Controlled Electrosynthesis of Metal-Organic Frameworks

Achieving controllable synthesis of metal-organic frameworks (MOFs) with precisely defined crystallinity, phase, orientation, thickness, and hierarchical architecture is essential for tailoring their properties across diverse applications, including gas separation, catalysis, and sensing. Electrochemical synthesis offers unique advantages by enabling room temperature operation and decoupled regulation of nucleation and growth kinetics through electrical parameters. In this Perspective, we review the fundamental mechanisms of MOF electrosynthesis based on anodic dissolution, metal ion oxidation, ligand oxidation, reductive deprotonation as well as metal ion reduction and discuss how applied potential, current density, and electric field govern the key microstructural outcomes. Despite notable progress, the field still relies heavily on empirical optimization rather than predictive design. Major challenges include decoupling electrochemical and chemical reaction steps, understanding direct electric field effects on crystallization, and overcoming self-inhibition in insulating MOF films. Addressing these issues will require operando characterization, rational decoupling of kinetic regimes, scalable manufacturing strategies, and data driven optimization.