The Importance of Metal-Organic Framework Linker Atoms for CO2 Reduction: A DFT Study.

Although the metal within the secondary building unit of a metal-organic framework is frequently studied as an active site, there is significantly less work exploring the linker effects. This work employs density functional theory (DFT) calculations to evaluate how linker atoms influence the carbon dioxide reduction reaction (CO2RR) in a series of 2D copper-based metal-organic frameworks (Cu MOFs). Regarding CO2RR selectivity, our results suggest that linker and copper single atoms preferentially facilitate *COOH and *OCHO intermediate formation, respectively, and that linker atoms facilitate H-shuttling to metal sites. Further, we find that the three Cu MOFs featuring NH-coordinated copper atoms exhibit the highest activity as predicted by DFT calculations. Analysis of the atomic electronic structure reveals linker electrostatics as a descriptor for CO2 activation and proton adsorption.