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.