Solid‐Liquid‐Gas Three‐Phase Indirect Electrolysis Enabled by Affinity Auxiliary Imparted Covalent Organic Frameworks

The design of efficient heterogeneous redox mediators with favorable affinity to substrate and electrolyte are much desired yet still challenging for the development of indirect electrolysis system. Herein, for the first time, we have developed a solid–liquid–gas three‐phase indirect electrolysis system based on a covalent organic framework (Dha−COF−Cu) as heterogeneous redox mediator for S−S coupling reaction. Dha−COF−Cu with the integration of high porosity, nanorod morphology, abundant hydroxyl groups and active Cu sites is much beneficial for the adsorption/activation of thiols, uniform dispersion and high wettability in electrolyte, and efficient interfacial electron transfer. Notably, Dha−COF−Cu as solid‐phase redox mediator exhibits excellent electrocatalytic efficiency for the formation of value‐added liquid‐phase S−S bond product (yields up to 99 %) coupling with the generation of gas‐phase product of H2 (~1.40 mmol g−1 h−1), resulting in a powerful three‐phase indirect electrolysis system. This is the first work about COFs that can be applied in three‐phase indirect electrolysis system, which might promote the development of porous crystalline materials in this field. A solid–liquid–gas three‐phase indirect electrolysis system has been developed based on a covalent organic framework (Dha−COF−Cu) as heterogeneous redox mediator for S−S coupling reaction.