The incorporation of molecular catalyst of energy relevance, i.e. compounds that catalyze water oxidation or proton and CO2 reduction, into metal-organic frameworks (MOFs) has become an increasingly popular strategy within artificial photosynthesis. The motivation for this approach is manifold: the molecular integrity of the catalysts is stabilized in the MOF compared to the situation in homogenous solution phase, leading to increased longevity of the catalyst and thus higher turnover numbers. Also, the heterogeneous nature of the MOF allows for recycling of the catalyst by simple centrifugation. Lastly, the periodicity and high order in MOFs potentially allows controlled synthetic modifications to the surroundings of the molecular catalyst. With judicious design, favorable interactions between the MOF and the molecular catalysts could be engineered that give rise to enhanced catalyst activity, similar to the situation of active sites in enzymes. In this presentation, we discuss a number of topics related to the function of molecular catalysts in MOFs. These include a study to localize molecular components within MOF crystals by Rutherford backscattering spectrometry (RBS), a method that has to the best of our knowledge not been used for MOF characterizations before. In particular, RBS will be used as a means to follow post-synthetic linker exchange (PSE). In addition, studies on substrate accessibility to MOF-incorporated catalysts will be presented.

Molecular catalysis of energy relevance in metal-organic frameworks

254th National Meeting (2017)

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