Direct electrochemical synthesis of metal‐organic frameworks : Cu3(BTC)2 and Cu(TCPP) on copper thin films and copper‐based microstructures

Abstract

Cu thin films and Cu2O microstructures were partially converted to the Metal-Organic Frameworks (MOFs) Cu3(BTC)2 or Cu(TCPP) using an electrochemical process with a higher control and at milder conditions compared to the traditional solvothermal MOF synthesis. Initially, either a Cu thin film was sputtered, or different kinds of Cu or Cu2O microstructures were electrochemically deposited onto a conductive ITO glass substrate. Then, these Cu thin films or Cu-based microstructures were subsequently coated with a thin layer of either Cu3(BTC)2 or Cu(TCPP) by controlled anodic dissolution of the Cu-based substrate at room temperature and in the presence of the desired organic linker molecules: 1,3,5-benzenetricarboxylic acid (BTC) or photoactive 4,4′,4′′,4′′′-(Porphine-5,10,15,20-tetrayl) tetrakis(benzoic acid) (TCPP) in the electrolyte. An increase in size of the Cu micro cubes with exposed planes [100] of 38,7 % for the Cu2O@Cu3(BTC)2 and a 68,9 % increase for the Cu2O@Cu(TCPP) was roughly estimated. Finally, XRD, Raman spectroscopy and UV–vis absorption spectroscopy were used to characterize the initial Cu films or Cu-based microstructures, and the obtained core-shell Cu2O@Cu(BTC) and Cu2O@Cu(TCPP) microstructures.