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The solid-state electrochemistry of Cu−MOF and Zn−MOF metal−organic frameworks (MOFs) in contact with different MeCN and aqueous electrolytes is described. Voltammetric data can be rationalized by assuming that Zn−MOF is reduced to Zn metal and subsequently oxidized to Zn 2+ ions in solution. The electrochemistry of Cu−MOF, however, involves the stepwise reduction of the parent Cu(II) species to Cu(I) and Cu metal. Peculiar laminar metallic deposits intercalated within the MOF crystals appear. The electrodeposition mechanism depends on the applied potential and involves successive steps controlled by ion insertion and/or partial lattice disintegration, followed by instantaneous nucleation and 3D diffusive growth and layer-by-layer deposition.
Doménech‐Carbó et al. (Tue,) studied this question.