Two-dimensional π-conjugated metal–organic frameworks as highly efficient catalysts for CO2 electroreduction

Abstract

With fossil fuel reserves diminishing, designing and synthesizing electrocatalysts with controllable active sites is essential for converting carbon dioxide (CO₂) into valuable chemicals. Inspired by the experimental advancement of two-dimensional π-conjugated metal–organic framework (2D c-MOF) nanosheets, we have performed a computational screening to identify optimal single-atom catalysts for the CO₂ reduction reaction (CO₂RR) across eleven 2D c-MOFs (HTHATN-TM). These frameworks comprise transition metals (TM = Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, or Ag) and hexathiohexaazatrinaphthylene (HTHATN) organic ligands. Our first-principles calculations reveal that HTHATN-Cr and HTHATN-Ru emerge as highly promising CO₂RR catalysts, exhibiting low limiting potentials of −0.38 V and −0.53 V, respectively, and favoring the production of HCOOH and CH₄. These findings provide valuable insights for the development of more efficient CO₂RR catalysts.