Semiconductor@Metal–Organic Framework Core–Shell Heterostructures: A Case of ZnO@ZIF‑8 Nanorods with Selective Photoelectrochemical Response

Metal–organic frameworks (MOFs) and related material classes are attracting considerable attention for their applications in gas storage/separation as well as catalysis. In contrast, research concerning potential uses in electronic devices (such as sensors) is in its infancy, which might be due to a great challenge in the fabrication of MOFs and semiconductor composites with well-designed structures. In this paper, we proposed a simple self-template strategy to fabricate metal oxide semiconductor@MOF core–shell heterostructures, and successfully obtained freestanding ZnO@ZIF-8 nanorods as well as vertically standing arrays (including nanorod arrays and nanotube arrays). In this synthetic process, ZnO nanorods not only act as the template but also provide Zn²⁺ ions for the formation of ZIF-8. In addition, we have demonstrated that solvent composition and reaction temperature are two crucial factors for successfully fabricating well-defined ZnO@ZIF-8 heterostructures. As we expect, the as-prepared ZnO@ZIF-8 nanorod arrays display distinct photoelectrochemical response to hole scavengers with different molecule sizes (e.g., H₂O₂ and ascorbic acid) owing to the limitation of the aperture of the ZIF-8 shell. Excitingly, such ZnO@ZIF-8 nanorod arrays were successfully applied to the detection of H₂O₂ in the presence of serous buffer solution. Therefore, it is reasonable to believe that the semiconductor@MOFs heterostructure potentially has promising applications in many electronic devices including sensors