Hollow Hierarchical Cu2O‐Derived Electrocatalysts Steering CO2 Reduction to Multi‐Carbon Chemicals at Low Overpotentials

• Published in: Advanced materials (Weinheim) 2023-06, Vol.35 (26), p.n/a
• Main Authors: Li, Jinhan, Xu, Keqiang, Liu, Fangming, Li, Youzeng, Hu, Yanfang, Chen, Xijie, Wang, Huan, Xu, Wence, Ni, Youxuan, Ding, Guoyu, Zhao, Tete, Yu, Meng, Xie, Wei, Cheng, Fangyi
• Format: Article
• Language: English
• Subjects: Carbon dioxide; carbon dioxide reduction; Chemical reduction; Copper; Dimerization; Electric fields; electrocatalysis; Electrocatalysts; Electrochemical activation; heteroseed‐induced synthesis; hollow hierarchical microstructure; Materials science; Morphology; multi‐carbon chemicals; Steering
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202301127

The electrochemical reduction of carbon dioxide into multi‐carbon products (C2+) 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, the dilemma is circumvented by elaborately devising the OD‐Cu morphology. First, computational studies propose a hollow and hierarchical OD‐Cu microstructure that can generate a core–shell microenvironment to inhibit CO evolution and accelerate *CO dimerization via intermediate confinement and electric field enhancement, thereby boosting C2+ generation. Experimentally, the designed nanoarchitectures are synthesized through a heteroseed‐induced 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 reversible hydrogen electrode. Through rational design of catalyst morphology and elaborate calculations, a heteroseed‐induced crystallization strategy is developed for the synthesis of hollow hierarchical vertex Cu/Cu2O catalysts that can provide intermediate confinement and surface electric field enhancement for CO intermediate dimerization, thereby boosting electrocatalytic CO2 reduction to multi‐carbon products at low overpotentials.