Solvothermal Preparation of an Electrocatalytic Metalloporphyrin MOF Thin Film and its Redox Hopping Charge-Transfer Mechanism

A thin film of a metalloporphyrin metal–organic framework consisting of [5,10,15,20-(4-carboxyphenyl)porphyrin]Co(III) (CoTCPP) struts bound by linear trinuclear CoII-carboxylate clusters has been prepared solvothermally on conductive fluorine-doped tin oxide substrates. Characterization of this mesoporous thin film material, designated as CoPIZA/FTO, which is equipped with large cavities and access to metal active sites, reveals an electrochemically active material. Cyclic voltammetry displays a reversible peak with E 1/2 at −1.04 V vs ferrocyanide attributed to the (CoIII/IITCPP)CoPIZA redox couple and a quasi-reversible peak at −1.45 V vs ferrocyanide, which corresponds to the reduction of (CoII/ITCPP)CoPIZA. Analysis of the spectroelectrochemical response for the (CoII/ITCPP)CoPIZA redox couple revealed non-Nernstian reduction with a nonideality factor of 2 and an E 1/2 of −1.39 V vs ferrocyanide. The film was shown to retain its structural integrity with applied potential, as was demonstrated spectroelectrochemically with maintenance of isosbestic points at 430, 458, and 544 nm corresponding to the (CoIII/IITCPP)CoPIZA transition and at 390 and 449 nm corresponding to the (CoII/ITCPP)CoPIZA transition. The mechanism of charge transport through the film is proposed to be a redox hopping mechanism, which is supported by both cyclic voltammetry and spectroelectrochemistry. A fit of the time-dependent spectroelectrochemical data to a modified Cottrell equation gave an apparent diffusion coefficient of 7.55 (±0.05) × 10–14 cm2/s for ambipolar electron and cation transport throughout the film. Upon reduction of the metalloporphyrin struts to (CoITCPP)CoPIZA, the CoPIZA thin film demonstrated catalytic activity for the reduction of carbon tetrachloride.