Molecular Electrocatalyst Enables Direct Electrochemical Capture and Conversion of CO 2 up to Atmospheric Concentration

ABSTRACT

The conversion of low‐concentration CO
2
streams into fuel is highly desirable for industrial applications, avoiding energy‐intensive CO
2
capture and concentration. Here, we report a highly active molecular electrocatalyst,
fac
‐[Mn(CO)
3
(bis‐MeNHC)(MeCN)]
+
(

1‐MeCN
+

), which enables the direct electrochemical reduction of near‐atmospheric CO
2
concentrations to CO with up to 100% Faradaic efficiency. Voltammetric analysis at varying CO
2
concentrations reveals a clear transition between distinct kinetic regimes, shifting from pure kinetic control to a regime dominated by CO
2
depletion. Kinetic analysis in the 5%–100% CO
2
range reveals a first‐order dependence on substrate concentration. Infrared spectroelectrochemistry confirms that the electrogenerated anionic catalyst remains active under extremely diluted CO
2
conditions. Computational modeling further supports that the CO
2
‐to‐CO conversion mediated by the doubly reduced species is kinetically accessible at atmospheric CO
2
levels. This work demonstrates molecular electrocatalysis even at CO
2
concentrations as low as 420 ppm (i.e. atmospheric CO
2
partial pressure).