Molecular architectures of iron complexes for oxygen reduction catalysis-Activity enhancement by hydroxide ions coupling.

Developing cost-effective and high-performance electrocatalysts for oxygen reduction reaction (ORR) is critical for clean energy generation. Here, we propose an approach to the synthesis of iron phthalocyanine nanotubes (FePc NTs) as a highly active and selective electrocatalyst for ORR. The performance is significantly superior to FePc in randomly aggregated and molecularly dispersed states, as well as the commercial Pt/C catalyst. When FePc NTs are anchored on graphene, the resulting architecture shifts the ORR potentials above the redox potentials of Fe2+/3+ sites. This does not obey the redox-mediated mechanism operative on conventional FePc with a Fe2+-N moiety serving as the active sites. Pourbaix analysis shows that the redox of Fe2+/3+ sites couples with HO- ions transfer, forming a HO-Fe3+-N moiety serving as the ORR active sites under the turnover condition. The chemisorption of ORR intermediates is appropriately weakened on the HO-Fe3+-N moiety compared to the Fe2+-N state and thus is intrinsically more ORR active.

Importing Antibonding-Orbital Occupancy through Pd-O-Gd Bridge Promotes Electrocatalytic Oxygen Reduction.

The active-site density, intrinsic activity, and durability of Pd-based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series of carbon-based rare-earth (RE) oxides (Gd2 O3 , Sm2 O3 , Eu2 O3 , and CeO2 ) by using RE metal-organic frameworks to tune the ORR performance of the Pd sites through the Pd-REx Oy interface interaction. Taking Pd-Gd2 O3 /C as a representative, it is identified that the strong coupling between Pd and Gd2 O3 induces the formation of the Pd-O-Gd bridge, which triggers charge redistribution of Pd and Gd2 O3 . The screened Pd-Gd2 O3 /C exhibits impressive ORR performance with high onset potential (0.986 VRHE ), half-wave potential (0.877 VRHE ), and excellent stability. Similar ORR results are also found for Pd-Sm2 O3 /C, Pd-Eu2 O3 /C, and Pd-CeO2 /C catalysts. Theoretical analyses reveal that the coupling between Pd and Gd2 O3 promotes electron transfer through the Pd-O-Gd bridge, which induces the antibonding-orbital occupancy of Pd-*OH for the optimization of *OH adsorption in the rate-determining step of ORR. The pH-dependent microkinetic modeling shows that Pd-Gd2 O3 is close to the theoretical optimal activity for ORR, outperforming Pt under the same conditions. By its ascendancy in ORR, the Pd-Gd2 O3 /C exhibits superior performance in Zn-air battery as an air cathode, implying its excellent practicability.