Boosting CO₂ Electroreduction to C₂H₄ via Unconventional Hybridization: High-Order Ce⁴⁺ 4f and O 2p Interaction in...

Efficient conversion of carbon dioxide (CO₂) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions and close the anthropogenic carbon loop. Recently, there has been intense interest in Cu₂O-based catalysts for the CO₂ reduction reaction (CO₂RR), owing to their capabilities in enhancing C-C coupling. However, the electrochemical instability of Cu⁺ in Cu₂O leads to its inevitable reduction to Cu⁰, resulting in poor selectivity for C₂₊ products. Herein, we propose an unconventional and feasible strategy for stabilizing Cu⁺ through the construction of a Ce⁴⁺ 4f-O 2p-Cu⁺ 3d network structure in Ce-Cu₂O. Experimental results and theoretical calculations confirm that the unconventional orbital hybridization near E_f based on the high-order Ce⁴⁺ 4f and 2p can more effectively inhibit the leaching of lattice oxygen, thereby stabilizing Cu⁺ in Ce-Cu₂O, compared with traditional d-p hybridization. Compared to pure Cu₂O, the Ce-Cu₂O catalyst increased the ratio of C₂H₄/CO by 1.69-fold during the CO₂RR at -1.3 V. Furthermore, in situ and ex situ spectroscopic techniques were utilized to track the oxidation valency of copper under CO₂RR conditions with time resolution, identifying the well-maintained Cu⁺ species in the Ce-Cu₂O catalyst. This work not only presents an avenue to CO₂RR catalyst design involving the high-order 4f and 2p orbital hybridization but also provides deep insights into the metal-oxidation-state-dependent selectivity of catalysts.