Intermediate Binding Control Using Metal–Organic Frameworks Enhances Electrochemical CO2 Reduction

In the electrochemical CO₂ reduction reaction (CO₂RR), control over the binding of intermediates is key for tuning product selectivity and catalytic activity. Here we report the use of reticular chemistry to control the binding of CO₂RR intermediates on metal catalysts encapsulated inside metal-organic frameworks (MOFs), thereby allowing us to improve CO₂RR electrocatalysis. By varying systematically both the organic linker and the metal node in a face-centered cubic (fcu) MOF, we tune the adsorption of CO₂, pore openness, and Lewis acidity of the MOFs. Using operando X-ray absorption spectroscopy (XAS) and in situ Raman spectroscopy, we reveal that the MOFs are stable under operating conditions and that this tuning plays the role of optimizing the *CO binding mode on the surface of Ag nanoparticles incorporated inside the MOFs with the increase of local CO₂ concentration. As a result, we improve the CO selectivity from 74% for Ag/Zr-fcu-MOF-1,4-benzenedicarboxylic acid (BDC) to 94% for Ag/Zr-fcu-MOF-1,4-naphthalenedicarboxylic acid (NDC). The work offers a further avenue to utilize MOFs in the pursuit of materials design for CO₂RR.