Gridized Nanopolymer Catalysis with Atomically Dispersed Iron Achieves the Nearly 100% Selective Electrosynthesis of Methanol From CO 2

Abstract The electrochemical reduction of CO 2 to methanol (CH 3 OH) offers a highly promising avenue for zero‐emission carbon recycling and renewable energy storage. However, achieving high CH 3 OH selectivity and long‐term stability in catalysts remains rare, presenting central challenges on the path to their commercialization. It is emerging to make multiscale design of metal centers of active sites and their surrounding environments under the crucial mechanism of pathway selection. Herein, the gridized nanomolecular and nanopolymer catalysts are reported for high effective electroreduction of CO 2 to CH 3 OH. An A‐type nanogrid (AG) and its organic nanopolymers with atomically dispersed iron (Fe) are well identified with the unique catalytic active sites of Fe‐N 1 C 3 Cl 1 . Notably, Fe‐based AG nanopolymer (FePAG) catalyst exhibits a CH 3 OH Faradaic efficiency of 60.5%, a CH 3 OH selectivity of 98.3%, and a stability of up to 100 h, outperforming currently reported molecular catalysts. The superior selectivity is probably attributed to the cooperation between the stronger *CO adsorption and the super‐hindrance that suppresses aggregates to guarantee the dispersion of single active sites. This study provides new insights in the exploration of nanomolecular and nanopolymer catalysis.