Nanoconfinement Engineering over Hollow Multi-Shell Structured Copper towards Efficient Electrocatalytical C-C coupling

Angew Chem Int Ed Engl. 2022 Jan 17;61(3):e202113498. doi: 10.1002/anie.202113498. Epub 2021 Dec 2.

Abstract

Nanoconfinement provides a promising solution to promote electrocatalytic C-C coupling, by dramatically altering the diffusion kinetics to ensure a high local concentration of C1 intermediates for carbon dimerization. Herein, under the guidance of finite-element method simulations results, a series of Cu2 O hollow multi-shell structures (HoMSs) with tunable shell numbers were synthesized via Ostwald ripening. When applied in CO2 electroreduction (CO2 RR), the in situ formed Cu HoMSs showed a positive correlation between shell numbers and selectivity for C2+ products, reaching a maximum C2+ Faradaic efficiency of 77.0±0.3 % at a conversion rate of 513.7±0.7 mA cm-2 in a neutral electrolyte. Mechanistic studies clarified the confinement effect of HoMSs that superposition of Cu shells leads to a higher coverage of localized CO adsorbate inside the cavity for enhanced dimerization. This work provides valuable insights for the delicate design of efficient C-C coupling catalysts.

Keywords: CO2 electroreduction; C−C coupling; Diffusion kinetics; Nanoconfinement.