Ion Insertion-Driven Electrochemistry of MOFs

FIG (J RE 5.2 Square-wave voltammograms of Cu-MOF immersed into (a) 0.10 M BtqNPI y,/ MeCN, (b) 0.10 M Et4NClO4/MeCN, and (c) 0.10 M LiClO4/MeCN. Potential scan initiated at +1.65 V vs. AgCl/Ag in the negative direction. Potential step increment, 4 mV square-wave amplitude, 25 mV frequency, 5 Hz. (From Domenech et al., 2006d. Electrochem. Commun. 8 1830-1834, with permission.) 

Reduction of Cu + centers to CiC ones can, in principle, occur via four different electrochemical pathways  

Topotactic solid-state transformation coupled with the ingress of electrolyte cations, M, into the solid  

Proton-assisted topotactic solid-state transformation involving the protonation of organic groups in the solid lattice  

Reductive reorganization involving the loss of organic polyfunctional units  

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