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 Cu2 O 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 Cu2 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 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 Cu2 O@Cu3 (BTC)2 and a 68,9 % increase for the Cu2 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 Cu2 O@Cu(BTC) and Cu2 O@Cu(TCPP) microstructures.

Coating the surface of interconnected Cu2O 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 Cu2O@MOF nanowires standing on a conductive support with extensive control over the crystallization of the MOF nanoparticles at the surface of the Cu2O nanowires. Cu2O nanowires were first prepared via templated electrodeposition, and then partially converted into the well-known Cu-MOF HKUST-1 by pulsed electrochemical oxidation. We show that the use of PVP as a capping agent during the electrochemical oxidation of Cu2O into HKUST-1 provides control over the growth of the MOF nanocrystals on the surface of the Cu2O nanowires, and that the size of the MOF crystals obtained can be tuned by changing the concentration of PVP dissolved in the electrolyte. In addition, we propose the use of benzoic acid as an alternative to achieve control over the size of the obtained MOF nanocrystals when the use of a capping agent should be avoided.