Electrochemical Doping and Structural Modulation of Conductive Metal‐Organic Frameworks

Abstract In this study, we introduce an electrochemical doping strategy aimed at manipulating the structure and composition of electrically conductive metal‐organic frameworks (c‐MOFs). Our methodology is exemplified through a representative c‐MOF, Ni 3 (HITP) 2 (HITP=2, 3, 6, 7, 10, 11‐hexaiminotriphenylene), synthesized into porous thin films supported by nanocellulose. While the c‐MOF exhibits characteristic capacitive behavior in neutral electrolyte; it manifests redox behaviors in both acidic and alkaline electrolytes. Evidence indicates that the organic ligands within c‐MOF undergo oxidation (p‐doping) and reduction (n‐doping) when exposed to specific electrochemical potentials in acidic and alkaline electrolyte, respectively. Interestingly, the p‐doping process proves reversible, with the c‐MOF structure remaining stable across cyclic p‐doping/de‐doping. In contrast, the n‐doping is irreversible, leading to the gradual decomposition of the framework into inorganic species over a few cycles. Drawing on these findings, we showcase the versatile electrochemical applications of c‐MOFs and their derived composites, encompassing electrochemical energy storage, electrocatalysis, and ultrafast actuation. This study provides profound insights into the doping of c‐MOFs, offering a new avenue for modulating their chemical and electronic structure, thereby broadening their potential for diverse electrochemical applications.