Dynamic Confinement of Cu3 Clusters in T-C3N2 Pores: An Adaptive Interface for Selective CO Electroreduction to C3 Products

Abstract

The rational design of catalysts with dynamically adaptive active sites is crucial for steering multi-carbon product formation in CO electroreduction. Herein, we propose a confined and flexible triatomic Cu3 cluster anchored within the pores of a twodimensional carbon nitride T-C3N2 monolayer (Cu3@T-C3N2) as an efficient electrocatalyst. The suitable pore size (5.534 Å) of T-C3N2 not only stabilizes the Cu3 cluster but also allows its dynamic structural adaptation during reaction. This unique configuration facilitates the optimal adsorption and aggregation of *CO intermediates, and can promote the trimerization of *CO through a synergistic coupling pathway. Consequently, the catalyst achieves remarkably low limiting potentials of -0.18 V for n-propanol and -0.24 V for propene, significantly outperforming conventional static Cu-based catalysts.Furthermore, the confined and adaptive structure effectively suppresses competing hydrogen evolution and C1/C2 pathways, resulting in superior C3 selectivity with a propanol-to-methane ratio up to 2.59×10 3 :1. This study establishes Cu3@T-C3N2 as a highly efficient triatomic CORR catalyst and provides a general design principle for confined, adaptive electrocatalysts.