Fluorine-Tuned Atomically Dispersed Magnesium Sites for Highly Efficient CO2 Electrocatalytic Reduction
Article
Liu, H, Gao, M, Cheng, W et al. (2025). Fluorine-Tuned Atomically Dispersed Magnesium Sites for Highly Efficient CO2 Electrocatalytic Reduction
. ADVANCED FUNCTIONAL MATERIALS, 10.1002/adfm.202521705
Liu, H, Gao, M, Cheng, W et al. (2025). Fluorine-Tuned Atomically Dispersed Magnesium Sites for Highly Efficient CO2 Electrocatalytic Reduction
. ADVANCED FUNCTIONAL MATERIALS, 10.1002/adfm.202521705
The electrochemical carbon dioxide reduction reaction (CO2RR) represents a promising strategy for converting CO2 into CO. Atomically dispersed transition metal sites have an exceptional ability to activate CO2. However, the strong hybridization between the 3d orbitals of these transition metals and the 5σ or 2π* orbital of CO significantly impedes *CO desorption, thereby limiting the overall CO generation activity. In contrast, s-block metals, with diffuse 3s electron clouds, exhibit weaker interactions with *CO. Nevertheless, their practical application is hindered by the high energy barrier associated with the formation of the *COOH intermediate. To address these challenges, a fluorine(F)-tuned magnesium single-atom catalyst (Mg-SAC) is developed. Remarkably, this catalyst achieved a CO Faraday efficiency of 97.3% and a current density of 260.4 mA cm−2 at −0.4 V vs the reversible hydrogen electrode in a flow cell, surpassing the performance of most state-of-the-art SACs and transition metal catalysts reported in the literature. Mechanistic studies reveal that *CO desorption on Mg sites is significantly easier compared to that on Fe and Co sites. Furthermore, the incorporation of F atoms modifies the electronic structure of the MgN4 sites, substantially lowering the energy barrier for the formation of the critical *COOH intermediate.
