A Heterogenized Copper Phenanthroline System to Catalyze the Oxygen Reduction Reaction.

Upon the electrochemical reduction of an in situ generated 5-diazo-1,10-phenanthroline ion, phenanthroline was covalently attached to a gold electrode. The grafted molecules act as a ligand when brought in contact with a copper-containing electrolyte solution. As the ligands are limited in spatial movement, the exclusive formation of the active species with only one phenanthroline ligand coordinated was expected. The in situ generated complexes have been investigated for activity in the oxygen reduction reaction, for which an overpotential of 800 mV is observed. During catalysis, initially a thick copper layer is formed on top of an organic layer that is still present on the gold surface. Upon deterioration of the organic layer underneath the copper over time, the amount of copper on the electrode and thereby the electrocatalytic activity decreases.

Crosslinker-Induced Effects on the Gelation Pathway of a Low Molecular Weight Hydrogel.

The use of polymeric crosslinkers is an attractive method to modify the mechanical properties of supramolecular materials, but their effects on the self-assembly of the underlying supramolecular polymer networks are poorly understood. Modulation of the gelation pathway of a reaction-coupled low molecular weight hydrogelator is demonstrated using (bio)polymeric crosslinkers of disparate physicochemical identities, providing a handle for control over materials properties.