Breaking the linear scaling relationship in BN-supported metal catalysts for efficient CO2RR towards C1 and C2 products

Abstract

The catalytic activity and selectivity of CO₂ reduction reaction (CO₂RR) towards C1 and C2 products are fundamentally restricted by the inherent linear scaling relationship among the adsorption-free energies of intermediates. To face this challenge, we have proposed a novel multifunctional M₁M₂@BN electrocatalysts to break the linear scaling relationships in CO₂RR and efficiently obtain C1 and C2 products. Our results reveal that the optimal limiting potential is increased from −0.58 V for M@BN to −0.39 V for M₁M₂@BN, which achieves ultrahigh activity of CO₂RR. Further mechanism analysis illuminates that M₁M₂@BN can selectivity modulate the adsorption strength of OCHO* and OCH₂O*/OCHOH*, breaking the linear scaling relationship of adsorption-free energies of key intermediates to achieve the enhanced catalytic activity. Notably, the sufficient active sites on M₁M₂@BN electrocatalysts can promote the sluggish C–C coupling by capturing two CO intermediates simultaneously, further generating high-value multi-carbon (CH₂CH₂OH) products. Meanwhile, the thermodynamic stability of M₁M₂@BN has been demonstrated by ab initio molecular dynamics (AIMD) simulations, which shows the feasibility of commercial application in CO₂RR. Our findings provide a novel strategy to modulate the binding strength of intermediates and develop the design of efficient multi-active-site CO₂RR electrocatalysts.