsorption, C–H bond activation, and HCHO desorption energy relative to the pristine α‐Fe2O3, resulting in excellent methanol conversion efficiency.
A spinel‐CoFe2O4‐decorated α‐Fe2O3 nanotube arrays (NTAs) photoanode is developed for the oxidation of methanol to formaldehyde. The superiority of the co‐edged FeO6 octahedral structure in the Formox process is demonstrated. Impressively, the heterostructure and the interfacial effect of α‐Fe2O3 and CoFe2O4 facilitates the separation and transport of photogenerated carriers, resulting in superior PEC methanol conversion efficiency and formaldehyde selectivity.