Cathodic Electrodeposition of MOF Films Using Hydrogen Peroxide

Metal-organic framework (MOF) films can be made by cathodic electrodeposition, where a Brønsted base is formed electrochemically which deprotonates the MOF linkers that are present in solution as undissociated/partially dissociated weak acids. However, the co-deposition of metal and the narrow range of possible metal nodes limit the scope of this method. In this work, we propose the use of hydrogen peroxide (hydrogen peroxide assisted cathodic deposition or HPACD), to overcome these limitations. Electrochemical measurements indicate that in DMF, hydrogen peroxide is reduced to superoxide anions that deprotonate the carboxylic ligands. This single-electron reduction happens at much higher potentials than all previous reported methods. This prevents the co-deposition of metal and extends the range of possible metal nodes. Various pure MOF films (HKUST-1, MIL-53(Fe) and MOF-5) were prepared via this approach. HPACD was also used for the preparation of patterned MOF films and of flexible Cu-BTC coated paper membranes which reject 99.1 % of Rose Bengal from water with a permeance of 8.4 L m^-2  h^-1  bar^-1 .