Decoupling‐Facilitated Mass‐Charge Transfer via Dual‐Interface Engineering for Efficient CO 2 Electrolysis

ABSTRACT The gas‐electrolyte‐electrode triple‐phase interfaces (TPIs) critically govern the kinetics of the electrochemical CO 2 reduction reaction (CO 2 RR) by regulating concerted proton‐electron transfer processes. However, sluggish mass transfer and the unbalanced adsorption of key intermediates within the local microenvironment of TPI remain major obstacles to efficient multicarbon product formation. Here, we report a dual‐interface strategy featuring amphiphilic and biphasic architectures to decouple mass‐charge transfer, achieved through in‐situ electrochemical activation of a polydimethylsiloxane (PDMS)‐modified Cu‐BTC electrode. The hydrophilic/hydrophobic interface promotes the synergistic mass transfer of CO 2 and protons within the TPI microenvironment, whereas the amorphous/crystalline interface modulates the electronic structure of catalytic active sites to optimize the adsorption kinetics of key intermediates. Such decoupling‐mediation accelerated C 2 H 4 Faradaic efficiency (FE) exceeding 86% at ‐0.9 V (vs. reversible hydrogen electrode, RHE), over 2.5 times higher than that of the control groups. This work highlights the potential of dual‐interface decoupling engineering to simultaneously optimize CO 2 mass transport pathways and intermediate adsorption kinetics, thereby enabling highly efficient electrosynthesis of C 2 H 4 .