Impact of 3d-metals on M-Pt@Cu dual-atom alloy for CO2 electroreduction: Scaling descriptors

Abstract

Effectively reduce CO₂ to high-value chemicals is a crucial approach to achieving carbon neutrality. Herein, we utilized density functional theory (DFT) calculations to screen out a series of dual-atom alloys (DAAs) M-Pt@Cu, involving transition metal (TM), Pt-co-loaded on the surface of Cu(111), for electrochemical CO₂ reduction (eCO₂RR). Concerning the electronic properties of 3d TMs (e.g. Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Zn), the dependence of the activation of *CO₂ and the adsorption energy of *H on the number of valence electrons shows a volcano-like relationship, shedding light on V-Pt@Cu suppressing hydrogen evolution reaction (HER) and promoting eCO₂RR. Specially, the free energy calculation results reveal that V-Pt@Cu significantly inhibits the HER and directs eCO₂RR towards the C₂ product, CH₃CH₃. Subsequently, catalytic simulation results under external potential demonstrated that regardless of the pH value, CH₃CH₃ always requires a more positive potential than CH₄, suggesting that products are always produced toward CH₃CH₃ under the wide pH range. Utilizing the sure independence screening and sparsifying operation (SISSO) method, electronic descriptors have been screened out to identify the activation degree of CO₂ and H adsorption of M-Pt@Cu. These descriptors are closely related to the valence electron number, atomic mass, first ionization energy, and electronegativity of TM. Furthermore, the correlation analysis of these descriptors validated that the V-Pt@Cu system is a favorable catalyst for eCO₂RR. The results of this study provide a new perspective for the electrocatalysis of CO₂ in DAAs and facilitate the rational design of effective eCO₂RR electrocatalysts.