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

Cu thin films and Cu O microstructures were partially converted to the Metal-Organic Frameworks (MOFs) Cu (BTC) 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 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 (BTC) 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.

Coating the surface of interconnected CuO nanowire arrays with HKUST-1 nanocrystals via electrochemical oxidation.

Controlling the crystallization of Metal-Organic Frameworks (MOFs) at the nanoscale is currently challenging, and this hinders their utilization for multiple applications including photo(electro)chemistry and sensors. In this work, we show a synthetic protocol that enables the preparation of highly homogeneous CuO@MOF nanowires standing on a conductive support with extensive control over the crystallization of the MOF nanoparticles at the surface of the CuO nanowires. CuO nanowires were first prepared via templated electrodeposition, and then partially converted into the well-known Cu-MOF HKUST-1 by pulsed electrochemical oxidation.