LAUSR

The electrochemical reduction of carbon dioxide into multi-carbon products using renewably generated electricity provides a promising pathway for energy and environmental sustainability. Various oxide-derived copper (OD-Cu) catalysts have been showcased, but still require high overpotential to drive C2+ production owing to sluggish carbon-carbon bond formation and low CO intermediate (*CO) coverage. Here, we circumvent the dilemma by elaborately devising OD-Cu morphology. Firstly, computational studies propose a hollow and hierarchical OD-Cu microstructure that can generate core-shell microenvironment to inhibit CO evolution and accelerate *CO dimerization via intermediate confinement and electric field enhancement, thereby boosting C2+ generation. Experimentally, we synthesize the designed nanoarchitectures through a hetero-seed inducing approach followed by electrochemical activation. In situ spectroscopic studies further elaborate correlation between *CO dimerization and designed architectures. Remarkably, the hierarchical OD-Cu manifests morphology-dependent selectivity of CO2 reduction, giving a C2+ Faradaic efficiency of 75.6% at a considerably positive potential of -0.55 V versus a reversible hydrogen electrode. This article is protected by copyright. All rights reserved.