Metallocene implanted metalloporphyrin organic framework for highly selective CO2 electroreduction

Abstract Metal organic frameworks (MOFs) with tunable porosity and metal sites have been considered as excellent candidates for electrochemical CO2 reduction reaction (CO2RR). However, the poor electron conductivity and electron-donating capability of MOFs constrain the improvement of catalytic efficiency. Herein, we implant metallocene in MOFs through a facile chemical vapor deposition method and thus-obtained catalysts present excellent CO2RR electrocatalysis performances. For instance, the FECO of CoCp2@MOF-545-Co can be as high as 97% at −0.7 V. The high performances might be attributed to the strong binding-interaction between metallocene and metalloporphyrin that can largely reduce the adsorption energy of CO2 as revealed by density functional theory calculations. The introduction of metallocene can serve as electron donator and carrier to create continuous electron transfer channel in MOFs and provide strong binding-interaction with metalloporphyrin during CO2RR process to enhance the CO2RR activity. This method might shed light on development of highly-selective CO2RR electrocatalysts.