Engineering Atomic Single Metal-FeN4Cl Sites with Enhanced Oxygen-Reduction Activity for High-Performance Proton Exchange Membrane Fuel Cells

Fe-N-C single-atomic metal site catalysts (SACs) have garnered tremendous interest in the oxygen reduction reaction (ORR) to substitute Pt-based catalysts in proton exchange membrane fuel cells. Nowadays, efforts have been devoted to modulating the electronic structure of metal single-atomic sites for enhancing the catalytic activities of Fe- N-C SACs, like doping heteroatoms to modulate the electronic structure of the Fe-N-x active center. However, most strategies use uncontrolled long-range interactions with heteroatoms on the Fe-N-x substrate, and thus the effect may not precisely control near-range coordinated interactions. Herein, the chlorine (Cl) is used to adjust the Fe-N-x active center via a near-range coordinated interaction. The synthesized FeN4Cl SAC likely contains the FeN4Cl active sites in the carbon matrix. The additional Fe-Cl coordination improves the instrinsic ORR activity compared with normal FeNx SAC, evidenced by density functional theory calculations, the measured ORR half-wave potential (E-1/2, 0.818 V), and excellent membrane electrode assembly performance.

Automated summary

Fe-N-C single-atomic metal site catalysts (SACs) have attracted great interest as substitutes for Pt-based catalysts in the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. Efforts have been made to modulate the electronic structure of metal single-atomic sites to enhance the catalytic activities. This study uses chlorine to adjust the active center via a near-range coordinated interaction, improving the intrinsic ORR activity.