Porous Solid Electrolyte Reactors for Function-Oriented Off-Electrode Electrosynthesis.

Electrosynthesis offers an attractive route to sustainable chemical manufacturing when coupled with renewable electricity. As electrosynthesis capability advances towards high-purity products, the traditional proximity of reaction products to the electrode surface, where the reaction happens, increasingly becomes a limiting factor. In addition, the formation and transport of reactive species are confined in the same chamber, resulting in electrolyte contamination of the product. Porous solid electrolyte (PSE) reactors address this spatial constraint by introducing an additional ion-conductive middle layer between the cathode and anode, enabling a versatile off-electrode space for product formation and transportation. Here, we frame PSE reactors as function-oriented platforms for off-electrode electrosynthesis, in which the PSE middle layer serves as a functional reaction space that enables ionic recombination, reaction-environment regulation, and improved management of reactive intermediates. By linking the underlying ionic-species transport mechanisms and reactor design principles, we establish a structure-transport-function framework for understanding how PSE reactors extend electrosynthesis beyond the electrode surface confinement and guide the rational design of scalable electrosynthesis reactors as on-site chemical manufacturing platforms.