cAIMD Simulations Guided Design of Atomic Praseodymium Doping In–Bi Nanofibers for High‐Energy‐Efficiency CO2 Electrolysis to Formate in Ultra‐Wide Potential Window

Abstract The electrochemical CO 2 reduction reaction (ECO 2 RR) has emerged as a promising technology for achieving carbon neutralization. Even though considerable efforts are dedicated to gain deep insight into the understanding of ECO 2 RR on a mechanism level through density functional theory (DFT) studies, effects of solvent molecules and temperature have long been neglected by conventional DFT calculations as a consequence of limitations in current technologies and computational power of supercomputers. Under this context, the lack of comprehensive understanding over the energy changes in the reaction derived from the only concern on free energy changes between reaction intermediates have arouse an urgent call for exploring feasible calculation options toward generalized theoretical study. Here, a systematic mechanism study is provided toward ECO 2 RR via constrained ab initio molecular dynamics (cAIMD) simulations, in which the effects of solvent water molecules and temperature are taken into consideration to guide the synthesis of single‐atom alloy (SAA) catalyst. Consequently, the resultant Pr 0.05 /InBi achieves a maximum Faradic efficiency (FE) of 96.4% and an energy efficacy (EE) of 59.41% for formate. This work offers a novel approach to the design and screening of SAA catalysts, presenting foreseeable future in accelerating the industrial application process of ECO 2 RR.