Controllable Regulation of CO2 Adsorption Behavior via Precise Charge Donation Modulation for Highly Selective CO2 Electroreduction to Formic Acid

Abstract The synthesis of value‐added products via CO 2 electroreduction (CO 2 ER) is of great significance, but the development of efficient and versatile strategies for the controllable selectivity tuning is extremely challenging. Herein, the tuning of CO 2 ER selectivity through the modulation of CO 2 adsorption behavior is proposed. Using the constructed zeolitic MOF (SNNU‐339), CO 2 adsorption behavior is controllably changed from *CO 2 to CO 2 * via the precise ligand‐to‐metal charge donation (LTMCD) regulation. It is confirmed that the high electronegativity of the coordinate ligand directly restricts the LTMCD, reduces the charge density on the metal sites, lowers the Gibbs free energy for CO 2 * adsorption, and leads to the transformation of CO 2 adsorption mode from *CO 2 to CO 2 *. Owing to the modulated CO 2 adsorption behavior and regulated kinetics, SNNU‐339 exhibits superior HCOOH selectivity (≈330% promotion, 85.6% Faradaic efficiency) and high CO 2 ER activity. The wide applicability of the proposed approach sheds light on the efficient CO 2 ER. This study provides a competitive strategy for rational catalyst design and underscores the significance of adsorption behavior tuning in electrocatalysis.