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 Cu 2 O microstructures were partially converted to the Metal‐Organic Frameworks (MOFs) Cu 3 (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 Cu 2 O 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 Cu 3 (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 Cu 2 O@Cu 3 (BTC) 2 and a 68,9 % increase for the Cu 2 O@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 Cu 2 O@Cu(BTC) and Cu 2 O@Cu(TCPP) microstructures.