Enhanced Photoelectrochemical Water Oxidation Using TiO(2)-Co(3)O(4) p–n Heterostructures Derived from in Situ-Loaded ZIF-67

Exposing catalytically active metal sites in metal–organic frameworks (MOFs) while maintaining porosity is beneficial for increasing electron transport to achieve better electrochemical energy conversion performance. Herein, we propose an in situ method for MOF formation and loading onto TiO(2) nanorods (NR) using a simple solution-processable method followed by annealing to obtain TiO(2)-Co(3)O(4). The as-prepared TiO(2)-ZIF-67 based photoanodes were annealed at 350, 450, and 550 °C to study the effect of carbonization on photo-electrochemical water oxidation. The successful loading of ZIF-67 on TiO(2) and the formation of TiO(2)-Co(3)O(4) heterojunction were confirmed by XRD, XPS, FE-SEM, and HRTEM analyses. TiO(2)-Co(3)O(4)-450 (the sample annealed at 450 °C) showed an enhanced photocurrent of 2.4 mA/cm(2), which was 2.6 times larger than that of pristine TiO(2). The improved photocurrent might be ascribed to the prepared p–n heterostructures (Co(3)O(4) and TiO(2)), which promote electron–hole separation and charge transfer within the system and improve the photoelectrochemical performance. Moreover, the preparation of Co(3)O(4) from the MOF carbonization process improved the electrical conductivity and significantly increased the number of exposed active sites and enhanced the photoresponse performance. The as-prepared ZIF-67 derived TiO(2)-Co(3)O(4) based photoanodes demonstrate high PEC water oxidation, and the controlled carbonization method paves the way toward the synthesis of low-cost and efficient electrocatalysts.