Porphyrins and metalloporphyrins have been proposed for various applications such as solar cells, catalytic systems, and electrocatalysis. Given several advantages of metal-organic frameworks (MOFs) including regular porosity and ultrahigh surface area, various MOFs constructed from porphyrin-based linkers have been widely reported. In order to apply porphyrin MOFs for electrocatalysis, porphyrin MOF thin films must be grown on conducting substrates. However, only a few studies reported the growth of porphyrin MOF thin films in literature.<br/>In this study, uniform thin films of a MOF, which is constructed from the meso-tetra(4-carboxyphenyl)porphine linkers and hexa-zirconium nodes (MOF-525), are grown on conducting glass substrates by solvothermal approach (Fig. 1). Since the porphyrin center cannot be metalated with Zr during the synthesis of MOF, the linkers of MOF-525 are still free-base porphyrins. Thus, the obtained MOF-525 thin film is expected to act as a platform for the post metalation of its linkers with any desired metal. To the best of our knowledge, to date there are no studies reporting either MOF-525 thin films or the post metalations of any Zr-based porphyrin MOF film. Zn and Co are selected for post metalation in this study. All the MOF-525 and metalated MOF-525 thin films are electrochemically addressable, which opens up the opportunities for utilizing them for the electrocatalysis involving porphyrinic or various metalloporphyrinic units. By using the MOF-525 thin film, a significant electrocatalytic current for the oxidation of nitrite is observed in aqueous media, which is about 270 times higher than that achieved by using a bare substrate.

Solvothermally grown porphyrin metal-organic framework (MOF) thin films: Post metalation and electrocatalysis

249th National Meeting (2015)

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