Modulating Active Center Microenvironment in Phthalocyanine‐Based Covalent Organic Frameworks for Enhanced Electrocatalytic CO ₂ to CH ₃ OH

Developing catalysts for electrocatalytic CO₂ to CH₃OH still faces great challenge due to the involvement of multiple proton-coupled electron transfer (PCET) processes. Molecular phthalocyanine electrocatalysts on carbon nanotubes have achieved production of methanol as the sole liquid-phase product but with the activity and stability far from meeting industrial demands. Herein, phthalocyaninato cobalt is fabricated into covalent organic frameworks PE-COF via polymerization with ellagic acid. Subsequent hydrolyzation of the ester groups in this framework affords COOH/OH-containing PEH-COF, resulting in the successful modulation over the local microenvironment of Co as electrochemical active center and in turn rendering the production of CH₃OH with high yield and durability. Experimental and theoretical investigations reveal that construction of the COOH group and H₂O participated catalytic cages in PEH-COF can effectively fix hydrated potassium ions, which efficiently enhances the PCET kinetics and lowers the energy barriers for the conversion of CO₂ to CH₃OH. The partial current density (j) and Faraday efficiency of methanol for PEH-COF could reach 100.9 mA cm^-2 and 38.5%, respectively. Moreover, the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics><mml:msub><mml:mi>j</mml:mi> <mml:mrow> <mml:msub><mml:mrow><mml:mi>C</mml:mi> <mml:mi>H</mml:mi></mml:mrow> <mml:mn>3</mml:mn></mml:msub> <mml:mi>O</mml:mi> <mml:mi>H</mml:mi></mml:mrow> </mml:msub> <mml:annotation>$\mathrm{j}_{{CH}_3OH}$</mml:annotation></mml:semantics> </mml:math> of PEH-COF can be maintained at 100.4 mA cm^-2 after 9 h of electrocatalysis, superior to the thus far reported catalysts.