Gridized polynanomer catalysis with atomically dispersed iron achieve the nearly 100% selective electroreduction of CO2 to methanol

The electrochemical reduction of CO₂ to high-energy-density CH₃OH (15.6 MJ/L) under ambient temperature and pressure provides a strategic pathway to achieve carbon neutrality and mitigate energy crisis^1-4 (Fig. 1a). Although rationally designed nanocluster/alloy, single-atom catalysts, nanozyme and molecular catalysts have been continuously reported, both high selectivity and long-term recyclability are still rare that become the central challenges on the path to their commercialization ^5,6. It is emerging to make multiscale design of both metal centers of active sites and their cross-scale surrounding environments under the crucial mechanism of pathway selection (Fig. 1b) ^5,7-9. Herein, we reported the gridized nanomolecular and nanopolymer catalysts for high effective electroreduction of CO₂ to CH₃OH. An A-type nanogrid (A-grid) and its organic nanopolymers with atomically dispersed irons have been well identified with the unique catalytic active sites of Fe-N₁C₃Cl₁. Fe-based A-grid catalyst (FeAG) achieved a world-record CH₃OH selectivity of 96.8%. Notably, Fe-based A-grid nanopolymer (FePAG) catalyst exhibited a CH₃OH Faradaic efficiency (FE) of 60.5%, a CH₃OH selectivity of 98.3%, and a stability of up to 100 hours, outperforming currently reported molecular catalysts. The superior selectivity is probably attributed to the cooperation between the stronger *CO adsorption on FeAG and the super-hindrance that suppresses aggregates to guarantee the dispersion of single active sites. Our study provides new insights in the exploration of nanomolecular and polynanomer catalysis.