Tuning the Size and Shape of NanoMOFs via Templated Electrodeposition and Subsequent Electrochemical Oxidation

The control over the size and shape of nanoMOFs is essential for their exploitation in integrated devices such as sensors, membranes for gas separation, photoelectrodes, etc. Here, we demonstrate the synthesis of nanowires and three-dimensionally interconnected nanowire networks of Cu-based metal-organic frameworks (MOFs) by a combination of ion-track technology and electrochemical methods. In particular, Cu nanowires and nanowire networks were electrodeposited inside polymeric etched ion-track membranes and subsequently converted by electrochemical oxidation into different Cu-based MOFs such as the well-known Cu₃(BTC)₂ (also known as HKUST-1) and the lesser-known MOF Cu(INA)₂. The MOFs are formed inside the template, therefore adopting the shape of the host nanochannels. The synthesized MOF nanowires exhibit tunable diameters between 80 and 260 nm. Characterization by X-ray diffraction, thermogravimetric analysis/differential scanning calorimetry, scanning electron microscopy, and transmission electron microscopy indicates that the employed electrochemical conversion includes the formation of Cu₂O as an intermediate, as well as the initial formation of an amorphous MOF phase, which crystallizes upon longer reaction times.