Dual Metal Site Fe Single Atom Catalyst with Improved Stability in Acidic Conditions

Dual atom catalysts (DACs) not only retain uniform active sites and high atomic utilization efficiency as the single atom catalysts, but the two adjacent metal sites also cooperate and play a synergistic role to achieve additional benefits. However, the relationships connecting their dual-site synergistic effects on catalytic performance are not well rationalized due to limited pairs available from experiments. Herein, Fe/M dual sites supported by nitrogen doped carbon (Fe/M-N-C whereby M from 3 d–5 d electron containing transition metals) have been screened as an oxygen reduction reaction (ORR) catalyst. The results show that the absorption strength of ORR intermediates on four nitrogen coordinated metals is weaker than the three coordinated metals, which promotes favourable ORR activities. As a result, we recommended FeIr, FeRh, FeRu and FeOs as promising ORR catalysts. Ab initio molecular dynamic (AIMD) simulations suggest Fe/M-N-C (M = Ir, Rh, Ru and Os) catalysts with encouraging structural stability at room temperature. Furthermore, it is found that the nitrogen atoms in-between metals are vulnerable sites for proton attacking, yet the protonation process demands high energy, even under O2 atmosphere, which underlines good tolerance under acidic conditions. This work provides a broad understanding of Fe based catalyst and a new direction for catalytic design.