Direct Electrochemical Synthesis of Metal-Organic Frameworks: Cu3(BTC)2 and Cu(TCPP) on Copper Thin films and Copper-Based Microstructures

Cu thin films and Cu2O 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 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 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 Cu2O@Cu-3(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.

Automated summary

Cu thin films and Cu2O microstructures were converted to MOFs Cu-3(BTC)(2) or Cu(TCPP) using an electrochemical process, providing higher control and milder conditions compared to the traditional solvothermal MOF synthesis. Cu thin films or different types of Cu or Cu2O microstructures were prepared and subsequently coated with Cu-3(BTC)(2) or Cu(TCPP) through controlled anodic dissolution at room temperature. The size of Cu microcubes increased by a certain percentage.