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

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 it-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.