Abstract
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 O(2) 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 measurements 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 H(2)O(2) 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.