Dodecanol‐Regulated Dynamic Reconstruction of Cu ₂ O Superparticles Enables Selective Ampere‐Level CO ₂ Electroreduction to C ₂₊ Products

ABSTRACT Copper‐based catalysts are promising for converting CO ₂ to multicarbon (C ₂₊ ) products toward carbon neutrality, yet their industrial deployment is hindered by difficulty maintaining high selectivity at high current densities. Here, 1‐dodecanol‐functionalized Cu ₂ O superparticles (D‐Cu ₂ O‐SP) were synthesized via a wet chemical method, achieving a maximum Faradaic efficiency (FE) of 79.8% for C ₂₊ products and a C ₂₊ partial current density of 992 mA cm ⁻² . Characterizations revealed that 1‐dodecanol modification plays a dual role: stabilizing crucial *CO intermediates to enhance surface coverage and regulating D‐Cu ₂ O‐SP reconstruction to promote selective exposure of Cu (100) facets. The electrochemically active surface area (ECSA) increased to nearly 1.5 times that of pristine Cu ₂ O superparticles. Density functional theory (DFT) calculations indicate that dodecanol modification lowers the energy barrier for asymmetric C‐C coupling between *CO and *CHO intermediates. This work provides a feasible strategy for designing industrial‐grade electrocatalysts with high activity and selectivity while offering theoretical insights into the C ₂₊ formation mechanism.