A pyridinic Fe-N<sub>4</sub> macrocycle models the active sites in Fe/N-doped carbon electrocatalysts.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 33077736.
- Also identified by DOI 10.1038/s41467-020-18969-6 and PMC identifier 7572418.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Iron- and nitrogen-doped carbon (Fe-N-C) materials are leading candidates to replace platinum catalysts for the oxygen reduction reaction (ORR) in fuel cells; however, their active site structures remain poorly understood. A leading postulate is that the iron-containing active sites exist primarily in a pyridinic Fe-N<sub>4</sub> ligation environment, yet, molecular model catalysts generally feature pyrrolic coordination. Herein, we report a molecular pyridinic hexaazacyclophane macrocycle, (phen<sub>2</sub>N<sub>2</sub>)Fe, and compare its spectroscopic, electrochemical, and catalytic properties for ORR to a typical Fe-N-C material and prototypical pyrrolic iron macrocycles. N 1s XPS and XAS signatures for (phen<sub>2</sub>N<sub>2</sub>)Fe are remarkably similar to those of Fe-N-C. Electrochemical studies reveal that (phen<sub>2</sub>N<sub>2</sub>)Fe has a relatively high Fe(III/II) potential with a correlated ORR onset potential within 150 mV of Fe-N-C. Unlike the pyrrolic macrocycles, (phen<sub>2</sub>N<sub>2</sub>)Fe displays excellent selectivity for four-electron ORR, comparable to Fe-N-C materials. The aggregate spectroscopic and electrochemical data demonstrate that (phen<sub>2</sub>N<sub>2</sub>)Fe is a more effective model of Fe-N-C active sites relative to the pyrrolic iron macrocycles, thereby establishing a new molecular platform that can aid understanding of this important class of catalytic materials.