Thousand-fold increase in O2 electroreduction rates with conductive MOFs

Molecular materials must deliver high current densities to be competitive with traditional heterogeneous catalysts. Despite their high density of active sites, it has been unclear why the reported O2 reduction reaction (ORR) activity of molecularly defined conductive metal-organic frameworks (MOFs) have been very low: ca. -1 mA cm(-2). Here, we use a combination of gas diffusion electrolyses and nanoelectrochemical measure-ments to lift multiscale O-2 transport limitations and show that the intrinsic electrocatalytic ORR activity of a model 2D conductive MOF, Ni-3(HITP)(2), has been underestimated by at least 3 orders of magnitude. When it is supported on a gas diffusion electrode (GDE), Ni-3(HITP)(2) can deliver ORR activities >-150 mA cm(-2) and gravimetric H2O2 electrosynthesis rates exceeding or on par with those of prior heterogeneous electrocatalysts. Enforcing the fastest accessible mass transport rates using scanning electrochemical cell microscopy revealed that Ni-3(HITP)(2) is capable of ORR current densities exceeding -1200 mA cm(-2) and at least another 130-fold higher ORR mass activity than has been observed in GDEs. Our results directly implicate precise control over multiscale mass transport to achieve high-current-density electrocatalysis in molecular materials.

Automated summary

Molecular materials have been found to have low electrocatalytic activity, possibly due to limitations in O2 transport. Through experiments, it was discovered that the actual electrocatalytic activity of a 2D conductive MOF material was underestimated by at least three orders of magnitude. When this material is supported on a gas diffusion electrode, it can achieve high ORR activity and electrosynthesis rates. Precise control over multiscale mass transport can enable high-current-density electrocatalysis in molecular materials.