  Electrocatalytic CO2 reduction technology is key to mitigating greenhouse gas
emissions and the energy crisis. However, controlling the selectivity of CO2RR
products at low overpotential remains a challenge. In this paper, we predicted
five high-performance CO2RR electrocatalysts with different product-specific
selectivities at the theoretical level based on the advantages of the
compositional structure and the tunable pore size of 2D {\pi}-conjugated MOFs.
In addition, through the reaction mechanism and electronic structure analysis,
we found that the synergistic interaction between metal atoms and organic
linkers of 2D MOFs can effectively regulate the electronic structure of the
active center. Their pore size as well as the diversity of carbon materials can
regulate the spin magnetic moments of the metal atoms, thus affecting the
improvement of their catalytic performance. Meanwhile, the oxygen or carbon
affinity of the catalyst surface determines the differences in the formation of
key intermediates, which ultimately determines the reaction path and product
selectivity. These insights we present will be useful for the development and
design of highly active CO2RR electrocatalysts.
